JPH07166472A - Sizing agent for warp - Google Patents

Abstract

PURPOSE:To obtain a sizing agent for warp, exhibiting excellent weaving properties, comprising a PVA, an acrylic resin and a starch esterified with an alkenylsuccinic acid having excellent fitness with an oil agent. CONSTITUTION:100 pts.wt. of a starch (chemically modified starch is included) is reacted with 0.5-20 pts.wt. of a compound selected from octenylsuccinic anhydride, decenylsuccinic anhydride, dodecenylsuccinic anhydride, tetradecenylsuccinic anhydride, etc., as an alkenylsuccinic acid to give a starch esterified with the alkenylsuccinic acid having <=1,000CPS viscosity of 10wt.% of an aqueous solution at 70 deg.C. 100 pts.wt. of the starch is mixed with 5-500 pts.wt. of a PVA-based resin, 5-300 pts.wt. of starch, 5-100 pts.wt. of an acrylic resin and 3-150 pts.wt. of an oil agent to give a sizing agent for warp capable of uniformly sizing spun yarn and exhibiting excellent weaving properties not separating a coating film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a warp sizing agent. More specifically, polyvinyl alcohol resin (hereinafter, P
It has good compatibility with VA), acrylic resin (hereinafter abbreviated as acrylic), and oil agent, and evenly sized yarn can be obtained when sizing to spun yarn, resulting in good weaving property. The present invention relates to a warp sizing agent.

[0002]

BACKGROUND OF THE INVENTION Starch, modified starch, CMC, PVA, acrylic and the like have been known as warp sizing agents.
It is actually used. Of these, starch has long been used as a warp sizing agent and is still used as a sizing agent for spun yarn because of its low price. However, the use of modified starch is increasing because the viscosity is too high and the adhesive strength is weak. Modified starch has low viscosity and improved sizing workability and viscosity stability, but when sizing with a formulation having a high starch ratio, it is necessary to increase the amount of adhesion to the yarn.

On the other hand, PVA has an excellent film forming property,
It is used as the main component of warp sizing agents because the strength of the sizing coat is stronger than other sizing agents. However, PV in the paste
If the A compounding ratio is too large, after gluing and drying,
When the sheet-shaped sizing yarn bundle is divided into individual sizing yarns (during a so-called divide), this strong glue coating strength causes damage, and thread breakage caused by a large resistance at the time of division, The strength of the yarn may be reduced or fuzz may occur. In order to solve these problems, it has already been widely attempted to blend starch and PVA to improve the drawbacks of both, and it is widely used as a sizing agent for spun yarns centering on 100% cotton yarns.

However, the warp sizing agent in which starch and PVA are mixed has a drawback in that the compatibility is poor and phase separation occurs and stable sizing cannot be performed. Further, the oil agent is blended for the purpose of improving the smoothness of the yarn surface and reducing the frictional force at the time of contact between the yarn during weaving and the dropper, heald, and the lube of the loom or between the yarns. However, since an oil that is originally insoluble in water, such as paraffin, is used by emulsifying it with an emulsifying agent and the like, it is not dispersed evenly in the glue coating and the glue coating strength is significantly reduced. It was

[0005]

DISCLOSURE OF THE INVENTION The present invention has good compatibility with PVA, acrylics, and oil agents, and can be stably sized for a long period of time without phase separation, thereby obtaining a uniform sized yarn. As a result, it is an object of the present invention to provide a warp sizing agent for spun yarn, which can obtain good weaving properties and sizing workability.

[0006]

[Means for Solving the Problems] As a result of intensive studies on the warp sizing agent, the present inventors have obtained a warp sizing agent which eliminates the above-mentioned drawbacks by incorporating alkenyl succinic acid esterified starch into the warp sizing agent. The present invention has been completed and the present invention has been completed. That is, the present invention provides a sizing agent for warp yarns comprising an alkenyl succinic acid esterified starch, starch, PVA, acryl, and an oil agent.

As the starch used in the present invention, raw starch such as cornstarch, tapioca starch, wheat starch, potato starch, etc., pregelatinized (gelatinizing) starch, and oxidation derived from these raw starch by a known method. Esterified starches such as starch, starch acetate, phosphate starch, urea phosphate starch, etc., hydroxyalkylated starch, carboxymethylated starch, alkylated starch, etherified starch such as cationized starch, acid treated starch, crosslinked starch, dextrin Chemically modified starch such as.

The PVA used in the present invention is obtained by saponifying polyvinyl acetate obtained by polymerizing or copolymerizing vinyl acetate by a known polymerization method such as bulk, solution, suspension and emulsification by a known method. To be The saponification degree of PVA is preferably 60 to 99.9 mol%,
0-99 ,. 5 mol% is more preferable, and 80 to 99 mol% is particularly preferable. The degree of polymerization of PVA used in the present invention is preferably 300 to 30000, and 500 to 10
000 is more preferable, and 700 to 5000 is even more preferable. Here, the degree of polymerization of PVA is a viscosity average degree of polymerization obtained by a usual method from the viscosity of an aqueous solution of the completely saponified product of PVA. Further, the PVA used in the present invention may be a mixture of two or more different types of PVA. The PVA used in the present invention may be copolymerized with other monomers, and those having a polymer terminal modified with a chain transfer agent can also be used.

The acrylic used in the present invention includes acrylic acid and methacrylic acid and their ester monomers (for example,
It is a polymer of monomers such as acrylic acid ethyl ester) and acrylic amide, and there are many types due to the combination of various monomers, changes in the copolymerization ratio, changes in the degree of polymerization, and changes in the degree of neutralization. When roughly classified, soda salts and the like of copolymers such as sodium polyacrylate, polyacrylic amide, acrylic (methacrylic) acid-acrylic (meth) acrylic acid ester-acrylic amide and the like can be mentioned.

The alkenyl succinic acid esterified starch used in the present invention is 0.5 to 20 parts by weight, preferably 1.0 part by weight of alkenyl succinic anhydride per 100 parts by weight of starch.
˜15 parts by weight, more preferably 2.0 to 10 parts by weight. The esterification is carried out by suspending the starch in water and stirring the mixture with a known alkalizing agent (caustic soda, caustic potash, triethanolamine, ammonia, etc.) to a pH of 6 to 9, preferably a pH of 7.5 to 8.
The reaction can be carried out for 2 to 20 hours at a reaction temperature of 30 to 50 ° C. If the amount of alkenyl succinic anhydride is less than 0.5 parts by weight with respect to 100 parts by weight of starch, phase separation of the paste solution tends to occur easily. On the other hand, even if the amount of alkenyl succinic anhydride is more than 20 parts by weight, the effect of the present invention does not change, but the higher the degree of esterification, the higher the cost.

Examples of the alkenyl succinic anhydride used in the present invention include octenyl succinic anhydride, decenyl succinic anhydride, dodecenyl succinic anhydride, tetradecenyl succinic anhydride, hexadecenyl succinic anhydride, octadecenyl succinic anhydride and the like.

The starch before esterification of the alkenyl succinic acid esterified starch used in the present invention includes raw starch, oxidized starch, etherified starch, esterified starch, acid-treated starch, cross-linked starch, and modified starch of grafted starch. Can be used.

The aqueous solution viscosity of the alkenyl succinic acid esterified starch used in the present invention is 10% by weight of an aqueous solution which is gelatinized under the gelatinization condition of 85 ° C. or higher for 10 minutes at 70 ° C. and 30 rpm using a B type viscometer. Viscosity of 1000c
ps or less is preferable, 500 cps is more preferable, 1
00 cps is more preferable. When the viscosity is higher than 1000 cps, the fluidity of the sizing liquid during sizing becomes poor. Although the lower limit of the viscosity is not particularly limited, it is preferably 2 cps or more. When the viscosity is lower than 2 cps, the adhesive strength is lowered and the coating becomes brittle, which is not preferable.

The blending ratio of the alkenyl succinic acid esterified starch and PVA in the warp sizing agent of the present invention is such that PVA is 100 parts by weight based on 100 parts by weight of the alkenyl succinic acid esterified starch.
5 to 500 parts by weight is preferred, 30 to 400 parts by weight is more preferred, and 50 to 300 parts by weight is even more preferred. If the PVA is more than 500 parts by weight, yarn breakage increases when sizing, which leads to weaving problems, which is not preferable. On the other hand, if the PVA is less than 5 parts by weight, warp breakage will increase during weaving and weaving efficiency will decrease, which is not preferable.

In the warp paste of the present invention, the mixing ratio of the alkenyl succinic acid esterified starch and the starch including the modified starch mentioned above is 100 parts by weight of the alkenyl succinic acid esterified starch to 5 parts of the starch. To 300 parts by weight is preferable, and 50 to 200 is more preferable. If the amount of starch is more than 300 parts by weight, the characteristics of the alkenyl succinic acid esterified starch are small, while if the amount of starch is less than 5 parts by weight, the effect of adding starch is not obtained, which is not preferable.

The blending ratio of the alkenyl succinic acid esterified starch and the acrylic in the warp sizing agent of the present invention is preferably 5 to 100 parts by weight, more preferably 10 to 70 parts by weight, based on 100 parts by weight of the alkenyl succinic acid esterified starch. More preferable. If the amount of acrylic is more than 100 parts by weight, the hygroscopicity and flexibility of the adhesive coating will be too large, while if the amount of acrylic is less than 5 parts by weight, the effect of adding acrylic will be small, which is not preferable. Most of acrylic is supplied as an aqueous solution, but the weight is pure weight.

The mixing ratio of the alkenyl succinic acid esterified starch and the oil agent in the warp sizing agent of the present invention is 3 to 1 oil agent per 100 parts by weight of the alkenyl succinic acid esterified starch.
50 parts by weight is preferable, and 8 to 50 parts by weight is more preferable. When the amount of the oil agent is more than 150 parts by weight, the paste coating becomes too weak, and when the amount of the oil agent is less than 3 parts by weight, the smoothness of the warp is not sufficiently improved, which is preferable.

The sizing liquid concentration at the time of sizing using the sizing agent of the present invention is preferably 3 to 18% by weight, more preferably 7 to 15% by weight. When the sizing liquid concentration is 3% by weight, the amount of sizing agent adhered to the yarn (pasting ratio) becomes too low during ordinary slasher sizing, and the yarn reinforcing effect, which is the original purpose of sizing, becomes too small, which is preferable. Absent. When the concentration of the sizing liquid is higher than 18% by weight, the amount of the sizing agent attached to the yarn is too large during ordinary slasher sizing, which is not economical, but the flexibility of the yarn is lost and the warp is often broken. Not preferable.

The warp sizing agent of the present invention can be produced by preparing an alkenyl succinic acid esterified starch, starch, PVA, acryl and an oil agent together with water and the like into a sizing solution by a method known per se. CMC, other auxiliaries (defoamer, antistatic agent,
Antifungal agents, etc.) can be used together.

[0020]

The present invention will be described in more detail with reference to the following 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. In addition, in the following examples, what is simply referred to as the degree of polymerization of PVA is the viscosity average degree of polymerization obtained by the usual method from the viscosity of the aqueous solution of PVA, as described above. In the following examples, the value expressed simply as the sizing rate is the fluff at the time of desizing and washing described in “warp thread sizing” (Kaname Fukada, Teruhiko Hitomi, published by The Japan Textile Machinery Society) p299-302. It is the value measured by the method of correcting the dropout part. In the following examples, the value simply expressed as the viscosity is a value measured at a rotor rotation speed of 60 rpm using a B-type viscometer manufactured by Tokyo Keiki.

Example 1 200 kg of commercially available cornstarch was added to 800 g of caustic soda.
Was dissolved in 260 kg of water with stirring and dispersed, and then 30 kg of sodium hypochlorite was gradually added, and the reaction was carried out for 10 hours while maintaining the pH at 10, neutralized, washed with water, dehydrated and dried to obtain oxidized starch. . To this oxidized starch, octenyl succinic anhydride, decenyl succinic anhydride, dodecenyl succinic anhydride, tetradecenyl succinic anhydride, hexadecenyl succinic anhydride,
Octadecenyl succinic anhydride was added to oxidized starch 20k, respectively.
1 kg was added to g, the pH was maintained at 7.5 while stirring, and the mixture was reacted at 40 ° C. for 8 hours, neutralized, washed with water, dehydrated, and dried to obtain various alkenyl succinic acid esterified starches. 10% by weight aqueous solution viscosity of the obtained oxidized starch and various alkenyl succinic acid esterified starch (B-type viscometer, 70 ° C., 30 r
(measured in pm) Table 1 shows.

[0022]

[Table 1]

20 kg of various alkenyl succinic acid esterified starch, PVA having a degree of polymerization of 1700 and a degree of saponification of 88 mol%
60 kg, oxidized starch 20 kg, oil agent (Matsumoto Yushi Co., Ltd.)
Manufactured by Maconol TS-254) 7 kg (alkenyl succinate esterified starch: starch: PVA: oil = 100: 1
(00: 300: 35) was added to 500 liters of water, and the mixture was dissolved by blowing steam under stirring to prepare a paste solution. A slight amount of warm water was added to the obtained paste solution to adjust the concentration of the paste solution to obtain a paste solution having a solid content concentration of 12 to 13%. To measure the size stability of the size solution obtained,
After leaving at 0 to 80 ° C. for 5 hours, almost no phase separation of the liquid was observed. Further, when the glue solution was dried on a polyester film to form a film and observed, the film had a good compatibility and a uniform film. This sizing liquid was used for sizing and weaving under the following conditions. The results are shown in Table 2.

(1) Gluing conditions Raw yarn: 40th cotton single yarn Glue temperature: 90 ° C Drying temperature: 130 ° C Gluing speed: 40 m / min (2) Weaving conditions Loom: Air jet loom manufactured by Tsudakoma Industries Co., Ltd. Item name: (Book / inch): Warp 140 x Weft 75 Weave width:
48-inch loom rotation speed: 650 rpm Air-conditioning condition: 25 ° C., 70% RH (3) Results of sizing The sizing thread was sampled at the time of observing the sizing workability and replacing the winding beam to measure the sizing rate. (4) Weaving test results The amount of dropping of the paste and the cotton wool during weaving was observed, and the number of warp breaks (threads / hour) and the number of weft stops (threads / hour) were evaluated.

[Table 2]

Example 2 In place of the oxidized starch used in Example 1, corn starch or starch acetate (NIC Starch Products Z-10) was used.
0) or grafted starch (Nippon Starch Chemical Co., Ltd. Petrosize L-2B) was used in the same manner as in Example 1, except that
The stability of the sizing liquid, the compatibility of the coating film, and the sizing-weaving test were performed. The results are shown in Table 3.

[Table 3]

Example 3 20 kg of various alkenyl succinic acid esterified starches obtained in Example 1, PV having a degree of polymerization of 1700 and a degree of saponification of 88 mol%
A 70 kg, corn starch 10 kg, acrylic (MARPOSOL TS-189 manufactured by Matsumoto Yushi-Seiyaku Co., Ltd., pure 20
%) 30 kg (6 kg pure), oil agent (Maconol TS-254 manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.) 6 kg (alkenyl succinic acid esterified starch: starch: PVA: acrylic: oil agent = 100: 50: 350: 30: 30) Was poured into 50 liters of water and dissolved by blowing steam under stirring to prepare a paste solution. Adjust the concentration of the paste solution by adding a little warm water to the obtained paste solution to obtain a solid content concentration of 12 to 13%.
It was used as a glue solution. Polyester / cotton = under gluing conditions
The stability of the sizing liquid, the compatibility of the coating, and the sizing-weaving test were conducted in the same manner as in Example 1 except that the 65/65 mixed yarn, 45-stitch single yarn was used. The results are shown in Table 4.

[Table 4]

Example 4 10 kg of various alkenyl succinic acid esterified starches obtained in Example 1, 15 kg of corn starch, and a degree of polymerization of 1300
6 kg of PVA having a saponification degree of 88 mol%, 13 kg of an oil agent (Solvill Wax FF manufactured by Yushiro Chemical Industry Co., Ltd.) (alkenyl succinic acid esterified starch: starch: PVA: oil agent = 1
(00: 150: 60: 130) was added to 1000 liters of water, and the mixture was dissolved by blowing steam under stirring to prepare a paste solution. A slight amount of warm water was added to the obtained paste liquid to adjust the concentration of the paste liquid to obtain a paste liquid having a solid content concentration of 3%. The compatibility of the paste solution and the coating film was good. Under the sizing conditions, a 20th cotton single yarn is used for the pile yarn of a towel, the sizing liquid temperature is 90 ° C., the drying temperature is 110 ° C., and the sizing speed is 70 m / min.
Woven at pm. The sizing workability was good, the pile formation during weaving was good, and the feel was soft.

Comparative Example 1 In the paste composition containing the alkenyl succinic acid esterified starch used in Examples 1 and 2, all the alkenyl succinic acid esterified starches were replaced with oxidized starches, and Examples 1 and 2 were used. Measure the stability of the glue solution in the same manner as
A sizing-weaving test was performed. 90% of paste solution without stirring
When left at 80 ° C. for 5 hours, phase separation of the liquid was observed. In the sizing operation using this sizing solution, yarn breakage occasionally occurred in the divider part of the slasher, and stable operation could not be performed. In addition, warp yarn breakage, which is thought to be caused by yarn breakage during sizing at the time of weaving, frequently occurred, and the number of weft stops also increased as compared with the examples. Phase separation of the coating was also observed. The results are shown in Table 5.

[Table 5]

Comparative Example 2 The procedure of Example 3 was repeated except that the alkenyl succinic acid esterified starch used in Example 3 was replaced with oxidized starch.
The stability of the sizing liquid was measured, and the sizing-weaving test was performed. The paste solution was left for 5 hours at 90 to 80 ° C. without stirring, and phase separation of the solution was observed. In the sizing operation using this sizing solution, yarn breakage occasionally occurred in the slasher no-divide portion, and stable operation was not possible. Also,
Warp breakage, which is thought to be caused by thread breakage at the time of sizing at the time of weaving, frequently occurred, and the number of weft stops also increased as compared with the examples.
Phase separation of the coating was also observed. The results are shown in Table 6.

[Table 6]

Comparative Example 3 The stability of the sizing liquid and the sizing-weaving test were conducted in the same manner as in Example 4 except that all the alkenyl succinic acid esterified starch used in Example 4 was replaced with corn starch. The paste solution was left for 5 hours at 90 to 80 ° C. without stirring, and phase separation of the solution was observed. Phase separation of the coating was also observed. In the weaving of pile yarns using this sizing solution, pile formation was not smooth, and a thing with a triangular shape was also observed and the touch was not good.

[0031]

EFFECT OF THE INVENTION The warp sizing agent of the present invention has a good compatibility with the sizing liquid and does not cause phase separation even if the sizing liquid is stored without stirring or under weak stirring, and stable sizing can be performed for a long time. . Further, a uniform paste coating is formed on the warp surface without phase separation of the coating.
As a result, the sizing yarn can be uniformly applied, the sizing yarn can be provided with good weaving properties, and the sizing workability can be improved, which is extremely high in industrial value.

Claims (4)

[Claims] 1. A warp sizing agent comprising alkenyl succinic acid esterified starch. 2. An alkenyl succinate esterified starch,
With respect to 100 parts by weight of starch, octenyl succinic anhydride,
0.5 to 20 parts by weight of one or more reaction reagents selected from decenyl succinic anhydride, dodecenyl succinic anhydride, tetradecenyl succinic anhydride, hexadecenyl succinic anhydride, octadecenyl succinic anhydride, 70
The warp sizing agent according to claim 1, which has a 10% by weight aqueous solution viscosity at 1000C of 1000 cps or less. 3. Alkenyl succinate esterified starch 10
Polyvinyl alcohol resin 5 to 5 parts by weight
A warp sizing agent containing 100 parts by weight. 4. Alkenyl succinate esterified starch 10
5 parts by weight to 300 parts by weight, polyvinyl alcohol resin 5 to 500 parts by weight, acrylic resin 5 to 0 parts by weight
~ 100 parts by weight and 3 to 150 parts by weight of oil agent, a warp sizing agent.