JP2001064676A - Liquid detergent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid detergent simultaneously satisfying both high detergency for smudges of a collar and a cuff and high detergency for sebaceous smudges causing yellowing of underwear. SOLUTION: This liquid detergent comprises (a) 2-60 wt.% of a nonionic surfactant represented by general formula I: R1O(EO)m/(PO)nH (R1 is an 8-20C primary alkyl group, or the like; EO is ethyleneoxy group; PO is propyleneoxy group; (m) and (n) are each a mean number of added mol; (m) is 4-16; (n) is 1-5; EO and PO may be in the form of either of random addition and block addition and the additional sequence of EO and PO are not limited) and (b) 0.5-30 wt.% of a compound represented by general formula II: R2OCH2CH(OH) CH2OH (R2 is a 2-8C alkyl group, or the like). Besides, the liquid detergent preferably further contains (c) 1-20 wt.% of a nonionic surfactant represented by the formula III: R3O(EO)k/(PO)lH (R3 is an 8-20C secondary alkyl group; EO is ethyleneoxy group; PO is propyleneoxy group; (m) and (n) are each a mean number of added mol; (k) is 3-15; (l) is 0-5; EO and PO may be in the form of either of random addition and block addition and the additional sequence of EO and PO are not limited).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a liquid detergent.

[0002]

2. Description of the Related Art Liquid detergents have advantages such as rapid solubility in washing water and direct application to soiled portions for use. Because of the high cleaning power when applied directly, commercial liquid cleaning agents are recommended to be used directly on soiled areas, and liquid detergents for partial soiling are also on the market. Partial use of the liquid detergent is particularly effective for the typical stains on the collar and cuffs, and is widely used in general. On the other hand, attention is paid to greasy stains that cause the yellowing of underwear, and the expectation for liquid detergents for removing these stains is further increasing.

A general liquid detergent contains a surfactant as a main component, and particularly for greasy stains, mainly the stain of the surfactant/surface activity at the water interface, the emulsifying power for the stain, and the affinity with the stain. The physical properties related to the interaction between the dirt and the surfactant, such as, have a great influence on the detergency. Therefore, optimization of the surfactant composition for the purpose of removing a specific greasy soil is actively carried out in the art because the direction of the physical properties of the surfactant is technically clear. However, in order to obtain a surfactant composition with high detergency at the same time for a plurality of greasy stains such as greasy stains on collars and cuffs, greasy stains that cause yellowing of underwear, the optimum interface physical properties for each stain are required. Since they are different, technical innovation is required. There is a demand for the development of a liquid cleaning agent with a wide variety of stains/range capable of exhibiting so-called high cleaning power.

[0004]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
It is an object of the present invention to provide a liquid cleaning agent that simultaneously satisfies a high detergency against cuff stains and a high detergency against greasy stains that cause yellowing of underwear.

[0005]

[Wherein R ¹ is a primary alkyl or alkenyl group having 8 to 20 carbon atoms. EO is an ethyleneoxy group and PO is a propyleneoxy group. m and n are average addition mole numbers, m is 4 to 16 and n is 1 to 5. EO and PO may be added randomly or in blocks, and the order of adding EO and PO does not matter. ]

(B) Compound represented by formula (II) 0.5 to 30
Weight% R ² OCH ₂ CH(OH)CH ₂ OH (II) [wherein R ² is a hydrocarbon group having 1 to 16 carbon atoms]. ] The liquid detergent containing is provided.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION As the nonionic surfactant represented by the general formula (I), which is the component (a), those which are usually commercially available may be used, and the nonionic surfactant synthesized by a well-known method or natural It can be produced by adding ethylene oxide (hereinafter referred to as EO) and propylene oxide (hereinafter referred to as PO) to an alcohol having an alkyl group of R ¹ derived from fats and oils by a known method. In particular, by using a nonionic surfactant represented by the following general formula (IV) as the component (a), it is possible to obtain a high detergency particularly against stains on collars and cuffs.

R ⁴ O(EO) _p (PO) _q (EO) _r H (IV) [R ⁴ is the same as R ¹ and EO and PO are the same as those of formula (I). p, q and r represent the average number of moles added, p>0, q=1 to 4, r>
0, p+q+r=6 to 14, and p+r=5 to 12.
Preferably, p+q+r=7-14, p+r=6-12,
q=1 to 2. ].

The nonionic surfactant represented by the general formula (IV) is, for example, EO or PO in an alcohol having an alkyl group of R ^4.
After being added in this order, EO is added again to synthesize.

The liquid detergent of the present invention may contain the nonionic surfactant as the component (a) in an amount of preferably 5 to 50% by weight, particularly preferably 20 to 40% by weight.

Component (b) The component (b) used in the present invention is a compound represented by the general formula (II). R ² —OCH ₂ CH(OH)CH ₂ OH (II) [In the formula, R ² is a hydrocarbon group having 1 to 16 carbon atoms. ].

In particular, R ² in the general formula (II) has 2 to 8 carbon atoms, preferably 4 to 8 carbon atoms, more preferably 5 to 8 carbon atoms, from the viewpoint of cleaning performance against stubborn sebum stains in coating cleaning.
Particularly preferably, an alkyl group having 8 or a carbon number of 3 to 10
Preferably 6-10, more preferably 7-10, particularly preferably 8 alkenyl groups.

The compound of the general formula (II) comprises R ² --OH and an epoxy compound such as epihalohydrin or glycidol and BF.
A method of producing by reacting with an acid catalyst such as ₃ is generally used. However, the reaction between the alcohol and the epoxy compound randomly reacts at the 1-position and the 2-position of the epoxy compound, and a polyadduct is also formed. Therefore, in addition to the compound of the general formula (II) in which the alcohol is added to the 1-position, 2-alkoxy-1,3 propanediol as an isomer and a multimer in which a large number of glyceryl groups are added (for example, alkyl diglyceryl ether) Exists. In the present invention, a compound in which the above isomers and multimers are mixed may be used, but from the viewpoint of improving the cleaning performance, the aluminum catalyst of the general formula (V) is used to reduce the isomers and multimers. It is preferred to use to prepare compounds of general formula (II). _{^{Al (OSO 2 -R 5) a}} (OR 6) b (OR 7) c (V) wherein, R ⁵ represents a substituted hydrocarbon which may have a substituent, R ⁶ and R ⁷ are the same Or, differently, it represents a hydrocarbon group which may have a substituent. a is 1 to 3, b and c are 0 to 2, and a+b+c=3. ].

The catalyst can be produced, for example, by reacting a trialkylaluminum, a trialkoxyaluminum, a trihalogenated aluminum or the like with a sulfonic acid or the like to convert an alkyl group, an alkoxyl group or a halogen group of the aluminum compound with the sulfonate. After partial or total substitution, it can be produced by further substituting the remaining alkyl group, alkoxyl group or halogen group with a suitable alcohol or phenol. The substitution reaction is carried out by heating and mixing in a solvent such as hydrocarbon or alcohol.

When the above aluminum catalyst is used in the present invention, an epoxy compound such as epihalohydrin or glycidol is added in an amount of 0.5 to 1.5 molar equivalents relative to R ² -OH,
Preferably, 1.0 to 1.2 molar equivalents are used, and the aluminum catalyst of the general formula (V) is 0.0 to R ² —OH.
01-0.1 molar equivalent, preferably 0.01-0.05
It is good to carry out the reaction at a reaction temperature of 10 to 120° C., preferably 70 to 110° C. for 1 to 5 hours using a molar equivalent amount.

In the present invention, such a component (b) is blended in a liquid detergent in an amount of 0.5 to 30% by weight, preferably 1 to 20% by weight, and particularly 1 to 15% by weight, whereby the yellowing of underwear is reduced. It is possible to obtain high detergency against greasy stains that cause

The liquid detergent of the present invention further comprises (c) the following formula:
The nonionic surfactant represented by (III) may be contained in an amount of 1 to 20% by weight. R ³ O(EO) _k /(PO) ₁ H (III) [In the formula, R ³ is a secondary alkyl group having 8 to 20 carbon atoms.
EO is an ethyleneoxy group and PO is a propyleneoxy group. k and l are average addition mole numbers, and k is 3 to 1.
5, 1 is 0-5. EO and PO may be added randomly or in blocks, and the order of adding EO and PO does not matter. ].

The nonionic surfactant represented by the general formula (III), which is the component (c), may be a commercially available one, or may be derived from a natural fat or oil synthesized by a known method. It can be produced by adding EO or EO and PO to an alcohol having an alkyl group of R ³ . In the formula (III), R ³ is preferably a secondary alkyl group having 10 to 18 carbon atoms. Also, k is 5 to 13,
1 is preferably 0 to 2. The blending amount of the component (c) in the liquid detergent is preferably 2 to 15% by weight from the viewpoint of improving phase stability and detergency.

The liquid detergent of the present invention may contain (d) at least one selected from the following anionic surfactants and 1 to 20% by weight in total. Alkylbenzene sulfonate having an alkyl group having an average carbon number of 8 to 16 An alkyl ether sulfate having an alkyl group having an average carbon number of 10 to 18 and having an average of 0.5 to 5 mol of EO added in one molecule.

Among the above, as the alkylbenzene sulfonate, for example, the average carbon number of the alkyl chain is 8 to 1
Any of 6 may be used, and for example, Neoperex F25 manufactured by Kao Corporation, Dobs102 manufactured by Shell, and the like can be used. It can also be industrially obtained by sulfonation of alkylbenzene, which is widely used as a raw material for detergents, with an oxidizing agent such as chlorosulfonic acid or sulfurous acid gas. The average carbon number of the alkyl group is preferably 10-14.

As the alkyl ether sulfate, EO is added to an alcohol having an average carbon number of 10 to 18, for example, a linear or branched primary or linear secondary alcohol.
It can be obtained by adding 0.5 to 5 moles per molecule on average and sulfating this using, for example, the method described in JP-A-9-137188. The average carbon number of the alkyl group is 1
0-16 are preferable.

The liquid detergent of the present invention preferably contains the anionic surfactant of component (d) and at least one selected from the total of 2 to 15% by weight.

The components (a) to (d) are contained in the liquid detergent in a weight ratio of [component (a)+component (b)+component (c)]>[component (d)×1. 5], and more preferably in the same weight ratio [component (a)+component (b)+component (c)]>[component (d)×2]. To be done.

Furthermore, the liquid detergent of the present invention comprises (a)
Other surfactants other than the components (c) and (d) can be contained. As other surfactants, conventionally known surfactants can be used as long as the effects of the present invention are not impaired.

For example, as the anionic surfactant, an alkyl sulfate ester salt, an alkenyl sulfate ester salt, an alpha sulfo fatty acid alkyl ester salt, an olefin sulfonate, an alkane sulfonic acid or the like may be used. You may mix a small amount of fatty acid salt. As the counterion of the anionic surfactant, in addition to alkali metals such as sodium and potassium, alkaline earth metals such as magnesium and/or alkanolamines such as mono-, di-, triethanolamine and the like are used, but especially alkanolamines. The use of is preferable because the liquid stability is improved. When blending these anionic surfactants,
It may be added to the detergent composition in the acid form, or may be neutralized with an alkali agent (alkanolamine etc.) added separately in the composition.

Further, as the nonionic surfactant, polyoxyethylene primary alkyl ether, the following general formula (VI)
R ⁸ O-(R ⁹ O) _x G _y (VI) [wherein R ⁸ is a linear or branched alkyl group having 8 to 18 carbon atoms, or an alkenyl group] , Or an alkylphenyl group, R ⁹
Represents an alkylene group having 2 to 4 carbon atoms, G represents a residue derived from a reducing sugar having 5 or 6 carbon atoms, x represents a number having an average value of 0 to 6, and y represents a number having an average value of 1 to 10. ] And fatty acid alkanolamides, polyhydroxy fatty acid amides and the like.

In order to improve the texture, it is preferable to use a cationic surfactant such as a mono long-chain alkyl quaternary ammonium salt in combination. As the amphoteric surfactant, amine oxide, alkylcarbobetaine, alkylsulfobetaine, alkylamidohydroxysulfobetaine, alkylamidoamine type betaine, alkylimidazoline type betaine and the like can be blended. In the present invention, the surfactant is 1 to 60% by weight, preferably 2 to 50% by weight.
It is preferable to contain.

The liquid detergent of the present invention has a water content of 50% by weight.
Below, especially 40% by weight or less. The balance of the liquid detergent of the present invention may be water, but it is relatively stable even when the amount of water is small.

Further, in the liquid detergent of the present invention, as an optional component, alkali agents such as alkali metal hydroxides, silicates, carbonates and alkanolamines; alcohols such as ethanol, ethylene glycol, molecular weight of 200 or more. ~
Thousands of low molecular weight glycols such as polyethylene glycol and propylene glycol, paratoluene sulfonic acid, benzoate (also effective as a preservative) and urea and other viscosity reducers and solubilizers; polyoxyalkylenebenzyl Phase modifiers and detergency improvers such as ethers and polyoxyalkylene phenyl ethers; nitrilotriacetic acid salts, ethylenediaminetetraacetic acid salts, iminodiacetic acid salts, diethylenetriaminepentaacetic acid salts, glycol etherdiaminetetraacetic acid salts, hydroxyethyliminodiacetic acid salts Salts and aminopolyacetates such as triethylenetetramine hexaacetate, malonic acid, succinic acid, diglycolic acid, malic acid, tartaric acid, citric acid and the like; polyacrylic acid, polymaleic acid, carboxymethyl cellulose, and an average molecular weight of 5,000 or more. Polyethylene glycol, maleic anhydride-diisobutylene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-isobutylene copolymer, maleic anhydride-vinyl acetate copolymer, pentene-maleic acid copolymer and These salts, naphthalene sulfonate formalin condensates, etc., redeposition inhibitors or dispersants such as polymers described in JP-A-59-62614; anti-transfer agents such as polyvinylpyrrolidone; amylase, protease, lipase, Enzymes such as cellulases; enzyme stabilizers such as calcium chloride, calcium sulfate, formic acid, boric acid (boron compounds); fluorescent dyes such as Chinopearl CBS (manufactured by Ciba Specialty Chemicals) and Whitex SA (manufactured by Sumitomo Chemical) Defoaming agents such as silica and silicone, or flexibility imparting agents; antioxidants such as butylhydroxytoluene, distyrenated cresol, sodium sulfite, and sodium bisulfite; bluing agents; perfumes; antibacterial preservatives and the like.

[0029]

The liquid cleaning agent of the present invention is excellent in cleaning power for greasy stains on collars/cuffs and yellowing of underwear.

[0030]

EXAMPLES Synthesis Example 1 (Synthesis of pentyl glyceryl ether) n-pentyl alcohol (1.78 mol), aluminum triisopropoxide 3.61 g (17.7 mmo)
1) and 9.40 g of p-phenolsulfonic acid (5.4
(mol) was placed in a 1 L reaction tank and heated to 90° C. with stirring. After further stirring under reduced pressure (200 mmHg) for 1 hour, the temperature is raised to 100° C. and 170 g of epichlorohydrin
Was added dropwise over 30 minutes, and the mixture was further stirred for 3 hours. The reaction mixture was kept at 50° C. and a 48% aqueous sodium hydroxide solution 80
0 ml was added dropwise in 1 hour, and after stirring for 3 hours, 400m
l of water was added and the layers were separated. After removing the aqueous layer, the oil layer was washed twice with 500 ml of water to obtain 280 g of a crude reaction product. Next, 140 g of the crude reaction product, 140 g of water, 7.64 g of lauric acid and 2.14 g of potassium hydroxide were placed in a 2 L autoclave and the temperature was raised to 157° C. with stirring.
After stirring for 5 hours, the mixture was cooled to room temperature, the reaction product was extracted with 500 ml of ethyl acetate, washed twice with 300 ml of water, and the ethyl acetate was distilled off under reduced pressure to give R ² n in the general formula (II). A compound of the pentyl group was obtained.

Synthesis Example 2 (Synthesis of Octyl Glyceryl Ether) Instead of n-pentyl alcohol in Synthesis Example 1, n was used.
A compound in which R ² in the general formula (II) was n-octyl group was obtained by the same method except that 1.78 mol of -octanol was used.

Example The liquid detergents shown in Table 1 were prepared, and the following methods were used to evaluate the ability to clean collar stains and detergency against greasy stains that cause yellowing of underwear.

<Evaluation Method> (1) Preparation of Evaluation of Detergency of Collar Soil (1-1) Stain of Collar Stain Specimen A cotton/polyester blended shirt that has been worn for 3 days is cut and collected. It was divided into 5 groups, and the collar pieces of the second group from the one with the most dirt were used for cleaning evaluation. (1-2) Washing conditions 40L of tap water was put into the washing tub of a two-tub type washing machine (Toshiba Galaxy 3.6), and 1.4kg of cotton unweared underwear and 0.6kg of cotton/polyester Put on a blended shirt that is not worn. 5×30×30cm cotton cloth with cleaning evaluation collar
Prepare one sewn piece and apply 3 mL of the liquid cleaning agent in the table to each piece of the collar. After applying a total of 15 mL for 5 pieces of collar pieces, the cotton cloth with the collar pieces is put into a washing tub.
In addition, the same liquid detergent applied to the collar piece 11.6
After adding 7 mL to the washing tub, wash normally for 10 minutes.
Then, dehydration is carried out for 1 minute, followed by rinsing with running water for 8 minutes with tap water having an amount of 15 L/minute. Then, it is dehydrated for 5 minutes and naturally dried in the room. (1-3) Criteria for Detergency Detergent A stain cleaning ability of a collar was judged by one skilled panelist (hereinafter referred to as one skilled panelist) according to the following criteria. Table 1
Shows the result. ◯: Stain is removed and satisfactory level ▽; Stain is slightly left but satisfactory level △: Stain is slightly left and unsatisfactory level x: Stain is not removed much and unsatisfactory level One skilled panel The reliability of this judgment result was confirmed by Scheffe's one-pair comparison method by 10 other panelists. That is, among the collar stain test pieces judged by one skilled panelist, the test pieces whose results are adjacent to each other such as ○ and ▽, ▽ and △, and △ and × are used as samples and other 1
When 0 panelists tested by Scheffe's one-pair comparison method, it was determined that one expert panelist had a significant difference at the 95% confidence limit.

(2) Degreasing power for greasy soil (2-1) Undergarment piece for evaluation 20 new test subjects are provided with new undergarments in which numbers 1 to 20 are written so that who can give which underwear can be distinguished. .
After being worn for one day, it is collected, washed with 20 sheets of standard type compact powder detergent in the same bath, and then naturally dried. After that, give each subject the same underwear as the first one, and ask them to wear it again. After being worn for one day, it is collected, washed with 20 sheets of standard type compact powder detergent in the same bath, and then naturally dried. This cycle was repeated, and after wearing 10 times, all the underwear was collected and the underwear piece for evaluation was prepared.
Eight pieces of cloth each having a size of 5×5 cm are cut out from one piece of underwear, and it is confirmed that the degree of yellowing of the eight pieces is almost the same.

(2-2) Washing conditions Among the above, those with undergarment numbers 1 to 5 were selected, and one underwear piece (cutout piece) for cleaning evaluation of each number was prepared (5 pieces in total) 30×30 cm. Prepare 8 pieces sewn on the cotton cloth. This is used as a cleaning test cloth, and one of them is shown in Table 1.
Using one of the above liquid cleaning agents, cleaning is performed in the same manner as in the evaluation of the collar dirt cleaning power. After washing, allow the test cloth to dry naturally,
The sample was allowed to stand for 1 week in a thermo-hygrostat at a temperature of -65% RH for aging.

(2-3) Criteria for Detergency Detergent: A trained panelist compares the yellowing of the underwear cut-out pieces (8 pieces each) of the same number after washing and aging with each liquid detergent in the table. Then, from 1 to 8 points in order of increasing yellowing, a score of 1 to 8 points is given for each point. A score was assigned to all of the No. 1 to 5 skin wear pieces, and a total score of 5 sheets of No. 1 to 5 corresponding to each liquid detergent was used as a yellowing evaluation point by washing with the detergent. The theoretical maximum score is 40 and the minimum score is 5, with higher evaluation points indicating less yellowing. This evaluation was carried out by 3 panelists, and the average of the yellowing evaluation points of 3 people is shown in Table 1.

[0037]

[Table 1]

The components in Table 1 are as follows. Nonionic surfactant (a1): linear primary alcohol having 10 to 14 carbon atoms, EO on average 5 mol, PO on average 2
Mol, EO with an average of 5 mol blocks added ・Nonionic surfactant (a2): an average of 7 mol of EO and an average of 2 of PO in a linear primary alcohol having 10 to 14 carbon atoms.
Mol, EO with an average of 5 mol blocks added ・Nonionic surfactant (x): a linear primary alcohol having 10 to 14 carbon atoms with an average of 8 mol of EO added ・nonionic surfactant (C1): C10-14 linear secondary alcohol with an average of 7 moles of EO added ・Nonionic surfactant (c2): C10-14 linear secondary alcohol EO 7 mol on average, PO on average 1
Molecule added-Compound (b1): Pentyl glyceryl ether-Compound (b2): Octyl glyceryl ether-LAS-S agent: Linear alkylbenzene sulfonic acid having 10 to 14 carbon atoms in the alkyl group-ES-S agent : Polyoxyethylene alkyl ether sulfuric acid (alkyl group average carbon number 10 to 12, EO average addition mole number 2.5)-fatty acid: coconut oil fatty acid having 12 to 14 carbon atoms-polymer compound: pentene-maleic acid (mol Ratio 50/
50) Copolymer, average molecular weight 5000 Enzyme: Durazyme 16.0 L/protease (Novo Nordisk Bioindustry Co., Ltd.)

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomoki Yanagisawa 1334 Minato Minato, Wakayama Prefecture Wakayama Prefecture Kao Corporation Research Laboratory F-term (reference) 4H003 AB19 AB31 AC08 AC09 AC23 BA12 DA01 DA03 DB01 EA12 EB04 EB06 EB07 EB14 EB22 EB32 EC02 ED02 ED28

Claims (3)

[Claims] 1. A nonionic surfactant represented by the general formula (I): 2 to 60% by weight R ¹ O(EO) _m /(PO) _n H (I) [wherein R ¹ is carbon; It is a primary alkyl group or alkenyl group of the number 8 to 20. EO is an ethyleneoxy group and PO is a propyleneoxy group. m and n are average addition mole numbers, m is 4 to 16 and n is 1 to 5. EO and PO may be either random addition or block addition.
The order of adding PO and PO does not matter. ] (B) Compound represented by general formula (II) 0.5 to 30
Weight% R ² OCH ₂ CH(OH)CH ₂ OH (II) [wherein R ² is a hydrocarbon group having 1 to 16 carbon atoms]. ] The liquid cleaning agent containing. 2. The method according to claim 1, further comprising (c) 1 to 20% by weight of a nonionic surfactant represented by the following formula (III).
The liquid detergent described. R ³ O(EO) _k /(PO) ₁ H (III) [In the formula, R ³ is a secondary alkyl group having 8 to 20 carbon atoms.
EO is an ethyleneoxy group and PO is a propyleneoxy group. k and l are average addition mole numbers, and k is 3 to 1.
5, 1 is 0-5. EO and PO may be added randomly or in blocks, and the order of adding EO and PO does not matter. ] 3. The liquid detergent according to claim 1, further comprising (d) at least one selected from the following anionic surfactants and 1 to 20% by weight in total. Alkylbenzene sulfonate having an alkyl group having an average of 8 to 16 carbon atoms An alkyl ether sulfate having an alkyl group having an average of 10 to 18 carbon atoms and having an average of 0.5 to 5 mol of ethylene oxide added in one molecule.