JPS5951622B2 - Weaving oil - Google Patents

Description

[Detailed description of the invention] The present invention relates to a weaving oil having good scouring properties.

Conventionally, various waxes have been used during weaving for the purpose of improving smoothness, weavability, and fabric quality.

For example, mineral waxes such as paraffin wax and microcrystalline wax, animal and vegetable waxes such as carnauba wax, beeswax, and candelilla wax, and synthetic waxes such as polyethylene wax are added to the yarn during the weaving preparation process to improve smoothness. contributes to

These waxes are sometimes used alone, but in many cases they are used in combination with each other, and are also mixed with anionic surfactants and nonionic surfactants, and used in the form of emulsification or dispersion in water. There is.

Among these waxes, animal and vegetable waxes are superior in terms of smoothness, emulsifying and dispersing properties, and scouring properties, but these waxes are extremely expensive, and mineral waxes are clearly preferred from an economic point of view. is advantageous.

Therefore, mineral waxes, especially paraffin wax, are the most widely used from an economic point of view, but they have poor scouring properties in post-processing, and in the recent long-term recession in the textile industry, it is difficult to rationalize each process. As a result, the time and amount of scouring agent used in the scouring process have been shortened, resulting in the phenomenon of poor scouring.

Particularly in the case of printed fabrics, dye penetration spots occur and the fabric is likely to be defective.

In view of the current situation, the present inventors believed that the above-mentioned scouring problems could be solved if a self-dispersing wax could be obtained at a low cost, and as a result of intensive research, they found that mineral wax,
That is, paraffin wax or microcrystalline wax is oxidized with a hydroxyl value of 40 to 100 and a melting point of 50 to 90.
It has been shown that by applying esterified oxidized wax with an acid value of 40 to 100, which is obtained by partially esterifying oxidized wax at a temperature of 100°C with a polybasic acid, as an oil for weaving, an oil with good scouring properties and extremely high weaving efficiency can be obtained. This discovery led to the completion of the present invention.

The esterified oxidized wax according to the present invention has an ester group and a carboxyl group in its molecule, and has good smoothness. It has the property of dissolving or dispersing in hot water when mixed with water, and because it is dispersed and dissolved in the dilute solution of soda ash or sodium hydroxide normally used during scouring, it has good scouring removal properties and the wax that has fallen off does not attach again. , has extremely excellent characteristics.

In the oil agent according to the present invention, first, a hydrocarbon wax such as paraffin wax or microcrystalline wax is oxidized to bond hydroxyl groups in the molecule.

In addition to hydroxyl groups, carboxyl groups and ester groups are also generated during the oxidation process, but there is no problem in using it for this purpose.

The hydroxyl value needs to be between 40 and 100.If it is less than 40, even if half-esterified with a polybasic acid, water solubility or water dispersibility will be insufficient and there will be little contribution to scouring properties, and if it is more than 100, oxidation will progress too much and the surface will become smooth. It is undesirable because it causes a lack of properties and a decrease in melting point.

A melting point of 50 to 90°C is required; a melting point below 50°C causes insufficient smoothness, and a melting point above 90°C impairs scouring properties, both of which are undesirable.

The acid value and ester value of the oxidized wax are not particularly limited, but usually the acid value is 10 to 40 and the saponification value is 30 to 100.
It has a certain degree.

These oxidized waxes include NFS (
(manufactured by Nippon Seiro Co., Ltd.) etc. can be used.

Polybasic acids for esterifying these oxidized waxes include maleic acid, fumaric acid, succinic acid, itaconic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid. In addition to aliphatic and aromatic dibasic acids, oxyacids such as tartaric acid and citric acid can also be used.

In addition, lower alcohol esters and acid anhydrides such as monomethyl esters and monoethyl esters of these polybasic acids can also be used, and in the case of acid anhydrides, they are half-esterified with the hydroxyl group of the oxidized wax without a catalyst and remain. Most preferred because it has an acid group.

Esterification of the oxidized wax with a polybasic acid is carried out by a known method.

That is, an oxidized wax and a polybasic acid are mixed in the presence of a catalyst such as para-toluenesulfonic acid, sulfuric acid, phosphoric acid, or boric acid for 150 min.
Heat to ~200°C to esterify.

When polybasic acid anhydrides are used, they do not require a catalyst and can be partially esterified quantitatively at relatively low temperatures.
This method is most preferred because an esterified oxidized wax having an appropriate acid value can be obtained with almost no diesterization.

The ratio of polybasic acid to hydroxyl groups in the oxidized wax is preferably about 1 mole of polybasic acid per hydroxyl group, but this ratio is not necessarily critical.

However, if the polybasic acid is extremely less than 1 mole, not only will the acid value be too low even at the stage of partial esterification, but
Further, diesterification proceeds with excess oxidized wax, and the oxidized wax does not have a carboxyl group bonded to it, making it undesirable because it is not water-soluble or water-dispersible even in the presence of an alkali.

In order to prevent diesterification, it is preferable to use 1 mole or more of the polybasic acid, but if a large amount of excess polybasic acid remains, smoothness will be impaired, so in such cases, it is necessary to wash the polybasic acid with water after esterification. It is preferable to remove the polybasic acid by means.

The acid value of the esterified oxidized wax needs to be 40 to 100; if it is less than 40, the dispersibility in alkaline liquid will be insufficient and the scouring property will be poor, and if it is more than 100, the crystallinity will increase and the lipophilicity will decrease. This undesirably reduces smoothness.

The esterified oxidized wax obtained by the above method can be applied to fibers in various ways.

That is, the esterified oxidized wax alone can be used, or it can be used in combination with waxes such as paraffin wax, microcrystalline wax, carnauba wax, hardened tallow oil, hardened wax, and polyethylene wax.

In this case, the content of the esterified oxidized wax is preferably 50% or more in the total wax, and if it is less than that, poor scouring properties tend to occur.

In addition, esterified oxidized wax alone or mixed wax with other waxes can be further blended with nonionic activators or anionic activators and applied to fibers as a solid wax, for example in the form of ring wax, or in a molten state. It can be applied as afterwax gingerol or in an emulsified state and used in combination with a glue solution, but it can also be applied to fibers in an emulsion or solubilized state as a glue-free sizing agent.

Furthermore, it can be used as a smoothing agent not only for warp yarns but also for weft yarns.

Next, the excellent performance of the esterified oxidized wax according to the present invention will be explained by showing the details.

[Test method] (a) Wax smooth polyester 75-tenile/36-filament yarn with a roller so that it adheres to about 1%, and then heat at 90°C for 10 minutes to spread it evenly.

Regarding this yarn, the static friction coefficient (μS) and the dynamic friction coefficient (μd) at 1120 cm/min are measured by the radar method.

(B) Scouring and shedding property Approximately 0.02 g of the compound is attached to the center of a 10 cm x 10 cm polyester taffeta, and heated and spread until it becomes a circle with a diameter of about 3 cm.

This taffeta is then scoured in a scouring bath at 95° C. for 1 minute, 3 minutes, and 5 minutes, and the scouring property is determined by the repellency of the taffeta against water.

Scouring bath composition Soda ash 2g/l Nonionic activator 1g/l (Lauryl alcohol-ethylene oxide 10 mole adduct) Judgment ○: Permeability of water to surrounding area is not changed at all.

△: Water penetration is slightly slower than the surrounding area. of.

×: Penetration in the circular part is clearly slow. of.

(c) Solubility: Dissolve the compound to about 1% in a scouring bath with the above composition, and
Observe the state of dissolution at °C.

As a result, the esterified oxidized wax according to the present invention has good smoothness and scouring property, but the esterified oxidized wax AV15 and paraffin wax, which were compared at the same time, have good smoothness but poor scouring property, and esterified oxidized wax has good smoothness and scouring property. Wax AV120 and stearic acid have good scouring properties but lack smoothness.

Furthermore, wood wax has relatively good smoothness and scouring properties, but is expensive.

The specific measuring method for limiting the esterified oxidized wax is as follows.

[Measurement method]

(a) Hydroxyl value Edited by Japan Oil Chemists' Association, Standard Oil and Fat Analysis Test Methods 2, in accordance with 4.9.2.

(b) Melting point (mp) Same as 2.3.4.1.

(c) Acid value (AV) After carrying out the following operation to remove polybasic acids that are not bound to the oxidized wax, measure according to 2.4.1 above.

Removal of free polybasic acids: Approximately 3 g of esterified oxidized wax was rig-processed into approximately 30 m1.
and washed three times with 20 ml of methanol-water (2:l volume).

Add 30 ml of ethyl alcohol to the upper glue groin solution and titrate using phenolphthalein as an indicator.

Next, in order to further embody the structure and effects of the present invention, examples will be given and explained.

Example 1 Oxidized wax (NFS-9) with a hydroxyl value of 66 and a melting point of 52°C
0.1 kg of maleic anhydride was reacted with 0.1 kg of maleic anhydride at 140° C. for 3 hours to obtain esterified oxidized wax A with an acid value of 65.

0.55 kg of this esterified oxidized wax and 0.1 kg of oxidized polyethylene (AC polyethylene 629 manufactured by Niallide Chemical Co., Ltd.).

0.35 kg of 130°F paraffin is mixed with 0.2 kg of polyoxyethylene (10 moles) cetyl ether as emulsifiers, 0.1 kg of polyoxyethylene (7 moles) stearate, and 0.1 kg of 10% sodium hydroxide solution. Add 25 kg and emulsify near the boiling point to reduce the purity to 3.
4.4 kg of 0% emulsion A-1 is obtained.

Polyvinyl alcohol (average degree of polymerization 500, partially saponified product) 4.5%, polyacrylic acid ester glue (Plus Size T-823: manufactured by Gooh Kagaku Kogyo Co., Ltd.) 5.5%
%, polyester filament yarn (75 denier, 36 filament) was glued with a glue solution containing 0.6% of the above emulsion A-1 (adhesion amount: 4.5%), number of warp threads: 5
000 pieces of taffeta were woven using an ordinary loom.

There are no problems such as gum up or thread breakage in the sizing process and weaving process, the weaving efficiency is 95%, and the A reversal rate of the gray fabric is 96.
It was a good result of %.

Further, as a result of continuous scouring with 2g/l of nonionic activator and 2g/l solution of soda carbonate, there was no problem in scouring performance.

Example 2 Oxidized wax (NPS-9) with a hydroxyl value of 43 and a melting point of 72°C
140: Manufactured by Nippon Seiro Co., Ltd.) 0 succinic anhydride per kg
．． 09 kg was reacted at 170° C. for 3 hours to obtain esterified oxidized wax B having an acid value of 58.

Mix 0.8 kg of this esterified oxidized wax and 0.2 kg of 140°F paraffin, and add 0.2 kg of polyoxyethylene (7 mol) lauryl ether as an emulsifier.
and 0.05 kg of 25% ammonia water, purity 35
% emulsion B-1 was obtained.

Polyacrylic ester adhesive (plus size J-1
6: Gooh Chemical Industry Co., Ltd.) 5%, the above emulsion B-1
polyamide filament I with a glue solution containing 0.8%
As a result of gluing yarn (70 strands, 24 to filament 1) and weaving taffeta with 6394 warp threads (adhesion amount 3.4%) in a water jet loom, there were no problems and the weaving efficiency was 94%. , weaving quality (A reversal rate) 9
This was a good result of 6%.

Further, as a result of scouring in the same manner as in Example 1, there was no problem in scouring performance.

Example 3 To 1 kg of the esterified oxidized wax A of Example 1, 0.12 kg of polyoxyethylene (11 mol) stearate and 0.0 sorbitan monostearate were added as emulsifiers.
Mix 6 kg and add 1.18 kg of afterwaxing agent A-2.
Get kg.

Polyacrylic acid ester glue (plus size J-6
Sizing a 50-tenure polyester filament yarn (to 24 filaments 1) using a warping slasher with an 8% solution (manufactured by Gooh Kagaku Kogyo Co., Ltd.) and applying the above-mentioned afterwaxing agent A-2. Apply after wax using a waxing roller (adhesion amount 0.5%).

As a result of weaving a Frepon with 6058 warp threads in a water jet loom using this adhesive light, the smoothness was extremely good and the weaving efficiency was also good.

Furthermore, as a result of scouring the obtained gray fabric in a scouring bath containing 5 g/l of sodium hydroxide and 1 g/l of a nonionic activator, the scouring result was extremely good with no spots of water penetration.

Furthermore, when weaving and refining under the same conditions using a conventional afterwaxing agent mainly consisting of paraffin wax, slight water penetration spots were observed even if the amount of nonionic activator was increased to 4 g/l. .

Example 4 Emulsion B-1 of esterified oxidized wax of Example 2
0% aqueous solution (solid content 3.5%), 75 degrees, 24
A filament polyester processed yarn (300 T/m) is oiled (adhesion amount: 2.1% as solid content).

Using this thread as the warp, the density is 6277, and the weft is polyester and rayon blend yarn No. 40 single yarn, and as a result of weaving the twill on an ordinary loom, it has good smoothness and bunching, and the weaving efficiency is 9.
It was 3%.

Further, the scouring properties were good, and no adverse effects due to wax were observed.

Example 5 Oxidized wax (NFS12) with a hydroxyl value of 83 and a melting point of 70°C
10: Manufactured by Nippon Seiwa Co., Ltd.) 0 sebacic acid per kg,
18 kg was reacted at 160 to 180°C for 5 hours, and the acid value was 7.
Esterified oxidized wax C of No. 7 was obtained.

0.6 kg of this esterified oxidized wax, 125°F
Mix 0.2 kg of paraffin and 0.2 kg of hardened beef tallow, add 0.05 kg of polyoxyethylene (5 mol) cetyl ether, and 1 to 0.03 kg of sorbitan monostearate.
kg and 0.13 kg of 20% sodium hydroxide,
A waxy oil C-1 with a purity of 95% is obtained.

Polyvinyl alcohol (average degree of polymerization 1700, partially saponified product) 6.5%, cornstarch 5.6%, acrylic glue (Plus Size 663: manufactured by Gooh Chemical Industry Co., Ltd.)
A glue solution containing 0.3% and 0.6% of the above-mentioned waxy oil C-1 was prepared, and a No. 45 single yarn of blended yarn made of 65% polyester and 35% cotton was glued thereon.

Moisture 2.3%, adhesive amount 13.1%, strength 348.5
g. A glued light with an elongation of 11.6% was obtained, and a broad cloth with 5168 warps was woven using this warp on an ordinary loom. As a result, there was little gluing, no warp breakage, and a weaving efficiency of 95%. A good result of 95% in gray quality (A reversal rate) was obtained.

Furthermore, the above adhesive was stable, had little foaming, and had no sizing problems.

Claims (1)

[Claims] 1. A weaving oil containing an esterified oxidized wax having an acid value of 40 to 100 obtained from an oxidized wax with a hydroxyl value of 40 to 100 and a melting point of 50 to 90°C and a polybasic acid.