KR920009254B1 - Polyvinyl alcohol based wax-free size composition - Google Patents

Abstract

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Description

[Name of invention]

Wax-Free Arc Composition Based on Polyvinyl Alcohol

Detailed description of the invention

TECHNICAL FIELD This invention relates to a lake composition, and more specifically, to a lake composition containing polyvinyl alcohol containing a low-ethylene oxide adduct additive.

The spun warp must be fed with a water soluble polymer that provides a protective surface coating on it, which is a required process during weaving the yarn into a fabric. Raw fabrics produced after weaving must be stripped of protective coatings by plunging before various processing operations and in particular during the dyeing step. Pastes based on polyvinylalcohol or a combination of polyvinylalcohol and starch are usually used with wax additives present in the formulation to minimize adhesion on the dryer drum in the slasher during application of the paste. These wax additives are difficult to remove from the raw fabric during the extraction process with certain solvents and during the degassing process requiring the higher temperature of the degassing bath. As a result, the processing plant is faced with higher production costs, higher energy costs and higher rates of second-order raw fabrics due to increased process complexity.

The use of a polyvinyl alcohol-based appeal solution containing small amounts of quaternary ammonium salts or quaternary amidazolinium salts was disclosed in US Pat. No. 4,383,063, which additives provide excellent workability and processing performance in the absence of wax. It allows us to produce this improved fabric. However, such formulations have serious drawbacks that frequently indicate the non-regeneration of grass feeding operations, which is due to the irregular and unexpected removal of cationic additives by interaction with anionic contaminants that tend to accumulate in the solution. It is. The main source of these anionic contaminants is the spinning chamber where the grass is fed.

The addition of very small amounts (up to 0.05% by weight, based on polyvinyl alcohol) as a defoaming agent to the low-ethoxylate adducts of linear alcohols in pools based on polyvinyl alcohol is disclosed in US Pat. No. 4,251,403; However, such materials have been found to be ineffective as wax substitutes and are therefore not used as wax substitutes in warp lamination compositions that do not use wax.

According to the present invention there is provided a composition consisting essentially of the following (a)-(f).

(a) is selected from polyvinyl alcohol, vinyl alcohol / methyl methacrylate copolymer, and polyvinyl alcohol containing dissolved comonomers other than methyl methacrylate with a saponification value of about 1-160 and a 4% solution viscosity of 20 ° C. About 45.5-99.9% by weight of a vinyl alcohol polymer having about 3-7 mpa · s; (b) a liquid nonionic low-ethylene oxide adduct of a mixed side chain alcohol or branched chain alcohol, wherein the average content of ethylene oxide is about 1-7 units and the average carbon content of the alcohol is about 8-18 (carbon atoms). 3 wt%; (c) 0-49.9% by weight starch; (d) 0- about 5 weight percent of an ethylene oxide oligomer having a (number average) molecular weight of about 200-800; (e) low ethylene oxide adducts (average content of ethylene oxide: 0- about 49.9% by weight of carboxymethyl cellulose and (f) linear alcohols or linear alcohol mixtures (average carbon content: about 8-18 units) At least one selected from the group consisting of medium to high ethylene oxide adducts (average content of ethylene oxide: about 8-40 units) of linear or branched alcohols (average carbon content: about 8-18 units); 0-about 1% by weight of an auxiliary ethylene oxide adduct of the star, provided that the sum of the weights of starch and carboxymethyl cellulose should not exceed the weight of the vinylalcohol polymer.

Furthermore, according to the present invention, a wax-free aqueous binder solution composed of a composition of the present invention having a solid content of 2-20% by weight, a concentrate of a low-ethylene oxide admixture mixed with a vinylalcohol polymer, a wax-free aqueous A method of feeding grass to filament yarns using a solution and a yarn fed yarn consisting of a spinning chamber having a wax-free protective surface coating of the composition of the present invention is provided.

Essentially, as used herein. The term “consisting of” refers to the fact that the named ingredients are essential, but other ingredients may be included that do not prevent the benefits of the present invention from being implemented.

When the liquid, non-ionic and low-ethylene oxide adducts of the side chain alcohol are added in an amount of 3% or less to the auxiliary composition based on the vinyl alcohol polymer, the glued thread does not adhere to the drying vessel in the slasher. It has been found that a loose, unwrapped raw fabric is produced, which provides good weaving efficiency and can be easily removed under mild pull conditions, resulting in good dye solubility.

It is recommended that the inventive compositions of the present invention be used in conventional grass feed, heat setting and aqueous grass extraction operations currently used in spinning room textile mills.

For the purposes of the topical composition according to the invention, the vinylalcohol polymer may have a saponification value of about 1-160 (mg of KOH to neutralize 1 g of polymer) and a 4% solution viscosity of about 30-70 mpa.s.

Examples of suitable vinyl alcohol polymers include the following:

(a) Fully hydrolyzed vinyl alcohol / methyl methacrylate copolymer (about 3.5-6 mole percent methyl methacrylate) having a viscosity of about 3-60 mpa.s (measured at 20 ° C. using 4% aqueous solution) contain). Such copolymers can be prepared by the alcoholic decomposition of vinyl acetate / methyl methacrylate copolymers; (b) partially hydrolyzed polyvinyl alcohol containing about 4-12 mole percent vinyl acetate, having a viscosity of about 3-60 mpa · s; (c) fully hydrolyzed polyvinyl alcohol having a viscosity of about 3-70 mpa · s; (d) polyvinyl alcohols containing “dissolving comonomers” such as methyl acrylate and methyl hydrogen maleate other than methyl methacrylate; (e) Various mixtures of the vinyl alcohol polymers.

Nonionic additives of the present invention are low-ethylene oxide adducts (average content of ethylene oxide: about 1-7 units) of branched alcohols or branched alcohol mixtures (average carbon content: about 8-18 units). Preferred constituents of the additive are side chain alcohols containing on average about 10-15 carbon atoms and adducts containing about 2-5 units of ethylene oxide. Most preferred are additives consisting of branched alcohols containing on average about 13 carbon atoms and on average about 3 units of ethylene oxide. The product “Tergitol” 15-S-3 produced by Union Carbide is this most preferred additive.

The amount of vinyl alcohol polymer in the composition according to the invention is about 45.5-99.9% by weight. The preferred range is about 63-99.8% and the most preferred range is about 72.7-99.6%. In a typical polyvinylalcohol-based adjuvant formulation, the higher the polyvinylalcohol content of the grass, the higher the weaving efficiency exhibited by the grass fed yarn. In general, the required amount of pooling is gradually reduced as the polyvinyl alcohol content of the pool is increased.

The amount of nonionic additives according to the invention is about 0.1-3% by weight. About 0.1% by weight of additives are needed to allow for significant separation from the dryer drum, while additives above about 3% by weight can result in reduced weaving efficiency. The preferred range of additives is about 0.2-1.5% by weight, with this amount most of the advantages of the present invention can be achieved. The most preferred concentration range of the additive is about 0.4-0.8% by weight, wherein the composition containing the additive in this amount provides drum adhesion performance balance, abrasion resistance and dye solubility after bleeding.

Optionally, starch may be added in an amount of up to about 49.9% by weight in the inventive composition of the present invention. The addition of starch up to this amount clearly reveals the benefits of the wax-free additive according to the invention. The preferred upper limit of starch addition amount is up to about 33% by weight, with the most preferred upper limit being up to about 25% by weight. The efficacy of the nonionic additives according to the invention in the most preferred vinyl alcohol polymer / starch mixtures is similar to that in the case of compositions containing vinyl alcohol polymer as the only polymer component. Various types of starch and derived starch will act as optional additives in the compositions of the present invention.

As examples of these, ＂Kofilm＂ 50 [acetylated starch; National Starch Co.] and Penick and Ford Co. Astrogum # 3010 (medium carboxymethylated starch with moderate viscosity) and Astrogum 3020 (sodium carboxymethylated starch with low viscosity).

Carboxymethyl cellulose (CMC) may also be used as an optional component in the compositions of the present invention in an amount of up to about 50% by weight, preferably up to about 33% by weight and most preferably up to about 25% by weight.

The combined weight of starch and CMC components should not exceed the weight of the vinylalcohol polymer present in the composition.

Another optional additive is an oligomer of low to medium molecular weight (number average: 200-800) of ethylene oxide, which is often added to a vinyl alcohol polymer as a vibration damper. US Pat. No. 4,389,506 describes the use of 3% by weight Carbowax 600 (manufactured by Union Carbide) in producing the most preferred powderless products. The use of Carbowax 600 at concentrations of up to about 5% only reduces the benefits derived from the presence of the nonionic additives of the present invention, which is the recommended upper limit of the additive. The preferred upper limit is 3% by weight, while the most preferred upper limit of this type of additive is 1.5% by weight. The benefits derived from the nonionic additives of the present invention at the most preferred upper concentrations can be realized almost completely.

Other optional additives include linear alcohols or linear alcohol mixtures (average carbon content: about 8-18 units), auxiliary low-ethylene oxide adducts (average content of ethylene oxide: about 1-7 units), or linear or branched chain alcohols ( Average carbon content: about 8-18 units) to medium to high-ethylene oxide adducts (ethylene oxide content: about 8-40 units). These additives may be present at low concentrations, ie up to about 1% by weight, in the compositions of the present invention.

The aqueous appeal solution of the present invention usually has a solids content of about 2-20% by weight. The preferred solids content of the bath is about 5-15% by weight, while the most preferred combination contains about 7-12% by weight of solids, since in most cases using a solid in this amount will result in a sufficient amount of This is because it provides proper wear resistance to glued yarn. Aqueous aqueous solutions based on polyvinyl alcohol are considered unique because they usually do not contain wax additives that must be present under factory conditions.

Aqueous aqueous solution is prepared by slurrying polyvinyl alcohol with water at ambient temperature. In addition to the nonionic additive, any optional additives are then introduced. The resulting mixture is heated with stirring at about 77 ° C. until a complete solution is made.

In addition, the inventive solution may be prepared directly from the mixture of the small amount of the nonionic additive of the present invention and the vinyl alcohol polymer. The polyvinyl alcohol / nonionic additive mixture according to the present invention is produced by dry mixing various polyvinyl alcohols and additive (s) under conditions of strong mixing temperature and strength at which the additive component (s) can become liquid (s). do. Furthermore, if more than one nonionic additive is used, it can be premixed and added as a single component. For example, using a Readco Sigma Blade mixer manufactured by Read Co., York, PA, polyvinyl alcohol and Tergitol ＂15-S-3 or Tergitol＂ 15 by mixing at temperatures above about 20 ° C. for about 30 minutes. The -S-3 / Carbowax 600 mixture was converted to a homogeneous mixture. This method of preparation is carried out by slurrying the required vinylalcohol polymer / nonionic additive mixture in water at ambient temperature to obtain the desired bath tub assembly. The resulting mixture is heated with stirring at a temperature of about 77 ° C. until a complete solution is made.

The inventive solution of the invention can also be prepared by using a concentrate of the nonionic additive according to the invention in a vinyl alcohol polymer. This concentrate consists essentially of about 45-90% by weight of the vinylalcohol polymer and about 10-55% by weight of the liquid nonionic low-ethylene oxide adduct additive according to the present invention. The concentrate may optionally contain up to about 45% starch, up to about 45% carbowax, up to about 45% carboxymethyl cellulose and up to about 45% linear alcohol or low-ethylene oxide adducts of the linear alcohol mixture. Or medium to high ethylene oxide adducts of linear or branched alcohols. This concentrate is used to prepare the inventive composition of the present invention by adding the required amount of the concentrate to form a vinyl alcohol polymer solution in advance. The use of such concentrates can provide unique and surprising advantages. Even when the vinyl alcohol polymer is added to a hot aqueous solution while being vigorously shaken, the vinyl alcohol component is very difficult to dissolve and dissolve upon contact with hot water. In contrast to the concentrate described above, if the concentrate contains at least about 30% by weight of the nonionic additive of the present invention, it becomes relatively easy to disperse when added directly to hot water. The most preferred amount of nonionic additive is about 40% -50%. Above about 50% vinyl alcohol polymers tend not to absorb all additives. The use of the concentrates described above provides a very desirable advantage to meet certain plant requirements by rapidly preparing the amount of nonionic additives according to the invention in a given hot bath bath.

Preferably, the concentrate comprises about 45-70 weight percent vinyl alcohol polymer, about 30-55 weight percent nonionic additive, up to about 20 weight percent starch, up to about 20 weight percent Carbowax and about 20 weight percent To carboxymethyl cellulose. Very preferably the concentrate is from about 50-60% vinyl alcohol polymer, about 40-50% nonionic additive, up to about 5% starch, up to about 5% carbowax and up to about 5% Will contain carboxymethylcellulose.

The agent is applied to the fabric or slay using a slasher. The slasher is equipped with a heated reservoir container containing the formulation of the agent. Unpasted sleds are passed through a hot squeeze solution, through a compression roll to remove excess squeeze solution, through a series of heat drying drums and through a rupture rod assembly to separate the sleds into individual warp yarns. The grass is fed by drawing it out of the collecting bed. When the required glued slay is collected non-clinically, it is placed in a loom where the yarn is woven into the raw fabric.

The pooled spinning yarns produced using the inventive composition have a wax-free protective surface coating and exhibit the unique properties of providing excellent weaving performance, despite the absence of wax in the foam based on vinyl alcohol polymers. Indicates. Moreover, the raw fabrics produced without wax are easily released under mild pull-out conditions to give a loose fabric having excellent dye solubility. The grass pulling operation is performed by passing the grass fed raw fabric through an alkaline scouring bath and then rinsing several times with hot water (about 65-85 ° C.). Fabrics made using conventional wax-containing lubricants require much more stringent refining and cleaning conditions than would be required when using the inventive formulations. In order to allow for effective and reproducible dyeing and other processing operations on the fabric, a large amount of appealing components must be removed from the raw fabric prior to being processed in the fabrication machine. Therefore, wax-free glued yarns and wax-free raw fabrics produced therefrom are considered unique.

The wax-free auxiliary composition according to the invention is particularly suitable for use with polyester / cotton spinning yarn blends. This is especially useful for mixing 65/35, 50/50 and 40/60 polyester / cotton yarns. The present compositions also have utility for 100% cotton yarns.

The addition of the wax-free additives of the present invention to a blend formulation based on a vinylalcohol polymer provides excellent slab suitable for producing various types of fabrics under typical weaving conditions (e.g., shuttle, air spray, rapier loom). It facilitates the manufacture of glued yarns with scouring and weaving properties, while allowing for the exclusion of wax as an additive. Induction fabrics produced without the use of waxes are characterized by easy removal of loosening, and unwrapped fabrics exhibit excellent dye solubility.

The following examples are given for the purpose of illustrating the present invention. All parts and percentages are by weight unless otherwise indicated.

[Examples]

A stock solution was prepared in a vapor coat by adding the vinyl alcohol polymer to the required amount of water (ambient temperature) to obtain the desired bath tub solid. While stirring, the temperature of the slurry was raised to 77 ° C. Any additives to be tested in the formulation were added at this stage.

The resultant glue solution was used to feed the 24 ends of the polyester / cotton spinning chamber, which was used in the Callaway Slasher® Model 51 (West Point Foundry and Machine Co) using pressure in a compression roll. Operating at 10 m / min). After the grass was fed to the yarn, the addition amount of the scavenger was measured by the loss weight after the grass fed yarn was extracted with boiling water. Evaluation of the performance of the appeal formulations in slashing and the characteristics of the glued thread itself was carried out using the following test procedure.

(a) deposition on drums

The extent to which deposits form on No. 1 dry drums in the slashers is directly related to the tendency of a given hoist formulation to cause sticking of the individual warp ends to the dry drums in the slashers. Therefore, in order to minimize the sticking of the seal in the drying section of the slasher, the effect of the release agent added to the auxiliary formulation can be accurately measured. When the Callaway Slasher is operated under the conditions described above, the temperature of the drying drum is set to 190 ° C. and the remaining three drums are kept at 220 ° C., the amount of deposit accumulated on the No. 1 drum will reach an equilibrium value in about 1 minute. will be. Once equilibrated, the sediment on the drum is quantitatively separated using a rubber cleaner during one full revolution of the drum and then the precipitate is dried and weighed. The amount of sediment collected provides a direct measure of the performance of the appeal formulation. That is, the greater the amount of drum deposit, the greater the tendency for the blend to cause dry drum sticking. Of the various formulations based on all vinyl alcohol polymers evaluated during the course of this study, the highest drum deposition rate was unmodified PVA No. 2 (4% solution viscosity of 13.5 mpa.s and saponification value of 40). Hydrolyzed vinyl alcohol / methyl acrylate copolymer). In each of the illustrated examples, the actual drum deposition values observed and the ratings given as percentages for the PVA No. 2 values (unless otherwise noted). A grade of 0.200 or lower is believed to be essential for operation under typical factory conditions for 100% vinyl alcohol polymer aids.

(b) Wear resistance of grass fed yarn is measured using a laboratory wear tester. The test method used consists of tensioning the 21 ends of the thread fed yarn through a conventional weaving body section and then applying a control tension to the individual warp ends. The body is allowed to vibrate at 1 cycle / second with respect to the warp ends and record the number of cycles required to cause breakage of each end. The second set of 21 ends is then tested in the same way. The two sets of data obtained are averaged statistically to give the number of cycles required to break 50% of the warp ends used in the test. This amount in the cycle is referred to as the F ₅₀ grade for a given appeal formulation.

Abrasion resistance depends a lot on the addition of the inhibitor. For comparison purposes, all F ₅₀ data should be normalized to the amount of additive given, ie 10%. This is preferably done by obtaining F ₅₀ values at 6 or more additions for a given adjuvant formulation and linear regression analysis of the calculated data. All F ₅₀ data described in the characterization of the various illustrated examples are processed in this manner. The F ₅₀ maximum is observed in a stock formulation prepared using PVA No. 1 (fully hydrolyzed vinylalcohol / methyl methacrylate copolymer with a 4% solution viscosity of 28 mpa · s and a saponification value of 30). In all of the illustrated examples, the actual F ₅₀ values observed and the comparative ratings with PVA No. 1 agents are given, which compares the log F ₅₀ values of PVA No. 1 agents with 10% added dose. Set to 1 and calculated by proportioning the log F ₅₀ value observed at the 10% addition amount to the inventive formulation of Example. Under the addition of 10%, a grade of 0.875 or higher is considered to be a working requirement under typical factory conditions using 100% vinylalcohol polymer aids.

(c) dye-soluble

By passing the glued yarn to be used in this test through an oven at 200 ° C (purification time: 45 seconds), this is first heat treated. The heat treated yarn consists of immersing the yarn in a 0.5% alkanol WXN (modified alkyl sodium arylsulfonate product from EIdu Pontde Nemours and Company) solution at 55 ° C. for 15 seconds and rinsing three times at 75 ° C. for 45 seconds. Loosening is removed under mild conditions. Pass through the ringer and allow the thread to dry completely. Using the dry, unwrapped yarn, its dye solubility is measured by measuring the time (in seconds) that the aqueous solution of the agrochemical green dye penetrates 1 inch of the skein of the dry yarn. Poor dye solubility is observed using PVA No. 1 containing 8% of Synchem® 110 wax (solid resin wax dispersed in hot water, manufactured by Milliken). Set this value to 1 and proportionate all other dye solubility values for the illustrated example. Thus, in each given example, the observed dye solubility and dye solubility grades are described. It is believed that 3.5 or higher grades are required to achieve good dye solubility under standard plant conditions.

[Examples 1 and 2 and Comparative Examples 1 and 2]

Test solution based on PVA No. 2 containing 0.4% Tergitol X 15-S-3 (Example 1) was tested at 12 doses of added amounts ranging from 5-15% (based on the weight of the yarn) and this Similar formulations prepared using only No. 2 (Example C-1), similar formulations prepared using PVA No. 2 containing 8% of Synchem® 110 wax (typical factory formulation) (Example C-2 And similar formulations made from PVA No. 2 containing 0.4% Tergitol 15-S-3 and 1.5% of Carbowax 600 (Example 2). The results are summarized in Table 1.

TABLE 1

As can be seen from the above data, Examples 1 and 2, which specifically illustrate the present invention, provide yarns with good characteristics of all three main performances, and Comparative Examples 1 and 2 are drum-shaped for C-1. It is not preferable because the deposition rate is too high and the dye solubility of C-2 is extremely poor.

[Examples 3 and 4 and Comparative Examples 3 and 4]

A solution based on PVA No. 1 containing 0.4% Tergitol® 15-S-3 (Example 3) was evaluated at 12 addition amounts of the agent ranging from 5-15% (based on the weight of the yarn) and Similar formulations based only on No. 1 (Example C-3), Similar formulations based on PVA No. 1 + 8% Synchem ＂110 wax (typical factory formulation) (Example C-4) and Tergitol # 15 Compared to similar formulations based on PVA No. 1 containing 0.4% of S-3 and 1.5% of Carbowax 600 (Example 4). The results are summarized in Table 2.

TABLE 2

The data illustrate that the benefits of the present invention in combination with optional grades of vinyl alcohol polymers can be realized.

[Example 5 and Comparative Examples 5 and 6]

In this example, 75/25 mixture of Vinol # 425 / Vinol # 205 polyvinyl alcohol (product of Air Products) is used. ＂Vinol＂ 425 is a hydrolyzed (94% by weight hydrolyzed) intermediate and ＂Vinol＂ 205 is a partially hydrolyzed (88% by weight hydrolyzed) PVA. A mixture of these polyvinyl alcohols and a solution containing 0.4% of ＂Tergitol®15-S-3 (Example 5) was evaluated at 12 addition amounts in the range of 5-15% (based on the weight of the yarn). , A similar formulation prepared using an unmodified mixture (Example C-5) and a similar formulation prepared using a mixture containing 8% of SyncHex®110 wax (Example C-6). The results are summarized in Table 3.

TABLE 3

As can be seen from the above data, the additives according to the invention were observed in the vinylalcohol polymer compositions described in Examples 1,2,3 and 4 together with compositions based on intermediates and partially hydrolyzed polyvinylalcohols. It provides the same advantages as

[Example 6 and Comparative Examples 7 and 8]

5-15% of the blend formulation (Example 6) containing 75/25 PVA No. 2 / Kofilm ＂50 starch mixture, 0.4Tergitol＂ 15-S-3 0.4% and Carbowax600 1.5% Similar formulations (Example C-8) evaluated using 12 additives in the range (by weight) and containing no additives and prepared using 8% of Synchem® 110 wax (Example C-8) Compare with The results are summarized in Table 4.

TABLE 4

footnote

(1) Set the performance observed in Comparative Example 7 to 1.

It can be seen from the above-mentioned data that the additive according to the invention in a system based on PVA / starch significantly reduces the deposition rate on the drum and increases the dye solubility of the yarn. It was observed that the adverse effect of the additive of the present invention on the abrasion resistance was not greater than that caused by the Synchem 110 wax.

Example 7 and Comparative Examples 9 and 10

5-15% of the formulation (derived in Example 7) derived from 50/50 PVA No. 2 / Kofilm ＂50 starch mixture and containing 0.4% of“ Tergitol-15-S-3 ”and“ Carbowax ”600 1.5% Preference formulations, evaluated using twelve additives in the range (based on the weight of the yarn) and prepared using a formulation containing no additives (Example C-9) and Synthesis 100 wax 110 8% (Example C-10). The results are summarized in Table 5.

TABLE 5

Each week

(1) The performance grade of Comparative Example 9 is set to 1.

As can be seen from the above data, the use of the additive according to the present invention in combination with a 50/50 vinylalcohol polymer / starch mixture provides a beneficial effect on deposition performance on drums and dye solubility. The additive reduces wear resistance to approximately the same degree as the Synchem 110 wax additive.

Comparative Example 11-13

Some low-ethylene oxide adducts of linear alcohols, namely “Tergitol® 25-L-3,“ Alfonic ”1012-40 and“ Alfonic ”1412-30, are used to prepare a combination of formulations based on PVA No.2. (Examples C-11 to C-13).

Data characterizing the low-ethylene oxide adducts are summarized in the table below.

The linear alcohols in the "Alfonic" product and the "Tergitol" 25-L-3 are hydrophobic in the case of the "Tergitol" 15-S-3. It can be seen from the above data that "Alfonic" 1412-40 and "Tergitol" 25-L-3 are almost accurate linear counterparts of "Tergitol" 15-S-3. The Alfonic product is supplied by Conoco, while the Tergitol product is supplied by Union Carbide.

Table 6 shows the composition and properties of the above formulations derived from the ethylene oxide adduct and the additive formulation prepared using the additive of the present invention (Example 1).

TABLE 6

As can be seen from the above data, formulations containing linear alcohol-based additives (Examples C-11 to 13) give much lower drum deposition and wear resistance performance than observed with the additives of the present invention. do.

Example 8-10 and Comparative Example 14-20

PVA No. 2 modified with a ＂Tergitol＂ 15-S product containing 3-40 units of ethylene oxide (ie, ＂Tergitol＂ 15-S-3 to ＂Tergitol＂ 15-S-40) Prepare the blend. The amount of Tergotitol additive is 0.4% by weight and 3.0% of Carbowax 600 is also present in the formulation. Table 7 shows the characteristics for these formulations and formulations containing only Carbowax 600 additives.

TABLE 7

As can be seen from the data in Table 7, the additives of the present invention (＂Tergitol＂ 15-S-3,15-S-5 and 15-S-7) show improved results (Examples 8-10). Provide. “Tergitols” 15-S-9 to 40 (Examples C-15 to 20) provide significantly poor drum deposition performance. Moreover, the observed abrasion resistance value becomes lower and lower as the number of ethylene oxide units in the "Tergitol" additive is increased.

Example 11 and Comparative Example 21

Fabric swatches prepared from yarns fed with the inventive solution of the invention are compared to the same fabric swatches in all respects except that they are made using yarns to be fed with commercial PVA / resin wax formulations. Both specimens are removed under mild conditions (e.g. soak for 15 seconds at 55 ° C and rinsed three times with water at 65 ° C). The dye water solubility of the fabric obtained using the inventive agents is eight times greater than the dye water solubility of the fabric obtained using conventional wax-containing agents. Moreover, while the dye uptake by the agents of the present invention is regular and uniform, the dye uptake by conventional agents is very irregular and nonuniform.

The fabrics used in Examples 11 and 21 consisted of 65/35 polyester / cotton warps with 36 single-ply cotton, with 100% polyester weft to obtain a 92/83 structure (ratio of warp to weft). Fill it. The warp is fed with a paste formulation containing 12.5% solids and the added amount of paste is 15.0%. The lake solution used in Example 11 is exactly the same as that used in Example 2. The lake solution used in Comparative Example 21 is the same as that used in Comparative Example 2 except that it contains 10%. Synchem 110 wax is instead 8%.

Claims (20)

A composition comprising the following (a)-(f): (a) selected from the group consisting of polyvinyl alcohol, vinyl alcohol / methyl methacrylate copolymer, and polyvinyl alcohol containing dissolved comonomers other than methyl methacrylate 45.5-99.9% by weight of a vinyl alcohol polymer having a saponification value of 1-160 and a 4% solution viscosity of 3-70 mpa · s at 20 ° C .; (b) 0.1-3% by weight of a liquid nonionic low-ethylene oxide adduct of a branched alcohol or branched alcohol mixture, wherein the average content of ethylene oxide is 1-7 units and the average carbon content of the alcohol is 8-18 (carbon atoms). ; (c) 0-49.9% by weight starch; (d) 0-5% by weight of an ethylene oxide oligomer having a (number average) molecular weight of 200-800; (e) 0-49.9% by weight of carboxymethyl cellulose; (f) low-ethylene oxide adducts (average content of ethylene oxide: 1-7 units) of linear alcohols or linear alcohol mixtures (average carbon content: 8-18 units) and linear or branched chain alcohols (average carbon content: 8- 0-1% by weight of one or more auxiliary ethylene oxide adducts selected from the group consisting of 18 units) of medium to high ethylene oxide adducts (average content of ethylene oxide: 3-40 units), with starch and carboxy The sum of the weights of methyl cellulose should not exceed the weight of the vinylalcohol polymer). The fully hydrolyzed polyvinyl alcohol having a viscosity of 3-70 mpa.s, a complete valence containing 3.5-6% by weight of copolymerized methyl methacrylate comonomer having a viscosity of 3-60 mpa.s. Decomposed vinyl alcohol / methyl methacrylate copolymer, partially hydrolyzed polyvinyl alcohol having a viscosity of 3-60 mPa.s and containing 4-12 mol% vinyl acetate, having a viscosity of 3-70 mPa.s and methyl A composition wherein a vinyl alcohol polymer is selected from the group consisting of polyvinyl alcohols containing a dissolved comonomer selected from the group consisting of acrylates and methyl hydrogen maleates, and mixtures of the aforementioned vinyl alcohol polymers. The amount of vinyl alcohol polymer is 63-99.8% by weight, the amount of ethylene oxide adduct is 0.2-1% by weight, the amount of starch is 0-33% by weight, the amount of ethylene oxide oligomer is 0-3% %, The amount of carboxymethyl cellulose is 0-33% by weight, the average content of ethylene oxide of the ethylene oxide adduct is 2-5, and the average carbon content of alcohol is 10-15 (carbon atoms). The amount of vinyl alcohol polymer is 72.7-99.6% by weight, the amount of ethylene oxide adduct is 0.4-0.8% by weight, the amount of starch is 0-25% by weight, the amount of ethylene oxide oligomer is 0-1.5% %, The amount of carboxymethyl cellulose is 0-25% by weight, the average content of ethylene oxide of the ethylene oxide adduct is 3, and the carbon content of the alcohol is 13 (carbon atoms). A composition comprising the following (a)-(f): (a) In the group consisting of polyvinyl alcohol and vinyl alcohol / methyl methacrylate copolymer, and polyvinyl alcohol containing a dissolved comonomer other than methyl methacrylate 45-90 weight percent vinyl alcohol polymer having a saponification value of 1-160 and a 4% solution viscosity of 3-70 mPa · s at 20 ° C .; (b) 10-55% by weight of a liquid nonionic low-ethylene oxide adduct of a branched alcohol or branched alcohol mixture having an average content of ethylene oxide of 2-7 units and an average carbon content of alcohol of 8-18 carbon atoms. ; (c) 0-45% by weight starch; (d) 0-45% by weight of an ethylene oxide oligomer having a (number average) molecular weight of 200-800; (e) 0-45% by weight of carboxymethyl cellulose; (f) low-ethylene oxide adducts (average content of ethylene oxide: 1-7 units) of linear alcohols or linear alcohol mixtures (average carbon content: 8-18 units) and linear or branched chain alcohols (average carbon content: 8- 0-45% by weight of a secondary ethylene oxide adduct selected from the group consisting of 18 units) of medium to high ethylene oxide adducts (average content of ethylene oxide: 8-40 units). The fully hydrolyzed polyvinyl alcohol having a viscosity of 3-70 mPa · s, a complete valence containing 3.5-6% by weight of copolymerized methyl methacrylate comonomer having a viscosity of 3-60 mPa · s. Decomposed vinyl alcohol / methyl methacrylate copolymer, partially hydrolyzed polyvinyl alcohol having a viscosity of 3-60 mPa.s and containing 4-12 mol% vinyl acetate, a viscosity of 3-70 mPa.s and methylacrylic A vinyl alcohol polymer is selected from the group consisting of polyvinyl alcohol containing a dissolved comonomer selected from the group consisting of latex and methyl hydrogen maleate and a mixture of said vinyl alcohol polymers. The amount of the vinyl alcohol polymer is 45-70% by weight, the amount of ethylene oxide adduct is 30-55% by weight, the amount of starch 0-25% by weight, the amount of ethylene oxide oligomer 0-25% %, The amount of carboxymethyl cellulose is 0-25% by weight, the average content of ethylene oxide of the ethylene oxide adduct is 3-5 and the average carbon content of alcohol is 10-19 (carbon atoms). The amount of vinyl alcohol polymer is 50-60% by weight, the amount of ethylene oxide adduct is 40-50% by weight, the amount of starch is 0-5% by weight, the amount of ethylene oxide oligomer is 0-5% by weight. %, The amount of carboxymethyl cellulose is 0-5% by weight, the average content of ethylene oxide of the ethylene oxide adduct is 3 and the average carbon content of alcohol is 13 (carbon atom). A wax-free aqueous appeal solution composed of the composition of claims 1, 2, 3 or 4 having a solids content of 2-20% by weight. A wax-free aqueous appeal solution consisting of the composition of claims 1, 2, 3 or 4 having a solids content of 5-15% by weight. A wax-free aqueous appeal solution consisting of the composition of claims 1, 2, 3 or 4 having a solids content of 7-12% by weight. A method of feeding grass to a spinning chamber using a wax-free aqueous solution comprising 2-20% by weight of solids and consisting of the composition of claims 1, 2, 3 or 4. A method of feeding grass to a spinning chamber using a wax-free aqueous solution consisting of 5-15% by weight of solids and comprising the composition of claims 1, 2, 3 or 4. A method of feeding grass to a spinning chamber using a wax-free aqueous solution composed of the composition of claims 1, 2, 3 or 4, wherein the solid content is 7-12% by weight. A threaded yarn consisting of a spinning chamber having a wax-free protective surface coating of the composition of claims 1, 2, 3 or 4. A threaded yarn selected from cotton and polyester / cotton yarn and consisting of a yarn having a wax-free protective surface coating of the composition of claims 1, 2, 3 or 4. Spinning is selected from 65/35, 50/50 and 40/60 polyester / cotton spinning chambers and has a wax-free protective surface coating of the composition of claims 1, 2, 3 or 4. A grass fed thread composed of threads. Spinning is selected from 65/35, 50/50 and 40/60 polyester / cotton spinning chambers and has a wax-free protective surface coating of the composition of claims 1, 2, 3 or 4. Fabrics made from glued yarns consisting of yarns. A fabric made from glued yarns consisting of a yarn having a wax-free protective surface coating of the composition of claims 1, 2, 3 or 4. Prepared from glued yarns selected from cotton and polyester / cotton yarns and consisting of yarns with wax-free protective surface coatings of the compositions of claims 1, 2, 3 or 4. textile.