JP2001172871A - Sizing agent for yarn - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a yarn sizing agent for providing a sized yarn having not only physical properties for enduring even a high-speed weaving machine when various yarns are woven but also sufficient hardness without reducing water solubility in desizing, capable of improving weave performances and qualities of woven fabric. SOLUTION: This sizing agent for yarn comprises a PVA containing 1.8-3.5 mol% 1,2-glycol bond and, to improve performances further, 2-19 mol% of <=4C α-olefin unit.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber sizing agent having excellent weaving performance when weaving using various fibers. More specifically, prior to weaving with shuttle looms and shuttle-less looms, gluing is performed on fiber yarns such as filament yarns, processed yarns, twisted yarns and spun yarns to improve conjugation and abrasion resistance. The present invention relates to an industrially useful sizing agent for fibers that can reduce the weaving defects due to the inflow of warp yarns on a loom because the sizing yarn can be hardened without deteriorating the yarn.

[0002]

2. Description of the Related Art Conventionally, polyvinyl alcohol resins (hereinafter abbreviated as PVA), starches, carboxymethylcellulose, water-soluble acrylic sizing agents, etc. have been used as sizing agents for the purpose of reinforcing the warp of textiles. I have.
Of these, starch is a natural water-soluble polymer that has been used for warp sizing since the oldest, and is widely used mainly for warp sizing for spun yarn because of its low price. Since the size of the glue film was weak, it was necessary to increase the amount of glue attached to the yarn with a high starch ratio. In this respect, PVA has been used as a main component of a paste instead of starch because it is effective as a water-soluble paste for long-term storage without decay, and the strength of the obtained film is extremely strong. However, if the blending ratio of PVA in the sizing agent is too large, the sizing glue is applied to the sheet at the time of sizing and then dried, and then the sheet-shaped sizing thread bundle is divided into individual sizing threads. In some cases, the strong glue film strength was disturbed to cause yarn breakage, reduced yarn strength or fuzz. In order to solve this problem, attempts to improve the disadvantages of both by blending starch and PVA have already been made widely, and they are widely used as warp sizing agents for spun yarns, mainly 100% cotton yarns.

[0003]

In recent years, the weaving method has been rapidly accelerated along with the use of air jets in looms, and if a sized yarn having physical properties that can withstand high-speed weaving cannot be obtained, industrial weaving is required. There is no value at all. If the warp breaks under high-speed weaving conditions, the broken yarn will become entangled with the next glued yarn, and the loom will not be able to detect the warp break and weaving will continue, eventually resulting in a weaving defect. There is a problem. In order to solve such a problem, a method of hardening the glued yarn itself, that is, a method of hardening the size of the glue film is effective. In some cases, a completely saponified PVA having low hygroscopicity is used. However, fully saponified PVA undergoes heat treatment in the drying process during sizing and crystallization progresses, and the PVA removal rate deteriorates in the desizing process after weaving. It is thought that the industrial value will be higher if there is a technique for hardening the steel.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to solve such problems, and as a result, have found that 1,2-
PVA containing 1.8 to 3.5 mol% of glycol bonds
By using, it was found that not only a glued yarn having sufficient hardness at the time of weaving was obtained, but also that the water solubility at the time of desizing was good and that desizing could be performed well, and the present invention was completed. . In the present invention, it was also found that weaving performance was further improved when PVA containing 2 to 19 mol% of α-olefin units having 4 or less carbon atoms in the molecule was used.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The PVA used for the fiber sizing agent of the present invention is not particularly limited in its production method, and is a polyvinyl ester resin obtained by polymerizing or copolymerizing a vinyl ester by a known polymerization method such as bulk, solution, suspension or emulsification. Is saponified by a known method. The vinyl ester is not particularly limited, and includes vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, and the like. Vinyl acetate is often used.

It is essential that the PVA of the present invention contains 1.8 to 3.5 mol% of 1,2-glycol bonds in the molecule, but it is preferably 1.9 to 3.1 mol%, and more preferably 1.9 to 3.1 mol%. Is 2
More preferably, it is contained in an amount of 3 mol%. 1.8 mol%
If it is less than 30, the water solubility at the time of desizing is not sufficient.
Even if the content exceeds 3.5 mol%, good desizing properties are not only saturated, but also problems such as increased hygroscopicity appear, so that the effects of the present invention cannot be obtained. 1,
As a method for introducing a 2-glycol bond into PVA,
Polymerization is carried out by raising the temperature of the polymerization reaction solution above the boiling point of the reaction solution under atmospheric pressure. For example, polymerization is carried out under pressure at a temperature of 75 to 200 ° C., or vinylene carbonate is introduced by a copolymerization reaction. However, the method is not limited to these. The 1,2-glycol bond content of the PVA of the present invention can be determined from NMR peaks. Saponification degree 9
After saponification to 9.9 mol% or more, the PVA was thoroughly washed with methanol and dried at 90 ° C. under reduced pressure for 2 days.
A sample dissolved in SO-d6 and added with a few drops of trifluoroacetic acid was subjected to 500 MHz proton NMR (JOEL GX-
500) at 80 ° C. The peak derived from methine in the vinyl alcohol unit is assigned to 3.2 to 4.0 ppm (integral value A), and the peak derived from one methine with 1,2-glycol bond is assigned to 3.25 ppm (integral value B). The 1,2-glycol bond content was calculated. 1,2-glycol bond content (mol%) = B / A × 1
00

The viscosity average polymerization degree (hereinafter abbreviated as polymerization degree) of PVA containing 1.8 to 3.5 mol% of 1,2-glycol bond in the molecule of the present invention is preferably 100 to 4
000, more preferably 200 to 3000, and most preferably 300 to 2500. When the degree of polymerization is less than 100, the strength of the obtained sized yarn may be reduced, and satisfactory weaving properties may not be obtained. If the degree of polymerization exceeds 4,000, the viscosity of the aqueous solution at the time of sizing becomes high, the workability deteriorates, and the use thereof may be restricted. The degree of polymerization (P) of PVA is
It is measured according to JIS-K6726. That is, P
It is determined from the intrinsic viscosity [η] measured in water at 30 ° C. after re-saponifiing and purifying VA according to the following equation. P = ([η] × 10 ³ /8.29) ^{(1 / 0.62)}

The degree of saponification of the vinyl ester portion of the PVA used for the fiber sizing agent of the present invention is not particularly limited, but is usually from 60 to 100 mol%, more preferably from 70 to 99.9 mol%. When the saponification degree is less than 60 mol%,
The water solubility or water dispersibility tends to decrease, and the viscosity at the time of sizing may become unstable, or the desizing of the woven fabric may be limited. Further, two or more of these PVAs having different degrees of polymerization and saponification may be mixed and used. Further, as long as the effect of the present invention is not impaired, it may be used by mixing with unmodified PVA or modified PVA with another modified species.

The object of the present invention can be attained by using PVA having a 1,2-glycol bond in the molecule of 1.8 to 3.5 mol% in a fiber sizing agent. However, in many cases, the effect of the present invention can be further enhanced when PVA is obtained by copolymerizing an α-olefin unit having 4 or less carbon atoms in the molecule. As the α-olefin unit having 4 or less carbon atoms,
For example, ethylene, propylene, n-butene, isobutene and the like can be mentioned, but ethylene is preferably used. The content of the α-olefin having 4 or less carbon atoms is not particularly limited as long as the effects of the present invention are not impaired, but is preferably 2 to 19 mol%, more preferably 2.5 to 17 mol%. Most are 3 to 15 mol%, and even 3.5 to 13 mol%
In many cases, in particular, the effects of the present invention can be widely enjoyed. If it exceeds 19 mol%, the water solubility or water dispersibility tends to decrease, and the proportion of enjoying the effects of the present invention tends to decrease. The content of the α-olefin unit is determined by the proton NM at 500 MHz of the α-olefin-containing polyvinyl ester which is a precursor of the PVA.
It measured using R (JEOL GX-500).

[0010] The PVA used in the fiber sizing agent of the present invention has a 1,2-glycol bond in the molecule of 1.8 to 3.5 mol%.
And preferably contains 2 to 19 mol% of an α-olefin unit having 4 or less carbon atoms, and further modified with a modified species other than the above in view of the water solubility or water dispersibility of the PVA. can do. The comonomer unit is not particularly limited as long as it can be copolymerized with a vinyl ester. For example, α-olefins having 5 or more carbon atoms, itaconic acid (anhydride), maleic acid (anhydride), acrylic acid, methacrylic acid Acid, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, trimethyl- (3-acrylamido-3-dimethylpropyl) -ammonium chloride, ethyl vinyl ether,
Butyl vinyl ether, N-vinylpyrrolidone, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, acrylamido-2-methylpropanesulfonic acid and its sodium salt, sodium vinyl sulfonate, allyl sulfone But not limited thereto. The comonomer content is often used at 10 mol% or less. When the content of the comonomer is 10 mol%
If the amount exceeds the above range, the effect of the present invention may be impaired, and the use may be restricted.

In addition, a vinyl ester monomer such as vinyl acetate is copolymerized with ethylene in the presence of a thiol compound such as 2-mercaptoethanol or n-dodecylmercapto, and a terminal obtained by saponifying the copolymer. It may be a denatured product.

There is no particular limitation on the type of yarn to which the sizing agent of the present invention can be used, and it is suitably used for a single yarn such as cotton, polyester, rayon, hemp, nylon, wool, and acrylic, or a mixed yarn thereof. In the preparation of the sizing solution, the sizing conditions can be selected and used appropriately according to the target warp yarn, and there is no particular limitation. In general, in the case of spun yarn, the sizing liquid viscosity of the sizing agent for the warp sizing may cause fluffiness. Used with relatively high viscosity to improve. For example, the viscosity at a gluing temperature of 70 to 95 ° C. is often 50 to 200 mPa · s in many cases. The solid content concentration of the size liquid is not particularly limited, but is generally 3 to 15% by weight.

The amount of glue adhering to the fiber is determined by
It is appropriately selected depending on the equipment used, such as a loom and a sizing machine, but is often selected from 5% to 25%. In general, in the case of spun yarn, the main purpose is to reinforce the surface of the glued yarn by fluffing and internal permeation. Therefore, the amount of the glue applied is determined in consideration of the required size of the glued yarn. In general, the larger the amount of glue adhered, the better the abrasion resistance and fluffing effect of the sized yarn and the less warp breakage during weaving.

The fiber sizing agent used in the present invention includes a water-soluble polymer such as starch, a water-soluble cellulose compound and a water-soluble acryl sizing agent, and a smoothing agent such as wax and oil, as long as the effect is not impaired. Agents and other additives can include antifoaming agents, antistatic agents, preservatives, fungicides, and the like. As the starch, raw starch or processed starch obtained by subjecting raw starch to gelatinization (gelatinization), oxidation, esterification, etherification, grafting, carboxymethylation and the like can be suitably used. As the raw materials for these starches, those produced from natural grains such as corn, potato, wheat, tapioca, and rice can be used. Examples of the water-soluble cellulose compound include, but are not limited to, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, and the like. Similarly, the water-soluble acrylic paste, leveling agent, and other additives can be used without any particular limitation.

Further, the gluing method of the present invention is not particularly limited, and examples thereof include, but are not limited to, simultaneous slasher gluing, partial warping gluing, tape gluing, and cheese gluing.

Although the warp sizing agent has been described above as an example, the fiber sizing agent of the present invention can be effectively used as a resin treatment for woven fabrics, a sizing agent for washing, a sizing agent for printing, or a binder for felt or nonwoven fabric. Available.

[0017]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following, “parts” and “%” mean “parts by weight” and “% by weight”, respectively, unless otherwise specified. Further, the obtained PVA was analyzed and the physical properties of the sized yarn were measured in the following manner.

The analysis method of PVA was in accordance with JIS-K6726 unless otherwise specified. The 1,2-glycol bond content and α-olefin unit content of the PVA of the present invention were measured at 500 MHz proton NMR (JOEL).
GX-500).

The physical properties of the glued yarn were measured by the following methods. (1) Amount of gluing: A method for correcting the part of the fluff falling off at the time of desizing cleaning described in pages 299-302 of "Warp glue" (Kazuka Fukada, Teruhiko Kazumi, published by The Japan Textile Machine Society) It was measured. (2) Hardness of glued yarn: 20 ° C, 65% RH (relative humidity)
The glued yarn conditioned under the following conditions was tested with a DI-type yarn frictional binding tester (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) with a load of 50 g /
This machine is operated until the glued yarn is cut with a twist number of 0.5, and then the cut portion of the glued yarn is slid from a 7 cm high table.
Slide amount (cm) from the upper horizontal plane until it hangs 5cm
Was measured to determine the hardness of the glued thread (the greater the slide amount, the harder). (3) Desizing property: Treating the sized yarn in a 0.1% aqueous sodium hydroxide solution at 60 ° C. for 30 minutes, washing away the alkali with 40 ° C. hot running water for 1 minute, drying, and then measuring the iodine color The desizing property was determined according to the following criteria. (4) Abrasion strength: The number of times to cut at a load of 100 g / piece was measured with a TM-type embracing force tester (manufactured by Daiei Kagaku Seiki Seisaku-sho, Ltd.)

<Judgment Criteria> ：: good △: slightly bad ×: bad

Example 1 3000 g of vinyl acetate and 0.090 g of tartaric acid were placed in a 5 L pressurized reaction vessel equipped with a stirrer, a nitrogen inlet, and an initiator inlet.
The operation of raising the pressure of the reactor to 2.0 MPa and leaving it to stand for 10 minutes while bubbling with nitrogen gas at room temperature, and then releasing the pressure was repeated three times to replace the system with nitrogen. A 0.1 g / L solution of 2,2′-azobis (cyclohexane-1-carbonitrile) (V-40) dissolved in methanol was prepared as an initiator, and the solution was replaced with nitrogen by bubbling with nitrogen gas. Next, the temperature in the polymerization tank was raised to 120 ° C. At this time, the reactor pressure was 0.4 MPa. Next, 6.0 ml of the above initiator solution was injected to initiate polymerization. During the polymerization, the polymerization temperature was maintained at 120 ° C, and the polymerization was continued for 2 hours using the above initiator solution.
The polymerization was carried out by continuously adding V-40 at 3.9 ml / hr. The reactor pressure during the polymerization was 0.4 MPa. 4
After an hour, the polymerization was stopped by cooling. At this time, the solid content concentration was 35%. Next, unreacted vinyl acetate monomer was removed while occasionally adding methanol under reduced pressure at 30 ° C., and a methanol solution of polyvinyl acetate (concentration: 33%)
I got Methanol was added to the obtained polyvinyl acetate solution to add 400 g of a methanol solution of polyvinyl acetate (100 g of polyvinyl acetate in the solution) adjusted to have a concentration of 25% at 4 ° C. at 46.4 g (polyacetic acid). Molar ratio (MR) of 0.1 to vinyl acetate unit in vinyl
Saponification was performed by adding an alkali solution (0) (a 10% methanol solution of NaOH). The gel that was gelled in about 1 minute after the addition of the alkali was pulverized by a pulverizer and left for 1 hour to progress the saponification. Then, 1000 g of methyl acetate was added to neutralize the remaining alkali. After confirming the completion of the neutralization using a phenolphthalein indicator, 1000 g of methanol was added to the white solid PVA obtained by filtration, and the mixture was allowed to stand at room temperature for 3 hours for washing. After repeating the above washing operation three times, the PVA obtained by centrifugal drainage was dried at 70 ° C. for 2 hours in a drier.
It was left for days to obtain dry PVA (PVA-1). The degree of saponification was 99.2 mol%. After saponification of a methanol solution of polyvinyl acetate obtained by removing unreacted vinyl acetate monomer after polymerization at an alkali molar ratio of 0.5,
After the pulverized product was left at 60 ° C. for 5 hours to progress saponification, Soxhlet washing with methanol was performed for 3 days, and then dried under reduced pressure at 80 ° C. for 3 days to purify the purified PV.
A was obtained. The degree of polymerization of the PVA is determined by a conventional method JIS K672.
It was 1700 when measured according to 6. The purified P
The amount of 1,2-glycol bond in VA was determined by measurement with a 500 MHz proton NMR (JEOL GX-500) apparatus as described above, and was 2.2 mol%.

A size liquid having the following formulation was prepared, glued with a test sizer, and the physical properties of the size of the sized yarn instead of the weaving property were measured. (1) Glue formulation A glue formulation comprising PVA-1 and 92 parts of a wax for fiber sizing agent (Wapset 600 manufactured by Takemoto Yushi Co., Ltd.) in 92 parts was prepared. Using a sizing solution obtained by dissolving this composition under stirring at 90 ° C. for 1 hour, a cotton yarn (“Goldfish” C40 / 1, manufactured by Toyobo Co., Ltd.) is sized to form a sizing agent that substitutes for weaving. The threading properties were measured. Table 2 shows the results. (2) Gluing conditions Gluing machine: 20 test sizers 1 box 1 sheet type Size liquid temperature: 90 ° C. Squeeze roll air pressure: 2.0 kg / cm ² Yarn speed: 40 m / min Drying temperature: 110 to 120 ° C

In addition, the polymerization temperature, the degree of polymerization, the degree of saponification, the degree of modification,
Table 1 shows the glycol bond content.

[0024]

[Table 1]

EXAMPLE 2 A paste solution of 54 parts of PVA-2, 38 parts of PVA-3, and 8 parts of wax for fiber sizing agent was prepared and subjected to the test described in Example 1. Table 2 shows the results.

Example 3 A size liquid consisting of 92 parts of PVA-4 and 8 parts of wax for fiber sizing was prepared, and the test described in Example 1 was conducted. Table 2 shows the results.

Example 4 A size liquid consisting of 46 parts of PVA-1, 46 parts of PVA-4, and 8 parts of wax for fiber sizing agent was prepared, and the test described in Example 1 was conducted. Table 2 shows the results.

Example 5 A paste liquid comprising 92 parts of PVA-5 and 8 parts of wax for fiber paste was prepared, and the test described in Example 1 was conducted.
Table 2 shows the results.

Example 6 80 parts of PVA-4 was added to a starch (manufactured by Sixi Mastachi;
A sizing solution comprising 12 parts of Mermaid M-200) and 8 parts of wax for fiber sizing agent was prepared, and the test described in Example 1 was performed. Table 2 shows the results.

Example 7 A sizing solution comprising 92 parts of PVA-4 and 8 parts of wax for a fiber sizing agent was prepared, and the raw yarn to be used was changed to a polyester / cotton blend yarn (1013C 45/1 manufactured by Kuraray Co., Ltd.). The test described in Example 1 was performed except for the change. Table 2 shows the results.

[0031]

[Table 2]

Comparative Example 1 PVA117 (degree of saponification: 98.5 mol%, degree of polymerization: 170)
(0,1,2-glycol bond content 1.5 mol%)
The test described in Example 1 was carried out using a size liquid consisting of 2 parts and 8 parts of a wax for fiber sizing agent (Wapset 600 manufactured by Takemoto Yushi Co., Ltd.). Table 3 shows the results.

COMPARATIVE EXAMPLE 2 A sizing solution comprising 92 parts of PVA-6 and 8 parts of wax for fiber sizing agent was prepared and subjected to the test described in Example 1.
Table 3 shows the results.

COMPARATIVE EXAMPLE 3 A sizing solution comprising 92 parts of PVA-7 and 8 parts of wax for a fiber sizing agent was prepared and subjected to the test described in Example 1.
Table 3 shows the results.

[0035]

[Table 3]

[0036]

The sizing agent for fibers of the present invention makes it possible to produce sized yarn having sufficient hardness during weaving without reducing the water solubility during desizing, and warp breakage even during high-speed weaving. Can be prevented from flowing.

Claims (3)

[Claims] 1. A 1,2-glycol bond in a molecule.
A sizing agent for fibers comprising a polyvinyl alcohol-based resin containing 8 to 3.5 mol%. 2. A polyvinyl alcohol resin having 2 to 19 mol% of α-olefin units having 4 or less carbon atoms in a molecule.
The paste for fibers according to claim 1, which is a polyvinyl alcohol-based resin contained therein. 3. The sizing agent according to claim 2, wherein the α-olefin unit having 4 or less carbon atoms is ethylene.