JPS641586B2 - - 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.
Generally, a method is used in which sizing is carried out as an aqueous solution with a concentration of 15% or less, but in this method, in order to gelatinize the starch component, the sizing is done using a steam-blown stirring dissolving device or a high-pressure cooker. 95~
The energy (steam) required to cook the paste is 15 minutes to 2 hours at 120℃.
is large. In addition, in the sizing process, the sizing liquid obtained as described above is maintained at 80 to 95°C, and the squeezing rate, that is, sizing amount/sizing liquid concentration x 100 (%), is in the range of 100 to 150%. 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. The present invention fundamentally solves the conventional problems as described above. The gluing composition of the present invention comprises a water-soluble polymer (A) that is soluble in water at a temperature of less than 50°C and a polyvinyl alcohol resin (B) that rapidly begins to dissolve in water at a temperature of 50°C or higher. It becomes more. In addition, the warp sizing method of the present invention includes adding a polyvinyl alcohol resin that rapidly dissolves in water at a temperature of 50°C or higher into an aqueous solution of a water-soluble polymer (A) that is soluble in water at a temperature of lower than 50°C. This method is characterized in that the warp yarns are sized using a sizing liquid in which the particles of (B) are dispersed. In the present invention, the polyvinyl alcohol resin (B) in the size liquid is dispersed as swollen particles and is not dissolved. In other words, since gelatinization of the polyvinyl alcohol resin (B) is not required, the heating required for preparing the size solution is only required to a temperature sufficient to dissolve the water-soluble polymer (A). It requires less energy. Furthermore, since it is sufficient to maintain the temperature of the size liquid during gluing at a temperature below the melting start temperature of the polyvinyl alcohol resin (B), less energy is required to maintain the temperature of the size liquid during gluing. Furthermore, in the present invention, since the polyvinyl alcohol resin (B) is only dispersed in the size liquid and not dissolved, the increase in viscosity of the system due to the polyvinyl alcohol resin (B) is small. Even if the sizing liquid has a high concentration such as % by weight, there will be no problem in the sizing operation. In the present invention, the aperture ratio is 90% or less,
Usually it is 30 to 80%, 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, the particles of the polyvinyl alcohol resin (B) are moderately swollen in the size solution, and in the drying process after pasting, the swollen particles are gelatinized to form a continuous film, which has good weavability and abrasion resistance. , a sizing thread with good conjugation properties can be obtained. The warp sizing composition of the present invention consists of a water-soluble polymer (A) that is soluble in water at a temperature of less than 50°C, and a polyvinyl alcohol resin (B) that begins to rapidly dissolve in water at a temperature of 50°C or higher. Consists of each component. As the water-soluble polymer (A), any of natural polymers, modified products thereof, and synthetic polymers can be used as long as they are soluble in water at a temperature of less than 50°C. Examples of such polymers include polyvinyl alcohol resin, polyacrylamide, acrylamide-sodium acrylate copolymer, polyacrylic acid or its salt, acrylic ester-acrylate copolymer, polyvinylpyrrolidone, polyethylene oxide, and methyl cellulose. , carboxymethyl cellulose, modified starch, modified starch, dextrin, pullulan, glue, gelatin, casein, albumin, gum arabic, gum tragacanth, fleur-de-lis, agar, konjac mannan, alginate, carrageenan, xanthan gum, guar gum, etc. Among these, polyvinyl alcohol resin is preferable for the purpose of warp sizing of the present invention, and
In addition to saponified polyvinyl acetate (polyvinyl alcohol) with any degree of polymerization and saponification within the range of water solubility at temperatures below, especially polyvinyl alcohol with a degree of polymerization of 200 to 3000 and a degree of saponification of 65 to 93 mol%,
Mainly vinyl acetate, this and other comonomers,
For example, unsaturated carboxylic acids or their salts, partial or complete esters, anhydrides, nitriles, amides, unsaturated carboxylic acids or their salts, α-olefins with 2 to 30 carbon acids, vinyl ethers, vinyl esters other than vinyl acetate, vinyl chloride. Saponified products of copolymers (copolymerized modified polyvinyl alcohol) and polyvinyl alcohol or copolymerized modified polyvinyl alcohol that is urethanized, etherified, esterified, acetalized, or grafted (post-modified polyvinyl alcohol) are also used. Furthermore, among these, unsaturated monocarboxylic acids or their salts such as acrylic acid, methacrylic acid, and crotonic acid, unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, or their salts, partial esters, anhydrides,
0.02 to 15 mol%, especially 0.05 to 10 mol% of unsaturated sulfonic acids or salts thereof such as ethylene sulfonic acid, allyl sulfonic acid, metaallylsulfonic acid, etc.
Copolymerized and the degree of saponification of vinyl acetate component is 50~
Particularly preferred is unsaturated acid-modified polyvinyl alcohol containing 100 mol%. Polyvinyl alcohol resin (B), which begins to rapidly dissolve in water at a temperature of 50℃ or higher, generally dissolves when its gelatinization behavior is measured using a Brabender amylograph at a solid content concentration of 5 to 20%. , the temperature at which the viscosity begins to rise suddenly in the temperature-viscosity curve, that is, the melting start temperature, is 50°C or higher. Polyvinyl alcohol resin (B) exhibiting such properties can be obtained by, for example, polyvinyl alcohol with a degree of polymerization of 200 to 3000 and a degree of saponification of 70 mol% or more, or copolymerized modified polyvinyl alcohol, or post-modified polyvinyl alcohol, which is subjected to dry heat treatment, moist heat treatment, etc. It is obtained by heat treatment. Although the particle size of the polyvinyl alcohol resin (B) is not particularly limited, it is generally preferable to use a fine powder, for example, a particle size of 10 to 100 μm is used. It is particularly desirable that the mixing ratio of the water-soluble polymer (A) and the polyvinyl alcohol resin (B) be selected from a range of 10:90 to 50:50 by weight. (A)
If the proportion of (B) is too small, the abrasion resistance of the sizing yarn during weaving will be impaired, leading to a decrease in weaving efficiency, while if the proportion of (B) is too small, an effective high-concentration sizing composition cannot be obtained. Because there is. Water-soluble polymer (A) and polyvinyl alcohol resin
(B) can be prepared by adding a mixed powder of powders (A) and (B) to water and heating and stirring to dissolve only (A); A method such as mixing powder of (B) into an aqueous solution of (B) is adopted. Various oils, auxiliary agents, and other known additives can be appropriately blended into the size liquid, if necessary. The solid content concentration in the size liquid can be 5 to 30% by weight, and within this range, a range of 10 to 30% by weight, and more preferably 15 to 30% by weight, is particularly preferable. One of the features of the present invention is that it can be done. If the solid content concentration is less than 5% by weight, the concentration will be low and it will be difficult to control the amount of adhesive, while if it exceeds 30% by weight, it will adhere to the surface and deteriorate the adhesive properties. The sizing liquid is kept at about 30° C. or higher and below the melting temperature of the polyvinyl alcohol resin (B), and the sizing operation is performed. That is, in the paste liquid, the water-soluble polymer (A) is dissolved to form a solution, but the particles of the polyvinyl alcohol resin (B) are dispersed in this solution. The drying temperature after gluing is selected to be 80 to 160℃, but in order to instantly dissolve the particles of polyvinyl alcohol resin (B) and form a film, it is best to use a temperature as high as possible, especially a temperature of 100℃ or higher. It is desirable that 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.
Measured at 500 mm and tensile speed of 500 mm/min. In addition, the friction test is a TM type binding force test 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 The warp yarns were sized and dried under the following conditions, and further weaving was performed. Glue recipe Water-soluble polyvinyl alcohol (A) 5.1% with degree of polymerization 1700, degree of saponification 87 mol%, degree of polymerization 1400, degree of saponification 99.4 mol%, average particle size
20 μ, heat-treated polyvinyl alcohol (B) with a melting start temperature of 73°C 11.9% Smoothing oil (Cytecs No. 315 manufactured by Gooh Kagaku Kogyo Co., Ltd.) 1.0% Water Remaining Add the powder of (A) to cold water and stir until 50°C. Raise the temperature to dissolve, then add (B) and oil and stir for 50 to 60 minutes.
It was kept at ℃. (A) is dissolved, but (B) is dispersed in a slurry form, and the resin content in the size solution is 17.0%. Target yarn Polyester/cotton = 65/35 blended yarn Textile structure = 45'S x 45'S/110 x 60 x Width 47'' x 5121 strands Sizing conditions Sizing temperature 50-55℃ Sizing speed 100 Yd/min Sizing roll Squeezing pressure 1.0-1.2Kg/cm ² Gluing machine Sucker 11C (Multi
Cylinder) type Drying temperature Cylinder 120℃~130℃ Sizing rate 13.5% Squeezing rate 75% Weaving conditions Loom TOYODA automatic loom GL-8 Rotation speed 180rpm Loom room conditions 25~30℃, 70~80%RH The result is glue Yarn strength 298g, elongation 8.3%, weaving rate
The abrasion resistance was 91%, and the wear resistance was 2nd grade by 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 formulation Polyvinyl alcohol (A) used in Example 1
4.8% Cornstarch 3.7% Oil agent (Solvil Wax SX-135A manufactured by Yushiro Chemical Co., Ltd.) 0.5% Water Remaining The above ingredients were heated and mixed at 90 to 95℃ for 2 hours to prepare a uniform paste solution, and mixed with hot water. Diluted to 9.0% solids
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% (Glue roll squeezing pressure, sizing machine, and drying temperature are the same as in Example 1.
Same conditions as in Example 1) Weaving conditions Same as Example 1 The results were: glue strength 291g, elongation 8.0%, weaving efficiency
The wear resistance was 88%, grade 4. Control example 2 Glue formulation Polyvinyl alcohol (A) used in Example 1
3.0% Polyvinyl alcohol (B) used in Example 1
7.0% Smoothing oil (used in Control Example 1) 0.5% Water Remaining The above ingredients were heated and mixed at 80-90℃ for 1.5 hours to prepare a uniform paste solution, and diluted with hot water to obtain a resin content of 10%. %
I made it so that 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 13.6
%, the efficacy rate was set at 130%. As a result, the strength of the sized yarn was 297 g, the elongation was 8.3%, the weaving efficiency was 90%, and the abrasion resistance was grade 3-4. Comparing Example 1 and Comparative Examples 1 and 2, apart from the sizing yarn physical properties and weavability, there are differences in required energy as shown in the following table.

[Table] That is, according to Example 1, compared to Control Examples 2 and 3, energy such as steam during size solution preparation, size solution temperature maintenance, and drying was greatly saved, and productivity was also greatly improved. I know that I can improve. 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 Sodium allylsulfonate modified polyvinyl alcohol (A) with a degree of polymerization of 600 obtained by saponifying 80 mol% of the vinyl acetate component of a sodium allylsulfonate vinyl acetate copolymer with a sodium allylsulfonate content of 0.8% 9.0 % Polyvinyl alcohol (B) used in Example 1
11.0% Smoothing oil (Sizing Wax V ₂ manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.) 1.0% Water Remaining Example 3 92 mol% of the vinyl acetate component of a monomethyl maleate-vinyl acetate copolymer with a monomethyl maleate content of 2.0 mol% Monomethyl maleate-modified polyvinyl alcohol (A) with a polymerization degree of 1700 obtained by saponifying 4.8% Polymerization degree 600, saponification degree 96 mol%, average particle size
35μ, heat-treated polyvinyl alcohol (B) with a melting start temperature of 64℃ 13.7% smoothing oil (manufactured by Kyoeisha Yushigaku Kogyo Co., Ltd.)
TY-653) 1.0% Water Remaining Example 4 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 fumaric acid content of 1.2 mol% ( A) 6.2% Polyvinyl alcohol (B) used in Example 3
13.3% Smoothing oil (used in Example 3) 1.0% Water Remaining Example 5 Obtained by saponifying 95 mol% of the vinyl acetate component of an acrylic acid-vinyl acetate copolymer with an acrylic acid content of 1.5 mol%. Acrylic acid-modified polyvinyl alcohol (A) 6.5% with a polymerization degree of 1100, polymerization degree of 500, saponification degree of 94.0 mol%, average particle size
80 μ, heat-treated polyvinyl alcohol (B) with a melting start temperature of 57°C 11.5% Smoothing oil (used in Example 2) 1.0% Water Remaining Example 6 Carboxymethylated starch (EMSIZE CMS manufactured by West German Emsland) (A ) 5.0% Polyvinyl alcohol (B) used in Example 1
12.0% Smoothing oil (used in Example 1) 1.0% Water Remaining Example 7 Carboxymethyl cellulose (Celogen 7A manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (A) 4.5% Polyvinyl alcohol used in Example 3 (B)
20.5% Smoothing oil (used in Example 1) 1.5% Water Residual The results of Examples 2 to 7 are shown in the following table.

[Table] Example 8 The warp threads were pasted and weaved under the following conditions. Glue formulation Soluble acetated starch (Tsuyanorin manufactured by Saiden Chemical Industry Co., Ltd.) (A) 3.5% Polyvinyl alcohol used in Example 5 (B)
3.5% 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 using this glue
120d dobby cloth (3540 pieces) glued, dried,
I did some weaving. Gluing conditions Gluing temperature 45℃ Gluing speed 120 Yd/min Gluing roll squeezing pressure 2.0 Kg/cm ² Gluing machine Tsudakoma Kogyo Co., Ltd. KSJ-H type Drying temperature Hot air 110℃ Cylinder 100℃ Sizing rate 3.9% Squeezing rate 53% Weaving conditions loom TOYODA automatic loom GFD3 (dobby type) rotation speed 160rpm loom room conditions 25~30℃, 65~75%RH The results showed that the sized yarn strength was 422g, the elongation was 14.5%, and the conjugation was good. A weaving efficiency of 92% was obtained.

Claims (1)

[Claims] 1. Water-soluble polymer (A) soluble in water at a temperature of less than 50°C
Polyvinyl alcohol resin particles that rapidly begin to dissolve in water at a temperature of 50°C or higher in an aqueous solution of
A warp sizing composition comprising (B) dispersed in a ratio of (A) to (B) of 10:90 to 50:50 by weight. 2. The composition according to claim 1, wherein (A) is a polyvinyl alcohol resin soluble in water at a temperature of less than 50°C. 3. The composition according to claim 1, wherein (A) is a modified polyvinyl alcohol copolymerized with 0.1 to 10 mol% of a comonomer having a carboxyl group or a sulfonic acid group. 4. The composition according to claim 1, wherein (B) is a polyvinyl alcohol resin of a type that begins to dissolve rapidly in water at a certain temperature in the range of 50 to 80°C.