JP2007254910A - Residual detergent-reducing fiber product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a residual detergent-reducing fiber product, which can ensure an excellent washing effect and excellent washing durability and can reduce the quantity of a residual detergent after washed, to provide a method for producing a residual detergent-reducing fiber product, and to provide a method for washing the fiber product. <P>SOLUTION: This residual detergent-reducing fiber product has anionic groups on the surface and inside fibers. The process for producing the residual detergent-reducing fiber product has a process for anionizing the surfaces and inside of the fibers. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a residual detergent-reducing fiber product, a method for producing a residual detergent-reducing fiber product, and a textile product washing capable of reducing the amount of residual detergent after washing while ensuring excellent cleaning effect and washing durability. It relates to the processing method.

As a method for washing textile products in a general household, washing using water and a detergent is common. Although the washing effect has recently increased due to advances in washing machines and detergents, it does not provide a sufficient washing effect on items such as socks and collar sleeves, spilled oil, oil stains and mud stains. There was a case. In order to solve such problems, in order to obtain a high detergency, current detergents for clothes include anionic surfactants as surfactants and fluorescent whitening agents, enzymes, builders, etc. as auxiliary agents. Detergents are mainly used.

However, there are a lot of synthetic detergents containing chemical substances such as these that have an adverse effect on the human body. In recent years, the number of patients with atopic dermatitis has increased remarkably and has become a social phenomenon. One characteristic of atopic dermatitis is that it is susceptible to irritation caused by chemical substances, etc. Patients with atopic dermatitis generally keep their skin clean by washing to remove irritation-causing substances from the skin. It is instructed to keep. However, if an atopic dermatitis patient wears a textile product that has been washed with a synthetic detergent containing such chemicals, it reacts sensitively to the chemicals remaining on the textiles, causing rough skin and inflammation. There was a concern that it would end up.

On the other hand, when washing textile products worn by patients with atopic dermatitis, the use of hypoallergenic detergents, soaps and composite soaps as shown in Patent Document 1 is performed. However, when these are used, there are problems such as that it takes more time than before and the cleaning effect on oil stains and mud stains is not sufficient. In addition, when soap is used, salt ions are exchanged between the metal ions of tap water and the alkali ions of the soap, and water-insoluble metal soap called soap scum is generated, which can cause skin irritation in patients with atopic dermatitis. Mitigation was not achieved.
Japanese Patent Laid-Open No. 2002-3900

In view of the above-described situation, the present invention provides a residual detergent-reducing fiber product and a method for producing a residual detergent-reducing fiber product capable of reducing the amount of residual detergent after washing while ensuring excellent cleaning effect and washing durability. And it aims at providing the washing processing method of textiles.

The present invention is a residual detergent-reducing fiber product having an anionic group on the surface and inside of the fiber.
The present invention is described in detail below.

As a result of intensive studies, the present inventors have introduced an anionic group into the surface and inside of the fiber constituting the fiber product, so that the surface of the fiber product can be obtained when washing is performed using such a fiber product. In addition, the anionic group in the interior and the anionic surfactant generally used as a detergent are repelled ionicly to effectively prevent the residue of the detergent, and the detergent inherent in the detergent The inventors have found that a sufficient cleaning effect can be obtained without impairing the present invention, and have completed the present invention.
JP-A-10-245775 discloses a detergent residue control in which an anionic group such as a carboxyl group, a hydroxyl group, or a sulfonic acid group is introduced on the surface of a fiber structure and a softening agent mainly composed of vegetable oil is provided. A functional fiber structure is disclosed. However, the detergent residue-suppressing fiber structure obtained by such a method has an anionic group introduced on the surface of the fiber, so that the durability against repeated washing is insufficient, and the use period is prolonged. There was a problem that the effect of suppressing the residual detergent was lowered. The residual detergent-reducing fiber product of the present invention not only has an anionic group but also has an inside of the fiber, so that the washing durability is improved as compared with the case where the anionic group is present only on the surface of the fiber. It can be greatly improved and the effect can be maintained for a long period of time. Moreover, it can prevent that the detergent which entered the inside of a fiber remains.

Examples of the anionic group include a carboxyl group, a sulfonic acid group, a sulfuric acid group, a phosphoric acid group, a phosphonic acid group, and an ester group such as a sulfuric acid ester and a phosphoric acid ester. Among these, a carboxyl group is preferable because it has low irritation to the skin and can be easily introduced into cellulose fibers. Among these, introduction of a carboxyl group as a carboxymethyl group is preferable because it can be easily introduced into cellulose fibers.
In addition, when a group having a sulfonic acid group or COO is introduced as the anionic group, it neutralizes odor components such as caproic acid and isovaleric acid, and imparts a deodorizing function to the fiber product to eliminate bromide. be able to.

The content of the anionic group in the residual detergent-reducing fiber product of the present invention is appropriately determined depending on the type of the anionic group, but should be set to such an extent that the fiber does not deteriorate due to yellowing or curing. Is preferred.

The form of the residual detergent-reducing fiber product of the present invention is not particularly limited. For example, yarns, cottons, woven and knitted fabrics, non-woven fabrics, polyethylene films, polypropylene films, and other papers, synthetic papers, and the like are used. Fiber products and the like.

The material of the fiber product used in the present invention is not particularly limited, and a material made of natural fiber, semi-synthetic fiber, synthetic fiber or the like can be used.
Examples of the natural fiber include wool, silk, cotton, hemp and the like.
Examples of the semisynthetic fiber include rayon, polynosic, cupra, and acetate.
Examples of the synthetic fiber include polyesters such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyhexamethylene terephthalate, polyamides such as nylon 6, nylon 6, 6, and the like, polyacryl, polypropylene, polyvinyl chloride, and polyvinyl alcohol. It is done.

Examples of uses of the residual detergent-reducing fiber product of the present invention include clothing supplies, miscellaneous goods, interior goods, bedding goods, and the like.
The above clothing items include outing clothing, sportswear, homewear, relaxation wear, pajamas, sleepwear, underwear, office wear, work clothes, food white clothes, nursing white clothes, patient clothes, nursing clothes, student clothes, kitchen clothes Etc. Examples of the miscellaneous goods include an apron, towels, gloves, mufflers, socks, hats, shoes, sandals, bags, umbrellas and the like. Examples of the interior goods include curtains, carpets, mats, kotatsu covers, sofa covers, cushion covers, sofa grounds, toilet seat covers, toilet seat mats, table cloths, and the like. Examples of the bedding article include a futon side, a blanket for blanket, a blanket, a blanket side, a pillow filler, a sheet, a waterproof sheet, a duvet cover, and a pillow cover.

The residual detergent-reducing fiber article of the present invention can be produced by performing a process of anionizing the surface and the inside of the fiber. Such a method for producing a residual detergent-reducing fiber article is also one aspect of the present invention.

Examples of the method for anionizing the surface and the inside of the fiber include a method of directly introducing an anionic group into the fiber and a method of introducing an anionic molecule into the fiber.

As a specific method for directly introducing the anionic group into the fiber, the anionic group is introduced by substituting with hydrogen of the hydroxyl group of cellulose constituting the cellulose fiber article having an anionic group such as a carboxyl group or a sulfonic acid group. Methods and the like.

One preferred embodiment of the method for introducing a carboxyl group into the cellulose fiber will be described. The above-mentioned carboxyl group can be easily produced in the form of carboxymethyl group by bringing a cellulose-based fiber into contact with a treatment liquid containing monochloroacetic acid or an alkali metal salt of monochloroacetic acid (for example, sodium salt or potassium salt). Can be introduced. The introduction of a carboxymethyl group in this way is hereinafter also referred to as carboxymethylation.

The concentration of monochloroacetic acid or the alkali metal salt of monochloroacetic acid in the treatment liquid in the case of performing carboxymethylation may be determined appropriately so as to obtain the desired degree of processing, but the preferred lower limit is 10 g / L, the preferred upper limit is 500 g / L, the more preferred lower limit is 50 g / L, the more preferred upper limit is 300 g / L, the still more preferred lower limit is 100 g / L, and the still more preferred upper limit is 200 g / L.

It is preferable to mix | blend alkali metal hydroxide, for example, sodium hydroxide, in the process liquid in the case of performing the said carboxymethylation. By blending sodium hydroxide, the degree of carboxymethylation of the resulting treated fiber can be improved. The reactivity tends to increase as the concentration of sodium hydroxide in the treatment liquid is increased, and it is usually preferably 20 g / L or more. However, if a large amount of sodium hydroxide is blended, the texture of the resulting fiber tends to deteriorate, so care must be taken.

Examples of the method of bringing the cellulosic fiber into contact with the treatment liquid include a liquid flow method in which the fiber is rotated in the treatment liquid; a method of padding (squeezing) after immersing the fiber in the treatment liquid, and the like. In terms of use efficiency, it is effective to lower the bath ratio (use ratio of the treatment liquid), and a method of padding after dipping in this respect is effective.
In addition, it does not specifically limit as temperature conditions at the time of making a cellulosic fiber and a process liquid contact, For example, it can be in the range of 5-50 degreeC.

The time for contacting the cellulosic fiber with the treatment liquid may be appropriately selected from various conditions such as the desired degree of carboxymethylation, the concentration of monochloroacetic acid during treatment, the concentration of sodium hydroxide, and the like. It may be contacted at room temperature for several hours to several days, and the time required can be shortened by heat treatment.

A preferable lower limit of the carboxymethylation degree is 0.1 mol%. If it is less than 0.1 mol%, sufficient moisture absorption may not be obtained. A more preferred lower limit is 1 mol%. The upper limit of the degree of carboxymethylation is not particularly limited, but the preferable upper limit is 10 mol%, and the more preferable upper limit is 5 mol%. In the present specification, the degree of carboxymethylation means the ratio (%) of OH groups of cellulose subjected to carboxymethylation reaction, that is, the number of COO groups after carboxymethylation with respect to the number of hydroxyl groups of untreated cellulose. Percentage (%). The number of COO groups in the cellulosic fiber is determined by quantifying the amount of Na used for the substitution after immersing it in a sodium hydroxide aqueous solution (0.1N) with all the COO groups of the cellulosic fiber as COOH groups. It can ask for. The amount of Na used for the substitution can be quantified by titrating a sodium hydroxide aqueous solution in which cellulosic fibers and the like are immersed using, for example, hydrochloric acid (0.1N). Specifically, the following measurement methods can be employed.

First, cellulose fibers (for example, small pieces of dough) are immersed in 0.3N hydrochloric acid for 1 hour under conditions of a bath ratio of 1:50 and a liquid temperature of 20 ° C. to make all COO groups COOH groups, dehydrated and dried. Residual HCl is removed and about 4 g is sampled and weighed in absolute dry weight (W (g)). Next, the cellulose fibers and the like weighed in absolute dry weight are immersed in 50 mL (B (mL)) of 0.1 N sodium hydroxide aqueous solution that has been precisely weighed and left overnight at a liquid temperature of 20 ° C. Is replaced with COONa. Further, in order to quantify Na used in the substitution, the liquid is titrated using 0.1N hydrochloric acid, and the titration value is set to X (mL). Phenolphthalein can be used as an indicator.

The degree of carboxymethylation is determined based on the absolute dry weight (W (g)) of the cellulosic fiber, the volume of sodium hydroxide aqueous solution (B (mL)), and the volume of hydrochloric acid required for titration (X (mL)). It can be calculated according to the following formula (1).

A specific method for introducing the molecule having an anionic group into the fiber includes, for example, a method of grafting a monomer having an anionic group in the molecule to the cellulose fiber. Examples of the monomer having an anionic group in the molecule include acrylic acid, methacrylic acid, crotonic acid, maleic acid, phthalic acid, itaconic acid, citraconic acid, vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamide-2- Examples include methylpropanesulfonic acid and mono-10-methacryloyloxydecyl phosphate. These may be used alone or in combination of two or more.

Examples of the grafting method include a method of polymerizing the monomer in a state where the monomer is brought into contact with the cellulosic fiber. Specifically, for example, a cellulosic fiber is immersed in a liquid containing the monomer and a polymerization initiator (for example, ammonium peroxodisulfate) and then squeezed and then heated, whereby the molecule having an anionic group is heated. Grafted cellulosic fibers can be obtained.

The amount of the molecule having an anionic group to be introduced by the grafting can be appropriately selected in consideration of the kind of the molecule having an anionic group, the moisture absorption required for the cellulosic fiber, and the like. The preferred lower limit of is 1%. If it is less than 1%, sufficient moisture absorption may not be obtained. A more preferred lower limit is 2%. The upper limit of the graft ratio is not particularly limited, but a preferable upper limit is 30%, a more preferable upper limit is 25%, and a further preferable upper limit is 20%.
In the present specification, the graft ratio is calculated from the following formula (absolute dry weight before treatment) and the absolute dry weight after treatment (absolute dry weight after treatment): 2).

In the above formula (2), the absolute dry weight is the weight of the weighing bottle, for example, by putting a piece of dough having a size of about 10 × 20 cm into a weighing bottle, drying it at 105 ° C. for 2 hours, weighing it, and weighing it in advance. Can be calculated by subtracting.

The amount of residual detergent is greatly increased by carrying out the washing process of washing the residual detergent-reducing fiber product of the present invention with a washing liquid containing an anionic surfactant and the rinsing process of removing the anionic surfactant. A laundry processing method that can be reduced can be realized.
Such a method for washing a textile product is also one aspect of the present invention.

In the textile processing washing method of the present invention, first, a washing process is performed in which the residual detergent-reducing textile product of the present invention is washed with a washing liquid containing an anionic surfactant.

Examples of the anionic surfactant used in the present invention include alcohol sulfate salts, alcohol ethoxylate sulfate salts, alkylbenzene sulfonates, paraffin sulfonates, α-olefin sulfonates, α -Sulfo fatty acid salts, α-sulfo fatty acid alkyl ester salts, fatty acid salts and the like can be used. In particular, linear alkylbenzene sulfonates having 8 to 18 carbon atoms in the alkyl chain and alkyl sulfate esters having 8 to 18 carbon atoms are preferred, and alkali metals and alkanolamine salts are preferred as the counter ion. Of these, sodium linear alkylbenzene sulfonate (LAS) is preferable.

When LAS is used as the anionic surfactant, the preferable lower limit of the LAS content in the washing liquid is 0.01% by weight, and the preferable upper limit is 0.3% by weight. If it is less than 0.01% by weight, the cleaning becomes insufficient, and if it exceeds 0.3% by weight, the surfactant is wasted and the residual detergent may increase.

In the present invention, various additives other than the anionic surfactant may be added to the washing liquid as long as the effects described above are not hindered. Examples of the additive include fragrance, fluorescent agent, bleach, bleach activator, enzyme, calcium scavenger, solvent, hydrotrope and the like.

In the present invention, a rinsing step for removing the anionic surfactant is then performed.
In the present invention, the anionic surfactant can be sufficiently removed by ionic repulsion between the anionized fiber product and the anionic surfactant.

ADVANTAGE OF THE INVENTION According to this invention, the washing processing method of the textiles which can reduce the quantity of the residual detergent after washing can be provided, ensuring the outstanding washing | cleaning effect and washing durability. Thereby, after washing the residual detergent-reducing fiber product of the present invention, even when atopic dermatitis patients wear it, the skin irritation and inflammation caused by the residual detergent are not caused and the skin irritation is reduced. Can be achieved.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

(Example)
After using cotton underwear as a base, dipping in a treatment solution containing sodium monochloroacetate (200 g / L) and sodium hydroxide (70 g / L) at a bath ratio of 1:20 and squeezing with padder The reaction was allowed to stand at 25 ° C. for 24 hours. Then, it washed with water and the unreacted substance was removed and the anionization treatment underwear was obtained.

(Control example)
The untreated cotton underwear used in Example 1 was used as a control fabric.

(Evaluation)
(1) Measurement of residual amount of detergent The anionized undergarment obtained in the examples and the undergarment of the control example were washed by a method based on the method 103 of JIS L 0217 using Attack (manufactured by Kao Corporation) as a detergent. The amount of residual detergent after the measurement was measured by the following method.
In addition, sodium decylbenzenesulfonate (LAS (C10)), sodium dodecylbenzenesulfonate (LAS (C12)), sodium tetradecylbenzenesulfonate (LAS (C14)) and heptaethylene glycol mono-n-dodecyl in detergents When the concentration of ether (AE (C12EO7)) was measured in advance using LS-MS / MS (manufactured by Shimadzu Corporation), the results shown in Table 1 were obtained, and LAS (C10), LAS (C12) and AE ( Since it was confirmed that a large amount of C12EO7) was contained, the measurement was performed on residual amounts of LAS (C10), LAS (C12), and AE (C12EO7). The results are shown in Table 2.

(1-1) Measurement of LAS Residual Amount 4 g was weighed out from the underwears of Examples and Controls, and 25 mL of methanol was added and extracted with shaking for 1 hour. Subsequently, ultrasonic waves were irradiated for 20 minutes, and the resulting solution was used as a sample solution.
The concentration of LAS (C10) and LAS (C12) in the obtained sample solution was measured under the following conditions using HPLC (manufactured by Shimadzu Corporation).
Column: atlantis 2.1 mm × 50 mm, 3 μm (40 ° C.)
Mobile phase: 10 mM ammonium acetate / acetonitrile, 3/7
Flow rate: 0.2 mL / min
Injection volume: 20 μL

(1-2) Measurement of residual amount of AE 2 g was weighed out from the underwear of the example and the control example, 25 mL of methanol was added, and the mixture was extracted by shaking for 1 hour. Subsequently, ultrasonic waves were irradiated for 20 minutes, and the resulting solution was used as a sample solution.
The concentration of AE (C12EO7) in the obtained sample solution was measured under the following conditions using HPLC (manufactured by Shimadzu Corporation).
Column: atlantis 2.1 mm × 50 mm, 3 μm (40 ° C.)
Mobile phase: 10 mM ammonium acetate / acetonitrile, 3/7
Flow rate: 0.2 mL / min
Injection volume: 10 μL

(2) Oleic acid detergency test After applying 10% owf of oleic acid and 2.5% owf of gelatin to the test cloth from which the underwear of the example and the control example was cut, a normal household washing machine (manufactured by Sharp Corporation, Using ES-S4A), as a detergent, Attack (manufactured by Kao) was added to a concentration of 0.67 g / L, and washing was performed by a method based on method 103 of JIS L 0217. After drying each test cloth after washing in the sun, the oleic acid remaining on the test cloth was extracted with methanol, and the residual amount of oleic acid was measured with a gas chromatograph (manufactured by Shimadzu Corporation, GC-17A). The acid residual ratio (%) was determined. The results are shown in Table 3.

As shown in Table 3, the oleic acid residual rate is lower in the case of using the underwear of the example than in the case of using the underwear of the control example, and a decrease in detergency due to the anionization treatment is seen. There wasn't.

ADVANTAGE OF THE INVENTION According to this invention, the washing processing method of the textiles which can reduce the quantity of the residual detergent after washing can be provided, ensuring the outstanding washing | cleaning effect and washing durability.

Claims (3)

A fiber product having reduced residual detergent, characterized by having an anionic group on the surface and inside of the fiber. A method for producing a fiber product with reduced residual detergent, comprising a step of anionizing the surface and the inside of a fiber. A textile product comprising: a washing step of washing the residual detergent-reducing fiber product according to claim 1 with a washing liquid containing an anionic surfactant; and a rinsing step of removing the anionic surfactant. Washing method.