JPS6261705B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a warp sizing method that allows sizing at high concentrations and at low temperatures. Conventional warp sizing methods include, for example, in the case of spun yarn, starch, polyvinyl alcohol, acrylic sizing agents, smoothing oils, etc. are mixed in appropriate proportions.
A method is used in which starch is applied as an aqueous solution with a concentration of about 5 to 12%, but in this method, in order to gelatinize the starch component, a steam-blown stirring dissolving device or a high-pressure cooker is used to cook the starch. Temperature 90~
The energy (steam) required to cook the glue is that it must be done at 120℃ for about 15 minutes to 3 hours.
is large. In the sizing process, the sizing liquid obtained as described above is kept at 80 to 95°C, and the squeezing rate, i.e., sizing amount/sizing liquid concentration x 100 (%), is in the range of 100 to 200%. Normally, it is disadvantageous in terms of energy to maintain the temperature of the size liquid at such a relatively high temperature, and a high squeezing ratio means that the amount of water that must be evaporated during the drying process is also large, which also causes an energy disadvantage. It is disadvantageous. However, in an attempt to overcome these problems,
A method has been proposed in which starch is dispersed in a size liquid at a temperature below its gelatinization temperature, the warp threads are sized using this size liquid, the starch is gelatinized by contact with steam, and then dried. (Japanese Patent Publication No. 7904/1983), it is said that polyvinyl alcohol may be used in this method.
However, since this method also requires steam treatment after pasting, it is industrially disadvantageous in terms of energy and equipment costs, as well as the fact that the area occupied by the equipment becomes large. The present invention fundamentally solves the above problems. In the warp sizing method of the present invention, starch (B) is dispersed in an aqueous solution of modified polyvinyl alcohol (A) copolymerized with 0.02 to 15 mol% of a comonomer having a carboxyl group or a sulfonic acid group. , and the usage ratio of (A) to (B) is 10:90 to 70:30 by weight.
The warp yarns are sized using a sizing solution with a solid content concentration of 3 to 40% by weight within the range of 3 to 40% by weight, and the warp threads are immediately subjected to a drying process after sizing. In the present invention, starch in the size liquid is dispersed as swollen particles and is not dissolved. In other words, since there is no need to gelatinize the starch, the heating required to prepare the size solution only needs to be below the gelatinization starting temperature of the starch, and the energy required for the size solution preparation is significantly reduced compared to the conventional method. can. Furthermore, since it is sufficient to maintain the temperature of the size solution at the time of sizing at a temperature below the gelatinization start temperature of starch, less energy is required to maintain the temperature of the size solution during sizing. Furthermore, in the present invention, since the starch is only dispersed in the size liquid and not dissolved, the thickening effect of the starch on the system is small, and therefore it is difficult to use a high concentration liquid such as 13 to 40% by weight. However, there is no problem in gluing operation. In the present invention, the aperture ratio is 30 to 100%.
This can be reduced to about half that of the conventional method. This means that when applying the same amount as the conventional method, the amount of water that must be evaporated is about half, which means that the energy required for drying can be halved, or the drying speed, which is the rate-limiting step in the gluing process, can be doubled. This has the advantage of improving productivity. In the present invention, after sizing, the starch is immediately subjected to a drying process without steam treatment, and in this drying process, a considerable portion of the swollen starch particles is gelatinized to form a continuous film. In addition, the particulate portions that have not yet become gelatinized are firmly adhered to the warp threads by the modified polyvinyl alcohol (A) and do not fall off. The sized yarn thus obtained exhibits excellent abrasion resistance and binding properties, and in this case, if ordinary polyvinyl alcohol was used instead of modified polyvinyl alcohol (A), particles remaining on the surface of the warp yarns would be removed. The degree of adhesion of the ungelatinized portion is small, and it cannot exhibit excellent abrasion resistance or conjugation. As the modified polyvinyl alcohol (A) in the present invention, polyvinyl alcohol modified with a comonomer having a carboxyl group or a sulfonic acid group is used. Such comonomers include unsaturated monocarboxylic acids or their salts such as acrylic acid, methacrylic acid, and crotonic acid, unsaturated polycarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, or their salts, partial esters, and anhydrides; Examples include unsaturated sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid, meta-allylsulfonic acid, and salts thereof. The copolymerization ratio of the above comonomers is 0.02 to 15
mol%, especially from the range of 0.05 to 10 mol%; if the proportion is too small, the wear resistance and conjugation properties will be insufficient, while if the proportion is too high, the abrasion resistance and conjugation properties will be deteriorated. Become. Modified polyvinyl alcohol (A) is obtained by saponifying the vinyl acetate component of a copolymer of the above comonomer and vinyl acetate, and the degree of saponification of the vinyl acetate component is not particularly limited, but is 80 mol%.
Above all, it is preferable that the content is 85 mol% or more, and as the degree of saponification decreases, there is a tendency for the wear resistance of the sized yarn to decrease. As starch (B), raw starches such as wheat starch, corn starch, rice starch, horse starch, amashiyo starch, tapioca starch, and sago coconut starch are used, and among these, corn starch and tapioca starch are particularly useful for practical purposes. is important. Low-modified starches with a gelatinization initiation temperature of 50°C or higher are also used, and examples of such modified starches include acetate esterified starch, acid-treated starch, carboxymethyl etherified starch, and hydroxyethyl etherified starch. It will be done. The ratio of modified polyvinyl alcohol (A) to starch (B) used is selected within the range of 10:90 to 70:30 by weight. If the ratio of (A) is too small, the abrasion resistance of the sized yarn during weaving will be impaired, leading to a decrease in weaving efficiency, while (B)
If the ratio is too small, effective high-density gluing cannot be achieved. A particularly preferred range is 20:80 to 60:40. In addition, swelling fractions of starch particles, water-soluble polymers, various oils, auxiliaries, etc. can be added to the size liquid. Among these, the swelling agents for starch particles include acids such as acetic acid, lactic acid, malic acid, citric acid, tartaric acid, succinic acid, adipic acid, acrylic acid, and fumaric acid, or their salts, soda carbonate, ammonia, tribasic sodium phosphate, etc. The amount added is usually 0.1 to 10% by weight based on starch (B). Water-soluble polymers include ordinary unmodified polyvinyl alcohol, copolymerized modified polyvinyl alcohol other than (A), post-modified polyvinyl alcohol,
Examples include methylcellulose, carboxymethylcellulose, polyvinylpyrrolidone, acrylamide polymers, polyethylene oxide, guar gum, sodium alginate, xanthan gum, agar, and carrageenan. The size solution can be prepared by making an aqueous solution of modified polyvinyl alcohol (A) and then adding starch (B) to it, or by pouring (A) and (B) into water and heating it. Any method can be used, such as a method of dissolving. However, the temperature of the size liquid must be kept lower than the gelatinization initiation temperature of starch (B). The solid content concentration in the size liquid is 3% by weight or more, usually 3% by weight or more.
Set to ~40% by weight. If it is less than 3% by weight, the viscosity will be low and it will be difficult to control the amount of glue, while if it exceeds 40% by weight, it will stick to the surface and reduce the gluing properties. Within the range of 3 to 40% by weight, the features of the present invention are more effectively utilized at higher concentrations such as 13 to 40% by weight. Gluing is carried out using a regular gluing machine such as the one-size sizing method or the warping sizer method. After pasting, it is immediately subjected to a drying process. Drying temperature is 80~
The temperature is preferably 160°C, particularly 100-150°C. The drying method may be either hot air drying or cylinder drying. Both spun yarn and filament yarn are used as target raw yarn. Next, the method of the present invention will be further explained with reference to Examples. The gelatinization start temperature is 10% by weight for unmodified starch using Brabender amylograph.
In the case of modified starch, it refers to the temperature at which the temperature-viscosity curve begins to rise when gelatinization behavior is measured at a solid content concentration of 15% by weight. Example 1 The warp yarns were sized and dried under the following conditions, and further weaving was performed. Glue formulation Modified polyvinyl alcohol with a degree of polymerization of 1700 obtained by saponifying 92 mol% of the vinyl acetate component of a monomethyl maleate-vinyl acetate copolymer with a monomethyl maleate content of 2.0 mol% 5.1% tapioca starch (gelatinization start temperature 67℃) 11.9% Oil agent (Cytecs No. manufactured by Gooh Chemical Industry Co., Ltd.)
315) 1.0% water remaining Mix the above ingredients at 50-60℃. The modified polyvinyl alcohol is dissolved, but the starch is dispersed in a slurry form. Solid content 18.0% Target yarn Polyentel/cotton = 65/35 blended yarn Textile structure = 45 ¹ S x 45 ¹ S/110 x 60 x Width 47
¹¹ x 5121 sticks Gluing conditions Gluing temperature 50~55℃ Gluing speed 100 Yd/min Gluing roll squeezing pressure 1.0~1.2 Kg/cm ² Gluing machine
Sucker 11C (multi-cylinder) type drying temperature Hot air 100℃ Cylinder 120℃ Sizing rate 13.5% Drawing rate 75% Weaving conditions Loom TOYODA automatic loom GL-8 Rotation speed 180rpm Loom room conditions 25-30℃, 70-80% The RH results were favorable, with a sized yarn strength of 295 g, elongation of 8.4%, weaving efficiency of 94%, and wear resistance of class 2 according to the TM type conjugation degree tester. Comparative Example 1 The warp threads were pasted and dried under the following conditions, and further weaving was performed. This control example is an example of a typical conventional polyvinyl alcohol/starch formulation. Glue recipe Polyvinyl alcohol with a polymerization degree of 1700 and a saponification degree of 87 mol% 4.8% Corn starch (gelatinization start temperature 73°C) 3.7% Oil agent (Solvil, manufactured by Yushiro Chemical Co., Ltd.)
Watkusu SX-135A) 0.5% water remaining Heat mix the above ingredients at 90-95℃ for 2 hours to prepare a uniform paste solution, dilute with hot water to obtain a solid content of 9.0%
I made it so that Target yarn Same sizing conditions as Example 1 Sizing temperature 90-95℃ Sizing speed 50 Yd/min Sizing rate 14.1% Squeezing rate 157% (Sizing roll squeezing pressure, sizing machine, and drying temperature are the same as Example 1) Conditions) Weaving conditions Same as Example 1 Results: Sized yarn strength 291g, elongation 8.0, weaving efficiency
The wear resistance was 88%, grade 4. Target example 2 Modified polyvinyl alcohol used in glue formulation example 1
4.8% tapioca starch (gelatinization start temperature 67℃)
3.7% Oil (used in Example 1) 0.7% Water Remaining The above ingredients were heated and mixed at 80 to 90°C for 1.5 hours to prepare a uniform paste solution, and diluted with hot water to give a solid content of 9.0.
%. Sizing, drying, and weaving were carried out in the same manner as in Control Example 1, except that the above-mentioned glue formulation was used. However, the glue rate is 13.4
%, and the aperture ratio was set to 149%. As a result, the strength of the sized yarn was 288 g, the elongation was 8.4%, the weaving efficiency was 90%, and the abrasion resistance was grade 3. Comparing Example 1 and Comparative Examples 1 and 2, apart from the sizing yarn physical properties and weavability, there are differences in the required energy as shown in the following table.

[Table] In other words, compared to Control Examples 1 and 2, Example 1 can significantly save energy such as steam during size solution preparation, size solution temperature maintenance, and drying, and can also greatly improve productivity. I understand. Control example 3 Polymerization degree instead of modified polyvinyl alcohol
The glue formulation was the same as in Example 1 except that polyvinyl alcohol 1700 and saponification degree of 87 mol% was used, and each component was mixed at 50 to 60°C so that the polyvinyl alcohol was dissolved, but the starch was in the form of a slurry. A paste solution in which the liquid was dispersed was prepared, and an experiment was conducted in the same manner as in Example 1. However, the adhesive rate was 14.4% and the squeezing rate was 80%. The results were a sized yarn strength of 279g, elongation of 7.9%, and weaving efficiency.
90%, wear resistance was 3rd to 4th grade, which was inferior to Example 1. Examples 2 to 7 Polyester/cotton blend yarns were sized in the same manner as in Example 1 using the following sizing formulations, and then subjected to weaving. Example 2 Itaconic acid-modified polyvinyl alcohol with a degree of polymerization of 1400 obtained by saponifying 96 mol% of the vinyl acetate component of an itaconic acid-vinyl acetate copolymer with an itaconic acid content of 3.2 mol% 7.5% corn starch (gelatinization start temperature 73℃) 10.0% Malic acid 0.3% Oil agent (TY manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.)
653) 1.0% Water Remaining Example 3 Monomethyl maleate-modified polyvinyl alcohol used in Example 1 5.1% Tapioca starch (gelatinization start temperature 67°C)
11.0% Hydroxyethyl etherified guar gum
0.9% oil agent (used in Example 1) 1.0% water Remaining Example 4 82 mol% of the vinyl acetate component of a sodium allylsulfonate-vinyl acetate copolymer with a sodium allylsulfonate content of 0.8 mol% was saponified. Obtained sodium allylsulfonate modified polyvinyl alcohol with a degree of polymerization of 600 10.0% tapioca starch (gelatinization start temperature 67°C)
10.0% Lactic acid 02% Oil agent (Sizing Wax V ₂ manufactured by Matsumoto Yushi Co., Ltd.) 1.0% Water Remaining Example 5 94 mol of vinyl acetate component of monomethyl maleate-vinyl acetate copolymer with monomethyl maleate content of 2.5 mol% % monomethyl maleate-modified polyvinyl alcohol with a degree of polymerization of 1500 obtained by saponifying 6.3% Corn starch (gelatinization start temperature 73°C) 11.7% Oil agent (used in Example 2) 0.9% Water Remaining Example 6 Fumaric acid Fumaric acid-modified polyvinyl alcohol with a degree of polymerization of 1400 obtained by saponifying 94 mol% of the vinyl acetate component of a fumaric acid-vinyl acetate copolymer with a content of 1.2 mol% 3.5% Modified starch with a gelatinization initiation temperature of 67°C (Oji) Cofilm #50 manufactured by Cons Co., Ltd. 13.0% Soda ash 0.3% Oil agent (used in Example 2) 1.0% Water Remaining Example 7 Vinyl acetate component of acrylic acid-vinyl acetate copolymer with acrylic acid content of 1.5 mol% Acrylic acid-modified polyvinyl alcohol with a degree of polymerization of 1100 obtained by saponifying 95 mol% of (used in Example 2) 1.0% water remainder The conditions and results of Examples 2 to 7 above are shown in the table below.

[Table] Example 8 The warp threads were pasted and weaved under the following conditions. Modified polyvinyl alcohol used in glue formulation Example 4
2.5% Acid-treated starch with a gelatinization start temperature of 53°C (N-100 manufactured by Nippon Star Chemical Co., Ltd.) 4.5% Softening and smoothing agent (Parallel manufactured by Sanyo Chemical Industries, Ltd.)
AB) 0.3% water remaining Mix the above ingredients and heat at 50℃ for 1 hour.
Only component (A) was dissolved to give a solid content of 7.3%. Rayon filament is made using this glue.
Glued, dried, and weaved 120d dobby cloth (3540 pieces). Gluing conditions Gluing temperature 45℃ Gluing speed 110 Yd/min Gluing roll squeezing pressure 2.0 Kg/cm ² Gluing machine KSJ-H type manufactured by Tsudakoma Kogyo Co., Ltd. Drying temperature Hot air 110℃ Cylinder 100℃ Sizing rate 4.1% Squeezing rate 56% Weaving conditions Loom TOYODA automatic loom GFD ₃ (dobby type) Rotation speed 160rpm Loom room conditions 25~30℃, 65~75%RH The results showed that the sized yarn strength was 411g, the elongation was 14.9%, and the conjugation was good. A weaving efficiency of 93% was obtained.

Claims (1)

[Scope of Claims] 1 Starch (B) is dispersed in an aqueous solution of modified polyvinyl alcohol (A) copolymerized with 0.02 to 15 mol% of a comonomer having a carboxyl group or a sulfonic acid group, and ( Solid content concentration 3 where the usage ratio of A) to (B) is within the range of 10:90 to 70:30 by weight
A method for sizing warp yarns, which comprises sizing the warp yarns using a sizing solution of up to 40% by weight, and immediately subjecting the warp yarns to a drying process after sizing. 2. The method according to claim 1, wherein the solid content concentration of the size liquid is 13 to 40% by weight. 3. The method according to claim 1, wherein the degree of saponification of (A) is 85 mol% or more. 4. Starch (B) is dispersed in an aqueous solution of modified polyvinyl alcohol (A) copolymerized with 0.02 to 15 mol% of a comonomer having a carboxyl group or sulfonic acid group, and a swelling agent for the starch particles is present. condition and the usage ratio of (A) to (B) is by weight.
Solid content concentration 3-40 within the range of 10:90-70:30
A method for sizing warp yarns, characterized in that the warp yarns are sized using a sizing solution of % by weight, and immediately subjected to a drying process after sizing.