JPS5933712B2 - Sizing agent for textiles - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a sizing agent for textiles which has significantly improved anti-slip properties.

Conventionally known warp sizing agents include polyvinyl alcohol with a degree of saponification of about 86 mol% or more, starch, acrylic resin, vinyl acetate-maleic anhydride copolymer, styrene-maleic anhydride copolymer, etc. When these are used alone, they lack adhesion to hydrophobic synthetic fibers such as polyester, nylon, polypropylene, and polyacrylonitrile, resulting in insufficient conjugation power, and compositions with improved adhesion have poor opening properties during weaving. There was a problem.

Therefore, glues that use a combination of polyvinyl alcohol with a degree of saponification of about 86 mol% or more and acrylic resins are currently in widespread use, but they still do not have sufficient conjugation power, can't ignore the drop-off, and especially There is a problem in that the accumulated droplets absorb moisture and tend to become gummy, and are not necessarily completely satisfactory.

However, the present inventors found that polyvinyl alcohol with a low saponification degree of 40 to 80 mol% has good adhesive strength even to hydrophobic synthetic fibers when used as a sizing agent.
We found that the binding power is excellent because the hygroscopicity and stickiness do not increase, and the amount of falling is also reduced, making it difficult for the falling to gum up. In some cases, the amount of falling motion was so large that it could not be ignored.

The amount of falling is thought to be greatly influenced by a special combination of conditions such as the processing conditions of polyester processed yarn, the type of yarn oil, and the amount of yarn oil attached. The shedding properties of each company's warp threads (polyester processed) with glue vary widely, as shown in the table below.

However, as a sizing agent, monomethyl maleate-modified low saponification polyvinyl alcohol with a monomethyl maleate content of 0.5 mol% and a saponification degree of vinyl acetate component of 70 mol% was used.
00, degree of saponification 88 mol%)/acrylic (copolymer of ethyl acrylate-methyl methacrylate-methacrylic acid-acrylic acid 50:35:10:5 by weight) combination sizing agent is also listed.

The oil agent used was a normal general-purpose oil agent in both adhesives.

The number of times of friction before falling is based on a falling evaluation which will be described in detail later, and the greater the number of times, the less likely it is to fall.

As is clear from the above example, low-saponification polyvinyl alcohol is more effective in preventing falling than the currently widely used glue consisting of polyvinyl alcohol and acrylic. There is also a remarkable effect that it is difficult for the movement to become a gum amplifier), but even in that case, depending on the type of warp threads, the anti-falling properties may not be sufficient.

As mentioned earlier, this variation is thought to be due to the difference in the adhesion of raw yarn oil.
If 1 or A2 is washed with a solvent to remove the raw thread oil and then pasted with a size, the falling movement is significantly prevented compared to a size that is applied as is.

However, setting up a process to remove the raw yarn oil before sizing increases the number of steps and increases costs, and there are site restrictions, so it is not practical to adopt it in an actual sizing factory, and eventually In any case, it goes without saying that it is desirable to develop a sizing agent for textiles that does not cause any trouble no matter what kind of warp threads are used.

The present inventors, therefore, conducted studies on a number of surfactants in an attempt to prevent the above-mentioned dropout by improving the oil agent.

The results showed that almost all surfactants had a tendency to have little effect in preventing falling, or even to increase the amount of falling, but among them, a very limited range of surfactants, that is, alkyl group has 8 or 9 carbon atoms, and the number of added moles of ethylene oxide (average number of added moles, hereinafter the same) is 5 to 1
Polyoxyethylene alkylphenol ether (No. 3) gives good results, and among them, polyoxyethylene nonylphenol ether with 9 carbon atoms and 6 to 9 moles of ethylene oxide is unique in that it is highly effective in preventing falling. After discovering this fact, we have completed the present invention.

Such remarkable effects can only be achieved when polyoxyethylene alkylphenol ethers in a very narrow range as mentioned above are used as oil agents, and nonionic surfactants other than polyoxyethylene alkylphenol ethers or general anionic surfactants are used. However, cationic surfactants cannot achieve the desired purpose.

Furthermore, even if it belongs to polyoxyethylene alkylphenol ether, those whose alkyl group has carbon atoms other than 8 or 9 cannot achieve the desired purpose.

Further, even if the polyoxyethylene alkylphenol ether has an alkyl group having 8 or 9 carbon atoms, the anti-slip effect will not be sufficient if the number of moles of ethylene oxide added is less than 5 or more than 13.

Among the above, the particularly excellent effect is that the alkyl group has 9 carbon atoms, that is, polyoxyethylene nonylphenol ether, and the number of moles of ethylene oxide added is 6.
It is exhibited in cases of ~9.

The polyvinyl alcohol used in the present invention is a low saponification degree polyvinyl alcohol with a saponification degree of 40 to 80 mol%. Those with a saponification degree of less than 40 mol% have poor desizing properties, and those with a saponification degree of more than 80 mol%. has insufficient adhesion to hydrophobic fibers.

A particularly preferred saponification degree range is 50 to 75 mol%.

Such low saponification degree polyvinyl alcohol may be a saponified homopolymer of vinyl acetate, but in this case, it is insoluble in water or has a low clouding point of about room temperature to 40°C, so it is difficult to use when preparing an aqueous solution or as a glue. A phenomenon in which a polymer precipitates from an aqueous solution and becomes cloudy at a certain temperature is usually observed.

This cloudy phenomenon impedes the preparation of a uniform size solution and also the uniform application of the size, so in such cases, in order to eliminate the cloud point, it is necessary to add alcohol such as methanol or ethanol to the size solution, or add a special solubilizing agent. Treatment is required.

On the other hand, in the present invention, modified polyvinyl alcohol with a low degree of saponification can also be used.

Among such modified polyvinyl alcohols, carboxylated polyvinyl alcohols with a degree of carboxylation of 0.02 to 2 mol% and sulfonated polyvinyl alcohols with a degree of sulfonation of 0.02 to 2 mol% are particularly preferred.

The system of polyvinyl alcohol modified in this way does not become cloudy even when the aqueous solution is heated, so it is easy to prepare the size liquid and apply the size uniformly, and it also has good results in terms of sizing agent performance such as binding power and prevention of falling. give.

Carboxylated polyvinyl alcohol is produced by copolymerizing unsaturated acids such as crotonic acid, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, monoalkyl maleate, fumaric acid, and itaconic acid with vinyl acetate, and then quenching the copolymer. It can be obtained by converting

Dialkyl maleate is converted into monoalkyl maleate type during polymerization or saponification reaction, and acrylic acid amide and methacrylic acid amide are also used as comonomers because they are at least partially converted into acrylic acid or methacrylic acid type during saponification reaction. can.

Sulfonated polyvinyl alcohol is obtained by copolymerizing an olefin sulfonic acid or salt such as ethylene sulfonic acid, allyl sulfonic acid, meta-allylsulfonic acid, etc. with vinyl acetate, and saponifying the copolymer.

Carboxylation or sulfonation is usually introduced by the copolymerization method described above, but it is also possible to introduce it by grafting or acetalizing polyvinyl alcohol using a monomer or aldehyde having a carboxyl group or sulfone group. be.

In any case, the degree of ruboxylation or sulfonation is preferably selected from the range of 2 mol% or less, preferably from 0.02 to 2 mol%; if it exceeds 2 mol%, the tackiness increases and it is not suitable for use as a fiber sizing agent. Performance tends to decrease.

In the present invention, polyvinyl alcohol, alkyl vinyl ether, alkyl vinyl ketone, acrylic resin copolymerized with α-olefins such as ethylene, propylene, isobutylene, α-pentene, α-octene, α-decene, α-dodecene, α-octadecene, etc. Polyvinyl alcohol copolymerized and modified with acid ester, methacrylic acid ester, saturated branched fatty acid vinyl, vinyl halide, vinylidene halide, acrylonitrile, methacrylonitrile, etc. can also be used.

The degree of modification is at most 10 mol%, usually 5 mol% or less.

Polyvinyl alcohol may be graft-modified with these seven polymers.

Further, polyvinyl alcohol may be subjected to post-denaturation such as urethanization or acetalization.

These modified polyvinyl alcohols may have a low electric point or be difficult to dissolve in some cases, but in such cases, measures to eliminate the electric point may be taken as in the case of saponified homopolymers of vinyl acetate. It is necessary to take solubilization measures.

In the present invention, the amount of polyoxyethylene alkylphenol ether whose alkyl group has 8 or 9 carbon atoms and the number of moles of ethylene oxide added is 5 to 13 is 0.01 to 10% by weight based on the low saponification degree polyvinyl alcohol. , especially in the range of 0.1 to 6% by weight.

If the amount used is too small, the effect of preventing falling will be insufficient, and if it is too large, the strength of the adhesive film will deteriorate and the falling will increase.

Although the specific polyoxyethylene alkyl phenol ether described above can be used alone as an oil agent for low saponification degree polyvinyl alcohol, it produces sufficient effects, but this does not preclude its use in combination with other oil agents.

In particular, it has been found that the combined use with an anionic surfactant is more effective in preventing falling and improving weaving efficiency.

The above-mentioned specific polyoxyethylene alkyl phenol ether can be incorporated into low saponification degree polyvinyl alcohol particles in advance and poured into water, or it can be added into water together with low saponification degree polyvinyl alcohol when preparing a size liquid. is prepared.

At this time, other known sizing agents may be used in combination with low saponification degree polyvinyl alcohol, and antifoaming agents, various oils, and auxiliaries may also be added.

The resin concentration is usually controlled to about 3 to 11% by weight.

The size solution prepared in this way is used for sizing filament yarn, woolly processed paper, spun yarn, etc., but it effectively prevents falling, regardless of the type of warp yarn or the adhesion status of raw yarn oil. Dogs are extremely helpful in contributing to this industry.

Next, the fiber sizing agent of the present invention will be further explained with reference to examples.

1% or less" indicates weight % unless otherwise specified.

Example 1 Monomethyl maleate with monomethyl maleate content of 0.5 mol% and degree of saponification of vinyl acetate component of 71.4 mol%.
Saponified vinyl acetate copolymer 7.6% polyoxyethylene nonylphenol ether with an added mole of ethylene oxide of 7 and an HLB value of 11.7
0.3% silicone smoothing agent (Cytex Silicone 51 manufactured by Goo Kagaku Co., Ltd.) 0.2% water
Using the rest of the size solution having the above composition, sizing, weaving, and desizing of the polyester processing system were carried out.

The results are shown in Table 1.

Gluing machine Tsudakoma KS-J type warping slatsher gluing condition frame Number of lines: 1050 lines Full load: 180-260 kg Sizing liquid temperature: 50°C Drying temperature: Chamber 120°C x 2 Cylinder 100°C x 2 Winding speed 95 m/m Size 7g 1.2% Draft sizing amount 9-10% Weaving conditions The woven fabric is 5-ply satin, the total number of warps is 8400, and the weave is 37.
．． 5 inches, weft density 107 A size.

The loom was an automatic loom I 6 orpm, and 40 stitches were woven, with each stitch being 50 m long.

Degreasing conditions 2 g/l! of soda and 2 g/IJ of detergent (Monogen, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) at a temperature of 90°C.
Continuous treatment at ~95°C for 30-60 seconds followed by water washing.

Comparative Examples 1 to 18 Sizing, weaving, and desizing of processed polyester yarns were carried out in the same manner as in Example 1, except that a sizing solution having the following composition was used.

The results are also shown in Table 1. Control example 1 (Current general-purpose polyvinyl alcohol/acrylic combined glue formulation) Polyvinyl alcohol with a degree of polymerization of 500 and a degree of saponification of 88 mol% 4.5% ethyl acrylate-methyl methacrylate-methacrylic acid-acrylic acid (50: 35) : 10:5 weight ratio) copolymer soda salt 4.5% Cytex T-294 f' IJ vinyl alcohol/acrylic combination (manufactured by Gooh Kagaku Co., Ltd.) (general-purpose oil used in company glue).

It consists of a mixture of several surfactants.

0.5% silicone smoothing agent (Cytex Silicone 51 manufactured by Goo Kagaku Co., Ltd.) 0.2%, water
Remaining Control Example 2 A size solution was prepared in the same manner as in Control Example 1, except that polyoxyethylene nonylphenol ether having an addition mole of ethylene oxide of 7, which was used in Example 1, was used in place of Cytex T-294.

Control Examples 3 to 18 A size solution was prepared in the same manner as in Example 1, except that the following surfactant was used in place of polyoxyethylene nonylphenol ether.

Control example 3 Cytex T-294 Control example 4 Polyoxyethylene monooleyl ether control example with an HLB value of 8.4 5 Polyoxyethylene monooleyl ether control example with an HLB value of 11.8 6 Dioctylsulfocobacic acid sodium control example 7 Polyoxyethylene lauryl ether control example with HLB value of 15.3 8 Polyoxyethylene oleyl ether control example with HLB value of 12.4 9 Polyoxyethylene cetyl ether control example with HLB value of 10.5 1° Polyoxyethylene lauryl ether control example with HLB value of 8.4 Oxyethylene diolate control example 11 Polyoxyethylene sorbitan monostearate control example with HLB value 14.9 12 Polyoxyethylene sorbitan triolate control example with HLB value 11.0 13 Glyceryl monostearate control example with HLB value 11.0 14 Sorbitan monolaurate control example with HLB value 8.6 1
5 Fluorinated nonionic surfactant control example 16 HLB value 15.0 sucrose fatty acid ester control example 17 HLB value 13.0 sucrose fatty acid ester control example 18 HLB value 8.0 sucrose fatty acid ester Table 1 As is clear from Control Example 1 (currently general-purpose polyvinyl alcohol/acrylic combination glue formulation),
The formulation of Comparative Example 1 may have less shedding depending on the warp type, but generally speaking, the anti-dropping properties are not very good.

In addition, there is a strong tendency for gum-up during falling, which is closely linked to a decline in fabric quality.

Comparative Example 2 is the same as Comparative Example 1 in which only the oil agent was changed, but even though polyoxyethylene nonylphenol ether, which has 7 moles of added ethylene oxide, which is extremely effective in the present invention, is used, the effect is almost the same as that of Comparative Example 1. And,
No improvement effect was observed.

Comparative Examples 4 to 18 use polyvinyl alcohol with a low degree of saponification, so they have generally better anti-drop properties than Comparative Example 1, and their major feature is that they have less tendency to gum up when falling. ing.

However, depending on the type of warp yarn, the anti-drop properties are still unsatisfactory.

Example 1 is not only compared with Control Examples 1 and 2, but also with Control Examples 3 and 1.
Compared to No. 8, the anti-drop performance is significantly improved.

Even if the warp yarns of the 31 types of company A, which are considered to have the highest amount of shedding, are used, no practical problems arise.

Examples 2 to 7 A size solution was prepared in the same manner as in Example 1, except that the following was used instead of polyoxyethylene nonylphenol ether with an addition mole number of 7 ethylene oxides, and the following sizing, weaving, and desizing procedures were carried out. I did it.

The results are shown in Table 2.

Example 2 Number of moles of added ethylene oxide is 7, HLB value is 11.
7 polyoxyethylene nonylphenol ether 80
% and linear secondary alkanesulfonate soda salt 20%.

Example 3 Number of moles of added ethylene oxide is 7, HLB value is 11.
7 polyoxyethylene nonylphenol ether 70
% and 30% sodium dioctyl sulfosuccinate.

Example 4 Number of moles of added ethylene oxide is 6, HLB value is 10.
9 polyoxyethylene nonylphenol ether.

Example 5 Number of moles of added ethylene oxide is 8, HLB value is 12.
2 polyoxyethylene nonylphenol ether.

Example 6 Number of moles of added ethylene oxide: 12, HLB value: 14
1 polyoxyethylene nonylphenol ether.

Example 7 Number of moles of added ethylene oxide is 9, HLB value 13.
1 polyoxyethylene octylphenol ether.

Control Example 19 Polyoxyethylene nonylphenol ether with an added mole of ethylene oxide of 4 and an HLB value of 89.

Control Example 20 Polyoxyethylene nonylphenol ether with an added mole of ethylene oxide of 14 and an HLB value of 14.7.

Comparing Examples 2 and 3 with Example 1, it can be seen that even better effects can be achieved by using an anionic surfactant in combination.

Comparing Example 1 with Examples 4 to 7, it can be seen that polyoxyethylene nonylphenol ether with an added mole number of ethylene oxide of 6 to 9 is particularly excellent.

Examples 8-12 In Example 1, only the resin components were changed as follows.

The results are shown in Table 3. Example 8 A saponified crotonic acid-vinyl acetate copolymer with a crotonic acid content of 1.0 mol% and a degree of saponification of the vinyl acetate component of 72 mol%.

Example 9 A saponified acrylic acid-vinyl acetate copolymer with an acrylic acid content of 1.0 mol% and a degree of saponification of the vinyl acetate component of 72 mol%.

Example 10 Allylsulfonic acid sorter content 0.2 mol%
, a saponified product of sodium allylsulfonic acid and vinyl acetate copolymer with a degree of saponification of the vinyl acetate component of 70 mol%.

Example 11 Saponified sodium methalylsulfonate-vinyl acetate copolymer with a sodium methalylsulfonate content of 0.3 mol% and a saponification degree of vinyl acetate component of 70 mol%.

Example 12 Polyvinyl alcohol with a degree of saponification of 73 mol% and a degree of polymerization of 800.

However, this polyvinyl alcohol has an equinox point of 32°C and becomes cloudy at the gluing temperature (glue bath 50"C), so
Equinox points were erased by replacing 10% of the water with methanol.

Claims (1)

[Scope of Claims] 1 The main component is polyvinyl alcohol with a low saponification degree of 40 to 80 mol%, the oil agent has an alkyl group of 8 or 9 carbon atoms, and the number of moles of ethylene oxide added is 5 to 1.
Fiber glue L2 containing polyoxyethylene alkyl phenol ether of No. 3 Polyoxyethylene alkyl phenol ether has an added mole number of ethylene oxide of 6 to 9
The fiber sizing agent according to claim 1, which is polyoxyethylene nonylphenol ether. 3. The fiber sizing agent according to claim 1, wherein the low saponification degree polyvinyl alcohol is carboxylated polyvinyl alcohol having a carboxylation degree of 0.02 to 2 mol%. 4 Low saponification degree polyvinyl alcohol has a sulfonation degree of 0
．． The fiber sizing agent according to claim 1, which is sulfonated polyvinyl alcohol with a content of 0.02 to 2 mol %.