JP2000160192A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid detergent composition having an excellent smell- masking effect and capable of exhibiting excellent odor stability even when stored for a long period, by mixing a specific terminal-blocked nonionic surfactant with a specific perfume component. SOLUTION: This liquid detergent composition contains (A) one or more kinds of terminal-blocked nonionic surfactants of formula I R1 is a 6-22C hydrocarbon; R2 is a 1-20C alkyl or the like; AO is a 3-8C oxyalkylene; EO is oxyethylene, provided that the addition molar distribution of EO satisfies the narrow degree of inequality II [(i) is a positive integer; Yi is the weight percent of the EO adduct having an addition molar number of (i); (nmax) is the addition molar number (positive integer) of the EO adduct contained in the maximum amount; 0<=(m)<=15, 0<(n)<=40, and (m)+(n)=2 to 50], etc., and (B) a perfume component comprising two or more perfumes selected from the group consisting of perfumes having 1-20C alcohol groups, perfumes having 1-20C aldehyde groups, perfumes having 3-20C ketone groups and perfumes having 4-25C lactone groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid detergent composition which is excellent in odor masking property and odor stability of a specific end-blocked nonionic surfactant.

[0002]

2. Description of the Related Art As nonionic surfactants incorporated in detergent compositions, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl allyl ethers, alkyl glycosides and the like are generally used. The development of fatty acid polyoxyalkylene alkyl ethers as surfactants has been promoted.

As a method for synthesizing a fatty acid polyoxyalkylene alkyl ether, a two-stage reaction method in which a polyoxyalkylene alkyl ether or a fatty acid polyoxyalkylene ether is synthesized and then esterified, or an alkylene oxide is directly added to the fatty acid alkyl ester. There is a one-step reaction method. The former reaction requires two steps of addition of an alkylene oxide and transesterification, and has the disadvantage that a large amount of by-products such as diesters and polyalkylene glycols are generated. The latter one-step reaction has been developed to solve this problem. As a characteristic catalyst, for example, magnesium oxide added with metal ions (Japanese Unexamined Patent Publication No.
No. 279552) and calcined hydrotalcite (Japanese Unexamined Patent Publication No. Hei 4-505449). A liquid detergent composition using a fatty acid polyoxyalkylene alkyl ether produced by the method described in JP-A-4-279552 (JP-A-5-202381,
JP-A-5-222396), those used in detergent compositions (JP-A-5-209191), and those used in high bulk density granular detergent compositions (JP-A-6-100887) are known. ing.

[0004] However, fatty acid polyoxyalkylene alkyl ethers synthesized with the above-mentioned catalysts have an extremely wide addition molar distribution of alkylene oxide, so that unreacted raw material esters remain and odors may cause the detergent composition to be degraded. It is difficult to put into practical use.

In order to overcome these disadvantages, a method for synthesizing a fatty acid polyoxyalkylene alkyl ether having a narrow addition molar distribution of an alkylene oxide has been disclosed in Japanese Patent Application Laid-Open No. H8-08258.
169860 and JP-A-8-169861. However, even with fatty acid polyoxyalkylene alkyl ethers having a narrow addition molar distribution of alkylene oxide synthesized by such a method, a peculiar off-odor remains, especially when mixed and stored in a liquid detergent composition. Occurred. Therefore, it is necessary to mask the activator odor by adding a fragrance, but it is difficult to mask the activator odor, and there is a problem that the fragrance changes during storage due to oxidation of the fragrance and the activator. .

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and has an excellent odor masking property of a fatty acid polyoxyalkylene alkyl ether having a narrower addition molar distribution of alkylene oxide than before, Moreover, an object of the present invention is to provide a liquid detergent composition having excellent aroma stability even after long-term storage.

[0007]

In order to solve the above-mentioned problems, the liquid detergent composition of the present invention comprises (A) a terminal-blocking nonionic interface represented by the following general formulas (I) and (II): At least one selected from activators, and (B) the following (a)
And a fragrance component including two or more groups selected from the group, (b) group, (c) group and (d) group.

R ¹ CO- (AO) _m- (EO) _n -OR ² (I)

[Wherein, R ¹ : a hydrocarbon group having 6 to 22 carbon atoms which may contain a substituent R ² : an alkyl group or an alkenyl group having 1 to 20 carbon atoms AO: an oxyalkylene group having 3 to 8 carbon atoms EO: oxyethylene group m: average addition mole number of alkylene oxide, 0 ≦ m ≦ 15 n: average addition mole number of ethylene oxide, 0 <n ≦ 40 m + n: 2 to 50 And it is essential that the additional molar distribution of EO satisfies the narrowness condition represented by the following equation (1).

[0010]

(Equation 3)

(Wherein, i: a positive integer, Y _i : an ethylene oxide adduct having an addition mole number of i (an ethylene oxide addition intermediate when m is not 0)
% By weight of _nmax : ethylene oxide adduct having the highest content (when m is not 0, ethylene oxide adduct)
Is the number of moles of addition, and represents a positive integer.)]

R ³ CO — [(AO) _s , (EO) _t ] —OR ⁴ (II)

[Wherein, R ³ : a hydrocarbon group having 6 to 22 carbon atoms which may contain a substituent R ⁴ : an alkyl group or an alkenyl group having 1 to 20 carbon atoms AO: an oxyalkylene group having 3 to 8 carbon atoms EO: oxyethylene group s: average addition mole number of alkylene oxide, 0 <s ≦ 15 t: average addition mole number of ethylene oxide, 0 <t ≦ 40 s + t: 2 to 50 And AO and EO are random additions, and it is essential that the mixed addition molar distribution of AO and EO satisfies the narrowness condition represented by the following equation (2).

[0014]

(Equation 4)

(Wherein, j: retention time (minutes) Y _j : weight% of the component having the retention time j v _max : retention time detected when the component having the largest content is subjected to high performance liquid chromatography (In minutes))]

Perfume component (a): a fragrance having an alcohol group having 1 to 20 carbon atoms (b) group: a fragrance having an aldehyde group having 1 to 20 carbon atoms (c) group: 3 to 20 carbon atoms (D) group: a fragrance having a lactone group having 4 to 25 carbon atoms

Further, the liquid detergent composition of the present invention preferably further contains an antioxidant.

Further, the liquid detergent composition of the present invention comprises:
It is preferable that the fatty acid alkyl ester content in the component (A) be 2% by weight or less.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION As the component (A) in the present invention, at least one selected from the terminal-blocking nonionic surfactants represented by the above general formulas (I) and (II) is used.

In the end-blocking nonionic surfactant represented by the above general formula (I), R ¹ is a hydrocarbon group having 6 to 22 carbon atoms, and has ^{1 to} 16 carbon atoms. Alkyl or alkenyl groups are particularly preferred. The hydrocarbon group R ¹ may be linear or branched, saturated or unsaturated, and may optionally contain a substituent such as a hydroxyl group. Among them, R ¹ is preferably a decyl group, a lauryl group, a myristyl group, a palmityl group, an oleyl group, an alkyl group derived from coconut fatty acid, or an alkyl group derived from tallow fatty acid.

R ² in the general formula (I) is an alkyl or alkenyl group having 1 to 20 carbon atoms,
It is preferably an alkyl or alkenyl group having 1 to 10 carbon atoms, particularly preferably an alkyl or alkenyl group having 1 to 4 carbon atoms. R ² may be linear or branched, and may be saturated or unsaturated. Among them, R ² is preferably a methyl group, an ethyl group, a propyl group, a butyl group or the like.

AO is at least one kind selected from oxyalkylene groups having 3 to 8 carbon atoms. In the case of two or more kinds, each may be divided into a plurality of blocks in the alkylene oxide block, or may be added at random. May be.
Further, from the viewpoint of detergency, foam performance and biodegradability, the number of carbon atoms is 3
As the oxyalkylene group having 8 to 8, an oxypropylene group or an oxybutylene group having 3 or 4 carbon atoms is particularly preferable.

The average addition mole number m of the alkylene oxide having 3 to 8 carbon atoms is in the range of 0 to 15, preferably in the range of 0 to 5;
A range of 5 is preferred. On the other hand, the average addition mole number n of ethylene oxide is in a range satisfying 0 <n ≦ 40, preferably in a range of 3 to 40, and more preferably in a range of 5 to 30. When the average number of added moles n exceeds 40, handling properties are reduced and biodegradability is also deteriorated. Further, m + n needs to be in the range of 2 to 50. When m + n is less than 2, many components to which ethylene oxide (or alkylene oxide and ethylene oxide) has not been added remain, which adversely affects detergency, rinsing properties and odor. Also,
If m + n exceeds 50, the handleability will deteriorate and the biodegradability will also deteriorate.

The terminal-blocking nonionic surfactant represented by the general formula (I) is essential that the addition molar distribution of ethylene oxide satisfies the narrowness condition represented by the above formula (1). However, the narrowness is more preferably 65% by weight or more, and particularly preferably 70% by weight or more. Formula (1) representing the above-mentioned narrowness is obtained from, for example, the case where the component having the largest content is an ethylene oxide addition (intermediate) body having an addition mole number of 9 (n _max = 9). Occupies 50% by weight or more of the whole (Y ₇ + Y ₈ + Y ₉ + Y ₁₀ + Y ₁₁ ≧ 50% by weight). This calculation does not include the weight of the component to which ethylene oxide is not added. That is, n _max is 1
Or 2, the narrowness equations are (Y ₁ + Y ₂ + Y
₃ ) and (Y ₁ + Y ₂ + Y ₃ + Y ₄ ).

Specific examples of the end-blocking nonionic surfactant represented by the general formula (I) are as follows. When m = 0, polyoxyethylene (7) methyl ether decanoate and polylaurate are exemplified. Oxyethylene (12) methyl ether, polyoxyethylene (9) ethyl laurate, polyoxyethylene (20) butyl ether laurate, polyoxyethylene (15) methyl ether myristate, polyoxyethylene palmitate (1)
8) Ethyl ether, coconut fatty acid polyoxyethylene (15) methyl ether, oleic acid polyoxyethylene (25) methyl ether, and the like, when m is not 0, examples of polyoxypropylene (2) polyoxyethylene decanoate ( 10) Methyl ether, polyoxypropylene (3) polyoxyethylene (5) methyl ether, laurate polyoxypropylene (3) polyoxyethylene (15) methyl ether, polyoxybutylene laurate (2) polyoxyethylene (10) Ethyl ether, polyoxypropylene laurate (5)
Polyoxyethylene (20) butyl ether, polyoxypropylene myristate (5) polyoxyethylene (10) methyl ether, polyoxybutylene palmitate (4) polyoxyethylene (18) ethyl ether, coconut fatty acid polyoxypropylene (2) Examples include, but are not limited to, polyoxyethylene (5) methyl ether, polyoxypropylene (7) polyoxyethylene (25) methyl ether oleate, and the like.

In the terminal-blocking nonionic surfactant represented by the general formula (II), R ³ is the same as R ¹ in the general formula (I), and R ⁴ is the same as R ¹ in the general formula (I).
^Same as ² . AO and EO are the same as AO and EO in the general formula (I), and s and t are the same as m and n in the general formula (I) except that s is not 0.

Further, in the terminal-blocking type nonionic surfactant represented by the general formula (II), it is essential that the final product satisfies the condition of narrowness represented by the above formula (2). The narrowness is more preferably 65% by weight or more, and particularly preferably 70% by weight or more. The expression (2) representing the narrowness is obtained when the component having the largest content is detected in a retention time of 10 minutes when the measurement is performed under the chromatographic conditions shown in the examples, and the retention time is from 6 minutes to 14 minutes. Means that the total amount of the components contained therein accounts for 50% by weight or more of the whole. However, if v _max is less than 4 minutes, the expression for the degree of narrowness is 0 min to v _max +
It shall represent the total amount of components having a retention time of up to 4 minutes.

The component (A), the terminal-blocking nonionic surfactant, may be synthesized or prepared by any method, and its production method is not particularly limited. It is preferable that ethylene oxide or ethylene oxide and alkylene oxide be addition-polymerized to the fatty acid alkyl ester.

As the catalyst to be used, a surface-modified composite metal oxide catalyst is exemplified. As the composite metal oxide catalyst, for example, first, a Mg compound obtained by calcining a compound represented by the following general formula (III) is used. —Al composite metal oxide.

AMgO.Al ₂ O ₃ .bH ₂ O (III)

The compound represented by the general formula (III) is alumina / magnesium hydroxide such as aluminum hydroxide / magnesium hydroxide coprecipitate. In the general formula (III), a and b are positive numbers and are not particularly limited, but a is 1 to 5, preferably 2 to 4, particularly preferably 2.2 to 2.
It is suitably 3.5 and b is 0-20, preferably 0-15, particularly preferably 0-12. Further, the calcination of the compound represented by the general formula (III) is 200 to 1000.
° C, preferably 300 to 950 ° C, particularly preferably 40 ° C.
The reaction is carried out at 0 to 800 ° C., and the calcination time is usually 30 to 400 minutes, preferably 30 to 300 minutes, particularly preferably 60 to 300 minutes.
~ 250 minutes. The reason for limiting the calcination temperature in this way is that if the temperature is lower than 200 ° C., the activity of the catalyst becomes insufficient. If the temperature is higher than 1000 ° C., the crystal structure changes, and the catalyst activity rapidly increases. It is because it falls to.

In particular, when alumina / magnesium hydroxide is used as the composite metal oxide, a large catalyst surface area can be obtained, and the reaction activity in the addition polymerization of ethylene oxide or ethylene oxide and alkylene oxide to the fatty acid alkyl ester. Is much higher than other composite metal oxides. That is, as a composite metal oxide,
The use of alumina / magnesium hydroxide is industrially advantageous because it allows a predetermined addition polymerization reaction to be efficiently achieved and the catalyst can be easily separated after the reaction.

Next, examples of the composite metal oxide catalyst include a metal ion-added magnesium oxide. Al ³⁺ , Ga ³⁺ , Zr
⁴⁺ , Ti4 ⁺ , In3 ⁺ , Tl3 ⁺ , Co3 ⁺ , Ni3 ⁺ , S
It is preferable to add one or more metal ions selected from the group consisting of c ³⁺ , La ³⁺ , Fe ³⁺ , Cu ²⁺ and Mn ²⁺ . The amount of metal ions added to the magnesium oxide is in the range of 0.1 to 40% by weight, preferably 0.5 to 20% by weight in the composite metal oxide.

A method for producing magnesium oxide with added metal ions is described in Japanese Patent Application Laid-Open No. 1-164437. However, as described below, the added metal ions are precipitated from an aqueous solution containing the added metal ions to form a metal. It is desirable to produce ionized magnesium oxide particles.

1) Impregnation method: MgO particles are added to an aqueous solution containing added metal ions such as an aqueous solution of aluminum nitrate, mixed, and then evaporated to dryness, crushed, and fired.
Obtain catalyst particles.

2) Coprecipitation method: A magnesium salt aqueous solution such as an aqueous solution of magnesium nitrate is mixed with an aqueous solution containing added metal ions such as an aqueous solution of aluminum nitrate, and a precipitant such as ammonia is added thereto. And the added metal are simultaneously precipitated as hydroxide, and the catalyst particles are produced by filtration → drying → pulverization → calcination.

3) Deposition method: An aqueous solution containing added metal ions is added to a dispersion in which magnesium oxide particles are dispersed,
A hydroxide of the added metal is precipitated and deposited on the surface of the magnesium oxide particles, and is filtered, dried and fired.

When the catalyst is produced by a precipitation method such as the above-mentioned coprecipitation method or deposition method, unnecessary anions present in the catalyst slurry after the precipitation treatment can be removed with an ion exchange resin, whereby the filtration can be carried out. The subsequent washing step can be omitted or simplified. The firing treatment can be performed in the same manner as in the case of the Mg-Al composite metal oxide.

The composite metal oxide catalyst further includes a calcined product of hydrotalcite represented by the following general formula (IV).

[Mg 2 ⁺ _{1 -x} Al ³⁺ _x (OH) ₂ ] ^{x +} [(A ^p− ) _{x / p} · qH ₂ O] ^x− (IV)

In the above general formula (IV), A ^{p-
_{O 3 2-, SO 4 2-,}} OH -, NO 3 -, Fe (CN) 6 3- or C
H ₃ COO ^- is. x is a positive number and is not particularly limited, but is usually 0 <x ≦ 0.33, preferably 0.25 ≦
Let x ≦ 0.3. Although not particularly limited, p is 1
-5, preferably 2-4, particularly preferably 2.2-3.
Suitably, q is 0 to 10, preferably 0.
To 8, particularly preferably 0 to 5. Hydrotalcite may be a natural product or a synthetic product prepared by coprecipitation or the like. The firing treatment can be performed in the same manner as in the case of the Mg-Al composite metal oxide.

The above-mentioned composite metal oxide catalyst is surface-modified with a metal hydroxide to obtain a modified composite metal oxide catalyst. By performing the surface modification in this way, in the production of the component (A), the added molar distribution of ethylene oxide or the mixed added molar distribution of ethylene oxide and alkylene oxide is narrowed to improve the quality, and the residual amount is not improved. The amount of the reactive fatty acid alkyl ester can be reduced.

A method for modifying a composite metal oxide is disclosed in
No. 169861. More specifically, a method in which the composite metal oxide is modified with a metal hydroxide and / or metal alkoxide of an alkali metal or an alkaline earth metal and then used as a reaction catalyst, In the above, the composite metal oxide and the metal hydroxide and / or metal alkoxide are mixed with the raw material fatty acid alkyl ester, and the surface of the composite metal oxide is modified in the reaction system. Or a method in which ethylene oxide and alkylene oxide are added to carry out the reaction. The former method is not particularly limited, but after spraying an aqueous solution or alcohol solution of metal hydroxide and / or metal alkoxide on the composite metal oxide,
Drying or baking is preferred. In the latter method, the order of adding the composite metal oxide and the metal hydroxide and / or metal alkoxide to the fatty acid alkyl ester as the raw material does not need to be particularly limited. At this time, it is also preferable to add a metal hydroxide and / or a metal alkoxide as a lower alcohol solution from the viewpoint of more uniformly and more selectively partially poisoning the acid surface of the catalyst.

The metal hydroxide is preferably a hydroxide of an alkali metal such as sodium hydroxide or potassium hydroxide, or a hydroxide of an alkaline earth metal such as calcium hydroxide or magnesium hydroxide. As the metal alkoxide, alkoxides of alkali metals such as sodium alkoxide and potassium alkoxide, and alkoxides of alkaline earth metals such as magnesium alkoxide are preferable. still,
The amount of the metal hydroxide and / or metal alkoxide used for modifying the composite metal oxide is in the range of 0.5 to 10% by weight, preferably 1 to 5% by weight based on the composite metal oxide. Is appropriate. Thus, the metal hydroxide and / or
The reason for limiting the amount of the metal alkoxide is that if the amount is less than 0.5% by weight, a sufficient reforming effect cannot be obtained. If the amount is more than 10% by weight, the catalytic activity is inhibited,
After all, sufficient activity cannot be obtained.

The starting materials used for producing the component (A) in the direct insertion reaction are fatty acid alkyl esters and ethylene oxide (or ethylene oxide and alkylene oxide). The fatty acid alkyl ester may be one kind or a mixture of two or more kinds.

The alkoxylation reaction in the method for producing the component (A) can be easily carried out under ordinary operating means and reaction conditions.

The reaction temperature in the alkoxylation reaction is in the range of 80 to 230 ° C., preferably 120 to 200 ° C., particularly preferably 120 to 180 ° C. The reason for defining the temperature in this manner is that if the temperature is lower than 80 ° C., the catalyst shows little activity, and if the temperature is higher than 230 ° C., an expensive apparatus is required, and the colored or reacted alkylene oxide chain is required. This is because decomposition occurs. The reaction pressure is
Usually, the pressure is suitably 0 to 20 atm, preferably 2 to 8 atm, particularly preferably 2 to 6 atm. The reason why the air pressure is defined in this way is that if it is higher than 20 atm, it is difficult to ensure safety.

The amount of the catalyst used is in the range of 0.01 to 20% by weight, preferably 0.05 to 10% by weight, particularly preferably 0.1 to 5% by weight, based on the fatty acid alkyl ester. Is appropriate. The reason for limiting the use amount in this way is that if the amount is less than 0.01% by weight, it takes a long time until the reaction is completed. If the amount is more than 20% by weight, the heat removal ability of the apparatus exceeds the limit. This is because it becomes difficult to maintain the reaction temperature or the product loss increases when the catalyst is removed after the reaction.

As an example of the method for producing the component (A), a fatty acid alkyl ester and a modified composite metal oxide catalyst are charged into an autoclave, degassed and dehydrated, and then subjected to a nitrogen atmosphere at a predetermined temperature and temperature. The reaction is carried out under pressure conditions by introducing ethylene oxide or ethylene oxide and alkylene oxide. The method of separating the catalyst is not particularly limited, but after the reaction is completed, after cooling the reaction product, for example, water is added to reduce the viscosity, and a diatomaceous earth, a cellulose resin, a filter aid such as activated clay is added. And a method of filtering off the catalyst.

In the case of the direct insertion reaction using a catalyst as described above, the end-blocking nonionic surfactant represented by the above general formula (I) (when m = 0) can be obtained by using only ethylene oxide. When ethylene oxide is added to the obtained fatty acid alkyl ester and then alkylene oxide having 3 to 8 carbon atoms is added, the end-blocking nonionic surfactant represented by the above general formula (I) (m is not 0) Case) is obtained. On the other hand, if ethylene oxide and alkylene oxide having 3 to 8 carbon atoms are mixed in advance and added to the fatty acid alkyl ester, the end-blocking nonionic surfactant represented by the above general formula (II) can be obtained. .

When the component (A) in the present invention satisfies the above-mentioned narrowness condition, not only the detergency and the foaming performance are remarkably improved, but also the unreacted unreacted components remaining when a direct insertion reaction is carried out. Odors derived from fatty acid alkyl esters are reduced. In the present invention, the content of the unreacted fatty acid alkyl ester in the component (A) is preferably 2% by weight or less, more preferably 1% by weight or less.

When a direct insertion reaction is carried out using the above-mentioned catalyst, the product contains about 0.3 to 5% by weight of polyalkylene glycol (weight average molecular weight of tens of thousands to hundreds of thousands). Polyethylene glycol includes polyethylene glycol when ethylene oxide is added, and polyoxyethylene polyoxyalkylene copolymer when ethylene oxide and alkylene oxide are added. In the case of the cleaning composition of the present invention, the content of the polyalkylene glycol is preferably 3% by weight or less, more preferably 2% by weight or less, and particularly preferably 0.1 to 2% by weight. preferable.
The removal of polyalkylene glycol is described in JP-A-9-262.
By performing filtration by the method described in Japanese Patent Application Publication No. 456 or the method described in Japanese Patent Application Laid-Open No. 10-7620, the amount can be reduced to a predetermined amount.

In the present invention, the component (A) may be used alone or in combination of two or more. The compounding amount varies depending on the use (such as a detergent for clothing or a detergent for hard surface), but is in the range of 0.1 to 50% by weight, preferably 0.1 to 30% by weight in the liquid detergent composition. It is. If the amount is less than 0.1% by weight, the detergency is insufficient, while if it exceeds 50% by weight, the viscosity of the composition increases, which is not preferable in terms of usability.

As the component (B) in the present invention, a mixed fragrance containing at least two groups selected from the above groups (a) to (d) is used. Specific examples of the fragrances of the groups (a) to (d) are shown below.

Group (a): As fragrances having an alcohol group having 1 to 20 carbon atoms, cis-3-hexenol, linalool, tetrahydrolinalool, terpineol, geraniol, citronellol, rhosinol, nerol,
Borneol, anethole, guaiacol, dimethyloctanol, lavandulol, mugol, myrcenol, dihydromyrcenol, menthol, mayol,
Farnesol, nerolidol, santalol, sandalore, cedrol, bacdanol, santalinol,
Octanol, Nonanol, Vetiverol, Benzyl Alcohol, β-Phenylethyl Alcohol, Synthetic Alcohol, Anis Alcohol, Dimethylbenzyl Carbinol, Isocamphyl Cyclohexanol, Ambrinol, Phenol, p-Ethylphenol, Cavicol, Thymol, Carvacrol, Hinokitiol, 2,6-dimethoxyphenol, cresol, eugenol, isoeugenol, banitrop, shogaol, zingeol, zingerone, raspberry ketone, oak moss no. 1, methyl salicylate, ethyl salicylate, butyl salicylate, isobutyl salicylate, amyl salicylate, isoamyl salicylate, hexyl salicylate, cis-3-hexenyl salicylate, cyclohexyl salicylate, phenyl salicylate, benzyl salicylate, phenylethyl salicylate, p-cresyl salicylate, etc. No.

Group (b): As the fragrance having an aldehyde group having 1 to 20 carbon atoms, citral, cinamic aldehyde, cyclocitral, safranal, myrtenal, tripral, cis-3-hexenal, α-methylcinnamic aldehyde , Α-amylcinnamic aldehyde, α-hexyl cinnamic aldehyde, trans-2-decenal, 2,6-nonadienal, trans-2-undecenal, trans-2-dodecenal, trans-2-tridecenal, 2,4-decadienal 2,4-undecadienal, trimethyldecadienal, o-methoxycinnamaldehyde, furfural, 5-methylfurfural, 5-hydroxymethyl-2-furfural, furylacrolein, α-
Methylene citronellal, octanal, nonanal,
Decenal, undecylaldehyde, undecylenaldehyde, dodecylaldehyde, citronellal, phenylacetaldehyde, helional, cyclamenaldehyde, liliar, liral, burgeonal, perilaldehyde, cuminaldehyde, benzaldehyde,
Examples include vanillin, ethyl vanillin, heliotropin, salicylaldehyde, anisaldehyde, o-methoxybenzaldehyde, formylethyltetramethyltetralin and the like.

Group (c): As fragrances having a ketone group having 3 to 20 carbon atoms, damasenone, damascon, isodamascon, α-dynascon, trimethylcyclohexenylbutene, yonone, methylyonone, pseudoyonone, iron, cashmere, carvone, Plegon, piperiton, piperitenone, diosphenol, acetylsedren, iso-E super, nootkatone, benzylideneacetone, acetylfuran, furaneol, sotolone, maltol, ethyl maltol, cis jasmon, isojasmon, vitalide, acetophenone, methyl naphthyl ketone, benzophenone, Propiophenone, methylacetophenone, p-methoxyacetophenone, musk ketone, phantolide, celestride, traseolide, tonalide, muscone, Beton, cyclopentadecanone,
Examples include dihydrocibetone, cyclohexadecenone, oxahex-2-one, and the like.

Group (d): Perfumes having a lactone group having 4 to 25 carbon atoms include γ-undecalactone, γ-nonalactone, γ-valerolactone, γ-hexalactone,
γ-octalactone, γ-decalactone, γ-dodecalactone, methyl-γ-decalactone, δ-hexalactone, δ-octalactone, δ-nonalactone, δ-decalactone, δ-undecalactone, δ-dodecalactone, coumarin , Lactoscatone, ambrettolide, cyclopentadecanolide, isoambrettolide, cyclohexadecanolide, 10-oxahexadecanolide, 1
1-oxahexadecanolide, 12-oxahexadecanolide, ethylene brassate, ethylene dodecandioate, jasmine lactone, butylphthalide, 14-
Methyl-hexadecenolide, 14-methylhexadecanolide and the like can be mentioned.

Natural fragrances containing the components of (a) to (d) also have a base odor masking effect, and thus fall under the component (B) in the present invention. For example, bergamot oil, bowed rose oil, lavender oil, linalool in rose oil, rose oil, citronellol in rose absolute, geraniol, β-phenylethyl alcohol, clove oil, clove leaf oil, pimenta oil, eugenol in bay oil, thyme Phenol, thymol, carvacrol in oil, perilaldehyde in perilla oil, lemon oil, lysacubeva oil, lime oil,
Citral in lemongrass oil, orange oil, vanilla, jasmine absolute in vanilla absolute, cis jasmon, carvone, cassia oil in spearmint oil, cinnamaldehyde in cinnamon oil, methyl salicylate in wintergreen oil, shogaol in ginger oil, zingeol , Zingerone, carvone in caraway oil,
Okemos No. in Okemos Absolute 1
And the like.

In the component (B), the mixing ratio of the groups (a) to (d) is such that the total amount of the two or more groups in the groups (a) to (d) is at least 5% by weight, preferably 10% by weight. that's all,
It is more preferably at least 30% by weight. It is particularly preferable to use three or more groups. 2 in group (a) to (d)
When the total amount of the group or more is less than 5% by weight, the odor masking property and odor stability of the specific end-blocked nonionic surfactant are not sufficient. The type used is (a) to
In the case of only one of the groups (d), the quality of the fragrance is not sufficient, so that the specific odor-blocking nonionic surfactant has poor odor masking properties. In the present invention, the meaning of “including two or more groups” means (a) to
(D) It means that the group having the second highest content ratio among the groups is at least 5% by weight or more with respect to the group having the highest content ratio.

As the fragrances other than the groups (a) to (d), natural fragrances include Ryuensho, Castorium, Avies oil, Angelica oil, Anise oil, Balsam copaiba oil, Peruvian balsam oil, Basil oil, Camomil oil, Elemi Oil, eucalyptus oil, galvanum oil, hop oil, hyacinth absolute, john kill absolute, juniper berry oil, mill oil, nutmeg oil, olibanum oil, opponax oil, turpentine oil, violet absolute,
Wormwood oil and the like.

Further, in synthetic flavors and isolated flavors, hydrocarbons such as limonene, β-caryophyllene, α-pinene, β-pinene, orange terpene, camphene, terpinolene, allocymene, ocimene, isoparaffin, p-cymene, and linalyl Acetate, dimethylbenzylcarbinyl acetate, methyldihydrojasmonate,
pt-butylcyclohexyl acetate, ot-butylcyclohexyl acetate, benzyl acetate,
Benzyl benzoate, citronellyl acetate, phenylethyl isobutyrate, geranyl acetate, neryl acetate, bornyl acetate, cis-3-hexenyl acetate, geranyl formate, citronellyl formate, ceryl acetate, terpinyl acetate, cinnamyl Acetate, eugenyl acetate,
β-phenylethyl acetate, anisyl formate, hexyl acetate, octenyl acetate, diacetyl, myrcenyl acetate, lavandulyl acetate, nerolidyl acetate, menthyl acetate,
Nopyr acetate, vetiveryl acetate, guayre acetate, rosamsk, tricyclodecenyl acetate, linalyl propionate, geranyl propionate, neryl propionate, bornyl propionate,
Benzyl propionate, styryl acetate, styryl propionate, cinnamyl propionate, phenoxyethyl propionate, cis-3-hexenyl butyrate, linalyl butyrate, geranyl butyrate, neryl butyrate, cyclohexyl butyrate , Esters such as benzyl butyrate, terpinyl butyrate, cinnamyl butyrate, ambroxane, rose oxide, nerol oxide, linalool oxide, diphenyl ether, glycalva, cineole, mentfuran, rose furan, yayala, nerolin bromelia , Ethers and oxides such as galaxolide, dihydroindenyl-2,4-dioxane, formaldehyde cyclododecylethyl acetal, acetaldehyde dimethyl acetal, Acetaldehyde diethyl acetal, acetaldehyde ethyl hexenyl acetal,
Magnolan, hexanol diethyl acetal, citral dimethyl acetal, citral diethyl acetal, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde diethyl acetal, amyl cinnamaldehyde dimethyl acetal, amyl cinamic aldehyde diethyl acetal, heliotropin dimethyl acetal, heliotropin diethyl acetal, vanillin, Propylene glycol acetal, acetyl acetoacetate ethylene glycol ketal,
Ethyl acetoacetate propylene glycol acetal, jasmonan, verdoxan, amber sage,
Acetals and ketals such as 2,5,5-trimethyl-2-phenyl-1,3-dioxane, indolene, ethyl anthranilate, butyl anthranilate, phenylethyl anthranilate, cinnamyl anthranilate, orlanchi Schiff bases such as oar, ligantral, heliotropyl anthranilate, α-amylcinnamic aldehyde-methyl anthranilate, acids such as acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, indole, skatole And 6-methylquinoline, isobutylquinoline, tetramethylpyrazine, geranyl nitrile, citronellyl nitrile, nitrogen compounds such as methyl anthranilate and dimethyl anthranilate.

The amount of the component (B) is in the range of 0.001 to 2% by weight, preferably 0.1 to 2% by weight in the liquid detergent composition.
The range is from 01 to 1% by weight. When the amount of the component (B) is less than 0.001% by weight, the effect of masking the odor of the specific end-blocking nonionic surfactant is insufficient, while when it exceeds 2% by weight, the masking property is sufficient. However, there is a problem in that the fragrance is too strong, giving unpleasant sensation during use and impairing the commercial value.

In the present invention, an antioxidant can be further added to improve the aroma stability of the liquid detergent composition. As antioxidants, dibutylhydroxytoluene, butylhydroxyanisole, parahydroxyanisole, propyl gallate, octyl gallate,
Erythorbic acid and its salts, ascorbic acid and its salts, dl-α-tocopherol, orthotolylbiguanide, dilauryl thiodipropionate, and the like.
These antioxidants may be used alone or in combination of two or more. Among these, the preferred antioxidant in the present invention is dibutylhydroxytoluene.

The content of the antioxidant is in the range of 0.0001 to 1% by weight, preferably 0.001 to 0.3% by weight in the liquid detergent composition. If the amount is less than 0.0001% by weight, the aroma stability is insufficient.
On the other hand, if it exceeds 1% by weight, not only is it economically unfavorable, but also the stability of the composition deteriorates, which is not preferable.

The liquid detergent composition of the present invention may optionally contain the following optional components as long as the effects of the present invention are not impaired.

Such optional components include anionic surfactants, cationic surfactants, amphoteric surfactants,
Other than the component (A), nonionic surfactants, chelating agents, ultraviolet absorbers, preservatives, solvents such as ethanol and isopropanol, and the like can be mentioned.

The method for producing the liquid detergent composition of the present invention is not particularly limited, but citric acid, sodium citrate, sulfuric acid, sodium hydroxide, alkanolamine and the like can be used as a pH adjusting agent for adjusting the pH. .

The liquid detergent composition of the present invention is used as a detergent for clothes or a detergent for hard surfaces such as toilets, bathrooms, floors, glass and plastics.

[0070]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples, “%” is “% by weight”.

A production example of the terminal-blocking nonionic surfactant used in the examples is shown below.

Production Example 1 Alumina / magnesium hydroxide having a chemical composition of 2.5 MgO.Al ₂ O ₃ .nH ₂ O (manufactured by Kyowa Chemical Industry Co., Ltd.)
25 g of Kyoward 300) were fired at 700 ° C. for 3 hours in a nitrogen atmosphere to obtain 14 g of fired alumina / magnesium hydroxide. 1.2 g of a calcined alumina / magnesium hydroxide (unmodified) catalyst, 1.3 g of a 5% methanol solution of potassium hydroxide, and 350 g of methyl laurate in 4 parts
A liter autoclave was charged, and the catalyst was reformed in the autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, and the temperature was set to 180 ° C. and the pressure was set to 3
While maintaining atm, 648 g of ethylene oxide was introduced and reacted with stirring. The resulting polyoxyethylene methyl ether laurate had an average ethylene oxide addition mole number of 9.0, a narrowness of 70%, and a polyethylene glycol content of 0.5%. Further, the reaction solution was cooled to 80 ° C., and 120 g of water and 5 g each of activated clay and diatomaceous earth were added as filter aids, and then the catalyst was separated by filtration. The content of polyethylene glycol after filtration was 0.2% or less. This was designated as Sample A, and the results are shown in Tables 1 and 2. The narrowness was calculated by measuring the molar distribution of ethylene oxide addition of the obtained polyoxyethylene methyl ether laurate. The ethylene oxide addition molar distribution, unreacted fatty acid ester content, polyethylene glycol (PEG) content and weight average molecular weight were measured by the following methods.

(Method of Measuring Ethylene Oxide Addition Molar Distribution and Unreacted Fatty Acid Ester Amount) High-performance liquid chromatography was performed under the following conditions to determine ethylene oxide addition molar distribution and unreacted fatty acid ester content. Apparatus: LC-6A (manufactured by Shimadzu Corporation) Detector: SPD-10A (manufactured by Shimadzu Corporation) Measurement wavelength: 220 nm Column: Zorbax C8 (4.6 mm in diameter x 0.25 m in length; Du Pont ( Mobile phase: acetonitrile / water = 60/40 (volume ratio) Flow rate: 1 mL / min Temperature: 20 ° C.

(Method of measuring PEG content) Gel filtration chromatography was performed under the following conditions to determine the PEG content. Apparatus: LC-6A (manufactured by Shimadzu Corporation) Detector: RID-6A (manufactured by Shimadzu Corporation) Column: Asahi Pack GS-310 (7.6 mm in diameter)
× length 0.5 m; manufactured by Showa Denko KK Mobile phase: acetonitrile / water = 45/55 (volume ratio) Flow rate: 1 mL / min Temperature: 30 ° C.

(Method for measuring weight average molecular weight of PEG) Gel filtration chromatography was performed under the following conditions,
Was determined. Apparatus: LC-6A (manufactured by Shimadzu Corporation) Detector: RID-10A (manufactured by Shimadzu Corporation) Column: Asahi Pack GF-510HQ (diameter 7.6)
mm × length 0.3 m; manufactured by Showa Denko KK Mobile phase: water Flow rate: 1 mL / min Temperature: 30 ° C.

Production Example 2 1.2 g of the calcined alumina / magnesium hydroxide (unmodified) catalyst obtained in Production Example 1, 0.12 g of a 40% aqueous potassium hydroxide solution, and 350 g of methyl myristate were placed in a 4-liter autoclave. The charge and the reforming of the catalyst were performed in an autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, the temperature was set to 180 ° C., and the pressure was set to 3a.
While maintaining the temperature at tm, 956 g of ethylene oxide was introduced and reacted with stirring. The average number of moles of ethylene oxide added to the obtained myristic acid polyoxyethylene methyl ether was 15.0, the narrowness was 65%, and the content of polyethylene glycol was 1.5%. Furthermore,
When the catalyst was separated by filtration in the same manner as in Sample A, the content of polyethylene glycol after filtration was 0.2% or less. This was designated as Sample B, and the results are shown in Tables 1 and 2.

Production Example 3 The above-mentioned alumina / magnesium hydroxide (Kyoward 3)
00) in a nitrogen atmosphere at 600 ° C. for 1 hour, 2.2 g of a calcined alumina / magnesium hydroxide (unmodified) catalyst, 2.9 mL of 0.5 N potassium hydroxide in ethanol, and laurin 350 g of methyl acid was charged into a 4-liter autoclave, and the catalyst was reformed in the autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, the temperature was set to 180 ° C., and the pressure was set to 3 atm.
, 1440 g of ethylene oxide was introduced and reacted while stirring. The resulting polyoxyethylene methyl ether laurate had an average ethylene oxide addition mole number of 20.0, a narrowness of 65%, and a polyethylene glycol content of 2.0%. Further, when the catalyst was separated by filtration in the same manner as in Sample A, the content of polyethylene glycol after filtration was 0.2% or less. This was designated as Sample C, and the results are shown in Tables 1 and 2.

Production Example 4 1.4 g of the calcined alumina / magnesium hydroxide (unmodified) catalyst obtained in Production Example 1, 0.14 g of a 40% aqueous potassium hydroxide solution, and 350 g of methyl laurate were placed in a 4-liter autoclave. The charge and the reforming of the catalyst were performed in an autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, the temperature was set to 180 ° C., and the pressure was set to 3 at.
m, while introducing 720 g of ethylene oxide, and reacted while stirring. When a small amount of this intermediate was extracted and analyzed, the average number of moles of ethylene oxide added was 10.0 and the narrowness was 70%. Subsequently, 95 g of propylene oxide was introduced and reacted while stirring. The average propylene oxide addition mole number of the obtained polyoxypropylene polyoxyethylene methyl ether laurate was 1.0, and the content of polyalkylene glycol was 1.1%. Further, when the catalyst was separated by filtration in the same manner as in Sample A, the content of polyalkylene glycol after filtration was 0.2% or less. This was designated as Sample D, and the results are shown in Tables 1 and 2. The narrowness was calculated by measuring the ethylene oxide addition molar distribution of the ethylene oxide addition intermediate in lauric acid polyoxypropylene polyoxyethylene methyl ether as described above. The ethylene oxide addition molar distribution and unreacted fatty acid ester content were calculated by performing the same high performance liquid chromatography measurement as in Production Example 1, and the content of polyalkylene glycol (PAG) was determined by gel filtration chromatography as in Production Example 1. It was calculated by performing measurements.

Production Example 5 1.4 g of the calcined alumina / magnesium hydroxide (unmodified) catalyst obtained in Production Example 1, 0.14 g of a 40% aqueous potassium hydroxide solution, and 350 g of methyl laurate were placed in a 4-liter autoclave. The charge and the reforming of the catalyst were performed in an autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, the temperature was set to 180 ° C., and the pressure was set to 3 at.
m, a mixture of 1080 g of ethylene oxide and 190 g of propylene oxide, which had been mixed in advance, was introduced and reacted while stirring. The obtained polyoxypropylene polyoxyethylene methyl ether laurate is obtained by random polymerization of ethylene oxide and propylene oxide, and has an average propylene oxide addition mole number of 2.0 and an average ethylene oxide addition mole number of 15.0. The narrowness was 65% and the content of polyalkylene glycol was 1.7%. Further, when the catalyst was separated by filtration in the same manner as in Sample A, the content of polyalkylene glycol after filtration was 0.2% or less. This was designated as Sample E, and the results are shown in Tables 1 and 2. The narrowness was calculated from the obtained polyoxypropylene polyoxyethylene methyl ether laurate by the same high performance liquid chromatography measurement as in Production Example 1 and according to the above mathematical formula (2).

Production Example 6 A 4-liter autoclave was charged with 11 g of an Al ion-added MgO catalyst and 350 g of methyl laurate prepared according to the method described in JP-A-4-279552, and the inside of the autoclave was replaced with nitrogen. 648 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure at 3 atm, and reacted while stirring. The average number of moles of ethylene oxide added to the obtained polyoxyethylene methyl ether laurate is 9.0, the narrowness is 35%, and the content of polyethylene glycol is 0.4%.
Met. This was designated as Sample F, and the results are shown in Tables 1 and 2.
Shown in

[0081]

Table 1 Structural formula Narrowness sample A C ₁₁ H ₂₃ CO (EO) ₉ OCH ₃ 70% Sample B C ₁₃ H ₂₇ CO (EO) ₁₅ OCH ₃ 65% Sample C C ₁₁ H ₂₃ CO (EO) ₂₀ OCH ₃ 65% sample _{D C 11 H 23 CO (PO} ) (EO) 10 OCH 3 70% sample _{E C 11 H 23 CO [(} PO) 2, (EO) 15] OCH 3 65% sample F C ₁₁ H ₂₃ CO (EO) ₉ OCH ₃ 35% PO stands for propylene oxide, and EO stands for ethylene oxide.

[0082]

Table 2 Fatty acid ester content PAG (PEG) content PEG molecular weight Sample A 0% 0.2% or less About 70,000 Sample B 0% 0.2% or less About 80,000 Sample C 0% 0.2% or less About 100,000 Sample D 0 % 0.2% or less-Sample E 0% 0.2% or less- Sample F 3% 0.4% Approx. 70000 PAG (PEG) molecular weight refers to weight average molecular weight

Examples of prescriptions of the fragrances of the groups (a) to (d) used in the examples are shown below, but are not limited thereto.

(A) Fragrance linalool 10% citronellol 15% geraniol 10% nerol 5% terpineol 8% cis-3-hexenol 2% dihydromyrcenol 5% tetrahydrolinalool 5% β-phenylethyl alcohol 10% cedrol 3% Santalinol 5% Bakdanol 8% Sandalore 4% Isocampyl cyclohexanol 10%

(B) Fragrance octane 1% Nonanal 1% Decenal 2% Lilyal 30% Anisaldehyde 10% Heliotropin 6% Lillal 10% α-Hexylcinnamic aldehyde 35% Cyclamenaldehyde 5%

(C) Fragrance Methyl Ionone 20% Iso E Super 10% Acetyl Cedrene 35% Kashmeran 5% Damascon 5% Damacenone 5% Tonalide 5% Cyclohexadecenone 15%

(D) Group perfume γ-undecalactone 8% Coumarin 15% γ-nonalactone 5% Cyclopentadecanolide 12% Ethylene dodecandioate 10% Ethylene brush rate 50%

Other fragrances Linalyl acetate 7% Dimethylbenzylcarbinyl acetate 15% Methyl dihydrojasmonate 15% pt-butylcyclohexyl acetate 8% ot-butylcyclohexyl acetate 5% Orange terpene 9.5% α- Pinene 5% Benzyl acetate 3% Benzyl benzoate 10% Citronellyl acetate 5% Rose oxide 2% Phenylethyl isobutyrate 7% Ambroxane 0.5% Galaxolide 8%

Examples 1 to 24 and Comparative Examples 1 to 12 The liquid detergent compositions shown in Tables 3 to 5 were adjusted to pH 7,
The odor masking property and odor stability of the specific end-blocking nonionic surfactant were evaluated by the following test methods. The test methods were as follows: samples were made of resin bottles and refillable thin bottles (made of polyethylene, polyethylene terephthalate, polypropylene, polypropylene / polyethylene), and refillable bags (made of nylon / polyethylene, polyethylene terephthalate / aluminum / nylon /
Sealed and stored in various containers of polyethylene, nylon / polypropylene / aluminum / polyethylene, nylon / aluminum / polyethylene, polyethylene terephthalate / nylon / polyethylene, nylon / polypropylene / polyethylene), and mask the odor of specific end-blocking nonionic surfactants The degree of change in the odor and the odor stability was evaluated as follows. The results are shown in Tables 3 to 5.

(Evaluation of Odor Masking Ability of Specific Nonblocking Nonionic Surfactant) The initial product was evaluated by 10 panelists specializing in odor determination according to the following evaluation criteria. In addition, the evaluation result showed the average value of various containers. A: Almost no odor of the specific terminal-blocking nonionic surfactant was observed. ：: Smell of a specific end-blocking nonionic surfactant was slightly observed. Δ: Odor of a specific terminal-blocking nonionic surfactant was observed. X: The odor of the specific end-blocking nonionic surfactant is considerably recognized.

(Evaluation of Aroma Stability) A product stored in a refrigerator at 5 ° C. for 30 days was used as a standard product, and a product stored in a thermostat at 50 ° C. for 30 days was used as a panel.
The evaluation was made according to the following evaluation criteria. In addition, the evaluation result showed the average value of various containers. 5: Little change is recognized as compared with the standard product. 4: Slight change is recognized as compared with the standard product. 3: Change is recognized as compared with the standard product. 2: A considerable change is recognized as compared with the standard product. 1: A change is remarkably recognized as compared with the standard product.

[0092]

[Table 3]

[0093]

[Table 4]

[0094]

[Table 5]

From the results of Tables 3 to 5, the liquid detergent compositions of the present invention (Examples 1 to 12) are excellent in the odor masking property and the odor stability of the specific end-blocking nonionic surfactant. Furthermore, the liquid detergent compositions of the present invention containing an antioxidant (Examples 13 to 24) have better fragrance stability. However, when the essential components in the present invention are missing (Comparative Examples 1 to 12), it can be seen that the specific odor-blocking nonionic surfactant has poor odor masking properties and odor stability.

Example 25 A liquid detergent composition for clothing having the following composition was prepared, and the odor masking property and the odor stability of the specific end-blocking nonionic surfactant were evaluated by the above method. Was also excellent.

(Liquid detergent component for clothing) Sample B 15% Specific fragrance ^{* 1} 0.3% AES ^{* 2} 15% Oleic acid 4.5% Sodium toluenesulfonate 5% Citric acid 2% Ethanol 5% Polyethylene glycol (Weight average molecular weight 1000) 1% Dibutylhydroxytoluene 0.03% Caisson CG ^{* 3} 0.01% Sodium hydroxide Appropriate amount (adjusted to pH 7) Purified water Balance

* 1: Group (a): Group (b): Group (c):
(D) group: other fragrance = 30: 25: 15: 5: 25
(Weight ratio) * 2: Sodium polyoxyethylene alkyl (C13) ether sulfate (average number of moles of ethylene oxide added = 3) * 3: Mixed solution of methylchloroisothiazolineon, methylisothiazolineon, magnesium salt, and water

Example 26 A liquid detergent composition for residential use having the following composition was prepared, and the odor masking property and the odor stability of a specific end-blocked nonionic surfactant were evaluated by the above method. Was also excellent.

(Detergent liquid detergent component) Sample D 0.2% Specific fragrance ^{* 4} 0.1% AES ^{* 5} 0.3% Butyl carbitol 2% Ethanol 2% Monoethanolamine Appropriate amount (adjusted to pH 8) Purified water balance

* 4: Group (a): Group (b): Group (c):
(D) group: other fragrance = 35: 15: 15: 5: 30
(Weight ratio) * 5: polyoxyethylene alkyl (C12 to C1)
3) Sodium ether sulfate (average number of moles of ethylene oxide added = 5)

[0102]

Industrial Applicability The liquid detergent composition of the present invention is one in which the specific end-blocking nonionic surfactant has excellent odor masking properties and odor stability.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Meiko Sakaki 3-7-7 Honjo, Sumida-ku, Tokyo Lion F-term (reference) 4H003 AB31 AC12 AC23 BA12 DA01 DA04 DA05 DA06 DA08 DA12 EB03 EB07 EB08 EB22 EB36 ED02 ED28 FA15 FA16 FA25 FA26 FA28

Claims (3)

[Claims] (A) one or more selected from end-blocking nonionic surfactants represented by the following general formulas (I) and (II), and (B) the following (a) group: (B) group,
A liquid detergent composition comprising a fragrance component containing at least two groups selected from the group (c) and the group (d). R ¹ CO— (AO) _m — (EO) _n —OR ² (I) wherein R ^{1 is} a hydrocarbon group having 6 to 22 carbon atoms which may contain a substituent R ² : a hydrocarbon group having 1 to 20 carbon atoms Alkyl or alkenyl group AO: at least one selected from oxyalkylene groups having 3 to 8 carbon atoms EO: oxyethylene group m: average addition mole number of alkylene oxide, 0 ≦ m ≦ 15 n: average of ethylene oxide It is an additional mole number, and 0 <n ≦ 40 m + n: a number of 2 to 50, and it is essential that the additional mole distribution of EO satisfies the narrowness condition represented by the following formula (1). (Equation 1) (Wherein, i: a positive integer, Y _i : an ethylene oxide adduct having an addition mole number of i (an ethylene oxide addition intermediate when m is not 0)
% By weight of _nmax : ethylene oxide adduct having the highest content (when m is not 0, ethylene oxide adduct)
A of addition mole number, positive represents an ^{integer)] R 3 CO - [(} AO) s, (EO) t] -OR 4 (II) [ wherein, R ^3: carbon atoms, which may contain a substituent 6 to 22 hydrocarbon groups R ⁴ : alkyl or alkenyl group having 1 to 20 carbon atoms AO: at least one selected from oxyalkylene groups having 3 to 8 carbon atoms EO: oxyethylene group s: average addition of alkylene oxide 0 <s ≦ 15 t: average addition mole number of ethylene oxide, 0 <t ≦ 40 s + t: 2 to 50, and AO and EO are random additions, and AO and EO It is essential that the mixed addition molar distribution satisfy the narrowness condition represented by the following equation (2). (Equation 2) (Wherein, j: retention time (minutes) Y _j : weight% of the component with retention time j v _max : retention time (minutes) detected when the component with the highest content is subjected to high performance liquid chromatography Perfume component) (a) group: a fragrance having an alcohol group having 1 to 20 carbon atoms (b) group: a fragrance having an aldehyde group having 1 to 20 carbon atoms (c) group: having 3 to 3 carbon atoms Perfume having 20 ketone groups (d) group: Perfume having a lactone group having 4 to 25 carbon atoms 2. The liquid detergent composition according to claim 1, further comprising an antioxidant. 3. The liquid detergent composition according to claim 1, wherein the fatty acid alkyl ester content in the component (A) is 2% by weight or less.