JPH0717847B2 - Water repellent resin aqueous composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is intended to impart water repellency by impregnating a textile product, paper, film, wood, structure, etc., and spraying or surface coating. Regarding a water-repellent resin aqueous composition that can be
In particular, it relates to a water-repellent resin water-based composition capable of imparting a desired texture to various textiles as well as water-repellent property. Particularly, by treating a non-woven fabric raw material using the composition as a non-woven fabric binder, water repellency can be obtained in one step. Relates to a water-repellent resin aqueous composition capable of producing a non-woven fabric excellent in excellent texture and, more specifically, a resin aqueous dispersion comprising one or more (co) polymer emulsions of a specific ethylene-based monomer. The present invention relates to a water-repellent resin aqueous composition, which comprises a specific amount of a fluorine-based water-repellent agent with respect to a liquid.

[Conventional technology]

Conventionally, various methods have been known as a water repellent treatment method, for example, a method in which a fluorine water repellent and a silicone water repellent are used simultaneously or separately (JP-A-54-55697).
JP-A-57-154466, JP-A-58-208473), a method of using a reactive resin in combination with a water-repellent resin (JP-A-55-76167, JP-A-55-84477). , JP-A-57-149557
No.) or a fluorine-based water repellent, which is characterized by its heat treatment (JP-A-61-138775).

However, in these proposals, only the water repellency is used, or the water repellent composition having an extremely large proportion of the water repellent is used, and it is possible to impart water repellency to the product, but the desired texture is obtained. Is unsuitable for imparting, particularly excellent in water repellency in one step using as a non-woven binder, in order to produce a non-woven fabric having a desired texture, there is a problem in terms of adhesiveness and texture, and Since the water repellent is extremely expensive, the cost is inevitable.

It is also known to use a composition obtained by thickening a fluorine-based water repellent with an ethylene-based carboxylic acid copolymer. For example, in JP-A-61-113882, hydrophilic properties such as cotton and rayon are disclosed. Of water-repellent treated cloth of fabric having various constituent fibers and a method for producing the same, more specifically, water-repellent one-sided surface having elasticity and moisture permeability and excellent water repellency and back surface For the purpose of providing a water absorbent processed cloth and its manufacturing method,
Fluorine-based water / oil repellent finishing agent 10-88% by weight, vinyl-based copolymer containing ethylenically unsaturated carboxylic acid and / or its derivative as a copolymerization component 10-88% by weight, softening agent 2-50% by weight %, And a treating agent substantially consisting of 0 to 50% by weight of a multi-functional crosslinking agent is applied to one side of the hydrophilic fiber-containing cloth in a proportion of 0.2 to 20 g / m ² as a total solid content. Is described for the one-sided water repellent cloth.

However, "a vinyl-based copolymer containing an ethylenically unsaturated carboxylic acid and / or a derivative thereof as a copolymerization component" in the above publication is a "fluorine-based water- and oil-repellent finishing agent".
It is a thickener for increasing the treating agent to 2000 to 20000 cps, and is completely different from the resin aqueous dispersion of the present invention, and is not for imparting desired texture and adhesiveness with water repellency. . Further, in the above-mentioned JP-A No. 61-113882, there is no description or suggestion regarding the use of an aromatic vinyl-based monomer and the special water-repellent effect therefor, which is an essential requirement of the present invention, and However, even if the treating agent described in the above publication is used as a binder for a nonwoven fabric, an excellent water-repellent nonwoven fabric cannot be obtained because the adhesiveness as a binder may be insufficient.

[Problems to be solved by the invention]

As described above, the conventional water-repellent composition can impart water repellency to various products, particularly textile products, but is not suitable for imparting a desired texture, and the use of the composition As a result, it was not possible to avoid a fairly large cost up.

Further, conventionally, when a water-repellent non-woven fabric is produced using an adhesive, for example, the non-woven fabric is produced by a method of immersing the non-woven fabric raw material in an ordinary non-woven fabric binder bath, squeezing with a roll or the like, and then drying. After that, a water repellent is applied to the nonwoven fabric by a method such as dipping or spraying and dried to give water repellency, which is usually a two-step production.
However, in the above-mentioned two-step manufacturing method, two liquids of a binder for a non-woven fabric and a water repellent such as a fluorine type must be used separately, and drying is also required twice, so that productivity and energy efficiency are improved. However, even if an attempt is made in a single step to use only the treating agent described in JP-A-61-113882 instead of using the two liquids, the resulting non-woven fabric is not water repellent as described above. It was difficult to obtain an excellent water-repellent non-woven fabric, because it was sufficient or the adhesiveness as a non-woven fabric binder was insufficient. Furthermore, even if an attempt is made to produce a water-repellent nonwoven fabric by incorporating the fluorine-based water repellent described in the above publications into an acrylic emulsion or the like which has been conventionally generally used as a binder for a nonwoven fabric, the water repellency is insufficient. Or, even if water repellency is obtained, there is a problem in that an extremely large amount of fluorine-based water repellent must be added.

Further, in the case of water repellent finishing of textile products, it is necessary that the water repellency and the change in texture are small even by washing or dry cleaning of these products. Among water-based nonwoven fabrics, particularly those used for interlining for clothes and the like are required to have resistance to adhesion to washing and adhesion, resistance to perkren, resistance to adhesion to organic solvents such as resistance to mineral terpenes, and the like.

The present invention imparts a desired texture and excellent water repellency to various water repellent treatments, particularly various textile products, and if necessary, changes in the texture even by washing or dry cleaning,
For the purpose of providing a water-repellent resin water-based composition having less deterioration in water repellency, particularly when used as a binder for a nonwoven fabric, it has excellent adhesiveness together with water repellency and a desired texture, and if necessary, It is intended to provide a water-repellent resin water-based composition having less water repellency, less adhesiveness, and less change in texture even by washing or dry cleaning, and a large amount of expensive fluorine-based water repellent. It is an object of the present invention to provide a water-repellent resin water-based composition which is excellent in economic efficiency and which can achieve the above object without using it.

[Means for solving problems]

The present invention relates to a fluorine-based water repellent in a solid content of about 100 parts by weight of a solid content of an aqueous resin dispersion containing one or more ethylene-based (co) polymer emulsions. 5
To about 50 parts by weight of a water-repellent resin aqueous composition, and comprising about 10% by weight or more of an aromatic vinyl-based monomer with respect to the total amount of the ethylene-based monomer. The water-repellent resin aqueous composition according to the present invention is provided.

"Aqueous resin dispersion comprising one or more ethylene copolymer (co) polymer emulsions" in the present invention
Means that an ethylene-based monomer is emulsion polymerized in the presence or absence of a surfactant and / or a protective colloid in an aqueous medium, or a (co) polymer polymerized by a method other than emulsion polymerization is post-emulsified. A single (co) polymer emulsion or a blend of a plurality of these (co) polymer emulsions obtained by, for example, is not particularly limited, but it is easy to produce, economical or the like. For the reason, it is preferably a homopolymer of a (co) polymer emulsion or a blend of a plurality of (co) polymer emulsions, which is usually obtained by emulsion polymerization.

Examples of the ethylene-based monomer that can be used in the present invention include methyl acrylate, ethyl acrylate,
n-butyl acrylate, isobutyl acrylate, 2
-Alkyl ester type monomers of acrylic acid such as ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate and stearyl acrylate; for example, methyl methacrylate, ethyl methacrylate, n-
Alkyl ester monomers of methacrylic acid such as butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, etc .; aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, ethylvinylbenzene, etc .; eg acetic acid Saturated fatty acid vinyl monomers such as vinyl, vinyl propionate and vinyl versatate; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; olefinic monomers such as ethylene, propylene and butadiene Body; for example, acrylic acid, methacrylic acid, crotonic acid, citraconic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, monoalkyl esters of ethylene-based dicarboxylic acids such as monobutyl maleic acid, and ammonium salts thereof. Ethylene carboxylic acids such as alkali metal salts; amides of ethylene carboxylic acids such as acrylamide, methacrylamide, diacetone acrylamide; N-methylol acrylamide, N-methylol methacrylamide, methylol diacetone acrylamide And methylol derivatives of ethylene-based carboxylic acid amides such as aerides (for example, N-isobutoxymethyl acrylamide) of these monomers with alcohols having 1 to 8 carbon atoms; and glycidyl acrylates thereof. , Esters of ethylene-based carboxylic acids such as glycidyl methacrylate and alcohols having an epoxy group;
Hydroxyalkyl esters of ethylene-based carboxylic acids such as hydroxyethyl acrylate, 2-hydroxypropyl acrylate and 2-hydroxyethyl methacrylate; ethylene-based carboxylic acids such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate and alcohols having amino groups And the like; monomers such as divinylbenzene, diallyl phthalate, triallyl cyanurate, diethylene glycol dimethacrylate, etc. containing two or more unsaturated groups;

In the present invention, with respect to the total amount of ethylene-based monomer,
It is necessary that the aromatic vinyl monomer as described above is contained in an amount of about 10% by weight or more. Here, the "total amount of ethylene-based monomer" refers to the total amount of ethylene-based monomer required for producing all (co) polymers present in the obtained resin aqueous dispersion. When the amount of the aromatic vinyl monomer is less than about 10% by weight, it is difficult to obtain the excellent water repellency aimed at by the present invention, which is not preferable. The aromatic vinyl-based monomer is preferably styrene because of its availability and suitability for the polymerization reaction (polymerization reaction rate, some risk of gelation, some gel-like substances, etc.).

The amount of the aromatic vinyl-based monomer can be appropriately selected in an amount of about 10% by weight or more depending on various physical properties required for the product to be subjected to the water repellent treatment. For example, flexibility and wash resistance when used as a nonwoven fabric binder for interlining of clothing,
Aromatic vinyl monomers should be used in the range of about 10 to about 30% by weight for water repellent finishing of products requiring organic solvent resistance, etc. On the other hand, the heat-crosslinkable ethylene-based carboxylic acid derivative-based monomer is about 0.5 to about 5
It preferably comprises wt.%.

Examples of the heat-crosslinkable ethylene-based carboxylic acid derivative-based monomer include amides of ethylene-based carboxylic acid; methylolated ethylene-carboxylic acid amides and derivatives thereof; Examples thereof include esters of carboxylic acids and alcohols having an epoxy group; hydroxyalkyl esters of ethylene-based carboxylic acids; and the like. These monomers can be used alone or in combination of two or more kinds, Among these, suitability for polymerization reaction, resistance to washing and organic solvent water repellency of the resulting product, and resistance to washing and organic solvent touch resistance, especially in the case of non-woven fabrics Resistance and wash feeling resistance (hereinafter sometimes abbreviated as wash resistance), organic solvent water repellency retention, organic solvent adhesion retention and organic solvent texture protection Sex from the viewpoint of excellence in (hereinafter sometimes abbreviated as solvent resistance) and the like, it is preferable to use a methylol compound of the ethylene-based carboxylic acid amides, to use N- methylol (meth) acrylamide is particularly preferred.

If the amount of the heat-crosslinkable ethylene-based carboxylic acid derivative-based monomer used is less than about 0.5% by weight, water resistance and solvent resistance may be insufficient, and if it exceeds about 5% by weight,
The monomer is preferably used in the range of about 0.5 to about 5% by weight because there may be a problem in suitability for the polymerization reaction.

Further, in the present invention, the above ethylene-based carboxylic acids are further added in an amount of about 0.5 to about 6 with respect to the total amount of the ethylene-based monomer.
Stability of the resulting water-repellent resin aqueous composition, and water repellency, adhesiveness, solvent resistance, etc., especially when a heat-crosslinkable ethylene-based carboxylic acid derivative-based monomer is used It is preferable from the viewpoint of excellence. As such ethylene-based carboxylic acids, acrylic acid, methacrylic acid and itaconic acid are preferably used from the above effects and suitability for polymerization reaction.

In addition, the texture of the obtained processed product, as the aromatic vinyl-based monomer, a heat-crosslinkable ethylene-based carboxylic acid derivative-based monomer and a monomer component other than ethylene-based carboxylic acids,
By appropriately selecting and using from the above-exemplified monomer group, it is possible to freely design, and when a soft feeling is required, 2-ethylhexyl acrylate, butyl acrylate, etc. are appropriately used. It may be selected, but it is also possible to make the texture hard, and in this case, methyl methacrylate, acrylonitrile or the like may be appropriately used.

Further, in the field where a relatively hard feeling is required, the aromatic vinyl-based monomer can be used in a range exceeding about 30% by weight. Also in this case, it is preferable to use the heat-crosslinkable ethylene-based carboxylic acid derivative-based monomer within the above range in order to improve the washing resistance.

The aqueous resin dispersion of the present invention is usually obtained by emulsion-polymerizing an ethylene-based monomer appropriately selected from the above monomer group in an aqueous medium in the presence of a surfactant and / or a protective colloid. It is a single substance of the (co) polymer emulsion obtained, or a blend of a plurality of these (co) polymer emulsions.

Examples of the above-mentioned surfactant include nonionic surfactants such as polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether; polyoxyethylene octylphenol ether and polyoxyethylene. Polyoxyalkylene alkylphenol ethers such as nonylphenol ether; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate; polyoxyalkylene sorbitan such as polyoxyethylene sorbitan monolaurate Fatty acid esters; polyoxyalkylene fatty acid esters such as polyoxyethylene monolaurate, polyoxyethylene monostearate; oleic acid Examples thereof include glycerin fatty acid esters such as noglyceride and stearic acid monoglyceride; polyoxyethylene / polyoxypropylene / block copolymers; and the like. Examples of anionic surfactants include sodium oleate and the like. Fatty acid salts; alkylaryl sulfonates such as sodium dodecylbenzene sulfonate; alkyl sulfate ester salts such as sodium lauryl sulfate; alkyl monosulfonates such as sodium monooctylsulfosuccinate, sodium dioctylsulfosuccinate, polyoxyethylene laurylsulfosuccinate, etc. Sulfosuccinic acid ester salts and derivatives thereof; polyoxyethylene lauryl ether sulfates and other polyoxyalkylene alkyl ether sulfuric acid ester salts; polyoxyethylene nonyl Polyoxyalkylene alkylaryl ether sulfate ester salts such as sodium enol ether sulfate; and the like, and cationic surfactants include, for example, alkylamine salts such as laurylamine acetate: lauryltrimethylammonium chloride, alkylbenzyldimethylammonium chloride. Examples thereof include quaternary ammonium salts such as; polyoxyethylalkylamines; and the like, and examples of amphoteric surfactants include alkylbetaines such as laurylbetaine. Further, those in which a part of hydrogen atoms of the alkyl group of these surfactants are replaced with fluorine can also be used. Further, a so-called reactive surfactant having a radical-polymerizable double bond in the molecular structure of the surfactant can also be used. Examples of such a reactive surfactant include sulfosuccinic acid alkylalkenyl ester salt type , Reactive ionic surfactants such as alkenyl succinic acid monoalkenyl ester salt type.

The amount of the surfactant used is usually about 0.1 to about 10% by weight with respect to the total amount of the ethylene-based monomer, water repellency,
About 0.5 to about 6% by weight from the viewpoint of adhesiveness and wash resistance
It is preferred to use a base, particularly preferably about 0.5 to about 4% by weight.

Examples of protective colloids that can be used in the present invention include, for example, polyvinyl alcohols such as saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, and modified polyvinyl alcohol; cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose salt. And natural polysaccharides such as guar gum; and the like, and these can be used alone or in combination of two or more kinds. The amount used can be appropriately selected, and for example, the amount used may be, for example, about 0 to about 10% by weight based on the total amount of the ethylene-based monomer used.

The "in an aqueous medium" in the present invention means in water or an aqueous solution of a water-soluble organic solvent, and such a water-soluble organic solvent is not particularly limited, and examples thereof include methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. Water-soluble alcohols; water-soluble ketones such as acetone;
Water-soluble ethers such as methyl cellosolve, cellosolve, butyl cellosolve, carbitol, and butyl carbitol; and the like can be used alone or in combination, and the amount thereof is 0 as the aqueous solution concentration of the water-soluble organic solvent. Can be exemplified about 50 wt%, but from the viewpoint of stability of the resulting resin aqueous dispersion and water repellency of the water repellent product, adhesion, washing resistance, solvent resistance, etc. It is preferable to carry out emulsion polymerization in water that does not contain these organic solvents.

Further, in emulsion polymerization, for example, persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate; organic peroxides such as tert-butyl hydroperoxide, cumene hydroperoxide, paramenthane hydroperoxide, etc. Polymerization initiators such as hydrogen peroxide and hydrogen peroxide can be used. These can also be used in any one kind or a combination of plural kinds. The amount used can be appropriately selected, but is, for example, about 0.05 to about 1%, more preferably about 0.1 to about 0.7%, especially about 0.1 to about 0.5%, relative to the total amount of the ethylene-based monomer used. The amount of use can be exemplified.

In addition, a reducing agent can be used in combination during emulsion polymerization, if desired. Examples thereof include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid and glucose; reducing inorganic compounds such as sodium thiosulfate, sodium sulfite, sodium bisulfite and sodium metabisulfite. The amount used can be appropriately selected, and for example, the amount used is about 0.05 to about 1% with respect to the total amount of the ethylene-based monomer used.

The aqueous resin dispersion used in the present invention is a single or a plurality of (co) polymers of the (co) polymer emulsion thus obtained.
It is preferably a blend of polymeric emulsions.
The blended product is not particularly limited, and examples thereof include a blended product of (co) polymer emulsions of ethylene-based monomers containing aromatic vinyl-based monomers and the emulsions and aromatic vinyl-based products. Examples thereof include blends with a (co) polymer emulsion of an ethylene-based monomer containing no monomer (for example, acrylic emulsion, vinyl acetate-acrylic copolymer emulsion, etc.). The amount of the aromatic vinyl-based monomer in the total amount of the ethylene-based monomer required to produce all (co) polymers present in the blend must be about 10% by weight or more. is there. In addition, as described above, in the resin aqueous dispersion containing a (co) polymer of a saturated fatty acid vinyl-based monomer such as vinyl acetate, the saturated fatty acid vinyl-based monomer is used in view of the wash resistance of the obtained product. The usage of the quantity is
It is preferably less than about 50% by weight, based on the total amount of ethylene monomer.

The solid content of the resin aqueous dispersion used in the present invention is not particularly limited, but is about 30 to about 65% by weight in view of productivity and ease of production.
The viscosity at a solid content of 50% by weight is about 2000 cps. (Rotational viscometer, 25 ° C, 20R.PM) or less from the viewpoint of water repellent processing suitability when used as a water repellent resin aqueous composition. Is preferred. The pH of the above-mentioned dispersion is not particularly limited, but from the viewpoint of the stability of the dispersion and the water repellency, adhesiveness, washing resistance and solvent resistance of the resulting water repellent product, a PH of about 4 is obtained. Is preferably about 6.5.

The water-repellent resin aqueous composition of the present invention comprises the resin aqueous dispersion as described above and a fluorine-based water repellent.

As the fluorine-based water repellent, a polyfluoroalkyl group-containing polymer, preferably an acrylic ester or methacrylic acid ester containing a perfluoroalkyl group at the terminal and the ethylene-based monomer A water- and oil-repellent agent aqueous dispersion in which a copolymer is emulsified and dispersed in an aqueous medium by a surfactant, for example, JP-B-53-2999, JP-B-53-3000, and JP-B-53-4159. And the water- and oil-repellent aqueous dispersions described in JP-A-60-40182.

Among the fluorine water repellents described above, from the viewpoint of water repellency of the obtained product, in the ethylene monomer for copolymerization, a heat-crosslinkable ethylene carboxylic acid derivative monomer, particularly N- A methylol (meth) acrylamide and / or diacetone acrylamide containing a methylol compound,
A thermosetting water- and oil-repellent aqueous dispersion is preferably used.

The amount of the fluorine-based water repellent used is about 5 to about 50 parts by weight, preferably about 10 to about 30 parts by weight, based on 100 parts by weight of the resin aqueous dispersion. . If the amount used is less than about 5% by weight, the water repellency of the obtained product tends to be insufficient, which is not preferable, and even if more than about 50 parts by weight is used, the water repellency is less than that when about 50 parts by weight is used. It does not improve so much, and when it is used as a binder for non-woven fabrics, the adhesiveness may be insufficient, and economically about 50
It is preferable to use it in an amount of not more than wt%.

The water-repellent resin aqueous composition of the present invention may contain a crosslinking agent and a crosslinking catalyst in addition to the resin aqueous dispersion and the fluorine-based water repellent. Examples of the cross-linking agent include aqueous solutions or water dispersions of amino resins such as urea-formaldehyde resin and melamine-formaldehyde resin; aqueous solutions or water dispersions of resole or novolak phenol resins; aqueous solutions or water of various epoxy resins. Dispersion; an aqueous solution or aqueous dispersion of a blocked isocyanate crosslinking agent; and the like, and the blending of an aqueous solution or aqueous dispersion of an amino resin is preferable from the viewpoints of easy availability, crosslinking reaction effect, and the like.
The blending amount of the cross-linking agent, solid content of the resin aqueous dispersion
The solid content can be used in the range of 0 to about 400 parts by weight based on 100 parts by weight. From the viewpoint of solvent resistance and feeling, etc., it is preferably used in the range of about 1 to about 10% by weight.

Cross-linking catalysts are often used especially in the use of amino resins and the like. For example, inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as (anhydrous) phthalic acid and paratoluenesulfonic acid, and these inorganic acids and organic acids. Examples thereof include ammonium salts of amines and amine salts, and the amount thereof is about 0.5 to 0.5 as an active ingredient based on 100 parts by weight of the solid content of the amino resin.
It can be appropriately used within a range of about 10 parts by weight.

Further, if desired, in an application range that does not impair the excellent effects of the present invention, an aqueous solution or an aqueous dispersion of a resin other than the above, such as a polyester resin and a polyurethane resin, can be blended, and titanium oxide, Organic or inorganic fillers such as clay, talc, calcium carbonate, silica, aluminum hydroxide, asbestos, carbon black, and phthalocyanine blue, pigments, dyes, and film-forming aids,
There is no problem even if a plasticizer, an antiaging agent, a preservative, an ultraviolet absorber, etc. are added.

The water-repellent resin aqueous composition of the present invention is as it is, or
It can be appropriately diluted with water or the like and applied to various products such as textile products by various methods such as impregnation, spraying, coating, and printing. In this case, the viscosity can be increased to a desired viscosity with polyvinyl alcohol, a cellulose derivative, a polycarboxylic acid resin, a surfactant thickener, etc., if necessary.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The preparation of test samples used in the above examples and the test method are as follows.

(1) Method for preparing test sample (i) Sample for texture and water repellency test Cotton broad # 40 was immersed in a water-repellent resin aqueous composition containing water to a solid content of 30% by weight, and then When squeezed with a manual mangle to give a pick-up of about 100 (weight)%, it is pre-dried at 100 ° C for 10 minutes, then heat-dried at 140 ° C for 10 minutes, and the temperature and humidity of 20 ° C and 65% RH are constant. After adjusting for about 24 hours under the conditions, it was cut into a square of about 20 cm × about 20 cm to obtain a sample for water repellency test.

(Ii) Nonwoven fabric test sample A web of rayon / polyester = about 40/60 was dipped in a 30% by weight aqueous solution of a water-repellent resin composition, then sandwiched between nylon gauze and wet with a manual mangle to give about 100 ( Weight)% Squeeze to make a pick-up, then attach to a pin tenter and pre-dry at 100 ° C for 10 minutes, then at 140 ° C for 10 minutes.
The material dried by heating for 1 minute was adjusted for about 24 hours under constant temperature and humidity conditions of 20 ° C. and 65% RH, and then cut into a square of about 20 cm × about 20 cm to obtain a non-woven fabric test sample.

(2) Test method (i) Normal texture The texture by touch of the sample prepared in (i) of (1) was examined and classified into 5 grades of (soft) SS, S, M, H, HH (hard). . In addition, when there is one located in the middle of these five stages, it is described as S to M, for example.

(Ii) Normal state water repellency test Using four samples prepared in (i) of (1), JIS L1
A water repellency test was conducted according to 092, and the average value was used as the normal water repellency.

(Iii) Washing water repellency and texture retention test Eight samples prepared in (i) of (1) together with about 40 liters of water and about 40 g of a neutral detergent (Procter & Kamble Co .; Monogen Uni) Put it in a commercial household washing machine (Toshiba; Galaxy VH-101), wash it for about 15 minutes in an automatic reverse flow, then wash it in about 40 liters of water for about 3 minutes, and then dehydrator attached to the washing machine After dehydration for about 1 minute at 100 ° C and drying for 10 minutes at 100 ° C, adjust at 20 ° C and 65% RH under constant temperature and humidity for about 24 hours, and then use four of them for JIS L1092. A water repellency test is carried out, calculation is carried out according to the following formula, and the average value is taken as the washing water repellency retention rate.

Further, the feeling of the remaining 4 samples after washing and adjustment was examined by the appearance and the touch, and compared with the normal feeling, and the degree of change was evaluated as follows.

○ …… Almost no change △ …… There is a change × …… Large change (iv) Solvent water repellency and texture retention test Eight samples prepared in (i) of (1) were dry-cleaned with about 4 liters of Perkren. Put in a tester (Suga Test Instruments Co., Ltd .; LM-D type), stir at a rotation speed of about 45 RPM for 15 minutes, then dry at about 40 ° C for about 1 hour, then at about 100 ° C for 10 minutes.
After being dried for a minute, then adjusted for about 24 hours under constant temperature and humidity conditions of 20 ° C and 65% RH, perform a water repellency test according to JIS L1092, and calculate according to the following formula, The average value is taken as the solvent water-repellent retention rate.

In addition, the feeling of the remaining 4 samples after solvent cleaning and adjustment was examined by the appearance and the touch, and the degree of change from the normal condition was evaluated as follows.

○: Almost no change △: There was a change ×: Large change (v) Non-woven fabric adhesion to washing retention 8 samples prepared in (ii) of (1) were processed in the same manner as (iii) of (2). After washing and adjusting, the adhesion state was examined by appearance and touch, and compared with the sample before washing, the degree of change was evaluated as follows.

○: Almost no change △: Fluffing Adhesiveness and deterioration.

×: Large dropout of fibers (vi) Non-woven fabric resistance to solvent adhesion retention After washing and adjusting eight samples prepared in (ii) of (1) in the same manner as (iv) of (2), the appearance and Check the adhesion state by touch, compare with the sample before washing,
The degree of the change was evaluated as follows.

○: Almost no change △: Fluffing ×: Large drop-off of fibers Example 1 (Production of aqueous resin dispersion) 368 g of water was added to a round-bottom flask equipped with a stirrer 2 l and heated to 7 ° C. After replacing the inside of the flask with nitrogen, 5 g of sodium dodecylbenzene sulfonate, polyethylene glycol nonylphenyl ether (the number of moles of ethylene oxide added is about
50) 15 g, N-methylol acrylamide (hereinafter, N-M
Aqueous solution of 6 g dissolved in 120 g of water, butyl acrylate (hereinafter sometimes abbreviated as BA) 510 g, styrene (hereinafter sometimes abbreviated as st) 72
g, a monomer mixture of 12 g of acrylic acid (hereinafter sometimes abbreviated as AA), 60 g of a 3% aqueous solution of sodium persulfate, and 60 g of a 3% aqueous solution of sodium metabisulfite are continuously added over 5 hours to react. After completion of the reaction, pH was adjusted with 25% aqueous ammonia. The obtained resin aqueous dispersion has a solid content of about 50% by weight, PH 4.5, and a viscosity of 270 cps. (B type rotary viscometer, 25 ° C., 20R.
PM).

(Production of Water-Repellent Resin Aqueous Composition) 15 parts by weight of a fluorine-based water repellent [Asahi Guard LS-317: manufactured by Asahi Glass Co., Ltd.] based on 100 parts by weight of solid content of the above-mentioned aqueous dispersion. The water-repellent resin aqueous composition was blended.

(Water repellency test and texture test) A texture and water repellency test sample was prepared according to the method (i) of the sample preparation method (1), and the samples (i) to (iii) of the test method (2) were prepared. The test was carried out according to the method of (1). The test results are shown in Table 1.

Example 2 A resin aqueous dispersion was produced in the same manner as in Example 1 except that BA510g → 450g and st72g → 132g were changed. Hereinafter, a water repellent resin aqueous composition was prepared in the same manner as in Example 1, A water test and a texture test were conducted. The test results are shown in Table 1.

Examples 3 to 7 and Comparative Example 1 A resin aqueous dispersion was produced in the same manner as in Example 1 except that the amounts of BA and st were changed, and the water repellent resin aqueous composition was prepared in the same manner as in Example 1 below. Then, a water repellency test and a texture test were conducted. The resin composition of the aqueous resin dispersion and the test results are shown in Table 1.

Examples 8 to 13 In Example 1, the amount of st is 132 g, and BA and / or N-
By changing the amount of MAM, 2-ethylhexyl acrylate (hereinafter sometimes abbreviated as 2EHA) / methyl methacrylate (hereinafter sometimes abbreviated as MMA), ethyl acrylate (hereinafter abbreviated as EA) instead of BA There is /)
Acrylonitrile (hereinafter sometimes referred to as AN),
Using EA / MMA, using MMA together with BA, or replacing AA with methacrylic acid (hereinafter, sometimes abbreviated as MAA) to produce an aqueous resin dispersion, and repeating the same procedure as in Example 1 below. Aqueous resin aqueous compositions were prepared and subjected to a water repellency test and a texture test. The resin composition of the aqueous resin dispersion and the test results are shown in Table 1.

Examples 14 to 18 and Comparative Example 2 Example 1 is the same as Example 1 except that the aqueous resin dispersion described in Example 2 is used and the compounding amount of the fluorine-based water repellent is changed.
A water-repellent resin aqueous composition was prepared in the same manner as above, and a water-repellent test and a texture test were conducted. The compounding amount of the fluorine-based water repellent and the test results are shown in Table 1.

Example 19 The resin aqueous dispersion described in Example 2 was used, and its solid content was 10%.
15 parts by weight of fluorine-based water repellent in solid content, 5 parts by weight of aqueous solution melamine resin [Sumitex M-3: Sumitomo Chemical Co., Ltd.] in solid content and curing catalyst [Sumi Tex accelerator ACX: manufactured by Sumitomo Chemical Co., Ltd.] in an amount of 1 part by weight to give a water-repellent resin aqueous composition. Using this water-repellent composition, a sample for texture, water repellency and adhesion retention test was prepared according to the methods (i) and (ii) of the sample preparation method (1), and the test method (2) was used. (I)
The test was conducted according to the method of (vi). The test results are shown in Table 2.

Examples 20 to 26 The same procedure as in Example 19 was repeated except that the resin aqueous dispersion described in Example 2 was replaced with the dispersions described in Examples 3 and 7 to 12. Aqueous resin aqueous compositions were prepared and various tests were conducted. The resin aqueous dispersion used and the test results are shown in Table 2.

Examples 27 to 31 A water-repellent resin aqueous composition was prepared in the same manner as in Example 19 except that the amount of the fluorine-based water repellent compounded was changed, and various tests were conducted. The compounding amount of the fluorine-based water repellent and the test results are shown in Table 2.

Examples 32 and 33 A water-repellent resin aqueous composition was prepared in the same manner as in Example 19 except that the blending amount of the water-soluble melamine resin was changed, and various tests were conducted. The compounding amount of water-soluble melamine resin and the test results are shown in Table 2.

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Claims (11)

[Claims] 1. A fluorine-based water repellent in a solid content relative to 100 parts by weight of a solid content of an aqueous resin dispersion comprising one or more of (co) polymer emulsions of ethylene-based monomers. A water-repellent resin aqueous composition containing about 5 to about 50 parts by weight, and containing about 10% by weight or more of an aromatic vinyl-based monomer with respect to the total amount of the ethylene-based monomer. A water-repellent resin aqueous composition characterized by: 2. The heat-crosslinkable ethylene-based carboxylic acid derivative-based monomer in an amount of about 0.5 to about 5% by weight based on the total amount of the ethylene-based monomer. The water-repellent resin aqueous composition according to the item (1). 3. The water-repellent material according to claim (2), wherein the heat-crosslinkable ethylene-based carboxylic acid derivative-based monomer is N-methylol acrylamide or N-methylol methacryl acrylamide. Aqueous resin composition. 4. An ethylene-based carboxylic acid is contained in an amount of about 0.5 to about 6% by weight, based on the total amount of the ethylene-based monomer, according to claim (1) or (2). ) Item. 5. The water-repellent resin aqueous composition according to claim (4), wherein the ethylene-based carboxylic acids are acrylic acid, methacrylic acid and / or itaconic acid. 6. The range (1) according to claim 1, wherein the aromatic vinyl monomer is contained in an amount of about 10 to about 30% by weight based on the total amount of the ethylene monomer. ~ Number (5)
Item 5. A water-repellent resin aqueous composition according to any one of items. 7. The aromatic vinyl-based monomer is contained in an amount of more than 30% by weight based on the total amount of the ethylene-based monomer, and the above-mentioned items (1) to (1) are included. Number (5)
Item 5. A water-repellent resin aqueous composition according to any one of items. 8. The aromatic vinyl-based monomer is styrene, and the scope of claims (1) to (7).
Item 5. A water-repellent resin aqueous composition according to any one of items. 9. The cross-linking agent is further contained in an amount of about 1 to about 10% by weight based on 100 parts by weight of the solid content of the resin aqueous dispersion, and the cross-linking agent is further included. Item-water-repellent resin aqueous composition according to item (8). 10. The water-repellent resin aqueous composition according to claim 9, wherein the crosslinking agent is an aqueous solution of an amino resin. 11. The water-repellent resin aqueous composition is used for textile processing, as claimed in claim (1).
Item 10. The water-repellent resin aqueous composition according to any one of items 10 to 10.