JPS6044429B2 - Sizing agent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention particularly relates to a fiber sizing composition used in the production of sized yarn.

More specifically, the present invention relates to a sizing agent composition suitable as a sizing agent for warp yarns that can be sized to fiber yarns such as filament yarns, twisted yarns, or spun yarns during weaving to exhibit excellent weaving properties.

Conventionally, many water-soluble polymers such as polyvinyl alcohol, starch, cellulose ether, acrylic acid polymers, styrene, maleic acid polymers, etc. have been mainly used as warp sizing agents. Although these water-soluble polymers are satisfactory for low-speed weaving of natural fibers such as cotton and rayon, they can be used for synthetic fibers such as polyester, polyamide, polypropylene, polyacrylic, and mixtures of such synthetic fibers and natural fibers. They each have some deficiencies, especially in high-speed weaving. In other words, polyvinyl alcohol has defects such as poor weavability due to rough hardening of the yarn and poor removability from sizing yarn, and starch has low sizing effect and is difficult to recover from desizing wastewater. Moreover, it has disadvantages such as high biochemical oxygen demand. Similarly to starch, cellulose ether has a low sizing effect and is difficult to recover. Acrylic acid polymers have good adhesive properties, but lack strength and have a low gluing effect, while styrene-maleic acid polymers have drawbacks such as a lack of adhesive strength. Therefore, for hydrophobic synthetic fibers, starch and polyvinyl alcohol are used in combination with water-soluble acrylic acid polymers, etc., but the adhesive distribution of the sizing agent is still not in a sufficiently satisfactory state. This results in the adhesion of an unnecessarily large amount of sizing agent, resulting in poor handling of the sized yarn after it dries, a decrease in abrasion resistance due to rough hardening of the sized yarn, falling off of the sizing agent during the weaving process, gum up, etc. This has the disadvantage of reducing weaving efficiency. The inventors of the present invention have conducted intensive research to develop a sizing agent that solves the above-mentioned drawbacks and provides a sized yarn with a large binding force and excellent weavability, and as a result, they have arrived at the sizing agent composition of the present invention.

That is, in the present invention, 50 to 99.0 parts of the carboxyl group-containing ethylenically unsaturated monomer is added to 10 parts by weight of the water-soluble linear polymer sizing agent. This is a sizing agent composition containing an alkali salt of a water-dispersible crosslinked copolymer copolymerized with heel weight % in a ratio of 0.05 to 1 part weight. The sizing agent composition of the present invention can exhibit particularly excellent effects as a warp sizing agent.

That is, when using the sizing agent composition of the present invention, the adhesion state of the sizing agent to the fibers is improved, so it is possible to greatly reduce the amount of sizing agent used for the warp yarns, and the flexibility of the sizing yarns is increased. Not only does this improve the handling of the yarn, but even if the amount of sizing agent used is reduced, it still provides excellent envelopment and abrasion resistance, and the occurrence of fuzz and yarn breakage is reduced, greatly improving weaving efficiency. It has the characteristics of being able to Therefore, it is particularly useful as a sizing agent for warp yarns made of spun yarn, and exhibits excellent yarn sabability and weavability in high-speed weaving, and can provide woven fabrics with good texture. Another major feature is that desizing properties are improved in the scouring and desizing step after weaving, and uniform dyeing properties can be easily obtained. In addition, since the amount of sizing agent used can be reduced, the BOD of desizing wastewater is
、． COD etc. can also be reduced accordingly. The water-soluble linear polymer sizing agents used in the present invention include vinyl alcohol polymers such as polyvinyl alcohol, partially saponified polyvinyl acetate, and partially saponified polyvinyl propionate, starch, acetylated starch, and carboxylmethylile starch. Examples include hydroxyl group-containing polymers such as starches and cellulose ethers, as well as acrylic polymers and water-soluble polyurethane polymers.

Particularly preferred is a polymer sizing agent mainly composed of polyvinyl alcohol and/or starch. Further, as the water-dispersible crosslinked copolymer used in the present invention, a carboxyl group-containing ethylenically unsaturated monomer of 50 to 99. Heel weight %, ethylenically unsaturated monomer not containing carboxyl group 0 to 49. Particularly preferred are copolymers comprising % heel weight and 0.1 to 5% by weight of polyfunctional ethylenically unsaturated monomers.

The carboxyl group-containing ethylenically unsaturated monomer in the copolymer includes ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and ethylenically unsaturated dicarboxylic acids such as maleic acid and fumaric acid. or its half ester, butentrylcarboxylic acid, etc., which may be used alone or in combination of two or more. Further, as the polyfunctional ethylenically unsaturated monomer, a monomer having two or more copolymerizable ethylenically unsaturated groups in the molecule is preferable, and examples of such a monomer include ethylene glycol diacrylate. , ethylene glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, trimethylolpropane di, triacrylate or di, tri-methacrylate, pentaerythritol di, tri, tetra-acrylate or di, tri, tetra-methacrylate, ethylenically unsaturated acid polyesters such as polyhydric alcohols and sugars, such as diacrylates or dimethacrylates of polymethylene glycols, diacrylates or dimethacrylates of polyalkylene ether glycols, polyacrylates or polymethacrylates of erythritol, mannitol, sorbitol; Polyvinyl alcohols and sugars such as ethylene glycol divinyl ether, butanediol divinyl ether, di- or tri-vinyl ether of trimethylolpropane, di-, tri- or tetravinyl ether of pentaerythritol, polyvinyl ethers such as sorbitol, erythritol, mannitol, etc. Ethers, diallyl fumarate, diallyl maleate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, dimethallyl phthalate, dimethallyl isophthalate,
Diallyl monohydrogen phosphate, triallyl phosphate, diallyl monomethyl phosphate, diallyl monoethyl phosphate, diallyl monophenyl phosphate, diallyl monobenzyl phosphate, diallyl monohydrogen phosphite, triallyl phosphite, diallyl monomethyl phosphite , polyallyl or polymethallyl esters of organic or inorganic acids such as diallyl monophenyl phosphite, diallyl monobenzyl phosphite, di- or triallyl ether of trimethylolpropane, di-, tri- or tetra-allyl ether of pentaerythritol. , erythritol polyallyl ether, erythritol polymethallyl ether, arabinose polyallyl ether, arabitol polyallyl ether, xyrose polyallyl ether, glycose polyallyl ether, mannose polyallyl ether, mannitol polyallyl ether, sorbitol polyallyl Polyalcohols such as ether, inositol polyallyl ether, sucrose polyallyl ether, polyallyl or polymethallyl ethers such as sugars, methylene bis acrylamide, methylene bis methacrylamide, ethylene bis acrylamide, ethylene bis methacrylamide, dihydroxymethylene Examples include polyunsaturated acid amides such as bisacrylamide, tris(acryloyl)hexahydro S-triazine, and divinyl ketone. However, particularly preferred are polyvinyl ethers and polyallyl ethers such as polyhydric alcohols and sugars. Furthermore, ethylenically unsaturated monomers without carboxyl groups (hereinafter referred to as additional unsaturated monomers) copolymerized with the above carboxyl group-containing ethylenically unsaturated monomers and polyfunctional ethylenically unsaturated monomers. ) as methyl acrylate, ethyl acrylate,
Acrylic esters such as butyl acrylate, ethylhexyl acrylate, stearyl acrylate,
Methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylhexyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethyl acrylate, t-
Methacrylic acid esters such as butylaminoethyl methacrylate, cyclohexyl methacrylate, and glycidyl methacrylate; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; vinyl ethers such as methyl vinyl ether and isobutyl vinyl ether; acrylamide; , methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-methylolacrylamide, N
-Unsaturated acid amides such as alkoxymethyl acrylamide, N-hydroxyethylacrylamide, itaconic acid amide, diacetone acrylamide, as well as acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, styrene, vinylpyrrolidone, ethylene, propylene, Examples include isobutylene, butadiene, dimethyl maleate, allyl glycidyl ether, diglycidyl maleate, and the like. The copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer, polyfunctional ethylenically unsaturated monomer, and additionally unsaturated monomer is usually 50 to 99.9:0.1 by weight. -5:0-49.9, preferably 60-99.9:0.1-5:0-39.9. Usually, the copolymer is a precipitate formed by polymerizing a carboxyl group-containing ethylenically unsaturated monomer in free acid form or salt form, preferably in one or more organic solvents or in an organic solvent/water mixture system. After separating and drying, it is manufactured by forming a powder frame if desired. Another example of the water-dispersible crosslinked copolymer used in the present invention is a carboxyl group-containing ethylenically unsaturated monomer of 50 to 99. During or after polymerization, a linear copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a reactivity with the amount of carbon dioxide, or a polymer consisting of an ethylenically unsaturated monomer containing a carboxyl group, the crosslinking density of which is It may also be a copolymer modified into a crosslinked type so as to have the same proportion as the polymer. The copolymer is an alkali salt type and swells significantly in water, appears to be dissolved in water, and exhibits high viscosity. The sizing agent composition in the present invention may be a composition in which a water-soluble linear high-k molecular sizing agent and a water-dispersible crosslinked copolymer alkali salt are blended in powder form; It may be a composition in which the sizing agent and the water-dispersible crosslinked copolymer are blended in powder form and dissolved or dispersed in water in the presence of an alkali to form an aqueous liquid.

Alternatively, it may be a composition in which aqueous solutions of a water-soluble linear polymer sizing agent and a water-dispersible crosslinked copolymer alkali salt are separately prepared and blended. In short, the sizing liquid may finally contain a sizing agent and a crosslinked copolymer in a specific ratio. By converting the crosslinked copolymer used in the present invention into an alkali salt, a highly viscous solution that appears to be dissolved in water can be obtained, but depending on the case, it is not always necessary to convert all of the carboxylic acid groups into an alkali salt. An inorganic or organic alkaline substance is used to convert the crosslinked copolymer into an alkali salt. Inorganic alkaline substances include, for example, ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, disodium phosphate, sodium phosphate, sodium perborate, sodium silicate, sodium acetate, sodium bicarbonate, potassium bicarbonate. etc. are exemplified. Examples of organic alkaline substances include monoethanolamine, diethanolamine, triethanolamine, propanolamine, butanolamine, monomethylethanolamine, monoethylethanolamine, diethylethanolamine, alkylolamine of glycerin,
Examples include substituted or unsubstituted alkanolamines such as 3-aminocyclohexyl alcohol and P-aminobenzyl alcohol. The blending ratio of the sizing agent and the crosslinked copolymer is 0.05 to 1 part by weight, preferably 0.2 to 5 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the sizing agent. It is 0.3 to 2 parts by weight. 0.05
If it is less than 1 part by weight, it is difficult to achieve the objectives such as reducing the amount of sizing agent and improving envelopment, and if it is more than 1 part by weight, the hygroscopicity of the sized yarn increases especially in high humidity, causing trouble during weaving. This is not desirable.

Generally, the composition of the present invention has a total content of the sizing agent and the crosslinked copolymer, which varies depending on the purpose of sizing, but is usually from 0.5 to 0.5.
It is used as an aqueous sizing solution of 15% by weight, preferably 2 to 10% by weight.

When the sizing liquid is used at a high temperature, for example, 80 to 100°C, it is preferable to incorporate a viscosity stabilizer, and examples of such stabilizers include rhodan ammonium, rhodan soda, rhodan potassium. mineral salts such as rhodan lithium, alkali metal halides such as lithium chloride, potassium iodide, and potassium bromide, and phosphates such as sodium phosphite and sodium hypophosphite. The compound, mercaptobenzimidazole thiodip! Examples include organic compounds such as kuchobionate, but koutan salts are particularly preferred. The blending amount is 5% based on the alkali salt of the crosslinked copolymer.
or less, and particularly preferably from 5 to 2% by weight. Natural or synthetic waxes, organopolysiloxanes, etc. can be added to the sizing solution containing the composition of the present invention, if desired. The present invention will be explained below with reference to Examples.

Note that parts and percentages in the examples are parts by weight and percentages by weight unless otherwise specified. Example 1 10 parts of a water-dispersible crosslinked copolymer consisting of 8 parts of acrylic acid, 2 parts of ethyl methacrylate, 1 part of acrylamide and 1 part of erythritol triacrylate, 11 parts of 25% caustic soda, 2.7 parts of mineral turbene, The mixture was poured into an emulsion consisting of 2J parts of liquid paraffin, 5 parts of Sorgen TW8O (Daiichi Kogyo Seiyaku Co., Ltd., nonionic activator) and 29 parts of water, and sufficiently stirred with a homomixer to form a uniform paste.

A sizing solution having the composition shown in Table 1 was prepared using the paste and a water-soluble linear polymer sizing agent, and sizing was carried out under the following conditions. The properties of the obtained sized yarn and the weavability when weaving using the sized yarn were tested, and the results shown in Table 1 were obtained. Sizing conditions Warp Thread: Polyester/cotton (65/35)
4-hat hand Sizing temperature: 90℃ Sizing speed: 40 yards/min Sizing machine: Cylinder type weavability test conditions Number of revolutions: 202 r'Pm Winding speed: 54.6 n1/min Density: Warp 13 pots/inch , 7 wefts/inch Total number of warps: 544 As a result, good results were obtained even if the amount of water-soluble polymer sizing agent was reduced by about 30% to 2 degrees by using a small amount of water-dispersible cross-linked copolymer. was gotten.

That is, a woven fabric with good weavability and texture with few thread breakages was obtained, as expected from the particularly high strength and elongation of the abrasion system. In addition, the woven fabric woven using the sizing agent of the present invention is easy to desize and has excellent level dyeing properties, and also has a COD of desizing wastewater. ．． It also has the advantage of reducing BOD. Example 2 No. in Example 1. Warp sizing and weaving were carried out in the same manner as in Example 1, except that 0.004% of rhodan ammonium was added as a viscosity stabilizer to the same sizing solution as in Example 3.

As a result, the viscosity stability of the sizing liquid is improved even during long-term sizing, and the amount of sizing remains constant throughout. A sized yarn with good weavability was obtained.

Table 3 shows the results of a model test on the effect of the viscosity stabilizer using a 2% aqueous solution of only the paste prepared in Example 1. *Heat in a glycerin bath at 10σC, and after a certain period of time, take a portion, cool it, and measure using a B8l (type viscometer (manufactured by Tokyo Keiki) with rotor #7 and 50 rpm.

Claims (1)

[Scope of Claims] 1. 50 to 99 parts by weight of the carboxyl group-containing ethylenically unsaturated monomer per 100 parts by weight of the water-soluble linear polymer sizing agent.
A sizing agent composition containing 0.05 parts by weight of an alkali salt of a water-dispersible crosslinked copolymer copolymerized with 9% by weight. 2. The sizing composition according to claim 1, which contains at least 50% by weight of at least one viscosity stabilizer based on the alkali salt of the water-dispersible crosslinked copolymer. 3. The sizing composition according to claim 1, wherein the water-soluble linear polymer sizing agent is mainly composed of polyvinyl alcohol and/or starch. 4 The alkali salt of the water-dispersible crosslinked copolymer contains 50 to 99.9% by weight of ethylenically unsaturated monomers containing carboxyl groups.
, ethylenically unsaturated monomer having no carboxyl group 0
The sizing composition according to claim 1, which is an alkali salt of a copolymer consisting of ~49.9% by weight and 0.1-5% by weight of a polyfunctional ethylenically unsaturated monomer. 5. The sizing composition according to claim 2, wherein the viscosity stabilizer is at least one selected from Rodan salts.