JPS6312195B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a warp sizing composition capable of sizing at high concentrations and at low temperatures, and a warp sizing method using the composition. 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. (Special Publication No. 41-7904). 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. The warp sizing composition of the present invention comprises a cationized vinyl acetate polymer or a cationized vinyl alcohol polymer (A) and starch or polyvinyl alcohol that begins to dissolve rapidly in water at a temperature of 50°C or higher. (B) and the usage ratio of (A) to (B) is 5:95 or more by weight.
It is within the range of 70:30. Further, in the warp sizing method of the present invention, the above (B) is dispersed in the aqueous solution of the above (A), and the usage ratio of (A) to (B) is 5:95 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 immediately after sizing, the warp threads are subjected to a drying process. In the present invention, starch particles in the size solution or 50
Polyvinyl alcohol particles of the type that rapidly begin to dissolve in water at a certain temperature above ℃ are dispersed as swollen particles and do not dissolve. i.e. particles
Since the gelatinization of (B) is not required, the heating required for preparing the size solution only needs to be below the gelatinization start temperature of (B), and the energy required for preparing the size solution is significantly lower than that of the conventional method. savings can be achieved. Furthermore, since it is sufficient to maintain the temperature of the size solution at a temperature below the gelatinization start temperature of (B) during pasting, less energy is required to maintain the temperature of the size fluid during pasting. Furthermore, in the present invention, since (B) is only dispersed in the size liquid and not dissolved, the thickening effect of (B) on the system is small. Even if the size liquid is used, there will be no problem in the gluing operation. In the present invention, the reduction ratio can be reduced to 30 to 100%, which is about half that of the conventional method. This means that the amount of water that must be evaporated is about half that of the conventional method, which means that the energy required for drying can be halved.
Alternatively, the drying rate, which is the rate-determining step in the gluing process, can be doubled, resulting in advantages such as improved productivity. In the present invention, after pasting, the particles are immediately subjected to a drying process without steam treatment, and in this drying process, a considerable portion of the swollen particles (B) is gelatinized to form a continuous film. In addition, the portions that remain in the form of particles that have not been gelatinized are firmly adhered to the warp by the cationized vinyl acetate polymer or the cationized vinyl alcohol polymer (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 in place of the cationized polymer (A), it would not remain on the warp surface. The degree of fixation of the non-gelatinized portions of the particles is small, and the polymer once permeated into the fibers tends to migrate to the surface during the drying process, so that it cannot exhibit excellent abrasion resistance or conjugation properties. Examples of the cationized vinyl acetate polymer or cationized vinyl alcohol polymer (A) in the present invention include the following. (i) Products whose main component is vinyl acetate, which is copolymerized with nitrogen-containing compounds such as those exemplified below;
Or a copolymer in which part or all of the vinyl acetate component is saponified to convert it into a vinyl alcohol component. Examples of nitrogen-containing compounds include N-acrylamidotrimethylammonium chloride, N-acrylamidoethyltrimethylammonium chloride, N-acrylamidopropyltrimethylammonium chloride, 2-acryloxyethyltrimethylammonium chloride,
-Methacryloxyethyltrimethylammonium chloride, 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride, N-methyldimethylaminoacrylamide, diethylaminoethyl methacrylate, acrylic trimethylammonium chloride, methalyltrimethylammonium chloride, 3-butene ammonium chloride, Examples include dimethylallylamine, dimethylmethacrylamine, dimethyldiallylammonium chloride, diethyldiallylammonium chloride, ethyldiallylamine, and methyldiallylamine. In addition, when copolymerizing vinyl acetate and the above nitrogen-containing compounds, other monomers such as α-olefins having 2 to 30 carbon atoms, acrylic esters, methacrylic esters, vinyl ethers, and vinyl esters other than vinyl acetate may be used. may be present in small amounts. (ii) Polyvinyl alcohol or vinyl alcohol copolymer reacted with a nitrogen-containing compound as exemplified below. Such nitrogen-containing compounds include 3-chloro-
2-hydroxypropyltrimethylammonium chloride, 3-chloroethyltrimethylammonium chloride, 3-chloropropyltrimethylammonium chloride, 3-chloro-2-hydroxyethyltrimethylammonium chloride, 2-chloroethylenediamine,
3-chloro-2-hydroxydimethylamine,
Examples include 2,3-epoxypropyltrimethylammonium chloride and 2-diethylaminoethyl chloride. The content of the nitrogen-containing compound in the above-mentioned cationized polymer (A) is preferably within the range of 0.1 to 30 mol%; if the content is too small, the wear resistance and conjugation properties will be poor; If the ratio is too high, the abrasion resistance and conjugation properties will deteriorate. Next, starch or the former starch in polyvinyl alcohol (B) that starts to dissolve rapidly in water at a temperature of 50°C or higher include wheat starch, corn starch, rice starch, horse starch, amashiyo starch, tapioca starch, Raw starches such as sago starch are used, and among these, corn starch and tapioca starch are particularly important in practical terms. 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. In addition, as for the latter polyvinyl alcohol, which begins to dissolve rapidly in water at a certain temperature of 50°C or higher, when its gelatinization behavior is measured using a Prabender Amylograph at a solid content concentration of 5 to 20%, its temperature vs. viscosity Examples of polyvinyl alcohols include those whose temperature at which the viscosity begins to rise suddenly in the curve, that is, the temperature at which dissolution begins, is 50°C or higher.
It is obtained by subjecting polyvinyl alcohol, copolymerized modified polyvinyl alcohol, or post-modified polyvinyl alcohol having a degree of saponification of 70 mol % or more to heat treatment such as dry heat treatment or moist heat treatment. The ratio of cationic polymer (A) to starch or polyvinyl alcohol (B) is 5:95 to 70:30 by weight.
selected from the range. If the proportion 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 if the proportion of (B) is too small, effective high-density sizing will not be possible. A particularly preferable range is
It is from 15:85 to 60:40. In addition, a swelling agent for starch particles, a water-soluble polymer, various oil agents, auxiliary agents, 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 the starch. Examples of water-soluble polymers include polyvinyl alcohol other than (A) and (B), methylcellulose, carboxymethylcellulose, polyvinylpyrrolidone, acrylamide polymer, polyethylene oxide,
Guar gum, sodium alginate, xanthan gum,
Examples include agar and carrageenan. To prepare the glue, make an aqueous solution of (A), then add (B) to this.
Any method can be used, such as adding particles of (A) and (B) into water, heating it, and dissolving only (A). However, the temperature of the size liquid must be kept lower than the gelatinization start temperature or dissolution start temperature of (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 performed using a regular gluing machine such as the simultaneous 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. The composition and method of the present invention will now be further explained with reference to Examples. In the following glue prescriptions, simply "%"
``%'' indicates "% by weight." The strength and elongation are determined based on the sample length in the autograph.
500mm and a tensile speed of 500mm/mm. In addition, the friction test was performed using a TM type binding force tester with a load of 400g/20
The fibers were rubbed with a book 500 times, and the fuzz condition of the glued yarn before and after the friction was observed and evaluated from grade 1 (good) to grade 5 (bad). Example 1 Sizing and drying of diameter threads were carried out under the following conditions, and further weaving was carried out. Glue recipe Cationized polyvinyl alcohol (A) with a cationic group content of 2.0 mol% obtained by reacting polyvinyl alcohol with a degree of polymerization of 1700 and a degree of saponification of 99 mol% and 3-chloro-2-hydroxypropyltrimethylammonium chloride.
4.5% tapioca starch (gelatinization start temperature 67℃) (B)
12.5% oil agent (Cytecs, manufactured by Goou Kagaku Kogyo Co., Ltd.)
No.315) 1.0% water, remainder Mix each of the above ingredients at 50-60℃. Polyvinyl alcohol (A) is dissolved, but starch (B) is dispersed in a slurry solid content 18.0% Target yarn Polyester/Cotton = 65/35 blended yarn Textile structure = 45S/1 x 45S/1/ 110×60×width 47″×5121
Main 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 Cylinder 120-130℃ Sizing rate 13.7% Drawing rate 76% Weaving conditions Loom TOYODA automatic loom GL-8 Rotation speed 180rpm Machine room conditions 25-30℃, 70-80%RH The results were favorable: sized yarn strength of 296 g, elongation of 8.2%, 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 were the same as in Example 1. Conditions) Weaving conditions Same as Example 1 The results were a sized yarn strength of 291 g, an elongation of 8.0%, a weaving efficiency of 88%, and a wear resistance of grade 4. Control example 2 Cationized polyvinyl alcohol used in glue formulation Example 1 (A) 4.8% tapioca starch (gelatinization start temperature 67°C) (B)
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 13.7
%, and the aperture ratio was set to 152%. As a result, the strength of the sized yarn was 289 g, the elongation was 8.3%, 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 The same glue formulation as in Example 1 was used, except that polyvinyl alcohol with a degree of polymerization of 1700 and a degree of saponification of 87 mol% was used in place of cationized polyvinyl alcohol (A), and each component was mixed at 50 to 60°C. A size solution was prepared in which the polyvinyl alcohol was dissolved but the starch was dispersed in a slurry form, and an experiment was conducted in the same manner as in Example 1. However, the adhesive rate is 14.4%,
The aperture ratio was set to 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 8 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 Cationized polyvinyl alcohol (A) used in Example 1 5.1% Polymerization degree 1400, saponification degree 99.4 mol%, average particle size 20μ, heat-treated polyvinyl alcohol (B) 11.9% oil agent (dissolution start temperature 73°C) (used in Example 1) 1.0% Water Remaining Example 3 Cation group content obtained by saponifying 88 mol% of the vinyl acetate component of vinyl acetate-allyltrimethylammonium chloride copolymer
1.0 mol%, degree of polymerization 1400 cationized polyvinyl alcohol (A) 5.0% tapioca starch (gelatinization start temperature 67°C) (B)
11.0% Hydroxyethyl etherified guar gum
1.0% Oil (used in Example 1) 1.0% Water Remaining Example 4 Cationized polyvinyl alcohol used in Example 3 (A) 7.0% Corn starch (gelatinization start temperature 73°C) (B)
9.5% Malic acid 0.3% Oil agent (TY manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.)
653) 1.0% Water Remaining Example 5 Vinyl acetate-N-acrylamidopropyl-
Cationized polyvinyl alcohol (A) with a cation group content of 7.2 mol% and a degree of polymerization of 1200 obtained by saponifying 82 mol% of the vinyl acetate component of a 3-trimethylammonium chloride copolymer.
5.5% Polymerization degree 600, saponification degree 96 mol%, average particle size
35 μ, heat-treated polyvinyl alcohol (B) with a melting start temperature of 64°C 13.7% Oil agent (used in Example 4) 1.0% Water Remaining Example 6 Vinyl acetate-dimethylallylammonium chloride copolymer (cationic group content 4.1 mol% , polymerization degree 600) (A) 8.2% Esterified starch with a gelatinization start temperature of 60°C (Petrosize A manufactured by Nippon Chemical Co., Ltd.) (B) 11.4% Smoothing oil (used in Example 1) 1.0% Water Remaining Example 7 Cationized polyvinyl alcohol with a cationic group content of 2.0 mol% obtained by saponifying 93 mol% of the vinyl acetate component of vinyl acetate-allyltrimethylammonium chloride-N-acrylamidoethyltrimethylammonium chloride copolymer ( A) 6.5% Heat-treated polyvinyl alcohol with a degree of polymerization of 500, a degree of saponification of 94.0 mol%, an average particle size of 80 μ, and a melting start temperature of 57°C (B) 11.5% Smoothing oil agent (used in Example 4) 1.0% Water Remaining Example 8 Cationized polyvinyl alcohol used in Example 7 (A) 4.5% Modified starch with a gelatinization initiation temperature of 67°C (Corfilm #50 manufactured by Oji Cons Co., Ltd.) (B) 13.0% Oil agent (Matsumoto Yushi Pharmaceutical Co., Ltd.) Sizing Wax _V2 ) 1.0% Water Residual The conditions and results of Examples 2 to 8 above are shown in the following table.

[Table] Example 9 The warp threads were pasted and weaved under the following conditions. Cationized polymer (A) used in paste formulation Example 6 2.5% Carboxymethylated starch with a gelatinization initiation temperature of 55°C (ASTRO manufactured by PENICK & FORD)
GUM3020) (B) 4.5% Softening and smoothing agent (Parallel AB manufactured by Sanyo Chemical Industries, Ltd.) 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.
120d dobby cloth (3540 pieces) glued, dried,
I did some weaving. Gluing conditions Gluing temperature 45℃ Gluing speed 110Yd/min Gluing roll squeezing pressure 2.0Kg/cm ² Gluing machine KSJ-H type manufactured by Tsudakoma Kogyo Co., Ltd. Drying temperature Hot air 120℃ Cylinder 100℃ Sizing rate 4.2% Squeezing rate 58% 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 420g, the elongation was 13.6%, and the conjugation was good. A weaving efficiency of 93% was obtained.

Claims (1)

[Claims] 1 Consisting of a cationized vinyl acetate polymer or a cationized vinyl alcohol polymer (A) and starch or polyvinyl alcohol (B) that begins to dissolve rapidly in water at a temperature of 50°C or higher, and (A)
A warp sizing composition in which the ratio of (B) to (B) is in the range of 5:95 to 70:30 by weight.