JP3413351B2 - Detergent composition for automatic dishwashers - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention
Automatic food that does not contain and shows excellent detergency against various stains
The present invention relates to a detergent for a dishwasher. 2. Description of the Related Art In recent years,
Automatic dishwashers have spread rapidly, not only for commercial use.
It has also been widely used in ordinary households. [0003] Representatively, such as rice cooked firmly on tableware
Pigment stains such as starchy stains and tea
Conventionally, as a detergent for automatic dishwashers to remove
Are amylolytic enzymes such as α-amylase and dichlor
Phosphorus containing chlorine bleach such as isocyanuric complex
Detergents have been mainly used. Meanwhile, enzymes, fragrances, dyes
Is unstable to chlorine-based bleach,
Phosphorus detergent using oxygen bleach instead of bleach
(JP-A-60-60198). However, many cleaning agents are not available.
At present, where detergents are the mainstream, phosphate
Detergents can be a social problem. So, automatic food
Detergent power for various types of dirt is reduced with the spread of dishwashers
There has been a strong demand for a technology that eliminates phosphorus without the need. Means for Solving the Problems [0005] The present inventors have proposed such a method.
As a result of intensive research to meet the demands, a specific nonionic interface
If a surfactant and a specific polyoxypropylene are used together,
Detergent composition with excellent detergency and performance equivalent to detergent
It was found that a product was obtained, and the present invention was completed. That is, the present invention is represented by the following general formula (I):
A non-ionic surfactant (a) and an oxypropylene group
Polyoxypropylene (b) having a degree of polycondensation of 10 to 90 and
Providing a detergent composition for automatic dishwashers containing
It is. RO- (AO) _n -(A'O) _m -R '(I) wherein R is an alkyl group having 8 to 18 carbon atoms, and R' is
An alkyl group having from 10 to 10, A is an alkylene group having 2 to 3 carbon atoms,
A 'represents an alkylene group having 3 to 4 carbon atoms, and A and A' are the same
It may be. n and m are average number of moles added, and n is
1 to 10, m is 0 to 5. DETAILED DESCRIPTION OF THE INVENTION Non-ionic component (a) of the present invention
The surfactant is represented by the above general formula (I),
R in the general formula (I) has 8 to 8 carbon atoms in terms of solubility and detergency.
18 alkyl groups are used, either linear or branched
Is also good. R preferably has 9 to 15 carbon atoms. In general formula (I)
The nonionic surfactant represented can be a commercial product.
For example, the BASF “PullaFac LF” series
Available. A nonionic surfactant represented by the general formula (I)
Are also suitable compounds represented by the following general formula (Ia)
You. RO- (EO) _n -(A'O) _m -CH _Three (Ia) wherein R, A ', n and m have the above-mentioned meaning, and EO is
Tylene oxide. ]. The polyoxypropyl component (b) of the present invention
Rene has an average degree of condensation of oxypropylene groups of 10 to 90,
Preferably it is 30-50. Those in this range have excellent detergency
ing. The polyoxypropylene used in the present invention
Therefore, those with an average molecular weight of 600 or more and 5000 or less are preferred.
In particular, those having 2,000 to 4,000 are preferable. In the present invention
Thus, such polyoxypropylene is present in the composition at 0.001%.
-10% by weight, more preferably
0.005 to 5% by weight. Formulation of polyoxypropylene
If the amount is less than 0.001% by weight, sufficient cleaning effect
If it is not obtained and contains more than 10% by weight,
Cleaning efficiency is impaired. In the present invention, the component (a) and the component (b)
(a) / (b) = 1/1 to 10/1 by weight.
And more preferably (a) / (b) = 1/5 to 5/1.
You. Also, the components (a) and (b) are added in a total amount of (a) + (b) of 0.1.
-20% by weight, more preferably 1.
0 to 10% by weight. (a) component and (b) component within this range
The use provides a desired detergency. The composition of the present invention may contain an enzyme.
Is preferred. Amylase, protein
Ze, cellulase, lipase, pullulanase, isopulla
1 selected from the group consisting of an enzyme and an isoamylase
More than one type of enzyme is included. The enzyme is present in the composition at 0.1
It is preferable to mix 10% by weight, more preferably 0.2%
~ 5% by weight. It is to be noted that the enzyme is compounded based on the activity value.
Can also. In this case, the activity of each enzyme is as follows
Measured. <Lipase> Method for measuring specific activity of lipase
Is based on the hydrolysis of triolein at constant pH
The activity is indicated by the activity per 1 g of enzyme.
You. The activity unit is “LU / g”, and 1 LU is
Nyl alcohol (PVA) as an emulsifier, 30
Decompose and produce fatty acid esters at pH 10.5 ° C
The number of moles of fatty acid to be added is divided by the time required (min).
Value, ie 1 μmol (micromol) of fat per minute
It is the amount of the enzyme that produces fatty acids. Specifically, pH10.
As a buffer solution of No. 5, a 50 mM glycine buffer solution was used as an emulsifier.
Is PVA with a polymerization degree of 1700 in 1000 ml of distilled water.
18 g (manufactured by Katayama Chemical Co., Ltd.) and PVA having a polymerization degree of 500
2% PVA water with 2 g dissolved (Wako Pure Chemical Industries, Ltd.)
Prepare a solution and add 2% PVA aqueous solution to the substrate emulsion
To 10 ml, homogenate 1.0 g of triolein (manufactured by SIGMA)
What was emulsified for 5 minutes or more with a diner was used. Activity
The measurement was performed using Y.Kondoh using high performance liquid chromatography.
and S. Takano, Analytical Chemistry, vol.58, pp2
380-2383 (1986). The composition of the reaction solution is shown below.
You. Lipolytic enzyme solution 1.5 ml (Dissolve enzyme with 50 mM glycine buffer (pH 10.5)
Solved) 1.0 ml of substrate emulsion. The method for calculating the specific activity is described below.
Shown in Preparation of calibration curve: 9.02 mM 1-mono ole on the horizontal axis
(1-MO, SIGMA) injection volume, and the vertical axis shows the peak area.
A calibration curve was prepared. LU measurement: One sample was added to the above reaction solution to which lipolytic enzyme was added.
Give constant stirring power and react at 30 ° C for 30 minutes.
Stop solution [50% ethanol (Wako Pure Chemical Industries, Ltd.), 10%
Sodium dodecyl sulfate (Wako Pure Chemical Industries, Ltd.)] 0.5 m
l, and add nitrogen gas in a water bath at 100 ° C.
The solvent was removed while purging. 5.0m to this
of acetone (Wako Pure Chemical Industries, Ltd.), stir well, and filter.
I have. Further, a filter obtained by analyzing 30 μl of the filtrate is obtained.
From the results of the chromatograph, Geolein (DO), Mono Ole
(MO) and glycerin (GLY) calibration curve from peak area
Each volume in 30 μl was determined. Calculation of specific activity value: From the concentration obtained in
To determine the specific activity value (P). Total fatty acid content (μmol / micromol) = (DO content + MO content)
× 2 + GLY volume × 3) × 5000μl / 30μl × 10 ^-3 [Note: μl is microliter] Therefore, specific activity value P: LU / g = (total amount of generated fatty acid: μmol) /
[(Amount of enzyme added: g) × (reaction time: min)] The lipase used in the present invention is supplied in the form of a granular material before it is supplied.
From 0.1 g / g based on the specific activity of the enzyme
It is preferable to mix to be 10,000 LU / g.
is there. <Cellulase> Cellulose-degrading enzyme (cell
Rase) is preferably carboxymethylcellulose
Is the optimal pH of 7 or more when
Or relative activity of more than 50% relative to optimal conditions at pH 8 or higher
Alkali-active cellulolytic enzyme with the above activity
preferable. Such cellulase-degrading enzymes are disclosed in
Cellulase described in JP-A-63-264699 is preferred.
As a production strain, Bacillus sp. Is good
More specifically, specifically, Bacillus sp. KSM
-635 strain (FERM BP-1485), KSM-
521 (FERM BP-1570) and KSM-52
2 (FERM BP-1512) and KSM-580
(FERM BP-1511) and KSM-534 (F
ERM BP-1508) and KSM-539 (FER
MBP-1509) and KSM-577 (FERM)
BP-1510) and KSM-588 (FERM BP)
-1513), the same KSM-597 (FERM BP-1)
514). Cellulose content from these strains
A method for producing a degrading enzyme is described in JP-A-63-26469.
No. 9 can be referred to. In the present invention, the cellulolytic enzyme comprises:
CMC degradation per 1g of the following enzymes supplied in granular form
After determining the activity, 0.5-10000 U / g in 1 g,
Preferably, it is blended to be 1 to 50 U / g.
preferable. Carboxylase enzyme activity is carboxy
Indicated by decomposition activity to methylcellulose (CMC)
And the CMC degradation activity is measured by the method shown below.
be able to. CMC (manufactured by Nippon Paper Industries Co., Ltd .: viscosity 7 to 20)
cp (1%, 25 ° C.), substitution degree 0.65 to 0.75)
0.4 ml of 2.5% aqueous solution, 0.5 M glycine buffer
(PH 9.0) 0.2 ml and deionized water 0.3 ml
0.1 ml of enzyme solution to a substrate solution consisting of
React for 0 minutes. After the reaction, 3,5-dinitrosalicylic acid
[3,5-Dinitorosalicylic acid (DNS)] method
Quantify reducing sugars. That is, 1.0 ml of the reaction solution
NS reagent (1.6% sodium hydroxide, 3,5-dinit
Rosalicylic acid 0.5% and potassium sodium tartrate 4
Hydrate (30% aqueous solution) at 100 ° C. for 5 minutes.
After heating, add 4.0 ml of deionized water after cooling.
And colorimetrically quantitate it at a wavelength of 535 nm. enzyme
The titer was 1 μmol of glucose per minute under the above conditions.
1 unit (U) of the amount of enzyme that produces reducing sugars
And <Protease> Measurement of protease activity
Is based on the Anson-hemoglobin method (Anson. ML.
J. Gen. Physiol. , Vol. 22, p79
(1938)). That is,
The final concentration of urea-modified hemoglobin used as a substrate was 1
In a solution prepared to be 4.7 mg / ml,
After reacting at 25 ° C and pH 10.5 for 10 minutes,
Trichloroacetic acid was added to the solution to a final concentration of 31.25 mg / ml.
So that the trichloroacetic acid soluble matter is
Color with reagent. This color degree is 1 mmol
Reaction 10 minutes from the calibration curve with the coloration of rosin as 1 APU
Per activity and convert it to per minute
And by measuring. Therefore, in the present invention, 1AP
U is defined as 1 mmol of tyrosine by phenol reagent
Trichloroacetic acid soluble matter of the same color degree as that of color development for 1 minute
It refers to the amount of alkaline protease given in between. Book
In the invention, the protease is provided in particulate form;
The amount whose enzyme activity becomes 0.1-30000 APU / g
It is compounded by. It is preferable that the enzyme activity is less than 0.1 APU / g.
Good detergency cannot be obtained and 30,000 APU / g
Exceeding blending is preferred on balance of blending with other ingredients
I don't. <Amylase and pullulanase>
Are amylase, isoamylase, pullulanase,
Amylolytic enzymes such as lulanase can be used.
Wear. Here, pullulanase, isopullulanase and i
Soamylase is the same as α-amylase and β-amylase.
Is involved in starch degradation as described above,
Amylase and β-amylase in amylose and amylopectin
Cleaves the α-1,4 bond of
And amylase are α-
1,6 bond, isopullulanase is near the α-1,6 bond of the sugar chain.
Known as an enzyme that selectively cleaves the nearby α-1,4 bond
That is, in that it cleaves the branched chains in amylopectin.
Different from α-amylase and β-amylase. Ma
Α-amylase is present in amylose and amylopectin.
Is an end type that randomly breaks internal bonds of
Β-amylase cleaves regularly from the terminal group
It is an exo-type amylase. The above-mentioned starch debranching enzyme used in the present invention
Can be obtained from various sources, but is generally derived from fungi
Is done. Suitable starch debranching enzymes belong to the genus Klebsiella
Fungi, bacteria belonging to the genus Bacillus, belonging to the genus Aspergillus
Amylope obtained from fungi, bacteria belonging to the genus Pseudomonas
Pullulaner showing Kuching-6-glucanohydrase activity
, Isopluranase and isoamylase. The starch branching enzyme according to the present invention is commercially available.
Commercial products can also be used. Commercially available pull runner
As for zea, “Splentase” (registered trademark, Amano Pharmaceutical)
Co., Ltd.), “Promozyme 200L” (registered trademark, Novo I
Industries) and “isoamylases”
Mirase "(reagent, Seikagaku Corporation). These starch debranching enzymes are generally used in the form of granules.
And its enzyme activity is about 10 ^Three ~Ten ⁸ unit
/ G. In the present invention, the pH is adjusted to alkaline, especially pH 8-11.
And a starch debranching enzyme having an optimal action is preferred.
Lucalipurulanase is preferred. The optimal pH is
It is measured by the method described in JP-A-3-87176. Alkaline
As lulanase, Bacillus sp. KSM-AP1876
No. 10887) is available. The starch debranching enzyme is EYCLee and WJ W
helan, "Glycogen and Starch Debranching Enzymes in
the Enzymes "Vol.5 (PDBoyer ed.) pp192-234, Acad
emicPress, New York. From plant-based pull runner
It is defined as a feature of ze (R enzyme), α-1,6
Enzyme that specifically cleaves an amylopectin
Reduces the viscosity, increases iodine coloration, and increases reducing power.
I do. Also, due to the presence of this enzyme, β-amylase
Report that the degradation is significantly accelerated. Also, among the enzymes that can be used in the present invention, α
-Amylase is a commonly used detergent enzyme
So you can use them. Suitable α-amylase
Bacillus licheniformis and Bacillus subtili
is an enzyme obtained from “Tamamil” (registered trademark)
Marko, Novo Industries, Inc., “Maxamil” (registered)
Trademark, Gist). Also, β-Amirror
Bacteria such as Bacillus sp., Soybean, malt, etc.
The enzyme obtained from can be used.
No ”(registered trademark, Amano Pharmaceutical Co., Ltd.),“ Multitome ”
(Registered trademark, Nagase Seikagaku Corporation)
You. These enzymes are generally supplied in particulate form,
Enzyme activity is about 10 ^Three ~Ten ⁸ Unit / g. In particular
In the light of alkali, alkaline α-
Amylase is preferred. As alkaline α-amylase
For the above, the above-mentioned “termamill” can be used. These enzymes include pullulanase, isopul
An enzyme (A) selected from lanase and isoamylase,
Enzymes selected from α-amylase and β-amylase
(B) is the total amount of (A) and (B) in the composition, usually 0.1 to
20% by weight, preferably 0.1 to 15% by weight is blended. Ma
In addition, starch debranching enzyme (A) and α-amylase or β-amylase
The amylase (B) mixing ratio is (A) / (B)
= 10/1 to 1/100, preferably 2/1 to 1/50
It is good to use. Further, the cleaning composition of the present invention is used for cleaning.
When cleaning, combine the enzymes (A) and (B) in the cleaning solution.
Enzyme activity is measured by the DNS (3,5-dinitrosalicylic acid) method.
10 units / g or more (1 μmol / min)
The amount of the enzyme that produces glucose is defined as 1 unit (U).
Book), preferably 100 units / g or more.
It is preferred to use the inventive cleaning composition. The method for measuring the enzyme activity by the DNS method is described below.
It is shown below. This method combines enzymes (A) and (B)
Is to measure the activity of (1) Substrate: 0.5% by weight of potato-derived soluble starch (reagent,
(Guma Co.) Solution (2) Preparation of substrate solution 1.0 g of potato-derived soluble starch in 100 ml of ion-exchanged water
Dissolve. (3) Preparation of samplePour 0.5 ml of the substrate solution into a test tube, and add 100 mM Glycine-
0.4 ml of NaOH buffer (pH = 10.0), enzyme diluted appropriately
Add 0.1 ml of the solution and react in a thermostat at 50 ° C for 15 minutes.
After the reaction is completed, add 1 ml of DNS solution and add
After 5 minutes, immediately put in ice water bath and cool
I do. After cooling, add 4 ml of ion-exchanged water and mix well,
Immediately measure the absorbance at 535 nm. (4) Prepare 0.5 ml of the substrate solution in a blank test tube, and add 100 mM Glycine-
0.4 ml of NaOH buffer solution (pH = 10.0) and DNS solution
Add 1 ml and let it develop color in boiling water for exactly 5 minutes
Then, immediately put in an ice water bath and cool. After cooling, ion exchange
Add 4 ml of water exchange, mix well, and immediately at 535 nm
Measure the absorbance. (5) Preparation of calibration curvePour 0.5 ml of the substrate solution into a test tube, and add 100 mM Glycine-
0.4 ml of NaOH buffer (pH = 10.0) and glucose concentration
Glucose solution for the calibration curve so that the concentration becomes 250-1500 μmol / l.
Add 0.1 ml of the solution. 1 ml of the DNS solution was added thereto, and the mixture was boiled.
Allow the color to develop in boiling water for exactly 5 minutes.
Put in and cool. After cooling, add 4 ml of ion-exchanged water,
Mix well and immediately measure absorbance at 535 nm.
You. Determine the gradient by taking the glucose concentration on the horizontal axis and the absorbance on the vertical axis.
Therefore, the conversion coefficient (F) is calculated as follows. F = 1 / (slope) × 1/15 × 1 / 0.1 (6) Calculation of activity The enzyme activity is calculated by the following formula. Activity (U / L) = δ absorbance × F × dilution factor δ absorbance = (absorbance of sample) − (absorbance of blank)
(7) Preparation of DNS reagent (1 L) Dissolve 16 g of sodium hydroxide in 200 ml of deionized water
You. This is dissolved while gradually adding 5 g of DNS.
After complete dissolution of DNS, sodium potassium tartrate
And add 300g. After completely dissolving, add ion-exchanged water.
To make 100 ml. The composition of the present invention contains Ca (calcium).
It is preferable to add a scavenger. As a Ca scavenger
Are hydroxymono or polycarboxylic acids or
A salt of an aminocarboxylic acid having an iminodiacetic acid structure
Or its salts, silicate compounds, aluminosilicate compounds,
Crylate, acrylic acid / maleic acid copolymer salt, maleic acid
From the group consisting of the salts of copolymers of maleic acid and olefins
One or more selected Ca scavengers are included. Where
Droxoxymono or polyvalent carboxylic acids (salts)
Oxalic acid, malonic acid, succinic acid, citric acid, malic acid,
Rutalic acid and salts thereof. Imino vinegar
Examples of aminocarboxylic acids (salts) having an acid structure include ethyl
Diaminetetraacetic acid, nitrilotriacetic acid, etc. and their salts
No. In addition, hexametaphosphoric acid, aminotri
(Thylene sulfonic acid) and the like can also be blended. Ca capture
It is preferred that the agent be incorporated in the composition in an amount of 5 to 85% by weight.
And more preferably 5 to 20% by weight. The composition of the present invention may contain a bleaching agent.
Can be. Examples of bleaching agents include oxygen-based bleaching agents.
You. Oxygen bleaching agents include monoperoxyphthalic acid
Organic hydrochloric acid such as gnesium or its salt, alkali metal
Perborate (monohydrate or tetrahydrate), percarbonate and perborate
Peroxidation that generates hydrogen peroxide in aqueous solutions such as silicates
Things. Of these hydrogen peroxide adducts, preferred
New products are sodium perborate and sodium percarbonate
is there. Bleach reacts with hydrogen peroxide in water
Used together with a bleach activator to generate organic peracid
You can also. Tetraacetyl ester as a bleach activator
Tylenediamine (TAED), tetraacetylglyco
Ruuryl (TAGU), glucose pentaacetic acid (GP
A) and xylosetetraacetic acid (XTA) are commonly used.
Used. The bleach / bleach activator is 8/1 to 1 by weight.
/ 1 range. When blending bleach,
The compounding amount is 0.1 to 20% by weight, preferably 1 to 10% by weight in the composition.
%. If the bleach content is less than 0.1% by weight
If the bleaching effect is weak and contains more than 20% by weight
Inhibits other components such as enzymes. Also, bleach activator
When blended, the amount is 0.1 to 30% by weight of the composition
And preferably 1 to 15% by weight, particularly preferably 2 to 15% by weight.
10% by weight. Not more than 0.1% by weight of bleach activator
When it is full, no improvement in cleaning effect is observed, and it exceeds 30% by weight.
No further effect is obtained even if blended, and economically
It tends to be disadvantageous. The composition of the present invention may contain an alkali agent,
Surfactants other than the nonionic surfactant represented by the general formula (I)
A sexual agent can be blended. As the alkaline agent, sodium hydrogen carbonate
, Sodium carbonate, borax, sodium silicate, etc.
I can do it. Sodium silicate has metal corrosion inhibiting action
Therefore, it is desirable to use this in combination with another alkali agent.
In particular, sodium bicarbonate and sodium silicate (SiO _Two / Na
O ratio is 1/1 to 4/1, preferably 2/1 to 2.5 / 1)
Weight ratio of 35/1 to 2/1, or sodium carbonate and silica
Sodium acid (SiO _Two / Na _Two O ratio is 1/1 to 4/1, preferred
The weight ratio of 2/1 to 2.5 / 1) is 35/1 to 2/1.
It is most preferable to use it. In the present invention,
The amount of potash is preferably 5 to 85% by weight, more preferably
Or 20 to 70% by weight. Alkaline agent is 0.05-1% by weight
Adjust the concentration of detergent solution to pH 9.0-11.0.
Is desirable. The formula (I) used in the present invention is represented by the following formula:
Surfactants other than the nonionic surfactant to be
Common surfactants can be mentioned, but nonionic surfactants
Sexual agents are preferred. The nonionic surfactant is not particularly limited.
But not polyoxyethylene monoalkyl or monooxyethylene
Alkenyl ethers, polyoxyethylene alkyl esters
Phenyl ethers, polyoxypropylene monoalkyl
Or monoalkenyl ethers, polyoxybutylenemo
Noalkyl or monoalkenyl ethers, alkylene
Containing oxide-added monoalkyl or monoalkenyl group
Nonionic surfactant mixture, sucrose fatty acid esters,
Aliphatic alkanolamides, fatty acid glycerin monoe
Stels, amine oxides, ethylene oxide condensation type
One selected from surfactants and alkyl glycosides
Species or two or more are preferred. Such nonionic surfactant
Examples of the agent more specifically include the following (1) to (10)
You. (1) polyoxyethylene monoalkyl or
Monoalkenyl ethers which are alkyl groups or
The average carbon number of the alkenyl group is 10-20, and ethylene oxide
The number of moles of side addition is 1 to 30 moles on average. (2) Polyoxyethylene alkylphenyl
Ethers having an alkyl group having an average carbon number of 6 to 12;
And the number of moles of ethylene oxide added is 1 to 1 on average.
What is 25 moles. (3) Polyoxypropylene monoalkyl or
Is a monoalkenyl ether, an alkyl group or
The average carbon number of the alkenyl group is 10 to 20, and propylene
The number of moles of oxide added is 1 to 20 moles on average.
of. (4) polyoxybutylene monoalkyl or
Monoalkenyl ethers which are alkyl groups or
The average carbon number of the alkenyl group is 10 to 20, and
The number of moles added to the side is 1 to 20 moles on average. (5) An alkyl group or an alkenyl
Ethylene oxide and propylene oxide
(Molar ratio: 0.1 / 9.9-9.9 / 0.1) or ethyl
Oxide and butylene oxide (molar ratio: 0.1 / 9.
9 to 9.9 / 0.1) nonionic surfactant
Agent mixture, the average of alkyl or alkenyl groups
An alkylene oxide having 10 to 20 carbon atoms per molecule
The number of moles of side addition is 1 to 30 moles on average. (6) Higher grade represented by the following general formula (A)
Fatty acid alkanolamides or their alkylene oxa
Id adduct. Embedded image [Where R ^Three Is an alkyl group having 10 to 20 carbon atoms or
Is an alkenyl group, and R ^Four , R ^Five Are the same or different
Is CH _Three Where p is a number from 1 to 3 and q is a number from 0 to 3.
You. (7) Sucrose fatty acid esters, the average of fatty acid portions
Those having 10 to 20 carbon atoms. (8) Fatty acid glycerin monoesters
The fatty acid portion has an average carbon number of 10 to 20. (9) Amine oxides. For example, carbon number 1
From 24 to 24 linear or branched alkyl or alkenyl groups
Alkyl or alkenyl amine oxides
It is. More preferred amine oxides include the following
Alkylamine oxides represented by the general formula (B) include
I can do it. Embedded image In the above general formula (B), R ⁶ Is carbon number 8
~ 24 alkyl or alkenyl groups, especially carbon
Alkyl groups of the numbers 12 to 18 are preferred. R ⁷ , R ⁸ Has 1 to 1 carbon atoms
Although it is an alkyl group having 3 carbon atoms, a methyl group having 1 carbon atom is particularly preferable.
Good. (10) Alkyl polysaccharides. For example, the general
An alkyl polysaccharide represented by the formula (C). R ⁹ (OR ^Ten ) _x G _y (C) [wherein, R ⁹ Is an alkyl having 8 to 18 carbon atoms in a straight or branched chain.
Represents a kill group, an alkenyl group, or an alkylphenyl group.
Then R ^Ten Represents an alkylene group having 2 to 4 carbon atoms, and G represents
It is a residue derived from a reducing sugar having 5 to 6 carbon atoms. x
(Average value) is 0 to 5 and y (average value) is 1 to 5.
You. X in the above general formula (C) has an average value of 0 to 5
However, by changing this value, the water solubility of the detergent composition
And crystallinity can be adjusted. That is, if the value of x is large,
The higher the water solubility and the lower the crystallinity
You. Preferred values of x are 0 to 2, particularly preferably 0.
It is. On the other hand, if y is greater than 1,
That is, when a sugar chain of two or more saccharides is used as a hydrophilic group,
When the binding mode is 1-2, 1-3, 1-4, 1-6
An α-, β-pyranoside bond or a furanoside bond
And any mixtures having these mixed binding modes
Can be included. In addition, y of general formula (C)
The average value is 1 to 5, preferably 1 to 1.5, more preferably
1.1 to 1.4. Incidentally, the measured value of y was measured by proton NMR method.
It is due to. Also, R in the formula ⁹ Is soluble and washable
From the viewpoint of properties, an alkyl group having 10 to 14 carbon atoms is preferable. Ma
T, R ^Ten Is an alkylene having 2 to 3 carbon atoms from the viewpoint of water solubility.
Groups are preferred. Further, G is a source of monosaccharides or disaccharides or more.
The structure is determined by the material,
For monosaccharides, glucose, fructose, galacto
Sauce, xylose, mannose, lyxose, arabino
And mixtures thereof, and disaccharides or more.
Is maltose, xylobiose, isomaltose, cello
Biose, gentibiose, lactose, sucrose,
Nigerose, Turanose, Raffinose, Gentian
And melezitose, and mixtures thereof.
You. Of these, preferred raw materials are those that are readily available.
In terms of properties and costs, glucose and
Ktose; maltose and sucrose for disaccharides and higher
It is a source. Of these, glucose is particularly preferred in terms of availability.
Is preferred. Furthermore, pentaerythritol isos
Sorbito, a 1 mol adduct of teaaryl glycidyl ether
Addition of 1 mole of isopropyl isostearyl glycidyl ether
Body, mannitol 2-octyldodecylglycidyl ester
1 mol adduct of methyl, methyl glucoside isostear
Diglycerin, 1 mol adduct of lyl glycidyl ether
A 1 mol adduct of isostearyl glycidyl ether,
At least one long molecule in one molecule such as phytantriol
Chain-branched alkyl or alkenyl group and at least 3
And a nonionic surfactant having a hydroxyl group. Among these nonionic surfactants, (1)
, (5), (6), (9) and (10) are preferred, further (5),
(9) and (10) are particularly preferred. In the present invention, the distribution of other surfactants
The total amount is 0.0010 to 10% by weight, preferably 1 to 10% by weight.
You. If the amount of surfactant is less than 1% by weight
Insufficient cleaning effect is obtained, containing more than 10% by weight
In such a case, the degree of freedom of compounding is unfavorably reduced. The detergent composition for an automatic dishwasher of the present invention
Has a hydrocarbon chain length of about 8 to 18 to prevent copper corrosion.
0.1 to 5% by weight of
It is also effective to add zotriazole or the like. The detergent composition for an automatic dishwasher of the present invention is
Generally, it can be manufactured in the form of a dry powdery granular product. Ie this
Dry the powdered or granular components according to standard manufacturing techniques.
Formula mixing and then liquid components (such as nonionic surfactants)
It can also be produced by spraying on the mixture,
There is no particular limitation. The detergent for an automatic dishwasher according to the present invention comprises:
Certain nonionics without the use of strong alkali as described above
Sufficient detergency by using surfactant as an essential component
It is difficult to use strong alkali mainly.
Used for automatic home dishwashers. As described above, the automatic dishwasher of the present invention is used.
The cleaning agent is oil and oil, which is the basic performance of automatic dishwasher cleaning agents.
Tripoly with sufficient detergency against starch
Removes pigment stains that do not contain phosphate and settle on tableware
Automatic food with high practical value that also has castability, that is, bleaching performance
It is a cleaning agent for dishwashers. Next, the present invention will be described more specifically with reference to examples.
As will be explained, the invention is limited by these examples
Not something. In the following examples, “%” means “weight”
% ". Examples 1 to 7 and Comparative Examples 1 to 4 The compositions shown in Table 1 below were prepared, and washed under the following washing conditions.
The following detergency tests were performed and evaluated. Table 1 shows the results
Show. <Washing conditions> Washing machine used: Matsushita Electric Co., Ltd. fully automatic dishwasher (model
NP-820) A cleaning solution is sprayed from a rotating nozzle, and its spray trajectory
A type that cleans the dishes set on the top. Washing temperature; gradually increase from 5 ° C to 55 ° C. Washing water; detergent concentration of hardness 3.5 ° DH; 0.2% Washing time; washing 20 minutes-rinsing 20 minutes Circulating water volume during washing; about 2.5 liters. <Evaluation of detergency> [Measurement method for detergency of cooked rice] (Preparation of contaminated dish)
3g is spread on a 25cm diameter magnetic dish and painted.
Six pieces of the cloth were air-dried at room temperature for 24 hours, and then washed. (Evaluation method for cleaning effect of rice cooked soil)
Blue portion generated by iodine color reaction of cooked rice
Area (P) is measured by photographic judgment, and the initial contaminated area
From (S), the washing rate of each dish was determined by the following equation. Furthermore,
The washing rates of the six dishes were averaged to obtain an average washing rate (%). Washing rate of one dish (%) = [(S−P) / S] × 100 [Method for Measuring Complex Soil Detergency] (Preparation of Contaminated Dish) White Source (Heinz Can
Filled with 100g of margarine (Neosof made by Snow Brand)
G), add 10 g, heat to 60 ° C, mix well, and remove
I do. For each 25 cm diameter magnetic dish, combine
Then apply 5 g and bake at 120 ° C for 15 minutes. This one
After leaving it day and night, it was subjected to washing. (Washing test and washing power evaluation method) Put 5 contaminated dishes into the washing machine
Then, washing was performed under the above washing conditions. One dish after washing
Each sheet is judged according to the following criteria, and cleaning is evaluated according to the following formula.
Valuation points were calculated. Completely washed 5 points Slight residual stains 4 points A small amount of residual stains is observed Approximately 1/4 of the 3-point dishes have residual stains About 1/2 of the 2-point dishes are dirty. Residue is observed. 1 point was not washed at all. 0 point washing evaluation point = [sum of evaluation points of each contaminated dish] × 4. (Note) * 1: Pullulafak LF131 (manufactured by BASF), Formula (I) smell
R: C ₉ ~ C _Fifteen Alkyl group, R ': methyl group, ethylene
3-7 oxide addition moles, with propylene oxide
Added mole number 0.5 to 2 * 2: Pullrafak LF431 (manufactured by BASF), Formula (I) smell
R: C ₁₃ ~ C _Fifteen Alkyl group, R ': methyl group, ethyl
Average number of moles of added oxide 6.4, propylene oxide
Average number of moles added 3 * 3: polypropylene glycol, average molecular weight about 3000, flat
Polycondensation degree approx. 50 (diol type, Wako Pure Chemical Industries, Ltd.) * 4: Polypropylene glycol, average molecular weight approx. 1000, flat
Polycondensation degree approx. 17 (diol type, Wako Pure Chemical Industries, Ltd.) * 5: Termamyl 60T (Novo Nordisk Bio Indus)
* 6: Savinase 12.0T (Novo Nordisk Bio Ind.)
* 7: Softanol EP7085 (Nippon Shokubai Co., Ltd.)

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C11D 3/386 C11D 3/386 3/395 3/395 10/02 10/02 (56) References JP-A-8-73890 ( JP, A) JP-A-58-109598 (JP, A) JP-A-60-18591 (JP, A) JP-A-8-504220 (JP, A) WO 97/029172 (WO, A1) (58) Field surveyed (Int.Cl. ⁷ , DB name) C11D 1/72 C11D 1/722 C11D 1/825 C11D 3/33 C11D 3/37 C11D 3/386 C11D 3/395 C11D 10/02

Claims (1)

(57) [Claims 1] An average degree of condensation between a nonionic surfactant (a) represented by the following general formula (I) and an oxypropylene group is 10 to 9:
0.1 to 20 times in total with 0 polyoxypropylene (b)
% (A) and (b) = (a) / (b) = 1/2
A detergent composition for automatic dishwashers, which is 〜 to 1/1 . RO- (AO) _n- (A'O) _m -R '(I) wherein R is an alkyl group having 8 to 18 carbon atoms, and R' is a carbon atom having 1 carbon atom.
An alkyl group of up to 10; A is an alkylene group having 2 to 3 carbon atoms;
A ′ represents an alkylene group having 3 to 4 carbon atoms, and A and A ′ may be the same. n and m are average number of moles added, and n is 1
-10 and m are 0-5. ]