JPH11256479A - Sizing of fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable the sizing of a cloth to give excellent smoothness and abrasion resistance while suppressing the generation of fluffs by using a sizing agent composition produced by compounding a carboxyl-containing polyvinyl alcohol with a specific phosphoric acid ester compound. SOLUTION: A sizing agent composition is produced by compounding 100 pts.wt. of a polyvinyl alcohol resin containing 0.1-10 mol.% of carboxyl group and having an average polymerization degree of 100-10,000 with 0.1-20 pts.wt. of a phosphoric acid ester compound of formula [R is H, an alkyl or an alkylallyl; (n) is an integer; R' is H or R(CH2 CH2 O)n ] or its salt. An aqueous sizing liquid containing 2-20 wt.% of the sizing agent composition is applied to a yarn in an amount of 5-20 wt.%, preferably 5-10 wt.% and the fiber is oiled and dried to complete the sizing treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for sizing fibers, and more particularly, to a method for sizing fibers which has a small number of fluffs, is excellent in smoothness, abrasion resistance and excellent in weaving.

[0002]

2. Description of the Related Art Conventionally, warp yarn is glued by dipping a fiber bundle in a glue tank, gluing the fiber bundle, dividing the fiber bundle into upper and lower sheets by a divide rod (cylindrical pipe), and then drying it by a drying cylinder.
The dried sheet-like glued yarn is divided by a divide lot and wound around a loom beam. Usually, polyvinyl alcohol is used as a fiber sizing agent in such a method, but if used alone, problems such as fluffing and frequent yarn breakage are likely to occur when the divide resistance is too strong. At the present time, the use of such a combination causes a decrease in the strength of the adhesive film. As a solution to this problem, it has been studied to use polyvinyl alcohol and various surfactants in combination as a fiber sizing agent.

[0003]

However, even when polyvinyl alcohol and various surfactants are used in combination, the performance such as the number of fluffs, smoothness, friction resistance and weaving properties is still insufficient, and these performances are not sufficient. There is a need for a fiber sizing method that is practically satisfactory.

[0004]

The present inventors have conducted intensive studies in view of the above circumstances, and as a result, have found that a carboxyl group-containing polyvinyl alcohol resin (A) and a phosphoric acid represented by the following general formula (1): After the sizing composition containing the ester compound or its salt (B) is glued to fibers, treated with an oil agent and dried, the number of fluff is small, the smoothness and friction resistance are excellent, and the weaving property is improved. It has been found that a glued yarn excellent in the above can be obtained, and the present invention has been completed.

Embedded image (Where R is hydrogen, an alkyl group, or an alkylallyl group, n is an integer, R 'is hydrogen or R (CH ₂ CH ₂
O) represents an _n group. )

[0005]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail below.
The carboxyl group-containing polyvinyl alcohol resin (A) used in the present invention is not particularly limited, and may be used without any particular limitation as long as it contains a carboxyl group. For example, a vinyl ester compound and a carboxyl group-containing unsaturated monomer may be used. And a method of saponifying the obtained copolymer, a method of reacting a polyhydric carboxylic acid with a polyvinyl alcohol-based resin to partially esterify the copolymer, and the like.
Is practical from the viewpoint of resin production and performance.

Hereinafter, the following method will be described in detail. Examples of the carboxyl group-containing unsaturated monomer include unsaturated monocarboxylic acids such as crotonic acid, acrylic acid and methacrylic acid or salts thereof, maleic acid, fumaric acid, unsaturated dicarboxylic acids such as itaconic acid and salts thereof, and maleic acid. Monoalkyl esters, monoalkyl fumarate, monoalkyl esters of unsaturated dicarboxylic acids such as monoalkyl esters of itaconic acid or salts thereof, maleic anhydride,
And unsaturated carboxylic anhydrides such as itaconic anhydride. In the above method, any unsaturated monomer containing a functional group that can be easily converted to a carboxyl group during the saponification of the copolymer as the unsaturated monomer is not necessarily an unsaturated monomer containing a carboxyl group. It is not limited to a monomer,
Examples of such unsaturated monomers include unsaturated dicarboxylic acid dialkyl esters such as acrylamide, methacrylamide, maleic acid dialkyl ester, fumaric acid dialkyl ester, and itaconic acid dialkyl ester, and salts thereof.

[0007] The vinyl ester compounds include:
Vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatate, vinyl palmitate, vinyl stearate, etc. can be used alone or in combination, but vinyl acetate is particularly practical. High in nature.

In the present invention, in addition to the above-mentioned monomer having a carboxyl group and a vinyl ester compound during the polymerization, a monomer copolymerizable with the compound may be used.
The polymerization may be carried out in the presence of not more than mol%. There is no particular limitation on the copolymerization, and any known polymerization method may be used, but solution polymerization is usually performed using an alcohol such as methanol or ethanol as a solvent. In such a method, as a method for charging the monomers, first, the total amount of the vinyl ester-based compound and a part of the carboxyl group-containing unsaturated monomer are charged to start polymerization, and the remaining unsaturated monomers are polymerized for a polymerization period. Arbitrary means such as a method of adding the mixture continuously or in a divided manner, a method of batch charging, and the like may be used. The copolymerization reaction is carried out using a known radical polymerization catalyst such as azobisisobutyronitrile, acetyl peroxide, benzoyl peroxide, and lauroyl peroxide. The reaction temperature is selected from the range of 50 ° C. to the boiling point.

The copolymer obtained as described above is then saponified to obtain a carboxyl group-containing polyvinyl alcohol resin. The saponification is performed by dissolving the copolymer in an alcohol solvent and in the presence of an alkali catalyst or an acid. Examples of the alcohol include methanol, ethanol, and butanol. The concentration of the copolymer in the alcohol is selected from the range of 20 to 70% by weight. Examples of the saponification catalyst include hydroxides and alcoholates of alkali metals such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate and potassium methylate. It is necessary to use the catalyst in an amount of 1 to 100 millimoles equivalent to the vinyl ester compound.

The temperature during the saponification reaction is not particularly limited,
Usually, it is preferable to select from the range of 10 to 70 ° C, more preferably 30 to 50 ° C. The reaction is usually carried out for 2 to 5 hours, and the preferred degree of saponification is 10 to 100 mol%, particularly preferably 50 to 100 mol%, particularly preferably 70 to 100 mol%.
It is selected from the range of 100 mol%. The content of the carboxyl group in the carboxyl group-containing polyvinyl alcohol-based resin is preferably from 0.1 to 10 mol%, more preferably from 0.5 to 5 mol%.
If the amount is less than mol%, the divide resistance is increased, and thread breakage during sizing occurs frequently. On the other hand, if it exceeds 10 mol%, the yarn separating property during weaving deteriorates, which is not preferable.

The average degree of polymerization of the carboxyl group-containing polyvinyl alcohol resin (A) used in the present invention is 1
When the average degree of polymerization is less than 100, smoothness and friction resistance are poor, warp breakage occurs frequently, and when the average polymerization degree exceeds 10,000, the adhesiveness of the sizing agent composition is increased. It is not preferred because the adhesive permeability at the time of gluing is reduced. Next, the phosphate compound or its salt (B) is a compound represented by the following general formula (1) or a salt thereof, and the salt of the ester compound is a monoethanolamine salt, an ammonium salt, or a sodium salt. , Potassium salts, calcium salts and the like.

Embedded image (Where R is hydrogen, an alkyl group, or an alkylallyl group, n is an integer, R 'is hydrogen or R (CH ₂ CH ₂
O) represents an _n group. The phosphate ester compound is not particularly limited as long as it has the above structure. L. B. As 12 or less,
Further, 1 to 7 are preferable. The acid value is preferably 80 or more, more preferably 160 to 200. Further, n is preferably an integer of 1 to 30.

The sizing composition used in the present invention comprises a carboxyl group-containing polyvinyl alcohol resin (A) as described above.
And a phosphate ester compound represented by the above general formula (1) or a salt thereof (B), and the mixing ratio thereof is not particularly limited, but is based on 100 parts by weight of the carboxyl group-containing polyvinyl alcohol-based resin (A). On the other hand, the phosphoric ester compound or its salt (B) is added in an amount of 0.1 to
20 parts by weight, more preferably 2 to 10 parts by weight, if the content is less than 0.1 part by weight, the oil agent used in the post-treatment permeates the glued fiber, the treatment effect is insufficient, Conversely, if the amount exceeds 20 parts by weight, the glued yarn becomes too soft and the weaving property deteriorates, which is not preferable.

[0013] The sizing composition used in the present invention may contain, in addition to the carboxyl group-containing polyvinyl alcohol-based resin (A), the phosphate compound or its salt (B), if necessary, an antifoaming agent, a surfactant, and a preservative. Agents, known additives such as thickeners can also be added, and other fiber sizing agents within a range that does not impair the effects of the present invention, for example, other conventionally known polyvinyl alcohol-based resins, starch, Resins such as carboxymethyl cellulose and acrylic copolymer can also be mixed.

In the present invention, when gluing the fibers,
Carboxyl group-containing polyvinyl alcohol resin (A)
And after sizing the sizing composition comprising the phosphate compound represented by the general formula (1) or the salt (B) thereof, treating the fiber with an oil agent and drying without drying the fiber. The effect of the present invention cannot be sufficiently obtained by a method in which an oil agent is mixed with a sizing composition and sizing is performed, or a method in which the sizing is dried after sizing and then treated with an oil agent.

In sizing, first, the sizing composition is
Generally, it is dissolved in water to form a sizing solution. There is no particular limitation on the preparation of the sizing liquid. In short, water is mixed with the carboxyl group-containing polyvinyl alcohol-based resin (A) and the phosphate compound represented by the general formula (1) or a salt thereof (B). Good. The concentration may be appropriately adjusted depending on the purpose, and a particularly preferred concentration is usually selected from the range of about 2 to 20% by weight, and more preferably about 5 to 15% by weight in consideration of workability and the like. The temperature of the sizing liquid is 40 ~
90 ° C. is preferred. The yarn to be coated with the sizing composition in the present invention is not particularly limited, but, for example, a cotton synthetic fiber of spun yarn and a mixed spun yarn thereof are preferably used. The amount of sizing depends on the type of the target yarn, but is 5 to 20% by weight, preferably 5 to 10% by weight based on the yarn. When the content is 5% by weight or less, the number of fluffs increases, and the friction resistance tends to deteriorate.
Exceeding the weight% is undesirable because the elongation of the yarn is lost and the weaving efficiency is deteriorated. The glued yarn is subjected to an oil treatment as it is or, if necessary, by slightly adjusting the water content or the resin content by lightly drying or the like.

The oil agent is not particularly limited as long as it facilitates the splitting of the yarn, but is commonly used as an oil such as a sulfated oil, a fatty acid ester sulfate, a higher alkyl sulfate or an alkyl sulfonate. Cation activators such as ionic activators, fatty acid or acid chloride derivatives, fatty acid amides, aliphatic nitriles, aliphatic amines, etc., nonionic activators such as polyoxyethylene derivatives, polyhydric alcohol derivatives, and other synthetic hydrocarbons Oils, petroleum oils, animal and plant oils, and the like. Specifically, Maconol TS-797 (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), Xerox O
S (manufactured by Kyoeisha Chemical Co., Ltd.) and Warp Set K (manufactured by Takemoto Yushi Co., Ltd.) are preferably emulsified and dispersed in hot water of 30 to 80 ° C. to about 50 to 80% by weight. The amount of the oil agent used is 1 to 10% by weight, preferably 2 to 5% by weight based on the size of the sized yarn.
If it is less than 1% by weight, it is difficult to obtain the divide and weavability of the sized yarn, and if it exceeds 10% by weight, the sized yarn becomes hard and the oil agent drops off, which is not preferable.

The method for treating the oil agent is not particularly limited.
Examples of the method include immersing the glued yarn in the oil agent, attaching the glued yarn to the yarn with a roll coater partially immersed in the oil agent, and continuously spraying the oil agent.

After the oil agent is added to the glued yarn by the above method, the yarn is dried at 100 to 140 ° C., divided by a divide lot, wound around a loom beam, and then subjected to weaving.

[0019]

The present invention will be specifically described below with reference to examples. In the examples, “parts” and “%” are based on weight unless otherwise specified. Example 1 [Preparation of carboxyl group-containing polyvinyl alcohol-based resin (A)] A polymerization vessel was charged with 500 parts of vinyl acetate, 3.4 parts of maleic anhydride, and 85 parts of methanol. After raising the temperature and refluxing at 60 ° C. for 30 minutes, azobisisobutyronitrile was added at 0.08 mol% based on vinyl acetate, and polymerization was carried out for 6 hours. After the completion of the reaction, methanol vapor was blown in to remove unreacted vinyl acetate, and a methanol solution of the copolymer was obtained. Next, the methanol solution of the obtained copolymer was diluted with methanol to a concentration of 40%, and neutralized at 30 ° C. with sodium hydroxide. Further, sodium hydroxide is added to the vinyl acetate in the copolymer in an amount of 20 mmol% to effect saponification. The resulting saponified product is filtered, dried at 70 ° C., and dried at 70 ° C. to obtain a carboxyl group-containing polyvinyl alcohol resin (carboxyl group 0). 0.5 mol%, saponification degree 94.5 mol%, average polymerization degree 1400)
(A) was obtained. 100 parts of the above-mentioned carboxyl group-containing polyvinyl alcohol-based resin (A) and 3.4 parts of the phosphate ester compound salt (B) shown in Table 1 were dissolved in 16,000 parts of water to prepare a sizing solution.

A sizing treatment was performed using the sizing solution under the following conditions. Applicable yarn 100% cotton, 40th single yarn Gluing machine 1BOX type sizing machine manufactured by Kanamaru Tekko Co., Ltd. Gluing conditions Total drawing load 600kg Gluing liquid temperature 80 ° C Winding speed 85m / min Gluing amount 10% Next, as an oil agent An emulsion prepared by adding Maconol TS-797 (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) to hot water at 60 ° C. so as to have a concentration of 60% was placed in a bath, and a 1.5 mx 100 φ mm SU was prepared.
When the roll of S is 1/5 of the diameter of the roll, an oil agent (emulsion)
The roll was set so as to be immersed in the roll. The glued yarn sheet was continuously brought into contact with the roll, and the roll was rotated at a speed such that the amount of the oil agent adhered to the glued yarn was 3%, thereby causing the oil agent to adhere. Then, after drying at 120 ° C., it was wound up on a loom beam while being divided by a dividing rod.

The number of fluff, smoothness, abrasion resistance and weaving property of the wound glued yarn were evaluated by the following methods. The results are shown in Table 2. (Number of fluff) Toray Co., Ltd. fluff counting device (model number DT-10)
In 4), the number of fluffs (thickness of 3 mm or more) per meter was measured.

(Smoothness) Dynamic coefficient of friction The coefficient of dynamic friction between the sized yarns is μ meter (manufactured by Eiko).
Measured at (Friction resistance)-Number of frictions The number of frictions before cutting was measured at a comb angle of 116 ° and a load of 400 g / 10 with a TM-type embracing force tester (manufactured by Daiei Kagaku Kikai). (Wovenability)-Warp breakage Using a weaving machine for air jet loom, warp density: 123 yarns /
inch, 48 inch weaving width, 650 rpm automatic loom
Then, the number of warp breaks per hour was measured when the woven fabric was woven with broad. -Weaving efficiency The weaving efficiency is calculated by measuring the actual woven fabric length relative to the woven fabric length per unit time when the loom is not stopped at all during the above weaving. Table 2 shows the evaluation results.

Examples 2 to 4 Similar experiments were conducted in the same manner as in Example 1 except that the carboxyl group-containing polyvinyl alcohol resin (A) and the phosphate ester compound salt (B) as shown in Table 1 were used. .

Comparative Example 1 An experiment was performed in the same manner as in Example 1 except that unmodified polyvinyl alcohol (degree of saponification: 94.5 mol%, average degree of polymerization: 1400) was used as the polyvinyl alcohol resin. .

Comparative Example 2 An experiment was conducted in the same manner as in Example 1 except that the salt (B) of the phosphate compound was not added.

Comparative Example 3 In Example 1, in the sizing step, an oil agent was blended with the sizing composition and treated in the same manner. After drying at 120 ° C., the oil agent was applied in the same manner as in Example 1 and divide. An experiment was performed in the same manner as in Example 1 while winding the film on a loom beam at 50 yd / min while dividing the lot.

Comparative Example 4 In Example 1, immediately after completion of the sizing, drying was performed at 120 ° C., and then an oil agent (emulsion liquid) was prepared in the same manner as in Example 1, and the oil agent was put in a bathtub. The same experiment as in Example 1 was carried out by attaching the oil agent and winding it on a loom beam while dividing it by a divide lot. Examples 1-4, Comparative Examples 1
Table 2 shows the evaluation results of No. 4.

[0028]

Table 1 Polyvinyl alcohol-based resin (A) Phosphate ester compound (B) Carboxyl group content (mol%) Content (parts) Type * Content (parts) Example 1 0.5 100 3.4% 2 1.0 100 6.8 ３ 30.5 100 3.4 〃 4 1.0 100 6.8 Comparative Example 10 (unmodified) 100 3.4 〃 20.5 100 Not blended ３ 30. 5 100 3.4 ４ 40.5 100 3.4 *: Ethanolamine salt of a phosphate ester in which R = ethyl group, n = 2, and R ′ = hydrogen in the above general formula (1): The above general formula ( Ammonium salt of a phosphoric acid ester wherein R = methyl group, n = 10 and R ′ = CH ₃ (CH ₂ CH ₂ O) ₁₀ group in 1)

[0029]

[Table 2] Smooth abrasion resistance Weaving fluff Number Dynamic wear Wear Warp breakage Efficiency (number / m) Coefficient Number (number / hour) (%) Example 1 5.2 0.22 5230 0.4 95.6 〃 2 2.4 0.22 5440 0.4 96.2 〃 3 2.6 0.26 4340 0.6 95.0 〃 4 2.5 0.22 4620 0.5 97.5 Comparative Example 1 4.8 0.30 3310 0.8 88.0 〃 2 9.6 0.50 1980 1.2 83.0 ３ 3 6.5 0.32 3860 1.0 87.5 ４ 4 3.8 0.45 2020 1.6 82.5

[0030]

According to the present invention, a sizing composition containing a carboxyl group-containing polyvinyl alcohol-based resin (A) and a specific phosphate compound or its salt (B) is pasted to fibers, and then the oil composition , And then dried, a sizing method is performed, so that sizing fibers having a small number of fluffs, having excellent smoothness and abrasion resistance, and having excellent weaving properties can be obtained.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 14, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction contents]

[0019]

The present invention will be specifically described below with reference to examples. In the examples, “parts” and “%” are based on weight unless otherwise specified. Example 1 [Preparation of carboxyl group-containing polyvinyl alcohol-based resin (A)] A polymerization vessel was charged with 500 parts of vinyl acetate, 3.4 parts of maleic anhydride, and 85 parts of methanol. After raising the temperature and refluxing at 60 ° C. for 30 minutes, azobisisobutyronitrile was added at 0.08 mol% based on vinyl acetate, and polymerization was carried out for 6 hours. After the completion of the reaction, methanol vapor was blown in to remove unreacted vinyl acetate, and a methanol solution of the copolymer was obtained. Next, the methanol solution of the obtained copolymer was diluted with methanol to a concentration of 40%, and neutralized at 30 ° C. with sodium hydroxide. Further, sodium hydroxide is added to the vinyl acetate in the copolymer in an amount of 20 mmol% to effect saponification. The resulting saponified product is filtered, dried at 70 ° C., and dried at 70 ° C. to obtain a carboxyl group-containing polyvinyl alcohol resin (carboxyl group 0). 0.5 mol%, saponification degree 94.5 mol%, average polymerization degree 1400)
(A) was obtained. 100 parts of the carboxyl group-containing polyvinyl alcohol resin (A) and 3.4 parts of the phosphate ester compound salt (B) shown in Table 1 were dissolved in 1600 parts of water to prepare a sizing liquid.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction contents]

The number of fluff, smoothness, abrasion resistance and weaving property of the wound glued yarn were evaluated by the following methods. The results are shown in Table 2. (Number of fluff) Toray Co., Ltd. fluff counting device (model number DT-10)
In 4), the number of fluffs (thickness of 3 mm or more) per meter was measured.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0022

[Correction method] Change

[Correction contents]

(Smoothness) Dynamic coefficient of friction The coefficient of dynamic friction between the sized yarns is μ meter (manufactured by Eiko).
Measured at (Friction resistance)-Number of frictions The number of frictions before cutting was measured at a comb angle of 116 ° and a load of 400 g / 10 with a TM-type embracing force tester (manufactured by Daiei Kagaku Kikai). (Wovenability)-Warp breakage Using a weaving machine for air jet loom, warp density: 123 yarns /
inch, 48 inch weaving width, 650 rpm automatic loom
Then, the number of warp breaks per hour was measured when the woven fabric was woven with broad. -Weaving efficiency The weaving efficiency was calculated by measuring the length of the actually woven fabric relative to the length of the woven fabric per unit time when the loom did not stop at the time of the above weaving. Table 2 shows the evaluation results.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0029

[Correction method] Change

[Correction contents]

[0029]

[Table 2] Number of smooth and abrasion-resistant woven fluffs Dynamic wear Abrasion warp yarn cutting efficiency (books / m) Coefficient Number ( times / hour) (%) Example 1 5.2 0.22 5230 0.4 95.6 〃 2 2.4 0.22 5440 0.4 96.2 ３ 3 2.6 0.26 4340 0.6 95.0 ４ 4 2.5 0.22 4620 0.5 97.5 Comparative Example 1 4.8 0.30 3310 0.8 88.0 〃 2 9.6 0.50 1980 1.2 83.0 〃 3 6.5 0.32 3860 1.0 87.5 ４ 4 3.8 0.45 2020 1.6 82.5

Claims (4)

[Claims] 1. A sizing composition comprising a carboxyl group-containing polyvinyl alcohol-based resin (A) and a phosphate compound represented by the following general formula (1) or a salt thereof (B) is glued to fibers. Thereafter, the method is treated with an oil agent and then dried, followed by drying. Embedded image (Where R is hydrogen, an alkyl group, or an alkylallyl group, n is an integer, R 'is hydrogen or R (CH ₂ CH ₂
O) represents an _n group. ) 2. The carboxyl group content in the carboxyl group-containing polyvinyl alcohol-based resin (A) is from 0.1 to 0.1.
The fiber sizing method according to claim 1, wherein the amount is 10 mol%. 3. The content of the phosphate compound represented by the general formula (1) or a salt thereof (B) is 0.1 to 20 parts by weight based on 100 parts by weight of the carboxyl group-containing polyvinyl alcohol-based resin (A). 3. The method for sizing fibers according to claim 1, wherein the sizing composition is used. 4. The fiber sizing method according to claim 1, wherein the average degree of polymerization of the carboxyl group-containing polyvinyl alcohol resin (A) is 100 to 10,000.