JP5642465B2 - Liquid detergent composition for automatic dishwashers - Google Patents

Description

  The present invention relates to a liquid detergent composition, specifically a detergent composition for an automatic dishwasher.

  So far, in the technology of detergent compositions for automatic dishwashers, a technology that uses a non-crosslinked polycarboxylic acid polymer and polyoxyalkylene alkyl ether as a cleaning component for tea astringency, fogging of glass and oil stains has been studied. (Patent Documents 1 and 2).

JP 2007-23268 A JP 2003-277800 A

However, since non-crosslinked polycarboxylic acid polymers and polyoxyalkylene alkyl ethers may be difficult to dissolve in water, there is a problem that it is difficult to obtain a liquid detergent composition having a transparent appearance. On the other hand, a liquid detergent composition for an automatic dishwasher usually requires an appropriate viscosity in order to improve usability when it is put into an automatic dishwasher. Therefore, a cross-linked polycarboxylic acid polymer or the like is generally used as an additive for increasing the viscosity of the liquid detergent composition.
However, the cross-linked polycarboxylic acid polymer has a problem that it takes a long time to swell and dissolve, and the production efficiency is lowered.
Therefore, the present invention is a liquid detergent for an automatic dishwasher having excellent cleaning power such as tea astringency, fogging of glass and oil stains, which can be manufactured without reducing the manufacturing efficiency, and whose appearance is transparent and has an appropriate viscosity. It is an object to provide a composition.

In order to solve the above problems, as a result of intensive studies by the present inventors, it has been found that cationized cellulose has a tea astringent washing effect, and that it has a non-crosslinked polycarboxylic acid polymer and an alkyl glycoside compound. The combined use has found that the above-mentioned problems can be solved, and the present invention has been achieved.
That is, the present invention provides (A) a non-crosslinked polycarboxylic acid polymer,
(B) an alkyl glycoside compound represented by the following formula (1), and
R ¹ (OR ² ) _x G _y (1)
Wherein R ¹ is a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, and G is a reducing sugar having 5 to 6 carbon atoms. The average value of x is 0 to 5 and y is 1.0 to 4.2.)
(C) Provided is a liquid detergent composition for an automatic dishwasher comprising cationized cellulose.

  The composition of the present invention uses a cationized cellulose in place of a crosslinked polycarboxylic acid polymer in addition to a non-crosslinked polycarboxylic acid polymer, and blends an alkyl polyglucoside with a conventional liquid. The glass has a cloudy detergency and oil detergency equal to or higher than that of the detergent composition, and further has an improved tea astringency detergency. According to the present invention, a gel-like liquid detergent composition having a transparent appearance and an appropriate viscosity can be obtained in a shorter time.

(A) Non-crosslinked polycarboxylic acid polymer (A) The non-crosslinked polycarboxylic acid polymer used in the present invention is a cleaning component of an automatic dishwasher, and is particularly effective for cleaning tea astringent stains. At the same time, the finish of glass tableware can be improved.
The (A) non-crosslinked polycarboxylic acid polymer used in the present invention preferably has a weight average molecular weight of 1,000 or more measured by gel permeation chromatography using sodium polyacrylate as a standard substance. The thing of the range of 1,500-200,000 is more preferable, The thing of the range of 2,000-100,000 is further more preferable, The thing of the range of 10,000-100,000 is more preferable, 40,000- Most preferred is in the range of 60,000. When the weight average molecular weight of the non-crosslinked polycarboxylic acid polymer is 1,000 or more, the performance as a cloudy detergent for glass is improved, and when it is 200,000 or less, the viscosity of the liquid detergent composition is low. Excessive increase is suppressed.

  The (A) non-crosslinked polycarboxylic acid polymer used in the present invention may be a homopolymer of a monomer having a carboxyl group, and includes a monomer having a carboxyl group and another monomer having a carboxyl group or a carboxyl group. It may be a copolymer with a monomer that does not exist. Examples of the homopolymer or a salt thereof include poly (meth) acrylic acid or a salt thereof, polycrotonic acid or a salt thereof, polyitaconic acid or a salt thereof, polymaleic acid or a salt thereof, and the like. As a copolymer of a monomer having a carboxyl group and another monomer having a carboxyl group or a salt thereof, for example, a (meth) acrylic acid-maleic acid copolymer or a salt thereof, an acrylic acid-crotonic acid copolymer or a salt thereof Salt. Examples of the copolymer of a monomer having a carboxyl group and a monomer having no carboxyl group include an ethylene-maleic acid copolymer or a salt thereof, a methacrylic acid-ethyl acrylate copolymer or a salt thereof.

Among these, poly (meth) acrylic acid or a salt thereof, (meth) acrylic acid-maleic acid copolymer or a salt thereof, and ethylene-maleic acid copolymer or a salt thereof are preferable. Particularly preferred are acrylic acid / maleic acid copolymers or salts thereof, and polyacrylic acid or salts thereof. Further, a salt of acrylic acid / maleic acid copolymer is particularly preferable. The acrylic acid / maleic acid copolymer preferably has an acrylic acid / maleic acid molar ratio of 70/30 to 30/70.
When the non-crosslinked polycarboxylic acid polymer is in the form of a salt, preferred examples include sodium salt and potassium salt.
The component (A) to be used may be synthesized or commercially available. Examples of commercially available products include Aqualic TL400 (acrylic acid / maleic acid copolymer weight average molecular weight: 50000) manufactured by Nippon Shokubai Co., Ltd., and socarans CP7, CP5 and CP12S (both acrylic acid manufactured by BASF). / Maleic acid copolymer CP7 Weight average molecular weight: 50000, CP5 Weight average molecular weight: 70000, CP12S Weight average molecular weight 3000), Socalan PA30 and PA40 (Polyacrylic acid weight average molecular weight: PA30 8000, PA40 15000) and DL of Nippon Shokubai Series (polyacrylic acid, weight average molecular weight 3000-200000) and the like.

(B) Alkyl glycoside compound The alkyl glycoside compound in this invention plays the role which ensures the oil detergency and transparency of an external appearance in the composition of this invention.
The alkyl glycoside compound used in the present invention is represented by the following formula (1):
R ¹ (OR ² ) _x G _y (1)
In the formula, R ¹ is a linear or branched, preferably branched alkyl or alkenyl group having 2 to 10 carbon atoms, preferably 4 to 10 carbon atoms, more preferably 4 to 8 carbon atoms.
R ² represents an alkylene group having 2 to 4 carbon atoms, preferably 2 carbon atoms.
G is a residue derived from a reducing sugar having 5 or 6 carbon atoms. A preferred raw material for G is glucose because of its easy availability and price.
x has an average value of 0 to 5, preferably 0 to 2, and more preferably 0.
y has an average value of 1.0 to 4.2, preferably 1.0 to 3.0, more preferably 1.0 (that is, monosaccharide).
It is particularly preferred that the alkyl glycoside is 2-ethylhexyl glucoside.

  The alkyl glycoside compound of the formula (1) can be produced by a known method or a commercially available product can be used. Examples of commercially available products include AG6202 (2-ethylhexyl glucoside), AG6206 (hexyl glucoside), and AG6210 (octyl / decyl glucoside) manufactured by Lion Akzo.

(C) Cationized cellulose The cationized cellulose used in the present invention is a general term for cellulose derivatives having a cationic group. In the composition of the present invention, when it coexists with the component (A), it plays a role of improving the tea astringency while developing an appropriate viscosity.
Whether or not the cellulose derivative is cationized can be examined by a titration method using a reagent, a method based on an official document, or the like. For example, when the cationized cellulose has a nitrogen atom in the cationic group, it is formulated by cosmetic varieties by component standard (published April 18, 1997, first edition, Yakuji Nippo Co., Ltd., page 210 or quasi-drugs). It can be confirmed by the method described in Product Raw Material Standard 2006 (Pharmaceutical Daily Inc., page 555), for example, by the following method: The sample is dried at 105 ° C. for 3 hours, and about 1 g is accurately weighed, Add water to dissolve to 1000 ml solution, weigh out 5 ml of this solution, add water to make 50 ml, add 4 drops of toluidine blue reagent solution, and titrate with 0.0025 mol / L potassium polyvinyl sulfate solution. Similarly, add 4 drops of toluidine blue reagent solution to 50 ml of water to which no sample has been added, and titrate with 0.0025 mol / L potassium polyvinyl sulfate solution. The amount of nitrogen Ri determined. If the following expression results is 0, cellulose is not cationized with a cationic group having a nitrogen atom.
Amount of nitrogen (N) (%) = ((AB) x 70.03) / (S x (100-C))
A: Titration volume (mL) of 0.0025mol / L polyvinyl potassium sulfate test solution with respect to the solution containing the sample
B: Titration volume (mL) of 0.0025mol / L polyvinyl potassium sulfate reagent solution for the sample-free solution
S: Sample amount (1g)
C: (ignition residue (%) / dry residue (%)) x 100 x 0.8229
Ignition residue: It means the residue after heating in an electric furnace at 500 to 600 ° C. for 5 hours.
Dry residue: The residue after drying at 105 ° C. for 3 hours in a dryer.
0.8229: Coefficient for conversion of ignition residue (sodium sulfate) to sodium chloride

The cationized cellulose of the present invention preferably has an average of 0.09 to 0.6, preferably 0.1 to 0.5, cation groups per glucose unit. By setting the number of cationic groups within this range, the interaction between the non-crosslinked polycarboxylic acid polymer and the cationic group works moderately, and a desired composition viscosity can be obtained. When the number of cationic groups is less than 0.09, the interaction does not work sufficiently, so that it is difficult to obtain a sufficient viscosity. When the number exceeds 0.6, the interaction is too strong, the viscosity becomes excessively high and the usability may be deteriorated.
When the cation group of cationized cellulose contains a nitrogen atom, it preferably has an average of 0.5 to 2.4 mass%, preferably 0.8 to 2.0 mass% of nitrogen atoms per glucose unit. By setting the amount of nitrogen atoms within this range, the interaction between the non-crosslinked polycarboxylic acid polymer and the cationic group works moderately, and a desired composition viscosity can be obtained. If the nitrogen atom is less than 0.5%, the interaction does not work sufficiently, so that it is difficult to obtain a sufficient viscosity, and if it exceeds 2.4%, the interaction is too strong, the viscosity becomes excessively high and the usability may be deteriorated.
The viscosity of the cationized cellulose aqueous solution is preferably 50 to 10,000 mPa · s, more preferably 100 to 5,000 mPa · s, and further preferably 200 to 3000 mPa · s. The viscosity of the aqueous cationized cellulose solution is a 1% aqueous solution of cationized cellulose, and the viscosity at 25 ° C. is a BM type viscometer equipped with a No2 or No3 rotor. It can be determined by measuring.

The cationized cellulose can be produced, for example, by reacting an alkylene oxide derivative of cellulose with a glycidyl group-substituted ammonium salt.
An alkylene oxide derivative of cellulose is obtained by reacting a hydroxyl group of glucose constituting cellulose with an alkylene oxide such as ethylene oxide (EO) or propylene oxide (PO). For example, hydroxyethyl cellulose (HEC), hydroxypropyl A cellulose etc. are mentioned. As the alkylene oxide derivative of cellulose, one obtained by adding 1.5 to 3.0 moles of alkylene oxide per unit of anhydroglucose of cellulose is preferable.
The glycidyl group-substituted ammonium salt can be represented by the following formula (I).

In the above formula (I), R ^{3 to} R ⁵ may be the same or different and are each a linear or branched alkyl group or alkenyl having 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 3 carbon atoms. Represents a group.
X ⁻ is a halogen ion such as fluorine ion, chlorine ion or bromine ion, hydroxide ion, or glycolic acid, acetic acid, tartaric acid, propionic acid, lactic acid, citric acid, salicylic acid, succinic acid, malic acid, butyric acid, p-toluene. Represents organic acid anions such as sulfonic acid, higher fatty acid, L or DL-pyrrolidone carboxylic acid, acidic amino acid, pyroglutamic acid.
Specific examples of the glycidyl group-substituted ammonium salt include glycidyltrimethylammonium chloride, glycidyltriethylammonium chloride, glycidyltrimethylammonium bromide, and the like. Among these, glycidyltrimethylammonium chloride is more preferable.

  As a cationized cellulose compound used by this invention, what is represented by the following formula | equation (2) is preferable.

T in the above formula is a number of 50 to 10,000, preferably 75 to 7,500. R ^{6 to} R ^{13 in the} above formula may be the same or different and each represents a hydrogen atom or a group of the following formula (3) or (4).

R ¹⁴ , R ¹⁵ and R ¹⁶ in the formula may be the same or different and each represents a hydrogen atom or a methyl group. R ^17-1 , R ^17-2 and R ^17-3 may be the same or different and each have a linear or branched alkyl group having 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 3 carbon atoms. Or represents an alkenyl group. p, q and s may be the same or different and each is an integer of 0 to 10, preferably 0 to 3. r is an integer of 1 to 3, preferably 1 or 2. X ⁻ is a halogen ion, a hydroxide ion or an organic acid anion, preferably a halogen ion, more preferably a chlorine ion.

R ^18-1 , R ^18-2 and R ^18-3 in the formula may be the same or different and are each a straight chain having 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 3 carbon atoms. A branched alkyl group or an alkenyl group is represented. u is 0 or an integer of 1 to 4, preferably 1 to 3. v is an integer of 0-4, preferably 1-2. X ⁻ is as defined above, preferably a halogen ion, and more preferably a chlorine ion.
When the cationized cellulose is represented by the formula (2), it is preferable that the group of the formula (3) or (4) is contained in an average of 0.09 to 0.6, preferably 0.1 to 0.5, per glucose unit.

As the cationized cellulose, in the above formula (2), R ^{6 to} R ¹³ are each independently a hydrogen atom or a compound represented by the above formula (4). Among them, compounds in which R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹² and R ¹³ are hydrogen atoms and R ¹¹ is represented by the formula (4) are preferred, and in particular, in the formula (4) R ^18-1 , R ^18-2 and R ^18-3 are all preferably methyl groups. More particularly, O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose chloride is preferable. In particular, an aqueous solution having a solid content concentration of 2% by mass and having a viscosity of 300 to 800 mPa · s when measured with a B-type viscometer at 25 ° C. is preferable.
As the cationized cellulose, in the above formula (2), R ⁶ , R ⁸ , R ¹⁰ and R ¹³ are hydrogen atoms, and R ⁷ and R ¹¹ are the formula (4) (wherein R ^18-1 , R ^18-2 and R ^18-3 are both methyl groups), R ⁹ and R ¹² are the formula (4) (wherein R ^18-1 and R ^18-3 are methyl groups, R ¹⁸ Also preferred are compounds wherein ^-2 is a dodecyl group.
Commercially available cationized cellulose may be used, such as Lion's Leoguard MGP, Leoguard MGP-P, Leoguard GP, Leoguard LP, Amerchol softCAT PolymerSK-L, softCAT PolymerSK-MH, Rhodia's MIRAPOL PQ −10, Daicel Chemical Industries, Ltd. Gelner series and the like are preferable.

Other Components The detergent of the present invention can contain any component that is usually contained in a detergent for washing tableware unless it is contrary to the purpose of the present invention. Other ingredients include, for example, solvents such as ethanol, sorbitol and water, plant extracts, preservatives, antibacterial / bactericides, deodorants, stabilizers, surfactants, polymers, fragrances, sodium sulfate (sodium sulfate) and pH Examples include regulators.
As the surfactant, it is preferable to add a nonionic surfactant, particularly a polyoxyalkylene alkyl ether, which further improves the oil detergency of the liquid detergent composition. The polyoxyalkylene alkyl ether has the formula:
R ¹⁹ -O- (CH ₂ CH ₂ O) _n- (AO) _m -H
It is a compound which can be represented by these. In the formula, R ¹⁹ is a linear or branched alkyl group or alkenyl group having 2 to 30 carbon atoms, preferably an alkyl group or alkenyl group having 6 to 20 carbon atoms. AO is an alkylene oxide group having 3 or more carbon atoms, preferably 3 to 4 carbon atoms. n is the number of moles of ethylene oxide added, and is a number of 1 to 20, preferably 3 to 15. m is the number of added moles of alkylene oxide having 3 or more carbon atoms, and is a number of 1 to 20, preferably 2 to 10.
As other components, enzymes such as amylase and protease may also be blended.

Compounding amount of each component The component (A) can be blended in an amount of 4 to 40% by mass, preferably 8 to 30% by mass, more preferably 11 to 30% by mass with respect to the total mass of the liquid detergent composition. When the blending amount is 4% by mass or more, tea astringency cleaning power and glassy cloudy detergency can be exerted, and when the blending amount is 40% by mass or less, the occurrence of significant thickening and turbidity of the liquid detergent composition can be suppressed.
Component (B) can be blended in an amount of 1 to 15% by mass, preferably 3 to 10% by mass, more preferably 4 to 8% by mass, based on the total mass of the liquid detergent composition. When the blending amount is 1% by mass or more, a transparent appearance can be generated and the oil detergency can be improved. When the blending amount is 15% by mass or less, the stability of the liquid detergent composition during storage and foaming in the dishwasher can be achieved. Sex can be suppressed.
Component (C) may be blended in an amount of 0.05 to 5% by mass, preferably 0.1 to 2.5% by mass, more preferably 0.3 to 1.5% by mass, based on the total mass of the liquid detergent composition. In order to give a moderate viscosity to the tea astringent cleaning power and the effect of giving a transparent appearance and appropriate viscosity to the liquid detergent composition by setting the blending amount to 0.05% by mass or more and 5% by mass or less. It is possible to solve the problem that the cross-linked polycarboxylic acid polymer that has been blended has a long time to swell and dissolve and lowers the production efficiency.
Furthermore, the mass% ratio (B) / (C) of the component (B) and the component (C) is preferably 4 to 30, more preferably 5 to 15. The transparency of the external appearance of a liquid detergent composition improves by setting it as the said ratio.
There is no restriction | limiting in particular if the compounding quantity of the said other component is a range which does not prevent the objective of this invention.

Manufacturing method of composition of this invention It can manufacture by mix | blending (A) component, (B) component, (C) component, and another component as needed, and mixing them in arbitrary orders.

Viscosity of the composition of the present invention The composition of the present invention preferably has a viscosity of 100 to 6,000 mPa · s, preferably 200 to 5000 mPa · s, more preferably 300 to 4000 mPa · s. Viscosity should be measured after preparing a 1% aqueous solution of a liquid detergent composition and measuring the viscosity at 25 ° C after 120 seconds at 6-60 rpm with a BM viscometer equipped with a No1-No3 rotor. It can ask for.
The composition of the present invention is in a liquid to gel form at room temperature.

PH of the composition
The pH of the composition of the present invention is 7.0 to 7.6, preferably 7.1 to 7.5, more preferably 7.2 to 7.4. The pH can be measured with a pH meter (glass electrode).

A liquid detergent composition for an automatic dishwasher was prepared with the blending amounts shown in Table 1 below. Examples 4, 7, and 12 are reference examples . For preparation, add A component, B component, C component, polyoxyalkylene alkyl ether and common components other than pH adjuster and enzyme in any order in a 300 ml beaker, and maximum of 90 minutes at 700-1000 rpm Stirring was performed, and finally ion exchange water was added to prepare 100 parts by mass.
Each component and the amount used (the numbers in the table indicate the mass% of the active ingredient relative to the whole composition) are shown below.
<Non-crosslinked polycarboxylic acid polymer (A)>
(A1) Acrylic acid / maleic acid copolymer soda salt, manufactured by Nippon Shokubai Co., Ltd., trade name Aqualic TL-400 (weight average molecular weight 50,000)
(A2) Acrylic acid / maleic acid copolymer soda salt, manufactured by BASF, trade name Socaran CP7 (weight average molecular weight 50,000)
<Alkyl glycoside compound (B)>
2-ethylhexyl glucoside (R ¹ = 2-ethylhexyl group, x = 0, y = 1.0, G = glucose) Product name “AG6202” manufactured by Lion Akzo Co., Ltd.
<Cationized cellulose (C)>
(C1) Product name “Leoguard MGP-P” manufactured by Lion Akzo Co., Ltd. (Viscosity: 1000 mPa · s, number of cationic groups: 0.4, amount of nitrogen atom: 1.8 mass% (in formula (2), R ^{6 to} R ¹⁰ = hydrogen atom, R ¹¹ = group of formula (4), R ¹² and R ¹³ = hydrogen atom, t = 1250, R ^{18-1 to} R ^18-3 = methyl group, u = 1, v = 1, X ^- = chloride ion)
(C2) Product name “SoftCAT PolymerSK-L” manufactured by Amerchol (viscosity: 2400 mPa · s, number of cationic groups: 0.2, amount of nitrogen atom: 1.1 mass% (in formula (2), R ⁶ , R ⁸ , R ¹⁰ , R ¹³ = hydrogen atom, R ⁷ and R ¹¹ = the group of formula (4) and R ^{18-1 to} R ^18-3 = methyl group, u = 1, v = 1, R ⁹ and R ¹² = Group of formula (4) and R ^18-1, R ^18-3 = methyl group, R ^18-2 = dodecyl group, u = 1, v = 1, t = 1500, X ⁻ = chlorine ion)
<Comparison of (C)>
Product name "JAGUAR C-17" made by cationized guar gum Rhodia
Cross-linked polycarboxylic acid-based polymer manufactured by Sumitomo Seika Co., Ltd. Product name ACPEC HV-505ED

<Other components (mixing amount is mass% with respect to the total amount of the liquid detergent composition as it is)>
・ Product name NNAEP-3030 made by Lion Chemical Co., Ltd.
Common component X:
・ Polyoxyethylene chloride (15) Alkylmethylammonium products manufactured by Lion Akzo Co., Ltd. Product name “Esocard C / 25” 2%
・ Sorbit liquid ROQUETTE brand name “NEOSORB 70 / 02B” 12%
-Lavender extract Simrise Co., Ltd. product name "Flowerpon Lavender" 0.1%,
5-Chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one Mixed solution of magnesium salt and water Product name “Caisson CG” manufactured by Rohm and Haas 0.01 %
-2-bromo-2-nitro-1,3-propanediol BASF brand name "Myaside" 0.01%
・ Amylase Novozymes Japan Co., Ltd. Product name “Termamyl Mill 300L” 1%
・ Protease Novozymes Japan Co., Ltd. Product name “Sabinase 16XL” 1%
<PH adjuster>
The pH was adjusted to 7.3 using sodium hydroxide solution.

[Evaluation Method for Manufacturability (Easy Manufacturability) of Composition]
Common ingredients except A component, B component, C component, polyoxyalkylene alkyl ether, and pH regulator and enzyme after putting the raw materials described in Examples and Comparative Examples into a 300 mL beaker (φ70 mm) so that the total amount becomes 200 g Were added in any order and after stirring at 500 rpm for up to 90 minutes using a Heidon three-one motor type600G (stirring blade: φ50 mm, blade width 10 mm, blade mounting angle 45 °, blade interval 20 mm, number of sheets 2) The state of the raw material after stirring was evaluated as follows.
The evaluation of ◎ to ○ is passed.
Evaluation criteria:
A: Raw material is uniformly dissolved within 30 minutes and no undissolved residue is observed. ○: Raw material is uniformly dissolved within 30 minutes to 60 minutes and no undissolved residue is observed. Δ: Over 60 minutes to 90 minutes Ingredients are uniformly dissolved within, and no undissolved residue is observed. X: Even after stirring for 90 minutes, the raw material remains undissolved, and undissolved lumps are observed.

[Evaluation Method of Appearance Transparency]
Evaluation container:
A cube container made of a transparent acrylic plate with a thickness of 2 mm (inner dimensions: width 10 cm, depth 10 cm, height 10 cm, bottom surface is a regular square (one side: 10 cm) white paper with a large outer diameter at the center) Is attached from the outside of the bottom of the container so that it can be seen from the top of the container)
Evaluation method:
Carefully pour 800 mL of the composition into the container, taking care not to foam, and let stand. The composition in the container was visually observed so that the eye position was 20 cm above the bottom of the container, and the transparency of the liquid was evaluated according to the following criteria. The evaluation of ◎ to ○ is passed.
Evaluation criteria:
A: Uniform and transparent, no turbidity is observed, and the “」 ”mark on the bottom of the container is clearly visible.
○: Slight turbidity is observed, but it is uniform and the “◎” mark on the bottom of the container can be recognized.
Δ: Turbidity is observed and the presence of characters at the bottom of the container is understood, but cannot be recognized as “◎”.
X: Obvious turbidity is observed and the presence of characters at the bottom of the container is not understood.

[Measurement method of viscosity]
The composition was poured into a storage bottle having a diameter of 52 mm and a height of 95 mm, and the viscosity at 25 ° C. after 6 to 60 rpm and 120 seconds was measured with a BM type viscometer equipped with a No1 to No3 rotor.

[Evaluation method of tea astringency cleaning power]
After drinking tea with a coffee cup (inner diameter 70 mm, height 70 mm), the coffee cup was left standing at 25 ° C. and 50% RH for 10 days to prepare a coffee cup with tea stains. Three coffee cups were placed in an automatic dishwasher “Matsushita Electric Industrial Co., Ltd., Model NP-40SX2” and washed with a standard course using 6 g of the prepared composition. The washed coffee cup was subjected to sensory evaluation based on the following evaluation criteria.
The evaluation of ◎ to ○ is passed.
Evaluation criteria:
(Double-circle): A stain | pollution | contamination does not remain | survive at all and the discomfort, such as roughness, is not felt.
○: Residue of dirt is not visually recognized, but feels uncomfortable, such as slight roughness when touched.
Δ: Residue of dirt is slightly recognized visually.
X: Dirt is not removed.

[Evaluation method of fogging power of glass]
A glass cup (upper diameter 63 mm, lower diameter 53 mm, height 100 mm) was put in an automatic dishwasher, 1.2 g of sodium carbonate was put in the machine, and the entire process of washing to rinsing was performed with 30 ° C. hard water. I got a cup. This whitened cup was placed in an automatic dishwasher “Matsushita Electric Industrial Co., Ltd., Model NP-40SX2” and washed with a standard course using 6 g of the prepared composition. The glass cup after washing was subjected to sensory evaluation based on the following evaluation criteria.
The evaluation of ◎ to ○ is passed.
Evaluation criteria:
A: No whitened material remains and no discomfort such as roughness is felt.
○: Some whitening residue is slightly observed.
Δ: A slight amount of whitened product was visually observed, and the overall transparency was lost.
X: The residual amount of whitened material is not different from that before washing.

[Evaluation method of oil detergency]
Polypropylene lunch box (inside dimensions: length 113 mm, width 174 mm, depth 35 mm, top surface opened) with 2 g of salad oil (Nisshin Salad Oil, manufactured by Nisshin Oillio Group Co., Ltd.) Put it in an automatic dishwasher “Matsushita Electric Industrial Co., Ltd., Model NP-40SX2”, wash the standard course using 6 g of the prepared composition, and evaluate the following conditions of oil adhesion to the polypropylene lunch box Sensory evaluation was performed based on the criteria.
The evaluation of ◎ to ○ is passed.
Evaluation criteria:
A: No residual oil droplets were confirmed by visual observation, and when the finger was rubbed, no stickiness was felt.
○: No residual oil droplets are observed by visual inspection, but a slight luster is felt when rubbing with a finger.
Δ: Slightly residual oil droplets are visually observed.
X: Remarkable residual oil droplets are observed visually.

Claims (8)

(A) non-crosslinked polycarboxylic acid polymer,
(B) an alkyl glycoside compound represented by the following formula (1), and
R ¹ (OR ² ) _x G _y (1)
(Wherein R ¹ is a linear or branched alkyl group or alkenyl group having 2 to 10 carbon atoms, R ² represents an alkylene group having 2 to 4 carbon atoms, and G is a reducing sugar having 5 or 6 carbon atoms. The average value of x is 0 to 5 and y is 1.0 to 4.2.)
(C) looking contains a cationized cellulose, (B) component and (C) weight% ratio of component (B) / (C) is for automatic dishwashing liquid detergent composition is 5 to 15.   The liquid detergent composition for automatic dishwashers according to claim 1, wherein the cationized cellulose has an average of 0.09 to 0.6 cationic groups per glucose unit.   The liquid detergent composition for automatic dishwashers according to claim 1 or 2, wherein the cationized cellulose has an average of 0.5 to 2.4 mass% of nitrogen atoms per glucose unit.   The liquid detergent composition for automatic dishwashers according to any one of claims 1 to 3, wherein the viscosity of a 1% by mass aqueous solution of the cationized cellulose measured at 25 ° C is 50 to 10,000 mPa · s. .   The liquid detergent composition for an automatic dishwasher according to any one of claims 1 to 4, wherein the cationized cellulose is contained in an amount of 0.05 to 5% by mass, based on the total mass of the composition. The cationized cellulose is represented by the following formula (2):

(Wherein R ^{6 to} R ¹³ may be the same or different and each represents a hydrogen atom or a group of the following formula (3) or (4);

(In the formula, R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different, and each is a hydrogen atom or a methyl group, and R ^17-1 , R ^17-2 and R ^17-3 are the same or different. Each is a linear or branched alkyl group or alkenyl group having 1 to 15 carbon atoms, p, q and s may be the same or different, and each is a number of 0 to 10, and r is 1 A number of ˜3, and X ⁻ represents a halogen ion, a hydroxide ion or an organic acid anion.)

(In the formula, R ^18-1 , R ^18-2 and R ^18-3 may be the same or different and each represents 1 to 15 linear or branched alkyl or alkenyl groups; 4 is a number, v is a number from 0 to 4, and X ⁻ is as defined above.)
t is a number from 50 to 10,000. ),
And the liquid cleaning agent for automatic dishwashers of any one of Claims 1-5 in which 0.09-0.6 group of said Formula (3) or (4) is contained per glucose unit on average. Composition.   The liquid detergent composition for an automatic dishwasher according to any one of claims 1 to 6, wherein the non-crosslinked polycarboxylic acid polymer is a salt of an acrylic acid / maleic acid copolymer. The content of the component (A) is 11 to 30% by mass, the content of the component (B) is 4 to 15% by mass, and the content of the component (C) is 0.1% with respect to the total mass of the composition. The liquid detergent composition for automatic dishwashers according to any one of claims 1 to 7, which is 3 to 2.5% by mass .