TW201605999A - Fluorine-free water-repellent agent composition and water-repellent processing method - Google Patents

Abstract

Provided is a water-repellent agent composition which has excellent slippage resistance and is capable of imparting water repellency and water-repellent effect with excellent durability in terms of washing with use of a compound containing no fluorine. A water-repellent agent composition which contains an acrylic copolymer that is obtained by polymerizing 40% by weight or more but less than 80% by weight of a fluorine-free polymerizable monomer (A), which is a (meth)acrylate that has an alkyl group having 12-24 carbon atoms and not having a cyclic structure, and 10% by weight or more but less than 50% by weight of a fluorine-free polymerizable monomer (B), which is a polymerizable monomer that contains an aromatic ring having 6-12 carbon atoms, an aromatic ring having a substituent, a cycloalkane having 5-12 carbon atoms or a cycloalkane having a substituent.

Description

Fluoride-free water repellent composition and water treatment method

The present invention relates to a water repellent composition which does not contain fluorine and contains an acrylic copolymer in the field of water repellent processing of a fibrous product, and a water repellent processing method using the same.

In the method of treating a fibrous product using an aqueous dispersion to impart water repellency, an aqueous dispersion using a paraffin wax, a polyoxymethylene resin, or a fluorine resin is known. Since the fluorine-based resin exhibits more water repellency than the paraffin wax or the polyfluorene-based resin, it is widely used industrially in a method of imparting water repellency to a fiber product.

In 2000, it was pointed out that the perfluorooctanesulfonic acid (PFOS) was harmful, bioaccumulative, and environmentally polluting, and it was also indicated that all perfluorinated compounds containing 8 or more carbon atoms of perfluorooctanoic acid (PFOA) were also expressed. Worried. Therefore, the manufacturer of the fluorine-based water repellent develops a fluorine-based water repellent which does not contain such compounds and which does not contain such a compound as a decomposition product.

However, in recent years, irrespective of the carbon number, it is pointed out that the compound having a perfluoroalkyl group is inherently harmful and environmentally polluting. Therefore, in the field of water repellent processing of fibrous products, a water repellent agent to be used for the elimination of fluorine is also produced. The trend.

Conventionally, as a water-repellent composition containing no fluorine, a paraffin wax, a polyoxynene resin, or the like is known. However, these water repellency is worse than that of fluorine-based resins. Among them, in recent years, as a technique using a composition containing no fluorine, it has been proposed that the alkyl group having an ester moiety has a carbon number of 12 or more (meth) An aqueous dispersion of an olefin polymer is used as an aqueous dispersion which can replace a fluorine-based resin (Patent Document 1).

Further, as the same technique, an aqueous dispersion of a (meth) acrylate polymer containing no N-methylol compound and a paraffin wax having a melting point in the range of 58 to 80 ° C is disclosed, especially for woven fabrics, especially It is useful for water repellent processing of cotton, polyester or cotton-polyester blended fabric (Patent Document 2).

[Patent Document 1] JP-A-2006-328624

[Patent Document 2] Japanese Patent Publication No. 2012-522062

As a trend in recent years, in the field of demanding water-repellent processing, attention has been paid to lightweight and texture. From 55 to 110 dtex (50 to 100 d), the use of finer fibers of about 11 to 44 dtex (10 to 40 d) gradually increase. However, it has been found that when the fiber of 11 to 44 dtex is treated with an aqueous dispersion containing alkyl (meth)acrylate as a main component in Patent Document 1, the sliding resistance value becomes extremely large (sliding resistance is weak). tendency. Therefore, there is a problem that the thread is disconnected and the sewing portion is displaced at the time of sewing or wearing. Further, even if the paraffin wax appearing in Patent Document 2 is blended, the sliding resistance value cannot be improved.

Further, the copolymer having the alkyl (meth) acrylate as a main component in Patent Document 1 has insufficient emulsion stability, causing emulsification damage during fiber processing, resulting in adhesion of the resin to the processing apparatus or the treatment of the fabric. Happening.

In view of the above circumstances, an object of the present invention is to provide a water-repellent compound which can suppress the sliding resistance value and impart water repellency and excellent washing durability. The effect of the water repellent composition.

The inventors of the present invention have made an effort to study the above-mentioned problems, and have found that an acrylic copolymer obtained by copolymerizing a polymerizable monomer having a cyclic structure in a molecule has a water-repellent composition excellent in water repellency and sliding resistance. Further, it has been found that a (meth) acrylate having an alkyl group having 12 to 24 carbon atoms and an aromatic ring having a carbon number of 6 to 12 or a substituted aromatic ring or a cycloalkane having a carbon number of 5 to 12 ( A composition obtained by copolymerizing a polymerizable monomer of a cycloalkane having a substituent, or a water-repellent composition excellent in water repellency, washing durability, and sliding resistance, and excellent in emulsion stability, thereby completing this invention.

That is, the present invention relates to a water repellent composition comprising the following acrylic copolymer obtained by polymerizing a non-fluorine-containing polymerizable monomer (A) and (B).

The fluorine-free polymerizable monomer (A) has an alkyl (meth) acrylate having a carbon number of 12 to 24 and having no cyclic structure, and is 40% by weight or more and less than 80% by weight.

The fluorine-free polymerizable monomer (B) is a polymerizable monomer containing an aromatic ring having 6 to 12 carbon atoms or an aromatic ring having a substituent, or a cycloalkane having 5 to 12 carbon atoms or a cycloalkane having a substituent. 10% by weight or more, less than 50% by weight.

Further, the weight % indicates the weight ratio of each monomer to the acrylic copolymer.

More preferably, the alkyl group of the above (A) has a carbon number of 16 to 22.

The acrylic copolymer preferably further contains (C) a polymerizable monomer in an amount of 0.01% by weight or more and less than 10% by weight. The polymerizable monomer contains a hydroxyl group, an amine group, an epoxy group, and a blocked isocyanate group (blocked). At least one of the group consisting of isocyanate group), amidino group, N-hydroxymethyl group and fluorenyl group.

Further, the present invention relates to an aqueous dispersion containing the water repellent composition according to any one of the above and a nonionic surfactant. It is also preferred that the aqueous dispersion further contains a cationic surfactant.

Further, the present invention relates to a water-repellent processing method for a fibrous product, which comprises using the aqueous dispersion and (1) an aqueous dispersion or emulsion having a compound having two or more functional blocked isocyanate groups, and/or (2) N-methylol melamine.

Further, the present invention relates to a water-repellent processing method for a fibrous product, comprising: a step of immersing the fiber in a working liquid containing the aqueous dispersion; and, after the step, performing a heat treatment at a temperature of 100 ° C or higher.

Further, the present invention relates to a water-repellent fibrous product having the above-described water repellent composition.

The water repellent composition of the present invention does not contain fluorine, imparts excellent water repellency to the fiber, and is excellent in washing durability, and can suppress the sliding resistance value of the fiber after the treatment.

(water repellent composition)

The water repellent composition of the present invention contains an acrylic copolymer containing (A) A (meth) acrylate having no carbon group having a cyclic structure of 12 to 24 is used as a monomer.

a (meth) acrylate-based acrylic acid and/or methacrylic acid having an alkyl group having 12 to 24 carbon atoms and an alkyl group having a cyclic structure without a carbon number of 12 to 24, preferably 16 to 22 carbon atoms An ester of an alcohol, or a mixture of such esters. The alkyl group of the above alcohol may be a linear alkyl group or a branched alkyl group, and both of them may be used, and a linear alkyl group is preferred.

Examples of such (meth) acrylate include lauryl acrylate, cetyl acrylate, stearyl acrylate, isostearyl acrylate, behenyl acrylate, and lauryl methacrylate. And one or more of these may be used, such as hexadecyl methacrylate, stearyl methacrylate, isostearyl methacrylate, behenyl methacrylate, or the like.

The monomer (A) is contained in an amount of 40% by weight or more, preferably less than 80% by weight, preferably 60% by weight or more, and less than 80% by weight, based on the monomer unit of the acrylic copolymer. If it is less than 40% by weight, sufficient water repellency cannot be exhibited. On the other hand, when it is 80% by weight or more, it is difficult to simultaneously achieve water repellency and suppress the sliding resistance value.

In addition, the acrylic copolymer contains (B) an aromatic ring having a carbon number of 6 to 12 or an aromatic ring having a substituent, or a cycloalkane having 5 to 12 carbon atoms or a cycloalkane having a substituent. Polymerizable monomer.

Specific examples of the monomer (B) include styrene, α-methylstyrene, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, isodecyl (meth)acrylate, and Phenyloxyethyl methacrylate, naphthyl (meth) acrylate, (meth) acrylate 4 Polinylethyl ester, tetrahydrofurfuryl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tetramethylpiperidine methacrylate, cinnamon Methyl ester, ethyl cinnamate, and the like. Further, when the polymerizable monomer having a cyclic structure is a (meth) acrylate, the number of carbon atoms in the cyclic structure portion is preferably from 5 to 11.

The monomer (B) having a cyclic structure is contained in an amount of 10% by weight or more, preferably less than 50% by weight, preferably 15% by weight or more, and less than 40% by weight, based on the monomer unit of the acrylic copolymer. When it is less than 10% by weight, when it is processed into a fiber, the sliding resistance value cannot be sufficiently reduced, and if it is 50% by weight or more, the texture becomes hard and the water repellency is lowered.

Although not limited by the specific theory, it is considered that the water repellent composition of the present invention is obtained by using a (meth) acrylate having an alkyl group and a cyclic structure having a carbon number of a specific range. The ester is copolymerized, and a three-dimensional ring structure is disposed in the side chain of the copolymer. As a result, the smoothness of the fiber does not become excessively large, and the sliding resistance value (sliding resistance becomes strong) is suppressed.

The acrylic copolymer preferably further has (C) a polymerizable property containing at least one selected from the group consisting of a hydroxyl group, an amine group, an epoxy group, a blocked isocyanate group, a guanamine group, an N-methylol group, and a fluorenyl group. The monomer is 0.01% by weight or more, less than 10% by weight, preferably 0.1% by weight or more, and less than 5% by weight. By carrying out the copolymerization of these polymerizable monomers having a crosslinkable group, the washing durability can be improved. If it is less than 0.01% by weight, the effect of improving the washing durability may not be obtained. If it is 10% by weight or more, the water repellency may be affected.

Examples of the monomer (C) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxy-3-chloropropyl (meth)acrylate. 4-hydroxybutyl methacrylate, glycidyl (meth) acrylate, acrylamide, N-hydroxymethyl decylamine, polyalkylene glycol mono(meth) acrylate, methacrylic acid 2- [(3,5-Dimethylpyrazolyl)carbonylamino]ethyl ester, 2-(O-[1'-methylpropyleneamino]carboxyamino)ethyl methacrylate, etc., can be combined One or two or more kinds of polymerizable monomers selected from the group are used.

Further, in the range which does not impair the effects of the present invention, a known monomer other than the above may be contained in the acrylic copolymer. For example, it may contain a (meth) acrylate having a smaller carbon number (having a carbon number of 11 or less). Specifically, for example, it may contain methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, polyethylene glycol di (meth) acrylate, Methoxy polyethylene glycol methacrylate, methacrylic acid modified polyoxyl resin, vinyl chloride, vinylidene chloride, vinyl acetate, maleic acid diester, and the like.

As a method of producing the above acrylic copolymer, a known emulsion polymerization method can be used. For example, a monomer single addition method in which a monomer is added at a time; or a monomer dropping method in which a monomer is continuously added dropwise may be mentioned. Further, in the emulsification, in order to make the particles smaller, an emulsifier such as an ultrasonic wave or a homogenizer is preferably used.

The surfactant used for the emulsion polymerization is not particularly limited, and examples thereof include an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, and a polymer surfactant. In terms of treating the aqueous dispersion into a fibrous product, it is particularly preferable to use only a cationic surfactant or only a nonionic surfactant, or a cationic surfactant and a nonionic surfactant.

As the anionic surfactant, for example, various fatty acid salts, alkylbenzenesulfonates, alkanesulfonates, alkylsulfate salts, alkyl phosphate salts, polyoxyethylene alkyl ether sulfates, polyoxyethylenes can be used. Examples of the counter ion include sodium, potassium, calcium, ammonium, triethanolamine, and the like, but the present invention is not limited thereto.

As the nonionic surfactant, for example, a fatty acid ester such as various higher fatty acid glycerides, a polyoxyethylene alkyl ether, a polyoxypropylene alkyl ether, a polyoxyethylene fatty acid ester, a fatty acid alkanolamine, or an alkyl group can be used. Glucoside, higher alcohol, Pluronic active agent, Alkyl dimethylamine-N-oxide and the like.

As the cationic surfactant, for example, various alkyltrimethylammonium salts, alkyldimethylbenzylammonium salts, dialkyldimethylammonium salts, alkylpyridinium chloride salts, polyoxyethylenehexanes can be used. A quaternary salt such as a quaternary compound of a base amine, or an alkylamine salt, an alkyl dimethylamine salt, a polyoxyethylene alkylamine salt or the like, which can be obtained by neutralizing an amine with a suitable acid. Amine salt. Examples of the counter ion include chloride ion, bromide ion, sulfate ion, formate ion, acetate ion, methyl sulfate ion, and ethyl sulfate ion, but are not limited thereto.

Further, in the emulsion polymerization, in order to achieve emulsion stabilization and to improve the solubility of the polymerizable monomer, a known solvent can be used in combination. Examples of the solvent include ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether.

As the polymerization initiator used for the emulsion polymerization, a general radical initiator can be used. The radical polymerization initiator contains a water-soluble or oil-soluble persulfate, a peroxide, and an azobis compound. Specific examples thereof include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, benzammonium peroxide, t-butyl hydroperoxide, and t-butyl peroxybenzoate, 2, 2-azobisisobutyronitrile, 2,2-azobis(2-diaminopropane) hydrochloride, 2,2-azobis(2,4-dimethylvaleronitrile), etc., preferably It is water soluble.

The acrylic copolymer obtained by emulsion polymerization is used as an aqueous dispersion containing a water repellent composition, directly or optionally, through a known treatment step such as concentration, extraction, or purification.

In the aqueous dispersion of the present invention, in order to achieve water repellency improvement and texture adjustment, paraffin wax, methyl hydrogen polyoxynium oxide, octadecyl extended ethyl urea, alkyl ketene dimer, zirconyl octoate may be blended. An aqueous dispersion of a non-fluorine water repellent.

(Water treatment method for fiber products)

When the water repellent composition of the present invention is treated as a fibrous product, it is preferred to crosslink the (1) two or more functional blocked isocyanate aqueous emulsions, (2) N-methylol melamine or the like. The agent is used in combination with the above aqueous dispersion.

(1) The blocked isocyanate having two or more functional groups is obtained by reacting a bifunctional or higher isocyanate with a suitable blocking agent by a known method. Examples of the isocyanate include 4,4'-diisocyanate phenylmethane, toluene diisocyanate, hexamethylene diisocyanate, a diisocyanate trimer or a trimethylolpropane adduct.

Further, examples of the terminal blocking agent for isocyanate include secondary or tertiary alcohols, active methylene compounds, phenols, anthraquinones, substituted pyrazoles, and caprolactam. Usually, these blocked isocyanates are emulsified and dispersed by a surfactant by a well-known method. Further, after blocking 70 to 95% of all isocyanate groups in advance, a polyalkylene glycol having a suitable molecular weight, particularly polyethylene glycol, is reacted with a residual isocyanate group, whereby the blocked isocyanate is expressed. The emulsifiability not only improves the washing durability of the water repellent composition, but also exhibits an effect on the stability of the product.

Examples of the (2) N-methylol melamine include trimethylol melamine and hexamethylol melamine.

The water repellent composition of the present invention can be used to impart water repellency to an optical product having excellent washing durability. Therefore, the fibrous product is treated by a working fluid containing the water repellent composition of the present invention.

The processing liquid is obtained by diluting the above aqueous dispersion containing an acrylic copolymer or a surfactant, and the blocked isocyanate or N-methylol melamine into water by using water. Obtained by concentration. Further, other chemicals known in the field of finishing of fiber products, such as a softener, an antistatic agent, a flame retardant, etc., may be contained in the working fluid.

The water-repellent processing method for the fiber product is not particularly limited, and various methods can be employed as long as the required amount is attached to the fiber product to be subjected to water repellent processing, and examples thereof include a continuous method or a batch method.

The concentration of the acrylic copolymer in the working fluid is not particularly limited, and is appropriately selected depending on the treatment method or conditions. For example, when the treatment is carried out by a continuous method, the solid content concentration can be set to 0.3 to 5.0 by weight. %about. In the case of processing by the batch method, it can be set to about 0.3 to 3.0% o.w.f.

As a continuous method, first, the aqueous dispersion or the like of the present invention is diluted in water to adjust the working fluid. Next, the object to be processed is continuously fed into the impregnation apparatus filled with the fluid to be processed, and the processing liquid is impregnated with the processing liquid, and the unnecessary processing liquid is removed. The impregnation apparatus is not particularly limited, and a press dyeing machine, a spray type application device, a foam type application device, a coating type application device, or the like can be preferably used, and a pressure dyeing machine type is particularly preferable.

Then, an operation of removing the remaining water in the treated object using a dryer is performed. The dryer is not particularly limited, and is preferably a spreader such as a hot flue or a tenter. This continuous method is preferably used when the object to be treated is in the form of a fabric or the like.

The batch method consists of a step of immersing the workpiece in the processing liquid, and a step of removing water remaining in the workpiece after the step. The batch method is preferably used when the object to be treated is not cloth-like, for example, in the case where loose fibers, tops, yarns, or the like are not suitable for the continuous process. In the impregnation step, for example, a cotton dyeing machine, a yarn dyeing machine, a liquid flow dyeing machine, a warp beam dyeing machine, or the like can be used. In the operation of removing water, a dryer such as a bobbin dryer or a tumble dryer can be used. Dry machine, high frequency dryer, etc.

In either case, the drying (heat treatment) step of immersing the fiber as the object to be treated in the working solution may be carried out at 80 to 180 ° C, preferably at a temperature of 100 ° C or higher.

Hereinafter, the present invention will be described by way of examples. However, the invention is not limited to the embodiments.

[Example 1]

Manufacture of aqueous dispersion of acrylic copolymer (A)

60 g of hexadecyl methacrylate, 38 g of isodecyl methacrylate, 2 g of N-methylol acrylamide, 1 g of stearyl trimethylamine chloride, and polyoxyethylene (7 mol) were added to a 500 mL flask. Ear) 6 g of lauryl ether, 2 g of polyoxyethylene (21 mol) lauryl ether, 0.1 g of dodecyl mercaptan, 30 g of dipropylene glycol, and 224.7 g of ion-exchanged water, which were obtained by emulsification and dispersion at 50 ° C by high-speed stirring. Mixture. Thereafter, the mixture was treated at 40 MPa while maintaining the temperature at 40 ° C to obtain an emulsion. The emulsion was poured into a 500 mL three-necked flask equipped with a reflux cooling tube, and after cooling to room temperature, 0.3 g of azobis(isobutylphosphonium) dihydrochloride was added, and radical polymerization was carried out at 60 ° C under a nitrogen atmosphere. After 10 hours, 364 g of a product containing a polymer concentration of 30% by weight was obtained.

[Embodiment 2]

Method for producing aqueous dispersion of acrylic copolymer (B)

75 g of stearyl methacrylate, 20 g of styrene, 5 g of 2-hydroxyethyl methacrylate, 1 g of stearyl trimethylammonium chloride, and 6 g of polyoxyethylene (7 mol) lauryl ether were placed in a 500 mL flask. 2 g of polyoxyethylene (21 mol) lauryl ether, 0.1 g of dodecyl mercaptan, 30 g of dipropylene glycol, and 224.7 g of ion-exchanged water were emulsified and dispersed by stirring at 50 ° C to obtain a mixed liquid. Thereafter, the mixture was treated at 40 MPa while maintaining the temperature at 40 ° C to obtain an emulsion. The emulsion was poured into a 500 mL three-necked flask equipped with a reflux cooling tube, and after cooling to room temperature, 0.3 g of azobis(isobutylphosphonium) dihydrochloride was added, and radical polymerization was carried out at 60 ° C under a nitrogen atmosphere. After 10 hours, 364 g of a product containing 30% of a solid component was obtained.

[Example 3]

Method for producing aqueous dispersion of acrylic copolymer (C)

39.5 g of lauryl acrylate, 39.5 g of stearyl methacrylate, 18 g of cyclohexyl methacrylate, 3 g of N-methylol acrylamide, and 1 g of cocoalkyl trimethylammonium chloride were added to a 500 mL flask. Polyoxyethylene (10 mol) oleyl ether 6 g, polyoxyethylene (25 mol) oleyl ether 2 g, dodecyl mercaptan 0.1 g, dipropylene glycol 30 g and ion exchange water 224.7 g at 50 ° C by 50 ° C The mixture was emulsified and dispersed by high-speed stirring to obtain a mixed solution. Thereafter, the mixture was treated at 40 MPa while maintaining the temperature at 40 ° C to obtain an emulsion. The emulsion was poured into a 500 mL three-necked flask equipped with a reflux cooling tube, and after cooling to room temperature, 0.3 g of azobis(isobutylphosphonium) dihydrochloride was added, and radical polymerization was carried out at 60 ° C under a nitrogen atmosphere. After 10 hours, 364 g of an aqueous dispersion containing an acrylic copolymer having a solid content of 30% by weight was obtained.

[Example 4]

Method for producing aqueous dispersion of acrylic copolymer (D)

50 g of behenyl acrylate, 40 g of benzyl acrylate, 5 g of isodecyl methacrylate, 5 g of 2-hydroxyethyl methacrylate, 1 g of stearyl trimethylammonium chloride, and polyoxyethylene (7) were added to a 500 mL flask. Molar) 6 g of lauryl ether, 2 g of polyoxyethylene (21 mol) lauryl ether, 0.1 g of dodecyl mercaptan, 30 g of dipropylene glycol, and 224.7 g of ion-exchanged water, which were emulsified and dispersed by high-speed stirring at 50 ° C. A mixture was obtained. After that, use a high-pressure homogenizer while maintaining a temperature of 40 °C. The emulsion was treated under MPa to obtain an emulsion. The emulsion was poured into a 500 mL three-necked flask equipped with a reflux cooling tube, and after cooling to room temperature, 0.3 g of azobis(isobutylphosphonium) dihydrochloride was added, and radical polymerization was carried out at 60 ° C under a nitrogen atmosphere. After 10 hours, 364 g of an aqueous dispersion containing an acrylic copolymer having a solid content of 30% by weight was obtained.

[Example 5]

Method for producing aqueous dispersion of acrylic copolymer (E)

75 g of stearyl acrylate, 15 g of styrene, 8 g of methyl methacrylate, 2 g of 2-hydroxyethyl acrylate, 1 g of cocoalkyltrimethylammonium chloride, and polyoxyethylene (10 mol) were placed in a 500 mL flask. 6 g of oleyl ether, 2 g of polyoxyethylene (25 mol) oleyl ether, 0.1 g of dodecyl mercaptan, 30 g of dipropylene glycol, and 224.7 g of ion-exchanged water were obtained by emulsification and dispersion at 50 ° C by high-speed stirring. Mixture. Thereafter, the mixture was treated at 40 MPa while maintaining the temperature at 40 ° C to obtain an emulsion. The emulsion was poured into a 500 mL three-necked flask equipped with a reflux cooling tube, and after cooling to room temperature, 0.3 g of azobis(isobutylphosphonium) dihydrochloride was added, and radical polymerization was carried out at 60 ° C under a nitrogen atmosphere. After 10 hours, 364 g of an aqueous dispersion containing an acrylic copolymer having a solid content of 30% by weight was obtained.

[Comparative Example 1]

Method for producing aqueous dispersion of acrylic copolymer (F)

98 g of stearyl methacrylate, 2 g of 2-hydroxyethyl acrylate, 1 g of stearyl trimethylammonium chloride, 6 g of polyoxyethylene (7 mol) lauryl ether, and polyoxyethylene (21 Mo) were added to a 500 mL flask. Ears: 2 g of lauryl ether, 0.1 g of dodecyl mercaptan, 30 g of dipropylene glycol, and 224.7 g of ion-exchanged water were emulsified and dispersed by stirring at 50 ° C to obtain a mixed liquid. Thereafter, the mixture was treated at 40 MPa while maintaining the temperature at 40 ° C to obtain an emulsion. Backflow to the installation The emulsion was poured into a 500 mL three-necked flask of a cooling tube, and after cooling to room temperature, 0.3 g of azobis(isobutylphosphonium) dihydrochloride was added, and radical polymerization was carried out at 60 ° C for 10 hours under a nitrogen atmosphere to obtain 364 g of an aqueous dispersion containing an acrylic copolymer having 30% by weight of a solid content component.

[Comparative Example 2]

Method for producing aqueous dispersion of acrylic copolymer (G)

75 g of stearyl methacrylate, 5 g of benzyl acrylate, 20 g of ethyl methacrylate, 1 g of cocoalkyl trimethylammonium chloride, and polyoxyethylene (10 mol) were placed in a 500 mL flask. 6 g of oleyl ether, 2 g of polyoxyethylene (25 mol) oleyl ether, 0.1 g of dodecyl mercaptan, 30 g of dipropylene glycol, and 224.7 g of ion-exchanged water were obtained by emulsification and dispersion at 50 ° C by high-speed stirring. Mixture. Thereafter, the mixture was treated at 40 MPa while maintaining the temperature at 40 ° C to obtain an emulsion. The emulsion was poured into a 500 mL three-necked flask equipped with a reflux cooling tube, and after cooling to room temperature, 0.3 g of azobis(isobutylphosphonium) dihydrochloride was added, and radical polymerization was carried out at 60 ° C under a nitrogen atmosphere. After 10 hours, 364 g of an aqueous dispersion containing an acrylic copolymer having a solid content of 30% by weight was obtained.

[Comparative Example 3]

Method for producing aqueous dispersion of acrylic copolymer (H)

39 g of stearyl methacrylate, 8 g of 2-ethylhexyl acrylate, 50 g of styrene, 3 g of 2-hydroxyethyl methacrylate, 1 g of stearyl trimethylammonium chloride, and polyoxyethylene were placed in a 500 mL flask. (7 mol) 6 g of lauryl ether, 2 g of polyoxyethylene (21 mol) lauryl ether, 0.1 g of dodecyl mercaptan, 30 g of dipropylene glycol and 224.7 g of ion-exchanged water, which were emulsified by high-speed stirring at 50 ° C. Disperse to obtain a mixed solution. Thereafter, the mixture was treated at 40 MPa while maintaining the temperature at 40 ° C to obtain an emulsion. 500 mL three-necked flask equipped with a reflux cooling tube The emulsion was poured into the mixture, and after cooling to room temperature, 0.3 g of azobis(isobutylphosphonium) dihydrochloride was added, and radical polymerization was carried out at 60 ° C for 10 hours under a nitrogen atmosphere to obtain a solid content of 30 parts. An aqueous dispersion of 364 g of an acrylic copolymer.

[Comparative Example 4]

Method for producing aqueous dispersion of acrylic copolymer (I)

75 g of stearyl acrylate, 20 g of 2-ethylhexyl acrylate, 5 g of 2-hydroxyethyl methacrylate, 1 g of stearyl trimethylammonium chloride, and polyoxyethylene (7 mol) laurel were added to a 500 mL flask. 6 g of ether, 2 g of polyoxyethylene (21 mol) lauryl ether, 0.1 g of dodecyl mercaptan, 30 g of dipropylene glycol, and 224.7 g of ion-exchanged water were emulsified and dispersed by stirring at 50 ° C to obtain a mixed liquid. Thereafter, the mixture was treated at 40 MPa while maintaining the temperature at 40 ° C to obtain an emulsion. The emulsion was poured into a 500 mL three-necked flask equipped with a reflux cooling tube, and after cooling to room temperature, 0.3 g of azobis(isobutylphosphonium) dihydrochloride was added, and radical polymerization was carried out at 60 ° C under a nitrogen atmosphere. After 10 hours, 364 g of an aqueous dispersion containing an acrylic copolymer having a solid content of 30% by weight was obtained.

The composition of the acrylic copolymers of the above Examples 1 to 5 and Comparative Examples 1 to 4 is shown in Table 1.

<Evaluation of water repellency>

50 g/L of any of the acrylic copolymers of Examples 1 to 5 and the acrylic copolymers of Comparative Examples 1 to 4, and Beckamine M-3 (N-methylol melamine manufactured by Dainippon Ink Co., Ltd.: The active ingredient concentration is about 80%) 3g/L, Catalyst ACX (Amino alcohol salt manufactured by Dainippon Ink Co., Ltd.: active ingredient concentration: about 35%) 3g/L. The processing liquid diluted with water is adjusted and pressed. The polyester cloth and the nylon cloth were sandwiched by two rubber rolls (pickup rate: 55%), dried at 110 ° C for 2 minutes, and then cured at 170 ° C for 1 minute to prepare an evaluation cloth. The water repellency was evaluated by the spray method of JIS L 1092 (2009) using the obtained evaluation cloth. The evaluation fabric was naturally dried after washing in either case. In addition, the water repellency is described by the values of the five grades of 1 to 5 shown in Table 2, and when the number is accompanied by +(-), The evaluation of this number is slightly better (slightly worse). The results are shown in Table 3.

In addition, 10 g/L of Meikanate FM-1 (blocked isocyanate manufactured by Ming Seng Chemical Industry Co., Ltd.: active ingredient 30%) was used instead of Beckamine M-3 and Catalyst ACX, and cotton cloth was processed in the same manner to evaluate water repellency.

<Evaluation of washing durability of water repellency>

The evaluation cloth prepared was set to the number of times of washing (HL-0), and washed 10 times (HL-10) and 20 times (HL-20) according to the washing method described in JIS L 1092 (2009), and the same evaluation was made. Water-based.

[Comparative example]

As an example of water-repellent processing by a fluorine-based resin, AsahiGuard E-SERIES AG-E061 (manufactured by Asahi Glass Co., Ltd., fluorine-based water repellent, 20% by weight of solid content) 50 g/L, Beckamine M-33g /L, Catalyst ACX 3g/L method to adjust the water-diluted processing solution, dip dyed in polyester cloth, nylon cloth, clamped by two rubber rolls (pickup rate 55%), dried at 110 ° C After 2 minutes, it was cured at 170 ° C for 1 minute to prepare an evaluation cloth.

In addition, 10 g/L of Meikanate FM-1 (blocked isocyanate manufactured by Ming Seng Chemical Industry Co., Ltd.: active ingredient 30%) was used in place of Beckamine M-3 and Catalyst ACX, and cotton cloth was processed in the same manner as in Examples 1 to 5 and Comparative Example 1. ~4 The water repellency was evaluated in the same manner.

<Evaluation of seam slidability>

The polyester taffeta fabric and the nylon taffeta fabric were processed in the same manner as the water-repellent processing by the formulations of Examples 1 to 5, Comparative Examples 1 to 4, and the comparative examples, according to JIS L 1096- 99.8.21.1 Seam sliding method B method, test by warp sliding under a load of 117.2 N (12 kgw).

As shown in Table 3, Examples 1 to 5, Comparative Examples 1 to 4, and Comparative Examples were compared, and Examples 1 to 5 all exhibited water repellency and washing durability which were substantially the same as those of the comparative example (fluorine-based resin). , sliding resistance value. On the other hand, in Comparative Examples 1, 2, and 4 in which the polymerizable monomer having a cyclic structure was not copolymerized or reduced, the sliding resistance value exceeded 3 mm which is the basis of the quality standard. Further, in Comparative Example 3 in which a polymerizable monomer having a cyclic structure more than the patent application range was copolymerized, the water repellency was insufficient. In Comparative Example 2 in which the monomer having a crosslinkable functional group was not copolymerized, the washing durability of water repellency was insufficient.

Claims (8)

A water repellent composition comprising an acrylic copolymer obtained by polymerizing a monomer having no fluorine content (A): an alkyl group having a carbon number of 12 to 24 and having no cyclic structure (meth) acrylate, 40% by weight or more, less than 80% by weight; and a fluorine-free polymerizable monomer (B): an aromatic ring having a carbon number of 6 to 12 or an aromatic ring having a substituent, or The polymerizable monomer having a cycloalkane having 5 to 12 carbon atoms or a cycloalkane having a substituent is 10% by weight or more and less than 50% by weight. The water repellent composition according to claim 1, wherein the alkyl group of the polymerizable monomer (A) has a carbon number of 16 to 22. The water repellent composition according to claim 1 or 2, wherein the acrylic copolymer further contains (C) a polymerizable monomer in an amount of 0.01% by weight or more and less than 10% by weight, and the polymerizable monomer contains a polymerizable monomer selected from the group consisting of At least one of a group consisting of a hydroxyl group, an amine group, an epoxy group, a blocked isocyanate group, a guanamine group, an N-methylol group, and a fluorenyl group. An aqueous dispersion comprising the water repellent composition according to any one of claims 1 to 3 and a nonionic surfactant. An aqueous dispersion according to claim 4, which further comprises a cationic surfactant. A water-repellent processing method for a fibrous product, which comprises using an aqueous dispersion of the fourth or fifth aspect of the patent application, and (1) an aqueous dispersion or emulsion of a compound having a blocked functional group of two or more functional groups, and/or (2) N-methylol melamine. A water-repellent processing method for a fibrous product, comprising: a step of immersing a fiber in a working fluid containing the aqueous dispersion of claim 4 or 5; and after the step, heat-treating at a temperature of 100 ° C or higher step. A water-repellent fiber product having the water-repellent composition of any one of claims 1 to 3.