JPS6360153B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a cationic powdered fiber glue. More specifically, the present invention relates to a cationic powder fiber paste made of a cationic resin powder obtained by drying and powdering an aqueous emulsion of a cationic vinyl polymer. Traditionally, fiber glues used to improve the hardness and texture of fabrics have been starch, water-soluble polymer compounds such as carboxymethyl cellulose and polyvinyl alcohol, or synthetic resin emulsions such as polyvinyl acetate resin emulsion and polyacrylate resin emulsion. has been used. In particular, synthetic resin emulsion is widely used as a textile glue because its hardness can be freely changed by changing the polymerization composition of the synthetic resin, and it is easy to impart desired hardness and texture to cloth. However, fiber glues made of synthetic resin emulsions have had problems with their stability. Synthetic resin emulsion is made of synthetic resin dispersed in water as minute particles, so if it is stored for a long period of time, the synthetic resin particles may settle or the surface may dry and a film may peel off. However, there were problems such as foaming during transportation and freezing in the winter, destroying the emulsion state. In order to solve these problems, stability has traditionally been improved by using large amounts of emulsifiers, adding antifoaming agents, antifreeze agents, etc., but these methods do not solve the fundamental problems. It didn't happen. If fiber glue made of synthetic resin emulsion can be powdered, this problem of stability can be fundamentally solved, but there are problems with the redispersibility of powdered fiber glue in water and its adhesion to fibers. Gender was an issue. It cannot be used as fiber glue unless it is redispersed in water, but even if it is redispersed, if the redispersed synthetic resin particles have poor adhesion to fibers, sufficient gluing effect cannot be obtained, so it cannot be used for practical purposes. I couldn't do that. As a result of intensive research on powdered fiber glue made of synthetic resin, the present inventors discovered that cationic resin powder has good redispersibility in water and also has excellent adhesion to fibers. . That is, the present invention relates to a cationic powder fiber paste made of water-dispersible cationic resin powder obtained by drying and powdering an aqueous emulsion of a cationic vinyl polymer. Furthermore, as a result of continuing research on a method for further improving the redispersibility of the cationic powdered fiber glue of the present invention in water, we found that (a) a water-soluble polymer compound and (b) a cationic vinyl polymer. It has been found that redispersibility in water is significantly improved when a cationic powder fiber glue made of water-dispersible cationic resin powder is obtained by drying and powdering an aqueous composition containing an aqueous emulsion. I found it. Since the fiber glue of the present invention is in powder form, there is no problem with the stability of conventional synthetic resin aqueous emulsion fiber glue. The powdered fiber glue of the present invention can be redispersed in water and return to a state similar to that of a synthetic resin aqueous emulsion by simply adding it to water at the time of use. It can be used for. As powdered fiber glue, powders of natural or synthetic water-soluble polymer substances such as starch and polyvinyl alcohol have conventionally been used. The powdered fiber glue of the present invention is completely different from conventional powdered fiber glues in that the powdered fiber glue of the present invention is water-insoluble. In other words, since conventional powdered fiber glue is water-soluble, it does not provide any water resistance.
Since the powdered fiber paste of the present invention is water-insoluble, it is possible to improve water resistance. The feature of the present invention is how to improve redispersibility in water and adhesion to fibers of water-insoluble powdered fiber glue, and by cationizing the powdered fiber glue, these can be improved. In order to solve this problem and to make the water-insoluble powdered fiber glue easier to use, we significantly improved its redispersibility rather than its solubility in water. Powdered fiber glue having such excellent characteristics has not been known until now. The cationic resin powder, which is the main ingredient of the cationic powder fiber paste of the present invention, is obtained by drying and powdering an aqueous emulsion of a cationic vinyl polymer. The aqueous emulsion of a cationic vinyl polymer is a cationic vinyl polymer obtained by emulsion polymerizing a vinyl monomer in an emulsion polymerization system designed to introduce a compound containing a cationic group. It is an aqueous emulsion of a polymer. Vinyl monomers used in the present invention include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl versatate (having 10 carbon atoms, α
Fatty acid vinyl esters such as vinyl esters of carboxylic acids branched at the - position (trade name manufactured by Schiel Chemical Co., Ltd.); acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate; methyl methacrylate, ethyl methacrylate One or more methacrylic esters such as butyl methacrylate are used. Particularly preferred is vinyl acetate. In addition, vinyl monomers and monomers copolymerized with the monomers (e.g. ethylene,
(styrene, etc.) can also be used in combination. As a method for introducing carboxyl groups into a polymer, a copolymerizable unsaturated carboxylic acid is used in combination with a vinyl monomer. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid.
More than one species is used. Preferably crotonic acid is used. When a carboxyl group is introduced into a polymer, the hydrophilicity of the carboxyl group improves the hydrophilicity of the polymer, which significantly improves the redispersibility of the final cationic powder fiber paste in water. can be improved. Aqueous emulsions of cationic vinyl polymers are obtained by emulsion polymerization of vinyl monomers in an emulsion polymerization system designed to introduce a compound having a cationic group. Methods for introducing a compound having a cationic group into the emulsion polymerization system include a method of using an emulsifier having a cationic group as an emulsifier, and a method of using a copolymerizable monomer having a cationic group in combination with a vinyl monomer. , a method of using a polymerization catalyst having a cationic group as a polymerization catalyst, etc., and one or more methods can be adopted. Examples of emulsifiers having a cationic group include cationic starch, cationic polyvinyl alcohol, protective colloids having a cationic group such as quaternary ammonium salt polymers, alkylamines, alkyltrimethylammonium salts, alkylaminoethanol, and alkylpyridium. Examples include cationic surfactants such as halides. Examples of copolymerizable monomers having a cationic group include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, vinylpyrrolidone,
Examples include N-methylvinylpyridium chloride. As a polymerization catalyst having a cationic group, 2,
Examples include azobis-based polymerization catalysts such as 2'-azobis (2-amidinopropane). Except for the means of introducing a compound having a cationic group into the emulsion polymerization system, ordinary emulsion polymerization means can be used or combined to emulsion polymerize the vinyl monomer described above, thereby producing an aqueous cationic vinyl polymer. An emulsion is obtained. The cationic powdered fiber paste can be obtained by drying and powdering the aqueous emulsion of the cationic vinyl polymer described above. When drying an aqueous emulsion of a cationic vinyl polymer, forced drying is necessary because the redispersibility of the powdered fiber paste in water is extremely poor if air drying is used, and spray drying, freeze drying, etc. It is preferable to dry and powder it by drying means. When drying an aqueous emulsion of a cationic vinyl polymer, if a water-soluble polymer compound is added to the aqueous emulsion of a cationic vinyl polymer and dried, the polymer particles in the emulsion will fuse together and re-dry. Since it prevents the formation of water-insoluble polymer blocks with no dispersibility, redispersibility can be improved. As the water-soluble polymer compound, any of natural, semi-synthetic, or synthetic water-soluble polymer compounds such as starch, cellulose derivatives, polyvinyl alcohol, and polyacrylic acid amide can be used. Also, during spray drying, an anti-caking agent is added at the same time as the emulsion to prevent the powdered resin from sticking to the wall or fusing with each other, and to improve redispersibility in water. It is also possible to adopt a method in which the liquid is ejected from a separate nozzle. Suitable anti-caking agents for this use range from about 0.01 to
such as aluminum silicate, calcium carbonate or silicic anhydride with an average particle size of 0.5 μm. The amount used is preferably 2 to 20% by weight based on the solid content of the emulsion. Additives conventionally used in general fiber glues and other additives can be added to the cationic powdered fiber glue of the present invention, if necessary. For example, additives such as ironing suitability improvers, fragrances, fluorescent dyes, pigments, alkali agents, plasticizers, bactericides, preservatives, and the like are added as appropriate.
Additives can also be added directly to the cationic powdered fiber glue, but if the additives are non-volatile,
It is preferable to add it to an aqueous emulsion of a cationic vinyl polymer before drying, dry it, and turn it into a powder because the addition can be done uniformly. Next, an example will be given and explained. Example 1 Cationic powdered fiber paste produced by the following method (a) Production of aqueous emulsion of cationic vinyl polymer Cationic polyvinyl alcohol (degree of cationization 2.5 mol% with quaternary ammonium cation groups) An aqueous solution of 10 parts by weight and 0.6 parts by weight of potassium persulfate dissolved in 165 parts by weight of water was placed in a four-necked flask, heated to approximately 70°C, and while stirring, 100 parts by weight of vinyl acetate was added dropwise over approximately 3 hours. After completion of the dropwise addition, the mixture was aged at about 80° C. for 1 hour to obtain an aqueous emulsion of a cationic vinyl polymer having a solid content concentration of about 40% by weight. (b) Production of cationic powdered fiber glue The aqueous emulsion of the cationic vinyl polymer obtained in (a) was dried and powdered using a high-speed rotating disc spray dryer to obtain a cationic powdered fiber glue. Example 2 Cationic powdered fiber paste produced by the following method A cationic starch aqueous solution was added to the aqueous emulsion of the cationic vinyl polymer obtained in (a) of Example 1 at a solid content of 9:1. The aqueous emulsion containing the cationic vinyl polymer thus mixed was dried and powdered using a high-speed rotating disc spray dryer to obtain a cationic powder fiber paste. Example 3 Cationic powdered fiber paste produced by the following method (a) Production of aqueous emulsion of cationic vinyl polymer 5 parts by weight of polyoxyethylene octyl phenol ether and 0.6 parts by weight of potassium persulfate were dissolved in water.
Pour the aqueous solution dissolved in 157 parts by weight into a four-necked flask, heat it to about 70°C, and while stirring, add 98 parts by weight of vinyl acetate and dimethylaminoethyl methacrylate (a copolymerizable monomer having a cationic group).
Polymerization was carried out by dropping 2 parts by weight over a period of about 3 hours, and after completion of the dropwise addition, the mixture was aged at about 80° C. for 1 hour to obtain an aqueous emulsion of a cationic vinyl polymer having a solid content concentration of about 40% by weight. (b) Production of cationic powder fiber glue A cationic vinyl polymer prepared by mixing an aqueous polyvinyl alcohol solution with the aqueous emulsion of the cationic vinyl polymer obtained in (a) at a solid content of 4:1. The aqueous emulsion contained therein was dried and powdered using a high-speed rotating disc spray dryer to obtain a cationic powdered fiber paste. Example 4 Cationic powdered fiber paste produced by the following method (a) Production of aqueous emulsion of cationic vinyl polymer Cationic polyvinyl alcohol (with a degree of cationization of 2.5 mol% with quaternary ammonium cation groups) ) 10 parts by weight and 2,2′-azobis(2-
An aqueous solution prepared by dissolving 0.6 parts by weight of (amidinopropane) in 165 parts by weight of water was placed in a four-necked flask, heated to approximately 70°C, and while stirring, 94 parts by weight of vinyl acetate and 6 parts by weight of crotonic acid were added to the flask for approximately 3 hours. Polymerization was carried out by dropping the mixture over a period of time, and after completion of the dropwise addition, it was aged at about 80° C. for 1 hour to obtain an aqueous emulsion of a cationic vinyl polymer having a solid content concentration of about 40% by weight. (b) Production of cationic powdered fiber glue The aqueous emulsion of the cationic vinyl polymer obtained in (a) was dried and powdered using a high-speed rotating disc spray dryer to obtain a cationic powdered fiber glue. Example 5 Cationic powdered fiber paste produced by the following method (a) Production of aqueous emulsion of cationic vinyl polymer Lauryltrimethylammonium chloride 2
An aqueous solution of 157 parts by weight of polyoxyethylene octyl phenol ether and 3 parts by weight of polyoxyethylene octyl phenol ether dissolved in 157 parts by weight of water was placed in a four-necked flask, heated to approximately 60°C, and while stirring, 80 parts by weight of vinyl acetate and butyl acrylate were dissolved. Polymerization is carried out by dropping 20 parts by weight and 0.2 parts by weight of a redox polymerization catalyst consisting of hydrogen peroxide and ascorbic acid over a period of about 4 hours.
After dropping, it is aged at about 70℃ for 1 hour to reach a solid concentration of approx.
A 40% by weight aqueous emulsion of a cationic vinyl polymer was obtained. (b) Production of cationic powder fiber glue Add cationic polyvinyl alcohol (quaternary ammonium cation group with cationization degree of 2.5) to the aqueous emulsion of the cationic vinyl polymer obtained in (a).
A cationic vinyl polymer-containing aqueous emulsion prepared by mixing an aqueous solution with a solid content of 4:1 (expressed as mol%) was dried and powdered using a high-speed rotating disc spray dryer to obtain a cationic powdered fiber paste. Ta. Example 6 Cationic powdered fiber paste produced by the following method (a) Production of aqueous emulsion of cationic polymer 6 parts by weight of cationic starch (degree of substitution 0.1) and 4 parts by weight of hydroxyethyl cellulose were mixed with water.
Pour the aqueous solution dissolved in 165 parts by weight into a four-necked flask, heat it to about 70°C, and mix it with 96 parts by weight of vinyl acetate, 4 parts by weight of crotonic acid, and 0.6 parts by weight of potassium persulfate for about 3 hours while stirring. Polymerization was carried out by dropping the mixture over a period of time, and after completion of the dropwise addition, it was aged at about 80° C. for 1 hour to obtain an aqueous emulsion of a cationic vinyl polymer having a solid content concentration of about 40% by weight. (b) Production of cationic powder fiber glue A cationic vinyl polymer prepared by mixing an aqueous polyvinyl alcohol solution with the aqueous emulsion of the cationic vinyl polymer obtained in (a) at a solid content of 9:1. The aqueous emulsion contained therein was dried and powdered using a high-speed rotating disc spray dryer to obtain a cationic powdered fiber paste. Comparative Example 1 Non-cationic powdered resin produced by the following method An aqueous solution of 10 parts by weight of polyvinyl alcohol and 0.6 parts by weight of potassium persulfate dissolved in 165 parts by weight of water was placed in a four-necked flask and heated to approximately 70°C. While heating and stirring, 100 parts by weight of vinyl acetate is added dropwise over about 3 hours to polymerize, and after the addition is finished, it is aged at about 80°C for 1 hour to form a vinyl polymer with a solid content concentration of about 40% by weight. An aqueous emulsion was obtained. The obtained aqueous vinyl polymer emulsion was directly dried and powdered using a high-speed rotating disc spray dryer to obtain a non-cationic powdered resin. Comparative Example 2 Non-cationic powdered resin produced by the following method (a) Production of vinyl acetate copolymer emulsion Polyvinyl alcohol (Gohsenol GL-05,
A four-necked flask containing 200 parts by weight of an aqueous solution containing 15 parts by weight of Nippon Gosei Kagaku Kogyo Co., Ltd.), 4.0 parts by weight of polyoxyethylene nonyl phenyl ether, and 1.0 parts by weight of ammonium persulfate was heated to 60 to 90°C. While stirring, a mixture of 175.5 parts by weight of vinyl acetate and 3.6 parts by weight of crotonic acid was added dropwise over about 3 hours, and after the addition was completed, the reaction was continued at the same temperature for 6 to 8 hours until the solid content concentration was about 50% by weight and the average particle size was reached. is about
A stable emulsion of 0.4 μm was obtained. (b) Production of non-cationic powdered resin The vinyl acetate copolymer emulsion obtained in (a) was dried and powdered using a high-speed rotating disc spray dryer to obtain a non-cationic powdered resin. Comparative Example 3 Non-cationic powdered resin produced by the following method: 100 parts by weight of potato starch was suspended in 147 parts by weight of water, and 1 part by weight of boric acid was added, and the solution was gelatinized at 130 to 140°C. It was later dried. 90 parts by weight of the obtained α-potato starch powder and 7 parts by weight of the vinyl acetate copolymer powder obtained in Comparative Example 2 were uniformly mixed to obtain a non-cationic powdered resin composition. Comparative Example 4 A non-cationic powdered resin was obtained in the same manner as in Example 4, except that the cationic polyvinyl alcohol used in Example 4 was replaced with the polyvinyl alcohol used in Comparative Example 2. Test Example 1 Using the cationic powdered fiber glue obtained in Examples 1 to 6 and the non-cationic powdered resin obtained in Comparative Example 1, glue was applied to #40 cotton broadcloth using the following method, and the paste was applied using the cantilever method. Therefore, the quality of the redispersibility was measured by the cloth hardness and the glue white residue test. The results were as shown in Table 1. (Gluing method) Use cationic powdered fiber glue and non-cationic powdered resin as samples, and add 0.4g of the sample to 300ml of tap water.
A sizing solution was prepared by uniformly dispersing the sizing solution and 14 g of cotton broadcloth #40, and the sizing solution and 14 g of cotton broadcloth #40 were set in a strong washing fastness tester and stirred for 5 minutes to perform sizing. After dehydrating the starched cotton broadcloth for 1 minute in a household washer/extractor, air dry it and press it with an iron.
It was stored in a constant temperature and humidity room at 20°C and 65%RH. (Glue White Residue Test) For a test cloth made by gluing black cotton broadcloth #40 in the same manner as described above and iron-pressing it, it was visually judged whether or not white glue residue remained on the test cloth. ○ None △ Somewhat × Quite a bit

[Table] As can be seen, the cationic powdered fiber glue has a greater hardness in fabric application, and the results of the glue white residue test show that it has excellent redispersibility. Test Example 2 Put 20ml of water into a household washing machine and use the cationic powdered fiber pastes obtained in Examples 1 to 6 and Comparative Examples 1 to 4.
15g each of the non-cationic powdered resin obtained in
10 types of sizing liquids were prepared by adding and stirring the mixture and uniformly dispersing it. 1 kg of cotton broadcloth was added to each sizing solution and stirred for 3 minutes to perform sizing treatment on the cotton broadcloth. The absorbance of the sizing solution before and after treatment was measured using 660 nm light, and the formula: Absorbance before treatment - Absorbance after treatment / Absorbance before treatment x
The degree of gluing was evaluated using a score of 100. The results are shown in Table 2.

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Claims (1)

[Scope of Claims] 1. A cationic powdered fiber paste comprising a water-dispersible cationic resin powder obtained by drying and powdering an aqueous emulsion of a cationic vinyl polymer. 2. The cationic powdery fiber paste according to claim 1, wherein the cationic vinyl polymer in the aqueous emulsion of the cationic vinyl polymer is a cationic vinyl polymer containing a carboxyl group. 3 Consists of water-dispersible cationic resin powder obtained by drying and powdering an aqueous composition containing (a) a water-soluble polymer compound and (b) an aqueous emulsion of a cationic vinyl polymer. Cationic powdered fiber glue.