JPS597831B2 - It's difficult to understand - Google Patents

Description

[Detailed description of the invention] The present invention relates to a lubricant for glueless weaving.

Up until now, many studies have been conducted on glueless weaving.
(1) Mixing a hydrophilic vinyl polymer into an oil agent, (2) increasing single fiber strength, (3) attaching solid wax during warping, (4) attaching a high viscosity polyurethane compound. Other methods have been proposed.

However, these methods have drawbacks such as frequent fluff and thread breakage during the operation process, adhesive deposits on guides and other surfaces, hard texture of the product, and limitations in terms of use. It has not yet been implemented.

In addition, the industrial significance of glue-free weaving is that drying in the conventional sizing process can be omitted, contributing to resource conservation. In order to make it adhere uniformly to the thread, it is necessary to dilute it with a large amount of water from the viewpoint of workability, stability, viscosity, etc.

Therefore, this method requires a drying step as in the case of using conventional sizing agents, and the industrial value of non-sizing is halved.

Furthermore, the treatment of smelting wastewater is becoming a social problem due to environmental pollution, and no suitable solution has necessarily been found in this regard.

In view of the current situation, the present inventors conducted research on oil agents for glueless weaving, and as a result, they arrived at the present invention.

That is, the present invention provides an alkyl group having 1 to 22 carbon atoms and/or
Alternatively, a water-insoluble polyether urethane compound obtained by using an organic hydroxyl compound having an alkylene group having 4 to 12 carbon atoms is reacted with a polybasic acid to form a carboxyl compound with an acid value of 6.5 to 50. This is a glue-free weaving oil agent whose main component is a modified polyurethane compound or its salts into which a group has been introduced.

Alkyl group having 1 to 22 carbon atoms and/or 4 to 12 carbon atoms
A polyurethane compound obtained using an organic hydroxyl compound having an alkylene group is insoluble in water and has excellent smoothness and wear resistance, but it requires the help of an emulsifier to apply it to the warp threads as an aqueous solution. Moreover, even during scouring, it has poor shedding properties and causes dyeing spots, and is therefore not satisfactory as an oil for glueless weaving.

However, modified polyurethane compounds or their salts, which are made by reacting polybasic acids to introduce carboxyl groups, become water-soluble or water-dispersible without the aid of emulsifiers, making them economical and easy to apply to warp yarns. It is an excellent lubricant for glue-free weaving because it can be easily removed during scouring as well as moisturizing.

In addition, although the ammonium salt is water-soluble, it has good water resistance after drying, making it ideal for use in water jet looms.In this case, it can be made water-soluble again by using caustic soda or soda carbonate during scouring. It can easily fall off.

Furthermore, the scouring wastewater that has become water-soluble and falls off can be easily coagulated and removed by adding acids, polyvalent metal salts such as aluminum sulfate, and various cationic polymers due to the introduced carboxyl groups, which is useful for preventing pollution. It also has excellent properties.

In order to produce a water-insoluble polyether urethane compound which is an intermediate for the glueless weaving oil agent of the present invention, a carbon number of 1 to
It is obtained by reacting an organic hydroxyl compound having 22 alkyl groups and/or an alkylene group having 4 to 12 carbon atoms with a polyalkylene glycol and a diisocyanate.

The polyalkylene glycol used here includes polyethylene glycol with a molecular weight of 3000 or less, poly-1
, 2-propylene glycol, poly-1,2-butylene glycol, poly-1,2-dodecylene glycol and other glycols or ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 1, 2
- Block or random copolymers of oxides such as dodecylene oxide are used, as well as organic hydroxyl compounds having an alkyl UN having 1 to 22 carbon atoms and/or an alkylene group having 4 to 12 carbon atoms as shown below. Glycols having polyoxyalkylene groups can also be used.

Alkyl group having 1 to 22 carbon atoms and/or 4 to 12 carbon atoms
Examples of organic hydroxyl compounds having an alkylene group include methyl alcohol, ethyl alcohol, isopropyl alcohol, phtyl alcohol, 2-ethylhexyl alcohol, octyl alcohol, laurylalconopedocosanol, oleyl alcohol, nonylphenol, and 1,4-butylene. Saturated or unsaturated monools having linear or side chains such as glycol monoethyl ether and 1,6-hexylene glycol monolauryl ether, and these alcohols or alkylphenols with ethylene oxide, propylene oxide or butylene oxide. polyoxyalkylene glycol monoalkyl ether with added
Examples include ethers such as alkyl phenyl ethers, and polyoxyalkylene glycol monoalkyl esters in which alkylene oxide is added to acetic acid, propionic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc. .

Next, as diols, polyalkylene glycols other than the above-mentioned polyethylene glycol, and 1,2-
Propylene glycol, 1,2-j tylene glycol,
α,β-glycols such as 1,2-dihydroxydodecane and 1,2-dihydroxyoctadecane, and alkylene oxide adducts thereof, propionic acid amide,
Alkylene oxide adducts of alkylamides such as lauric acid amide and oleic acid amide, and carbon atoms of 4 to 1
Diols having 2 alkylene groups include 1,4-butylene glycol, 1,6-hexylene glycol, 1,
Examples include 12-dodecamethylene glycol and alkylene oxide adducts thereof.

As mentioned above, the organic hydroxyl compound having an alkyl group having 1 to 22 carbon atoms and/or an alkylene group having 4 to 12 carbon atoms and the polyalkylene glycol may be separate compounds; Oxyalkylene group and alkyl group having 1 to 22 carbon atoms and/or 4 carbon atoms
to 12 alkylene groups.

Examples of the isocyanate include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, diphenylethane diisocyanate, diphenylpropane diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, and decamethylene diisocyanate. , dodecamethylene diisocyanate, etc. are used.

When obtaining a water-insoluble polyether urethane compound as an intermediate, only a diol may be reacted with a diisocyanate within the range of the ratio listed below as an organic hydroxyl compound. When a monool is used in combination with a diol, The ratio of monool to 1 mole of diol is preferably 0.5 mole or less, and if the monool is greater than this, the molecular weight will be too low and convergence will be poor, which is not preferred.

Furthermore, in order to make the polyether urethane compound insoluble in water, an organic hydroxyl compound having an alkyl group having 1 to 22 carbon atoms and/or an alkylene group having 4 to 12 carbon atoms is used.

Among these, when the diol or monool having a long chain alkyl group having 8 or more carbon atoms is present in at least 10 mol % of the total organic hydroxyl compound, smoothness and water resistance are improved.

However, even if it is less than 10 mol%, increasing the molar ratio of organic hydroxyl compounds having lower alkyl groups or increasing the alkylene glycol having 4 to 12 carbon atoms can increase hydrophobicity and make it insoluble in water. .

To produce the intermediate polyether urethane, for 1 equivalent of total hydroxyl groups based on the organic hydroxyl compound,
The isocyanate group is 0.5 to 0.9 equivalent, preferably 0.
It is preferable to react the incyanate compound so that the amount becomes 7 to 0.9 equivalents.

If it is less than 0.5 equivalent, not only will the molecular weight not increase, but the abrasion resistance due to the urethane group will be insufficient, making it undesirable as a focusing oil, and if it is more than 0.9 equivalent, the degree of carboxyl modification by polybasic acid will be low. Therefore, the effects of the present invention cannot be fully exhibited.

Urethane formation is carried out by a known method, that is, by reacting an organic hydroxyl compound and a diisocyanate at a temperature ranging from room temperature to 150° C. or less for 1 to 10 hours.

Catalysts such as organic amines or metal salts can also be used in combination, if necessary.

The polyether urethane compound thus obtained has an excess of hydroxyl groups, which can be treated with polybasic acids such as malonic acid, maleic acid, succinic acid, itaconic acid, adipic acid, phthalic acid, and trimellitic acid, or their anhydrides. When esterified by reaction with a compound, a modified polyurethane compound having a carboxyl group is obtained.

The degree of carboxyl modification is preferably such that the acid value is in the range of 6.5 to 50.

When the acid value is less than 6.5, the effect of modification is difficult to exhibit, and when it is more than 50, the effect on smoothness and water resistance is small.

When applying a modified polyurethane compound to fibers, it may be applied unneutralized or with salts such as Na, K, NH4, alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, or mixtures thereof. Part or all of the salt is used as an aqueous solution or dispersion.

Further, part of the water may be replaced with a water-soluble organic solvent such as ethyl alcohol or isopropyl alcohol.

Alternatively, it may be applied to the warp yarns without being neutralized by dissolving it in an organic solvent such as ethyl alcohol or isopropyl alcohol.

If unneutralized, it will not dissolve in water, but will dissolve in organic solvents such as alcohol, and when applied to warp threads, it will exhibit excellent performance as a glue-free weaving oil, while improving scouring properties and scouring drainage. The effect of carboxyl modification is fully exhibited in the aggregation treatment.

Mineral oil, solid paraffin, butyl stearate, in-butyl stearate, in-octyl palmitate, in-octyl laurate, mineral oil with a viscosity of 30 to 500 seconds measured with a redwood viscometer to improve smoothness and antistatic properties, if desired. Fatty acid esters such as isooctyl oleate and trimethylolpropane trilaurate, K salts of sulfonic acids such as alkyl sulfonic acids, alkylbenzenesulfonic acids, dialkyl sulfosuccinic acids, and reaction products of higher alcohols or higher fatty acids with butane sultone and propane sultone. , Na salts, NH4 salts, alkanolamine salts, etc., alkyl phosphates, dialkyl phosphates, phosphoric acid esters of higher alcohol oxidized ethylene adducts, or their Na salts, K salts, NH4 salts, alkanolamine salts,
Polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid monoester, etc. can be blended in an amount of 40% by weight or less based on the modified polyurethane compound.

The amount of the modified polyurethane compound according to the present invention attached to the thread is preferably 0.5 to 5% by weight; if it is less than 0.5% by weight, the cohesiveness is poor, and if it exceeds 5% by weight, it is not only economically disadvantageous but also Problems such as generation of scum on the guide etc. occur.

Any method may be used to attach the modified polyurethane compound; for example, during rough warping in the weaving preparation process, warping is performed while adding oil using a contact roller device, and then beaming is performed from several rough winding beams. The method is preferably used, but the point is that it is sufficient that the reactant of the present invention is attached to the warp yarns on the loom, and a method of attaching it as a finishing oil agent at the yarn manufacturing stage may also be used.

The warp yarns to which the oil for glue-free weaving of the present invention is applied are significantly streamlined compared to the past sized yarns to which the conventional acrylic-PVA type glue is applied, and are particularly economical in that they do not require a dry phosphorus process. The industrial significance of the present invention is extremely high, as it greatly contributes to resource recovery, and scouring wastewater is easily agglomerated by acids, aluminum sulfate, cationic polymers, etc. due to its carboxyl group, contributing to the prevention of environmental pollution. big.

In addition, as a glue-less weaving oil for water jet looms with high weaving efficiency, it has excellent cohesiveness, smoothness, abrasion resistance, and water resistance, and has extremely high industrial value.

The acid value in the following examples is calculated by dissolving 5 g of a sample in ethyl alcohol and titrating with a 0.5 N KOH alcohol solution until phenolphthalein develops a color.
It is indicated by the number of KOH per hit.

Example 1 Polyethylene glycol (molecular weight 1000)7. 0
1<g (molar ratio 0.7), holJ7'ropylene glycol monobutyl ether (molecular weight 650) 0.65 kg
(molar ratio O, 1) and oleyl alcohol 0. 5 4
kg (molar ratio: 0.2) and reacted with 1.26 kg of tolylene diisocyanate (0.85 equivalent to total hydroxyl groups) at 50°C for 2 hours and then at 80°C for 3 hours.

The resulting polyether urethane compound is insoluble in water.

Then, 0.22 kg of succinic anhydride was reacted at the same temperature to obtain 9.67 kg of a modified polyurethane compound into which carboxyl groups were introduced.

The obtained modified polyurethane compound had an acid value of 12.4, was not soluble in water, and was mixed with 25% ammonia water at 0.00%. 1
It becomes water-soluble when neutralized with 2 kg.

When this is dissolved in water to give a total amount of 38.8 ky, a 25% by weight aqueous solution of the ammonium salt of the modified polyurethane compound is obtained.

Polyester fiber, semi-dull 50 denier 24 filaments are arranged in the warp, 75 denier 36 filaments of the same material are arranged in the weft, warp density 75 threads/2 threads/whale size, weft density 115 threads/whale size in a water jet loom. In weaving the tuck, the warp yarns were prepared as follows.

The warp yarns were pulled out from the creel, and while being relubricated with a 25% by weight solution of the polyurethane compound mentioned above, the oil was applied at a speed of 250 m/min so that the total oil content was 2.5% to create a roughing beam. Yarns were pulled out from several of these loose beams at the same time, and beaming was performed to create the loose beams required for textile standards.

The weaving conditions in the water jet loom are extremely good, and in addition to proper convergence due to the raw thread oil and oil replenisher, the warp fuzz is extremely low due to the excellent smoothing effect, and the weaving efficiency is 88.0% and the length of 50 meters is 88.0%. (1) The number of times the machine stopped due to fluffing of the fibers during weaving was 2.15.

Furthermore, the quality of the obtained gray fabric was greatly improved by the fact that it was industrially simpler than the conventional gluing method, and was of high quality with almost no warp stripes.

Example 2 2.12 kg of tolylene diisocyanate (0.8 equivalent to total hydroxyl groups) and 0.79 kg of polyoxyethylene (7 moles of ethylene oxide) lauryl ether (mole ratio 0.
1) was reacted at 40°C.

Next, polyethylene glycol (molecular weight 1500) 16
．． A mixture of 8 kg (molar ratio 0.7) and 1,2-dihydroxydodecane 0.65 kg (molar ratio 0.2) was reacted, and after 2 hours, the mixture was heated to 90°C and reacted for an additional 3 hours.

The resulting polyether urethane compound is insoluble in water.

When 0.3 kg of maleic anhydride is added to this and the reaction is further carried out for 1 hour, 20.6 kg of a polyurethane compound into which a carboxyl group has been introduced is obtained.

The obtained modified polyurethane compound has an acid value of 8.3 and is neutralized with 0.06 kg of sodium hydroxide and 0.06 kg of 25% aqueous ammonia, and the total amount is made up to 69.0 kg with water to form an aqueous solution. sodium·
A 30% aqueous solution of ammonium mixed salt is obtained.

Polyester fiber semi-dull 50 denier 24 filament interlaced yarn is arranged in the warp, 75 denier of the same material
Denier 36 filament is placed in the weft, warp density is 75 feathers/2 pieces/whale size, weft 11 in water jet loom.
To weave 5 pieces of whale-sized taffeta, the warp yarns were prepared by adding oil with a 30% by weight solution of the above-mentioned modified polyurethane compound in the same manner as in Example 1, and the yarns were oiled with a total oil content of 2.8%. I did some weaving.

The weaving efficiency was 95.0% and the number of stops was 100, indicating extremely excellent weaving properties and the quality of the obtained gray fabric was also good.

Example 3 Ethylene oxide-propylene oxide copolymer (
Molar ratio 8:2, molecular weight 2000) 24.0 kg (molar ratio 0.6), butylene glycol 0. A mixture of 36 kg (molar ratio 0.2) and polyoxypropylene (propylene oxide 3 mol) cetyl ether 2.02 kg (molar ratio 0.2) was reacted with 1.81 kg of hexamethylene diisocyanate at 70°C for 2 hours. Thereafter, 4.06 kg of xylylene diisocyanate (equivalent of total incyanate groups to total hydroxyl groups: 0.9) was added, and the mixture was heated to 11.0°C and reacted for a total of 6 hours.

The resulting polyether urethane compound is insoluble in water.

0.42 kg of adipic acid and 160 g of para-toluenesulfonic acid as a catalyst are added to this and esterified at 120 to 130°C to obtain 32.5 kg of a carboxy-modified polyurethane compound having an acid value of 6.5.

Add 0.22 kg of 25% ammonia water to this, and add 64 kg of water.
．． 5 kg and 10.8 k9 of isopropyl alcohol give 108 kg of a 30% solution of a partial ammonium salt of a modified polyurethane compound.

False twisted polyester fiber semi-dull 150 denier 48 filaments are arranged in the warp and weft, warp density 33
．． When weaving a twill fabric with a weft density of 75 wefts/inch using a water jet loom, warps were prepared under the following conditions.

The warp threads were pulled out from the creel, and the total oil content was 1.8% at a speed of 200 m/miyt while adding oil with a 30% by weight solution of partial ammonium salt of the modified polyurethane compound.
A rough winding beam was created by attaching an oil agent to the yarn, and threads were pulled out from several of these rough winding beams at the same time, and beaming was performed to create a roomy beam of warp threads required as a textile standard.

The weaving conditions in the water jet loom are extremely good, with proper focusing due to the refueling agent and excellent smoothness, warp fuzzing is completely infrequent, and the weaving efficiency is 98.5%.
The number of machine stoppages due to warp fuzz during weaving of about 50 meters (1 square) was 1.02 times.

Furthermore, the amount of fuzz and oil scum that adhered to the healds during weaving was extremely small, and did not cause any problems during weaving.

The resulting gray cloth is of excellent quality and is soft because it does not have warp glue.
The quality and texture after dyeing were far superior to those obtained by conventional pasting methods.

Example 4 Ethylene glycol (molecular weight 600) 3.6k
g (molar ratio 0.3), poly-1,2-propylene glycol (molecular weight 400) 4. okg (molar ratio 0.
5) and 1,6-hexylene glycol 0.47k9 (
2.63 kg of tolylene diisocyanate (0.7 equivalent to total hydroxyl groups) was mixed with 40
It was added dropwise at ~50°C, and after the heat generation had stopped, it was heated to 80°C and reacted for an additional 2 hours.

The resulting polyether urethane compound is insoluble in water.

When this is reacted with 0.98 kg of maleic anhydride at the same temperature, 11.68 kg of a modified polyurethane compound into which a carboxyl group has been introduced is obtained.

The obtained modified polyurethane compound has an acid value of 48.0 and only has a methyl group with one carbon number, but it does not dissolve in water and becomes water-soluble when neutralized with caustic soda.

When 11 kg of modified polyurethane compound is dissolved in 22 kg of isopropyl alcohol without being neutralized, the purity is 33%.
33 kg of solution is obtained.

Polyamide fiber (nylon 6) semi-dull 50 denier 1
7 filaments are placed in the warp and 17 filaments of 50 denier of the same material are placed in the weft, and the warp density is 7 on an ordinary loom.
In weaving a tack with a weft density of 8 feathers/2 pieces/whale size and a weft density of 105 pieces/whale size, the warp yarns were prepared as follows.

The warp threads were pulled out from the creel, and while being relubricated with a 33% by weight solution of the polyurethane compound mentioned above, a roughing beam was created by applying an oil to a total oil content of 2.0% at a speed of 300 m/-. Yarn was pulled out from several beams at the same time and beaming was performed to create the looms beam required as a textile standard.

The weaving conditions on an ordinary loom are extremely good, and in addition to the appropriate convergence due to the raw thread oil and oil additive, the fuzzing of the warp threads is extremely low due to the excellent smoothing effect, and the weaving efficiency is 90%, and the weaving efficiency is 90%, and the weaving efficiency is 90%. ) The number of stops due to warp fuzz during weaving was 2,00.

Furthermore, no problems occurred in weaving.

The resulting gray cloth is of excellent quality and is soft because it does not have warp glue.
The quality and texture after dyeing were extremely superior to those obtained by conventional pasting methods.

Claims (1)

[Claims] 1 Alkyl group having 1 to 22 carbon atoms and/or 4 to 22 carbon atoms
Modification in which a water-insoluble polyether urethane compound obtained using an organic hydroxyl compound having 12 alkylene groups is reacted with a polybasic acid to introduce a carboxyl group to an acid value of 6.5 to 50. A glue-free weaving oil agent whose main component is a polyurethane compound or its salts.