JP2001107083A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent composition excellent in the effect of preventing color-patterned clothing from being discolored or faded by repeated washing and highly effective to soften closing or the like. SOLUTION: This composition contains (a) a compound represented by the general formula (I) and (b) a surfactant in a specified ratio. In the formula, R1 is hydrogen or a 4-20C hydrocarbon group; R2 is hydrogen, a 1-5C alkyl or hydroxyalkyl, or -(CH2CH2NH)mH, wherein m=1-10; and n is a number of 1-5. Desirably, the composition comprises 0.1-10 wt.% compound (a) and 5-60 wt.% surfactant (b).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a cleaning composition.

[0002]

2. Description of the Related Art Discoloration and discoloration of textiles during washing have become a problem. It is considered that the discoloration of the textile products is affected by residual chlorine used for sterilization in tap water, and studies have been made to mix ammonium sulfate and the like in detergents in order to eliminate these effects (JP-A-Hei. 8-53698, JP-T 5-507745, JP-A-62-2632
No. 96, JP-A-60-44599). However, while the effect of residual chlorine in tap water on textiles also acts during rinsing, in the rinsing step, these anti-fading agents flow out and cannot exert a sufficient effect, In particular, the cumulative washing in which washing is repeated many times was insufficient. An object of the present invention is to provide a cleaning composition having a high discoloration prevention effect, particularly when cumulative cleaning is performed.

[0003]

According to the present invention, there is provided (a) a compound represented by the following general formula (I): 0.1 to 10% by weight;
(B) a detergent composition containing 5 to 60% by weight of a surfactant.

[0004]

Embedded image

[Wherein R¹Is a hydrogen atom or a carbon number of 4 to 2
A hydrocarbon group of 0, R^TwoIs a hydrogen atom, an alkyl having 1 to 5 carbon atoms
A kill group or a hydroxyalkyl group, or-(CH_TwoC
H_TwoNH) _mH (m = 1 to 10), n indicates the number of 1 to 5
You. ]

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the component (a) of the present invention, R ¹ in the general formula (I) preferably has 12 to 20 carbon atoms, more preferably an alkyl group having 14 to 18 carbon atoms, and R ² is hydroxy. preferably an ethyl group or -CH ₂ CH ₂ NH _2,
n is preferably 1 or 2, and particularly preferably 1. Further, from the viewpoint of flexibility, R ¹ preferably has 14 to 20 carbon atoms, and particularly preferably an alkyl group having 16 to 18 carbon atoms. From the viewpoint of stability, R ¹ in the formula preferably has 4 to 10 carbon atoms, particularly preferably an alkyl group having 5 to 8 carbon atoms, and the balance of R ¹ , R ² and n is X / (Y × n) = 0.1-20 is preferable,
Further, 1 to 10, particularly preferably 1 to 5, is preferable. Where X is R
¹ represents the number of carbon atoms and Y represents the number of nitrogen atoms and the number of carbon atoms in NHR ² .

[0007] The component (a) of the present invention is contained in a detergent composition.
0.1 to 10% by weight, preferably 1 to 10% by weight is blended. By blending the component (a), the fiber product is excellent in the effect of preventing discoloration and discoloration during cumulative washing, and the flexibility to clothing and the like is improved.

The compound represented by the general formula (I) can be produced according to the following. That is, the compound represented by the general formula (II) or (III) and the compound represented by the general formula (IV) are mixed at preferably 10 ° C. to 150 ° C., more preferably 50 ° C. to 100 ° C., and preferably 0.1 ° C. It can be produced by reacting for 5 to 5 hours. In that case, the compound represented by the general formula (IV) is preferably used in an amount of 1 to 10 molar equivalents, more preferably 2 to 5 molar equivalents, with respect to the compound represented by the general formula (II) or (III). Further, a method of dropping the compound represented by the general formula (II) or (III) to the compound represented by the general formula (IV) is more preferable.

[0009]

Embedded image

Wherein R ¹ , R ² and n have the same meaning as described above. X represents a halogen atom. The reaction-terminated product obtained by the above method can be used as it is, or if necessary, an excess of the compound represented by the general formula (IV) may be distilled off by topping.

The compound represented by formula (II) or (III) can be produced by the following method. For example, when producing a halohydrin compound represented by the formula (II),
The alcohol represented by the formula (V) R ¹ OH (V) (R ¹ is the same as above) and epihalohydrin are converted to a mineral acid such as sulfuric acid or a Lewis acid catalyst such as BF ₃ O (CH ₂ CH ₃ ) _2. You can get it. When the epoxy compound represented by the formula (III) is produced, it can be obtained by cyclizing the halohydrin compound (II) obtained by the above method with an alkali, or the alcohol compound of the formula (V) and epihalohydrin can be reacted with an alkali catalyst. And a reaction in the presence of a phase transfer catalyst.

The surfactant (b) of the present invention includes:
Conventionally known surfactants can be used.
In order to enhance detergency, it is preferable to use an anionic surfactant or a nonionic surfactant as a main surfactant. When used in combination with a cationic surfactant to further enhance flexibility, it is preferable to use a nonionic surfactant as a main surfactant. In the present invention,
The component (b) is 5 to 60% by weight, preferably 10 to 60% by weight of the composition.
５０50% by weight. Here, the component (a) and the component (b)
The ratio of the components is (a) / (b) in terms of molar ratio in terms of economy.
= 1/100 to 1/1, particularly preferably 1/30 to 1/5.

The anionic surfactant is preferably an alkali metal salt such as a linear alkyl benzene sulfonate, an alkyl sulfate, a polyoxyalkylene alkyl or alkenyl ether sulfate, or an alpha sulfo fatty acid alkyl ester. A small amount of a fatty acid salt derived therefrom may be blended. As the counter ion of the anionic surfactant, besides alkali metals such as sodium and potassium,
Alkaline earth metals and / or things such as magnesium,
Although alkanolamines such as diethanolamine and triethanolamine are used, it is particularly preferable to use alkanolamine since the liquid stability is improved. In that case, the blending amount of the anionic surfactant is preferably 1 to 50% by weight, particularly preferably 2 to 50% by weight in the detergent composition.

When the component (a) of the present invention is used in combination with an anionic surfactant, adsorption to clothing is promoted, and the effect of preventing fading is further improved. The molar ratio of the component (a) to the anionic surfactant is preferably (a) / anionic surfactant = 10/1 to 1/10, particularly 3/1 to 1/10.
/ 3 is preferred.

As the nonionic surfactant, the following (1) to (4) can be used. (1) having an alkyl group or alkenyl group having an average carbon number of 8 to 20, such as an alkyl group derived from a linear primary or linear secondary alcohol or an alkyl group or an alkenyl group derived from a branched alcohol, and ethylene oxide ( A polyoxyethylene alkyl or alkenyl ether to which 1 to 20 moles of EO is added on average. (2) Polyoxyalkylene alkyl or alkenyl having an alkyl group or alkenyl group having an average carbon number of 8 to 20, and having EO added on average of 1 to 15 mol and propylene oxide (hereinafter PO) on average of 1 to 5 mol. ether.
In this case, EO and PO may be either random addition or block addition. (3) A sugar or polysaccharide surfactant represented by the following general formula (VI). R ^21- (OR ²² ) _x G _y (VI) wherein R ²¹ is a hydrocarbon group having 8 to 18 carbon atoms, for example, a linear or branched alkyl group or alkenyl group;
Or an alkylphenyl group, R ²² is an alkylene group having 2 to 4 carbon atoms, G is a residue derived from a reducing sugar having 5 or 6 carbon atoms,
x shows the number of average values 0-6, and y shows the number of average values 1-10. (4) Fatty acid alkanolamides and polyhydroxy fatty acid amides.

In particular, (1) or (2) is preferred from the viewpoint of oily soil detergency. The amount of the nonionic surfactant in the detergent composition is preferably 5 to 50% by weight, particularly preferably 10 to 50% by weight.

Further, in order to further improve the flexibility to clothes and the like, a cationic surfactant such as a mono-long-chain alkyl quaternary ammonium salt is added to the detergent composition in an amount of 0.5 to 10% by weight, especially 1 to 10% by weight. It is preferable to mix 〜5% by weight. In terms of the effect of improving flexibility, the long-chain alkyl group has 12 to 22 carbon atoms,
In particular, a mono-long-chain trimethylammonium salt having 14 to 20 alkyl groups is preferable. As the counter ion of the cationic surfactant, a halogen atom, CH ₃ SO ₄ , C ₂ H ₅ SO
₄ , CH ₃ COO or HCOO is preferred. In order to further enhance the flexibility, the cationic surfactant is different from the anionic surfactant in that the cationic surfactant / anionic surfactant =
It is preferable to mix them in a molar ratio of 3/1 to 1/2, particularly 2/1 to 1/2.

Further, in terms of the stability of the liquid and the ability to wash mud and dirt,
An amphoteric surfactant may be blended. Alkyl carbobetaines, alkyl sulfobetaines as amphoteric surfactants,
Alkylamidohydroxysulfobetaine, alkylamidoamine betaine, alkylimidazoline betaine, and the like can be blended.

In order to further improve the feeling, it is preferable to add 0.1 to 2% by weight of a soft base such as silicone described in claim 1 of JP-A-10-60480. Further, the detergent composition of the present invention includes alkali metal hydroxides, silicates, carbonates such as sodium carbonate, and alkali agents such as alkanolamines in an amount of 0.01 to 10% by weight; alcohols such as ethanol; Glycols such as ethylene glycol and propylene glycol, p-toluenesulfonic acid, benzoate (which also has an effect as a preservative), and a thickener and a solubilizer such as urea 0.01 to 30
% By weight; phase adjusters such as polyoxyalkylene benzyl ether and polyoxyalkylene phenyl ether and detergency improvers 0.01 to 10% by weight; nitrilotriacetic acid salt;
Aminopolyacetates such as ethylenediaminetetraacetic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, glycol ether diaminetetraacetic acid, hydroxyethyliminodiacetic acid and triethylenetetramine hexaacetic acid, malonic acid, succinic acid, diglycolic acid 0.1-20% by weight of metal ion scavengers such as salts of malic acid, malic acid, tartaric acid and citric acid; polyacrylates, polymaleates, carboxymethylcellulose, polyethylene glycol having an average molecular weight of 5,000 or more, acrylic acid-maleic acid Copolymer, maleic anhydride-diisobutylene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-
Isobutylene copolymer, maleic anhydride-vinyl acetate copolymer and salts thereof, naphthalene sulfonate formalin condensate, and JP-A-59-62614, claims 1 to 21 (page 1, column 3, line 5 to 5). 0.01 to 10% by weight of a redeposition inhibitor and a dispersant such as a polymer described in page 3, column 4, line 14); a color transfer inhibitor such as polyvinylpyrrolidone 0.01 to 10% by weight.
10% by weight; bleaching agent such as sodium percarbonate or sodium perborate 0.01 to 10% by weight; tetraacetylethylenediamine, a compound represented by the general formula (I-) described in JP-A-6-316700.
2) 0.01 to 10% by weight of a bleaching activator such as a bleaching activator represented by (I-7); 0.001 to 2% by weight of an enzyme such as amylase, protease, pectinase, lipase and cellulase; 0.001-2% by weight of enzyme stabilizer such as calcium, calcium sulfate, formic acid, boric acid (boron compound); fluorescent dyes such as Tinopearl CBS (manufactured by Ciba Specialty Chemicals) and Whitetex SA (manufactured by Sumitomo Chemical) 0.001 to 1% by weight; antifoaming agent such as silica 0.01 to 2% by weight; antioxidant such as butylhydroxytoluene, distyrenated cresol, sodium sulfite and sodium hydrogen sulfite 0.01 to 2% by weight; blue Flavoring agents, flavors, antimicrobial preservatives and the like can be added. The cleaning composition of the present invention comprises the above (a) and (b)
And optional components and the balance of water.

[0020]

The cleaning composition of the present invention is characterized in that it has an excellent effect of preventing discoloration and fading of colored and patterned clothing due to cumulative washing, and also imparts flexibility to clothing and the like.

[0021]

EXAMPLES Synthesis Example 1 (Synthesis of Compound a) First, 231 g of octyl alcohol (1.78 mol)
l), 3.61 g of aluminum triisopropoxide
(17.7 mmol) and 9.40 g (5.4 mol) of p-phenolsulfonic acid in a 1 L flask,
The temperature was raised to 90 ° C. while stirring. Further under reduced pressure (200
(mmHg) After stirring for 1 hour, the temperature was raised to 100 ° C., 170 g of epichlorohydrin was added dropwise over 30 minutes, and the mixture was further stirred to obtain octylglycidyl ether.

Next, 66.0 g (1.08 mol) of ethanolamine was charged into a 300 mL four-necked flask, and the temperature was raised to 70 ° C. Next, 50.0 g (0.27 mol) of octyl glycidyl ether was added dropwise over 2 hours, and the mixture was stirred at 70 ° C. for 2 hours. The conversion of the raw material octyl glycidyl ether was 100%. After completion of the reaction, excess ethanolamine was distilled off under reduced pressure to give 1,5.
65 g of -dihydroxy-3-aza-7-oxapentadecane was obtained (yield; 98%).

Synthesis Example 2 (Synthesis of Compound b) Hexadecyl glycidyl ether was obtained in the same manner as in Synthesis Example 1, except that hexadecyl alcohol was used instead of octyl alcohol.

Next, 230 g (3.83 mol) of ethylenediamine was charged into a 500 mL four-necked flask, and the temperature was raised to 70 ° C. Next, 80.0 g (0.29 mol) of hexadecyl glycidyl ether was added dropwise over 2 hours, followed by stirring at 80 ° C. for 6 hours. The conversion of the raw material hexadecyl glycidyl ether was 100%.
After completion of the reaction, excess ethylenediamine was distilled off under reduced pressure to obtain 90 g of 1-amino-5-hydroxy-3-aza-7-oxatricosan (yield: 93%).

Example 1 A liquid detergent composition shown in Table 1 was prepared, and the obtained composition was evaluated for the following anti-fading property, flexibility and liquid stability. Table 1 shows the results.

[Evaluation of anti-fading property] Test cloth As the test cloth, cotton broad 2023 cloth was used as a dye Cibacron B
lue F-GFN (Ciba Specialty Chemicals) 5%
A cloth dyed with an aqueous solution was used.

Washing conditions A two-tub washing machine (Toshiba Galaxy 3.6 VH-360S1) was prepared, 40 L of 20 ° C. tap water was poured into the washing tub, and 1.4 kg of cotton underwear and 0 Place a 6 kg cotton / polyester blend unworn shirt. 30x3
One piece of a test cloth for evaluation sewn on a cotton cloth of 0 cm is prepared, put into a washing tub, and 26.67 mL of the liquid detergent composition shown in Table 1 is further put therein and washed normally for 10 minutes. Then one
Dehydrate for a minute and rinse twice for 4 minutes. Then 5
Dehydrate for a minute and allow to air dry indoors. This step was defined as one step, and cumulative cleaning was performed five times.

Colorimetry Method Colorimetry is performed using a color difference meter (Nippon Denshoku Industries Co., Ltd .: ND (F) -300A).
Is used to measure the L value, a value, and b value, and ΔE is calculated by the following equation.
The value was determined. The smaller the ΔE value, the less discoloration in the cumulative washing. ΔE = ｛(ΔL) ² + (Δa) ² + (Δb) ² ｝ ^1/2 ΔL; (L value of cloth after cleaning) − (L value of cloth before cleaning) Δa; (of cloth after cleaning) a value)-(a value of cloth before cleaning) Δb; (b value of cloth after cleaning)-(b value of cloth before cleaning).

[Evaluation of flexibility] Preparation of pre-treated cloth A two-tank type washing machine (Toshiba Galaxy 3.6 VH-360S1) was prepared, 40 L of tap water was put into the washing tub, and a total of 2.0 kg was added thereto. Mix cotton towels, cotton melias underwear, and acrylic jersey. Further, a compact type powder detergent is charged according to the standard usage amount, and washed for 10 minutes, dehydrated for 1 minute, rinsed with running water for 8 minutes (water amount of 15 L / min), and dried in a dryer. This washing cycle is repeated five times to obtain a pre-treated cloth.

Evaluation method 30 L of tap water is poured into the washing tub of the washing machine, and two cotton towels, two cotton melias non-wearing undergarments and one acrylic jersey are placed among the pretreatment cloths for evaluating flexibility. Table 1
20 mL of the liquid detergent composition of Example 1 and wash it for 10 minutes. Next, dehydrate for 1 minute, and rinse with 30 L of tap water twice for 5 minutes. Finally, it was dehydrated for 1 minute, air-dried indoors, and allowed to stand in a constant temperature / humidity room at 20 ° C./65% RH for one day.

Evaluation criteria for flexibility Two cotton towels, two cotton melias underwear, and one acrylic jersey were evaluated as follows by comparing the untouched products with the hand. The above evaluations were performed by five skilled panelists, and the flexibility was compared with the average score of the total of the five clothing items determined.

[Evaluation of Liquid Stability] A 50 mL sample bottle (No. 6 wide-mouthed bottle, made of glass, 40 mm in diameter,
The liquid detergent composition of Table 1 was added to 4
After filling with 0 mL and capping, the mixture was allowed to stand in a constant temperature room at 5 ° C. and 25 ° C. for 30 days. The stability of the liquid was visually evaluated for its appearance, and those having a uniform liquid phase at 5 ° C. and 25 ° C. were evaluated as “O”, and those separated or precipitated under any one of the conditions were evaluated as “X”.

[0033]

[Table 1]

The pH of each of the compositions in Table 1 was adjusted to 10.5 with sodium hydroxide or hydrochloric acid. The components in Table 1 are as follows. Compound a: 1,5-dihydroxy-3 obtained in Synthesis Example 1
-Aza-7-oxapentadecane Compound b: 1-amino-5-hydroxy-3-aza-7-oxatricosan obtained in Synthesis Example 2 Compound C: N, N-dimethylstearylamine Non-ionic surfactant Agent d: straight-chain first having 10 to 14 carbon atoms
Non-ionic surfactant e: An average of 12 moles of EO added to a branched-chain secondary alcohol having 10 to 14 carbon atoms. Non-ionic surfactant f: Non-ionic surfactant f: C1-C14 straight-chain first
5 mol of EO on average, 2 mol of PO on average,
EO obtained by block addition in the order of 3 moles on averageCationic surfactant g: mono long-chain alkyl (having 1 carbon atom)
6/18, the ratio of 16 to 18 carbon atoms is 3/7) trimethylammonium chloride LAS-S agent: linear alkylbenzene sulfonic acid having 10 to 14 carbon atoms

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Mitsuru Uno 1334 Minato, Wakayama-shi, Wakayama Prefecture F-term (reference) 4H003 AB19 AC08 AC09 AC23 AE05 BA12 DA01 EA12 EB04 EB13 EB14 EB38 ED02 ED28 FA14 FA16 FA22

Claims (1)

[Claims] (1) a compound represented by the following general formula (I)
0.1 to 10% by weight of the product, and (b) 5 to 60 surfactants
% Detergent composition. Embedded image[Wherein, R¹Is a hydrogen atom or a hydrocarbon having 4 to 20 carbon atoms
Group, R^TwoRepresents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or
Is a hydroxyalkyl group, or-(CH_TwoCH_TwoNH) _mH
(M = 1 to 10), and n indicates the number of 1 to 5. ]