JPH08199472A - Scouring detergent composition for fibers - Google Patents

Abstract

PURPOSE: To obtain a scouring and cleaning agent composition capable of effectively removing oily stain attached to a fiber in an aqueous system at a low temperature without using an organic solvent such as a fluorocarbon. CONSTITUTION: This scouring and cleaning agent is obtained by blending 3-70 pts.wt. of the first part composition comprising three or more kinds of compounds selected from a compound group expressed by the formula R1 O (AO)m H (R1 is a 2-20C alkyl, an alkenyl, an alkylphenyl or an alkenylphenyl; A is ethylene or propylene; 10>(m)>=0) with the second part composition comprising a nonionic surfactant expressed by the formula R2 O(AO)n H (R2 and A are respectively same as R1 and A; 7<=(n)<=30) and controlling the blend so that (m) in the formula of a compound having the highest content is within the range of 1-5 and total weight of the compound of the formula [(m) is 0] is <=10% of weight of the first part composition and an amount of at least one compound among total amount of compounds of formulas [(m) is 1-5], [(m) is 2-6] and [(m) is 3-7] becomes >=50% based on the first part composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a scouring detergent composition for fibers, and more specifically, it uses flon and halogen-containing organic solvent for oily stains such as machine oil adhering to fibers in the dyeing preparation step. The present invention relates to a scouring detergent composition that can be effectively removed in an aqueous system at low temperature without performing.

[0002]

2. Description of the Related Art Generally, when dyeing a textile product, a washing process (hereinafter referred to as scouring) is performed in advance to remove adhered machine oil, oily stains such as oiling agents for spinning, and inorganic stains such as earth and sand. There is a need.

There have been the following conventional techniques for removing the oily stains attached to the fibers.

First, there is a method of solvent refining with a chlorine-based solvent such as tetrachloroethylene or trichloroethylene, or a low boiling point petroleum (hydrocarbon) solvent such as kerosene or petroleum ether.

There is also a method of scouring and cleaning with an aqueous cleaning liquid containing various surfactants. For example, various surface active agents 0.
Using an aqueous cleaning solution containing 3 to 3.0 g / l, room temperature to 95
Scouring is carried out at a temperature of ° C for 5 to 30 minutes. As the surfactant to be used, fatty acid soap, alkyl sulfate, alkyl sulfonate, alkyl ether carboxylic acid, alkyl benzene sulfonate, polyoxyethylene (hereinafter abbreviated as POE) alkyl ether sulfate,
Anionic surfactants such as alkyl phosphates, N-methylacyl taurine, and fatty acid monoglyceride sulfates, and nonionic surfactants such as POE alkyl ethers and POE alkyl phenyl ethers.

[0006]

The reason why oily stains must be removed from fibers before dyeing is that the removal of oily stains such as machine oil and spinning oil is incomplete in the next dyeing step. This is because problems such as uneven dyeing occur. That is, the part to which the oily stain adheres is difficult to dye depending on the type of dye, or conversely is dyed in a dark color, and so-called uneven dyeing occurs.

Generally, when dyeing natural fibers such as cellulose fibers and wool with an ionic dye, the area where oily stains adhere is not dyed, and a sparingly water-soluble disperse dye is used to synthesize synthetic fibers such as polyester. In the case of dyeing, the part where the oily stain adheres is dyed more deeply.

Further, synthetic fibers such as polyester and nylon are heat treated (100 to 1) after scouring and washing and before dyeing process.
50 ° C. × 1 to 10 minutes) may be performed (presetting step), but in that case, if the cleaning of oily stains is insufficient,
The oil remaining in the fibers smokes due to the heat in the presetting process, which significantly deteriorates the working environment.

The reason why the oily stains adhere to the fibers is as follows.

The machine oil attached to the fiber is mainly used for spinning,
In the spinning process, reduce the friction between the yarn and the spinning machine, spinning machine,
It is for preventing troubles such as thread breakage, and directly lubricates the thread or contacts the thread with the machine (reel, guide, etc.)
Used to refuel. Specifically, hydrocarbon oils such as liquid paraffin, synthetic ester oils such as dioctyl sebacate, dioctyl adipate, and dioctyl phthalate, silicone oils such as dimethylpolysiloxane (less than 500 cSt), and the like are used. Compounds containing a solid lubricant such as molybdenum sulfide and silicone oil have been used as excellent lubricants.

In particular, in the field of swimwear, leotards, pantyhose, etc., which require stretch-back properties among fibers, nylon covered core spun yarns in which polyurethane elastic fibers are covered with nylon are widely used, To manufacture those core spun yarns,
Silicone oil is used to impart smoothness to the thread and prevent thread breakage during manufacturing.

[0012] Such silicone oil is particularly difficult to wash during scouring and washing, which causes uneven dyeing in the dyeing process.

When the spun or spun yarn is applied to a knitting machine or a shoveling machine to form a knitted fabric or a woven fabric, friction between the yarn and the machine is reduced, yarn breakage is prevented, and work efficiency is improved. Solid leveling agents such as oil and tallow alcohol, high melting point paraffin wax, natural wax (wood wax, carnauba wax, etc.) are used.

Particularly in the knitting machine, a large amount of hydrocarbon oil is used in order to reduce the friction between the needle and the yarn and realize high-speed machine operation, and it is difficult to remove them, so that the subsequent dyeing step is performed. Will be a major obstacle. A typical smooth hydrocarbon oil is Bexilla A (Shell Petroleum).

The conventional method of solvent refining with the chlorine-based solvent or the low boiling point petroleum (hydrocarbon) solvent has a high detergency, and especially for wool, there is a fear that the fiber may shrink due to water. It is widely used, especially in the wool industry. However, due to toxicity (human body and environment) and flammability problems, a completely closed special refining installation is necessary, and chlorine solvents cannot be used in the future.

Further, in the method of scouring and washing with an aqueous cleaning liquid containing the above-mentioned various surfactants, when the above-mentioned anionic surfactant is used, the oil stains are generally not sufficiently removed and the foaming property is large. Poor workability, and because of bubbles in the drainage, it harms the environment. On the other hand, in the case of using a nonionic surfactant, the oil stain removability is better than that of the anionic surfactant and is widely used. For example, a POE (7~12) C ₁₂ ~ ₁₄ oxo alcohols, POE (7 to 12) nonylphenyl ether, POE (7 to 12) Te Uri ether and the like. However, these are the requirements of the recent dyeing industry,
It has little effect on low temperature scouring (room temperature to 40 ° C.) and washing of silicone oil, hardly-washable hydrocarbon oil (Bexilla A) and the like. Further, it is not as effective in cleaning other general oil stains as solvent refining using a chlorine-based solvent such as tetrachloroethylene or trichlorethylene, a low boiling point petroleum (hydrocarbon) solvent such as kerosene or petroleum ether.

The present invention solves the above-mentioned problems of the prior art and uses an organic solvent for oily stains such as machine oil adhered to fibers in the dyeing preparation step, particularly stains such as silicone oil which are difficult to wash and remove. It is an object of the present invention to provide a scouring detergent composition that can be effectively removed at a low temperature.

[0018]

According to the present invention, the above objects can be achieved by the following scouring detergent composition for fibers.

R ₁ O (AO) _m H (formula (I)) (wherein R ₁ is _one of alkyl, alkenyl, alkylphenyl and alkenylphenyl having 2 to 20 carbon atoms, and A is Indicates ethylene or propylene,
m ≧ 0. 3 to 70 parts by weight of a first partial composition consisting of three or more compounds selected from the compounds represented by
HLB comprises 30 to 97 parts by weight of a second partial composition comprising one or more hydrophilic surfactants of 10 or more.
M in the chemical formula (I) of the compound having the highest content in the partial composition is in the range of 1 to 5, and the total weight of the compounds of m = 0 in the chemical formula (I) is the first 10% or less by weight of the partial composition, and m =
At least one of the total weight of the compounds 1 to 5, the total weight of the compounds of m = 2 to 6 and the total weight of the compounds of m = 3 to 7 is 50% or more of the weight of the first partial composition. A scouring detergent composition for a fiber (claim 1).

M in the chemical formula (I) is preferably
It is 10 or less (claim 2).

The hydrophilic surfactant having an HLB of 10 or more is preferably R ₂ O (AO) _n H (chemical formula (II)).
(Wherein R ₂ is the same as the above R ₁ , A is ethylene or propylene, and 7 ≦ n ≦ 30). One or more nonionic surfactants selected from the compounds (Claim 3).

The hydrophilic surfactant having an HLB of 10 or more is preferably other than the first partial composition (claim 4). For example, R ₁ may be different from each other.

Preferably,

Chemical formula (III)

Embedded image

Chemical formula (IV)

[Chemical 6]

Chemical formula (V)

[Chemical 7]

And chemical formula (VI)

Embedded image

One of the amine-based surfactants represented by
Contains more than one seed,

Weight N of the amine-based surfactant based on the total weight S of the first partial composition and the second partial composition.
The weight ratio S / N is 99/1 to 50/50 (Claim 5).

[0030]

In the above chemical formula (I), m having a value of 1 or more is a polyoxyalkylene alkyl nonionic surfactant. Such a nonionic surfactant is generally a mixture of various alkoxylated species having different molecular weights, and the compounds constituting the mixture also have a wide molecular weight distribution. Further, in many cases, a large amount of unreacted manufacturing raw material is contained. Therefore, not only is the content ratio of the alkoxylated species in the range showing detergency against a certain soil component not only small, but also other components that do not contribute much to detergency (more lipophilic or hydrophilic than the component exhibiting detergency). Properties and unreacted raw material components) have an adverse effect on the detergency, and the detergency is not preferable.

In the first partial composition of the present invention, m in the chemical formula (I) of the compound having the highest content is 1
Exists in the range of 5 to 5, and m = in the above chemical formula (I).
The total weight of the compounds of 0 is 10 of the total weight of the first partial composition.
% Or less and m = 1 in the chemical formula (I)
At least one of the total weight of the compounds of 5 to 5, the total weight of the compounds of m = 2 to 6 and the total weight of the compounds of m = 3 to 7 is 50% or more of the total weight of the first partial composition. ,
In addition, the first partial composition is mixed with HL in the specific weight ratio.
Since B is combined with the second partial composition consisting of one or more hydrophilic surfactants of 10 or more, it is effective at a low temperature for oily stains such as mechanical oils attached to fibers, spinning oiling agents, especially silicone oils. Can be removed selectively.

In the above chemical formula (I), a composition mainly composed of a compound having a large value of m (for example, a compound of 8 or more) has a number of added moles of ethylene oxide or propylene oxide of the compounds constituting the composition. Oily stains cannot be removed even if the width is as narrow as that of the present invention. Similarly, even if such a mixture is combined with a hydrophilic surfactant having an HLB of 10 or more, oily stains cannot be removed.

Even when the first partial composition specified in the present invention is used alone, it has a low HLB, is hardly dissolved in water, and does not show detergency against oily stains.

Further, when the range of the number of moles of added ethylene oxide or propylene oxide of the compound constituting the polyoxyalkylene alkyl nonionic surfactant is wider than that of the first partial composition of the present invention, HLB is used.
Irrespective of the value of, the detergency against oily soil is considerably inferior and, even in combination with the second partial composition of the invention, the detergency against oily soil is likewise inferior.

[0035]

Preferred Embodiments The first partial composition comprises at least three compounds selected from the compounds represented by the chemical formula (I).

R ₁ in the chemical formula (I) represents an alkyl, alkenyl, alkylphenyl or alkenylphenyl group having 2 to 20 carbon atoms, which may be linear or branched. The number of carbon atoms is preferably C
₆ -C ₁₈ (more preferably C ₈ -C ₁₈₎ To.

In the chemical formula (I), m is generally an integer, of the total weight of the compounds of m = 1-5, the total weight of the compounds of m = 2-6 and the total weight of the compounds of m = 3-7. At least one of them is preferably 70% by weight or more, more preferably 80% by weight or more, based on the total weight of the first partial composition.

The content of the compound of m = 0 in the first partial composition is 10% by weight or less, preferably 5% by weight or less.

In the chemical formula (I), R ₁ and A when two or more compounds are included in the range of m = 1 to 5 may be different from R ₁ and A of other compounds within the range. But,
Preferably they are the same. This means that m = 2-6
The same applies to the compounds included in the range of m and the compounds included in the range of m = 3 to 7.

The nonionic surfactant having a narrow polyoxyalkylene addition distribution in the present invention can be produced by a known method. For example, when reacting alkylene oxide with alkyl alcohol, as a reaction catalyst,
It can be produced by using a magnesium oxide catalyst (JP-A-1-164437) or a modified CaO catalyst (JP-B6-53695) to which a metal ion such as aluminum or gallium is added. It can also be produced by using a metal catalyst obtained by coprecipitating a metal ion such as aluminum, magnesium or silicon with an alkali to obtain a mixed crystal and further sintering at about 500 ° C. These catalysts are widely used as adsorbents for separation and purification of various chemical substances.

Examples of the alkyl alcohol used include lower alcohols such as ethanol, propanol and butanol, octanol, decanol and lauryl alcohol,
Examples thereof include medium to higher alcohols such as oleyl alcohol and stearyl alcohol, synthetic alcohols such as oxo alcohol and Ziegler alcohol, and alkylphenols such as nonylphenol, octylphenol and butylphenol.

The above-mentioned nonionic surfactant (first partial composition) having a narrow m distribution range specified in the present invention is synergistically effective when combined with a hydrophilic surfactant having an HLB of 10 or more. Shows detergency.

Examples of the hydrophilic surfactant having an HLB of 10 or more include fatty acid soaps such as Na laurate, Na oleate and Na stearate, alkyl sulphates such as Na lauryl sulphate Na and polyoxyethylene lauryl sulphate Na, dodecylbenzene. Na sulfonate, α
-Alkyl sulfonates such as Na olefin sulfonate, polyoxyethylene lauryl ether carboxylic acid N
Examples thereof include ether carboxylic acids such as a, alkyl phosphates such as monolauryl phosphate Na and dilauryl phosphate Na salt, and anionic surfactants such as amino acid type anionic surfactants such as N-methylacyl taurine.

Nonionic surfactants corresponding to hydrophilic surfactants having an HLB of 10 or more include POE lauryl ether, POE tridecyl ether, POE hexadecyl ether and other POE alkyl ethers having a POE addition mole number of 7 to 30. And POE alkylphenyl ethers such as POE nonyl phenyl ether and POE octyl phenyl ether having a POE addition mole number of 7 to 30.

A hydrophilic surfactant having an HLB of 10 or more is
The nonionic surfactant represented by the specific chemical formula (II) is particularly effective. There is no particular limitation on the polyoxyalkylene distribution as long as the HLB is 10 or more.
The added mole number n of polyoxyalkylene is 7 to 30, preferably 7 to 20, more preferably 7 to 15. The number of carbon atoms of R ₂ is 2 to 20 (hereinafter, indicated as C _{2 to} C ₂₀ ), more preferably C _{8 to} C ₂₀ , and further preferably C _{8 to} C ₁₈ .

The mixing ratio of the first partial composition / the second partial composition is 3/97 to 70/30 (weight ratio), preferably 10 /.
90-60 / 40, more preferably 30 / 70-60
/ 40.

For the first partial composition and the second partial composition,
When one or more kinds of the specific amine-based surfactants are contained in the specific weight ratio, a synergistic effect is exerted to further improve the detergency.

Examples of the amine-based surfactant represented by the chemical formula (III) include POE caprylamine and PO.
E lauryl amine, POE myristyl amine, POE oleyl amine, POE stearyl amine, etc. are mentioned.

Examples of the amine-based surfactant represented by the chemical formula (IV) include POE capryl amide and POE.
E Lauryl Amide, POE Myristyl Amide, PO
Examples include E oleyl amide and POE stearyl amide.

Examples of the amine-based surfactant represented by the chemical formula (V) include POE decylamine oxide and PO.
E lauryl amine oxide, POE oleyl amine oxide, etc. are mentioned.

Examples of the amine-based surfactant represented by the chemical formula (VI) include POEN-lauryl propylene diamine and POEN-stearyl propylene diamine.

The addition mole number a + b of the polyoxyalkylene of the amine-based surfactant represented by the chemical formulas (III) to (V) is 0 to 40, preferably 1 to 20, and more preferably 2 to 10. , And more preferably 2 to 5. Number of carbon atoms of R ₃ to R ₆ is, C ₂ ~C _20, it is preferably C ₈ -C _20, more preferably C ₈ -C _18.

The mixing ratio of the amine-based surfactant (weight N) to the first partial composition and the second partial composition (total weight S) is such that the weight ratio S / N is 99/1 to 50/50. Yes, preferably 95/5 to 70/30, more preferably 90/10 to 70/30.

The scouring detergent composition of the present invention contains 0.1 to 10.0 g without using any other organic solvent in the aqueous washing bath.
/ L, preferably 0.5 to 3.0 g / l, at room temperature
Scouring and washing can be carried out at a temperature of 95 ° C. (scouring time is 3 to 60 minutes, preferably 5 to 15 minutes, and bath ratio is 1: 5 to 5.
1:40). It is particularly effective for cleaning at a low temperature (room temperature to 40 ° C).

As equipment to be used, any of equipment generally used in dyeing factories, batch type equipment such as winks, jet winks, cheese dyeing machines, continuous equipment such as open soapers, continuous scouring machines and the like can be used. Since it is possible and has a low foaming property, there is no trouble caused by foaming.

The target fibers include cellulose fibers, protein fibers such as wool, polyester, nylon,
It can be used in any of synthetic fibers such as spandex, and can be used in any form such as yarn, knitted fabric, woven fabric and raw cotton.

[0057]

【Example】

(Example 1) Synthesis of first partial composition and composition of product of the present invention A predetermined raw material alcohol and the following metal catalyst (0.1% by weight relative to the raw material alcohol) were charged in an autoclave made of stainless steel, and after substitution with N ₂ gas , 5.0 kgG / cm ² ,
At 120 to 125 ° C, ethylene oxide or propylene oxide was continuously introduced over 3 hours. After the introduction, the mixture was cooled to about 80 ° C., the pressure was returned to normal pressure, neutralized with a 20% aqueous phosphoric acid solution, and heat filtered under pressure using Celite to obtain various first partial compositions (A). The catalyst is [Mg ₆ Al
₂ (OH) ₁₆ ] CO ₃ .4H ₂ O (commercially available reagent) was dried under reduced pressure in a silica gel desiccator for 24 hours before use.

[0058]

[Table 1]

The first partial composition in Table 1, eg PO
The E (m) lauryl ether NR is obtained by charging 1 mol of lauryl alcohol with 1 mol of ethylene oxide in a reactor and reacting it by the above-mentioned method. The constituent compounds have a narrow range of the number of moles of added ethylene oxide. That is,
m = 0 (unreacted raw material) is less than 10% by weight,
At least one of the total weight of the compounds of m = 1 to 5, the total weight of the compounds of m = 2 to 6 and the total weight of the compounds of m = 3 to 7 is 50 weight of the total weight of the first partial composition. %
That is all.

On the other hand, as shown in Table 2, ordinary POE (m) lauryl ether contains 5 to 35% by weight of unreacted raw materials such as alcohol, and the range of the number of moles of added ethylene oxide is wide. Is wide.

[0061]

[Table 2]

Compounds to which ethylene oxide or propylene oxide in Table 1 is added,
For those without NR, 5 to 5% of unreacted raw materials (alcohol etc.)
Raw material (alcohol, etc.) to be added containing 20% by weight 1
With respect to the number of moles of ethylene oxide or propylene oxide charged in the reactor, the number of moles of the added compound contained within the range of m ± 2 is 3 at the maximum.
5 to 45% by weight.

(Example 2) Evaluation of scouring and detergency for 100% cotton knit <Evaluation method> 100% cotton knit is cut into 3.0 g, and 0.1 g of the following oil is dropped on the central portion of a substantially square cloth. Dry at 100 ° C. for 3 hours with a hot air dryer to obtain a contaminated cloth sample. In the following scouring cleaning bath, the temperature is 25 ° C, 5
Washing is performed for 15 minutes at each temperature of 0 ° C and 80 ° C, and the bath ratio is 1:
30. Wash with water twice at a bath temperature of 25 ° C. Dyeing is carried out in the following dyeing bath at 95 ° C. for 2 minutes, and the degree of oil loss is visually judged.

<Oil> As oils, Bexilla Oil A (made by Shell Petroleum) and dimethyl silicone (200c
St) was used.

<Scouring and cleaning conditions> The scouring and cleaning composition of the present invention or the comparative example was 1.0 g / l and the bath ratio was 1:20.

A shaking type dyeing tester was used.

<Dyeing conditions> Using a shaking type dyeing tester, Serious Sprable-G (dye manufactured by BAYER), 0.
Dyeing was performed under the conditions of 1% owt and a bath ratio of 1:20.

The evaluation results are shown in Table 3.

[0069]

[Table 3]

(Example 3) Evaluation of scouring and detergency of 100% wool knit <Evaluation method> 100% cotton knit of Example 2 was used for wool 10
The same cleaning evaluation experiment was conducted by changing to 0% knit.

However, the dyeing conditions after washing were as follows.

<Dyeing conditions> Supranol blue RLW (dye manufactured by BAYER) 0.5% owf bath ratio 1:20

Table 4 shows the evaluation results.

[0074]

[Table 4]

(Example 4) Evaluation of scouring and detergency with respect to 100% polyester <Evaluation method> The same 100% polyester knit of Example 2 was changed to 100% polyester tropical, and the same cleaning evaluation experiment was conducted.

However, the dyeing conditions after washing are as follows.

<Dyeing conditions> The following two dyes were used at the following ratios at the same time. Resolin Blue FBL (BAYER) 0.2% owf Levegal PEW (NAYER) 0.5% owf

The results are shown in Table 5.

[0079]

[Table 5]

[0080]

The scouring detergent composition for fibers of the present invention is 3 selected from the compounds represented by the above-mentioned specific chemical formula (I).
3 to 70 parts by weight of a first partial composition comprising at least one compound, and 30 to 97 parts by weight of a second partial composition comprising at least one hydrophilic surfactant having an HLB of at least 10; M in the chemical formula (I) of the compound having the highest content in the partial composition is in the range of 1 to 5, and the total weight of the compounds of m = 0 in the chemical formula (I) is the first 10% or less by weight of the partial composition, and m
= 1 to 5 at least, at least one of the total weight of the compounds of m = 2 to 6 and the total weight of the compounds of m = 3 to 7 is 50% or more of the weight of the first partial composition. Therefore, it is possible to effectively remove the machine oil attached to the fiber, the oiling agent for spinning, especially the oily stain such as silicone oil even at a low temperature.

Claims (5)

[Claims] 1. R ₁ O (AO) _m H (formula (I)) (wherein R ₁ represents _one of alkyl, alkenyl, alkylphenyl and alkenylphenyl having 2 to 20 carbon atoms, A represents ethylene or propylene,
m ≧ 0. 3 to 70 parts by weight of a first partial composition consisting of three or more compounds selected from the compounds represented by
HLB comprises 30 to 97 parts by weight of the second partial composition consisting of one or more hydrophilic surfactants of 10 or more, and the compound having the highest content in the first partial composition is represented by the chemical formula (I). m is in the range of 1 to 5, the total weight of compounds of m = 0 in the chemical formula (I) is 10% or less of the weight of the first partial composition, and m = 1 to At least one of the total weight of the compound of 5, the total weight of the compound of m = 2 to 6 and the total weight of the compound of m = 3 to 7 is 50% or more of the weight of the first partial composition. A scouring detergent composition for fibers, comprising: 2. The scouring detergent composition for fibers according to claim 1, wherein m in the chemical formula (I) is 10 or less. 3. The hydrophilic surfactant having an HLB of 10 or more is R ₂ O (AO) _n H (chemical formula (II)) (where R ₂
Represents the same as R ₁ described above, A represents ethylene or propylene, and 7 ≦ n ≦ 30. ) A scouring detergent composition for fibers according to claim 1 or 2, which is one or more nonionic surfactants selected from compounds represented by the formula (1). 4. The scouring detergent composition for fibers according to claim 1, wherein the hydrophilic surfactant having an HLB of 10 or more is other than the first partial composition. Stuff. 5. A compound represented by the chemical formula (III): Chemical formula (IV) Chemical formula (V) Chemical formula (VI) And a total weight S of the first partial composition and the second partial composition containing at least one of the amine-based surfactants
Weight ratio of the weight N of the amine-based surfactant to
N is 99 / 1-50 / 50, The scouring detergent composition for fibers of Claim 1 characterized by the above-mentioned.