JP2015221952A - Water repellent composition containing no fluorine and water repellent processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water repellent composition capable of adding water repellent effect having water repellency and excellent cleaning durability while suppressing slippage resistance value by using a compound containing no fluorine.SOLUTION: There is provided a water repellent composition containing an acrylic copolymer by polymerizing a polymerizable monomer containing no fluorine (A):(meth)acrylate having an alkyl group having non cyclic structure with 12 to 24 carbon atoms:40 to 80 wt.%, a polymerizable monomer having no fluorine (B):a polymerizable monomer containing a C6 to 12 aromatic ring or an aromatic ring with a substituent, or C5 to 12 cycloalkane or cycloalkane having a substituent of 10 to 50 wt.%. Further there is provided a water repellent composition containing (C) a polymerizable monomer containing at lest one selected from a group consisting of a hydroxyl group, an amino group, an epoxy group, blocked isocyanate group, an amide group, a N-methylol group and a mercapto group of 0.01 to 10 wt.%.

Description

  The present invention relates to a water repellent composition that is an acrylic copolymer containing no fluorine in the field of water repellent processing of textile products, and a water repellent processing method using the same.

  It is known to use an aqueous dispersion of paraffin wax, silicone resin, or fluororesin in a method of imparting water repellency by treating a fiber product with an aqueous dispersion. Since the fluororesin exhibits water repellency superior to paraffin wax and silicone resin, it is widely used industrially in a method for imparting water repellency to textile products.

  In 2000, harmfulness, bioaccumulation and environmental pollution of perfluorooctane sulfonic acid (PFOS) were pointed out, and there were concerns about all perfluoro compounds containing 8 or more carbon atoms including perfluorooctanoic acid (PFOA). It came to be shown. For this reason, fluorine-based water repellent manufacturers have developed fluorine-based water repellents that do not contain these substances and that do not have a concern of being generated as decomposition products.

  However, in recent years, it has been pointed out that the perfluoroalkyl group-containing compound itself is harmful and environmentally pollutant regardless of the number of carbon atoms. There has also been a movement to cancel.

  Conventionally, paraffin wax, silicone resin, and the like are well known as water-repellent compositions that do not contain fluorine. However, water repellency has been inferior to fluorine-based resins. Among these, as a technique using a composition containing no fluorine in recent years, an aqueous dispersion of a (meth) acrylic acid ester polymer in which the alkyl group of the ester moiety has 12 or more carbon atoms is an aqueous dispersion of a fluororesin. (Patent Document 1).

  Further, as a similar technique, an aqueous dispersion of a (meth) acrylic acid ester polymer characterized by not containing an N-methylol compound and a paraffin wax having a melting point in the range of 58 to 80 ° C. is a woven fabric, In particular, it has been shown to be useful in water-repellent processing for cotton, polyester or cotton-polyester blended fabric (Patent Document 2).

JP 2006-328624 A Special table 2012-522062 gazette

  As a recent trend, in fields where durable water-repellent processing is required, thinner fibers with a weight of about 11 to 44 dtex (10 to 40 d) are more important than conventional 55 to 110 dtex (50 to 100 d) with an emphasis on weight reduction and texture. It has been increasingly used. However, when the fibers of 11 to 44 dtex were treated with an aqueous dispersion mainly composed of alkyl (meth) acrylate as in Patent Document 1, the slip resistance value tended to be extremely large. For this reason, there has been a problem of causing misalignment and misalignment of the sewn portion during sewing and wearing. Moreover, even if the paraffin wax found in Patent Document 2 was blended, the slip-off resistance value could not be improved.

  Moreover, since the copolymer which has an alkyl (meth) acrylate as a main component like patent document 1 has bad emulsification stability even if it uses an appropriate surfactant, an emulsion breakage occurs at the time of fiber processing, and a processing apparatus and processing There was a problem that the resin adhered to the fabric.

  In view of the above situation, the object of the present invention is to use a fluorine-free compound to suppress the slip resistance value and to impart a water repellency effect having water repellency and excellent washing durability. It is to provide a water repellent composition.

  The inventors have made extensive studies on the above problems, and the acrylic copolymer obtained by copolymerizing a polymerizable monomer having a cyclic structure in the molecule has a water repellency and a sliding resistance value. It has been found that the water-repellent composition is excellent. Further, (meth) acrylate having an alkyl group having 12 to 24 carbon atoms and an aromatic ring having 6 to 12 carbon atoms or a substituent, or a cycloalkane having 5 to 12 carbon atoms or a cyclohexane having a substituent. By a composition obtained by copolymerizing a polymerizable monomer having an alkane, a water-repellent composition excellent in water repellency, washing durability, slip-off resistance value, and also in emulsion stability is obtained. The present invention has been completed.

That is, the present invention relates to a water repellent composition containing an acrylic copolymer obtained by polymerizing the following polymerizable monomers (A) and (B) not containing fluorine.
(A) (meth) acrylate having an alkyl group having no cyclic structure having 12 to 24 carbon atoms, 40 wt% or more and less than 80 wt%.
(B) A polymerizable monomer having 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 wt% to 50 wt% %Less than.
In addition, this weight% shows the weight ratio of each monomer with respect to an acryl-type copolymer.

  The number of carbon atoms in the alkyl group (A) is more preferably 16-22.

  The acrylic copolymer further contains (C) a polymer containing at least one selected from the group consisting of a hydroxyl group, an amino group, an epoxy group, a blocked isocyanate group, an amide group, an N-methylol group, and a mercapto group. It is preferable to contain 0.01% by weight or more and less than 10% by weight of monomer.

  The present invention also relates to an aqueous dispersion containing the water repellent composition described above and a nonionic surfactant. It is preferable that the aqueous dispersion further contains a cationic surfactant.

In addition, the present invention, together with the aqueous dispersion,
(1) An aqueous dispersion or emulsion of a compound having a bifunctional or higher functional blocked isocyanate group and / or
(2) It relates to a water-repellent processing method for textiles using N-methylolmelamine.

  Moreover, this invention relates to the water-repellent processing method of a textile product including the process of immersing a fiber in the process liquid containing said aqueous dispersion, and the process heat-processed at the temperature of 100 degreeC or more after the said process.

  Moreover, this invention relates to the water-repellent fiber product which has said water-repellent agent composition.

  The water repellent composition according to the present invention does not contain fluorine, can impart excellent water repellency to the fiber, is excellent in washing durability, and suppresses the slip resistance value of the treated fiber. be able to.

(Water repellent composition)
The water repellent composition of the present invention is an acrylic copolymer, and the copolymer has (A) an alkyl group having 12 to 24 carbon atoms and no cyclic structure as a monomer (meta ) Contains acrylate.

  The (meth) acrylate having an alkyl group having 12 to 24 carbon atoms includes acrylic acid and / or methacrylic acid, and an alcohol having an alkyl group having 12 to 24 carbon atoms, preferably 16 to 22 carbon atoms and not having a cyclic structure. Or a mixture of such esters. The alkyl group of the alcohol may be a linear alkyl group or a branched alkyl group, and both may be used, but a linear alkyl group is preferred.

  Examples of such (meth) acrylates include lauryl acrylate, hexadecyl acrylate, stearyl acrylate, isostearyl acrylate, behenyl acrylate, lauryl methacrylate, hexadecyl methacrylate, stearyl methacrylate, isostearyl methacrylate, behenyl methacrylate, and the like. One or more of can be used.

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

  The acrylic copolymer of the present invention comprises, as a monomer, (B) 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 cyclohexane having a substituent. Including a polymerizable monomer having an alkane.

  Specific examples of the monomer (B) include styrene, α-methylstyrene, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, and naphthyl (meth). Acrylate, 4-morpholinoethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetramethylpiperidinyl methacrylate, methyl cinnamate, cinnamon Examples include ethyl acid. Further, when the polymerizable monomer having a cyclic structure is (meth) acrylate, the cyclic structure portion preferably has 5 to 11 carbon atoms.

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

  Although not bound by a specific theory, the water repellent composition of the present invention comprises (meth) acrylate having a cyclic structure having a specific number of carbon atoms in addition to (meth) acrylate having an alkyl group. By copolymerizing, a three-dimensional cyclic structure is arranged in the side chain of the copolymer, and as a result, the smoothness of the fiber does not become too large, and it is considered that the sliding resistance value can be suppressed. .

  The acrylic copolymer further comprises (C) a polymerizable monomer containing at least one selected from the group consisting of hydroxyl group, amino group, epoxy group, blocked isocyanate group, amide group, N-methylol group and mercapto group. It is preferable to have a monomer in an amount of 0.01 wt% or more and less than 10 wt%, preferably 0.1 wt% or more and less than 5 wt%. Washing durability can be enhanced by copolymerizing these polymerizable monomers having a crosslinkable group. If it is less than 0.01% by weight, a sufficient effect of improving the washing durability cannot be obtained, and 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, 2-hydroxy-3-chloropropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. , Glycidyl (meth) acrylate, acrylamide, N-methylolamide, polyalkylene glycol mono (meth) acrylate, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate, 2- (O- [1′-methyl Propylideneamino] carboxyamino) ethyl methacrylate and the like, and one or more polymerizable monomers selected from these groups can be used in combination.

  The acrylic copolymer of the present invention may contain known monomers other than those described above as long as the effects of the present invention are not impaired. For example, (meth) acrylic acid ester having fewer carbon atoms (having 11 or less carbon atoms) may be included. Specifically, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, polyethylene glycol di (meth) acrylate, methoxypolyethylene glycol methacrylate, methacryl-modified silicone resin, vinyl chloride, vinylidene chloride, vinyl acetate, Maleic acid diesters can be included.

  As a method for producing the above-mentioned acrylic copolymer, a known emulsion polymerization method can be used. For example, a monomer batch charging method in which monomers are charged at once, a monomer dropping method in which monomers are continuously dropped, and the like can be mentioned. In emulsification, it is preferable to use an emulsifier such as an ultrasonic wave or a homogenizer in order to make the particles smaller.

  The surfactant used for emulsion polymerization is not particularly limited. For example, anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, polymer surfactants, etc. Can be used. It is particularly preferable to treat the aqueous dispersion into a fiber product by using only the cationic surfactant, or only the nonionic surfactant, or using the cationic surfactant and the nonionic surfactant in combination.

  Examples of the anionic surfactant include various fatty acid salts, alkylbenzene sulfonates, alkane sulfonates, alkyl sulfate esters, alkyl phosphate esters, polyoxyethylene alkyl ether sulfates, polyoxyethylene substituted phenyl ether sulfates. Polycarboxylates can be used, and examples of the counter ion include, but are not limited to, sodium, potassium, calcium, ammonium, triethanolamine, and the like.

  Nonionic surfactants include, for example, various fatty acid esters such as higher fatty acid glycerin, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene fatty acid ester, fatty acid alkanolamide, alkyl glucoside, higher alcohol, and pluronic. Type activators, alkyldimethylamine-N-oxides and the like can be used.

  Examples of the cationic surfactant include quaternary salts such as various alkyltrimethylammonium salts, alkyldimethylbenzylammonium salts, dialkyldimethylammonium salts, alkylpyridinium chloride salts, quaternized products of polyoxyethylene alkylamines, and the like. An amine salt obtained by neutralizing an amine such as an alkylamine salt, an alkyldimethylamine salt, or a polyoxyethylene alkylamine salt with an appropriate acid can be used. Examples of the counter ion include, but are not limited to, chlorine ion, bromine ion, sulfate ion, formate ion, acetate ion, methyl sulfate ion, and ethyl sulfate ion.

  In emulsion polymerization, a known solvent may be used in combination for stabilizing the emulsion and improving the solubility of the polymerizable monomer. Examples of the solvent include ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and the like.

  As the polymerization initiator used for emulsion polymerization, a general radical initiator can be used. The radical polymerization initiator includes water-soluble or oil-soluble persulfates, peroxides, and azobis compounds. Specifically, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, benzoyl peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2 , 2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile), and the like are preferable.

  The acrylic copolymer obtained by emulsion polymerization is used as an aqueous dispersion containing a water repellent composition as it is or after passing through known processing steps such as concentration, extraction and purification as necessary.

  The aqueous dispersion of the present invention contains an aqueous dispersion of a non-fluorine water-repellent agent such as paraffin wax, methyl hydrogen silicone, octadecyl ethylene urea, alkyl ketene dimer, zirconyl octylate for improving water repellency and adjusting the texture. The body may be blended.

(Water repellent processing method for textile products)
When the water repellent composition of the present invention is processed into a textile product, together with the above aqueous dispersion, (1) an aqueous emulsion of a bifunctional or higher functional blocked isocyanate, (2) N-methylol melamine, etc. It is preferable to use a crosslinking agent in combination.

  (1) A bifunctional or higher functional blocked polyisocyanate can be obtained by reacting a bifunctional or higher functional isocyanate with an appropriate blocking agent by a known method. Examples of the isocyanate include 4,4 'bisisocyanatophenylmethane, toluene diisocyanate, hexamethylene diisocyanate, diisocyanate trimer and trimethylolpropane adduct.

  Examples of the isocyanate blocking agent include secondary or tertiary alcohols, active methylene compounds, phenols, oximes, substituted pyrazoles, and caprolactam. Usually, these blocked isocyanates are emulsified and dispersed using a surfactant by a known method. In addition, after blocking 70 to 95% of all isocyanate groups in advance, by reacting polyalkylene glycol having an appropriate molecular weight, particularly polyethylene glycol, with the remaining isocyanate groups, the blocked isocyanate exhibits self-emulsifying properties. This is effective not only in improving the washing durability of the liquid composition, but also in improving the stability of the product.

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

  The water repellent composition of the present invention is useful for imparting water repellency having excellent washing durability to textiles. For this purpose, the textile product is treated with a working fluid containing the water repellent composition of the present invention.

  The processing liquid can be obtained by diluting the above-mentioned aqueous dispersion containing the acrylic copolymer, the surfactant and the like, and the above-mentioned blocked isocyanate, N-methylolmelamine, etc. with water to a predetermined concentration. Further, further chemicals known in the field of textile finishing, for example, softening agents, antistatic agents, flame retardants, and the like may be contained in the processing liquid.

  The water-repellent processing method of the textile product is not particularly limited, and various methods can be adopted. A desired amount may be attached to the textile product to be water-repellent processed, and a continuous method or a batch method may be mentioned. It is done.

  The concentration of the acrylic copolymer in the working fluid is not particularly limited and is appropriately selected according to the processing method and conditions. For example, when the processing is performed by a continuous method, the solid content concentration is 0.3 to 5. It can be about 0% by weight. When processing by a batch method, it can be set as about 0.3-3.0% ofwf.

  As a continuous method, first, the aqueous dispersion of the present invention is diluted with water to prepare a processing liquid. Next, the processing object is continuously fed into the impregnation apparatus filled with the processing liquid, and the processing object is impregnated with the processing liquid, and then the unnecessary processing liquid is removed. The impregnation device is not particularly limited, and a padder, a spray-type application device, a foam-type application device, a coating-type application device and the like can be preferably used, and a padder type is particularly preferable.

  Subsequently, an operation of removing water remaining on the object to be processed is performed using a dryer. The dryer is not particularly limited, and a spread dryer such as a hot fluid or a tenter is preferable. The continuous method is preferably employed when the object to be treated is a fabric such as a woven fabric.

  The batch method includes a step of immersing an object to be processed in a working fluid and a step of removing water remaining on the object to be processed after the process. The batch method is preferably employed when the object to be treated is not in the form of a fabric, for example, when it is not suitable for a continuous method such as loose hair, top, yarn and the like. In the soaking step, for example, a cotton dyeing machine, a cheese dyeing machine, a liquid dyeing machine, a beam dyeing machine or the like can be used. In the operation of removing water, a hot air dryer such as a cheese dryer or a tumble dryer, a high-frequency dryer, or the like can be used.

  In either case, the drying (heat treatment) step after immersing the fibers to be treated in the processing liquid can be performed at 80 to 180 ° C., and is preferably heat treated at a temperature of 100 ° C. or higher.

  Hereinafter, the present invention will be described with reference to examples. However, the present invention is not limited to these examples.

[Example 1]
Preparation of aqueous dispersion of acrylic copolymer (A) In a 500 mL flask, 60 g of hexadecyl methacrylate, 38 g of isobornyl methacrylate, 2 g of N-methylolacrylamide, 1 g of stearyltrimethylammonium chloride, polyoxyethylene (7 mol) lauryl ether 6 g, 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 at 50 ° C. by high-speed stirring to obtain a mixed solution. Then, it processed at 40 Mpa using the high pressure homogenizer, keeping at 40 degreeC, and obtained the emulsion. The emulsion was transferred to a 500 mL three-necked flask equipped with a reflux condenser, cooled to room temperature, 0.3 g of azobis (isobutylamidine) dihydrochloride was added, and radical polymerization was performed at 60 ° C. for 10 hours in a nitrogen atmosphere. 364 g of product containing a polymer concentration of 30% by weight were obtained.

[Example 2]
Production method of aqueous dispersion of acrylic copolymer (B) In a 500 mL flask, 75 g of stearyl methacrylate, 20 g of styrene, 5 g of 2-hydroxyethyl methacrylate, 1 g of stearyltrimethylammonium chloride, 6 g of polyoxyethylene (7 mol) 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 were added and emulsified and dispersed by high-speed stirring at 50 ° C. to obtain a mixed solution. Then, it processed at 40 Mpa using the high pressure homogenizer, keeping at 40 degreeC, and obtained the emulsion. The emulsion was transferred to a 500 mL three-necked flask equipped with a reflux condenser, cooled to room temperature, 0.3 g of azobis (isobutylamidine) dihydrochloride was added, and radical polymerization was performed at 60 ° C. for 10 hours in a nitrogen atmosphere. 364 g of product containing 30% solids was obtained.

[Example 3]
Method for producing aqueous dispersion of acrylic copolymer (C) In a 500 mL flask, 39.5 g of lauryl acrylate, 39.5 g of stearyl methacrylate, 18 g of cyclohexyl methacrylate, 3 g of N-methylolacrylamide, 1 g of cocoalkyltrimethylammonium chloride, polyoxy 6 g of ethylene (10 mol) 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 are emulsified and dispersed at 50 ° C. by high-speed stirring. A mixture was obtained. Then, it processed at 40 Mpa using the high pressure homogenizer, keeping at 40 degreeC, and obtained the emulsion. The emulsion was transferred to a 500 mL three-necked flask equipped with a reflux condenser, cooled to room temperature, 0.3 g of azobis (isobutylamidine) dihydrochloride was added, and radical polymerization was performed at 60 ° C. for 10 hours in a nitrogen atmosphere. 364 g of an aqueous dispersion of an acrylic copolymer containing 30% by weight of solid content was obtained.

[Example 4]
Method for producing aqueous dispersion of acrylic copolymer (D) In a 500 mL flask, 50 g of behenyl acrylate, 40 g of benzyl acrylate, 5 g of isobornyl methacrylate, 5 g of 2-hydroxyethyl methacrylate, 1 g of stearyltrimethylammonium chloride, polyoxyethylene ( 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 were emulsified and dispersed by high-speed stirring at 50 ° C. to obtain a mixed solution Got. Then, it processed at 40 Mpa using the high pressure homogenizer, keeping at 40 degreeC, and obtained the emulsion. The emulsion was transferred to a 500 mL three-necked flask equipped with a reflux condenser, cooled to room temperature, 0.3 g of azobis (isobutylamidine) dihydrochloride was added, and radical polymerization was performed at 60 ° C. for 10 hours in a nitrogen atmosphere. 364 g of an aqueous dispersion of an acrylic copolymer containing 30% by weight of solid content was obtained.

[Example 5]
Manufacturing method of aqueous dispersion of acrylic copolymer (E) In a 500 mL flask, stearyl acrylate 75 g, styrene 15 g, methyl methacrylate 8 g, 2-hydroxyethyl acrylate 2 g, cocoalkyltrimethylammonium chloride 1 g, polyoxyethylene (10 mol) ) 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 emulsified and dispersed by high-speed stirring at 50 ° C. to obtain a mixed solution. It was. Then, it processed at 40 Mpa using the high pressure homogenizer, keeping at 40 degreeC, and obtained the emulsion. The emulsion was transferred to a 500 mL three-necked flask equipped with a reflux condenser, cooled to room temperature, 0.3 g of azobis (isobutylamidine) dihydrochloride was added, and radical polymerization was performed at 60 ° C. for 10 hours in a nitrogen atmosphere. 364 g of an aqueous dispersion of an acrylic copolymer containing 30% by weight of solid content was obtained.

[Comparative Example 1]
Method for producing aqueous dispersion of acrylic copolymer (F) In a 500 mL flask, 98 g of stearyl methacrylate, 2 g of 2-hydroxyethyl acrylate, 1 g of stearyltrimethylammonium chloride, 6 g of polyoxyethylene (7 mol) lauryl ether, polyoxyethylene (21 mol) 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 added and emulsified and dispersed by high-speed stirring at 50 ° C. to obtain a mixed solution. Then, it processed at 40 Mpa using the high pressure homogenizer, keeping at 40 degreeC, and obtained the emulsion. The emulsion was transferred to a 500 mL three-necked flask equipped with a reflux condenser, cooled to room temperature, 0.3 g of azobis (isobutylamidine) dihydrochloride was added, and radical polymerization was performed at 60 ° C. for 10 hours in a nitrogen atmosphere. 364 g of an aqueous dispersion of an acrylic copolymer containing 30% by weight of solid content was obtained.

[Comparative Example 2]
Method for producing aqueous dispersion of acrylic copolymer (G) In a 500 mL flask, 75 g of stearyl methacrylate, 5 g of benzyl acrylate, 20 g of ethyl methacrylate, 1 g of cocoalkyltrimethylammonium chloride, 6 g of polyoxyethylene (10 mol) oleyl ether, poly 2 g of oxyethylene (25 mol) oleyl ether, 0.1 g of dodecyl mercaptan, 30 g of dipropylene glycol and 224.7 g of ion-exchanged water were added and emulsified and dispersed by high-speed stirring at 50 ° C. to obtain a mixed solution. Then, it processed at 40 Mpa using the high pressure homogenizer, keeping at 40 degreeC, and obtained the emulsion. The emulsion was transferred to a 500 mL three-necked flask equipped with a reflux condenser, cooled to room temperature, 0.3 g of azobis (isobutylamidine) dihydrochloride was added, and radical polymerization was performed at 60 ° C. for 10 hours in a nitrogen atmosphere. 364 g of an aqueous dispersion of an acrylic copolymer containing 30% by weight of solid content was obtained.

[Comparative Example 3]
Method for producing aqueous dispersion of acrylic copolymer (H) In a 500 mL flask, 39 g of stearyl methacrylate, 8 g of 2-ethylhexyl acrylate, 50 g of styrene, 3 g of 2-hydroxyethyl methacrylate, 1 g of stearyltrimethylammonium chloride, polyoxyethylene (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 were emulsified and dispersed by high-speed stirring at 50 ° C. Obtained. Then, it processed at 40 Mpa using the high pressure homogenizer, keeping at 40 degreeC, and obtained the emulsion. The emulsion was transferred to a 500 mL three-necked flask equipped with a reflux condenser, cooled to room temperature, 0.3 g of azobis (isobutylamidine) dihydrochloride was added, and radical polymerization was performed at 60 ° C. for 10 hours in a nitrogen atmosphere. 364 g of an aqueous dispersion of an acrylic copolymer containing 30% by weight of solid content was obtained.

[Comparative Example 4]
Method for producing aqueous dispersion of acrylic copolymer (I) In a 500 mL flask, stearyl acrylate 75 g, 2-ethylhexyl acrylate 20 g, 2-hydroxyethyl methacrylate 5 g, stearyltrimethylammonium chloride 1 g, polyoxyethylene (7 mol) lauryl 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 added and emulsified and dispersed by high-speed stirring at 50 ° C. to obtain a mixed solution. Then, it processed at 40 Mpa using the high pressure homogenizer, keeping at 40 degreeC, and obtained the emulsion. The emulsion was transferred to a 500 mL three-necked flask equipped with a reflux condenser, cooled to room temperature, 0.3 g of azobis (isobutylamidine) dihydrochloride was added, and radical polymerization was performed at 60 ° C. for 10 hours in a nitrogen atmosphere. 364 g of an aqueous dispersion of an acrylic copolymer containing 30% by weight of solid content was obtained.

A summary of the compositions of the acrylic copolymers of Examples 1 to 5 and Comparative Examples 1 to 4 is shown in Table 1.

<Evaluation of water repellency>
Acrylic copolymer of Examples 1 to 5 and acrylic copolymer of Comparative Examples 1 to 4 50 g / L, Becamine M-3 (Dainippon Ink & Co., Ltd. N-methylolmelamine: active ingredient concentration about 80%) 3 g / L, Catalyst ACX (Dainippon Ink Co., Ltd. amino alcohol hydrochloride: active ingredient concentration: about 35%) Adjust the processing fluid diluted with water to 3 g / L, put on polyester cloth and nylon cloth, A nip (55% pickup) was made with a rubber roller, dried at 110 ° C. for 2 minutes, and then cured at 170 ° C. for 1 minute to prepare an evaluation fabric. Water repellency was evaluated by the spray method of JIS L 1092 (2009) using the obtained evaluation cloth. In any case, the evaluation fabric was naturally dried after washing. In addition, the water repellency is expressed by a numerical value of 5 levels from 1 to 5 shown in Table 2, and when + (−) is attached to a number, it indicates that it is slightly better (bad) than the evaluation of the number. . The results are shown in Table 3.
Further, instead of Becamine M-3 and Catalyst ACX, Mecanate FM-1 (Blocked isocyanate manufactured by Meisei Chemical Industry Co., Ltd .: active ingredient 30%) 10 g / L was similarly used to process a cotton fabric and water repellency. Evaluated.

<Evaluation of water-repellent washing durability>
After the created evaluation fabric is washed 0 times (HL-0) and washing is performed 10 times (HL-10) and 20 times (HL-20) according to the washing method described in JIS L 1092 (2009) Similarly, water repellency was evaluated.

[Control example]
As an example of water-repellent processing with a fluorine-based resin, AsahiGuard E-SERIES AG-E061 (Asahi Glass Co., Ltd., fluorine-based water-repellent, solid content 20% by weight) 50 g / L, Beccamin M-3 3g / L, catalyst ACX 3g / L diluted with water to adjust the processing liquid, put on polyester cloth and nylon cloth, niped with two rubber rollers (55% pickup), and 110 ° C And dried for 2 minutes, and then cured at 170 ° C. for 1 minute to prepare an evaluation cloth.
Further, instead of Becamine M-3 and catalyst ACX, Mecanate FM-1 (Madesei Chemical Industries, Ltd., blocked isocyanate: active ingredient 30%) 10 g / L was similarly used to process a cotton fabric. 5 and Comparative Examples 1 to 4 were evaluated for water repellency.

<Evaluation of seam slippage>
A polyester taffeta cloth and a nylon taffeta cloth were processed in the same manner as in the water-repellent processing according to the formulations of Examples 1 to 5, Comparative Examples 1 to 4 and the control example, and JIS L 1096-99.88.21.1 In accordance with Method B, the test was carried out with warp slipping at a load of 117.2 N (12 kgw).

  From Table 3, Examples 1 to 5 which are the present invention are not Comparative Examples 1 to 4 which are not the present invention and Comparative Examples which have been subjected to water-repellent processing with a fluororesin. Comparative Examples 1, 2 and 4 which have almost the same water repellency and washing durability as fluorine-based resins but are not copolymerized with a polymerizable monomer having a cyclic structure. It can be seen that the sliding resistance value exceeds 3 mm, which is the standard for quality standards. In addition, Comparative Example 3 in which more polymerizable monomers having a cyclic structure were copolymerized than the claims was insufficient in water repellency, and a comparison in which a monomer having a crosslinkable functional group was not copolymerized. In Example 2, the water-repellent washing durability was insufficient.

Claims (8)

Polymeric monomer (A) not containing fluorine: (meth) acrylate having an alkyl group having no cyclic structure having 12 to 24 carbon atoms, 40% by weight or more and less than 80% by weight,
as well as,
Fluorine-free polymerizable monomer (B): polymerization containing a C6-C12 aromatic ring or a substituted aromatic ring, or a C5-C12 cycloalkane or a substituted cycloalkane Monomer, 10 wt% or more and less than 50 wt%,
A water-repellent composition comprising an acrylic copolymer obtained by polymerizing. The water repellent composition according to claim 1, wherein the alkyl group of the polymerizable monomer (A) has 16 to 22 carbon atoms. The acrylic copolymer is further
(C) A polymerizable monomer containing at least one selected from the group consisting of a hydroxyl group, an amino group, an epoxy group, a blocked isocyanate group, an amide group, an N-methylol group and a mercapto group, 0.01% by weight or more The water-repellent composition according to claim 1 or 2, characterized by containing less than 10% by weight. An aqueous dispersion containing the water-repellent composition according to any one of claims 1 to 3 and a nonionic surfactant. The aqueous dispersion according to claim 4, further comprising a cationic surfactant. Along with the aqueous dispersion according to claim 4 or 5,
(1) An aqueous dispersion or emulsion of a compound having a bifunctional or higher functional blocked isocyanate group and / or
(2) A water-repellent processing method for textiles using N-methylolmelamine. A step of immersing the fibers in a processing liquid containing the aqueous dispersion according to claim 4 or 5,
A water-repellent processing method for a textile product, including a step of performing a heat treatment at a temperature of 100 ° C. or higher after the step. A water-repellent fiber product comprising the water-repellent composition according to claim 1.