JP4545099B2 - Dissolved chlorine scavenger and cleaning composition containing the same - Google Patents

Description

The present invention relates to a chlorine scavenger and a cleaning composition containing the same, which captures the chlorine by contacting or mixing with a substance containing chlorine having a strong oxidizing activity called free chlorine.
The chlorine scavenger and the detergent composition of the present invention are excellent in the ability to stably wash non-detergents that are denatured by dissolved chlorine in chlorine-containing water such as tap water. When used for washing modified fibers obtained by adding and adsorbing to fibers, fibers that have a characteristic of washing with less washing-off of adsorbed substances, especially supporting metal phthalocyanine derivatives that have antipruritic, antipruritic and anti-inflammatory effects・ Effective for washing cloth.

  According to the Waterworks Law, the lower limit of the residual chlorine concentration is defined as 0.1 ppm or more at normal time at the “end tap”, and 0.2 ppm or more when the presence of waterborne pathogen contamination is suspected. However, the upper limit is not specified. For this reason, in the period when bacteria are likely to propagate, a larger amount of residual chlorine may be contained in the tap water.

  On the other hand, fibers have been cationized with a quaternary ammonium salt and adsorbed substances are adsorbed on the fibers to modify the fibers. Conventionally, such modified fibers have been washed in dissolved chlorine-containing water. If applied, the adsorbed material may be oxidized and denatured by the oxidizing action of dissolved chlorine. Further, since the modifying substances for fibers as described above are generally weakly bonded to the fibers, dirt is removed, but it is required to be washed to such an extent that the modifying substances can be retained. If the cleaning agent contains a quaternary ammonium salt type cation used as a softening agent, there is a problem that the adsorbed modifying substance is peeled off, and a solution to these problems has been demanded.

Metal phthalocyanine has long been used as a dye and pigment, but recently it has been reported that it has antipruritic, antipruritic and anti-inflammatory effects.
Patent Document 1 discloses that a specific metal phthalocyanine derivative has a fiber / cloth having a deterrent, antiseptic, and anti-inflammatory effect on a human body by supporting the metal phthalocyanine derivative on the fiber at about 0.001 to 5% by weight. It has been disclosed that it can be obtained.
However, the specific metal phthalocyanine derivative-supporting fiber / fabric produced by the method described in Patent Document 1 is not only affected by dissolved chlorine, but is also supported on the fiber when continuously washed using a commercial clothing detergent. The phthalocyanine derivative thus peeled off from the fiber, and it was found that the antipruritic, antipruritic and anti-inflammatory effects were extremely reduced or disappeared. In addition, in the presence of a surfactant having a cationic property to impart a softening effect to the fiber / cloth, it is recognized that the color bleed becomes severe when the metal phthalocyanine derivative-supporting fiber / cloth is washed. There has been a demand for the development of a detergent composition having an effective softening effect on metal phthalocyanine derivative-supporting fibers and fabrics.

Although the technique of using taurine as a chlorine scavenger in dissolved chlorine-containing water is described in Patent Document 2, it is difficult to prepare tap water treated with taurine.
On the other hand, N-acyl silk peptide has been used as a moisturizing and hypoallergenic surfactant, especially as a component of a body cleanser, and has been described in Patent Document 3 as a detergent for clothing containing an acyl peptide. However, there is no literature that teaches the cleaning effect on modified fibers, especially phthalocyanine-supported fibers, in dissolved chlorine water.
Japanese Patent Publication No. 07-68128 JP 2002-320981 A JP-A-58-10200

The problem to be solved by the present invention is to dissolve and prevent the influence of dissolved chlorine by capturing or removing the chlorine by contacting or mixing with a substance containing chlorine having a strong oxidizing activity called free chlorine. It is to provide a chlorine scavenger and a cleaning composition containing the same.
The present invention also prevents alteration of the object to be cleaned due to dissolved chlorine even in water containing dissolved chlorine, and prevents or reduces dropping of the modified substance by dissolved chlorine in the fiber material modified by the modified substance. It is an object of the present invention to provide a chlorine scavenger or a cleaning composition containing the same.

The present inventors first search for substances having a scavenging effect on dissolved chlorine, and evaluate their ability to scavenge dissolved chlorine, whereby acyl hydrolyzed silk peptides having a polymerization degree of 2.1 or more themselves have a function of scavenging dissolved chlorine. I found that I have.
Furthermore, the dissolved chlorine-containing water cleaning composition of the present invention has an excellent anti-color-fading action in cleaning objects to be cleaned in which the dye compound modifies the fiber material, and a softener is used in cleaning the fiber material. The present invention was completed based on this finding and found to provide a practically excellent flexibility effect.

〔但し、上記式（１）中、Ｒ¹−ＣＯは１０〜２２個の炭素原子を含む脂肪酸の残基を表し、−ＮＨ−ＣＨ（Ｒ²）−ＣＯ−は、シルク蛋白質のペプチド残基を表し、Ｒ²は、シルク蛋白質の側鎖を表し、ｍは２．１以上の正数を表し、Ｍ¹はナトリウム原子、カリウム原子、アルカノールアミン残基又は、塩基性アミノ酸残基を表す〕
により表されるＮ−アシルペプチド化合物を含むことを特徴とするものである。
本発明の溶存塩素捕捉性洗浄剤組成物は、前記本発明の溶存塩素捕捉剤を含む塩素捕捉成分と、少なくとも１種の洗浄剤を含む洗浄成分とを含むものである。
本発明の修飾繊維材料の洗浄方法は、繊維材料を水中においてカチオン化剤を用いて処理し、このカチオン化繊維材料に、繊維材料用修飾物質を吸着させて製造された修飾繊維材料を、溶存塩素を含有する水中において洗浄するに際し、洗浄剤として、前記本発明の溶存塩素捕捉性洗浄剤組成物を用い、それによって、洗浄水中の溶存塩素を捕捉除去し、修飾繊維材料中の吸着物質の変質及び脱落を防止することを含むものである。
本発明の洗浄方法の一実施態様において、前記繊維材料を修飾する修飾物質が、下記一般式（２）：

〔但し、上記式（２）において、Ｒ³〜Ｒ⁶は、それぞれ、互いに独立に、カルボキシル基、スルホン酸基及びこれらの酸基を有する炭化水素基から選ばれた置換基を表し、ｎ¹〜ｎ⁴は、それぞれ互に独立に、０〜４の整数を表し、ＭはＦｅ，Ｃｏ，Ｍｎ，Ｔｉ，Ｖ，Ｎｉ，Ｃｕ，Ｚｎ，Ｗ及びＯｓから選ばれた金属原子を表す。〕
により表されるフタロシアニン化合物である。 The dissolved chlorine scavenger of the present invention has the following general formula (1):

[In the above formula (1), R ¹ —CO represents a fatty acid residue containing 10 to 22 carbon atoms, and —NH—CH (R ² ) —CO— represents a peptide residue of a silk protein. R ² represents a side chain of the silk protein, m represents a positive number of 2.1 or more, and M ¹ represents a sodium atom, a potassium atom, an alkanolamine residue, or a basic amino acid residue.
The N-acyl peptide compound represented by these is included, It is characterized by the above-mentioned.
The dissolved chlorine scavenger cleaning composition of the present invention comprises a chlorine scavenging component containing the dissolved chlorine scavenger of the present invention and a cleaning component containing at least one cleaning agent.
In the method for cleaning a modified fiber material of the present invention, a modified fiber material produced by treating a fiber material with a cationizing agent in water and adsorbing the modified material for the fiber material to the cationized fiber material is dissolved. When cleaning in water containing chlorine, the dissolved chlorine scavenging detergent composition of the present invention is used as a cleaning agent, whereby the dissolved chlorine in the cleaning water is captured and removed, and the adsorbed substance in the modified fiber material is removed. It includes preventing alteration and dropout.
In one embodiment of the cleaning method of the present invention, the modifying substance for modifying the fiber material is represented by the following general formula (2):

[However, in the above formula (2), R ³ ~R ⁶ are each, independently of one another, a carboxyl group, a sulfonic acid group and substituted groups selected from hydrocarbon groups having these acid groups, n ¹ ˜n ⁴ each independently represents an integer of 0 to 4, and M represents a metal atom selected from Fe, Co, Mn, Ti, V, Ni, Cu, Zn, W and Os. ]
It is a phthalocyanine compound represented by.

The dissolved chlorine scavenger of the present invention has a cleaning effect and a flexibility imparting effect on various materials, for example, fiber materials, and the chlorine-containing water cleaning composition containing the present chlorine scavenger is: After the fiber is cationized, the modified substance obtained by bringing the modified fiber into contact with the modified substance is protected from oxidation reaction by dissolved chlorine to prevent or reduce the peeling, and excellent cleaning of the modified fiber is performed. Has performance.
Furthermore, the detergent composition for water containing dissolved chlorine of the present invention is excellent in foaming property at the time of rinsing, for example, has an excellent softening effect on the phthalocyanine-supported fiber cloth after washing, and is hypoallergenic, It can prevent rough hand when using hand-washing.

For the dissolved chlorine in water, for example, the amount of free chlorine, the amount of bound chlorine, and the total amount of chlorine represented by the total value thereof can be measured by the DPD method or the like.
Here, the amount of free chlorine is defined as the concentration of residual chlorine dissolved in water as dissolved gas (Cl ₂ ), hypochlorous acid (HOCl), and hypochlorite ion (OCl−). The greater the amount, the stronger the oxidizing power and the greater the effect on hair damage.
The amount of bound chlorine is defined as the amount of chlorine present in water chemically bound to natural water and ammonia or organic amines present in contaminated water. For example, the capture of dissolved chlorine by taurine is considered to be a reaction of free chlorine and taurine to form a chloramine-like substance, in which chlorine is trapped as bound chlorine. That is, it can be considered that the chlorine scavenger contains a compound having a function of converting free chlorine from dissolved chlorine into bound chlorine and detoxifying it.

  The present inventors added various anionic surfactants or amino group-containing substances to water having a certain concentration of dissolved chlorine, and then conducted colorimetric determination of the amount of free chlorine, the amount of bound chlorine, and the total amount of chlorine by the DPD method. It was found that an acyl-hydrolyzed silk peptide having a degree of peptide polymerization of 2.1 or more has a function of trapping dissolved chlorine.

The acyl-hydrolyzed silk peptide having a peptide polymerization degree of 2.1 or more is represented by the general formula (1) and is a main component of the dissolved chlorine scavenger of the present invention.
In the general formula (1), m represents the average degree of polymerization of the hydrolyzed silk peptide residues, and it is important that the value is 2.1 or more, and the preferred value of m is 2.1-5. .0.
If m is larger than 5.0, the hydrolyzed silk peptide may be precipitated as a water-insoluble matter depending on conditions such as temperature and hardness of washing water.
In the general formula (1), R ² represents a side chain of the hydrolyzed silk amino acid, and the configuration of the hydrolyzed silk amino acid is as shown in Table 1, and R ² is specifically a hydrogen atom, a methyl group , A hydroxyalkyl group, a carboxymethyl group, and the like.

  The reason why the acyl-hydrolyzed silk peptide having a degree of peptide polymerization of 2.1 or higher in the present invention has a dissolved chlorine scavenging function is unknown, but dissolved chlorine (in this case mainly free chlorine in this case) with respect to the NH group constituting the peptide bond. ) Is likely to react and bind like chloramine (-NCl-). It is presumed that the effect of the present invention is expressed by capturing free chlorine by this effect and preventing the oxidation reaction of dissolved chlorine with respect to the substance adsorbed on the fiber.

  Further, it has been experimentally confirmed that the cleaning composition containing the compound of formula (1), which is the main component of the dissolved chlorine scavenger of the present invention, as a chlorine scavenging component gives a softening effect to the fibers when the fibers are washed. It was.

In the cleaning composition of the present invention, the compound of formula (1) is preferably contained in a content of 5.0 to 30% by weight.
Preferred examples of the compound of formula (1) include acyl laurate hydrolyzed silk peptide sodium salt (average polymerization degree m = 2.5), acyl laurate hydrolyzed silk peptide potassium salt (average polymerization degree m = 2.5). ), Acyl laurate hydrolyzed silk peptide triethanolamine salt (average polymerization degree m = 2.5), sodium laurate hydrolyzed silk peptide salt (average polymerization degree m = 5.0), acyl myristate hydrolyzed silk Peptide potassium salt (average polymerization degree m = 2.1), palm fatty acid acyl-hydrolyzed silk peptide (average polymerization degree m = 2.5) sodium salt and the like.

The cleaning component contained in the chlorine scavenging cleaning composition of the present invention contains at least one cleaning agent.
(1) Anions such as fatty acid soap, higher alkyl sulfate ester salt, POE alkyl ether sulfate ester salt, N-acyl amino acid salt, higher fatty acid amide sulfonate salt, phosphate ester salt, sulfosuccinate salt, higher fatty acid ester sulfate ester salt Surfactant,
(2) Amphoteric surfactants such as amidoamine-based amphoteric surfactants, amidoacetic acid betaine-type amphoteric surfactants, alkylacetic acid betaine-type surfactants,
(3) Amphoteric surfactants such as alkyl sulfobetaine type surfactants and amide sulfobetaine type surfactants,
(4) Semipolar surfactants such as alkylamine oxide and amidoamine oxide, and (5) glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid Nonionic surfactants such as esters, polyethylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, fatty acid alkanolamides, polyoxyethylene alkanolamides, acetylene glycols, etc. Preferably used.

Moreover, it is possible to more effectively suppress the influence of the dissolved chlorine and clean it by using a conventionally known dissolved chlorine scavenger in combination with the chlorine scavenger of the present invention.
Preferable examples of conventionally known dissolved chlorine scavengers include taurine, glycine, alanine, glutamic acid, aspartic acid and the like.
In the present invention, the dissolved chlorine-containing water cleaning composition can contain components that are usually used in cosmetics, as long as the effects of the invention are not hindered.

  The dissolved chlorine scavenging detergent composition of the present invention can be used in a method for cleaning a modified fiber material. That is, when the fiber material is treated with a cationizing agent in water, and the modified fiber material produced by modifying the cationized fiber material with a modifier for fiber material is washed in water containing dissolved chlorine, As the cleaning agent, the dissolved chlorine scavenging cleaning composition of the present invention is used, whereby the dissolved chlorine in the cleaning water can be captured and removed, and the modification and dropping of the modifying substance in the modified fiber material can be prevented.

  Examples of the modifier include pigment materials for coloring fiber materials, adsorbent materials for adsorbing allergens and the like, and antipruritics, antipruritic agents, anti-inflammatory agents, etc. for calming itchiness. The fiber material is adsorbed or sorbed at a modification concentration of 0.0000001 to 10% by weight with respect to its mass and fixed. For example, when the modifying substance contains the phthalocyanine compound represented by the general formula (2), the chlorine scavenging detergent composition of the present invention removes the phthalocyanine compound from the fiber material modified with the phthalocyanine compound. It is possible to clean the fiber material without giving it and to impart a softening effect to the fiber material. At this time, it is preferable that the fiber material generally contains fibers such as cotton, wool, feathers, and nylon.

The dissolved chlorine scavenger of the present invention, the cleaning composition containing the same and the cleaning method will be further described in the following examples.
In the following examples and comparative examples, the free chlorine-containing concentration and the total chlorine-containing concentration in the chlorine-containing aqueous solution were measured by the following methods.

Example 1 and Comparative Examples 1 to 4
In each of Example 1 and Comparative Examples 1 to 4, the compounds listed in Table 1 were added to the sodium hypochlorite aqueous solution as a chlorine scavenger at a solid pure content addition amount of 1.00 g, and Was measured. The measurement results are shown in Table 2.

  From Table 2, it can be seen that the lauroyl hydrolyzed silk type surfactant (Example 1) represented by the general formula (1), m = 2.5 has an extremely high ability to capture free chlorine. Moreover, it turns out that the lauroyl silk amino acid (Comparative Example 2) which hydrolyzed the silk peptide completely does not have the ability to capture free chlorine. The other anionic compounds were also tested in the same manner, but the anionic surfactant having the ability to trap free chlorine with a surfactant whose counter ion is an alkali metal is lauroyl represented by the general formula (1). Only hydrolyzed silk type surfactant.

Example 2 and Comparative Examples 5-11
In each of Example 2 and Comparative Examples 5 to 11, cotton fiber fabrics colored by the phthalocyanine dye produced by the method described in Japanese Patent Publication No. 07-68128, [0029] Immerse it in a test solution of pure 1.0% by weight distilled aqueous solution (however, Comparative Examples 5 and 6 are test solutions containing distilled water and tap water only) at 25 ° C. for 24 hours, take out and dry in a 60 ° incubator for 3 hours. did. The color difference (ΔE) of the colored fabric before and after the treatment was measured.
In Example 2, the same lauroyl hydrolyzed silk sodium 1% (mass) tap water solution as described in Example 1 was used, in Comparative Example 5, only distilled water was used, and in Comparative Example 6, Only tap water was used. In each of Comparative Examples 7 to 11, a 1% by mass tap water solution of the compounds described in Table 3 was used. Table 3 shows the ΔE measurement results.

Separately, in each of Example 2 and Comparative Examples 5 to 9, a detergency test using a wet artificially contaminated cloth by Terg-O-Tometer was performed. The measurement conditions were 0.5% distilled aqueous solution of the substances listed in Table 3 (however, in Comparative Examples 5 and 6, test solutions consisting only of distilled water and tap water were used, respectively), and a bath ratio of 40. , 40 degrees, 100 rpm, washed for 10 minutes, rinsed at 100 rpm for 2 minutes × 2, measured reflectance before washing (RS) and after washing (RW), reflectance of white cloth before contamination ( The cleaning rate was calculated according to the following calculation formula.
Cleaning rate (%) = [(RW-RS) / (RO-RS)] × 100
In the formula, RO represents the reflectance of the white cloth before contamination, RS represents the reflectance of the contaminated cloth before cleaning, and RW represents the reflectance of the contaminated cloth after cleaning. Table 3 shows the measurement results.

As is clear from Table 3, the colored cloth with the phthalocyanine dye was confirmed to be discolored by dissolved chlorine even when immersed in tap water for a long period of time, but lauroyl hydrolysis represented by the general formula (1) m = 2.3 No discoloration was observed in the treatment liquid containing silk sodium (Example 2). This is presumably because the dissolved chlorine capture function worked effectively.
In the surfactant-containing treatment liquids of Comparative Examples 7 to 11, it was confirmed that the color of the fabric colored with the phthalocyanine dye was faded more than tap water (Comparative Example 6). Moreover, the result of the detergency test using the wet artificially contaminated cloth of Example 2 was almost the same as the surfactants of Comparative Examples 7 to 11, and it was confirmed that the detergency against artificial dirt was sufficiently high.

Example 3 and Comparative Example 12
In each of Example 3 and Comparative Example 12, a cleaning composition having the composition shown in Table 4 was prepared and colored with a phthalocyanine dye in the same manner as in Example 2. ΔE, detergency and flexibility were measured using a cotton fiber fabric and an artificial wet-contaminated fabric. However, for the evaluation of flexibility, sensory evaluation of the flexibility of the test fabric before and after the treatment was performed with five monitors, and the number of persons judged to have a flexibility improvement effect out of the five was counted. It was. The results are shown in Table 4.

As is clear from Table 4, the cleaning liquid of Example 3 had a cleaning power comparable to that of Comparative Example 12, and the phthalocyanine dye was stably held on the fiber fabric, and decolorization was slight.
Moreover, the number of persons who determined that the flexibility of the fabric washed with the washing liquid of Example 3 was higher than that before washing was 3 out of 5 persons. However, in Comparative Example 12, no improvement in flexibility due to washing was observed.

Example 3
A powder detergent composition having the following composition was prepared.
Powder detergent composition by mass%
Lauroyl sarcosine sodium (100%) 10.0
Lauroyl hydrolyzed silk sodium (20% solution)
(General formula (1), m = 2.3) 10.0
Powdered soap 10.0
Sodium carbonate 25.0
(Lauryl / myristyl) glycol hydroxypropyl ether 1.5
Sodium sulfate to 100
Using the above powder detergent composition, the washing of the colored fabric with the same phthalocyanine dye as in Example 3, the detergency test on the wet artificially contaminated cloth, and the flexibility improvement effect by washing were measured. As a result, almost the same as in Example 3, the pigmented fabric with the phthalocyanine pigment did not fall off, the cleaning power for the wet artificial soiled fabric was practically sufficient, and the improvement in flexibility due to the cleaning was recognized.

Claims (4)

The following general formula (1):

[In the above formula (1), R ¹ —CO represents a fatty acid residue containing 10 to 22 carbon atoms, and —NH—CH (R ² ) —CO— represents a peptide residue of a silk protein. R ² represents a side chain of the silk protein, m represents a positive number of 2.1 or more, and M ¹ represents a sodium atom, a potassium atom, an alkanolamine residue, or a basic amino acid residue.
A dissolved chlorine scavenger comprising an N-acyl peptide compound represented by:   A dissolved chlorine scavenging cleaning composition comprising a chlorine scavenging component comprising the dissolved chlorine scavenger according to claim 1 and a cleaning component comprising at least one cleaning agent.   When a fiber material is treated with a cationizing agent in water and the cationized fiber material is modified with a fiber material modifier, the modified fiber material is washed in water containing dissolved chlorine. As a modified fiber material, the dissolved chlorine scavenging detergent composition according to claim 2 is used, whereby dissolved chlorine in the wash water is captured and removed, and modification of the modified substance in the modified fiber material and prevention of dropping are prevented. Cleaning method. The modifying substance that modifies the fiber material is represented by the following general formula (2):

[However, in the above formula (2), R ³ ~R ⁶ are each, independently of one another, a carboxyl group, a sulfonic acid group and substituted groups selected from hydrocarbon groups having these acid groups, n ¹ ˜n ⁴ each independently represents an integer of 0 to 4, and M represents a metal atom selected from Fe, Co, Mn, Ti, V, Ni, Cu, Zn, W and Os. ]
The washing | cleaning method of Claim 3 which is a phthalocyanine compound represented by these.