TWI862679B - Detergent composition for fiber products - Google Patents

Abstract

The subject of this invention is to inhibit damage to fiber products such as clothing, while improving the cleaning performance of blood stains.

The cleaning agent composition for fiber products in the implementation form of the solution contains a phosphate (A) represented by the following general formula (1) and an alkali metal carbonate (B), and the pH of the aqueous solution at a concentration of 1 mass % is 9.5-11.5. In formula (1), R represents an aliphatic alkyl group with 8-18 carbon atoms or a styrenated phenyl group, AO represents an oxyalkylene group with 2-4 carbon atoms, n represents 0-10, M represents a hydrogen atom, an alkali metal, ammonium or an organic ammonium, and m represents 1 or 2.

Description

Detergent composition for fiber products

The present invention relates to a detergent composition for fiber products.

For detergent compositions used to clean fiber products such as clothing, for example, Patent Document 1 discloses that the cleaning performance of mud stains can be improved by mixing anions of organic phosphates with cations of organic amine derivatives and non-ionic surfactants. However, the detergent described in Patent Document 1 is difficult to remove blood stains attached to fiber products.

In general, if a detergent with a high pH is used, blood stains can be removed, but detergents with a high pH will cause damage to fiber products.

[Prior technical literature]

[Patent Literature]

Patent document 1: Japanese Patent Publication No. 2000-008078

The purpose of the embodiment of the present invention is to provide a detergent composition for fiber products, which can inhibit damage to fiber products and improve the cleaning performance of blood stains.

The detergent composition for fiber products according to the embodiment of the present invention contains a phosphate (A) represented by the following general formula (1) and an alkali metal carbonate (B), and the pH value measured when the solution is prepared into a 1% by mass aqueous solution is 9.5 to 11.5.

In formula (1), R represents an aliphatic alkyl group with 8 to 18 carbon atoms or a styrenated phenyl group, AO represents an oxyalkylene group with 2 to 4 carbon atoms, n represents the average addition molar number and is a number from 0 to 10, and M represents a hydrogen atom, an alkali metal, ammonium or an organic ammonium. m represents 1 or 2, and the aforementioned phosphate ester (A) is a monoester with m=1, a diester with m=2, or a mixture of a monoester and a diester.

If the present invention is implemented, it can suppress damage to fiber products such as clothing, and at the same time improve the cleaning performance of blood stains.

The following will describe the implementation of the present invention in detail.

[Phosphate (A)]

The phosphate ester (A) (hereinafter also referred to as "component (A)") used in this embodiment is a cationic surfactant and is represented by the following general formula (1).

In formula (1), R represents an aliphatic alkyl group having 8 to 18 carbon atoms or a styrenated phenyl group. When a plurality of R are contained in one molecule, they may be the same or different from each other. In addition, in terms of the component (A) as a whole, R may be all the same or may be a mixture of compounds in which R is different.

The aforementioned aliphatic alkyl group of R may be straight chain or branched. The carbon number of the aliphatic alkyl group is preferably 8 to 15. The aliphatic alkyl group may be saturated or unsaturated, and is preferably an alkyl or alkenyl group, and an alkyl group is preferred. Specific examples of the aliphatic alkyl group include straight chain alkyl groups such as n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, etc., branched chain alkyl groups such as 2-ethylhexyl, isodecyl, 2-hexyldecyl, isostearyl, etc., and alkenyl groups such as oleyl, etc.

The aforementioned styrenated phenyl group of R is represented by the following general formula (2). In the formula, k is the number of substituents (i.e., the number of styrene residues), which is 1 to 3 as an average value (rounded to the first decimal place), and component (A) may also be a mixture of compounds with different k values. The position of the substituent is preferably ortho and/or para.

The aforementioned R is preferably a linear or branched alkyl group with 8 to 18 carbon atoms, or a styrenated phenyl group, and preferably a linear or branched alkyl group with 8 to 15 carbon atoms, or a styrenated phenyl group.

AO in formula (1) represents an oxyalkylene group having 2 to 4 carbon atoms. That is, A represents an oxyalkylene group having 2 to 4 carbon atoms (i.e., an alkanediyl group), which may be a linear or branched group. The oxyalkylene group represented by AO may be an oxyethylene group, an oxypropylene group, an oxybutylene group, or the like. The (AO) _n part in formula (1) is an addition polymer formed by using one or more of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran (1,4-butylene oxide), or the like as the oxyalkylene group having 2 to 4 carbon atoms. The addition form of the oxyalkylene group is not particularly limited, and may be a single addition product using one oxyalkylene group, or may be a random addition product, a block addition product, or a combination of such random additions and block additions using two or more oxyalkylene groups.

The above-mentioned oxyalkylene group is particularly preferably an oxyethylene group. When two or more oxyalkylene groups are selected, preferably one of them is an oxyethylene group. The (AO) _n chain portion is preferably an oxyalkylene chain containing 50-100 mol% of oxyethylene groups, and preferably a (poly)oxyalkylene chain containing 70-100 mol% of oxyethylene groups. It is more preferably composed of _{oxyethylene groups only, that is, (CH2CH2O ) n} .

n represents the average added molar number of alkylene oxide (rounded to the first decimal place), and is a number between 0 and 10, preferably between 1 and 9, and more preferably between 2 and 8.

M in formula (1) represents a hydrogen atom, an alkali metal, ammonium or an organic ammonium. When a plurality of M are contained in a molecule, they may be the same or different from each other. In addition, as for the component (A) as a whole, all M may be the same, or a mixture of different compounds. Alkali metals include sodium and potassium. Organic ammonium includes alkyl ammoniums such as monomethyl ammonium and dipropyl ammonium, and alkoxide ammoniums such as monoethoxide ammonium, diethoxide ammonium, and triethoxide ammonium. M is preferably a hydrogen atom or an alkali metal, and preferably a hydrogen atom, sodium or potassium.

In formula (1), m represents 1 or 2. When m=1, it is a monoester, and when m=2, it is a diester. Component (A) may be a monoester: RO(AO) _nP (=O)(OM) ₂ , a diester: [RO(AO) _n ] _2P (=O)(OM), or a mixture of a monoester and a diester. It can usually be obtained in the form of a mixture of a monoester and a diester, and the molar ratio of the two is not particularly limited. For example, the molar ratio of the monoester/diester may be 20/80 to 90/10, or 50/50 to 80/20.

In one embodiment, R in formula (1) represents _a linear or branched alkyl group having 8 to 18 carbon atoms, or a styrenated phenyl group, (AO) _n represents ( _CH2CH2O ) _n , and the average addition molar number n is 0 to 10, M represents a hydrogen atom, sodium or potassium, m represents 1 or 2, and component (A) is a monoester, a diester or a mixture of the monoester and the diester.

[Alkali metal carbonates (B)]

The alkali metal carbonate (B) (hereinafter also referred to as "(B) component") used in this embodiment may be, for example, sodium carbonate or potassium carbonate, and may be used alone or in combination.

[Polyoxyalkyl alkyl ether sulfate and its salt (C)]

At least one of the polyoxyalkylene alkyl ether sulfate and its salt (C) (hereinafter also referred to as "component (C)") used in this embodiment is a sulfate-type cationic surfactant.

Regarding component (C), the carbon number of the alkyl group as the hydrophobic group is not particularly limited, and is preferably 8 to 18, more preferably 8 to 15, and may also be 10 to 14. It may also be a mixture of two or more alkyl groups having different carbon numbers.

Regarding the polyoxyalkylene chain of component (C), the oxyalkylene group may be a group with 2 to 4 carbon atoms, i.e., oxyethylene, oxypropylene, oxybutylene, etc., and is preferably oxyethylene. The addition form of the oxyalkylene group is not particularly limited, and may be a single addition product, or may be a random addition product of two or more types, or a block addition product. The average addition molar number of the oxyalkylene group (rounded to the first decimal place) may be 1 to 30, 1 to 20, or 2 to 10. In addition, the polyoxyalkylene chain preferably contains 50 to 100 mol% of oxyethylene groups, preferably 70 to 100 mol% of oxyethylene groups, and more preferably is composed only of oxyethylene groups.

The salt of the anionic hydrophilic group in the component (C) may be an alkali metal salt, ammonium salt, alkanolamine salt (e.g., ethanolamine salt), etc., and preferably an alkali metal salt such as sodium salt, potassium salt, or ammonium salt.

[Detergent composition for fiber products]

The detergent composition for fiber products of this embodiment contains the above-mentioned phosphate ester (A) and alkaline metal carbonate (B), and the pH of the aqueous solution at a concentration of 1 mass% is in the range of 9.5 to 11.5. This can suppress damage to fiber products such as clothing, and at the same time improve the cleaning performance of blood stains. Specifically, for those containing components (A) and (B), the pH is further above 9.5, thereby improving the cleaning performance of blood stains; and the pH is below 11.5, thereby suppressing damage to fiber products.

The so-called pH in a 1% by mass aqueous solution is the pH of the aqueous solution measured at 25°C (measured according to the glass electrode method of JIS Z8802) when the fiber product detergent composition is dissolved in water or diluted with water to prepare an aqueous solution with a solid content concentration (non-volatile component concentration) of 1% by mass. The pH in a 1% by mass aqueous solution should be 9.8~11.2, and 10.0~11.0 is preferred.

The detergent composition for fiber products of this embodiment is preferably a liquid detergent composition containing component (A) and component (B), and also containing water. In the liquid detergent composition, at least a portion of component (A) is neutralized by component (B). Therefore, even if component (A) is an acid type, that is, even if all M in formula (1) is a hydrogen atom, at least a portion of it will be neutralized to become an alkali metal. The solid concentration of the liquid detergent composition is not particularly limited, and can be, for example, 10 to 50% by mass, or 20 to 40% by mass.

The blending ratio (A)/(B) of the ratio of component (A) to component (B) is preferably 0.3~2.0. That is, the fiber product detergent composition is preferably blended with phosphate (A) and carbonate of alkaline metal (B) at a mass ratio (A)/(B) of 0.3~2.0, that is, mixed. By blending such a large amount of component (B), the cleaning performance against blood stains can be improved. The blending ratio (A)/(B) is preferably 0.5~1.5, and preferably 0.6~1.2.

There is no particular limitation on the amount of component (A) blended in the detergent composition for fiber products. For example, if the solid portion (non-volatile component) is 100% by mass, it can be 5-65% by mass, 10-50% by mass, or 15-40% by mass.

The fiber product detergent composition of this embodiment preferably contains component (A) and component (B), and at least one of polyoxyethylene alkyl ether sulfate and its salt (C). By blending component (A) and component (B) together with component (C), the cleaning performance against sebum stains can be enhanced.

The blending amount of component (C) is not particularly limited. When component (C) is blended with component (A) and component (B) at the same time, the blending ratio (C)/(B) of component (C) to component (B) is preferably 0.5-4.0. In other words, component (C) and component (B) are preferably blended at a mass ratio (C)/(B) of 0.5-4.0. The blending ratio (C)/(B) is more preferably 1.5-3.5.

In addition to component (A), component (B), component (C) and water, the detergent composition for fiber products of this embodiment may be mixed with other components within the range that does not hinder the effect. Other components include, for example, anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, chelating agents, pH adjusters (sodium hydroxide, potassium hydroxide, sulfuric acid, hydrochloric acid, etc.), bleaching agents, softeners, fluorescent agents, enzymes, preservatives, fragrances, colorants, defoaming agents, and hydrophilic solvents (monohydric alcohols, dihydric alcohols, etc.) other than the above-mentioned components (A) and (C).

Specific examples of non-ionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenyl ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, sucrose fatty acid esters, fatty acid alkanolamides, etc. Here, the polyoxyalkylene group is preferably a polyoxyethylene group.

The fiber product detergent composition of this embodiment can be used as a detergent for washing fiber products such as clothes. The washing method is not particularly limited. For example, a washing machine such as a drum washing machine or a pulsator washing machine can be used to put the fiber product detergent composition into water such as tap water and stir it with the fiber products to wash them. In addition, the fiber products can also be washed by immersing or rubbing in a washing liquid prepared by dissolving or diluting the fiber product detergent composition in water. Alternatively, the fiber product detergent composition may be directly applied to the stained area of the fiber product and then washed in water.

There is no particular limitation on the amount of the detergent composition for fiber products. The solid concentration in the detergent solution prepared by mixing the detergent composition for fiber products with water can be 0.01-2 mass %, or 0.1-1 mass %. The bath ratio (volume (L) of the detergent solution used to wash 1 kg of the object to be washed) is also not particularly limited, for example, it can be 1:3-1:40, or 1:5-1:30.

Fiber products include, for example, fabrics such as woven fabrics, knitted fabrics, and non-woven fabrics made from synthetic fibers such as polyester fibers, polyamide fibers, and acrylic fibers, natural fibers such as cotton, linen, and silk, and organic fibers such as cellulose-based fibers such as rayon and acetate, as well as clothing and other fabric products (e.g., towels and bed sheets) obtained using such fibers.

[Implementation example]

The following is a more detailed description using an example, but the present invention is not limited thereto.

The following components (A), (B), (B'), (C), nonionic surfactant, chelating agent and water are used, and the components are mixed according to the blending formula (parts by mass) listed in Table 1 to prepare a detergent composition.

(A) Ingredients:

‧A-1: Polyoxyethyl octyl ether phosphate

0.17 mol of tetraphosphorus decaoxide was added to polyoxyethyl octyl ether and reacted to obtain a 55:45 (molar ratio) mixture of a monoester with R=2-ethylhexyl, AO=oxyethyl, n=3, M=hydrogen atom, m=1 and a diester with m=2 in formula (1); the polyoxyethyl octyl ether was obtained by adding 3 mol of ethylene oxide to 1 mol of C8 alcohol (trade name: OCTANOL, manufactured by KH Neochem Co., Ltd.).

‧A-2: Polyoxyethyl lauryl ether phosphate

Except for adding 4 mol of ethylene oxide to 1 mol of C12 alcohol (trade name: KALCOL 2098, manufactured by Kao Corporation), the same operation as A-1 was performed to obtain a mixture of 58:42 (molar ratio) of a monoester with m=1 and a diester with m=2 in formula (1), R=n-dodecyl, AO=oxyethyl, n=4, M=hydrogen atom.

‧A-3: Polyoxyethylene tridecyl ether phosphate

Except for adding 6 mol of ethylene oxide to 1 mol of C13 alcohol (trade name: TRIDECANOL, manufactured by KH Neochem Co., Ltd.), the same operation as A-1 was performed to obtain a 60:40 (molar ratio) mixture of a monoester with m=1 and a diester with m=2 in formula (1), where R=tridecyl, AO=oxyethyl, n=6, M=hydrogen atom.

‧A-4: Polyoxyethyl styrene phenyl ether phosphate

Except for adding 8 mol of ethylene oxide to 1 mol of styrenated phenol (trade name: distyrenated phenol, manufactured by Yokkaichi Synthetic Co., Ltd.), the same operation as A-1 was performed to obtain a mixture of 75:25 (molar ratio) of monoester with m=1 and diester with m=2 in formula (1), R=styrenated phenyl (k=2) represented by formula (2), AO=ethylene oxide, n=8, M=hydrogen atom, and diester with m=1.

(B) Ingredients:

‧B-1: Sodium carbonate

‧B-2: Potassium carbonate

(B’) Ingredients:

‧B’-1: Sodium hydroxide

‧B’-2: Sodium silicate

(C) Ingredients:

‧C-1: Sodium polyoxyethyl lauryl ether sulfate

It is obtained by reacting 1 mol of chlorosulfonic acid with polyoxyethylene lauryl ether and neutralizing it with an aqueous sodium hydroxide solution; the aforementioned polyoxyethylene lauryl ether is obtained by adding 2 mols of ethylene oxide to 1 mol of C12 alcohol (trade name: KALCOL 2098, manufactured by Kao Corporation). The average number of moles of ethylene oxide added = 2.

‧C-2: Polyoxyethyl lauryl ether ammonium sulfate

It is obtained by reacting 1 mol of aminosulfonic acid with polyoxyethylene lauryl ether; the aforementioned polyoxyethylene lauryl ether is obtained by reacting 1 mol of C12 alcohol (trade name: KALCOL 2098, manufactured by Kao Corporation) with 6 mols of ethylene oxide. The average number of moles of ethylene oxide added = 6.

‧C-3: Sodium polyoxyethylene tridecyl ether sulfate

It is obtained by reacting 1 mol of chlorosulfonic acid with polyoxyethylene tridecyl ether and neutralizing it with an aqueous sodium hydroxide solution; the aforementioned polyoxyethylene tridecyl ether is obtained by adding 3 mols of ethylene oxide to 1 mol of C13 alcohol (trade name: TRIDECANOL, manufactured by KH Neochem Co., Ltd.). The average number of moles of ethylene oxide added = 3.

‧Non-ionic surfactant: polyoxyalkylene decyl ether, "NOIGEN XL-80" manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.

‧Chelating agent: Tetrasodium ethylenediaminetetraacetate

Each detergent composition was diluted with water to prepare an aqueous solution with a solid content concentration of 1 mass %, and the pH of the aqueous solution was measured at 25°C using a pH meter ("pH METER F-71" manufactured by Horiba, Ltd.). In addition, the following evaluation method was used to evaluate the cleaning properties of each detergent composition for blood stains, cloth damage after cleaning, sebum stains, and red wine stains.

‧Blood stain washability: Cut standard artificially stained cloth (EMPA111, Swissatest) into 6cm×6cm pieces as the object to be washed and conduct the wash test. Immerse the stained cloth in 1L of detergent solution diluted with water to 2% by mass (50 times dilution) of each detergent composition and stir for 10 minutes. After that, take out the stained cloth, rinse it with 1L of tap water for 10 seconds, and then rinse it again with 1L of tap water for 10 seconds, and dry it at room temperature. After drying, measure the Y value of reflection with a colorimeter and evaluate it according to the following standards.

Evaluation criteria○: Y value is above 70

△: Y value is above 65 and less than 70

×: Y value is less than 65

‧Damage to cloth after washing: When evaluating the cleansing performance of blood stains, visually check the surface of the cloth after washing to check for any roughness and evaluate based on the following criteria.

Evaluation criteria ○: No noticeable roughness

×: Roughness can be confirmed on the surface of the cloth

‧Sebum stain washability: The standard artificially stained cloth was changed to WFK10D (made by WFK), and the Y value was measured in the same way as the blood stain washability, and the evaluation was based on the following criteria.

Evaluation criteria○: Y value is above 55

△: Y value is above 50 and less than 55

×: Y value is less than 50

‧Red wine stain cleanability: The standard artificially stained cloth was replaced with WFK10LI (made by WFK), and the Y value was measured in the same way as the blood stain cleanability, and the evaluation was based on the following criteria.

Evaluation criteria○: Y value is above 65

△: Y value is above 60 and less than 65

×: Y value is less than 60

[Table 1]

The results are shown in Table 1. Comparative Examples 1, 2, and 6 use phosphate (A), but do not mix with carbonate of alkaline metal (B), but mix with sodium hydroxide and sodium silicate (B') as alkali. The pH of Comparative Examples 1, 2, and 6 is high, so the cleaning performance of blood stains is excellent, but cloth damage can be observed after cleaning. Compared with Comparative Examples 1, 2, and 6, the amount of alkali in Comparative Examples 3 and 4 is reduced, and the pH is lowered, so the cloth damage after cleaning is improved, but the cleaning performance of blood stains is not good. Furthermore, the cleaning performance of Comparative Examples 1 to 4 and 6 on red wine stains is not good. Moreover, Comparative Examples 2 and 4, which use sodium silicate as an alkali, also have poor cleaning performance on sebum stains.

Although Comparative Example 5 uses phosphate ester (A) and alkali metal carbonate (B) together, the amount of alkali metal carbonate (B) mixed is small and the pH is low, so the cleaning performance of blood stains and sebum stains is poor. Although Comparative Example 7 uses phosphate ester (A) and alkali metal carbonate (B) together, sodium hydroxide (B') is mixed and the pH is high, so the cloth damage can be seen after cleaning.

In contrast, if phosphate (A) and alkali metal carbonate (B) are used together and the pH is set in the range of 9.5 to 11.5 in Examples 1 to 15, the damage to the cloth after washing can be suppressed and blood stains can be removed at the same time, and the blood stain cleaning performance is excellent. In addition, if Examples 1 to 15 are used, the cleaning performance of red wine stains is also excellent. Furthermore, if Examples 1 to 14 are used in addition to phosphate (A) and alkali metal carbonate (B), polyoxyalkylene alkyl ether sulfate (C) is also mixed, the cleaning performance of sebum stains is also excellent.

The above describes several embodiments of the present invention, but these embodiments are only provided as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and can be omitted, replaced, and changed in various ways without departing from the scope of the gist of the invention. These embodiments, their omissions, replacements, and changes are also included in the scope and gist of the invention, and are also included in the invention described in the scope of the patent application and its equivalent scope.

Claims (2)

A detergent composition for fiber products, comprising a phosphate (A) represented by the following general formula (1) and an alkali metal carbonate (B), and having a pH of 9.5 to 11.5 when prepared as a 1% by mass aqueous solution; the detergent composition for fiber products is prepared by blending the phosphate (A) and the alkali metal carbonate (B) at a mass ratio (A)/(B) of 0.3 to 2.0, and further comprising at least one of a polyoxyalkylene alkyl ether sulfate and a salt thereof (C);

In formula (1), R represents an aliphatic alkyl group having 8 to 15 carbon atoms or a styrenated phenyl group, AO represents an oxyalkylene group having 2 to 4 carbon atoms, n represents the average addition molar number and is a number from 0 to 10, M represents a hydrogen atom, an alkali metal, ammonium or an organic ammonium; m represents 1 or 2, and the aforementioned phosphate ester (A) is a monoester with m=1, a diester with m=2, or a mixture of a monoester and a diester. For example, the detergent composition for fiber products in claim 1 is a liquid detergent composition containing water.