JPS62289673A - Size agent for fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention Industrial Application Field The present invention relates to a fiber sizing agent with good weavability.
The present invention relates to a fiber sizing agent with very good weavability, which contains a polyvinyl alcohol-based polymer having a long-chain alkyl group of ~50, starch, and an oil agent.

Traditional, natural fibers such as cotton and wool, and semi-synthetic fibers such as rayon, acetate, penvelve, etc. When weaving synthetic fibers such as AI 4I, nylon, polyester, and acrylic, there are gripper rooms, rapier rooms, water jet looms, air jet looms, etc. in addition to shuttle rooms as looms. Due to the orientation towards weaving the edges of objects, even stricter performance is required for the warp glue used in the four stages of weaving in order to weave at high efficiency.

As the sizing agent for warp thread sizing, V-type sizing agents, polyvinyl alcohol (hereinafter abbreviated as PVA), polyacrylic acid ester sizing agents, etc. are used alone or as a mixture, and in addition, oil agents and carboxymethyl cellulose are used. etc. have been used together. Among them, PVA is widely used, and in addition to normal fully saponified PVA and partially saponified PVA, products using anion-modified PVA and cation-modified PVA are also known. In addition, modified PVA in which hydrophobic groups are copolymerized (JP-A-56-55440, JP-A-58-174683) is already known. All of these are aimed at improving the adhesion of hydrophobic In1I when pasting hydrophobic fibers such as polyester and nylon, thereby improving binding force, abrasion resistance, and fluffing effect. be.

The production technology of PVA-based polymers having long-chain hydrocarbon alkyl groups at the ends is already known (Japanese Patent Publication No. 183-1983).
1. Japanese Patent Publication No. 58-108207, Japanese Patent Application Publication No. 59-102
946). In addition, when these PVA and fibers are used, the wear resistance is improved by lowering the friction coefficient (Special Publication Publication No. 44-22).
218), it is already known technology that these PVAs are used to modify the surface of molded products (Japanese Patent Publication No. 46
-18258).

Generally, PVA and starch are used together as a warp sizing agent for the F-point span that H is intended to use, but since PVA is a synthetic polymer, its quality is stable and it is easy to form a film. It is widely used because it has good performance, good film properties, and good adhesion to fibers. On the other hand, starch is used because it is cheap and easily available. However, since PVA and starch are both polymeric compounds, their compatibility is poor, and mixed aqueous solutions of PVA and starch are unstable and separate easily, and starch also tends to age, so if these aqueous solutions are left alone, After 1 to 2 days, the performance of the adhesive deteriorates rapidly, and it is almost impossible to reuse it.

Acrylic glue, oil, or carboxymethyl cellulose is appropriately added to PVA or starch, and the oil is generally used to (1) impart smoothness to the surface of the yarn;

(2) Promote penetration of the solution.

(3) Adding hygroscopicity to the sized yarn.

(4) Preventing static electricity.

(5) Prevent the thread from adhering to the drying cylinder of the W4 attachment machine.

(6) Give flexibility to the thread.

(7) Improve thread handling.

It is said that Oil agents include various vegetable oils, paraffin wax, surfactants, etc., but the above (1), (
When the main purpose is to achieve the effects of 5), (13), and (7), those based on paraffin wax or vegetable oil are generally used. These paraffin waxes and vegetable oils can be emulsified and dispersed in water by using an emulsifier consisting of a nonionic surfactant or an ionic surfactant, but essentially they are not mixed with PVA or starch. The compatibility is poor and the stability of the paste solution is poor. Furthermore, when this size liquid is dried to form a film, the homogeneity of the film is impaired, and therefore, although flexibility can be imparted, the strength and elongation of the film is reduced. In particular, the drop in elongation is large and the entire film becomes brittle, reducing its resistance to friction.
This is not sufficient for high-speed looms such as air jet looms, and the work efficiency is not good.

To deal with this situation, warp sizing agents using anion-modified PVA, cation-modified PVA, or PVA copolymerized with hydrophobic groups were prepared by heating and dissolving the sizing agent in water to prepare a sizing solution. In some cases, the stability of the size liquid improves somewhat, but it is still not sufficient, and the film after drying the size liquid is not homogeneous enough, making it difficult to weave with high quality fabrics or high-speed looms. I cannot say that.

Furthermore, when an acrylic ester type sizing agent is added to a mixture of PVA, starch, and an oil agent, the overall compatibility is slightly improved, but this is still insufficient.

By adding a PVA-based polymer having a long chain alkyl group with 4 to 50 carbon atoms at the end to a fiber glue containing such PVA5R powder and an oil agent, , the compatibility between PVA and V coating is improved, the emulsification and dispersion of the oil agent is also good, the stability of the size liquid is also good, the film made from the size liquid is also homogeneous, and the yarn coated with this size agent is The inventors have completed the present invention by discovering that they have high elongation, flexibility, good abrasion resistance and fluffing effect, and exhibit excellent performance as a sizing agent for fiber sizing.

The terminal hydrophobic group-modified PVA polymer (B) having a long chain alkyl group having 4 to 50 carbon atoms at the terminal used in the present invention will be explained. As the terminal long-chain alkyl group, one having 4 to 50 carbon atoms is suitable. When the number of carbon atoms is less than 4, it is not much different from unmodified PVA and its compatibility with starch is also poor. In addition, polymers with carbon numbers exceeding 50 have too strong hydrophobicity, resulting in poor water solubility of the polymer itself, resulting in poor compatibility with starch, which also fails to achieve the purpose of the present invention, and has 4 to 5 carbon atoms.
The number of carbon atoms is preferably 0, but preferably 8 to 24 carbon atoms. Examples of such groups include straight-chain alkyl groups, branched alkyl groups, and alkylaryl groups having 4 to 50 carbon atoms, which have a linking group composed of atoms such as 0, N, and S. Also includes things.

Next, the degree of polymerization of the polymer is closely related to the amount of terminal groups introduced, but is 10 to 3000, preferably 50 to 250.
0 is appropriate. There are no particular restrictions on the degree of saponification, but it is usually 50 mol% or more, preferably 7
It is 0 mol% or more.

The polymer may also contain small amounts of units in addition to vinyl alcohol units and residual vinyl ester units such as vinyl acetate; examples of these include α-olefins such as ethylene, propylene, and isobutyne; Acid, unsaturated acids such as methacrylic acid, crotonic acid, maleic acid, itaconic acid, maleic anhydride or their salts or alkyl esters, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, alkyl vinyl ether, N,N-dimethylacrylamide , N-
Examples include vinylpyrrolidone, vinyl chloride, vinylidene chloride, vinyl propionate, vinyl persate, 2-acrylamidopropanesulfonic acid and salts thereof. However, it is not necessarily limited to these.

The PVA-based polymer (B) having a long-chain alkyl group with 4 to 50 carbon atoms at the terminal as described above can be produced by several methods, but industrially, long-chain alkyl groups with 4 to 50 carbon atoms can be produced. The most preferred method is to polymerize a monomer mainly consisting of a vinyl ester such as vinyl acetate in the presence of a mercaptan having a group, and to form the resulting polyvinyl ester polymer by a conventional method.

Also, PVA (A) and Lru, polymerization degree 100-300
0, preferably 200-2500. Degree of formalization 50 mol%
In addition to the above-mentioned, preferably 70 mol% or more of normal PVA, it may be anion-modified, cation-modified, or other nonion-modified PVA polymers having long-chain alkyl groups at the terminals.

On the other hand, as starch (C), flours obtained from wheat, corn, rice, horseradish, sweet potato, tapioca, sago palm, etc. are used, but corn starch is generally suitable.

Further, chemical products such as oxidized starch, etherified starch, esterified starch, cationized starch, etc. manufactured using the above-mentioned raw flour as raw materials may also be used.

The oil agent (D) includes various vegetable oils, paraffin wax, surfactants, etc., but paraffin is used to improve the smoothness of the sized yarn, give it flexibility, prevent it from adhering to the drying cylinder, and improve yarn handling. Oils such as wax and vegetable oil are mainly used.

Next, PVA (A), PV having a long chain alkyl group at the end
The blending ratios of the A-based polymer (B), starch (C) and oil agent (D) will be described.

First, (C) is suitably used in an amount of 10 to 19 parts by weight based on 1100 parts by weight of [(A)+(B)]. (If the CI is less than 10 parts by weight, there will be problems with the dividing property during sizing, while if it exceeds 1,900 parts by weight, the physical properties of the sizing agent film will be poor and the weaving properties will be poor.

(D) is [0 for 1100 parts by weight of (A) + (B)
．． 1 to 20031i parts is suitable. 0. If it is less than 1 part by weight, there is no effect of adding the oil agent, and if it exceeds 200 parts by weight, the physical properties of the sizing agent film will deteriorate and problems will also arise in weavability.

Also, PVA (A) is O per 100 parts by weight of (B).
~10000ffiJ1 part is appropriate.

PVA-based polymer (B)i having a long-chain alkyl group at the end
f, 1 part by weight or more, preferably 3 parts by weight or more per 100 parts by weight of starch (C). Less than 1 part by weight has no effect.

In addition, (B) should be used in an amount of 0.1 part by weight or more, preferably 1 part by weight or more, based on 100 parts by weight of the oil agent (D).If it is less than 0.1 part by weight, it will not be effective in improving the emulsification and dispersion of the oil agent. be.

It can be estimated from the viscosity behavior of a mixed aqueous solution of (B) and (C) that the PVA-based polymer (B) having a long-chain alkyl group at the terminal has a unique interaction with the polymer (C). That is, it has a C12825-alkyl group at the end and a polymerization degree of 1.
00. A mixture of PVA-based polymer with a saponification degree of 99.2 mol% and cornstarch in various ratios was poured into water, and gelatinized by heating at 95°C for 2 hours with sufficient stirring to obtain a concentration of 5.
A % by weight aqueous solution was prepared. The viscosity of this aqueous solution at 90°C was measured using a B-type viscometer. Next, PVA with a degree of polymerization of 550 and a degree of saponification of 98.5 mol% (Kuraray Boval PVA
-105)/cornstarch system, the viscosity was similarly measured. The results are shown in Figure 1. In Figure 1, the solid line 1 represents PV having a long chain alkyl group at the end.
It is a polymer A/cornstarch system, and the viscosity behavior of the PVA-105/cornstarch system is represented by the dotted line 2. While the viscosity of PVA-105/cornstarch aqueous solutions decreases as the PVA content increases, PVA-based polymers/cornstarch aqueous solutions with long chain alkyl groups at the ends generally have PVA-105/cornstarch solutions. 105
/Higher viscosity than cornstarch-based aqueous solutions (this P
The viscosity of the aqueous solution of the VA polymer itself is lower than the viscosity of the aqueous solution of PVA-105), and it shows a maximum when the content of the PVA polymer having a long chain alkyl group at the end is 10 to 30% by weight. This clearly shows that a PVA-based polymer having a long-chain alkyl group at the end and corn starch have a unique interaction.

Modified PVA copolymerized with long-chain alkyl groups also has the effect of improving the stability of mixed aqueous solutions, but it still has a tendency to gel, and is said to have no effect on modified starches. On the other hand, the PVA-based polymer (B) having a long-chain alkyl group at the end has a block-like bond between the long-chain alkyl group as the hydrophobic group at the end and the PVA moiety as the hydrophilic group. In addition to having surfactant ability, the long chain alkyl group present at the end improves compatibility with starch, and the PVA part at one end has affinity with other PVA, making these mixtures very compatible. This is considered to be an improvement in the quality of the product, and this point is different from copolymerized modified PVA in which long-chain alkyl groups are randomly included.

The change in aqueous viscosity of the composition of the present invention over time is very small, which indicates that it is effective in preventing the aging phenomenon of starch. Starch generally consists of amylose and amylopectin, and this aging phenomenon is said to be caused by the crystallization of amylose in the starch. It is a known fact that this amylose interacts with higher fatty acids and has good compatibility. The PVA-based polymer having a long-chain alkyl group at the end used in the present invention also has a long-chain alkyl group at the end similar to higher fatty acids, so it interacts with amylose, which causes starch This is thought to be the reason why it has the effect of preventing the aging phenomenon.

Although not much is known about the interaction with amylopectin, which is another component in one of the two, it is important to note that the interaction of PV with a long-chain alkyl group at the end used in the present invention
It was found that the A-based polymer interacts with amylopectin as well as with amylose. That is, amylopectin separated from corn starch and C12825-
It has a long chain alkyl group with a degree of polymerization of 280 and a degree of saponification of 98.
．． A mixture of 5 mol % PVA-based polymer at various ratios was poured into water and gelatinized by heating at 95° C. for 2 hours to prepare an aqueous solution with a concentration of 1.5% by weight. 20℃ of this aqueous solution
The viscosity and transmittance were measured.

0 Measurement method of transmittance of aqueous solution Hitachi spectrophotometer (manufactured by Hitachi, Ltd.) Wavelength used: 65
Table 1 shows the results for a cell width of 0 nm and a cell width of 10 mm.

Table-1 *Proportion of PVA polymer in total solid content
．． The viscosity of 5% by weight at 20°C is about 1 centipoise, which is almost the same as water, but as the proportion of the PVA polymer with long chain alkyl groups at the end increases, the viscosity increases and the transmittance also increases. It has become. The viscosity of ordinary PVA (Kuraray Boval PVA-105) and amylopectin water solution with a polymerization degree of 5501 and a saponification degree of 98.5 mol% is about 8 centipoise, which does not change even when PVA-105 is added, and the transmittance is 16 to 18. % was almost unchanged. From this, it is presumed that the PVA-based polymer having a long-chain alkyl group at the terminal has a unique interaction with amylopectin.

This word PV made by randomly copolymerizing long-chain alkyl groups.
This is a feature not found in A or other PVA-based polymers.

The interaction of PVA-based polymers with long-chain alkyl groups at the ends with not only amylose but also amylopectin may be the reason for their good compatibility not only with raw flour but also with oxidized starch and other modified starches. Seem.

A system consisting of PVA, starch and oil, with 4 to 4 carbon atoms at the end.
When the PVA polymer (B) having 50 long-chain alkyl groups is added, the emulsification and dispersion of paraffin wax and vegetable oil is very good, and therefore there is no phase separation of the size liquid, and the viscosity stability is good. When a film is created using this paste, a very homogeneous film can be obtained. In this case, PVA polymer (B)
The appropriate amount to be used is 0.1 part by weight or more, preferably 1 part by weight or more, per 100 parts by weight of the oil agent (D). 0.
Less than 1 part by weight has almost no effect.

If paraffin wax or vegetable oil is used without using the PVA-based polymer (B) that has a long-chain alkyl group at the end, the stability of the size solution will be poor because these oils have poor compatibility with PVA and starch. Moreover, the homogeneity of the film prepared from this m liquid was not sufficient, and the elongation of the film tended to decrease. On the other hand, when a PVA-based polymer having a long-chain alkyl group at the end is used, the stability of the size liquid is improved because the oil agent is uniformly dispersed, and the fluidity is also good, and the film created from the size liquid is Rather than decreasing the elongation due to the homogeneity of the adhesive, there is even a tendency for the elongation to increase when the wax content in the sizing agent is about 10 to 12% by weight.

When this film was examined under a microscope, it was observed that paraffin wax and vegetable oil were distributed in the form of small particles with uniform size. PVA-based polymers having long-chain alkyl groups at the ends have very strong surface activity, and it is presumed that this contributes to improved emulsification and dispersion. However, modified PVA copolymerized with similar hydrophobic groups
Since such a remarkable effect is not observed, it is not just a matter of surface activity, but the reason is not clear, but it is not because hydrophobic groups are randomly included in the polymer wires as in copolymers. This is thought to be largely influenced by the presence of hydrophobic groups only at the ends. In other words, PVA that has a hydrophobic group at the end has a hydrophobic group only at the end, and one end is hydrophilic and has a block of PVA that has good film-forming performance. The coalescence itself forms a good film, and it also has good compatibility with normal PVA, anion-modified PVA, cation-modified PVA, and other modified PVA, and the film-forming ability of the entire glue improves the film properties. considered to be a thing.

The accessibility of PVA-based polymers having long chain alkyl groups at the ends to fibers is no different from that of ordinary PVA or other modified PVA.

From these facts, PVA with a long chain alkyl group at the end
A sizing agent using this type of polymer can be used as a sizing agent that greatly affects the weavability of weaving fabrics and high-speed looms.

There is no problem in using a blended sizing agent consisting of PVA, a PVA polymer with a long-chain alkyl group at the end, V powder, and an oil agent in combination with acrylic sizing agents, carboxymethyl cellulose, antifoaming agents, and other additives. It is.

In this way, fiber sizing agents using PVA-based polymers having long chain alkyl groups at the terminals show extremely excellent weavability for high-grade textiles and high-speed looms, but they also have excellent weavability for other textiles and looms. Of course, it shows excellent weavability.

The sizing agent for textiles of the present invention contains PVA (A) and starch (C).
, a glue containing an oil (D) has 4 to 4 carbon atoms at the end.
By using a PVA-based polymer having 50 alkyl groups, the compatibility between PVA and starch is improved, and the emulsification and dispersion of the oil agent is good, and the stability of the wiping liquid is increased, making it easier to handle. PVA-based polymers with alkyl groups improve the compatibility of the entire size agent, and the film after drying the size liquid becomes homogeneous, resulting in high strength and elongation of the film, and improved abrasion resistance and fluffing effect. Therefore, it has extremely excellent weaving performance, and is especially effective for high-quality textiles and high-speed looms such as air jet looms! ! 1. Glue for maintenance.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the following Examples are not intended to limit the present invention in any way. In addition, all parts and percentages in the examples are based on weight unless otherwise specified.

The details of the PVA-based polymer having a long-chain alkyl group at the end used are shown in Table 2.

(Hereinafter, blank space) Example 1 As Examples 1 to 8 of the present invention, the degree of polymerization was 1750. Saponification degree 98.
5 mol% PVA (Kuraray Boval PVA-117)
To 55 parts, add 32 parts of cornstarch, 7 parts of Maconol TS-253 (manufactured by Matsumoto Yushi Seiyaku Wa) as an oil agent, and 10 parts of acrylic Marposol TS-189 (20% aqueous solution, manufactured by Matsumoto Yushi Seiyaku QP), and further A Wi liquid with a concentration of 12% was prepared by adding 1 to 5 parts of a PVA-based polymer having a long chain alkyl group at the end, and the stability of the Wi liquid was examined. The stability of the size liquid at 90°C and 30°C was very good when a PVA-based polymer having a long-chain alkyl group at the end was added.

Furthermore, this size liquid was cast onto a drum at about 70°C to create a film of about 60 μm, and this film was heated at 20°C x 65%.
The physical properties of the humidity conditioner film were measured under RH for 7 days. The results are shown in Table-3. A sizing agent containing a PVA-based polymer having a long-chain alkyl group at the end has high strength and elongation, particularly high elongation, and increased flexibility.

As Comparative Example 1, 32 parts of cornstarch, 7 parts of Maconol TS-253, PVA-117e55fill,
A glue solution containing 10 parts of Mahozo-JL, TS-189 (20x aqueous solution) was prepared in the same manner, and the stability of the m solution was investigated. A tendency to separate was observed at both 90°C and 30°C, indicating that the stability of the w4 liquid was poor.

As Comparative Example 2, 55 parts of PVA-117, 32 parts of corn starch, 7 parts of Maconol TS-253, 10 parts of Mavosol TS-189 (20X aqueous solution), and 5 parts of a PVA polymer having C3H7- at the end were used. When the physical properties of the added sizing agent were examined in the same way, they were not much different from those that did not contain the PVA-based polymer having a long-chain alkyl group at the end.
The number of carbon atoms is preferably 4 or more.

As Comparative Example 3, a polymerization degree of 70 was prepared by copolymerizing 55 parts of PVA-117, 32 parts of cornstarch, 7 parts of Maconol TS-253, 10 parts of Marpozol TS-189 (20χ aqueous solution), and 0.6 mol% of lauryl vinyl ether.
Modified PVA (PVA-L) with 0S saponification degree of 98.6 mol%
A sizing solution was prepared in the same manner using a sizing agent to which 5 parts of (abbreviated as) were added.

Further, as Comparative Example 4, 55 parts of PVA-117, 32 parts of cornstarch, 7 parts of Maconol TS-253, 10 parts of Marpozol TS-189 (20% aqueous solution), 3 mol% of versatic acid, and 1 mol% of itaconic acid were prepared. Mol% copolymerized modified PV with a polymerization degree of 700S and a saponification degree of 98.5 mol%
A sizing solution was similarly prepared using a sizing agent to which 5 parts of A (abbreviated as PVA-V) was added. When the stability of the size liquid and the physical properties of the film were investigated for Comparative Examples 3 and 4, it was found that Comparative Example 1
Although the stability of the size liquid was improved compared to that of the sizing agent, there was still a slight tendency to separate, and it was less stable than the sizing agent using a PVA-based polymer having a long chain alkyl group at the end of the example of the present invention. . Furthermore, the elongation of the film is lower than that of the examples of the present invention and is insufficient.

These results are shown in Table 3.

*Method of determining stability of glue solution (a) State of paste liquid after filtration at 90°C for 5 hours.

(b) State of paste after being left at 30°C for 24 hours.

0 Very good O Good △ Slight tendency to separate × Separates * Measuring method of film physical properties Shimadzu Autograph DC3-100 model (manufactured by Shimadzu Corporation) 2
Sample diameter: 15 mm, thickness: approximately 60 μm 1 So-called constant length: 50 mm, tensile speed: 500 mm/min Example 2 As Example 9 of the present invention, Cl282! degree of polymerization with l- 1700. 55 parts of PVA polymer (P-4) with saponification degree of 88.5 mol%, 32 parts of cornstarch, 7 parts of Maconol 222 (specially manufactured by Matsumoto Yushi Seiyaku) as an oil agent,
10 parts of Marposol TS-189 (2 oz aqueous solution) was dissolved in water to prepare a paste having a concentration of 12%: A. The stability of this paste liquid at 90°C and 30°C was very good.

Further, using this paste solution, a film was formed on a drum in the same manner as in Example 1, and the physical properties of the film were measured. The film is homogeneous, 20℃ x 65
The film strength at %RH was 1.3 kg/-1 degree of 86%, showing good physical properties in terms of strength and elongation.

Example 3 As Invention Example 10, the degree of polymerization was 1750. Saponification degree 88.5
Mol% of PVA (Kuraray Boval PVA-217)
80 parts, 20 parts of modified starch Cofilm 80 (manufactured by Tamako National Co., Ltd.), 10 parts of Maconol TS-253, and a terminal with a polymerization degree of 500 and a saponification degree of 88.5 mol% having Cl21 (25-) at the terminal. and 10 parts of a long-chain alkyl group PVA polymer (P-6) were dissolved in water to prepare a paste with a concentration of 12%.This paste was heated at 90°C and 30°C.
The stability was very good. Further, using this size solution, the physical properties of the film were measured on a drum in the same manner as in Example 1. Both strength and elongation are good.

As Invention Example 11, 80 parts of Kuraraybovar PVA-217, 20 parts of Cofilm 80, Marbosol TS
-10 parts of 189 (20% aqueous solution), Maconol TS-
253 in 5 parts, Cl8H37- at the end, polymerization degree 1
00. PVA polymer with saponification degree of 99.0 mol% (P-9
) was dissolved in water to prepare a glue solution with a concentration of 12%. The stability of this paste liquid at 90°C and 30°C was very good. Further, using this paste solution, a film was formed on a drum in the same manner as in Example 1, and the physical properties of the film were measured. Good strength and elongation.

As Comparative Example 5, Kuraray Bovar PVA-217 was used at 80%
20 parts of Corfilm 80, Maconol TS-2
A W4 solution with a concentration of 12% was prepared by dissolving 10 parts of 53 in water. During this period (at night, at 90°C and 30°C, stability was checked and both showed poor separation.Furthermore, using this talI solution, a film was formed on a drum in the same manner as in Example 1, and the physical properties of the film were measured. .The strength and elongation are inferior to Invention Example 10.

As Comparative Example 6, Kuraray Bovar PVA-217 was used at 80%
1 part, 20 parts of Corfilm 80, Marbosol 'l'
10 parts of S-189 (20X aqueous solution), Maconol T
Add 5 parts of S-253 and dissolve it in water to make a concentration of 12
% glue solution was prepared. When the stability of this paste liquid was examined at 90°C and 30°C, it was found that the paste did not separate well. Also, using this paste solution, a film was formed on a drum in the same manner as in Example 1, and the physical properties of the film were measured. The strength and elongation are inferior to Invention Example 11.

As Comparative Example 7, Kuraray Bovar PVA-217 was used at 80%
1 part, 20 parts of Corfilm 80, Marbosol TS-1
10 parts of 89 (20χ aqueous solution), Maconol TS-25
Polymerization degree is 700.3 by copolymerizing 5 parts of lauryl vinyl ether with 0.6 mol% Modified PV with M degree of 98.6 mol%
A ta++ solution with a concentration of 12% was prepared by dissolving 5 parts of A (PVA-L) in water. 90℃ of this m liquid
When looking at the stability at 30° C., although it was somewhat better than Comparative Example 6, it still did not separate well.

Further, using this paste solution, a film was formed on a drum in the same manner as in Example 1, and the physical properties of the film were measured. The strength and elongation are inferior to Invention Example 11.

These results are shown in Table-4.

(Left below) Example 4 As Invention Example 12, the degree of polymerization was 1750. Saponification degree 88.5
Mol% of PVA (Kuraray Boval PVA-217)
55 parts, 32 parts of cornstarch, Marbosol TS-1
89 (20χ aqueous solution), 5 parts of PVA-based polymer (P-3) having Cl2825- at the end and having a degree of polymerization of 500 and a degree of saponification of 99.0 mol%, and 5 parts of Maconol TS-253.
~15 parts were dissolved in water to prepare a glue solution with a concentration of 10%. Further, using this paste solution, a film was formed on a drum in the same manner as in Example 1, and the physical properties of the film were measured.

As Comparative Example 8, 55% of Kuraray Bovar PVA-217 was used.
parts, cornstarch 32 parts, polymerization degree 550, saponification degree 8
8.5 mol% PVA (Kuraray Boval PVA-20
5), 10 parts of Marposol TS-189 (20X aqueous solution 1), 5 to 1 part of Vco/-ol TS-253.
5 parts of the mixture was dissolved in water to prepare a glue solution with a concentration of 10%. Using this paste solution, a film was formed on a drum in the same manner as in Example 1, and the physical properties of the film were measured.

As Comparative Example 9, 55% of Kuraray Bovar PVA-217 was used.
part, 32 parts of corn starch, and 0.6 mol% of lauryl vinyl ether were copolymerized, with a degree of polymerization of 700 and a degree of SI&I of 98.
．． A mixture of 5 parts of 6 mol% modified PVA (PVA-L), 10 parts of Mavosol TS-189 (20% aqueous solution), and 5 to 15 parts of Maconol TS-253 is dissolved in water to give a 10% a degree. A glue solution was prepared. Using this paste solution, a film was formed on a drum in the same manner as in Example 1, and the physical properties of the film were measured.

The results are shown in Table 5, and it can be seen that adhesives that do not use terminal hydrophobic group-modified PVA tend to have lower elongation as the amount of oil used increases; Even if up to about 10 parts of oil were added to the paste using the combination, the elongation increased, indicating that the homogeneity of the film was increased.

(The following is a blank space) Example 5 Invention examples 13 to 15 include Invention examples 2.4 of Example 1.
．． Cotton yarn was sized using a sizing agent having the same composition as in Example 7, and weaving was performed using the sized yarn to obtain the results shown in Table 6. In addition, as Comparative Example 10.11, cotton yarn was laminated using a sizing agent with the same composition as Comparative Example 1.3 of Example 1, and weaving was performed using the sizing yarn, and the results shown in Table 6 were obtained. Ta.

P having a long chain alkyl group at the end of Invention Examples 13 to 15
It can be seen that the sized yarn using the VA polymer has better physical properties and better weavability than those of Comparative Examples 10 and 11.

Yarn: Cotton 503'l Type of fabric: Plain weave Broad fabric density: Warp 150/ind weft 120
Book/Inch Sizing Machine Baba 2 Box Type Gluing Temperature
90℃ Gluing speed 45/min 1 machine 0 production air jet rotation speed
500 rpm *Measuring method of strength and elongation of grated yarn Shimadzu Autograph DC3-100 model used 20℃ x 65%
After conditioning the humidity for 72 hours or more at RH, the test piece was measured at an interval of 200 mm, a tensile speed of 200 mm/min, and a wear strength measurement method using a TM type stand resultant force tester. represent.

*Weaving efficiency The ratio of the actual weaving amount to the weaving amount when the loom does not stop due to problems such as thread breakage.

(The following is a blank space) 4. Description of the drawings FIG. 1 is a diagram showing the relationship between the content of the PVA-based polymer in the PVA-based polymer and cornstarch mixture and the viscosity of the aqueous solution. In the figure, X represents the content (wt%) of the PVA polymer in the total solid content, and Y represents the viscosity of the water IF liquid at 20° C. as measured by a B-type viscometer.

Claims (1)

[Claims] Polyvinyl alcohol (A), with 4 to 50 carbon atoms at the end
It consists of a polyvinyl alcohol polymer (B) having a long chain alkyl group, starch (C) and an oil agent (D), and [
(A) + (B)] 10 to 100 parts by weight of (C)
1900 parts by weight, and (D) is [(A)+(B)]1
0.1 to 200 parts by weight per 00 parts by weight, and (A) is 0 to 10,000 parts by weight per 100 parts by weight of (B).
Parts by weight, and (B) is 1 part by weight per 100 parts by weight of (C).
A sizing agent for fibers, in which the amount of (B) is 0.1 part by weight or more based on 100 parts by weight of (D).