JP5793335B2 - Liquid cleaning agent - Google Patents

Description

  The present invention relates to a liquid detergent containing a protease having a high enzyme activity even under low temperature conditions.

In detergents for clothing, in addition to a surfactant that exhibits a cleaning effect, a chelating agent (as an auxiliary component for removing metal ions such as calcium ions and magnesium ions, which hinders the cleaning action or blending stability) A metal sequestering agent) is generally blended.
In addition, some detergents for clothes are formulated with an enzyme to further enhance the cleaning power together with the surfactant. For example, protein stains contained in clothing collars and cuff stains are stains that cannot be sufficiently removed with surfactants alone. On the other hand, by adding a proteolytic enzyme (protease), the protein soil is decomposed and easily removed.

In recent years, the demand for liquid detergents has been increasing for reasons such as little undissolved residue.
However, the enzyme has a problem that its structure is broken in a liquid, particularly by the action of a chelating agent, and it is easily deactivated. For this reason, the reality is that the stability of the enzyme in the liquid detergent is lower than that in the case of the powder detergent.
Conventionally, as a technique for stabilizing an enzyme in a liquid detergent containing a chelating agent, a method of blending a calcium salt that generates free calcium ions together with a chelating agent (see Patent Document 1), a short-chain carboxylate (formate) , Lactate) and a chelating agent (see Patent Document 2) and the like are disclosed.

Japanese Patent Laid-Open No. 5-179291 Japanese Patent Laid-Open No. 5-179292

By the way, from the viewpoint of increasing awareness of environmental measures, a so-called “concentrated type” liquid that contains a high concentration (40% by mass or more) surfactant and exhibits a high cleaning effect with a small amount of cleaning agent used. Cleaning agents have been used. On the other hand, washing conditions in Japan are changing (low temperature, saving water, shortening of washing time, etc.) as water-saving drum-type washing machines become widespread.
Therefore, in order to develop a high cleaning effect even under a small amount of detergent used under such washing conditions, a concentrated liquid detergent containing a highly active enzyme is required.
However, as described above, the enzyme is easily deactivated in the liquid by the action of the chelating agent, and the enzyme is more easily deactivated as the surfactant concentration is higher. Furthermore, the higher the activity of the enzyme, the higher the reactivity, so that it tends to be deactivated.
On the other hand, it has been difficult to stabilize a highly active enzyme in the presence of a high concentration of a surfactant in the conventional technology for stabilizing an enzyme in a liquid detergent.

  The present invention has been made in view of the above circumstances, and contains a highly active enzyme, which is stabilized even in the presence of a high-concentration surfactant and has a high detergency. It is an issue to provide.

As a result of intensive studies, the present inventors provide the following means in order to solve the above problems.
That is, the liquid detergent of the present invention is 40% by mass or more of the nonionic surfactant (A), derived from the genus Bacillus, and the enzyme activity value at 10 ° C. is 6% of the enzyme activity value at 35 ° C. It contains the protease (B) as described above, a water-miscible organic solvent (C) represented by the following general formula (c1), and a chelating agent (D). However, the enzyme activity value of the component (B) is a value measured using milk casein as a substrate.

［式中、Ｒ^１ は炭素数１〜８のアルキル基、フェニル基又はベンジル基である。ｍはＰＯの平均繰返し数、ｎはＥＯの平均繰返し数を表し、ｍは０〜３の数、ｎは０〜３の数であり、１≦ｍ＋ｎ≦６である。ＥＯはオキシエチレン基、ＰＯはオキシプロピレン基を表し、ＥＯとＰＯとは混在して配列してもよい。］

[In the formula, ^{R 1} is an alkyl group, a phenyl group or a benzyl group having a carbon number of 1-8. m represents the average number of repetitions of PO, n represents the average number of repetitions of EO, m is a number of 0 to 3, n is a number of 0 to 3, and 1 ≦ m + n ≦ 6. EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO may be mixed and arranged. ]

  In the liquid detergent of the present invention, the chelating agent (D) is at least selected from the group consisting of malonic acid, succinic acid, malic acid, diglycolic acid, citric acid, methylglycine diacetic acid, and salts thereof. One type is preferable.

  According to the present invention, it is possible to provide a liquid detergent having a high detergency, containing a highly active enzyme, stabilizing the enzyme even in the presence of a high concentration of a surfactant.

The liquid detergent of the present invention is 40% by mass or more of the nonionic surfactant (A), derived from the genus Bacillus, and the enzyme activity value at 10 ° C. is 6% or more of the enzyme activity value at 35 ° C. Contains a certain protease (B), a water-miscible organic solvent (C) represented by the general formula (c1), and a chelating agent (D). Also referred to as B) component, (C) component, and (D) component.

[Nonionic surfactant (A)]
The component (A) is mainly used for imparting detergency in the liquid detergent of the present invention.
(A) As a component, the polyoxyalkylene type nonionic surfactant represented by the following general formula (a1) and the polyoxyalkylene type nonionic surfactant represented by the following general formula (a2) are mentioned suitably. It is done.

［式中、Ｒ^１１は炭素数８〜１８の疎水基である。ＸはＯ、ＣＯＯ又はＣＯＮＨである。Ｒ^１２は水素原子、炭素数１〜６のアルキル基、又は炭素数２〜６のアルケニル基である。ｓはＥＯの平均繰返し数を表し、３〜２０の数である。ｔはＰＯの平均繰返し数を表し、０〜６の数である。ＥＯはオキシエチレン基、ＰＯはオキシプロピレン基を表し、ＥＯとＰＯとは混在して配列してもよい。］

[Wherein R ¹¹ is a hydrophobic group having 8 to 18 carbon atoms. X is O, COO or CONH. R ¹² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. s represents the average number of repetitions of EO and is a number from 3 to 20. t represents the average number of repetitions of PO and is a number from 0 to 6. EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO may be mixed and arranged. ]

In Formula (a1), R ¹¹ is preferably a hydrophobic group having 10 to 18 carbon atoms because of good detergency, and may be linear or branched. Examples of the hydrophobic group include those derived from raw materials such as primary or secondary higher alcohols, higher fatty acids, higher fatty acid amides and the like.
The alkyl group for R ¹² is preferably an alkyl group having 1 to 3 carbon atoms. The alkenyl group for R ¹² is preferably an alkenyl group having 2 to 3 carbon atoms.
X is preferably O or COO.

In the formula (a1), when X is O, the component (A) is an alcohol alkoxylate. In this case, since the detergency is good, it is preferable that the carbon number of R ¹¹ is 10 to 18, R ¹¹ may have an unsaturated bond. In this case, R ¹² is preferably a hydrogen atom.
In the formula (a1), when X is COO, the component (A) is a fatty acid ester type nonionic surfactant. In this case, since the detergency is ^good, it is preferable that the carbon number of ^{R 11} is 9-18, more preferably 11 to 18. R ¹¹ may have an unsaturated bond. In this case, R ¹² is preferably an alkyl group having 1 to 3 carbon atoms.

In the formula (a1), s is preferably a number of 5 to 18. When s exceeds 20, the HLB value becomes too high and the cleaning power tends to decrease. On the other hand, when s is less than 3, the raw material odor of the component (A) itself tends to deteriorate.
t is preferably a number from 0 to 3. When t exceeds 6, the storage stability of the liquid detergent at high temperature tends to be lowered.
EO and PO may be mixed and arranged, and (EO) s / (PO) t may be added in a random form or in a block form.

In the component (A) represented by the formula (a1), the addition mole number distribution of EO or PO is not particularly limited, and is likely to vary depending on the reaction method when the component (A) is produced. For example, the addition mole number distribution of EO or PO is obtained by using ethylene oxide or propylene oxide as a hydrophobic group raw material (primary or secondary higher alcohol, higher fatty acid) using a general alkali catalyst such as sodium hydroxide or potassium hydroxide. , Higher fatty acid amides, etc.) tend to have a relatively wide distribution. Also, specific alkoxylation such as magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^{2+ and the} like described in Japanese Patent Publication No. 6-15038 are added. When ethylene oxide or propylene oxide is added to the hydrophobic group raw material using a catalyst, the distribution tends to be relatively narrow.

  Specific examples of the component (A) represented by the formula (a1) include a product name Diadol (C13, C represents the number of carbon atoms, manufactured by Mitsubishi Chemical Corporation), and a product name Neodol (manufactured by Shell). A mixture of C12 and C13), a product name Safol 23 (mixture of C12 and C13) manufactured by Sasol, and the like, with 12 mol equivalent or 15 mol equivalent ethylene oxide added; product manufactured by P & G A product obtained by adding 12 moles or 15 moles of ethylene oxide to a natural alcohol such as CO-1214 or CO-1270; 7 mole equivalent ethylene oxide added to the alcohol (trade name Lutensol TO7 manufactured by BASF) A product obtained by adding 9 moles of ethylene oxide to C10 alcohol obtained by subjecting pentanol to garvet reaction (trade name Lutensol XP90 manufactured by BASF); to C10 alcohol obtained by subjecting pentanol to garvet reaction 7 mol equivalent of ethylene oxide added (trade name Lutensol XL70 manufactured by BASF); 6 mol equivalent of ethylene oxide added to C10 alcohol obtained by subjecting pentanol to garvet reaction (BASF Corp.) Product name: Lutensol XA60): 9 mol equivalent or 15 mol equivalent ethylene oxide added to a secondary alcohol having 12 to 14 carbon atoms (trade names Softanol 90, Softanol 150 manufactured by Nippon Shokubai Co., Ltd.) Etc. The

［式中、Ｒ^１３は炭素数８〜１８の疎水基である。ｐはＥＯの平均繰返し数を表し、ｑはＰＯの平均繰返し数を表し、ｒはＥＯの平均繰返し数を表し、ｐ、ｑ、ｒはｐ＞１、ｒ≧０、０＜ｑ≦３、ｐ＋ｒ＝１０〜３０を満たす数である。ＥＯはオキシエチレン基、ＰＯはオキシプロピレン基を表し、（ＥＯ）ｐ／（ＰＯ）ｑにおけるＥＯとＰＯとは混在して配列してもよい。］

[Wherein R ¹³ is a hydrophobic group having 8 to 18 carbon atoms. p represents the average number of repetitions of EO, q represents the average number of repetitions of PO, r represents the average number of repetitions of EO, p, q, r are p> 1, r ≧ 0, 0 <q ≦ 3, p + r = 10-30. EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO in (EO) p / (PO) q may be mixed and arranged. ]

In the formula (a2), R ¹³ is preferably an alkyl group or alkenyl group having 8 to 18 carbon atoms, and may be linear or branched.
In the formula (a2), r is r ≧ 0, preferably r ≧ 1. It is a number satisfying p + r = 10-30, and preferably a number satisfying p + r = 14-20.
In the formula (a2), the ratio of EO and PO is preferably 0.1 to 0.5, more preferably 0.1 to 0.3, as a ratio represented by q / (p + r). is there.
When the ratio represented by q / (p + r) is equal to or higher than the lower limit value, bubbles are not excessively formed and foaming is easily optimized. When it is at most the upper limit value, an appropriate viscosity is easily obtained, and gelation is easily suppressed.
Only one of EO and PO in (EO) p / (PO) q may exist, or they may be mixed and arranged. In (EO) p / (PO) q, EO and PO may be added randomly, or may be added in blocks.

The component (A) represented by the formula (a2) can be produced by a known method. Specifically, after an addition reaction of ethylene oxide and propylene oxide in this order to an alcohol having an R ¹³ hydrophobic group derived from natural fats and oils, or after mixed addition of ethylene oxide and propylene oxide (random addition), It can be produced again by adding ethylene oxide.
When the component (A) represented by the formula (a2) is used, the liquid detergent can easily obtain an appropriate viscosity, and gelation is also suppressed. Moreover, foamability improves and biodegradability also becomes better.

(A) A component may be used individually by 1 type or in combination of 2 or more types.
Among the above, as the component (A), a polyoxyalkylene type nonionic surfactant is preferable, one represented by the formula (a1) is more preferable, and alcohol alkoxylate is particularly preferable among them.

(A) Content of a component is 40 mass% or more with respect to the total mass of a liquid detergent, 40-70 mass% is preferable, More preferably, it is 40-60 mass%, More preferably, 40- 55% by mass.
When the content of the component (A) is 40% by mass or more, the effect of the present invention is remarkably exhibited. Moreover, a high cleaning power can be imparted to the liquid detergent composition. When the content of the component (A) is not more than the upper limit value, the storage stability (appearance stability, film formability on the liquid surface, etc.) of the liquid detergent is improved.
Conventionally, a nonionic surfactant such as a primary alcohol ethoxylate is known as a main cleaning component, but since the primary alcohol ethoxylate has a large gelation region, it is 40% by mass or more. It is difficult to blend into a concentrated liquid detergent.

[Protease (B)]
In the liquid detergent of the present invention, the component (B) has an effect of further enhancing the detergency, mainly with the surfactant. In particular, the component (B) exhibits high activity even at a low temperature (5 to 15 ° C.). On the other hand, it has higher reactivity than conventional enzymes and is difficult to stabilize.

In the present invention, the “enzyme activity value” refers to a value measured as follows using milk casein as a substrate.
Milk casein (Casein, Bovine Milk, Carbohydrate and Fatty Acid Free / Calbiochem (registered trademark)) is dissolved in 1N sodium hydroxide (1 mol / L sodium hydroxide solution (1N), manufactured by Kanto Chemical Co., Inc.) to adjust the pH to 10. 5 and diluted with 0.05M boric acid (boric acid (special grade), manufactured by Kanto Chemical Co., Ltd.) aqueous solution so that the concentration of milk casein is 0.6% by mass to obtain a protease substrate.
Next, the enzyme preparation is dissolved in ion exchange water to prepare an enzyme preparation aqueous solution having a concentration of 0.4% by mass.
A solution obtained by diluting 1 g of the enzyme preparation aqueous solution with calcium chloride (calcium chloride (special grade), manufactured by Kanto Chemical Co., Inc.) 3 ° DH hard water 25 times is used as a sample solution.
5 g of the protease substrate is added to 1 g of the sample solution, and the mixture is stirred with a vortex mixer for 10 seconds, and then allowed to stand at 10 ° C. or 35 ° C. for 30 minutes to advance the enzyme reaction.
Thereafter, 5 g of 0.44M aqueous solution of enzyme reaction stopper TCA (trichloroacetic acid (special grade), manufactured by Kanto Chemical Co., Inc.) was added, stirred for 10 seconds with a vortex mixer, and then allowed to stand at 20 ° C. for 30 minutes to precipitate. Unreacted substrate is removed with a 0.45 μm filter, and the filtrate is recovered.
The absorbance (absorbance A) at a wavelength of 275 nm of the collected filtrate was measured using an ultraviolet-visible spectrophotometer UV-160 manufactured by Shimadzu Corporation, and the absorbance at a reaction temperature of 10 ° C. and the absorbance at a reaction temperature of 35 ° C. Compare. At this time, the greater the absorbance A, the greater the amount of tyrosine (produced by the protease degrading the protease substrate) present in the filtrate.
In order to remove the influence of absorption other than the target component, 5 g of TCA was separately added to 1 g of the sample solution, stirred for 10 seconds with a vortex mixer, then added with 5 g of protease substrate, stirred for 10 seconds with a vortex mixer, and 0.45 μm. The filtrate is recovered by removing with a filter, and the absorbance (absorbance B) at a wavelength of 275 nm of the filtrate is measured using the UV-160.

[Comparison of protease activity value at 10 ° C and protease activity value at 35 ° C]
From the above measurement results, the protease activity value at 10 ° C. and the protease activity value at 35 ° C. are compared by the following formula. The absorbance value at a wavelength of 275 nm of each sample to be substituted into the following formula is used by subtracting the absorbance value at 600 nm measured simultaneously in order to exclude the influence of scattered light such as bubbles.
Protease activity value (%) at 10 ° C. when the enzyme activity value at 35 ° C. is defined as 100% = (Absorbance of 10 ° C. reaction product A−Absorbance B of 10 ° C. reaction product) / (35 ° C. reaction product) Absorbance A-35 ° C reaction product absorbance B) × 100

The (B) component protease is derived from the genus Bacillus, and the enzyme activity value at 10 ° C. is 6% or more, preferably 7% or more, more preferably 10% or more of the enzyme activity value at 35 ° C. On the other hand, the higher the upper limit value, the better.
When the enzyme activity value at 10 ° C. is 6% or more of the enzyme activity value at 35 ° C., high activity is exhibited even when low-temperature water is used, and in particular, the detergency against protein soil is higher than that of conventional proteases. .

  Specific examples of the component (B) include protease preparations such as Coronase 48L, Liquanase 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL (manufactured by Novozymes); Properase 1600L (Genencore) Can be mentioned.

As the component (B), one type may be used alone, or two or more types may be used in combination.
The content of the component (B) in the liquid detergent is preferably 0.01 to 2% by mass, more preferably 0.1 to 2% by mass with respect to the total mass of the liquid detergent, It is especially preferable that it is 0.2-1 mass%.
When the content of the component (B) is equal to or higher than the lower limit, the effect of the present invention is easily exhibited. Moreover, the cleaning power of the liquid detergent composition is further increased. When the content of the component (B) is less than or equal to the upper limit value, the storage stability (such as appearance stability) of the liquid detergent is improved, and turbidity and precipitation are less likely to occur. Further, the cost is further reduced.

[Water-miscible organic solvent (C)]
The component (C) is a water-miscible organic solvent represented by the following general formula (c1).
In the present invention, the “water-miscible organic solvent” refers to an organic solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C.

［式中、Ｒ^１は水素原子、炭素数１〜８のアルキル基、フェニル基又はベンジル基である。ｍはＰＯの平均繰返し数、ｎはＥＯの平均繰返し数を表し、ｍは０〜３の数、ｎは０〜３の数であり、１≦ｍ＋ｎ≦６である。ＥＯはオキシエチレン基、ＰＯはオキシプロピレン基を表し、ＥＯとＰＯとは混在して配列してもよい。］

[Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a benzyl group. m represents the average number of repetitions of PO, n represents the average number of repetitions of EO, m is a number of 0 to 3, n is a number of 0 to 3, and 1 ≦ m + n ≦ 6. EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO may be mixed and arranged. ]

In said formula (c1), R < ¹ > is a hydrogen atom, a C1-C8 alkyl group, a phenyl group, or a benzyl group. The alkyl group in R ¹ may be linear or branched.
Only one of EO and PO in (EO) n / (PO) m may exist, or they may be mixed and arranged. In (EO) n / (PO) m, EO and PO may be added randomly, or may be added in blocks.

The component (C) includes (poly) alkylene glycol having 1 to 3 carbon atoms of an alkylene glycol unit and (poly) alkylene glycol (mono or di) alkyl ether having 1 to 8 carbon atoms; And aromatic ethers of (poly) alkylene glycol having -3 alkylene glycol units.
Specific examples of the component (C) include diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether. , Diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono 2-ethylhexyl ether, triethylene glycol monobutyl ether, oxyethylene (Poly) alkylene glycol (mono or di) alkyl ethers such as oxypropylene glycol monobutyl ether; ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monobenzyl ether, etc. And aromatic ethers.

As the component (C), one type may be used alone, or two or more types may be used in combination.
Among these, as the component (C), the component (D) is contained, and since the enzyme stability in the presence of a high concentration surfactant is easily maintained, the number of carbon atoms is 1 to 3. A (poly) alkylene glycol (mono or di) alkyl ether consisting of a (poly) alkylene glycol having an alkylene glycol unit of 1 to 8 and an alkanol having 1 to 8 carbon atoms is preferred, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether Ether, dipropylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol - hexyl ether to mono-2-ethyl, triethylene glycol monobutyl ether, oxyethylene-dioxy propylene glycol monobutyl ether is more preferable.

The content of the component (C) in the liquid detergent is preferably 7 to 40% by mass, more preferably 8 to 35% by mass, and more preferably 10 to 25% by mass with respect to the total mass of the liquid detergent. % Is particularly preferred.
If content of (C) component is more than a lower limit, both the storage stability of a liquid cleaning agent (it is hard to form a film | membrane on a liquid level), and fluidity | liquidity will improve. When the content of the component (C) exceeds the upper limit value, the amount of water in the liquid detergent composition decreases, and the enzyme stability may decrease.

[Chelating agent (D)]
In the liquid cleaning agent of the present invention, by containing the component (D), the transparency uniformity of the liquid cleaning agent is mainly increased, and the appearance stability is improved.
Among the components (D), preferable are at least one selected from the group consisting of malonic acid, succinic acid, malic acid, diglycolic acid, citric acid, methylglycine diacetic acid, and salts thereof. It is done.
Among these, as the component (D), since the appearance stability is more easily improved, at least one selected from the group consisting of citric acid, methylglycine diacetic acid, and salts thereof is more preferable. A combination of the salt and methylglycine diacetic acid or a salt thereof is particularly preferred.

As the component (D), one type may be used alone, or two or more types may be used in combination.
The content of the component (D) in the liquid detergent is preferably 0.01 to 3% by mass, more preferably 0.01 to 1% by mass with respect to the total mass of the liquid detergent, It is especially preferable that it is 0.01-0.5 mass%.
If content of (D) component is more than a lower limit, the storage stability (appearance stability etc.) of a liquid detergent will improve. When the content of the component (D) is not more than the upper limit value, the enzyme is more stabilized.

[Solvent: Water]
The liquid detergent of the present invention preferably contains water as a solvent from the viewpoint of ease of preparation of the liquid detergent, solubility in water when used, and the like.
The content of water in the liquid detergent is preferably 10 to 50 mass%, more preferably 10 to 40 mass%, further preferably 10 to 30 mass%, based on the total mass of the liquid detergent.
If the water content is at least the lower limit, the liquid stability of the liquid detergent with time will be better, and if it is not more than the upper limit, the liquid viscosity will be reasonably low, which is good from the viewpoint of usability. .

[Other ingredients]
In the liquid cleaning agent of the present invention, other components other than the components described above may be blended as necessary within a range not impairing the effects of the present invention.
Other components are not particularly limited, and components usually used in liquid detergent compositions for clothing can be blended, and specific examples include the following.

The liquid detergent of the present invention may contain a general surfactant such as an anionic surfactant, a cationic surfactant, and an amphoteric surfactant. Especially, it is preferable to use an anionic surfactant from the surface of cleaning performance.
Examples of the anionic surfactant include alkyl carboxylates, alkyl sulfonates, alkyl benzene sulfonates, alkyl sulfate esters, alkyl phosphate esters, and the like, preferably alkyl benzene sulfonates.
Examples of amphoteric surfactants include carboxylic acid type amphoteric surfactants (amino type and betaine type), sulfate ester type amphoteric surfactants, sulfonic acid type amphoteric surfactants, and phosphate ester type amphoteric surfactants. .
In addition to these, other surfactants include natural surfactants, derivatives of protein hydrolysates, polymer surfactants, surfactants containing titanium and silicon, fluorocarbon surfactants, and the like. May be.

In addition, the liquid cleaning agent of the present invention has an enzyme other than the component (B) (lipase, cellulase, etc.), an organic solvent other than the component (C), a thickener for the purpose of improving the cleaning performance and blending stability. (Long-chain fatty acid alkylamides, etc.), texture improvers, pH adjusters, preservatives, dye transfer inhibitors, pearl agents, antioxidants, soil release agents, hydrotropes and the like can be blended.
Examples of the organic solvent other than the component (C) include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, alkylene glycols having 2 to 6 carbon atoms such as a copolymer of ethylene glycol and propylene glycol; ethanol, methanol, Examples include alcohols such as propanol and butanol. Among these, propylene glycol can be used in combination with the component (C) because it is difficult to form a film on the surface of the liquid detergent and gelation in a high concentration surfactant composition is easily suppressed. preferable. The content of alcohol is preferably 3% by mass or less with respect to the total mass of the liquid detergent. By making content of alcohol into 3 mass% or less, an enzyme becomes more difficult to deactivate.
As the pH adjuster, sulfuric acid, sodium hydroxide, potassium hydroxide and the like are preferable from the viewpoint of liquid stability.
Examples of the hydrotrope include paratoluenesulfonic acid, cumene sulfonate, xylene sulfonate, and the like.

  Moreover, you may mix | blend fluorescent whitening agents, such as a distyryl biphenyl type, with the liquid detergent of this invention for the purpose of the whiteness improvement of white clothing. The content of the optical brightener is preferably 0 to 1% by mass with respect to the total mass of the liquid detergent.

Furthermore, a coloring agent, a flavoring agent, an emulsifying agent, etc. can also be mix | blended with the liquid detergent of this invention for the purpose of the added value improvement of goods, etc.
As the colorant, general-purpose dyes and pigments such as Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, and Turquoise P-GR (all trade names) can be used. The content of the colorant is preferably about 0.00005 to 0.0005% by mass with respect to the total mass of the liquid detergent.
As a flavoring agent, the fragrance compositions A, B, C, D and the like described in Tables 11 to 18 of JP-A-2002-146399 can be used. The content of the flavoring agent is preferably 0.1 to 1% by mass with respect to the total mass of the liquid detergent.
Examples of the emulsifying agent include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is suitably used. Specific examples include polystyrene emulsion (Saiden Chemical Co., Ltd., “Cybinol RPX-196 PE-3”, solid content 40% by mass). The content of the emulsifying agent is preferably 0.01 to 0.5% by mass with respect to the total mass of the liquid detergent.

The pH of the liquid detergent of the present invention is preferably 7 to 9.5 at 25 ° C., more preferably 7 to 9.
When the pH of the liquid detergent is within the above range, particularly when the liquid detergent is stored for a long period of time, the enzyme activity is particularly maintained and good detergency is easily maintained.
In the present invention, the pH of the liquid detergent (controlled at 25 ° C.) indicates a value measured by a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.) or the like.

The liquid detergent of the present invention contains a highly active enzyme, stabilizes the enzyme even in the presence of a high concentration of surfactant, and has a high detergency.
In the liquid detergent of the present invention, the activity of an enzyme that is difficult to stabilize in a liquid is high. In addition, according to the present invention, the enzyme is highly active even in a low temperature region as compared with the conventional enzyme, and on the other hand, the enzyme is easily deactivated due to its high reactivity.
The reason why such an effect is obtained is not clear, but is estimated as follows.
In a liquid detergent containing an enzyme and a chelating agent, in general, by the action of the chelating agent, metal ions such as calcium ions that maintain the structure of the enzyme are extracted, and the structure of the enzyme collapses. Enzyme activity is significantly reduced.
In the present invention, a specific water-miscible organic solvent (C) is used together with a specific protease (B) in the presence of a high concentration (40% by mass or more) of a nonionic surfactant (A) and a chelating agent (D). ).
When a monohydric alcohol such as ethanol is used as the water-miscible organic solvent, the chelate constant of component (D) increases, so that calcium ions in component (B) are easily extracted and enzyme activity is significantly reduced. It becomes easy. On the other hand, when the component (C) is used, the chelate constant of the component (D) hardly changes. Therefore, compared to the case of using a monohydric alcohol, calcium ions in the component (B) are not extracted, It is thought that the structure is easily maintained. As described above, the reason why there is a difference in the effect between the case where the monohydric alcohol is used and the case where the component (C) is used is that the liquid detergent of the present invention is a system having a relatively small amount of water.
From the above, in the present invention, it is presumed that the enzyme can be stabilized even in the presence of a high concentration of a surfactant or even a highly active protease.

Conventional concentrated liquid detergents have a high surfactant concentration, etc., so that the viscosity increases and gelation and solidification are likely to occur. In addition, it is easy to form a film on the liquid detergent surface, and it is difficult to ensure fluidity.
In the present invention, by selecting a specific component (C), gelation and solidification of the liquid cleaning agent is further suppressed, the transparency uniformity and fluidity are good, and a film is formed on the liquid surface. Hard to do. Moreover, by containing a chelating agent (D), the liquid cleaning agent of this invention suppresses precipitation by low-temperature storage, and a transparent uniformity improves.
The liquid cleaning agent of the present invention exhibits a high cleaning effect with a small amount of cleaning agent used.
The liquid detergent of the present invention is particularly suitable for clothing, and is suitable for a composition having a high surfactant concentration (concentrated composition).

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. “%” Means “% by mass” unless otherwise specified.

The compositions of the liquid detergents in each example are shown in Tables 2-4.
The raw materials used in this example are as follows.

[Nonionic surfactant (A)]
A-1: A synthetic product obtained by adding 12 moles of ethylene oxide to a natural alcohol (trade name CO-1214 manufactured by P & G) synthesized as follows [LMAO (C12 / 14-15EO)]. The synthesis was performed as follows.
861.2 g of a trade name “CO-1214” manufactured by P & G Co. and 2.0 g of a 30% by mass NaOH aqueous solution were collected in a pressure-resistant reaction vessel, and the inside of the 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. Next, while stirring the reaction solution, 760.6 g of ethylene oxide (gaseous) was gradually added to the reaction solution. At this time, it added, adjusting the addition rate so that reaction temperature might not exceed 180 degreeC using the 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, and LMAO (C12 / 14 -15EO).

A-2: A coconut fatty acid methyl (a mixture of methyl laurate / methyl myristate = 8/2 in mass ratio) added with 15 moles of ethylene oxide using an alkoxylation catalyst [MEE (C12 / 14-15EO)], a synthetic product. The synthesis was performed as follows.
The synthesis was carried out according to the synthesis method described in JP 2000-144179 A (corresponding to sample D). That is, alumina hydroxide / magnesium hydroxide having a chemical composition of 2.5 MgO.Al ₂ O ₃ .nH ₂ O (trade name “KYOWARD 330” manufactured by Kyowa Chemical Industry Co., Ltd.) is kept at 600 ° C. for 1 hour in a nitrogen atmosphere. A calcined alumina hydroxide / magnesium (unmodified) catalyst (2.2 g) obtained by firing, 2.9 mL of 0.5 N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester, and 70 g of myristic acid methyl ester Were charged into a 4 L autoclave and the catalyst was reformed in the autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, and while maintaining the temperature at 180 ° C. and the pressure at 3 × 10 ⁵ Pa, 1052 g of ethylene oxide was introduced and reacted while stirring. Further, the reaction solution was cooled to 80 ° C., 159 g of water and 5 g of activated clay and diatomaceous earth were added as filter aids, respectively, and the catalyst was filtered off to obtain MEE (C12 / 14-15EO). .

A-3: A product obtained by adding 9 mol of ethylene oxide to a secondary alcohol having 12 to 14 carbon atoms (manufactured by Nippon Shokubai Co., Ltd., trade name Softanol 90).
A-4: A product obtained by adding 9 moles of ethylene oxide to a C10 alcohol obtained by subjecting pentanol to a gerbet reaction (BASF, trade name Lutensol XP90).

[Protease (B)]
B-1: Coronase (manufactured by Novozymes, trade name Coronase 48L), derived bacterium Bacillus clausii, molecular weight 27 kDa, isoelectric point 10.1;
B-2: Recanase (manufactured by Novozymes, trade name Liquanase 2.5L), derived bacterium Bacillus clausii, molecular weight 27 kDa, isoelectric point 10.1;
B-3: Properase (product name Properase 1600L, manufactured by Genencor Corporation).

・ Comparison component (B ′) of component (B)
B′-1: Everase (trade name Everlas 16L TYPE EX manufactured by Novozymes), derived bacterium Bacillus clausii, molecular weight 27 kDa, isoelectric point 10.1;
B′-2: Sabinase (manufactured by Novozymes, trade name Savinase 16L), derived bacterium Bacillus clausii, molecular weight 27 kDa, isoelectric point 10.1.
B′-3: Purefect (manufactured by Genencor, trade name: Purefect 4000L).

The enzyme activity values of component (B) and component (B ′) were measured by the following procedure using milk casein as a substrate. The results are shown in Table 1.
(Measurement method of enzyme activity value)
Milk casein (Casein, Bovine Milk, Carbohydrate and Fatty Acid Free / Calbiochem (registered trademark)) is dissolved in 1N sodium hydroxide (1 mol / L sodium hydroxide solution (1N), manufactured by Kanto Chemical Co., Inc.) to adjust the pH to 10. 5 and diluted with 0.05M boric acid (boric acid (special grade), manufactured by Kanto Chemical Co., Ltd.) aqueous solution so that the concentration of milk casein was 0.6% by mass to obtain a protease substrate.
Subsequently, the enzyme preparation was dissolved in ion-exchanged water to prepare an enzyme preparation aqueous solution having a concentration of 0.4% by mass.
A solution obtained by diluting 1 g of the enzyme preparation aqueous solution 25 times with calcium chloride (calcium chloride (special grade), manufactured by Kanto Chemical Co., Inc.) 3 ° DH hard water was used as a sample solution.
5 g of the protease substrate was added to 1 g of the sample solution, stirred for 10 seconds with a vortex mixer, and allowed to stand at 10 ° C. or 35 ° C. for 30 minutes to proceed the enzyme reaction.
Thereafter, 5 g of 0.44M aqueous solution of enzyme reaction stopper TCA (trichloroacetic acid (special grade), manufactured by Kanto Chemical Co., Inc.) was added, stirred for 10 seconds with a vortex mixer, and then allowed to stand at 20 ° C. for 30 minutes to precipitate. Unreacted substrate was removed with a 0.45 μm filter, and the filtrate was recovered.
The absorbance (absorbance A) at a wavelength of 275 nm of the collected filtrate was measured using an ultraviolet-visible spectrophotometer UV-160 manufactured by Shimadzu Corporation, and the absorbance at a reaction temperature of 10 ° C. and the absorbance at a reaction temperature of 35 ° C. Compared.
In order to remove the influence of absorption other than the target component, 5 g of TCA was separately added to 1 g of the sample solution, stirred for 10 seconds with a vortex mixer, then added with 5 g of protease substrate, stirred for 10 seconds with a vortex mixer, and 0.45 μm. The filtrate was recovered by removing with a filter, and the absorbance (absorbance B) at a wavelength of 275 nm of the filtrate was measured using the UV-160.

[Comparison of protease activity value at 10 ° C and protease activity value at 35 ° C]
From the above measurement results, the protease activity value at 10 ° C. and the protease activity value at 35 ° C. were compared by the following formula. The absorbance value at a wavelength of 275 nm of each sample to be substituted into the following formula was used by subtracting the 600 nm absorbance value measured at the same time in order to exclude the influence of scattered light such as bubbles.
Protease activity value (%) at 10 ° C. when the enzyme activity value at 35 ° C. is defined as 100% = (Absorbance of 10 ° C. reaction product A−Absorbance B of 10 ° C. reaction product) / (35 ° C. reaction product) Absorbance A-35 ° C reaction product absorbance B) × 100

[Water-miscible organic solvent (C)]
C-1: A compound in which R ¹ = CH ₃ , m = 0, and n = 2 in the above general formula (c1).
C-2: A compound in which R ¹ = C ₄ H ₉ , m = 0, n = 2 in the above general formula (c1).
C-3: A compound in which R ¹ = C ₄ H ₉ , m = 0, n = 3 in the general formula (c1).
C-4: A compound in which R ¹ = C ₄ H ₉ , m = 2, and n = 1 in the general formula (c1).
C-5: A compound in which R ¹ = C ₄ H ₉ , m = 2, and n = 0 in the above general formula (c1).

・ Comparison component (C ′) of component (C)
C′-1: Ethanol (manufactured by Nippon Alcohol Sales Co., Ltd., trade name “specific alcohol 95 ° synthesis”).
C′-2: methanol.
C′-3: butanol.

[Chelating agent (D)]
D-1: Methyl glycine diacetate (BASF Japan K.K., trade name “Trilon M”).
D-2: Citric acid (manufactured by Fuso Chemical Industry Co., Ltd., trade name “liquid citric acid”).

[Other ingredients]
Propylene glycol: manufactured by Asahi Glass Co., Ltd.
LAS-H: linear alkyl (C10-14) benzenesulfonic acid [manufactured by Lion Co., Ltd., Rypon LH-200 (LAS-H pure 96% by mass)].
PTS: p-toluenesulfonic acid (Kyowa Hakko Kogyo Co., Ltd., trade name “PTS acid”).
MEA: Monoethanolamine (manufactured by Nippon Shokubai Co., Ltd.).
pH adjuster: 2M-sodium hydroxide (manufactured by Tsurumi Soda Co., Ltd.), 6M-sulfuric acid (manufactured by Toho Zinc Co., Ltd.).
Ion exchange water

<Example of manufacturing liquid detergent>
According to the composition components and contents (mass%) of the compositions shown in Tables 2 to 4, liquid detergents of each example were produced by the following production methods (when there are blank composition components in the table, the composition components are Not blended).
In the table, the content of the compounding component indicates a pure equivalent amount. The “balance” indicating the water content indicates a blending amount adjusted so that the total amount of the liquid cleaning agent as the final preparation is 100% by mass.
The “appropriate amount” indicating the content of the pH adjusting agent indicates an amount blended for adjusting the pH (25 ° C.) of the liquid cleaning agent to the pH shown in the table.

(Examples 1 to 24, Comparative Examples 1 to 10, Reference Example 1)
In a 500 mL beaker, add (C) component or (C ′) component, (D) component, propylene glycol, PTS, MEA, and LAS-H with the contents (mass%) shown in the table. And stirred.
Subsequently, using 2M-sodium hydroxide and 6M-sulfuric acid as a pH adjuster, the pH of the solution (25 ° C.) was adjusted to the value shown in the table.
Next, after adding (A) component and stirring, adding (B) component or (B ′) component and stirring, and then adding ion-exchanged water so that the total amount of the final preparation is 100 mass%. As a result, the liquid detergents of the respective examples were obtained.
The pH of the solution (25 ° C.) was adjusted to a temperature adjusted to 25 ° C. using a pH meter (product name: HM-30G, manufactured by Toa DKK Corporation), and the pH meter electrode was added after 2 minutes. It was measured by reading the value.

<Evaluation of liquid detergent>
With respect to the liquid detergents of the respective examples, “detergency”, “appearance stability”, and “film formation property on the liquid surface” were evaluated by the following evaluation methods. The results are also shown in Tables 2-4.

[Evaluation of cleaning power]
As the liquid cleaning agent in each example, a product immediately after production (immediate product) and a product after storage in a thermostatic bath at 5 ° C. for 1 month (stored product at 5 ° C. and 1M) were used.
As the soiled cloth, EMPA117 (EMPA Testmateliaien, Polyester / cotton, 65/35, soiled with blood / milk / ink) cut into 5 cm × 5 cm square was used.
As a cleaning tester, Terg-O-meter (manufactured by UNITED STATES TESTING) was used.
As a cleaning solution, a solution prepared by adding 300 μL of a liquid cleaning agent to 90 mL of water and stirring for 30 seconds was used.

The cleaning tester was charged with 900 mL of the cleaning liquid, 10 pieces of the soiled cloth, and a cleaning knitted cloth, and washed at 120 rpm and 10 ° C. for 20 minutes in accordance with the bath ratio of 20 times.
Then, it moved to the 2 tank type washing machine (Mitsubishi Electric Corp. make: product name CW-C30A1-H1), dehydrated for 1 minute, rinsed in 30 L of tap water (15 degreeC, 4 degree DH) for 3 minutes, and air-dried.
The color difference meter (Nippon Denshoku Co., Ltd.) reflects the reflectance of unstained cloth (here, unstained cloth refers to a reference white cloth that is not soiled), unwashed EMPA117, and washed EMPA117. The washing rate (%) was determined by the following formula.
Cleaning rate (%) = (K / S of soiled cloth before cleaning−K / S of soiled cloth after cleaning) / (K / S of soiled cloth before cleaning−K / S of unsoiled cloth) × 100
However, K / S is (1-R / 100) ² / (2R / 100) (R represents the unwashed cloth and the reflectance (%) of EMPA 117 before and after washing).

Based on the cleaning rate (%) calculated by the above formula, the cleaning power of each liquid cleaning agent was evaluated based on the following criteria.
A: The cleaning rate is 55% or more.
○: The cleaning rate is 45% or more and less than 55%.
Δ: The cleaning rate is 35% or more and less than 45%.
X: The cleaning rate is less than 35%.
In addition, it can be said that the smaller the difference between the washing rate of the product immediately after production and the washing rate of the product stored at 5 ° C. and 1M, the more stable the enzyme is.
In addition, since the liquid cleaning agent of the comparative example 5 did not melt | dissolve in water and the cleaning liquid was not able to be prepared, the cleaning power was not evaluated.

[Evaluation of appearance stability]
30 mL of the liquid cleaning agent in each example was taken in a cylindrical glass bottle and sealed with the lid closed. In this state, it was left in a thermostatic bath at 5 ° C. and stored for 1 month.
Then, it took out from this thermostat, the transparent uniformity and fluidity | liquidity of 5 degreeC liquid detergent were observed, and the external stability of the liquid detergent of each example was evaluated based on the following reference | standard, respectively.
(Double-circle): It was transparent and uniform and showed fluidity.
○: Some gelation was observed.
X: Solidification or precipitation was observed.

[Evaluation of film formability on liquid surface]
5 g of the liquid cleaning agent of each example was collected in a container (manufactured by Maruemu, MAJY case, model number SS) having a length of 5.3 cm, a width of 3.3 cm, and a height of 1.5 cm. The liquid level of each of the liquid cleaning agents in each example was observed based on the following criteria by observing the liquid level after leaving it to stand at 5 ° C. for 24 hours without opening the lid on the vertical and horizontal surfaces. The film forming property on the surface was evaluated.
○: No film formation was observed on the liquid surface, and the liquid detergent had fluidity.
Δ: Formation of a film on the liquid surface was recognized, but the liquid detergent had fluidity.
X: The liquid detergent was gelled or solidified as a whole.

From the results shown in Tables 2 to 4, the liquid detergents of Examples 1 to 24 contain a highly active enzyme, and the enzyme is stabilized even in the presence of a high concentration of surfactant. It was confirmed that it had.
From the comparison between Examples 1, 10, and 11 and Comparative Examples 3 and 4, it can be seen that the detergency is further increased by selecting enzymes B-1 to B-3.
It was also confirmed that the liquid detergents of Examples 1 to 24 exhibited a high washing effect with a small amount of detergent used.

Claims (2)

40% by mass or more of the nonionic surfactant (A),
A protease (B) derived from the genus Bacillus and having an enzyme activity value at 10 ° C. of 6% or more of the enzyme activity value at 35 ° C .;
A water-miscible organic solvent (C) represented by the following general formula (c1);
A liquid detergent containing a chelating agent (D).
However, the enzyme activity value of the component (B) is a value measured using milk casein as a substrate.

[In the formula, ^{R 1} is an alkyl group, a phenyl group or a benzyl group having a carbon number of 1-8. m represents the average number of repetitions of PO, n represents the average number of repetitions of EO, m is a number of 0 to 3, n is a number of 0 to 3, and 1 ≦ m + n ≦ 6. EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO may be mixed and arranged. ]   The chelating agent (D) is at least one selected from the group consisting of malonic acid, succinic acid, malic acid, diglycolic acid, citric acid, methylglycine diacetic acid, and salts thereof. Liquid detergent.