KR100689941B1 - Aqueous Dispersion Composition Comprising Agent Repelling Water and Oil - Google Patents

Abstract

From the (A) fluorine-containing polymer and (B) the polyoxyethylene block of the present invention, the polyoxyalkylene block (the alkylene group has 3 or more carbon atoms) on the outside of the molecule such that the polyoxyalkylene block exists. The water- and oil-repellent aqueous dispersion composition, wherein the polyoxyethylene block contains a nonionic surfactant which is a copolymer having a structure inside the molecule, has a better water- and oil-repellent property than the conventional water- and oil-repellent aqueous dispersion composition. It is excellent in processing stability.

Aqueous dispersion compositions, water and oil repellent, fluorine-containing polymers, surfactants

Description

Aqueous Dispersion Composition Comprising Agent Repelling Water and Oil}

The present invention relates to a water-dispersible water-repellent oil repellent agent and a method for producing the water-repellent oil repellent property, particularly in particular to nylon is significantly improved imparting to the synthetic fiber.

It is known that polymers of polymerizable compounds having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group or a methacrylic acid group are useful as a water / oil repellent agent of a textile fabric, in particular dispersing the polymer in an aqueous medium by an emulsifier. Aqueous dispersions have been widely used industrially. WO00 / 37583 proposes a method for providing a water-dispersible water and oil repellent having a durable water and oil repellency and good storage stability using a specific organic solvent. Japanese Patent Laid-Open Publication No. 2002-275453 discloses a polyoxyethylene chain at both ends of a polyoxyalkylene chain which is a specific emulsifier in order to obtain a water-dispersible water and oil repellent composition having good water and oil repellency and excellent manufacturing stability and product storage stability. A manufacturing method using the block copolymer which arrange | positioned and the specific polymerization initiator is proposed. However, also in the said water- and oil-repellent composition, it did not provide what shows satisfactory water- and oil-repellent property, especially oil-repellency according to the variety of recent water- and oil-repellent processes.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a water-dispersible oil- and oil-repellent aqueous dispersion composition having excellent water and oil repellency, in particular oil repellency, and excellent processing stability than the conventional water and oil repellent composition.

The present invention relates to (A) at least one homopolymer or copolymer of a polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group or a methacrylic acid group or an α-substituted acrylic acid group, or a polymerizable compound copolymerizable therewith. A fluorine-containing polymer that is a copolymer with and (B) a polyoxyalkylene block (the alkylene group has 3 or more carbon atoms) on the outside of the molecule such that the polyoxyalkylene block exists from the polyoxyethylene block toward the outside of the molecule; It provides a water- and oil-repellent aqueous dispersion composition, characterized in that the polyoxyethylene block contains a nonionic surfactant which is a copolymer having a structure inside the molecule.

The present invention is characterized in that the water- and oil-repellent aqueous dispersion composition is applied to a gas, and the polymer (A) is attached to the gas, and the gas is treated with the water- and oil-repellent aqueous dispersion composition. The obtained processed material is also provided.

In the fluorine-containing polymer (A), of a copolymer with another polymerizable compound copolymerizable with a fluoro-containing polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group or a methacrylic acid group or an α-substituted acrylic acid group. In the case, the former is 25 weight% or more in a copolymer, Preferably it is 40 weight% or more.

Examples of the fluorine-containing polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group or a methacrylic acid group or an α-substituted acrylic acid group include a (meth) acrylate ester represented by the following formula.

(1)

(One)

(2)

(2)

(3)

(3)

(4)

(4)

(5)

(5)

(6)

(6)

Wherein Rf is a perfluoroalkyl group or a perfluoroalkenyl group having 1 to 21 carbon atoms (for example, 3 to 21),

R ¹ is hydrogen or an alkyl group having 1 to 10 carbon atoms,

R ² is an alkylene group having 1 to 10 carbon atoms,

R ³ is a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom) , A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group,

Ar is an aryl group which may have a substituent,

n represents the integer of 1-10.

In the above formula, Rf group is preferably a perfluoroalkyl group. The carbon number of the Rf group is 1 to 21, further 2 to 20, particularly 4 to 16, for example, 6 to 14. The carbon number of the Rf group may be 1 to 6, in particular 1 to 4. An example of the Rf group

And so on.

The specific example of the fluorine-containing polymeric compound which has an acrylic acid group or a methacrylic acid group is as follows.

In the α-substituted acrylic acid group, examples of the α-substituent include an alkyl group (eg, a monofluoromethyl group and a difluoromethyl group) in which a hydrogen atom is substituted with a halogen atom or a halogen atom (eg, having 1 to 21 carbon atoms). , Cyano group, and aromatic group (for example, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl group).

Specific examples of the fluorine-containing polymerizable compound having an α-substituted acrylic acid group are as follows.

In formula, Rf is a C1-C21 linear or branched perfluoroalkyl group or a perfluoro alkenyl group.

There are various kinds of other copolymerizable polymerizable compounds.

(1) acrylic acid and methacrylic acid and their methyl, ethyl, butyl, isobutyl, t-butyl, propyl, 2-ethylhexyl, hexyl, decyl, lauryl, stearyl, isobornyl, β-hydroxyethyl , Glycidyl, phenyl, benzyl, 4-cyanophenyl esters,

(2) vinyl esters of fatty acids such as acetic acid, propionic acid, caprylic acid, lauryl acid, stearic acid,

(3) Styrene-based compounds, such as styrene, (alpha) -methylstyrene, and p-methylstyrene,

(4) vinyl halide or vinylidene compounds such as vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride and vinylidene chloride;

(5) aliphatic allyl esters such as allyl heptanoic acid, allyl caprylic acid, and allyl caproic acid;

(6) vinyl alkyl ketones such as vinyl methyl ketone and vinyl ethyl ketone;

(7) acrylamides such as N-methylacrylamide and N-methylol methacrylamide, and

(8) dienes such as 2,3-dichloro-1,3-butadiene, isoprene and the like can be exemplified.

As other polymerizable compounds, it is preferable to include chlorine-containing polymerizable compounds (for example, vinyl chloride and vinylidene chloride) (in an amount of, for example, 1 to 50% by weight relative to the polymer).

The average molecular weight of the fluoropolymer (A) may be 1000 to 10000000, for example 1000 to 1000000.

The composition of the present invention comprises a surfactant (B). The surfactant (B) has a polyoxyalkylene block (the alkylene group has 3 or more carbon atoms) on the outside of the molecule such that the polyoxyalkylene block exists from the polyoxyethylene block toward the outside of the molecule. It has a chemical structure inside of a molecule. In surfactant (B), the number of polyoxyethylene blocks is one or more, and the number of polyoxyalkylene blocks is two or more. For example, surfactant (B) is a triblock type copolymer which is a structure which arrange | positions the polyoxyethylene block in the center of (1) molecule, and arranges the polyoxyalkylene block in the both ends, or (2) It may be a copolymer having a 2 to 6 valent organic group (eg, a tetravalent ethylenediamine group) in the center of the molecule, and a polyoxyethylene block-polyoxyalkylene block bonded to the organic group.

The polyoxyethylene block is hydrophilic and the polyoxyalkylene block (the alkylene group has 3 or more carbon atoms) is hydrophobic. Carbon number in oxyalkylene may be 3-10, for example. As oxyalkylene, oxypropylene, oxybutylene, etc. are mentioned, Especially, oxypropylene is preferable.

Examples of the surfactant (B) are copolymers represented by the following general formula (1) and copolymers represented by the following general formula (2).

^{A 11 0- (R 11 0)} a - (CH 2 CH 2 O) b - (R 12 O) c -A 12

In formula, A <^11> and A <^12> are a hydrogen atom, a C1-C22 alkyl group, a C2-C22 alkenyl group, or R <^13> C (= O)-(where R <^13> is a C1-C22 alkyl group or C2 To alkenyl groups), R ¹¹ and R ¹² are alkylene groups having 3 or more carbon atoms, a, b and c are 2 or more numbers, and b is a weight ratio of 5 to 80 polyoxyethylene blocks with respect to the copolymer. It is the number to be weight%.

In formula, A <^21> , A <^22> , A <^23> and A <^24> are a hydrogen atom, a C1-C22 alkyl group, a C2-C22 alkenyl group, or R <^13> C (= O)-(where R <^13> is C1-C1- An alkyl group of 22 or an alkenyl group having 2 to 22 carbon atoms,

Each R ²¹ is the same or different and is an alkylene group having 3 or more carbon atoms,

Each x and y is the same or different and is two or more numbers, and x is a number such that the weight ratio of polyoxyethylene blocks to the copolymer is from 5 to 80% by weight.

The average molecular weight of the surfactant (B) may be 500 to 20000, for example 1000 to 15000. It is preferable that the average molecular weight of the copolymer of Formula (1) is 1000-10000, and it is preferable that the average molecular weight of the copolymer of Formula (2) is 2000-15000. The average molecular weight is measured by gel permeation chromatography (GPC) in terms of standard polyethylene glycol.

The specific example of surfactant (B) is as follows.

Wherein a, b, c, x and y are two or more numbers.

The proportion of the polyoxyethylene block has a lower limit of 5% by weight, for example 7% by weight, in particular 10% by weight, with an upper limit of 80% by weight, for example 50, based on the molecular weight of the surfactant (B) (copolymer). The ratio may be 40% by weight, in particular 40% by weight, in particular 35% by weight. Surfactant (B) may be used individually by 1 type, and may use 2 or more types together.

The surfactant (B) is added to the polymerization liquid as a protective colloid before emulsifying the monomer, or after polymerization after emulsification, or after polymerization of the monomer, in order to improve the stability of the emulsion. The amount of the surfactant (B) may be 0.01 to 30 parts by weight, for example 1 to 20 parts by weight, per 100 parts by weight of the polymer (A), but the storage stability and the texture are not impaired depending on the amount to be added.

In this invention, in addition to surfactant (B), it is preferable to use surfactant (C) other than surfactant (B) together. Although cationic, anionic or nonionic emulsifiers are mentioned as surfactant (C), It is preferable that they are a cationic emulsifier, a nonionic emulsifier, or a mixture of both.

Cationic emulsifiers include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl) trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi (hydro Polyoxyethylene) ammonium chloride, benzyldodecyldi (hydropolyoxyethylene) ammonium chloride, di-cured tallow alkyldimethylammonium chloride, N- [2- (diethylamino) ethyl] oleamide hydrochloride.

Nonionic emulsifiers include ethylene oxide and hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkanes (C ₁₂ to C ₁₆ ) thiol, sorbitan monofatty acid (C ₇ to C ₁₉ ) or alkyl (C ₁₂ to C _18). ) Condensation products with amines and the like.

The surfactant (C) is added to the polymerization liquid before emulsifying the monomer, or after polymerization after emulsification, or after polymerizing the monomer.

The amount of the surfactant (C) may be 40 parts by weight or less, preferably 0.01 to 30 parts by weight, for example 1 to 20 parts by weight, per 100 parts by weight of the polymer (A).

In this invention, an organic solvent can be added as needed for the purpose of the dispersibility improvement of a polymer. Examples of the organic solvent include ketones such as acetone and methyl ethyl ketone, ethylene glycol derivatives such as ethylene glycol and polyethylene glycol, and alkyl ethers of ethylene glycol derivatives such as polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether and polyethylene glycol monobutyl ether. , Propylene glycol derivatives such as propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, polyethers such as cyclodextrin, dextrin, esters such as methyl acetate and ethyl acetate, and N-alkylpyrrolidone. Can be. The amount of the organic solvent may be 5 to 200 parts by weight, for example 10 to 100 parts by weight, in particular 20 to 80 parts by weight, per 100 parts by weight of the polymer.

In order to manufacture the aqueous dispersion liquid of this invention, emulsion polymerization of a polymeric compound is carried out in the water which added the organic solvent in presence of a polymerization initiator and surfactant as needed, and the emulsion of a polymer is obtained. If necessary, water and / or surfactant are added to the emulsion. Moreover, an organic acid can also be used as needed.

In addition, additives such as crosslinking agents, other polymers, other water repellents, oil repellents, antifouling agents, insect repellents, flame retardants, antistatic agents, dye stabilizers, anti-wrinkle agents, flame retardants, texture agents, soft finish agents, antifoaming agents, etc. It may also include.

As a crosslinking agent, a blocked isocyanate compound, a melamine resin compound, a glyoxal resin compound, a urea resin compound, and a crosslinkable monomer (N-methylol acrylamide, a block product of 2-isocyanate ethyl methacrylate, etc.) are used as essential polymerization units. A polymer etc. are mentioned, A blocked isocyanate compound or a melamine resin compound is preferable. Here, as a blocked isocyanate compound, it is a compound which does not have a polymerizable unsaturated group, and the structure of the structure which blocked the isocyanate group of polyisocyanate with the blocking agent is preferable. Trimethylol melamine, hexamethylol melamine, etc. are mentioned as a melamine resin compound.

Suitable gases to which the aqueous dispersions of the present invention are applied are films, fibers, yarns, wovens, carpets and articles made of filaments, fibers or yarns obtained from natural or modified polymeric or synthetic polymeric materials. The gas is preferably a fibrous product in the form of fibers, yarns or cloth.

The base is preferably composed of nylon fibers alone or a mixture of nylon fibers and other fiber materials. Nylon is manufactured and sold in several kinds according to the manufacturing method, but any may be used regardless of the manufacturing method. Examples thereof include nylon 6, nylon 66, nylon 610, nylon 12, and copolymerized nylon having a raw material component used for the production thereof. As a mixture of nylon fibers and other fiber materials, for example, a mixture of nylon and polyester, a mixture of nylon and cotton, a mixture of nylon and polyurethane, a mixture of nylon, cotton and polyurethane, a mixture of nylon and wool, nylon, A mixture of acrylic and polyurethane, a mixture of nylon, polyester and hemp; and the like.

In order to apply the aqueous dispersion to the gas, preference is given to applying, dipping, blowing, padding, roll coating or a combination of these methods. For example, it is used as a pad bath by making solid content of a bath into 0.1 to 10 weight%. The gas is padded in this bath and then the excess liquid is usually removed with a tightening roll so that the dry absorption (weight of the dry polymer on the gas) is about 0.01 to 1% by weight of the gas. Subsequently, the treatment gas is preferably heated to 100 to 200 ° C.

Hereinafter, an Example and a comparative example are given and this invention is demonstrated in detail.

The characteristic was measured as follows.

Water repellent

The treatment liquid is prepared by diluting the polymer dispersion with water so that the solid content concentration is 0.5% by weight. Nylon taffeta cloth (Nature, Kanebo, nylon 6, navy blue dyeing cloth) was immersed in the treatment liquid and tightened with mangle, dried at 100 ° C. for 2 minutes at a wet pick-up rate of 40%, and heat treated at 160 ° C. for 1 minute. After that, the water and oil repellency of the treated cloth is evaluated.

Water repellency is shown by the water repellency number (refer Table 1 below) by the spray method of JIS-L-1092.

Oil repellency is caused by AATCC-TM118 dropping two drops of the test solution shown in Table 2 on the test cloth and observing the penetration state after 30 seconds to obtain the highest oil repellency provided by the test solution without immersion. Do it with a meteor.

Water repellent number condition 5  Free from adhesion wetting to the surface 4  Slightly adhering to the surface 3  With partial wetting on the surface 2  Showing wetting on the surface One  Showing wetting throughout the surface

Oil repellent Test solution Surface tension (dyne / cm, 25 ℃) 8  n-heptane 20.0 7  n-octane 21.8 6  n-decane 23.5 5  n-dodecane 25.0 4  n-tetradecane 26.7 3  n-hexadecane 27.3 2  n-hexadecane 35 / nusol 65 mixed solution 29.6 One  Nusol 31.2 0  Less than one -

Water repellent Oil-repellent  Laundry durability

The washing by JIS L-0217-103 method is repeatedly performed three times, and subsequent water / oil repellency is evaluated (HL-3).

Storage stability

The aqueous dispersion (solid weight 30% by weight) is stored at 40 ° C. for 1 month, and sedimentation is observed.

○: no sedimentation at all

△: slightly settling

×: much sedimentation

Texture

The nylon (Ny) cloth which processed 5% of concentrations was prepared, and these differences were judged by the following reference | standards by the finger touch.

○: almost same as untreated cloth

△: slightly harder than untreated cloth, but not a problem

×: Harder than untreated cloth

<Example 1>

100 g, stearylacrylate 50 g of C _n F _{2n +1} CH ₂ CH ₂ OCOCH = CH ₂ (a mixture of compounds of n = 6, 8, 10, 12, 14 (n average 8)) in a 1 L flask g, N-methylol acrylamide 2 g, pure water 200 g, dipropylene glycol monomethyl ether 50 g, acetic acid 0.3 g, polyoxyethylene lauryl ether 4 g, polyoxyethylene cetyl ether 10 g, polyoxypropylene- polyoxyethylene-polyoxypropylene triblock copolymer _{[HO- (C 3 H 6 O} ) a - (CH 2 CH 2 O) b - of _c -H (formula _{(C 3 H 6 O),} a, b and c is a number of 2 or more) (average molecular weight 3100, oxyethylene ratio of 20% by weight)] 4 g was added and emulsified and dispersed ultrasonically at 60 ° C. for 15 minutes under stirring. 0.75 g of 2,2'-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer.

The properties of the aqueous dispersions were evaluated. The results are shown in Table 3 below.

<Example 2>

A flask of _{1 L C n F 2n +1 CH} 2 CH 2 OCOCH = CH ( a mixture of compounds of n = 6, 8, 10, 12, 14 (n average 8)) ₂ 100 g, stearyl methacrylate 50 g, 2 g of 3-chloro-2-hydroxypropylmethacrylate, 200 g of pure water, 40 g of tripropylene glycol, 0.3 g of acetic acid, 4 g of octadecyltrimethylammonium chloride, 10 g of polyoxyethylene lauryl ether The mixture was emulsified and ultrasonically dispersed at 60 ° C. for 15 minutes under stirring. 0.75 g of 2,2'-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. Further, in the water-based dispersion of polyoxypropylene-polyoxyethylene-polyoxypropylene triblock copolymer _{[HO- (C 3 H 6 O} ) a - (CH 2 CH 2 O) b - (C 3 H 6 O) c 3 g of -H (wherein a, b and c are two or more water) (average molecular weight 3100, oxyethylene ratio 20 wt%) was added thereto, and the mixture was stirred for 1 hour to obtain an aqueous dispersion.

The properties of the aqueous dispersions were evaluated. The results are shown in Table 3.

<Example 3>

100 g, stearylacrylate 25, C _n F _{2n +1} CH ₂ CH ₂ OCOCH = CH ₂ (mixture of compounds of n = 6, 8, 10, 12, 14 (average of n 8)) in a 1 L flask g, 2-ethylhexyl methacrylate 25 g, diacetone acrylamide 1.2 g, 3-chloro-2-hydroxypropyl methacrylate 0.8 g, pure water 200 g, tripropylene glycol 80 g, acetic acid 0.3 g, octa decyl trimethyl ammonium chloride 4 g, polyoxyethylene cetyl ether 6 g, polyoxypropylene-polyoxyethylene-polyoxypropylene triblock copolymer _{[HO- (C 3 H 6 O} ) a - (CH 2 CH 2 O) b -(C ₃ H ₆ O) _c -H (wherein a, b and c are numbers of 2 or more) (average molecular weight 2800, ratio of oxyethylene 10 wt%)] 4 g was added and stirred at 60 ° C. for 15 minutes. Emulsified and dispersed by ultrasound. 0.75 g of 2,2'-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. Further, in the water-based dispersion of polyoxypropylene-polyoxyethylene-polyoxypropylene triblock copolymer _{[HO- (C 3 H 6 O} ) a - (CH 2 CH 2 O) b - (C 3 H 6 O) c 3 g of -H (wherein a, b and c are two or more water) (average molecular weight 2800, polyoxyethylene ratio 10 wt%)] was added thereto, and the mixture was stirred for 1 hour to obtain an aqueous dispersion.

The properties of the aqueous dispersions were evaluated. The results are shown in Table 3.

<Example 4>

150 g, stearyl acrylate, in a 1 L autoclave C _n F _{2n +1} CH ₂ CH ₂ OCOCH = CH ₂ (mixture of compounds of n = 6, 8, 10, 12, 14 (n average 8)) 75 g, diacetone acrylamide 3 g, pure water 300 g, dipropylene glycol monomethyl ether 75 g, acetic acid 0.45 g, di-cured tallow alkyldimethylammonium chloride 6 g, polyoxyethylene cetyl ether 9 g, polyoxypropylene- polyoxyethylene-polyoxypropylene triblock copolymer _{[HO- (C 3 H 6 O} ) a - (CH 2 CH 2 O) b - of _c -H (formula _{(C 3 H 6 O),} a, b and c is a number of 2 or more) (average molecular weight 3100, oxyethylene ratio of 20% by weight)] 6 g was added and emulsified and dispersed ultrasonically at 60 ° C. for 15 minutes under stirring. After emulsification, 1.5 g of n-dodecyl mercaptan was added, and 45 g of vinyl chloride was further press-filled. Further, 1.12 g of 2,2'-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer.

The properties of the aqueous dispersions were evaluated. The results are shown in Table 3.

<Example 5>

150 g, stearyl acrylate, in a 1 L autoclave C _n F _{2n +1} CH ₂ CH ₂ OCOCH = CH ₂ (mixture of compounds of n = 6, 8, 10, 12, 14 (n average 8)) 37.5 g, lauryl acrylate 37.5 g, N-methylol acrylamide 1.8 g, 3-chloro-2-hydroxypropyl methacrylate 1.2 g, pure water 300 g, tripropylene glycol 75 g, ethylene glycol 15 g, 0.45 g of acetic acid, 6 g of di-cured tallow alkyldimethylammonium chloride, and 15 g of polyoxyethylene lauryl ether were added thereto, and the mixture was emulsified and dispersed ultrasonically at 60 ° C. for 15 minutes under stirring. After emulsification, 1.5 g of n-dodecyl mercaptan was added, and 45 g of vinyl chloride was further press-filled. Further, 1.12 g of 2,2'-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. Further, in the water-based dispersion of polyoxypropylene-polyoxyethylene-polyoxypropylene triblock copolymer _{[HO- (C 3 H 6 O} ) a - (CH 2 CH 2 O) b - (C 3 H 6 O) c -H (wherein a, b and c are two or more water) (average molecular weight 2800, oxyethylene ratio of 10 wt%)] was added 4.5 g, and the mixture was stirred for 1 hour to obtain an aqueous dispersion.

The properties of the aqueous dispersions were evaluated. The results are shown in Table 3.

Comparative Example 1

100 g, stearylacrylate 50 g of C _n F _{2n +1} CH ₂ CH ₂ OCOCH = CH ₂ (a mixture of compounds of n = 6, 8, 10, 12, 14 (n average 8)) in a 1 L flask g, N-methylol acrylamide 1.2 g, 3-chloro-2-hydroxypropyl methacrylate 0.8 g, pure water 200 g, dipropylene glycol monomethyl ether 30 g, acetic acid 0.3 g, octadecyltrimethylammonium chloride 4 g and 10 g of polyoxyethylene lauryl ether were added and emulsified and dispersed ultrasonically at 60 ° C. for 15 minutes under stirring. Further, 0.75 g of 2,2'-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer.

The properties of the aqueous dispersions were evaluated. The results are shown in Table 3.

Comparative Example 2

A flask of _{1 L C n F 2n +1 CH} 2 CH 2 OCOCH = CH ( a mixture of compounds of n = 6, 8, 10, 12, 14 (n average 8)) ₂ 100 g, stearyl methacrylate 50 g, 2 g of 3-chloro-2-hydroxypropylmethacrylate, 200 g of pure water, 40 g of tripropylene glycol, 0.3 g of acetic acid, 4 g of octadecyltrimethylammonium chloride, 6 g of polyoxyethylene cetyl ether, poly Oxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer [HO- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q- (CH ₂ CH ₂ O) _r -H , q and r are two or more water) (average molecular weight 2900, polyoxyethylene ratio of 40 wt%)] 4 g was added and emulsified and dispersed ultrasonically at 60 ° C. for 15 minutes under stirring. 0.75 g of 2,2'-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer.

The properties of the aqueous dispersions were evaluated. The results are shown in Table 3.

Comparative Example 3

100 g, stearylacrylate 25, C _n F _{2n +1} CH ₂ CH ₂ OCOCH = CH ₂ (mixture of compounds of n = 6, 8, 10, 12, 14 (average of n 8)) in a 1 L flask g, 2-ethylhexyl methacrylate 25 g, diacetone acrylamide 1.2 g, 3-chloro-2-hydroxypropyl methacrylate 0.8 g, pure water 200 g, tripropylene glycol 80 g, acetic acid 0.3 g, di 4 g of cured tallow alkyldimethylammonium chloride and 10 g of polyoxyethylene lauryl ether were added thereto, and the resultant was emulsified and dispersed ultrasonically at 60 ° C. for 15 minutes under stirring. Further, 0.75 g of 2,2'-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. Furthermore, in this aqueous dispersion, a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer [HO- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q- (CH ₂ CH ₂ O) _r -H (wherein p, q and r are two or more water) (average molecular weight 2900, polyoxyethylene ratio 40 wt%)] was added thereto, and the mixture was stirred for 1 hour to obtain an aqueous dispersion.

The properties of the aqueous dispersions were evaluated. The results are shown in Table 3.

<Comparative Example 4>

150 g, stearyl acrylate, in a 1 L autoclave C _n F _{2n +1} CH ₂ CH ₂ OCOCH = CH ₂ (mixture of compounds of n = 6, 8, 10, 12, 14 (n average 8)) 75 g, diacetone acrylamide 3 g, pure water 300 g, dipropylene glycol monomethyl ether 75 g, acetic acid 0.45 g, di-cured tallow alkyldimethylammonium chloride 6 g, polyoxyethylene cetyl ether 15 g and stirred Emulsion dispersion was sonicated at 15 ° C. for 15 minutes. After emulsification, 1.5 g of n-dodecyl mercaptan was added, and 45 g of vinyl chloride was further press-filled. Further, 1.12 g of 2,2'-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer.

The properties of the aqueous dispersions were evaluated. The results are shown in Table 3.

Comparative Example 5

150 g, stearyl acrylate, in a 1 L autoclave C _n F _{2n +1} CH ₂ CH ₂ OCOCH = CH ₂ (mixture of compounds of n = 6, 8, 10, 12, 14 (n average 8)) 37.5 g, lauryl acrylate 37.5 g, N-methylol acrylamide 1.8 g, 3-chloro-2-hydroxypropyl methacrylate 1.2 g, pure water 300 g, tripropylene glycol 75 g, ethylene glycol 15 g, 0.45 g of acetic acid, 6 g of di-cured tallow alkyldimethylammonium chloride, and 15 g of polyoxyethylene lauryl ether were added thereto, and the mixture was emulsified and dispersed ultrasonically at 60 ° C. for 15 minutes under stirring. After emulsification, 1.5 g of n-dodecyl mercaptan was added, and 45 g of vinyl chloride was further press-filled. Further, 1.12 g of 2,2'-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. Furthermore, in this aqueous dispersion, a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer [HO- (CH ₂ CH ₂ O) _p- (C ₃ H ₆ O) _q- (CH ₂ CH ₂ O) _r 6 g of -H (wherein p, q and r are two or more water) (average molecular weight 2900, polyoxyethylene ratio 40 wt%)] was added thereto, and the mixture was stirred for 1 hour to obtain an aqueous dispersion.

The properties of the aqueous dispersions were evaluated. The results are shown in Table 3.

According to the present invention, it is possible to obtain a water-dispersible oil and oil repellent aqueous dispersion composition excellent in water and oil repellency, in particular oil and oil repellency, and excellent in process stability than conventional water and oil repellent aqueous dispersion compositions.

Claims (10)

(A) at least one homopolymer or copolymer of a polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group or a methacrylic acid group or an α-substituted acrylic acid group, or a polymerizable compound copolymerizable with these A fluorine-containing polymer which is a copolymer, and (B) The polyoxyalkylene block (the number of carbon atoms of the alkylene group is 3 or more) is on the outside of the molecule so that the polyoxyalkylene block exists from the polyoxyethylene block toward the outside of the molecule, and the polyoxyethylene block is on the inside of the molecule. A water- and oil-repellent aqueous dispersion composition comprising a nonionic surfactant, which is a copolymer having a structure in it. The composition according to claim 1, wherein the surfactant (B) is a triblock copolymer having a structure in which a polyoxyethylene block is arranged at the center of the molecule and a polyoxyalkylene block is arranged at both ends thereof. The composition according to claim 2, wherein the surfactant (B) is a copolymer represented by the following formula (1). <Formula 1> ^{A 11 0- (R 11 0)} a - (CH 2 CH 2 O) b - (R 12 O) c -A 12 Wherein A ¹¹ and A ¹² represent a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, or R ¹³ C (═O) — (wherein R ¹³ is an alkyl group having 1 to 22 carbon atoms or 2 carbon atoms) To alkenyl groups), R ¹¹ and R ¹² are alkylene groups having 3 or more carbon atoms, a, b and c are 2 or more numbers, and b is a weight ratio of 5 to 80 polyoxyethylene blocks with respect to the copolymer. It is the number to be weight%. The composition according to claim 1, wherein the surfactant (B) is a copolymer having a 2 to 6 valent organic group in the center of the molecule and a polyoxyethylene block-polyoxyalkylene block bonded to the organic group. The composition according to claim 4, wherein the surfactant (B) is a copolymer represented by the following formula (2). <Formula 2>

In formula, A <^21> , A <^22> , A <^23> and A <^24> are a hydrogen atom, a C1-C22 alkyl group, a C2-C22 alkenyl group, or R <^13> C (= O)-(where R <^13> is C1-C1- Alkyl group of 22 or alkenyl group having 2 to 22 carbon atoms, Each R ²¹ is the same or different and is an alkylene group having 3 or more carbon atoms, Each x and y is the same or different and is two or more numbers, and x is a number such that the weight ratio of polyoxyethylene blocks to the copolymer is from 5 to 80% by weight. The composition according to claim 1, wherein the polyoxyalkylene block in the surfactant (B) is a polyoxypropylene block. The water- and oil-repellent agent aqueous dispersion composition of Claim 1 is applied to a base, and the fluorine-containing polymer (A) is made to adhere to a base, The processing method of the gas characterized by the above-mentioned. 8. The method of claim 7, wherein the gas is nylon fibers alone or a mixture of nylon fibers and other fibers. 8. The method of claim 7, wherein the water / oil repellent aqueous dispersion composition is prepared by adding a surfactant (B) to a liquid comprising a fluorine-containing polymer (A). A treated product obtained by treating a gas with the water / oil repellent aqueous dispersion composition according to claim 1, wherein the gas is nylon fiber alone or a mixture of nylon fibers and other fibers.