JPH11323399A - Scouring agent for fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a scouring agent for fibers having excellent ability in removing glues, scutching waxes, oils and the like by employing a higher secondary alcohol alkoxylate. SOLUTION: A higher secondary alcohol alkoxylate prepared by the addition reaction of an 8-30C olefin with a (poly)alkylene glycol and/or a higher secondary alcohol alkoxylate obtained by further reacting the higher secondary alcohol alkoxylate with a 2-8C alkylene oxide is employed. The 8-30C olefin is a 8-30C aliphatic hydrocarbon having one double bond and can be linear or branched. The double bond may locate at the α-position or inside of the chain. As the (poly)alkylene glycols are employed those represented by the formula: HO(MO)m H (wherein M is 2-6C alkylene; and m is 1-20). Among these monoalkylene glycols are preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a scouring agent for fibers.

[0002]

2. Description of the Related Art Fiber scouring agents used for scouring fibers include nonylphenol ethoxylate,
A higher alcohol alkoxylate and a higher alcohol sulfate salt are used alone or in combination of two or more. These scouring agents for fibers are generally used in an aqueous system.

[0003] However, conventional scouring agents for fibers are insufficient in removing the wax or oil for knitting or fiber-making which adheres to the fibers, or the removed oil re-adheres to the fibers. There were problems such as causing troubles in the dyeing process.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a glue,
It is an object of the present invention to provide a scouring agent for fibers which has an excellent performance of removing wax and oil for fiber making.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have prepared a higher secondary alcohol alkoxylate (A) obtained by an addition reaction between an olefin and a (poly) alkylene glycol.
(Hereinafter sometimes simply referred to as "alcohol alkoxylate (A)"), or higher secondary alcohol alkoxylate (B) obtained by further reacting this alcohol alkoxylate (A) with an alkylene oxide.
(Hereinafter sometimes simply referred to as “alcohol alkoxylate (B)”) has been found to be excellent in the performance of removing paste, wax for fibermaking, oil, etc., and suitable as a scouring agent for fibers. Thus, the present invention has been completed.

That is, the present invention relates to a higher secondary alcohol alkoxylate (A) obtained by an addition reaction of an olefin having 8 to 30 carbon atoms and a (poly) alkylene glycol, and / or the alcohol alkoxylate (A). Is further reacted with an alkylene oxide having 2 to 8 carbon atoms to obtain a higher secondary alcohol alkoxylate (B).

[0007]

DETAILED DESCRIPTION OF THE INVENTION The olefin having 8 to 30 carbon atoms, which is a starting material of the present invention, is an aliphatic hydrocarbon having 8 to 30 carbon atoms, preferably 10 to 20 carbon atoms, having one double bond. Yes, it may be linear or branched. The position of the double bond is not particularly limited, and may be at the α-position or the inner position. Representative examples of the above-mentioned olefin having 8 to 30 carbon atoms (hereinafter sometimes simply referred to as “olefin”) include octene, decene, dodecene, tetradecene, hexadecene, octadecene, eicosene and the like. These can be used alone or in combination of two or more.

As a starting material, an ethylenically unsaturated hydrocarbon (α-olefin) having a double bond at the α-position is generally used, but the inner olefin is generally more thermodynamic than the α-olefin. To be stable,
During the addition reaction, isomerization of the α-olefin to the inner olefin occurs. In addition, since this addition reaction is generally carried out by circulating unreacted olefins or the like, the olefin component is added to (poly) alkylene glycol as a mixture of α-olefin and inner olefin. Become.

The (poly) alkylene glycol as another starting material is represented by the general formula (1): HO (MO) mH (1) (wherein M is an alkylene group having 2 to 6 carbon atoms, m is a number from 1 to 20), and typical examples thereof include monoethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (m is 20 or less on average), monopropylene glycol, and dipropylene glycol. Propylene glycol, tripropylene glycol, polypropylene glycol (m is 20 or less on average), 1,3-propanediol, 1,2-butanediol, 2,3-butanediol, 1,4-butanediol, 1,6- Hexanediol and the like can be mentioned. Of these, monoalkylene glycols such as monoethylene glycol and monopropylene glycol are preferably used.

The alcohol alkoxylate (A) as the fiber scouring agent of the present invention is obtained by an addition reaction of the above-mentioned olefin with a (poly) alkylene glycol. The production of the corresponding alcohol alkoxylate (A) by the addition reaction of this olefin with a (poly) alkylene glycol is known per se. For example, JP-B-61-51570, JP-A-3-1482
No. 33, and JP-A-9-52856. The alcohol alkoxylate (A) of the present invention is not limited by the production method, and those obtained by any method can be used. As for the catalyst, an acidic catalyst such as a strongly acidic ion exchange resin, crystalline aluminosilicate, dodecylbenzenesulfonic acid, or the like can be used.

[0011] For example, according to the method described in JP-A-9-52856, a crystalline metallosilicate is used as a catalyst with an olefin and a (poly) alkylene glycol at 50 to 250 ° C in the presence or absence of a solvent. It is preferably obtained by performing an addition reaction at 100 to 200 ° C. The pressure may be either normal pressure or pressurized, but is usually appropriately selected from the range of normal pressure to 20 kg / cm ² . As the solvent, nitromethane, nitroethane, nitrobenzene, dioxane, ethylene glycol dimethyl ether, sulfolane, benzene, toluene, xylene, hexane, cyclohexane, decane, paraffin, and the like can be used. The molar ratio of (poly) alkylene glycol to olefin (olefin / (poly) alkylene glycol) can be appropriately determined without particular limitation, but is usually 0.05 / 1 to 20/1, and is preferably 0.05 / 1 to 20/1. 0.1 / 1 to 10/1. The amount of the catalyst used is usually 0.1 to 10 of the starting olefin.
0% by weight, preferably 0.5 to 50% by weight.

After the reaction, after separating the catalyst, the reaction solution is separated into an olefin phase and a (poly) alkylene glycol phase, and the olefin phase is distilled to distill off the unreacted olefin. to recover. The alcohol alkoxylate (A) from which the unreacted olefin is separated may be used as it is as a fiber refining agent,
Usually, it is preferable to use the recovered alcohol alkoxylate (A) by rectification. Since the rectification conditions vary depending on the starting materials used and the like, they cannot be specified unconditionally, but it is preferable to remove at least impurities such as an olefin polymer by-produced during the reaction.

The addition reaction between the olefin and the (poly) alkylene glycol can be carried out according to a generally used method such as a batch reaction or a continuous reaction. When a batch reactor is used, after the reaction is completed, the catalyst is separated from the reaction solution by a method such as centrifugation or filtration. Then, after the above phase separation, the desired alcohol alkoxylate (A) is subjected to distillation or the like to remove the olefin phase. Collect from Unreacted raw materials can be used for the next reaction.
When a continuous reactor is used, any of a fluidized bed type, a fixed bed type, and a stirred tank type may be used, and the reaction proceeds while appropriately circulating unreacted raw materials. Separation of the catalyst, recovery of the product alcohol alkoxylate (A), and the like are the same as in the case of using a batch reactor.

The alcohol alkoxylate (A) of the present invention has the following general formula (2):

[0015]

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(Wherein R ¹ and R ² are alkyl groups, the total carbon number of which is 7 to 29, and R ¹ ≦ R ² , and M and m are the same as defined in the general formula (1). Are the same). When two or more different (poly) alkylene glycols are used, the group represented by (MO) differs accordingly.

Among the above-mentioned alcohol alkoxylates (A), in the general formula (2), 30 to 90 mol% of the alcohol alkoxylate (A1) wherein R ¹ is a methyl group and R ¹ is an alkyl group having 2 or more carbon atoms. Of the alcohol alkoxylate (A2) of 70 to 10 mol% is suitably used. In particular, those composed of 40 to 80 mol% of the alcohol alkoxylate (A1) and 60 to 20 mol% of the alcohol alkoxylate (A2) are preferably used.

In order to prepare the alcohol alkoxylate (A) having the above composition, for example, when 1-dodecene is used as a starting olefin,
Heat treatment of dodecene in the presence of an acid or base catalyst to convert a part of 1-dodecene to innerdodecene, and to obtain a mixture of 1-dodecene and innerdodecene (for example, 25:75 (mol%) )) May be used to carry out the addition reaction. In addition, an α-olefin may be used as a raw material, an unreacted inner olefin may be recovered and circulated, and reacted as a mixture of the α-olefin and the inner olefin.

Next, the alcohol alkoxylate (B) as the fiber refining agent of the present invention will be described. The alcohol alkoxylate (B) is obtained by further performing an addition reaction of the alcohol alkoxylate (A) with an alkylene oxide having 2 to 8 carbon atoms.

Representative examples of the above alkylene oxide having 2 to 8 carbon atoms (hereinafter sometimes simply referred to as "alkylene oxide") include ethylene oxide, propylene oxide, butylene oxide and styrene oxide. These can be used alone or in combination of two or more.

The addition reaction between the alcohol alkoxylate (A) and the alkylene oxide can be easily carried out by using an alkali catalyst as a catalyst. The molar ratio of the alkylene oxide to the alcohol alkoxylate (A) (alkylene oxide / alcohol alkoxylate (A)) can be appropriately determined without particular limitation, and is usually 1/1 to 30/1,
It is preferably from 4/1 to 20/1.

As the alkali catalyst, there can be used a hydroxide of an alkali metal or an alkaline earth metal, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide and the like. The amount of the alkali catalyst to be used is generally 0.01 to 2% by weight, preferably 0.02 to 0.5% by weight, based on the alcohol alkoxylate (A). The alkali catalyst may be added in the form of a powder, granules, or an aqueous solution.

The reaction temperature is usually from 50 to 250 ° C, preferably from 100 to 200 ° C. The reaction pressure may be normal pressure or pressurization, and is usually appropriately selected from the range of normal pressure to 20 kg / cm ² . Note that the reaction is preferably performed in an inert gas, for example, a nitrogen atmosphere. Even if solvent is used,
However, the addition reaction is usually performed without using a solvent.

The addition reaction between the alcohol alkoxylate (A) and the alkylene oxide is carried out according to a generally used method such as a batch reaction or a continuous reaction, as in the case of the production of the alcohol alkoxylate (A). Can be.

The alcohol alkoxylate (B) can be represented by the following general formula (3).

[0026]

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In the formula, R ¹ , R ² , M and m have the same meaning as defined in the general formula (2), N is an alkyl group having 2 to 8 carbon atoms, and n is an average addition mole of alkylene oxide. Indicates a number and is a number from 1 to 30.

At the time of the above addition reaction, (A1) and (A2) in the alcohol alkoxylate (A) as a starting material
In the alcohol alkoxylate (B), there is no change in the ratio of R ¹ in the general formula (3).
Is an alcohol alkoxylate having a methyl group (B1)
An alcohol alkoxylate (B2) in which 30 to 90 mol% and R ¹ is an alkyl group having 2 or more carbon atoms and 70 to 10 mol% is suitably used. In particular, those composed of 40 to 80 mol% of the alcohol alkoxylate (B1) and 60 to 20 mol% of the alcohol alkoxylate (B2) are preferably used.

The reaction mixture after the above addition reaction can be used as it is as a fiber scouring agent. In addition,
The alkali catalyst in the alcohol alkoxylate (B) may be neutralized with acetic acid or the like before use.

The scouring agent for fibers of the present invention contains an alcohol alkoxylate (A) or an alcohol alkoxylate (B), or a mixture of an alcohol alkoxylate (A) and an alcohol alkoxylate (B). When the alcohol alkoxylate (A) and the alcohol alkoxylate (B) are used in combination, the ratio can be appropriately determined in an optimum range according to the purpose of use.

Among the refining agents for fibers of the present invention, 30 to 90 mol% of alcohol alkoxylate (A1) and 70 to 10 mol% of alcohol alkoxylate (A2), particularly 40 to 80 mol% of alcohol alkoxylate (A1). And / or alcohol alkoxylate (B1) 30 comprising alcohol alkoxylate (A2) 60 to 20 mol%
~ 90 mol% and alcohol alkoxylate (B2) 7
0 to 10 mol%, especially alcohol alkoxylate (B
1) A scouring agent for fibers containing an alcohol alkoxylate (B) composed of 40 to 80 mol% and an alcohol alkoxylate (B2) of 60 to 20 mol% is suitably used because of its excellent refining property and the like.

The amount of the alcohol alkoxylate (A) and / or the alcohol alkoxylate (B) to be added to the scouring agent for fibers may be an effective amount, for example, 3 to 60% by weight of the scouring agent. It is.

The scouring agent for fibers of the present invention is usually used in the form of an aqueous solution. The alcohol alkoxylate (A) in which m is 2 or less in the general formula (2) is insoluble or hardly soluble in water, but the alcohol alkoxylate (B) obtained by adding an alkylene oxide thereto is water-soluble. Therefore, in the case of an alcohol alkoxylate (A) which is insoluble or hardly soluble in water, an alkylene oxide may be added to the alcohol alkoxylate (A) and used as the alcohol alkoxylate (B). The concentration of the alcohol alkoxylate (A) and / or the alcohol alkoxylate (B) in the aqueous solution can be appropriately determined.
For example, it is 0.1 to 5% by weight.

The fiber scouring agent of the present invention may contain other scouring surfactants, inorganic builders, water-soluble organic solvents, defoaming agents, etc. as long as the performance is not impaired. . Other scouring surfactants include anionic surfactants such as alkyl benzene sulfonate, alkyl sulfate, α-olefin sulfonate, alkyl sulfonate, dialkyl sulfosuccinate, and aliphatic amide sulfonate. Cationic surfactants such as alkylamine salts and quaternary ammonium salts; and zwitterionic surfactants such as alkyl betaines. As the inorganic builder and the organic solvent, those used in general scouring agents can be used.

The scouring agent for fibers of the present invention can be applied to any of natural fibers, synthetic fibers and blended fibers, without any limitation on the type of fiber. Representative examples of natural fibers include cotton, hemp, wool, and the like. Representative examples of synthetic fibers include regenerated cellulose fibers such as rayon and acetate, and synthetic fibers such as acryl, polyester, and nylon.

The refining method using the fiber refining agent of the present invention is not particularly limited, and can be carried out by a method generally used for refining fibers. For example, it may be used by dissolving or dispersing in a fiber material treatment bath, usually in the form of yarn or knitted fabric to be scoured. The scouring temperature may be appropriately determined in accordance with the type of the fiber to be scoured. Usually, the scouring temperature is 5 to 100 ° C.

The amount of the fiber scouring agent of the present invention is not particularly limited, and may be used in an amount effective for scouring. Usually, 0.05 to 10 g / L (liter) per fiber volume,
Preferably it is 0.1-1 g / L.

The scouring agent for fibers of the present invention is usually used in a scouring process as a pre-process for dyeing fibers. It may be used for purposes.

[0039]

The scouring agent for fibers of the present invention is excellent in removing glue, oil for fiber-making, wax and the like.

[0040]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples.

Example 1 (Preparation of Alcohol Alkoxylate (A)) 1-dodecene was converted to BEA type zeolite (trade name: VAL, manufactured by PQ).
FOR CP811 BL-25)
The mixture was reacted in the liquid phase at 0 ° C. for 10 hours to obtain a dodecene isomer mixture consisting of 25 mol% of 1-dodecene and 75 mol% of innerdodecene.

810 g of this dodecene isomer mixture, 900 g of monoethylene glycol and BEA zeolite (trade name: VALFOR CP 811BL-25, P
100 g) (provided with a stirrer and a reflux condenser)
2,000 ml glass reactor, under nitrogen atmosphere,
The reaction was performed at 150 ° C. for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the upper separated dodecene phase was separated.
Distilled. After distilling off unreacted dodecene, the pressure was reduced to 2
155 g of secondary dodecanol monoethoxylate (alcohol alkoxylate (A)) was obtained in a boiling point range of 129 to 131 ° C. in mmHg.

In the secondary dodecanol ethoxylate, in the general formula (2), the proportion of the ethoxylate (A1) in which R ¹ is a methyl group is 71 mol%, and the remainder is that R ¹ is an ethyl group or more. Ethoxylate (A2). This ratio was determined by NMR analysis.

(Preparation of alcohol alkoxylate (B)) 155 g of the above secondary dodecanol ethoxylate
(0.67 mol) and 0.2 g of sodium hydroxide in an autoclave made of stainless steel,
The temperature was raised to 0 ° C, and 217 g (4.93 mol) of ethylene oxide
Was introduced for 3 hours, and then kept at 150 ° C. for another 1 hour, cooled, and purged with an internal gas to obtain a polyethoxylate (alcohol alkoxylate (B)) as a reaction product. In this polyethoxylate, the number of moles of ethylene oxide added was 7.3 mol (in the general formula (3), n = 7.3).

(Refining Test) Polyester The above alcohol alkoxylate (B) 0.15% by weight
An aqueous solution of 0.20% by weight of caustic soda was prepared and used as a scouring bath (bath ratio 1:20). After immersing polyester-processed yarn woven fabric in this refining bath at 80 ° C. for 15 minutes, washing with water for 5 minutes, dehydrating and drying, and using a Soxhlet extractor, cyclohexane / ethanol = 2/1 (volume).
Was used as an extraction solvent and extracted under reflux for 4 hours, and the percentage of residual fat was measured. As a result, the percentage of residual fat was 0.15%.

Cotton 0.20% by weight of the above-mentioned alcohol alkoxylate (B)
A 0.50% by weight aqueous solution of caustic soda was prepared, and this was used as a scouring bath (bath ratio 1:20). A cotton plain weave is immersed in this refining bath at 80 ° C. for 20 minutes, washed with water for 5 minutes, dehydrated, and dried. Extraction was performed under reflux for 4 hours, and the percentage of residual fat was measured. As a result, the percentage of residual fat was 0.41%.

Example 2 (Preparation of alcohol alkoxylate (A)) Dodecene (25 mol% of 1-dodecene obtained in the same manner as in Example 1)
A mixture consisting of:
0 g, 1000 g of triethylene glycol and BEA
Type zeolite (Product name: VALFOR CP 811B)
L-25, manufactured by PQ) was charged into a 3000 ml glass reactor equipped with a stirrer and a reflux condenser, and reacted at 150 ° C. for 3 hours under a nitrogen atmosphere. After the completion of the reaction, the reaction solution was cooled to room temperature, and the upper layer of the separated dodecene phase was separated and distilled. After distilling off unreacted dodecene, 135 g of secondary dodecanol triethoxylate (alcohol alkoxylate (A)) was obtained at a reduced pressure of 2 mmHg and a boiling point range of 205 to 210 ° C.

This secondary dodecanol ethoxylate was analyzed by H-NMR to find that the above-mentioned general formula (2)
In the ethoxylate (A) wherein R ¹ is a methyl group
The ratio of 1) was 65 mol%, and the remainder was an ethoxylate (A2) in which R ¹ was a methyl group or more.

(Scouring test) Polyester and cotton were carried out in the same manner as in Example 1. The residual fat percentage in the case of polyester is 0.18%, and the residual fat percentage in the case of cotton is 0.45%.
%Met.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshiyuki Onda 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd.

Claims (1)

[Claims] 1. An olefin having 8 to 30 carbon atoms and (poly)
Higher secondary alcohol alkoxylate (A) obtained by addition reaction with alkylene glycol and / or higher secondary alcohol obtained by further reacting alcohol alkoxylate (A) with alkylene oxide having 2 to 8 carbon atoms A scouring agent for fibers containing an alcohol alkoxylate (B).