JPH0730514B2 - Sizing agent for fiber sizing - Google Patents

Description

TECHNICAL FIELD The present invention relates to a sizing agent for fiber sizing having good weaving property, more specifically, polyvinyl alcohol and a long-chain alkyl group having 4 to 50 carbon atoms at the terminal. The present invention relates to a sizing agent for fiber sizing, which contains a polyvinyl alcohol-based polymer, starch, and an oil agent and has excellent weavability.

Conventional technology Conventionally, natural fibers such as cotton and wool, rayon, acetate,
Semi-synthetic fibers such as Bemberg, nylon, polyester,
When manufacturing synthetic fibers such as acrylics, there are shuttle rooms as well as gripper rooms, rapier rooms, water jet rooms, air jet rooms, etc. as weaving machines. For the warp sizing agent used in the preparatory stage, more and more severe performance is required for weaving with high efficiency.

As these sizing agents for warp sizing, starch, polyvinyl alcohol (hereinafter abbreviated as PVA), polyacrylic acid ester-based sizing agents and the like are used alone or usually as a mixture, and an oil agent, carboxymethyl cellulose, etc. Has been used together. Among them, PVA is widely used.In addition to normal fully saponified PVA and partially saponified PVA, anion-modified PV
Those using A or cation-modified PVA are also known. In addition, a modified PVA copolymerized with a hydrophobic group (Japanese Patent Application No. 56-55440)
58-174683) is already known. All of these are aimed at improving the adhesiveness of hydrophobic fibers such as polyester and nylon to the hydrophobic fibers when they are glued, thereby improving the tying force, the abrasion resistance and the downing effect. is there.

A technique for producing a PVA-based polymer having a long-chain hydrocarbon group at the terminal is already known (Japanese Patent Publication No. 183-131, Japanese Patent Publication No. 58-108207, Japanese Patent Publication No. 59-102946). Further, it is already known that these PVA are used for surface modification of molded articles by improving wear resistance by decreasing the friction coefficient when these PVA are made into fibers (Japanese Patent Publication No. 44-22218). (Japanese Patent Publication No. Sho 46-18258).

Problems to be Solved by the Invention As warp sizing agents for spans, it is common to use PVA and starch in combination, but since PVA is a synthetic polymer, the quality is stable and film formation It is widely used because of its good performance, good film properties, and good adhesion to fibers. On the other hand, starch is used because it is inexpensive and easy to obtain. However, since both PVA and starch are high-molecular compounds, they have poor compatibility, the stability of the mixed aqueous solution of PVA and starch is poor, and they are separated immediately. Since starch also has an aging phenomenon, leaving these aqueous solutions unattended The gluing performance deteriorates rapidly within 1 to 2 days, making it almost impossible to reuse.

Acrylic pastes, oils or carboxymethylcellulose are appropriately added to these PVA and starch for use.
Generally, the purpose of using this oil agent is to (1) give the surface of the yarn smoothness.

(2) The penetration of the paste solution is promoted.

(3) It gives hygroscopicity to the sized yarn.

(4) Antistatic.

(5) Prevent the thread from sticking to the drying cylinder of the sizing machine.

(6) Give the yarn flexibility.

(7) Improve the thread handling.

Is said. There are various paraffin waxes and surfactants as the oil agent, but the above (1), (5),
When the functions (6) and (7) are mainly intended, paraffin wax is mainly used.
Although these paraffin waxes are supposed to be emulsified and dispersed in an aqueous solution by using an emulsifier composed of a nonionic surfactant or an ionic surfactant,
Essentially, the compatibility with PVA and starch is poor and the stability of the paste solution is poor. Further, when this paste solution is dried to form a film, the homogeneity of the film is impaired, and therefore the strength and elongation of the film decreases even though flexibility can be imparted. In particular, the reduction in elongation is large and the entire coating becomes brittle, reducing the resistance to friction, and when these sizing agents are glued onto warps for production, they are not sufficient for high-quality woven fabrics and high-speed looms such as air jet loom. The weaving efficiency is not good.

For such a state, a warp glue paste agent using an anion-modified PVA, a cation-modified PVA, or a PVA in which a hydrophobic group is copolymerized is heated in water to dissolve the paste agent to prepare a paste solution. At times, it can be seen that the size of the sizing solution is slightly improved, but it is not enough, and the homogeneity of the film after the sizing liquid is dried is insufficient, so that the weaving property is sufficient for high-class fabrics and high-speed looms. I cannot say that.

When an acrylic acid ester paste is added to a mixture of PVA, starch and an oil agent, the overall compatibility is slightly improved, but this is still insufficient.

Means for Solving the Problem For such fiber paste containing PVA, starch and oil, PV having a long chain alkyl group having 4 to 50 carbon atoms at the end
By adding the A-based polymer, the compatibility between PVA and starch is improved, the emulsion dispersion of the oil agent is also good, the stability of the paste solution is good, and the film made from the paste solution is homogeneous, The yarn glued with this sizing agent has a large elongation and flexibility,
The present inventors have completed the present invention by discovering that they have excellent wear resistance and downing effect and exhibit excellent performance as a fiber sizing glue.

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 described. The terminal long-chain alkyl group has 4 to 4 carbon atoms.
50 is suitable. Unmodified PV with less than 4 carbon atoms
It is not so different from A and the compatibility with starch is not good. Further, those having a carbon number of more than 50 have too strong hydrophobicity to have poor water solubility of the polymer itself, resulting in poor compatibility with starch and again failing to attain the object of the present invention. Are suitable, but those having 8 to 24 carbon atoms are preferable. Examples of such a group include a linear alkyl group having 4 to 50 carbon atoms, a branched alkyl group, an alkylaryl group, and the like, which have a linking group composed of O, N, S, etc. atoms. Things are included.

Next, the degree of polymerization of the polymer is closely related to the amount of introduced terminal groups, but is preferably 10 to 3000, and more preferably 50 to 2500. The degree of saponification is not particularly limited, but is usually 50 mol% or more, preferably 70 mol% or more.

Further, the polymer can contain a small amount of units in addition to vinyl alcohol units, residual vinyl ester units such as vinyl acetate, and examples of these include α-olefins such as ethylene, propylene and isobutene, and acrylics. Unsaturated acids such as acids, methacrylic acid, crotonic acid, maleic acid, itaconic acid, maleic anhydride or salts or alkyl esters thereof, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, alkyl vinyl ether, N, N-dimethylacrylamide , N-vinylpyrrolidone, vinyl chloride, vinylidene chloride, vinyl propionate, vinyl versaticate, 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 having 4 to 50 carbon atoms at the terminal as described above can be produced by several methods, but industrially, a long chain alkyl group having 4 to 50 carbon atoms is produced. The most preferable method is to polymerize a vinyl ester-based monomer such as vinyl acetate in the presence of a mercaptan having a group, and saponify the obtained polyvinyl ester polymer by a conventional method.

The PVA (A) has a degree of polymerization of 100 to 3000, preferably
200 to 2500, saponification degree of 50 mol% or more, preferably 70 mol% or more, in addition to ordinary PVA, anion-modified, cation-modified or other nonion-modified like PVA-based polymer having a long-chain alkyl group at the terminal Anything is fine.

On the other hand, as the starch (C), starch obtained from wheat, corn, rice, horseradish, sweet potato, tapioca, sago palm and the like is used, but cornstarch is generally suitable.
In addition, modified starch such as oxidized starch, etherified starch, esterified starch and cationized starch produced by using the above-mentioned raw starch as a raw material may be used.

As the oil agent (D), there are various paraffin waxes, surfactants, etc., but paraffin wax, etc. for improving the smoothness of the sizing thread, imparting flexibility, preventing adhesion to the drying cylinder, and improving thread handling. The oil solution is mainly used.

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

First, (C) is 10 for 100 parts by weight of [(A) + (B)].
~ 1900 parts by weight is suitable. If the amount of (C) is less than 10 parts by weight, there will be a problem with the dividing property at the time of sizing, while if it exceeds 1900 parts by weight, the physical properties of the sizing agent film will be poor and the weaving property will be poor.

(D) is 0.1 to 20 per 100 parts by weight of [(A) + (B)].
0 parts by weight is suitable. If it is less than 0.1 parts by weight, the effect of adding the oil agent is not obtained, and if it exceeds 200 parts by weight, the physical properties of the sizing agent film are deteriorated and the weaving property is also problematic.

Further, the PVA (A) is suitable in an amount of 800 to 10,000 parts by weight based on 100 parts by weight of (B).

The PVA polymer (B) having a long chain alkyl group at the terminal is
1 part by weight or more, preferably 3 parts by weight or more is suitable for 100 parts by weight of starch (C). Less than 1 part by weight has no effect.

Further, (B) is appropriate in an amount of 0.1 parts by weight or more, preferably 1 part by weight or more, relative to 100 parts by weight of the oil agent (D), and if less than 0.1 parts by weight, there is no effect in improving the emulsified dispersion of the oil agent.

It can be estimated from the viscosity behavior of the mixed aqueous solution of (B) and (C) that the PVA polymer (B) having a long-chain alkyl group at the terminal has a specific interaction with the starch (C). That is, having a C ₁₂ H _25- alkyl group at the terminal, the degree of polymerization 100,
A mixture of PVA-based polymer having a saponification degree of 99.2 mol% and corn starch at various ratios was put into water, and gelatinized by heating at 95 ° C. for 2 hours with sufficient stirring to prepare an aqueous solution having a concentration of 5% by weight. The viscosity of this aqueous solution at 90 ° C. was measured with a B-type viscometer. Next, PVA with a degree of polymerization of 550 and a degree of saponification of 98.5 mol%
The viscosity of the (Kuraray Poval PVA-105) / corn starch system was measured in the same manner. The results are shown in Fig. 1. First
In the figure, what is represented by the solid line 1 is a PVA polymer / corn starch system having a long-chain alkyl group at the terminal,
What is indicated by the dotted line in 2 is the viscosity behavior of the PVA-105 / corn starch system. While the viscosity of the PVA-105 / corn starch aqueous solution decreases with the increase of the PVA content, the PVA polymer having a long chain alkyl group at the terminal /
The cornstarch-based aqueous solution generally has a higher viscosity than the PVA-105 / cornstarch-based aqueous solution (the viscosity of the aqueous solution of the PVA-based polymer itself is lower than that of the PVA-105 aqueous solution), and the long chain at the end It shows a maximum when the content of the PVA-based polymer having an alkyl group is 10 to 30% by weight, and clearly shows that the PVA-based polymer having a long-chain alkyl group at the terminal and corn starch have a unique interaction. ing.

Modified PVA obtained by copolymerizing a long-chain alkyl group also has the effect of improving the stability of the mixed aqueous solution, but it still has a tendency to easily gel, and it is said that it has no effect on modified starch. On the other hand, the PVA-based polymer (B) having a long-chain alkyl group at the terminal is very likely to have a long-chain alkyl group as a hydrophobic group at the terminal and a PVA moiety as a hydrophilic group, which are very block-shaped. In addition to having surface-active ability, the long-chain alkyl group existing at the end improves compatibility with starch, and the PVA portion at one end has an affinity with the other PVA,
It is considered that the compatibility of these mixtures became very good, and this point is different from the copolymer-modified PVA in which long-chain alkyl groups are randomly contained.

The change in the viscosity of the aqueous solution of the composition of the present invention with time is very small, which indicates that it has an effect of preventing the aging phenomenon of starch. Starch generally consists of amylose and amylopectin, and it is said that this aging phenomenon is caused by crystallization of amylose in starch. It is a known fact that this amylose interacts with higher fatty acids and has good compatibility. The PVA polymer having a long-chain alkyl group at the terminal used in the present invention also has a long-chain alkyl group at the terminal similar to a higher fatty acid, and therefore has an interaction with amylose. It is considered that this is the reason why it has the effect of preventing the aging phenomenon.

On the other hand, although the interaction with amylopectin, which is another component in starch, has not been known so far, the PVA having a long-chain alkyl group at the end used in the present invention is used.
It was found that the system-based polymer interacts with amylopectin as well as amylose. That is, PVA with amylopectin separated from corn starch and a C ₁₂ H _25- long-chain alkyl group at the end and having a polymerization degree of 280 and a saponification degree of 98.5 mol%
A mixture of the polymer with various ratios was put into water, and gelatinized by heating at 95 ° C. for 2 hours to prepare an aqueous solution having a concentration of 1.5% by weight. The viscosity and the transmittance of this aqueous solution at 20 ° C. were measured.

◎ Measurement method of transmittance of aqueous solution Using Hitachi spectrophotometer (manufactured by Hitachi, Ltd.) Wavelength 650 nm, cell width 10 mm Table 1 shows the results.

PVA-based polymer having a long-chain alkyl group at the end although the viscosity at 20 ° C of 1.5% by weight of only the PVA-based polymer having a long-chain alkyl group at the end is about 1 centipoise and is almost the same as water The viscosity increases and the transmittance also increases as the ratio of (1) increases. An aqueous solution of ordinary PVA (Kuraray Poval PVA-105) with a degree of polymerization of 550 and a degree of saponification of 98.5 mol% and amylopectin has a viscosity of about 8 centipoise and PVA-1.
The addition of 05 did not change, and the transmittance was 16 to 18%, which was almost unchanged. From this, it is estimated that the PVA polymer having a long-chain alkyl group at the end also has a specific interaction with amylopectin.

This is because PVA in which long-chain alkyl groups were randomly copolymerized
This is a feature not found in other PVA-based polymers.

In this way, the fact that the PVA-based polymer having a long-chain alkyl group at the terminal has an interaction not only with amylose but also with amylopectin may be the reason why it is compatible with not only raw starch but also oxidized starch and other modified starch. Seem.

A system consisting of PVA, starch and an oil, with 4 to 50 carbon atoms at the end
When the PVA polymer (B) having a long-chain alkyl group is added, the emulsification and dispersion of the paraffin wax is very good, and therefore the viscosity stability is good without phase separation of the paste solution. When a film is formed using this paste solution, a very uniform film is obtained. In this case, the amount of the PVA polymer (B) used is 0.1 parts by weight or more, preferably 1 part by weight, based on 100 parts by weight of the oil agent (D).
It is suitable that the amount is at least parts by weight. Less than 0.1 part by weight has almost no effect.

When paraffin wax is used without using the PVA-based polymer (B) having a long-chain alkyl group at the terminal, these oils have poor compatibility with PVA and starch, resulting in poor stability of the paste solution. The homogeneity of the film formed from this paste solution is not sufficient, and the elongation of the film tends 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 paste solution is improved because the oil agent is evenly dispersed, and the fluidity is good, and the film made from the paste solution is used. In addition to the decrease in elongation due to the homogeneity, even when the wax content in the sizing agent is up to about 10 to 12% by weight, the elongation tends to increase.

When the film is observed under a microscope, it is observed that the paraffin wax is distributed in the form of small particles and a uniform size. PV with long-chain alkyl group at the end
The A-based polymer has very strong surface activity, and it is speculated that this contributes to the improvement of emulsion dispersion. However, since such a remarkable effect is not seen in modified PVA in which a similar hydrophobic group is copolymerized, it is not only a problem of surface activity, but the reason is not clear, but the polymer chain like the copolymer is not. It is considered that the fact that the hydrophobic groups are not randomly contained in the inside, but that the hydrophobic groups are present only at the ends has a great influence. That is, PVA having a hydrophobic group at the end
Has a hydrophobic group only at the end, and one end is hydrophilic, and PVA with good film-forming ability exists in a block form.
It has surface activity and forms a good film with PVA polymer itself, and also has good compatibility with ordinary PVA, anion-modified PVA, cation-modified PVA and other modified PVA, and the film forming ability of the entire paste. It is thought that the physical properties of the coating are improved because of the good

The adhesion of the PVA-based polymer having a long-chain alkyl group to the fiber is not different from that of ordinary PVA or other modified PVA.

From these facts, the sizing agent using the PVA-based polymer having a long-chain alkyl group at the end can be used as a sizing agent having excellent weavability for high-grade woven fabrics and looms.

PVA, a PVA polymer having a long-chain alkyl group at the end, a compounded sizing agent consisting of starch and an oil agent may be used in combination with an acrylic sizing agent, carboxymethyl cellulose, an antifoaming agent and other additives. is there.

In this way, the sizing agent for fiber sizing using the PVA-based polymer having a long-chain alkyl group at the terminal shows very excellent weaving property for high-quality woven fabrics and high-speed looms, but for other woven fabrics and looms. Of course, it also shows excellent weavability.

Action and Effect of the Invention The sizing agent for fiber sizing of the present invention is a sizing agent containing PVA (A), starch (C), and oil agent (D), and PVA having an alkyl group having 4 to 50 carbon atoms at the end. By using the polymer in combination, the compatibility between PVA and starch is improved, and the emulsified dispersion of the oil agent is good, the stability of the paste solution is increased, and it is easy to handle, and the PVA-based heavy chain having a long-chain alkyl group at the end is used. The combination improves the compatibility of the entire sizing agent, and the coating becomes uniform after the sizing liquid is dried, resulting in high strength and elongation of the coating and improved abrasion resistance and downing effect. It is a sizing agent for fibers that has excellent properties and is especially effective for high-speed looms such as high-quality fabrics and air jet loom.

The present invention will be specifically described below with reference to examples, but the following examples do not limit the present invention. All parts and% 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.

Example 1 Inventive Examples 1 to 8 have a polymerization degree of 1750 and a saponification degree of 98.5 mol%.
55 parts of PVA (Kuraray Poval PVA-117), 32 parts of cornstarch, 7 parts of Maconol TS-253 (manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.) as an oil agent, acrylic Marpozol TS-18
10 parts of 9 (20% aqueous solution, Matsumoto Yushi-Seiyaku Co., Ltd.) was added, and 1 to 5 parts of PVA polymer having a long-chain alkyl group at the end was further added to prepare a paste solution having a concentration of 12%. The stability of the paste solution was investigated. The one in which the PVA polymer having a long-chain alkyl group at the end was added had very good stability of the paste solution at 90 ° C and 30 ° C.

Furthermore, this paste solution is cast on a drum at about 70 ° C
A 60 μm film is prepared, and this film is kept at 20 ° C × 65% RH for 7 days.
The physical properties of the film were measured after humidity control for a day. The results are shown in Table-3. The sizing agent to which a PVA polymer having a long-chain alkyl group at the end is added has both high strength and high elongation, particularly high elongation, and also increased flexibility.

As Comparative Example 1, 55 parts of PVA-117 and 32 parts of cornstarch
Part, Maconol TS-253 7 parts, Marpozol TS-189
10 parts of (20% aqueous solution) was prepared in the same manner, and the stability of the solution was examined. Separation tendency was observed at both 90 ° C and 30 ° C, and the stability of the paste solution was not good.

As Comparative Example 2, PVA-117 was added to 55 parts of corn starch 32.
Part, Maconol TS-253 7 parts, Marpozol TS-189
(20% aqueous solution) to 10 parts of a terminal to C ₃ H ₇ - PVA based polymer having a long chain alkyl group at the end was examined similarly the physical properties of the PVA based polymer 5 parts added glue agent with It does not change so much as does not contain, and carbon numbers of 4 or more are good.

As Comparative Example 3, 55 parts of PVA-117 and 32 parts of corn starch were used.
Part, Maconol TS-253 7 parts, Marpozol TS-189
Modified PVA with a degree of polymerization of 700 and a degree of saponification of 98.6 mol% obtained by copolymerizing 10 parts of (20% aqueous solution) with 0.6 mol% of lauryl vinyl ale.
A sizing solution was similarly prepared using a sizing agent containing 5 parts (abbreviated as PVA-L).

Also, as Comparative Example 4, 55 parts of PVA-117, 32 parts of corn starch, 7 parts of Maconol TS-253, and Marposol TS-1.
89 parts (20% aqueous solution) to 10 parts of versatic acid 3 mol%,
Polymerization degree of itaconic acid of 1 mol% 700, degree of saponification 98.
A sizing solution was prepared in the same manner by using a sizing agent containing 5 parts of 5 mol% modified PVA (abbreviated as PVA-V). Comparative Example 3 and Comparative Example 4
When the stability of the paste solution and the physical properties of the film of the product No. 1 were examined, the stability of the paste solution was improved as compared with that of Comparative Example 1, but
Again, there was a tendency to separate a little, and it was more unstable than the sizing agent using the PVA polymer having a long-chain alkyl group at the end of the present invention. Further, the elongation of the coating is lower than that of the examples of the present invention and is insufficient.

The results are shown in Table-3.

* Judgment method for stability of paste solution (a) State of paste solution after being left at 90 ° C for 5 hours.

(B) The state of the paste solution after being left at 30 ° C for 24 hours.

◎ Very good ○ Good △ There is a slight tendency to separate * Separate * Measurement method of film physical properties Using Shimadzu Autograph DCS-100 type (manufactured by Shimadzu Corporation) Sample width 15 mm, thickness about 60 μm, measurement length 50 mm, pulling speed 500 mm / min. Example 2 As Example 9 of the present invention, end C ₁₂ H ₂₅ to - polymerization degree 170 having a
0, 55 parts of PVA polymer (P-4) having a saponification degree of 88.5 mol%, 32 parts of corn starch, and maconol 222 as an oil agent.
(Matsumoto Yushi-Seiyaku Co., Ltd.) 7 parts, Marpozol TS-18
A solution containing 10 parts of 9 (20% aqueous solution) was dissolved in water to prepare a paste solution having a concentration of 12%. The stability of this paste solution at 90 ° C and 30 ° C was very good. Further, using this paste solution, a film was formed on the drum in the same manner as in Example 1, and the physical properties of the film were measured. The film is homogeneous, and the film strength at 20 ℃ × 65% RH is 1.3kg /
mm ² and an elongation of 86% showed good physical properties in both the strong elongation and the elongation.

Example 3 As Example 10 of the present invention, PV having a degree of polymerization of 1750 and a degree of saponification of 88.5 mol%
A (Kuraray Poval PVA-217) 80 parts, modified starch co-film 80 (manufactured by Oji National Co., Ltd.) 20 parts, Maconol TS-253 10 parts, C ₁₂ H _{25-at the} terminal polymerization degree 50
0, 10 parts of long-chain alkyl group PVA polymer (P-6) was added to the terminal with a saponification degree of 88.5 mol% and dissolved in water to give a concentration of 12
% Glue solution was prepared. The stability of this paste solution at 90 ° C and 30 ° C was very good. Further, using this glue solution, a film was formed on the drum in the same manner as in Example 1 and the physical properties of the film were measured. Both strength and elongation are good.

As Example 11 of the present invention, 80 parts of Kuraray Poval PVA-217, 20 parts of Cofilm 80, 10 parts of Marpozol TS-189 (20% aqueous solution), 5 parts of Maconol TS-253, and C ₁₈ H at the end.
_A polymer containing ₃₇ parts of PVA polymer (P-9) having a degree of polymerization of 100 and a degree of saponification of 99.0 mol% was dissolved in water to give a concentration of 12%.
Was prepared. The stability of this paste solution at 90 ° C and 30 ° C was very good. Further, using this paste solution, Example 1
In the same manner as above, a film was formed on the drum and the physical properties of the film were measured. Both strength and elongation are good.

As Comparative Example 5, 80 parts of Kuraray Poval PVA-217, 20 parts of Cofilm 80 and 10 parts of Maconol TS-253 were dissolved in water to prepare a paste solution having a concentration of 12%. The stability of this paste solution at 90 ° C. and 30 ° C. was not good because it decomposed. Further, using this glue solution, a film was formed on the drum in the same manner as in Example 1 and the physical properties of the film were measured. Invention Example 10
Strength and elongation are inferior to.

As Comparative Example 6, 80 parts of Kuraray Poval PVA-217, 20 parts of Cofilm 80, 10 parts of Marpozol TS-189 (20% aqueous solution), and 5 parts of Maconol TS-253 were dissolved in water. A paste solution having a concentration of 12% was prepared. 90 of this glue
When the stability at ℃ and 30 ℃ was observed, neither separated well. Further, using this glue solution, a film was formed on the 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 those of Example 11 of the present invention.

As Comparative Example 7, 80 parts of Kuraray Poval PVA-217, 20 parts of Cofilm 80, 10 parts of Marpozol TS-189 (20% aqueous solution), 5 parts of Maconol TS-253 and 0.6 mol% of lauryl vinyl ether were copolymerized. Degree of polymerization 700, degree of saponification 9
A solution containing 5 parts of 8.6 mol% modified PVA (PVA-L) was dissolved in water to prepare a paste solution having a concentration of 12%. 90 of this glue
As a result of stable production at ℃ and 30 ℃, it was slightly better than Comparative Example 6, but separation was not good.
Further, using this glue solution, a film was formed on the 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 those of Example 11 of the present invention.

The results are shown in Table-4.

Example 4 As Example 12 of the present invention, PV having a degree of polymerization of 1750 and a degree of saponification of 88.5 mol%
A (Kuraray Poval PVA-217) 55 parts cornstarch 3
2 parts, Marposol TS-189 (20% aqueous solution) 10 parts to the end
5 parts by weight of PVA-based polymer (P-3) having a C ₁₂ H ₂₅ − and a degree of polymerization of 500 and a degree of saponification of 99.0 mol% and 5-15 parts of Maconol TS-253.
What was added in part was dissolved in water to prepare a paste solution having a concentration of 10%. Further, using this glue solution, a film was formed on the drum in the same manner as in Example 1 and the physical properties of the film were measured.

As Comparative Example 8, 55 parts of Kuraray Poval PVA-217, 32 parts of corn starch, a polymerization degree of 550, and a saponification degree of 88.5 mol% PVA.
(Kuraray Poval PVA-250) 5 parts, Marpozol TS-
10 parts of 189 (20% aqueous solution) and 5 to 15 parts of Maconol TS-253 were added to dissolve in water to prepare a paste solution having a concentration of 10%. Using this glue 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 parts of Kuraray Poval PVA-217, 32 parts of corn starch and 0.6 mol% of lauryl vinyl ether.
Modified PVA (PV with a polymerization degree of 700 and a saponification degree of 98.6 mol%
A-L) 5 parts, Marpozol TS-189 (20% aqueous solution) 10
And 5 to 15 parts of Maconol TS-253 were dissolved in water to prepare a paste solution having a concentration of 10%. Using this glue 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. Although the sizing agent that does not use the terminal hydrophobic group-modified PVA has a tendency that the elongation tends to decrease as the amount of the oil agent used increases, it has a long-chain alkyl group at the terminal.
It is shown that the sizing agent using the PVA-based polymer, on the contrary, increases the elongation and increases the homogeneity of the film even when the oil agent is added up to about 10%.

Example 5 Inventive Examples 2 to 4 of Example 1 as Inventive Examples 13 to 15
A cotton thread was pasted with a sizing agent having the same composition as the above, and weaving was performed using the sizing thread, and the results shown in Table 6 were obtained. Comparative example
As Nos. 10 and 11, cotton yarn was pasted with a sizing agent having the same composition as in Comparative Examples 1 and 3 of Example 1, and weaving was performed using the sizing yarn, and the results shown in Table 6 were obtained.

Those using the PVA-based polymer having a long-chain alkyl group at the end of Examples 13 to 15 of the present invention have better physical properties of the sizing yarn than those of Comparative Examples 10 and 11, and are excellent in weaving property. I understand.

Raw yarn Cotton 50 ^{S / 1} Type of fabric Plain weave Broad Fabric density Warp 150 / inch Weft 120 / inch Sizing machine Baba 2-box type Gluing temperature 90 ℃ Gluing speed 45 / min Loom Nissan Airjet Rotating speed 500rpm ＊ Glue Measurement method of strength and elongation of yarn using Shimadzu Autograph DCS-100 type, measured after humidity control at 20 ℃ × 65% RH for 72 hours or more Specimen interval 200mm Peeling speed 200mm / min * Abrasion strength measurement method TM-type binding force Using a tester Loaded 600 g, angle 120 ° Expressed by the average number of times of friction until 2 out of 20 pieces are cut.

* Weaving efficiency The ratio of the actual amount of weaving to the amount of weaving when there is no stoppage of the loom due to trouble such as yarn breakage.

[Brief description of drawings]

Figure 1 shows PVA in a mixture of PVA polymer and corn starch.
It is a figure showing the relationship between the content of a system polymer and the viscosity of an aqueous solution. In the figure, X represents the content (% by weight) of the PVA polymer in the total solid content, and Y represents the viscosity of the aqueous solution at 20 ° C. measured by a B-type viscometer.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Junnosuke Yamauchi, 1621 Sakata, Kurashiki City, Okayama Prefecture, Kuraray Co., Ltd. (72) Takuji Okaya, 1621 Sakata, Kurashiki City, Okayama Prefecture, Kuraray Co., Ltd. (56) References JP-A-56-14544 (JP, A) JP-B-46-18258 (JP, B1)

Claims (1)

[Claims] 1. A polyvinyl alcohol (A), a polyvinyl alcohol polymer (B) having a long-chain alkyl group having 4 to 50 carbon atoms at the terminal, a starch (C) and an oil agent (D), and [( (A) + (B)] 100 parts by weight of (C)
Is 10 to 1900 parts by weight, and (D) is [(A) + (B)].
0.1 to 200 parts by weight per 100 parts by weight, and (A) is 800 to 10000 parts by weight per 100 parts by weight of (B),
A sizing agent for fiber sizing, wherein (B) is 1 part by weight or more with respect to 100 parts by weight of (C), and (B) is 0.1 part by weight or more with respect to 100 parts by weight of (D).