JPS63130692A - Aqueous composition of water-repellent resin - Google Patents

Abstract

PURPOSE:To obtain the title composition which can provide soft goods and paper with excellent feeling to touch and water repellency when they are impregnated therewith, by blending an aqueous resin dispersion consisting of a (co-)polymer emulsion of specified ethylene monomers and a fluorinated repellent. CONSTITUTION:Ethylenic monomers consisting of (i) at least 10wt% aromatic vinyl monomer (e.g. styrene), (ii) 0.5-5wt% thermally crosslinkable ethylenic carboxylic acid derivative monomer [e.g. N-methylol(meth)acrylamide], (iii) ethylenic carboxylic acids [e.g. (meth)acrylic acid] and (iv) other ethylenic monomer are submitted to an emulsion polymerization in an aqueous medium in the presence of a surface active agent and/or a protective colloid. One or more members of the resulting (co-)polymer emulsions are mixed to give an aqueous resin dispersion (A) containing 30-65wt% solid matter and having a viscosity of at most 2,000cps (determined with a rotating spindle viscometer at 25 deg.C, 20r.p.m.) and a pH of 4-6.5. 100pts.wt. ingredient (A) in terms of solid content is blended with 5-50pts.wt. (B) fluorinated water-repellent which is an aqueous dispersion of a polyfluoroalkyl-containing polymer in terms of solid content.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to imparting water repellency to textile products, paper, films, wood, structures, etc. by impregnating, spraying, or coating the surface. Regarding water-repellent resin aqueous compositions that can
In particular, regarding water-repellent resin aqueous compositions that can impart water repellency and desired texture to various textile products, in particular, by treating non-woven fabric raw materials using the composition as a non-woven fabric binder, water-repellent properties can be achieved in one step. Regarding an aqueous water-repellent resin composition capable of producing a nonwoven fabric having excellent properties and a desired texture, specifically, an aqueous resin dispersion comprising one or more (co)polymer emulsions of specific ethylene monomers. The present invention relates to an aqueous water-repellent resin composition characterized in that it contains a specific amount of a fluorine-based water repellent relative to liquid 9.

[Conventional technology]

Conventionally, various methods have been known as water repellent treatment methods.
No. 697, 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), or fluorine-based water repellent. A method using a heat treatment agent (Japanese Unexamined Patent Publication No. 8775/1983) has been proposed.

However, in these proposals, only a water repellent is used, or a water repellent composition containing an extremely high proportion of water repellent is used, and although it is possible to impart water repellency to the product, it is not possible to achieve the desired wind resistance. In particular, when used as a nonwoven fabric binder to produce a nonwoven fabric with excellent water repellency and a desired texture in one step, there are problems in terms of adhesion and texture. However, since water repellents are extremely expensive, costs inevitably increase.

It is also known to use a composition made by thickening a fluorine-based water repellent with an ethylene-based carboxylic acid copolymer. To provide a single-sided water-repellent fabric made of hydrophilic fibers and a method for producing the same, more specifically, to provide a single-sided water-repellent fabric that has elasticity and moisture permeability, and has excellent water repellency and durability; A fluorine-based water- and oil-repellent finishing agent that contains a molecular weight molecular unsaturated carboxylic acid and/or its derivatives as a copolymerization component, with a weight ratio of 0 to 88. Vinyl copolymer 10~88W
The total solid content of the processing agent, which consists essentially of kidney matter, a softening and smoothing agent of 2 to 50 weight range, and a polyfunctional crosslinking agent of 0 to 50 weight range, is 0.2 to 209/rr? This document describes a single-sided water-repellent treated fabric characterized in that a hydrophilic fiber-containing fabric is coated with a water-repellent coating on one side of the fabric.

However, the "vinyl copolymer containing an ethylenically unsaturated carboxylic acid and/or its derivative as a copolymerization component" in the above-mentioned publication is - It is a thickener to increase the viscosity to 20,000 cps, and is completely different from the aqueous resin dispersion of the present invention, and is not intended to impart desired texture and adhesiveness as well as water repellency. Also, the above-mentioned Japanese Patent Application Laid-Open No. 61-11)
Publication No. 882 does not contain any description or suggestion regarding the use of an aromatic vinyl monomer and its special water-repellent effect, which is an essential requirement of the present invention, and the processing agent described in the above publication does not contain any description or suggestion. Even when used as a binder for a nonwoven fabric, for example, it was not possible to obtain an excellent water-repellent nonwoven fabric, as the adhesiveness as a binder was sometimes insufficient.

[Problem that the invention seeks to solve]

As mentioned above, conventional water-repellent compositions can impart water resistance to various products, especially textile products, but they are unsuitable for imparting a desired texture. By using this method, a considerable increase in cost could not be avoided.

Conventionally, when producing a water-repellent nonwoven fabric using an adhesive, for example, the nonwoven fabric raw material is immersed in a common binder bath for nonwoven fabrics, squeezed with a roll or the like, and then dried. Generally, a two-step manufacturing process was used in which a water repellent agent was applied to the nonwoven fabric by dipping, spraying, etc., and then dried to impart water repellency.

However, in the above two-step manufacturing method, two liquids, the nonwoven fabric binder and the fluorine-based water repellent, must be used separately, and drying is also required twice, which reduces productivity and energy efficiency. Furthermore, even if one attempts to manufacture the product in one step using only the treatment agent described in JP-A-61-11)882 instead of using two liquids, as mentioned above, the water repellency of the resulting nonwoven fabric will be poor. It has been difficult to obtain excellent water-repellent nonwoven fabrics due to insufficient adhesion or insufficient adhesion as a binder for nonwoven fabrics.Furthermore, acrylic, which has conventionally been generally used as a binder for nonwoven fabrics, has been difficult to obtain. Even if an attempt is made to produce a water-repellent nonwoven fabric by blending the fluorine-based water repellent described in the above-mentioned publications with a water-based emulsion, etc., the water repellency is insufficient, or even if water repellency is obtained, the fluorine-based repellent is insufficient. There was a problem in that a very large amount of liquid medicine had to be added.

Furthermore, in the case of water-repellent finishing of textile products, it is necessary that there is little deterioration in water testability or change in texture even when these products are washed or dry-cleaned. Among these, those used as interlining materials for clothing are particularly required to have adhesive retention properties that are resistant to washing, adhesive retention properties that are resistant to organic solvents such as perchloride resistance, and mineral turpentine resistance.

The present invention is capable of imparting various water repellent finishes, particularly to imparting a desired texture and excellent water repellency to various textile products.
It is water repellent with little deterioration in water repellency, has the desired texture, and has excellent adhesive properties. The purpose is to provide an aqueous water-repellent resin composition with a small amount of water-repellent resin, and is also an excellent economical water-based resin composition that can achieve the above objectives without using large amounts of expensive fluorine-based water repellents. The purpose is to provide a composition.

[Failure to solve the problem]

In the present invention, a fluorine-based water repellent is added in a solid content of about 5 to 100 parts by weight of an aqueous resin dispersion consisting of one type or 2 ya or more of an ethylene monomer (co)polymer emulsion. A water-repellent resin aqueous composition containing about 50 parts by weight, and containing about 10 weight molecules or more of an aromatic vinyl monomer based on the total amount of the ethylene monomer. An object of the present invention is to provide a water-repellent resin aqueous composition.

"Resin aqueous dispersion consisting of one or more types of (co)polymer emulsions of ethylene monomers" as used in the present invention
refers to emulsion polymerization of ethylene monomers in an aqueous medium in the presence or absence of surfactants and/or protective colloids, or post-emulsification of (co)polymers polymerized under pressure by methods other than emulsion polymerization. Refers to a single (co)polymer emulsion obtained by or a blend of multiple (co)polymer emulsions, including but not limited to, ease of production, economic efficiency, etc. For this reason, it is preferable to use a single (co)polymer emulsion or a blend of multiple (co)polymer emulsions usually obtained by emulsion polymerization.As the ethylene monomer that can be used in the present invention, is, for example, methyl acrylate, ethyl acrylate, n
-butyl acrylate, isobutyl acrylate, 2-
Alkyl ester monomers of acrylic acid such as ethylhexyl acrylate, sn-octyl acrylate, lauryl acrylate, stearyl acrylate; for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, etc. Alkyl ester monomers of methacrylic acid such as: Aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, ethylvinylbenzene, etc.; Cyanide monomers such as vinyl acetate, vinyl propionate, etc. Vinyl monomer;
For example, olefin spinning wheel cover such as ethylene, propylene, butadiene, etc.: for example, acrylic acid, methacrylic acid, crotonic acid, citraconic acid, itaconic acid, maleic acid,
7-rA[, monoalkyl esters of ethylene dicarboxylic acids such as maleic anhydride, heptanobutylmaleic acid, ammonium salts thereof, and amides of ethylene carboxylic acids such as tonacrylamide, such as N-methylol acrylamide, N-methylolmethacrylamide, methylolated diacetone acrylamide and
Methylolated products of ethylene carboxylic acid amides such as etherified products of these monomers with alcohols having 1 to 8 carbon atoms (for example, N-isobutoxymethylacrylamide), and derivatives thereof: such as glycidyl acrylate, glycidyl Esters of ethylene carboxylic acid such as methacrylate and alcohol having an epoxy group: For example, hydroxyalkyl esters of ethylene carboxylic acid such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, etc. ; For example, esters of ethylene carboxylic acids such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc. and alcohols having an amino group; For example, 2 or more esters such as divinylbenzene, diallyl phthalate, triallyl cyanurate, diethylene glycol dimethacrylate, etc.; Monomers containing an unsaturated group can be mentioned.

- In the present invention, it is necessary that the aromatic vinyl monomer as described above be contained in an amount of about 10 parts or more based on the total amount of ethylene monomer. The term "total amount of ethylene monomers" refers to the total amount of ethylene monomers required to produce all (co)polymers present in the resulting aqueous resin dispersion. When the amount of the aromatic vinyl monomer is less than about 10 parts, it is difficult to obtain the excellent water repellency that is the object of the present invention, which is not preferred. The aromatic vinyl monomer is preferably styrene due to its ease of availability and suitability for polymerization reactions (polymerization reaction rate, risk of gelation, amount of gelatinous material, etc.). .

The amount of the aromatic vinyl monomer can be suitably selected from about 10 overlapping parts or more depending on various required physical properties of the product to be water-repellent treated. For example, for water-repellent treatment of products that require flexibility, washing resistance, organic solvent resistance, etc., such as when used as a nonwoven binder for clothing interlining,
It is preferable to use the aromatic vinyl monomer in an amount of about 10 to about 30% by weight, and about 0% of the thermally crosslinkable ethylene carboxylic acid derivative monomer based on the total amount of the ethylene monomer.
．． Preferably, it comprises a weight range of 5 to about 5.

Among the above-mentioned monomers, examples of the thermally crosslinkable ethylene carboxylic acid derivative monomers include: amides of ethylene carboxylic acids; methylolated products of ethylene carboxylic acid amides and derivatives thereof; Esters of carboxylic acid and alcohol having an epoxy group: hydroxyalkyl esters of ethylene carboxylic acid, etc., and these monomers can be used alone or in combination of two or more, Among these, polymerization reaction suitability, washing resistance and organic solvent water repellency retention of the resulting product, washing resistance and organic solvent resistance texture retention, washing resistance and water repellency retention in the case of nonwoven fabrics, and laundry resistance adhesiveness. Retention property and washing resistance texture retention property (hereinafter sometimes abbreviated as washing resistance), organic solvent resistance water repellency retention property, organic solvent resistance adhesive retention property and organic solvent resistance texture retention property (hereinafter referred to as solvent resistance) From the viewpoint of excellent properties such as properties (sometimes abbreviated as "property"), it is preferable to use a methylolated product of ethylene-based carboxylic acid amide, and it is particularly preferable to use N-methylol (meth)acrylamide.

If the amount of the thermally crosslinkable ethylene carboxylic acid derivative monomer used is less than about 0.5 weight molecules, the water resistance and solvent resistance may be insufficient, and if the amount exceeds about 5 weight molecules, Since problems may occur in polymerization reaction suitability, it is preferable to use the monomer in an amount of about 0.5 to about 5 weight percent.

In addition, in the present invention, the resulting water-repellent resin aqueous composition is stabilized by further containing about 0.5 to about 6 tIG, which is the ethylene-based carboxylic acid, based on the total amount of the ethylene-based monomer. It is preferable from the viewpoint of excellent water repellency, adhesiveness, solvent resistance, etc., especially when a thermally crosslinkable ethylene carboxylic acid derivative monomer is used. As such ethylene carboxylic acids, acrylic acid, methacrylic acid and itaconic acid are preferably used in view of the above-mentioned effects and polymerization reaction suitability.

The texture of the resulting processed product is determined by monomer components other than the aromatic vinyl monomer, thermally crosslinkable ethylene carboxylic acid derivative monomer, and ethylene carboxylic acids.
By appropriately selecting and using monomers from the above-mentioned monomer groups, it is possible to design freely. When a flexible texture is required, 2-ethylhexyl acrylate, butyl acrylate, etc. may be selected as appropriate, but it is also possible to make the texture harder, and in this case, methyl methacrylate, acrylonitrile, etc. may be used as appropriate.

Furthermore, in fields where a relatively hard feel is required, aromatic vinyl monomers can be used in an amount exceeding about 30% by weight. In this case as well, it is preferable to use the thermally crosslinkable ethylene carboxylic acid derivative monomer within the above range in order to improve washing resistance.

The aqueous resin dispersion of the present invention is usually obtained by emulsion polymerization of an ethylene monomer appropriately selected from the above monomer group in an aqueous medium in the presence of a surfactant and/or a protective colloid. (co)polymer emulsion, or a blend of a plurality of these (co)polymer emulsions. 'The above surfactants include nonionic surfactants such as polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol, etc. Polyoxyalkylene alkylphenol ethers such as ethers; Sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, etc.; Polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate:
Polyoxyalkylene fatty acid esters such as polyoxyethylene monolaurate and polyoxyethylene monostearate; glycerin fatty acid esters such as oleic acid monoglyceride and stearic acid monoglyceride; polyoxyethylene polyoxypropylene block copolymer: etc. Examples of anionic surfactants include fatty acid salts such as sodium oleate, alkylarylsulfone salts such as sodium nidodecylbenzenesulfonate, and alkyl sulfate esters such as sodium lauryl sulfate. Salts: Alkyl sulfosuccinate salts such as monooctyl sodium sulfosuccinate, dioctyl sodium sulfosuccinate, polyoxyethylene lauryl sodium sulfosuccinate, etc. and their derivatives: Polyoxyalkylene alkyl ether sulfates such as polyoxyethylene lauryl ether sodium sulfate, etc. Ester salts: polyoxyalkylene alkylaryl ether sulfate ester salts such as polyoxyethylene nonylphenol ether sodium sulfate, etc., and cationic surfactants such as alkylamino salts such as lauryl amino acetate, nilauryl trimethyl ammonium chloride, etc. , quaternary ammonium salts such as alkylpencil dimethylammonium chloride; polyoxyethylalkylamino: and the like. Examples of amphoteric surfactants include alkylbetaines such as laurylbetaine. Furthermore, surfactants in which some of the hydrogen atoms in the alkyl groups of these surfactants are replaced with fluorine can also be used. Furthermore, reactive anionic surfactants having a radically polymerizable double bond in the molecular structure of the surfactant, such as the so-called reactive surfactant ster salt type and alkenylsuccinic acid 7-alkenyl ester salt type, may be mentioned. I can do it.

The amount of surfactant used is usually 0.1 to about 10% by weight based on the total amount of the ethylene spinning wheel cover, and from the viewpoint of water repellency, adhesiveness, washing resistance, etc. 5 to about 6
Heavy! It is preferable to use %, about 0.5 to about 4%
It is particularly preferred to use

Examples of retained colloids that can be used in the present invention include polyvinyl alcohols such as partially saponified polyvinyl alcohol, completely saponified polyvinyl alcohol, and modified polyvinyl alcohol; hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose salts. and natural polysaccharides such as guar gum; these can be used alone or in combination of multiple types. The lid to be used can be selected as appropriate, but for example, the lid can be selected from θ to about 1 for the entire view of the ethylene monomer to be used.

In the present invention, "in an aqueous medium" means in water or in an aqueous solution of a water-soluble organic solvent, and such water-soluble organic solvents are not particularly limited, and examples include evaporated methyl alcohol, ethyl alcohol, and isopropyl alcohol. Water-soluble alcohols such as; water-soluble ketones such as acetone:
It is possible to use water-soluble ethers such as butyl cellosolve, cellosolve, butyl cellosolve, carbitol, butyl carpitol, etc. alone or in combination, and the amount used is 0 as the concentration of the aqueous solution of the water-soluble organic solvent.
~50% by weight, for example, but from the viewpoint of the stability of the resulting aqueous resin dispersion and the water repellency, adhesion, washing resistance, and solvent resistance of the water-repellent product, it is practically It is preferable to carry out the emulsion polymerization in water that does not contain these organic solvents.

Furthermore, in emulsion polymerization, persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate, etc.; tertiary butyl hydroperoxide,
Organic peroxides such as cumene hydroperoxide and paramenthane hydroperoxide, and polymerization initiators such as hydrogen peroxide can be used. These can also be used either singly or in combination.

The amount to be used can be appropriately selected, but is, for example, about 0.05 to about 1, more preferably about 0.05 to about 1, based on the total amount of the ethylene monomer used. 1 to about 0.7, especially about 0.
1 to about 0. An example of a usage amount is 5%.

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

The aqueous resin dispersion used in the present invention was thus obtained (
A single co)polymer emulsion or a blend of multiple (co)polymer emulsions is preferred. The above blend is not particularly limited,
For example, blends of (co)polymer emulsions of ethylene monomers containing aromatic vinyl monomers, or blends of emulsions of (co)polymers of ethylene monomers containing no aromatic vinyl monomers, and )″m coalesced emulsion (e.g.
acrylic emulsion, vinyl acetate/acrylic copolymer emulsion, etc.), and in this case, the ethylene monomers necessary to produce all (co)polymers present in the blend can be mentioned. The amount of the aromatic vinyl monomer based on the total amount of monomers needs to be about 10 parts by weight or more. In addition, as mentioned above, in an aqueous resin dispersion containing a (co)polymer of a saturated fatty acid vinyl monomer such as vinyl acetate, from the viewpoint of washing resistance of the resulting product, the saturated fatty acid vinyl spinning wheel lid is Preferably, the amount of ethylene monomer used is less than about 50 parts by weight, based on the total amount of ethylene monomer.

The solid content of the aqueous resin dispersion used in the present invention is not particularly limited, but it is preferably about 30 to about 65 wt % from the viewpoint of productivity and ease of manufacture, and the viscosity when the solid content is 50 wt % is , from the viewpoint of suitability for water-repellent finishing when made into a water-repellent resin aqueous composition, approximately 2000 (! p
0R, P, IVL) or less. Further, the pH of the dispersion is not particularly limited, but it is preferable that the pH of the dispersion be consistent with the stability of the dispersion.

The water-repellent resin aqueous composition of the present invention contains the above-mentioned resin aqueous dispersion and a fluorine-based water repellent.

The above-mentioned fluorine-based water repellent is a copolymer of a polymer containing a polyfluoroalkyl group, preferably an acrylic ester or a methacrylic ester containing a perfluoroalkyl group at the terminal, and the above-mentioned ethylene spinning wheel cover. It is an aqueous dispersion of a water and oil repellent in which the aggregate is emulsified and dispersed in an aqueous medium with a surfactant.
Examples include water- and oil-repellent aqueous dispersions described in Japanese Patent Publication No. 53-3000, Japanese Patent Publication No. 53-4159, and Japanese Patent Application Laid-Open No. 60-40182.

Among the above fluorine water repellents, from the viewpoint of water repellency of the resulting product, thermally crosslinkable ethylene carboxylic acid derivative monomers, especially N-methylol, are added to the ethylene monomer for copolymerization. A so-called thermosetting water/oil repellent aqueous dispersion containing a methylolated product of (meth)acrylamide and/or diacetone acrylamide is preferably used.

The amount of the fluorine-based water repellent used is about 5 to about 50 parts by solid content per 100 ii parts of solid content of the aqueous resin dispersion.
Parts by weight, preferably about 10 to about 30 parts by weight. If the amount used is less than about 5 weight molecules, the resulting product tends to have insufficient water repellency, which is undesirable, and even if more than about 50 parts by weight is used, the water repellency will not be as good as when using about 50 parts by weight. Furthermore, when used as a binder for nonwoven fabrics, the adhesion may be insufficient, and economically it is best to use the repellent in an amount of about 50 parts by weight or less. In addition to the aqueous resin dispersion and fluorine-based water repellent, the aqueous resin composition may also contain K, a crosslinking agent, and a crosslinking catalyst. Aqueous solutions or dispersions of the above-mentioned crosslinking agents; aqueous solutions or dispersions of niresol-based or novolak-based phenolic resins; aqueous solutions or dispersions of various epoxy resins; aqueous solutions or aqueous dispersions of niblocked isocyanate-based crosslinking agents; From the viewpoint of availability, crosslinking reaction effect, etc., it is preferable to formulate an aqueous solution or dispersion of the amino resin. The blending amount of the crosslinking agent is θ to about 4 parts by weight based on 100 parts by weight of the solid content of the aqueous resin dispersion.
00 parts by weight, but from the viewpoint of the stability of the resulting water-repellent resin aqueous composition and the water repellency, adhesion, washing resistance, solvent resistance, and texture of the resulting product, approximately Preferably, it is used in a range of 1 to about 10 folds.

Crosslinking catalysts are often used especially when using amino resins, for example, inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as (anhydrous) phthalic acid and p-toluenesulfonic acid, and the combination of these inorganic and organic acids. Ammonium salts, amino salts, etc. can be mentioned, and the amount used is about 0.5 parts as an active ingredient per 100 parts by weight of the solid content of the amino resin.
It can be used as appropriate in the range of 10 parts by weight to about 10 parts by weight.

Furthermore, if desired, aqueous solutions or dispersions of resins other than those mentioned above, such as polyester resins and polyurethane resins, may be blended within the range of use that does not impede the excellent effects of the present invention. , organic or inorganic fillers such as talc, calcium carbonate, silica, aluminum hydroxide, asbestos, carbon black, and phthalocyanine blue, pigments, dyes, and coating aids,
There is no problem in adding plasticizers, anti-aging agents, preservatives, ultraviolet absorbers, etc.

The water-repellent resin aqueous composition of the present invention can be used as 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 level using polyvinyl alcohol, cellulose derivatives, polycarboxylic acid resins, surfactant thickeners, etc., if necessary.

〔Example〕

Hereinafter, the present invention will be explained in more detail by giving Examples and Comparative Examples. The preparation and testing methods for the test samples used in the above examples are as follows.

(1) Method for preparing test samples (1) Sample for texture and water repellency test A piece of cotton broadcloth #40 was immersed in a bath containing water to the water-repellent resin aqueous composition to make the solid content 30 [L%]. Next, it was squeezed with a manual mangle to a wetness of about 100 (it)%, pre-dried at 100°C for 10 minutes, then heated and dried at 140°C for 10 minutes, and heated to 65q at 20°C.
After adjusting the bRH under constant temperature and humidity conditions for about 24 hours, it was cut into squares of about 20 x about 20 crn to prepare samples for water repellency testing.

(11) Sample for nonwoven fabric test A web of rayon/polyester = approximately 40/60, immersed in a 30 weight 11 cJ) aqueous solution of a water-repellent resin aqueous composition, then sandwiched between nylon gauze and manually mangled when wet: approximately 100 (Weight) After squeezing it so that it picks up %, attach it to a pin tenter, pre-dry it at 100℃ for 10 minutes, and then heat-dry it for 10 minutes at 140℃.
After adjusting for about 24 hours under constant temperature and humidity conditions of 0° C. and 654 RH, the samples were cut into about 20×203 squares to prepare nonwoven fabric test samples.

(2) Test method (+) Normal texture Examine the texture of the sample prepared in (1) of (1) (soft) 88. Classified into 5 levels: S, M, H, HH (hard). In addition, when there is a value located in the middle of these five stages, it is written as 8 to M, for example.

(it) Using the four samples prepared in (1) of normal water repellency test (1), JI
A water repellency test was conducted according to SL1092, and the average value was taken as the normal water repellency.

Qip washing water repellency and texture retention test (1) (+
) 8 samples made with 4 oz of water and 40
t neutral detergent (manufactured by Brocter & Gamble:
I put it in a commercially available household washing machine (Toshiba Corporation; Galaxy VH-101) K with Monogen Uni), washed it in an automatic reverse flow for about 15 minutes, then washed it in about 401 water for about 3 minutes, and then washed it with water that came with the washing machine. Dehydrated for about 1 minute in a dehydrator, dried at 100℃ for 10 minutes, conditioned for about 24 hours under constant temperature and humidity conditions of 20℃ and 65% RH, and then used 4 of them to repel water according to JISL1092. A water test is conducted and calculated according to the following formula, and the average value is taken as the washing resistance water repellency retention rate.

In addition, the appearance and feel of the remaining four samples after washing and conditioning were examined, and the degree of change was evaluated as follows by comparing with the normal texture. 'O: Almost no change Δ: Change ×: Large change: 1ψ Solvent-resistant water repellency and texture retention test (1) (1) The 8 samples prepared above were placed in a dry cleaning sample rR (manufactured by Suga Test Instruments Co., Ltd.: LM-D type) along with about 41 parts of perchlorine, and the number of revolutions was 45R.
, P, yL for 15 minutes, dried at about 40°C for about 1 hour, further dried at about 100°C for 10 minutes, then 2
After adjusting for about 24 hours under constant temperature and humidity conditions of 0°C and 65% RH, conduct a water repellency test according to JISL1092, calculate according to the following formula, and calculate the average value as the solvent-resistant water repellency retention rate. do.

In addition, the appearance and texture of the remaining four samples after solvent cleaning and adjustment were determined. :v4pe, the degree of change from the normal texture was evaluated as follows.

○: Almost no change Δ: Change ×: Large change Non-woven fabric washing resistance adhesive retention (ll) (ii) Tee preparation 8 pieces! ,(
2) ln (After washing and adjusting in the same manner as till, 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 Δ...Fuzzing. Adhesion and deterioration.

X...Fiber drop-off hole (vD) Nonwoven fabric solvent resistance adhesive retention After cleaning and adjusting the 8 samples prepared in (1) of (1) with solvent in the same manner as (ψ) of (2), The adhesion state was examined by appearance and touch, and compared with the sample before cleaning, and the degree of change was evaluated as follows.

○...... Almost no change Δ...- Hair standing leg ×... Fiber dropout hole Example 1 (Manufacture of resin aqueous dispersion) Pour 368f of water into a round bottom flask and heat to 7°C.
Warm to. After purging the inside of the flask with nitrogen, add 59° of sodium dodecylbenzenesulfonate and 15 f of polyethylene glycol nonylphenyl ether (50 moles of ethylene oxide added).

An aqueous solution of N-methylol acrylamide (hereinafter sometimes abbreviated as N-MAM) 6f dissolved in 120 tons of water, butyl acrylate (hereinafter sometimes abbreviated as BA) 510F, and styrene (hereinafter sometimes abbreviated as 8t). ) 72f, 12f of acrylic acid (sometimes abbreviated as AA) monomer mixture, and 60f of a 3-part sodium persulfate aqueous solution.

And 3% aqueous solution of sodium metabisulfite 60f! The mixture was continuously added and reacted for 5 hours, and after the reaction was completed, the pH was adjusted with 25% aqueous ammonia. The resulting aqueous resin dispersion had a solid mass of approximately 50 weight molecules, a pH of 4.5, and a viscosity of 270 cps.
(B-type rotational viscometer, 25° C., 20 P, M).

(Manufacture of water-repellent resin aqueous composition) Fluorine-based water repellent [Asahi Guard LS-317: manufactured by Asahi Glass ■] is added to 100 parts by weight of the solid content of the above aqueous dispersion.
A water-repellent resin aqueous composition was prepared by blending 15 parts of the solid content.

(Water repellency test and texture test) Samples for texture and water repellency tests were prepared according to the method in the sample preparation method (1) above, and the samples were prepared in accordance with the method in the sample preparation method (1).
The test was conducted according to the iD method. The test results will be shown in the first award.

Example 2 In Example I, BA510f→450f.

An aqueous resin dispersion was produced in the same manner except that E1t72f was changed to 1) 2 g. Thereafter, a water-repellent resin aqueous composition was prepared in the same manner as in Example 1, and a water repellency 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 the example except that the amounts of BA and 3t were changed, and a water-repellent resin aqueous composition was prepared in the same manner as in Example 1. A water repellency test and a texture test were conducted. The resin composition and test results of the aqueous resin dispersion are shown in Table 1.

Examples 8 to 1) In the examples, the 3t beam is 1) 2f, and BA and/or
Or, change the amount of N-MAM and use 2-ethylhexyl acrylate (hereinafter sometimes abbreviated as 2EHA)/methyl methacrylate (hereinafter sometimes abbreviated as ``Fu''), ethyl acrylate v-) instead of BA. (hereinafter sometimes abbreviated as EA)/acrylonitrile (hereinafter sometimes abbreviated as AN), using EA/MMA, using MMA together with BA, or replacing AA with methacrylic acid (hereinafter abbreviated as gogo) A water-repellent resin dispersion was prepared by substituting the same material as in Example 1, and a water-repellent resin aqueous composition was prepared in the same manner as in Example 1, and a water-repellent test and a texture test were conducted.

The resin composition and test results of the aqueous resin dispersion are shown in Table 1.

Example 14 to 18 and Comparative Example 2 A water-repellent resin was prepared in the same manner as in Example 1 except that the aqueous resin dispersion described in Example 2 was used and the amount of fluorine-based water repellent was changed. An aqueous composition was prepared and subjected to a water repellency test and a texture test.

The amount of the fluorine-based water repellent and the test results are shown in Table 1.

Example 19 Using the resin aqueous dispersion described in Example 2, the solid content was 1
00 parts by weight, 15 parts by weight of a fluorine-based water-refining agent, 5 parts by weight of an aqueous melamine resin [Sumitex Open-3: manufactured by Sumitomo Chemical Industries, Ltd.] and a curing catalyst [Sumitex Accessories]. Lator ACX: Manufactured by Sumitomo Chemical
One weight of each was mixed in the form of a water-repellent resin aqueous composition. Using this water-repellent composition, the above sample preparation method (1)
] and (II) to prepare samples for texture, water repellency and adhesion retention tests, and test method (1) of test method (2).
Tests were conducted according to the methods of ) to (■1). The test results are shown in Table 2.

Examples 20 to 26 In Example 19, the procedure was repeated in the same manner as in Example 19, except that the dispersions described in Examples 3 and 7 to 12 were used instead of the aqueous resin dispersion described in Example 2. A water-based water-repellent resin composition was prepared and various tests were conducted. The aqueous resin dispersion used and the test results are shown in Table 2.

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

Examples 32 and 33 Water-repellent resin aqueous compositions were prepared in the same manner as in Example 19 except that the amount of water-soluble melamine resin was changed, and various tests were conducted.

The blending amount of the water-soluble melamine resin and the test results are shown in Table 2.

Claims (11)

[Claims] (1) Solid content of an aqueous resin dispersion consisting of one or more types of (co)polymer emulsion of ethylene monomers: 1
00 parts by weight, the solid content of fluorine-based water repellent is about 5 to
A water-repellent resin aqueous composition containing about 50 parts by weight, and containing about 10% by weight or more of an aromatic vinyl monomer based on the total amount of the ethylene monomer. Water-repellent resin aqueous composition. (2) A thermally crosslinkable ethylene carboxylic acid derivative monomer is contained in an amount of about 0.5 to about 5% by weight based on the total amount of the ethylene monomer. (
The water-repellent resin aqueous composition described in item 1). (3) The aqueous water-repellent resin according to claim (2), wherein the thermally crosslinkable ethylene carboxylic acid derivative monomer is N-methylol acrylamide or N-methylol methacryl acrylamide. Composition. (4) Claims (1) or (2) contain about 0.5 to about 6% by weight of ethylene carboxylic acids based on the total amount of the ethylene monomer. ) The water-repellent resin aqueous composition described in item 1. (5) The water-repellent resin aqueous composition according to claim (4), wherein the ethylene carboxylic acid is acrylic acid, methacrylic acid and/or itaconic acid. (6) Claims (1) to (1) contain the aromatic vinyl monomer in an amount of about 10 to about 30% by weight based on the total amount of the ethylene monomer. The water-repellent resin aqueous composition according to any one of (5). (7) Claims (1) to (1) contain an aromatic vinyl monomer in an amount exceeding 30% by weight based on the total amount of the ethylene monomer. The water-repellent resin aqueous composition according to any one of item 5). (8) The water-repellent resin aqueous composition according to any one of claims (1) to (7), wherein the aromatic vinyl monomer is styrene. (9) The resin aqueous dispersion further contains about 1 to about 10% by weight of a crosslinking agent based on 100 parts by weight of the solid content of the aqueous resin dispersion. No. 8
) The water-repellent resin aqueous composition described in item 1. (10) The water-repellent resin aqueous composition according to claim (9), wherein the crosslinking agent is an aqueous solution of an amino resin. (11) Claims (1) to (1) characterized in that the water-repellent resin aqueous composition is used for fiber processing.
The water-repellent resin aqueous composition according to any one of item 0).