JPH04153370A - Cheese sizing agent composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, composed of a water-dispersible cationic size and a water-soluble anionic size and/or a water-dispersible anionic size containing specific groups and capable of uniformly and rapidly sizing yarn in a state of a cheese, etc. CONSTITUTION:A water-dispersible cationic size is used together with a water- soluble anionic size (e.g. CMC) and/or a water-dispersible anionic size containing one or more groups selected from carboxyl, hydroxyl and amino groups to uniformly and rapidly size various yarns scoured, bleached and dyed before the sizing in a state of a cheese or beam. A copolymer of vinyl ester of a 1-4C lower fatty acid or an acrylic or methacrylic acid ester polymerized with an unsaturated carboxylic acid in an amount of 0.5-15wt.% based on the aforementioned vinyl ester or acrylic or methacrylic acid ester can be exemplified as the aforementioned water-dispersible size. The cationic size is obtained by carrying out emulsion polymerization of a vinyl monomer and the unsaturated carboxylic acid in the presence of cationic starch, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a cheese sizing agent composition used for sizing yarn into warp threads in a so-called cheese state or beam state. The present invention relates to a cheese sizing agent composition that can be used to size yarns with a spun yarn count of 30 or higher, particularly those with a lot of fluff, in a cheese state to impart sufficient conjugation properties and make them usable for weaving.

[Conventional technology]

Current sizing of yarn-dyed yarns into warp yarns involves scouring and bleaching the yarn in a cheese dyeing machine or beam dyeing machine, dyeing it, drying it, rewinding it, and warping it in a warping machine or partial warping machine. After that, -
Processes such as uniform sizing and warp sizing are performed using a regular gluing machine.

For example, in the case of spun yarn, the method of sizing is to prepare starch, polyvinyl alcohol, acrylic sizing agents, smoothing oils, etc. in appropriate proportions and form an aqueous solution with a concentration of about 5 to 12%. In this method, in order to gelatinize the starch component, cooking the starch must be done using a steam blowing stirring dissolving device or a high-pressure comb at a temperature of 90 to 120°C for about 15 minutes to 3 hours. The energy (steam) required is large. In addition, in the sizing process, the size liquid obtained as described above is usually kept at 80 to 95°C, and the squeezing rate is in the range of 100 to 200%. It is disadvantageous in terms of energy efficiency to maintain a relatively high reduction rate, and the amount of water that must be evaporated during the drying process is also large.
This is still disadvantageous in terms of energy efficiency.

Furthermore, the yarn is disadvantageous in terms of energy efficiency because it must be dried twice after scouring, bleaching, and dyeing, and then dipped in a size solution again for sizing and then dried.

Furthermore, in conventional processes, the dyeing factory, sizing factory, and weaving factory are often located in different locations because they are separate corporate entities, and there is a need to transport them for sizing, and there is a long wait until the sizing process begins. Time delays are likely to occur, reducing productivity.

Currently, cotton yarn, rayon yarn, or blended yarns of these yarns, especially 20-count single yarns, are used as pile yarns and weft yarns for towels, but since the fiber structure of these yarns is relatively linear, In this case, the sizing process is carried out in a cheese dyeing machine using at most 5%, usually 2-4% starch and polyvinyl alcohol based on the yarn weight, together with a smoothing agent. Threads are not warps.

On the other hand, Japanese Patent Publication No. 34-6944 and Japanese Unexamined Patent Application Publication No. 62-299 have proposed sizing the warp yarns by using a cheese sizing dyeing machine or a beam dyeing machine for dyed yarns.
There is a method of using adhesives such as methyl cellulose and polyvinyl methyl ether, which are water-soluble at low temperatures and become insoluble gels at 50 to 60°C, as disclosed in Publication No. 579, but these are difficult to unwrap and have not been put to practical use. Not yet.

Japanese Patent Publication No. 45-28034 and Japanese Patent Publication No. 61-2713
64, JP-A-58-180683, and JP-A-6433279 propose a method of cheese sizing using cationic starch or cross-linked starch, but the viscosity of a 3% starch solution is 100cp even above 90°C
Because it exceeds s (centipoise, same below),
If a highly concentrated solution that adsorbs 5 to 15% of the sizing agent per fiber weight is created, it will place too much load on the circulation pumps of cheese dyeing machines and beam dyeing machines, making it impractical.

JP-A-59-9275 discloses that the average molecular weight is 20.0.
There is also a proposal to use polyester with polyalkylene oxide of 0.00 or higher, but except for cases where there is little reed abrasion, such as the pile yarn of towels, where 1-4% adhesion of the sizing agent is sufficient, 5-15% of the sizing agent is applied to the yarn. Since there is no means to adsorb it, it cannot be put to practical use.

(Problems to be Solved by the Invention) The present invention provides a cheese sizing agent composition used when sizing yarn dyed in a cheese shape or beam shape into warp yarns using a cheese dyeing machine or a beam dyeing machine. An object of the present invention is to provide a cheese sizing agent composition used for cheese sizing of warp threads, which can be sufficiently used for yarns with a lot of fuzz and a fine count of English cotton count 30 or higher.

In order to achieve this objective, it is necessary to: 1) be able to adsorb a uniform amount of sizing agent in the inner, middle and outer layers in a solid content of 5 to 15% per fiber weight; and 2) ensure that the cheese sizing process takes 20 minutes or more The process is completed within one hour, and the entire amount of sizing agent is absorbed into the thread. ■ After the sized cheese winding thread is dried, it is warped,
Since it is woven, the unwinding tension of the yarn must be sufficiently small; ■ In order to be able to weave it, the adhesive force between single yarns must be increased, and a high degree of conjugation must be required to prevent fuzzing even when worn by reeds, etc. ■ Also, after weaving, the sizing agent must be able to be easily desized with an alkali.

Cotton, hemp, racon, acetate, wool, nylon, acrylic, polyester, and blended yarns of these are subject to cheese sizing. However, since most fibers are negatively charged in water, the water-dispersible cationic sizing agent rapidly aggregates due to the Coulombic force of anions and cations, and as a result, adsorption becomes slow as the number of anion adsorption seats decreases.

On the other hand, the adsorption behavior of the water-dispersible cationic sizing agent varies greatly depending on the history of the yarn.

The history of yarn can be broadly divided into three types. The first type is scouring-bleaching yarn, scouring-bleaching-fluorescent whitening yarn or scouring-bleaching-dyed yarn, which has a zeta potential in water of about -20 mV, has sufficient anion adsorption seat, and has water-dispersible cations. For example, if the zeta potential is +50 mV, 1
0 to 12% solid content can be adsorbed by raising the temperature to about 80°C. However, it takes about 2 hours for complete adsorption.

The second type is thread dyed in deep colors with reactive dyes, etc.
In order to improve the deterioration of fastness to wet rubbing caused by sweat, etc., the dye is treated with a cationic polymer, such as a dicyandiamide fixing agent, polyethyleneimine, diallylamine fixing agent, etc., to insolubilize the dye. Therefore,
The thread is cationic, and the water-dispersible cationic glue is 8
Even if the temperature is raised to 0°C to promote adsorption, only about 3% solid content will be adsorbed.

The third type is yarns that have been bleached insufficiently or unbleached yarns.

These may be because heavy metals such as calcium, magnesium, and iron that adhere to the carboxyl groups of cotton from the soil during growth create metal soaps and sequester ions, or because the cotton has not been washed, the surface is covered with oil and fat components. Although it is unclear whether this is due to the fact that water-dispersible cationic glue
Even if the bath temperature is raised to C, only about 3% solid content is adsorbed.

In order to size these three types of yarns into warp yarns, the minimum
%, maximum 15%, preferably 7-10% sizing agent. As a countermeasure, it can be proposed to pre-treat the yarn with an anionic compound, which has some effect. For example, by pre-washing with higher alcohol ether sulfate, the adsorption amount of both the second dark colored thread and the third unbleached thread can be increased to about 5% solids. However, it takes about 2 hours to reach complete exhaustion, and the amount of glue adhered is still not sufficient.

[Means to solve the problem]

The present inventors uniformly and quickly adsorb a sizing agent having a solid content of 5 to 15% to all of the first to third fibers, and increase the adhesive force between single yarns. As a result of various studies on a cheese sizing agent composition that significantly improves and perfects binding power, we found a water-dispersible cationic sizing agent and a water-soluble and/or sizing agent having at least one of a carboxyl group, a hydroxyl group, and an amino group. Or, by using it in combination with a water-dispersible anionic sizing agent, ■ 5 to 15% solids per fiber weight can be uniformly adsorbed to any of the inner, middle, and outer layers; The time required is less than an hour, which is industrially acceptable. ■ The unwinding tension of the sizing yarn from the cheese is sufficiently small, at 40 g or less, so that no yarn breakage occurs during warping. ■ Applying a load of 400g to the TM type stand resultant force tester,
Exhibiting excellent conjugation properties, with the number of times until fluffing occurs 2,000 times or more; ■ Water-dispersible cationic glue and water-soluble or water-dispersible anionic glue can be used in combination with 1 to 2 g of soda carbonate. /! It was discovered that it was possible to dissolve and desize with a liquid, and the present invention was completed.

That is, the present invention provides a water-dispersible cationic sizing agent (1) and a water-soluble anionic sizing agent and/or water-dispersible anionic glue containing at least one group selected from a carboxyl group, a hydroxyl group, and an amino group. The present invention provides a cheese sizing agent composition comprising:

In the present invention, by treating yarn with a water-dispersible cationic sizing agent and a water-soluble and/or water-dispersible anionic sizing agent, secondary aggregates of dispersions are formed due to ionic bonds between the two. However, it is possible to obtain warp yarns with extremely high binding properties by the cheese sizing method.

The water-dispersible cationic sizing agent that can be used in the present invention is a copolymer obtained by coexisting a hydrophilic cationic polymer as a protective colloid during emulsion copolymerization of a vinyl monomer and an unsaturated carboxylic acid. It is a sizing agent made of a polymer, and examples of the hydrophilic cationic polymer mentioned here include cationic starch, cationic cellulose, cationic vinyl polymer, and ring-closing polymer of cationic diallyl compound.

Vinyl monomers used in the production of water-dispersible cationic sizing agents include lower fatty acid vinyl esters such as vinyl acetate, vinyl butyrate, and vinyl propionate, preferably (vinyl acetate, ethyl acrylate, butyl methacrylate, etc.).
An example is meth)acrylic acid ester. Furthermore, the following (1) ~ which can be copolymerized with these lower fatty acid vinyl esters, acrylic esters, and methacrylic esters
Monomers shown in (4) (in this case, vinyl ester monomer: the following copolymerizable monomers -50: 50 to 100:
O (weight ratio)) is also used.

(1) Diesters of α, β ethylenically unsaturated dicarboxylic acids, such as dibutyl maleate, diethyl maleate, and corresponding fumarates, itaconates,
Citraconic acid (2) Styrene, ethylene (3) α, β ethylenically unsaturated dicarboxylic acid amides and their N-alkylol derivatives, such as acrylamide and N-methylolamide (4) Unlike the lower fatty acid vinyl esters used above The monomer that can be copolymerized with lower fatty acid vinyl esters is preferably ethylene.

In addition, unsaturated carboxylic acids used in the production of water-dispersible cationic sizing agents include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, sorbic acid, cinnamic acid, citraconic acid, p -Vinylbenzoic acid and the like. Mention may also be made of alkyl half esters, partial esters or partial amides of unsaturated polycarboxylic acids such as itaconic acid, maleic acid and fumaric acid. Examples of alkyl half esters of unsaturated polycarboxylic acids include lower alkyl half esters having 1 to 6 carbon atoms such as monomethyl itaconate, monobutyl itaconate, monomethyl fumarate, monobutyl fumarate, and monobutyl maleate. Preferred examples of these unsaturated carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, and maleic acid.

The water-dispersible cationic sizing agent is a copolymer obtained by emulsion polymerization of 0.5 to 15% by weight of unsaturated carboxylic acid to vinyl acetate monomer in the presence of a hydrophilic cationic polymer. preferable.

Water-soluble anionic sizing agents that can be used in the present invention include carboxymethyl cellulose and its alkali salts;
Examples include, but are not limited to, carboxymethyl starch, alginates, vinyl acetate made by solution polymerization, alkali crotonic acid salts, acrylic ester/ammonium acrylic salt copolymers, and the like.

The water-dispersible anionic sizing agent that can be used in the present invention is preferably one that is alkaline, dissolves in water, and has good desizing properties from threads. The water-dispersible anionic sizing agent is preferably one made of a copolymer of a vinyl monomer such as a vinyl ester, acrylic ester, or methacrylic ester of a lower fatty acid and an unsaturated carboxylic acid.

In the present invention, the vinyl monomer used for producing the water-dispersible anionic sizing agent includes lower fatty acid vinyl esters such as vinyl acetate, vinyl acetate, and vinyl propionate, preferably vinyl acetate. Further examples include acrylic esters and methacrylic esters such as ethyl acrylate and butyl methacrylate. Furthermore, monomers shown in (1) to (5) below that can be copolymerized with these lower fatty acid vinyl ester monomers (in this case, vinyl ester monomer: the following monomer that can be copolymerized -50:
50-100:O (weight ratio)) is also used.

(1) Diesters of α, β ethylenically unsaturated dicarboxylic acids, such as dibutyl maley 1, diethyl maleate, and the corresponding fumarates 1, itaconate, citraconic acid (2), styrene, ethylene (3) α, β ethylenically unsaturated dicarboxylic acid amides and their N-alkylol derivatives, such as acrylamide and N-methylolamide (4) Lower fatty acid vinyl esters different from the lower fatty acid vinyl esters used previously (5) Allyl alcohol or allyl Alcohol/ethylene oxide adducts These copolymerizable monomers include preferably ethylene.

Examples of the unsaturated carboxylic acids used for producing the water-dispersible anionic sizing agent in the present invention include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, sorbic acid, cinnamic acid, and citraconic acid. Mention may be made of acids such as p-vinylbenzoic acid. Further examples include alkyl half esters, partial esters, or partial amides of unsaturated polycarboxylic acids such as itaconic acid, maleic acid, and fumaric acid. Examples of alkyl half esters of unsaturated polycarboxylic acids include lower alkyl half esters having 1 to 6 carbon atoms such as monomethyl itaconate, monobutyl itaconate, monomethyl fumarate, monobutyl fumarate, and monobutyl maleate. Preferred examples of these unsaturated carboxylic acids include acrylic acid, methacrylic acid,
Examples include crotonic acid and maleic acid.

The water-dispersible anionic sizing agent can be prepared by emulsion polymerization or suspension polymerization of the above-mentioned vinyl monomer and unsaturated carboxylic acid using the following emulsifier. First, anionic surfactants can be used as emulsifiers. Examples of anionic surfactants include higher fatty alcohol sulfates represented by sodium and potassium salts of sulfate esters of alcohols 08 to 1B such as lauryl alcohol, sodium, potassium, and triethanolamine of fatty acids of CI1 to 8. ethanolamine salts such as triethanolamine oleate, triethanolamine stearate, funnel oil, sulfonic compounds such as sulfated lysylinate, sodium monooctylbenzene sulfonate, sodium t
- Sulfonated alkylaryl compounds such as octylphenol sulfonate are exemplified.

The water-dispersible anionic sizing agent is a copolymer obtained by polymerizing 0.5 to 15% by weight of an unsaturated carboxylic acid to a vinyl ester or (meth)acrylic acid ester of a lower fatty acid having 1 to 1 carbon atoms, or A water-soluble anionic vinyl polymer made of a neutralized product obtained by neutralizing part or all of such a copolymer with ammonia or an alkali metal is preferred.

The best polymerization initiator that can be used to obtain the copolymer of the present invention is 2,2'-azobis(2-amidinopropane), but other initiators include hydrogen peroxide, t-butyl hydroperoxide, and cumene hydroperoxide. Peroxide, t-butyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, peracetic acid, perbenzoic acid, etc. can be used.

These polymerization initiators are used in an amount of 0.01 to 5 with respect to the vinyl monomer.
．． It is preferable to use it in a range of 0% by weight.

The reaction temperature is 40-120'C1, preferably 50-90
°C, and the pH during polymerization is 3-9, preferably 4-8.
Do it with At this time, as a buffering agent, inorganic salts such as sodium carbonate, sodium bicarbonate, sodium orthophosphate, sodium diphosphate, monosodium phosphate, sodium chloride, and sodium sulfate are added in an amount of 0 to 2% by weight, preferably 0%. It is preferable to use .1 to 1% by weight.

In the composition of the present invention, the water-dispersible cationic sizing agent, the water-soluble anionic sizing agent, and/or the water-dispersible anionic sizing agent have a total solid content of 10% by weight or more based on water.
It is desirable that the content is less than % by weight. If the blending amount is less than 5% by weight of the total solid content, the performance will not increase. There is no particular limit to the upper limit, but the water-dispersible cationic sizing agent is 15% by weight or less, and the water-soluble and/or water-dispersible anionic sizing agent is 10% by weight or less, that is, the total solid content is 25% by weight or less.
It is preferably less than % by weight.

Each component of the water-dispersible cationic sizing agent, water-soluble and/or water-dispersible anionic sizing agent containing at least one of a carboxyl group, a hydroxyl group, or an amino group according to the present invention has a solid content relative to the weight of the fiber. 5% by weight as a total of
It is preferable to use the above. If the amount used is less than 5% by weight, the performance will not increase. There is no particular upper limit, but a total of 20% by weight or less is advantageous in terms of handling and unwinding properties.

Further, the cheese sizing agent composition of the present invention can be added at any time of pre-addition, simultaneous addition, or post-addition in the sizing process.

A nonionic surfactant can be added to the composition of the present invention as an emulsifier, if necessary. Examples of nonionic surfactants include 07-II+alkyl group and 9-30
or alkylphenoxypolyethoxyethanol having more than ethylene oxide units, such as heptylphenoxypolyethoxyethanol, octylphenoxypolyethoxyethanol, methyloctylphenoxypolyethoxyethanol, nonylphenoxypolyethoxyethanol, dodecylphenoxypolyethoxyethanol, etc., or Polyethoxyethanol derivatives of alkylphenols linked by methylene bonds, mercaptans such as nonyl, dodecyl, and tetradecyl, sulfur-containing emulsifiers made by condensing C8-18 alkylthiophenol with the required amount of ethylene oxide, lauric acid, myristic acid,
Ethylene oxide derivatives of long chain carboxylic acids such as balmitic acid, oleic acid, tall oil mixed acids, ethylene oxide derivatives of etherified or esterified polyhydroxy compounds with hydrophobic hydrocarbon chains. The nonionic surfactant has a B of 12 to 19, preferably 1.
5 to 18 are used.

Nonionic water-soluble polymers can be used in combination to obtain emulsions that are stable over long periods of time.

Examples of the nonionic water-soluble polymer include polyvinyl alcohol, modified starch, and cellulose derivatives.

The modified starch that can be used in the present invention is a water-soluble modified starch, and includes, for example, hydroxyethylated starch, hydroxypropylated starch, and the like. Further, as polyvinyl alcohol that can be used in the present invention, completely or incompletely saponified products of vinyl acetate homopolymers or copolymers of vinyl acetate and other monomers, or polyvinyl alcohol derivatives obtained by modifying these with, for example, aldehydes, etc. The viscosity of the 5% aqueous solution is 5-1 at 30°C.
An example is one showing 0,000 centipoise. The nonionic cellulose derivative that can be used in the present invention is water-soluble hydroxyalkylated cellulose or alkylcellulose, whose 5% aqueous solution viscosity is 5% at 30°C.
~io, ooo centipoise, and examples thereof include hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose (methylation degree 10%), and the like. The amount of these added is 0 to 10% by weight, preferably 1.0 to 4.0% by weight, based on the water-dispersible anionic sizing agent emulsion system.

In addition, in order to increase the bonding force by increasing the adhesion between single filaments, it is necessary to use polymers that have hydrophilic groups such as carboxyl groups, hydroxyl groups, and amino groups and do not have ionicity, such as polyethylene glycol, tetra It is also effective to use polyalkylene polyamines such as ethylene pentamine, ethylene oxide such as polyethylene imine, propylene oxide adducts, and the like.

Although these compounds do not have the effect of promoting the adsorption of water-dispersible cationic sizing agents, they are effective means for increasing binding power, and can be used in combination in the present invention.

[Examples] The present invention will be described below using Examples, but the present invention is not limited thereto.

In addition, "parts" in the examples are parts by weight unless otherwise specified.

Synthesis Example 1 Synthesis of water-dispersible cationic sizing agent Trimethyl expressed by the following formula was placed in a five-separable flask equipped with a nitrogen inlet tube, a stirrer, a monomer quantitative dropping device, a thermometer, and a reflux condenser. Aminohydroxypropylated starch (nitrogen content 0.6%, 1% aqueous solution viscosity 40 cps)
Add 30 parts of vinyl acetate, 550 parts of ion-exchanged water, dissolve at 80"C, cool to 60°C, and add 20 parts of vinyl acetate,
2.2゛-azobis(2-amidinopropane) hydrochloride 0
．． Add 5 parts of polymerization initiator and 20 parts of ion-exchanged water to 70°
The temperature was raised to C to start polymerization. 30 minutes after 20 minutes from the start of polymerization
A mixed solution of X parts of various unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, or half esters of unsaturated polycarboxylic acids as shown in Table 1 and 7 parts of vinyl acetate was added dropwise over 0 minutes.

After the addition was completed, the temperature was raised to 80°C to terminate the reaction.

Synthesis Example 1 (8) In an autoclave equipped with a stirrer, 3 parts of polyvinyl alcohol with a degree of polymerization of 500 and a degree of saponification of 88 mol% and cationic starch etherified with a quaternary amine (W conversion degree of approx. 0.1
, nitrogen content approximately 0.7%) and 178 parts of ion-exchanged water.
After adding 50% of the solution and dissolving it by raising the internal temperature to 80"C,
An aqueous solution of 0.5 parts of sodium carbonate dissolved in 5 parts of ion-exchanged water was added, the air in the autoclave was replaced with ethylene, and the internal temperature was cooled to about 60°C. Then vinyl acetate 10
0 parts and 6 parts of crotonic acid were added, and while stirring, ethylene was introduced under pressure to 30 kg/cm2 to perform polymerization (1.0 parts of potassium persulfate was used as a polymerization initiator, polymerization temperature was 70°C). .

The polymerization reaction was carried out for about 5 hours, and after the completion of the reaction, the excess ethylene was released by cooling to obtain a stable cationic copolymer emulsion with a copolymer solid content of 40% (Size agent No. 1). 8)). Ethylene content in the copolymer: 15%, crotonic acid content: 5%, vinyl acetate content: 80%
%Met.

Synthesis Example 2 Synthesis of water-dispersible anionic sizing agent 5 equipped with a reflux condenser, thermometer, nitrogen inlet pipe, and monomer dripping device
10 parts of polyvinyl alcohol (partially saponified product, degree of saponification 88%, degree of polymerization 500), carboxymethyl cellulose (Sunrose A-011 (,
Add 10 parts of Dezumi Kokusaku Pulp), 24 parts of lauryl sulfate soda salt (Emar 2F, Kao ■), and 500 parts of ion-exchanged water, dissolve at 80°C, and cool to 60°C. , 0.3 parts of sodium carbonate, 20 parts of vinyl acetate, 2,2°-azobis(2-amidinopropane)
Add 0.5 parts of hydrochloride and 55 parts of ion-exchanged water, and heat to 70°C.
The temperature was raised to start polymerization.

Over a period of 20 minutes to 300 minutes from the start of polymerization, a solution containing 7 parts of vinyl acetate and various unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, half esters or amides of unsaturated polycarboxylic acids, and 7 parts of vinyl acetate was added as shown in Table 2. dripped. After the dropwise addition was completed, the temperature was raised to 80"C to terminate the reaction.

Table Example 1 Water-dispersible cationic sizing agent No. prepared in Synthesis Example 1,
1, (1) to (9) and (1) to (9) of the water-soluble anionic glue N092 prepared in Synthesis Example 2, or a commercially available water-soluble anionic polymer or water-soluble anionic vinyl polymer as the third Using the amounts shown in the table, pre-addition, simultaneous addition, or post-addition, cheese sizing is performed, and the adsorption time of the sizing agent, the adsorption amount of the inner layer, middle layer, and outer layer of cheese, and the conjugation ability of the sizing threads are evaluated. Adhesiveness was examined by the following method. The results are shown in Table 3.

Cheese sizing method> After scouring and bleaching 1 kg of cheese yarn made of No. 30 single yarn made of cotton card spun (Tsuzuki Spinning ■, TS grade), it was dyed with reactive dye Prodion Blue C-G 3% Tee, and then dyed with polyamine-based fibril. agent, Suprafix DFC (Japan Tohoku■)
The threads treated with 3% O, W, and F were used. A water-dispersible cationic sizing agent and a water-soluble or water-dispersible anionic sizing agent with a total solid content of 7 to 15% based on the weight of the fibers were added in different order at 40°C using a cheese dyeing machine (Japan). The dyeing machine was used at a bath ratio of 1:10 for alternating in-out and out-in for 3 minutes. The temperature was raised to 80°C at a rate of 2°C/min, and the process was continued until the adhesive liquid was exhausted and became transparent. After that, approximately 1% of the smoothing agent was adsorbed. After that, the liquid was removed under vacuum and heated to 110°C for 9 hours.
Dry for 0 minutes.

<Measurement of adsorption time> The time required for the sizing agent to be absorbed into the yarn using the above method was determined from the measurement of the solid content in the residual liquid.

<Measurement of adsorption amount> After sizing, the threads constituting the cheese were wound back and separated into three layers: inner layer, middle layer, and outer layer. 20 g of thread was taken from each part and extracted with ethyl acetate at boiling point for 3 hours. The amount of adsorption was determined.

<Coupling force> Take 20 pieces of yarn divided into three parts in the same way as above using the TM type platform combined force tester Daiei Kagaku■), apply a load of 400g,
The number of wears required until fuzzing clearly occurred was measured. The greater the number of times, the less fuzz there is and the easier weaving becomes, which means that the passing A reversal rate improves.

<Desizing property> Wind the cheese-sized thread into a string (approx. 10g)
. Add that to 1g of soda ash! , anionic scouring agent Scorerol 5-5201 (manufactured by Kao ■) Thoroughly wash in a 2glIt solution at 40 to 50"C, rinse, and dry. Extract for 3 hours with a reflux type extractor using ethyl acetate as a solvent. Then, the vinyl polymer remaining in the yarn was quantified.

Example 2 Kayacion S cotton combed #50 single yarn cheese
It was dyed with 1% carlet E-2G (manufactured by Nippon Kayaku), and then the water-dispersible cationic glue No. 1 (3) obtained in Synthesis Example 1 was added to 10% of the solid content per fiber.
% and circulated in a cheese dyeing machine at 40°C for 10 minutes, and further, 3% of the solid content (4) of the water-soluble anionic glue 2 obtained in Synthesis Example 2 was added. Divide into equal parts, 80°
It was added in 3 parts during the process of raising the temperature at 3°C/min until it reached C.
I exhausted it. After 40 minutes until exhaustion, 1% of anionic smoothing agent was added and this was also exhausted.

Thereafter, the liquid was removed, dried at 110°C for 90 minutes, and warped into a beam using a partial warping machine.

On a rapier loom, the warp density is 144 threads/inch and the weft thread density is 7.
The fabric was woven at a rate of 2 wood/inch, 240 times/min, and could be woven for 200 m without stagnation.

〔Effect of the invention〕

As is clear from Examples 1 and 2, uniform adsorption of the water-dispersible cationic sizing agent to cheese and improvement of the adsorption speed can be achieved by using the water-soluble anionic sizing agent or the water-dispersible anionic sizing agent of the present invention in combination. This can be easily achieved by adsorbing 5 to 15% of the solid content of the sizing agent per fiber type M1.

In addition, they can increase the binding power by increasing the adhesive strength between cotton single yarns, so the cheese sizing method can increase the binding power even for cotton yarns with a lot of fuzz, such as English count 30 or higher. I know that I can give.

That is, according to the cheese sizing agent composition of the present invention, the sizing agent can be applied evenly and quickly to unbleached yarn, bleached yarn, fluorescent white yarn, or dyed yarn that has been processed in the cheese or beam state even when it is still wet. By adsorbing it and drying it, it is possible to produce warp yarns that can be warped smoothly in the subsequent warping process and exhibit sufficient binding properties in the weaving process.

Claims (1)

[Scope of Claims] 1. A water-dispersible cationic sizing agent, and a water-soluble anionic sizing agent and/or water-dispersible anion containing at least one group selected from a carboxyl group, a hydroxyl group, and an amino group. A cheese sizing agent composition comprising a glue. 2. The cheese sizing agent composition according to claim 1, wherein the water-soluble anionic sizing agent is one or more selected from the group consisting of carboxymethyl cellulose, carboxymethyl starch, and alginate. 3 The water-dispersible anionic sizing agent is made from a copolymer obtained by polymerizing 0.5 to 15% by weight of an unsaturated carboxylic acid to a vinyl ester or (meth)acrylic acid ester of a lower fatty acid having 1 to 4 carbon atoms. The cheese sizing agent composition according to claim 1. 4. A water-dispersible anionic sizing agent is a copolymer obtained by solution polymerizing 0.5 to 15% by weight of an unsaturated carboxylic acid to a vinyl ester or (meth)acrylic acid ester of a lower fatty acid having 1 to 4 carbon atoms. The cheese sizing agent composition according to claim 1, which is a water-soluble anionic vinyl polymer paste comprising a neutralized product obtained by neutralizing part or all of with ammonia or an alkali metal. 5. The water-dispersible cationic sizing agent contains vinyl monomers using a hydrophilic cationic polymer selected from the group consisting of cationic starch, cationic cellulose, cationic vinyl polymer, and ring-closing polymer of cationic diallyl compound as a protective colloid. 2. The cheese sizing agent composition according to claim 1, comprising a copolymer obtained by emulsion polymerization of a polymer and an unsaturated carboxylic acid. 6 The water-dispersible cationic sizing agent is
The cheese sizing agent composition according to claim 5, comprising a polymer obtained by emulsion polymerization of 0.5 to 15% by weight of an unsaturated carboxylic acid. 7 A claim comprising a water-dispersible cationic sizing agent, a water-soluble anionic sizing agent, and/or a water-dispersible anionic sizing agent in a total solid content of 5% to 20% by weight based on the weight of the yarn. Cheese sizing agent composition according to item 1.