JP2008001858A - Detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent composition, even when simultaneously washing, with little water, much spoiled textile products composed mainly of cotton fiber and little spoiled textile products composed mainly of chemical fiber, which composition exhibits good detergency, suppresses resoiling and can give each of the textile products in good washed state. <P>SOLUTION: The detergent composition comprises following (a) to (d): (a) C<SB>n</SB>H<SB>2n+1</SB>O(EO)<SB>15</SB>H (n=12/14 mixture), (b) potassium carbonate, (c) calcium carbonate and (d) bis(2-hydroxyethyl) palm alkylamine. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a detergent composition, and more particularly, to a detergent composition suitable for washing clothes that can obtain a good wash with a small amount of organic matter even under low water washing conditions.

In order to reduce the environmental load caused by washing wastewater, not only the amount of organic substances in the detergent composition is reduced (Patent Document 1), but also the use of inorganic compounds having a builder effect (Patent Documents 2 and 3) Demonstrated. When washing is performed using such a detergent composition with a reduced amount of organic matter, the re-contamination property becomes remarkable with chemical fibers, and thus it can be suppressed by blending a specific polymer (Patent Document 4). ).
However, the effect is not sufficiently exerted under washing conditions where the amount of water used during washing is small, such as a recent drum type washing machine. Similarly, techniques for preventing recontamination with a detergent composition that does not reduce the amount of organic matter (Patent Documents 5 to 7) are not sufficiently effective under washing conditions where the amount of water used is small. The performance of the detergent composition using calcium carbonate as a builder (Patent Document 8) was evaluated under high-temperature European washing conditions. Under the recent Japanese washing conditions with low water consumption, detergency and recontamination The prevention effect was insufficient.

JP 2001-158899 A Japanese Patent Application No. 2005-368535 Japanese Patent Application No. 2005-368537 JP 2001-303096 A JP 49-027694 JP 53-043708 A JP 56-038399 JP 49-063705

  The present invention has a good detergency and suppresses re-contamination even if a textile product mainly made of cotton fibers with a lot of dirt and a textile product mainly made of chemical fibers with a little dirt are washed with a small amount of water at the same time. An object of the present invention is to provide a detergent composition that can ensure a good wash-up of any of the textile products.

  The present inventors, when used when laundering clothes with tap water or the like in which calcium ions or the like that adversely affect cleaning performance, are used, an alkylene oxide adduct of alkyl or alkylene alcohol and an alkali carbonate and / or Or by reducing the hardness in the washing liquid by the combined use of alkali metal hydrogen carbonate and alkaline earth metal carbonate, and adjusting the pH in the washing liquid to a range suitable for washing, the content of low organic matter It was also found that good cleaning performance can be obtained. Furthermore, it has been found that by using a nonionic surfactant and / or an amphoteric surfactant having a specific structure, the recontamination property is suppressed while the increase in the organic content is slight without adversely affecting the detergency. The present invention has been made based on these findings.

That is, this invention provides the detergent composition characterized by containing the following a) -d).
a) R—O— (AO) _p —H;
(Wherein R represents an alkyl group or alkenyl group having 8 to 20 carbon atoms,
AO: represents an ethylene oxide unit or a propylene oxide unit,
p: represents 1 to 40. )
b) alkali metal carbonates and / or alkali metal hydrogen carbonates;
c) alkaline earth metal carbonate; and d) one or more selected from compounds of formulas I-VII.

(In Formulas I-VII,
R ₁ represents an alkyl group or alkenyl group having 8 to 20 carbon atoms,
R ₂ represents an alkyl group having 2 to 6 carbon atoms,
R ₃ represents an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group,
n1 + n2 = 2-10, n3 + n4 = 2-10, n5 = 2-4,
X ^{+ represents} hydrogen or a monovalent cation of potassium, sodium, or ammonium. )

  According to the present invention, even when a textile product mainly made of cotton fibers with a lot of dirt and a textile product made mainly of chemical fibers with a little dirt are washed with a small amount of water at the same time, the detergency is good and re-contamination is suppressed. All fiber products can ensure good washing. The detergency when a textile product comprising cotton fibers is washed with a large amount of water using the composition of the present invention is comparable to or more than the detergency of conventional detergent compositions. Furthermore, the amount of organic matter contained in the composition of the present invention is smaller than that of conventional products, and the burden on the environment can be reduced.

[Component a)]
Component a) used in the present invention is a nonionic surfactant represented by the above formula a). In the formula a), R is a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms, preferably a linear or branched alkyl group.
AO is an ethylene oxide unit or a propylene oxide unit, and the ethylene oxide unit and the propylene oxide unit may be randomly added or block-added. AO is preferably an ethylene oxide unit.
p is an average added mole number of AO, which is 1 to 40, and preferably 3 to 20 on average and more preferably 5 to 18 on average from the viewpoint of detergency and recontamination prevention.
The compound of the formula a) can be produced using a known method, or a commercially available product can be used.
Component a) may be used alone or in admixture of two or more. Two or more kinds are preferably used in combination.
The blending amount of component a) is preferably 1 to 30%, more preferably 1 to 25%, still more preferably 2 to 20% based on the total amount of the composition. If it is less, good detergency cannot be obtained, and if it is more, the load on the environment may increase.

[Component b)]
Component b) is an alkali metal carbonate and / or an alkali metal hydrogen carbonate, and it is preferable to use the alkali metal carbonate alone or in combination with an alkali metal carbonate and an alkali metal hydrogen carbonate. Sodium and potassium are preferable as the alkali metal.
The amount of component b) is preferably 2-30%, more preferably 3-25%, based on the total amount of the composition. If the amount is too small, good detergency cannot be obtained, and if it is too large, the usability of the product may be adversely affected.

[Component c)]
Component c) is an alkaline earth metal carbonate, with calcium being preferred as the alkaline earth metal. The average particle diameter converted from the BET specific surface area is preferably 0.005 to 10 μm, more preferably 0.01 to 5 μm. When the average particle size is in such a range, the hardness of the washing liquid is reduced.
The blending amount of component c) is preferably 2 to 20%, more preferably 3 to 15%, based on the total amount of the composition. If it is small, good detergency cannot be obtained, and if it is large, it is deposited on clothing. May have adverse effects.

[Component d)]
Component d) is one or more selected from compounds of the structure of formulas I-VII.
Compound I is an ethylene oxide adduct of alkylamine represented by Structural Formula I above. In Formula I, R ₁ is a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms. n1 + n2 is 2-10 on average, preferably 2-8 on average, more preferably 2-5 on average.
Compound II is an ethylene oxide adduct of alkyloylamide represented by the above structural formula II. In the formula II, R ₁ is a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms. n3 + n4 is 2 to 10 on average, preferably 2 to 4 on average. Both n3 and n4 are numbers greater than zero.
Compound III is polyoxyethylene alkyloyl monoethanolamide represented by the above structural formula III. In the formula III, R ₁ is a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms. n5 is 2 to 4 on average.

Compound IV is a fatty acid amidopropyl betaine represented by the above structural formula IV. In the formula IV, R ₁ is a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms. R2 is a linear or branched alkyl group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.
Compound V is a fatty acid amidoalkyldimethylamine oxide represented by the structural formula V above. In Formula V, R ₁ is an alkyl or alkenyl group having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms. R ₂ is a linear or branched alkyl group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.
Compound VI is an alkylamino fatty acid salt represented by the above structural formula VI. In Formula VI, R ₁ is a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms. R ₂ is a linear or branched alkyl group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. X ⁺ is preferably a monovalent cation of potassium or sodium.
Compound VII is a fatty acid amidoalkylsulfobetaine or fatty acid amidoalkylhydroxysulfobetaine represented by the above structural formula VII. In Formula VII, R ₁ is a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms, and R ₂ is 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. A linear or branched alkyl group, R ₃ is a linear or branched alkyl group or a hydroxyalkyl group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

As component d), it is preferable to use a compound in which R ₁ is an alkyl group and a compound in which R ₁ is an alkenyl group in formulas I to VII. In particular, compounds I, II, III and IV are preferred, and compounds I and II are more preferred.
The amount of component d) is preferably 0.5 to 20%, more preferably 0.5 to 15%, still more preferably 1 to 10%, based on the total amount of the composition. If the amount is too small, the re-contamination is not sufficiently suppressed and a good washing cannot be obtained. If the amount is too large, the burden on the environment may increase.
[Product type]
As for the product form of the detergent composition of the present invention, good washing can be obtained in any form such as liquid, granular, powder, gel, tablet, briquette and bar. Among them, a detergent composition in a liquid, granular, and powder form is preferable, and a liquid product form is more preferable because there are few manufacturing restrictions in the blending of component d).
[Production method]
The composition of the present invention can be produced by methods known in the art. In the liquid state, for example, the components a) to d) can be produced by heating and stirring.

[Optional ingredients]
The detergent composition of the present invention can contain components usually used in detergent compositions in addition to the above-mentioned components a) to d). Specific examples include the following components.
(1) Surfactant other than component (a) and component (d) Cationic surfactant, nonionic surfactant, amphoteric surfactant (2) Optical brightener: bis (triazinylaminostilbene) disulfonic acid derivative Bis (sulfostyryl) biphenyl salts and the like.
(3) Anti-staining agent: Cellulose derivatives such as carboxymethylcellulose, polyvinylpyrrolidone and its derivatives, polyethylene terephthalate derivatives, and the like.
(4) Flexibility imparting agent: cationic surfactants such as dialkyl type quaternary ammonium salts, clay minerals such as smectite, and the like.
(5) Texture improving agent: polyether-modified silicone, amino polyether-modified silicone, etc. (6) Enzyme: protease, lipase, cellulase, amylase and the like.
(7) Antifoaming agent: silicone oil and the like.
(8) Perfume (9) Coloring agents such as water-soluble dyes and pigments

When the product form is liquid, it can further contain the following components.
(10) Stabilizer: Short chain alkylbenzene sulfonate such as sodium paratoluenesulfonate, alcohol, polyhydric alcohol, polyethylene (propylene) glycol alkyl ether, polyethylene (propylene) glycol phenyl ether, etc. (11) Preservative (12 ) Pearl agent (13) pH adjuster: sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine and the like. The pH is preferably 8-11.
(14) Viscosity modifier: xanthan gum, etc.

When the product form is powdery, granular, tablet-like, or the like, it can further contain the following components.
(15) Alkaline agent other than component (b): sodium silicate, crystalline layered sodium silicate, amorphous layered sodium silicate, etc. (16) Calcium scavenger other than component (c): A-type zeolite, P-type (17) Surface modifier: fine powder calcium carbonate, fine powder zeolite, granular zeolite, polyethylene glycol and the like.
(18) Porous oil absorbent: amorphous anhydrous silicic acid, calcium silicate and the like.
(19) Bleaching agents: sodium percarbonate, sodium perborate and the like.
(20) Bleach activator: tetraacetylethylenediamine (TAED), decanoyloxybenzoic acid, sodium dodecanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, and the like.
(21) Bleach activation catalyst (22) Neutral inorganic salt: sodium sulfate, sodium chloride, potassium chloride, etc.

[Preparation of detergent composition]
The liquid detergent composition is prepared according to Japanese Patent Application No. 2005-368535, and the granular detergent composition is prepared according to Japanese Patent Application Laid-Open No. 05-209200 [detergent composition evaluation method].
・ Cleaning evaluation method 1
Using Teg-O-meter of Testing Corp. in the United States as a washing tester, put 10 pieces of artificial dirt cloth (5 cm × 5 cm) and knitted cloth prepared using cotton cloth according to the examples described in JP-A-2001-64694, The detergent composition was added so that the detergent concentration was 667 ppm, and washed at 120 rpm and 15 ° C. for 10 minutes in accordance with the bath ratio of 30 times. The water used was 3 ° DH, the amount of the washing solution was 900 mL, and the rinse was washed with 900 mL of water for 3 minutes. After rinsing, the evaluation fabric was dried, and the cleaning rate was calculated according to the examples described in JP-A No. 2001-64694.

・ Cleaning evaluation method 2
Five artificial dirt cloths (5 cm × 5 cm) and five polyester jersey white cloths (5 cm × 5 cm) prepared using cotton cloth according to the examples described in JP-A-2001-64694 are sewn into fleece clothing, and fleece clothing 1 Sheets, 14 long-sleeved shirts, and 7 acrylic jersey long-sleeved shirts (total 3.5 kg) were placed in a fully automatic washing machine (MAW-V8QP, manufactured by Mitsubishi Electric Corporation). Tap water at 15 ° C. was poured, the detergent composition was added so that the detergent concentration was 667 ppm, and washing and rinsing were performed on a normal course. The bath ratio at that time was approximately 12. The evaluation fabric was dried, and the cleaning rate was calculated according to the examples described in JP-A No. 2001-64694. However, the washing rate of the polyester jersey white cloth was calculated by calculating the washing rate when the reflectance of the raw fabric was 120, and the average of the washing rates of the artificial dirt cloth and the polyester jersey white cloth was obtained.

・ Cleaning evaluation method 3
Five artificial dirt cloths (5 cm × 5 cm) and five polyester jersey white cloths (5 cm × 5 cm) prepared using cotton cloth according to the examples described in JP-A-2001-64694 are sewn into fleece clothing, and fleece clothing 1 Sheets, 14 long-sleeved shirts, and 7 acrylic jersey long-sleeved shirts (3.5 kg in total) were placed in a tanned drum type fully automatic washing machine (NV-80, manufactured by Matsushita Electric Industrial Co., Ltd.). Tap water at 15 ° C. was poured, the detergent composition was added so that the detergent concentration was 1400 ppm, and washing and rinsing were performed in a normal course. The bath ratio at that time was approximately 6. The evaluation fabric was dried, and the cleaning rate was calculated according to the examples described in JP-A No. 2001-64694. However, the washing rate of the polyester jersey white cloth was calculated by calculating the washing rate when the reflectance of the raw fabric was 120, and the average of the washing rates of the artificial dirt cloth and the polyester jersey white cloth was obtained.
・ Evaluation criteria ◎: Cleaning rate of 80% or more ○: Cleaning rate of 65% or more and less than 80% △: Cleaning rate of 50% or more and less than 65% ×: Cleaning rate of less than 50%

(Table 1)
[Evaluation results]

a) Component: Alkylene oxide adduct a1: C _n H _{2n + 1} O (EO) ₁₅ H (n = 12/14 mixture (mass ratio 71/29)), synthetic product.
(Synthesis method of a1)
Using 224.4 g of C12,14 alcohol (trade name “CO-1214”, branching rate ^{* 10} %) by P & G, 2.0 g of 30 mass% NaOH aqueous solution was collected in a pressure-resistant reaction vessel, Was replaced with nitrogen.
Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. While stirring the alcohol, 763.6 g of ethylene oxide (gaseous) was gradually added to the alcohol liquid while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. using a blowing tube.
After completion of the addition of ethylene oxide, aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature to 100 ° C. or lower, 70% by mass p-toluenesulfonic acid was added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product was about 7 to obtain a1.
* 1 Branching rate: The branching rate indicates a ratio in terms of the number of moles of alcohol having a branched alkyl group to the number of moles of the whole alcohol in the raw material alcohol.

a2: C _n H _{2n + 1} O (EO) ₇ H (average ethylene oxide 7 mol adduct of a linear alcohol with a mixture of n = 12/14, trade name “Leox CC70”, manufactured by Lion Corporation)
_{a3: C n H 2n + 1} O (EO) 15 H (n = 12/13 mixture (weight ratio 55/45)), synthetic.
(Synthesis method of a3)
Synthesis was carried out in the same manner as a1 using 224.4 g of C12,13 alcohol (trade name “Safol23”, branching rate ^{* 1} 50%) manufactured by Sasol.
a4: C ₁₃ H ₂₇ O (EO) ₇ H (average ethylene oxide 7 mol adduct of branched alcohol, trade name “Lutenzol TO7”, manufactured by BASF)

b) Component: Alkali metal carbonate or alkali hydrogen carbonate metal salt b1: Potassium carbonate (trade name “Potassium carbonate (powder), manufactured by Asahi Glass Co., Ltd.)
b2: Sodium carbonate (trade name “grain ash”, manufactured by Soda Ash Japan Co., Ltd.)
b3: Sodium bicarbonate (trade name “sodium bicarbonate”, manufactured by Asahi Glass Co., Ltd.)

c) Component: alkaline earth metal carbonate c1: calcium carbonate (trade name “NS1000”, manufactured by Nitto Flourishing Co., Ltd., average particle diameter 1.2 μm converted from BET specific surface area)
c2: Calcium carbonate (trade name “Whiteon P-10”, manufactured by Shiraishi Kogyo Co., Ltd., average particle diameter of 0.4 μm converted from BET specific surface area)
c3: Calcium carbonate (trade name “Brt-1500”, manufactured by Shiroishi Kogyo Co., Ltd., average particle diameter 0.2 μm converted from BET specific surface area)

d) Component: Nonionic activator or amphoteric activator having a specific structure d1: Bis (2-hydroxyethyl) cocoalkylamine (trade name “Esomine C / 12”, manufactured by Lion Akzo Co., Ltd.)
d2: Palm fatty acid diethanolamide (trade name “Amizole CDE”, manufactured by Kawaken Fine Chemical Co., Ltd.)
d3: Polyoxyethylene (2) lauroyl monoethanolamide (trade name “Amidette 2L”, manufactured by Kawaken Fine Chemical Co., Ltd.)
d4: Amidopropyl betaine laurate (trade name “Enazicol L-30B”, manufactured by Lion Akzo Co., Ltd.)
d5: Amidopropyl dimethylamine oxide laurate (trade name “SOFTAZOLINE LAO”, manufactured by Kawaken Fine Chemical Co., Ltd.)
d6: Sodium laurylaminopropionate (trade name “Amforak L-18”, manufactured by Lion Akzo Co., Ltd.)
d7: Amidopropyl hydroxypropyl sulfobetaine laurate (trade name “SOFTAZOLINE LSB”, manufactured by Kawaken Fine Chemical Co., Ltd.)

Other components, pTS-H: p-toluenesulfonic acid (manufactured by Kyowa Hakko Kogyo Co., Ltd.)
EtOH: 95 vol% synthetic ethanol (manufactured by NEDO)
• Xanthan gum: trade name “Kelzan T”, manufactured by Sanki Co., Ltd. • PVP: polyvinylpyrrolidone (trade name “K-30”, manufactured by Nippon Shokubai Co., Ltd.)
SRP: nonionic polymer compound in which a polyethylene glycol unit and a polypropylene glycol unit are added to an alkylene terephthalate unit composed of terephthalic acid and ethylene glycol (trade name “SRC-1” manufactured by Clariant)
・ Zeolite: Type A zeolite (trade name “Silton B”, manufactured by Mizusawa Chemical Co., Ltd.)
Silicic anhydride: Trade name “Tokuseal N” (manufactured by Tokuyama Corporation)
Enzyme 1: Trade name “Everlase 16L TYPE EX”, manufactured by Novozymes Enzyme 2: Trade name “Sabinase 12T” (manufactured by Novozymes), trade name “Lipex 100T” (manufactured by Novozymes) and trade name “Stainzyme 12T” ( A mixture of Novozymes) and the trade name “Celzyme 0.7T” (Novozymes) in 4: 2: 2: 2 (mass ratio) ・ Sulfuric acid Na: sodium sulfate (trade name “Neutral Anhydrous Glass”, Shikoku Kasei Kogyo ( Made by Co., Ltd.)

Claims (2)

A detergent composition comprising the following a) to d):
a) R—O— (AO) _p —H;
(Wherein R represents an alkyl group or alkenyl group having 8 to 20 carbon atoms,
AO: represents an ethylene oxide unit or a propylene oxide unit,
p: represents 1 to 40. )
b) alkali metal carbonates and / or alkali metal hydrogen carbonates;
c) alkaline earth metal carbonate; and d) one or more selected from compounds of formulas I-VII.

(In Formulas I-VII,
R ₁ represents an alkyl group or alkenyl group having 8 to 20 carbon atoms,
R ₂ represents an alkyl group having 2 to 6 carbon atoms,
R ₃ represents an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group,
n1 + n2 = 2-10, n3 + n4 = 2-10, n5 = 2-4,
X ^{+ represents} hydrogen or a monovalent cation of potassium, sodium, or ammonium. ) d) in the formulas I to VII
R ₁ represents an alkyl group or alkenyl group having 10 to 18 carbon atoms,
R ₂ represents an alkyl group having 2 to 4 carbon atoms,
R ₃ represents a hydroxyalkyl group having 1 to 6 carbon atoms,
The detergent composition according to claim 1, wherein n1 + n2 = 2 to 8, and n3 + n4 = 2 to 4 or more.