JP5234568B2 - Dishwashing detergent composition and precleaning detergent composition - Google Patents

Description

  The present invention relates to a cleaning composition for washing dishes and a cleaning composition for preliminary cleaning.

  In the kitchens of hotels, restaurants, lunch centers, etc., automatic dishwashers are rapidly used for the purpose of mechanizing or automating the cleaning of dishes, containers, cooking utensils, etc. It is popular. There are various types of cleaning agents used in this automatic dishwasher, but it is difficult to prevent the formation of protein film, starch film, etc. formed on the surface of the tableware. Therefore, it was difficult to prevent the formation of the attached protein film. For this reason, when such stains have become apparent on the surface of the tableware, it has been necessary to perform removal with a strong oxidizing agent such as sodium hypochlorite or physical removal by rubbing. However, these methods require damage to tableware and labor (cost), and cannot be said to be sufficient as a commercial tableware cleaning system.

  Therefore, a method of adding a cleaning booster containing an enzyme to a low alkali cleaning agent as an active substrate is used in starch film cleaning (see, for example, Patent Document 1). However, this method has a problem that the enzyme in the cleaning agent is deactivated due to long-term storage of the cleaning agent. Further, even if the enzyme is changed to one that is effective for protein washing, the enzyme is immediately deactivated as in the case of starch washing, and the protein cannot be washed effectively.

  Further, a dipping detergent composition containing a protease, which is an enzyme effective for protein washing, is known (see, for example, Patent Document 2). However, even in this method, the stability of the enzyme in the detergent stock solution cannot be obtained, and it was difficult to maintain the soil removal effect for a long time in a hot and humid kitchen environment.

  In addition, these detergents do not have sufficient foam suppression performance, and in recent years, when used in commercial dishwashers and mechanical dipping devices where spraying pressure has become strong, there is a problem of foaming. In some cases, it was not possible.

Japanese National Patent Publication No. 8-510397 JP-T 6-510802

  Therefore, the problem to be solved by the present invention is that the enzyme in the cleaning agent can be stably retained for a long period of time, and starch and protein stains can be effectively removed. It is providing the cleaning composition and the cleaning composition for preliminary cleaning.

Accordingly, the present inventors have intensively studied and stably maintained the enzyme in the cleaning agent for a long period of time, and can effectively remove starch and protein stains, and further have a sufficient foam-suppressing effect. And the cleaning composition for preliminary washing | cleaning was discovered and it came to this invention.
That is, the present invention includes (A) nonionic surfactant, (B) protease , (C) glycine, ( D1) specific boron-containing compound, (D2) specific calcium-containing compound, and (D3) specific polyhydric alcohol. It is a cleaning composition for dishwashing characterized by containing.

  The effect of the present invention is that the enzyme in the detergent can be stably retained for a long period of time, starch and protein soils can be removed, in particular, proteins can be removed, and the detergent composition for dishwashing having a sufficient foam-suppressing effect. And providing a cleaning composition for pre-cleaning. Hereinafter, the present invention will be described in detail based on preferred embodiments thereof.

  (A) which can be used in the present invention is a nonionic surfactant, such as an alkyl (or alkenyl) ether of a polyoxyethylene block copolymer, an alkyl (or alkenyl) of a polyoxyethylene polyoxypropylene block or a random copolymer. ) Ether, polyoxyethylene polyoxybutylene block or random copolymer alkyl (or alkenyl) ether, polyoxyethylene polyoxypropylene block or random copolymer alkyl (or alkenyl) phenyl ether, polyoxyethylene polyoxypropylene Block or random copolymer alkyl (or alkenyl) amine ether, polyoxyethylene polyoxypropylene block or random copolymer polyhydric alcohol ether, polyoxyethylene Polyoxypropylene block or random copolymer polyamine ether, polyoxyethylene polyoxypropylene block or random copolymer polysaccharide, monosaccharide or oligosaccharide ether and other ethers; polyoxyethylene polyoxypropylene block or random copolymer Examples include fatty acid esters of polymers and esters such as those obtained by esterifying a fatty acid with the above ethers. Among such compounds, a compound represented by the following general formula (1) having a good balance between two performances of detergency and antifoaming property is preferable.

(R ¹ represents an aliphatic hydrocarbon group having 10 to 18 carbon atoms, m represents a number of 5 to 30, n represents a number of 3 to 20, and m is larger than n.)

R ¹ represents an aliphatic hydrocarbon group having 10 to 18 carbon atoms, for example, a decyl group, a secondary decyl group, an undecyl group, a secondary undecyl group, a dodecyl group, a secondary dodecyl group, a tridecyl group, an isotridecyl group, 2 Alkyl groups such as primary tridecyl group, tetradecyl group, secondary tetradecyl group, hexadecyl group, secondary hexadecyl group and stearyl group; alkenyl groups such as decenyl group, undecenyl group, dodecenyl group, tetradecenyl group and oleyl group can be mentioned. Among these, an alkyl group is preferable from the viewpoint of detergency, and when the number of carbon atoms is less than 10 or greater than 18, the detergency may be deteriorated. Therefore, an alkyl group having 12 to 16 carbon atoms is more preferable.

  M and n represent the number of moles of ethylene oxide and propylene oxide added, respectively. m represents a number of 5 to 30, preferably a number of 10 to 25. On the other hand, n represents a number of 3 to 20, preferably a number of 5 to 15. m and n may be any number as long as they are the above numbers, but m must be larger than n. If m is smaller than n or the same number, the detergency may be inferior.

  When a compound represented by the following general formula (2) of (A) is further added, the defoaming property can be improved without impairing the cleaning property.

(R ² represents a residue obtained by removing a hydroxyl group from an r-valent alcohol having 3 to 10 carbon atoms, p represents a number of 2 to 15, q represents a number of 15 to 60, q is larger than p, r represents a number of 3 to 6.)

R ² represents a residue obtained by removing a hydroxyl group from a C 3-10 trivalent alcohol. Examples of such alcohols include glycerin, 1,2,3-butanetriol, 1,2,4-butanetriol, 2-methyl-1,2,3-propanetriol, 1,2,3-pentanetriol, 1 , 2,4-pentanetriol, 1,3,5-pentanetriol, 2,3,4-pentanetriol, 2-methyl-2,3,4-butanetriol, trimethylolethane, 2,3,4-hexane Triol, 2-ethyl-1,2,3-butanetriol, trimethylolpropane, 4-propyl-3,4,5-heptanetriol, pentamethylglycerin (2,4-dimethyl-2,3,4-pentanetriol ), Trihydric alcohols such as triethanolamine and triisopropanolamine; pentaerythritol, 1,2,3 -Pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,3,4,5-hexanetetrol, diglycerin, ditrimethylolpropane, sorbitan, Tetrahydric alcohols such as N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxyethyl) ethylenediamine; adonitol, arabitol, xylitol, tri Examples include pentavalent alcohols such as glycerin; hexavalent alcohols such as dipentaerythritol, sorbitol, mannitol, idiitol, inositol, dulcitol, talose, and allose. Among these alcohols, trivalent alcohols are preferable because of their good antifoaming properties, and glycerin, trimethylolpropane, and trimethylolethane are more preferable because of their high versatility.

  Moreover, p and q represent the addition mole number of ethylene oxide and propylene oxide, respectively. p represents a number of 2 to 15, preferably 3 to 12. On the other hand, q represents a number of 15 to 60, preferably 20 to 50. p and q may be any number as long as they are described above, but q must be larger than p. When p is the same as q, the detergency may be inferior.

Any known method can be used as the method for producing the compound of the general formula (2). As the most general method, for example, the above-mentioned alcohol represented by R ² (—OH) _r and a catalyst are put into an autoclave equipped with a stirrer and an alkylene oxide introduction tube, and then a specified amount of ethylene oxide is put. The reaction is completed by stirring at 50 ° C. to 180 ° C. for 1 to 10 hours under a pressure of 0.03 MPa to 1 MPa. Thereafter, a prescribed amount of propylene oxide is added, the reaction is completed under the same reaction conditions as ethylene oxide, and finally the catalyst is removed. The reaction temperature is preferably 70 ° C to 160 ° C, more preferably 80 ° C to 150 ° C. When the reaction temperature is 50 ° C. or lower, the reaction rate may be slow, so the reaction may not be terminated. When the reaction temperature exceeds 180 ° C., problems such as coloring may occur. Also, if the pressure is lower than 0.03 MPa, the amount of alkylene oxide that can be put into the reactor is too small, and the reaction may take time. If it exceeds 1 MPa, the alkylene oxide in the reactor In some cases, it becomes difficult to control the reaction.
Examples of catalysts that can be used include strong acids such as sulfuric acid and toluenesulfonic acid; metal halides such as titanium tetrachloride, hafnium chloride, zirconium chloride, aluminum chloride, gallium chloride, indium chloride, iron chloride, tin chloride, and boron fluoride. ; Hydroxides, alcoholates and carbonates of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide, sodium methylate and sodium carbonate; metals such as aluminum oxide, calcium oxide, barium oxide and sodium oxide Oxides; organometallic compounds such as tetraisopropyl titanate, dibutyltin dichloride, and dibutyltin oxide. The amount of catalyst added may be 0.01 to 1% by mass, preferably 0.05 to 0.5% by mass, based on the final product after addition of the alkylene oxide. If the amount of the catalyst is too small, the reaction rate becomes slow, and if it is too large, the final catalyst removal becomes difficult.

Can be (B) used in the present invention is Ru enzyme der. From the viewpoint of washing performance and cost, also for the best stabilizing efficiency of the enzyme, stabilization in detergent ever to use was difficult protease.

  (C) that can be used in the present invention is glycine. Glycine functions as an enzyme stabilizer, which is a function that has not been known so far, and exerts a great effect as a stabilizer for various enzymes, particularly proteases that are proteolytic enzymes.

  (D) that can be used in the present invention is one or more compounds selected from polyhydric alcohols other than boron-containing compounds, calcium-containing compounds, and compounds represented by the general formula (2). (D) also has the effect of stabilizing the enzyme in the same manner as (C), but when used together with (C), it can stabilize the enzyme more effectively than when (C) or (D) alone. it can.

Examples of the boron-containing compound, sodium boric acid, potassium borate, sodium tetraborate disodium, using a hydrate of disodium tetraborate. Among these, sodium borate and potassium borate are preferable because of their high enzyme stabilization effect.

As the calcium-containing compound, a calcium salt of carboxylic acid such as calcium formate, calcium acetate, calcium propionate, calcium citrate or the like is used . Among these, calcium formate and calcium acetate having a small molecular weight are preferable because an effect can be obtained with a small addition amount.

Examples of the polyhydric alcohol other than the compound represented by the general formula (2), d Ji glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5 pentanediol, neopentyl glycol, isoprene glycol (3-methyl-1,3-butanediol), 1,2-hexanediol, 1,6-hexanediol dihydric alcohols le; glycerin, 1,2,3-butane Triol, 1,2,4-butanetriol, 2-methyl-1,2,3-propanetriol, 1,2,3-pentanetriol, 1,2,4-pentanetriol, 1,3,5-pentanetriol 2,3,4-pentanetriol, 2-methyl-2,3,4-butanetriol, trimethylolethane, 2,3, -Hexanetriol, 2-ethyl-1,2,3-butanetriol, trimethylolpropane, 4-propyl-3,4,5-heptanetriol, pentamethylglycerin (2,4-dimethyl-2,3,4- pentane triol), triethanolamine, trihydric alcohols triisopropanolamine Amin; dipentaerythritol, 1,2,3,4-pen Thante trawl, 2,3,4,5-hexane tetrol, 2,4, 5-pentanetetrol, 1,3,4,5-hexanetetrol, diglycerin, ditrimethylolpropane, sorbitan, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine tetravalent alcohols; adonitol, arabinose Tall, xylitol, pentavalent alcohols triglyceride emissions; dipentaerythritol, sorbitol, mannitol, iditol, inositol, dulcitol, talose, hexavalent alcohols such as Arrow scan and the like. Among these alcohols, divalent and trivalent alcohols are preferable and divalent alcohols are more preferable because of their high enzyme stabilization effect.

  As a compounding quantity of the cleaning composition for tableware washing | cleaning of this invention, what is necessary is just to make it solid content become 0.01-50 mass% with respect to the whole composition. If it is less than 0.01% by mass, the detergency may be inferior. If it is more than 50% by mass, the viscosity of the entire composition may be excessively increased, making it difficult to handle or gelling. Also, the higher the concentration, the more efficient the transportation. Therefore, it is sufficient to dilute with water so that the solid content becomes 0.01 to 20% by mass, preferably 0.02 to 10% by mass, more preferably 0.02 to 5% by mass at the time of use.

  Moreover, each compounding quantity is (A) 10-10 mass parts, (B) is 0.1-10 mass parts, Preferably, it is 0.3-4 mass parts; (C) is 0.1-4 masses. Parts, preferably 0.2-3 parts by mass; (D) is 0.01-15 parts by mass, preferably 0.05-10 parts by mass.

  In addition to the above (A) to (D), the dishwashing detergent composition of the present invention may optionally further include a water-soluble polymer such as polyacrylic acid soda and acrylic acid sulfonic acid copolymer, sodium sulfate (sodium sulfate) ), Inorganic salts such as potassium sulfate; bleaching agents such as percarbonate, perborate, sulfonated phthalocyanine salt, hydrogen peroxide; ethanol, propanol, 2-propanol, lower alkyl ethoxylate, benzenesulfonate, para Solubilizers such as toluene sulfonate; chlorine scavengers such as ammonium sulfate, urea, guanidine hydrochloride, guanidine carbonate, guanidine sulfamate, thiourea dioxide, monoethanolamine; dyes, fragrances, water and the like can be blended.

  The cleaning composition for preliminary cleaning according to the present invention comprises the cleaning composition for cleaning dishes according to the present invention. The pre-cleaning is pre-cleaning in order to efficiently perform the main cleaning of an automatic dishwasher or the like, and has effects such as shortening the cleaning time of the main cleaning and eliminating the remaining washing. The cleaning composition for pre-cleaning of the present invention may be any known pre-cleaning method, for example, a method of immersing tableware in a cleaning solution stored in a sink or the like, And the like.

Hereinafter, the present invention will be specifically described by way of examples. In the following examples and the like,% and ppm are based on mass unless otherwise specified.
The following three tests (detergency test, foam suppression test, enzyme stability test) were performed on the compositions of Examples 1 to 5 shown in Table 1 and Comparative Examples 1 to 5 shown in Table 2. I went. The results are shown in each table. The cleaning compositions used in all the following experiments were those in which 800 ml was placed in a 1 liter polyethylene bottle and stored for 90 days in a thermostatic chamber at 40 ° C.
Example 1 is a reference example.

1. Detergency test <Cleaning conditions>
Washing machine used: JWD-6 (Ishikawajima-Harima Heavy Industries, Ltd. automatic dishwasher)
Washing temperature: 66 ° C
Cleaning time: 40 seconds Water used: Water with a hardness of 10 ° DH (adjusted with calcium chloride)
Detergent concentration: 0.1% (solid content conversion)

<Adjustment of items to be washed>
5 g of rice starch was dissolved in 20 g of water and stirred at 80 ° C. for 30 minutes for gelatinization. 20 g of beef tallow dissolved in this was added and stirred well, cooled to 53 ° C., and then emulsified by adding 10 g of egg yolk to make it dirty. 2 g of this soil was uniformly applied to a polypropylene dish (diameter: 15 cm) and dried at room temperature to obtain an object to be washed.

<Detergency evaluation method>
Five test articles prepared by the above method were placed in a fixed position of the washing machine, washed under the above washing conditions, and then lightly rinsed with running water. After washing, the remaining dirt on the object to be washed was sketched in a 5 mm square grid pattern, the clean grid pattern was counted, and the clean area rate was defined as the cleaning rate. It can be said that the larger the value of the cleaning rate, the better the cleaning power.

<Detergency evaluation criteria>
◎: Cleaning area ratio is 98% or more ○: Cleaning area ratio is 95% or more Δ: Cleaning area ratio is 85% or more ×: Cleaning area ratio is less than 85%

2. Antifoam test Washing machine: JWD-6 (Ishikawajima-Harima Heavy Industries, Ltd. automatic dishwasher)
Washing temperature: 40 ° C
Detergent concentration: 0.1% (solid content conversion)
Dirty conditions: Dirty dishes similar to the items to be cleaned (test items to be cleaned)

<Evaluation method of foam suppression performance>
Five test objects to be washed were put in a washing machine, and the washing process of the washing machine was continuously operated for 5 minutes under the above-mentioned conditions, and the rotation speed of the spray arm during that time was measured. When bubbles are generated in the cleaning liquid, the spraying pressure is lowered and the physical cleaning power is hindered. The rotational speed was evaluated according to the following criteria.

<Evaluation criteria for foam suppression>
A: No inhibition of spray arm rotation is observed.
○: A decrease in rotational speed of less than 2% is observed.
Δ: A decrease in rotational speed of 2% or more is observed.
X: Immediately after operation, the pump becomes difficult to operate due to bubbles.

3. Enzyme stability test Enzyme activity was measured by the following method to determine the remaining amount of enzyme.
<Protease activity measurement>
After 1 ml of the sample solution and 5 ml of 0.6% casein aqueous solution were reacted for 10 minutes under the conditions of pH 7.5 and 30 ° C., 5 ml of protein precipitation reagent (TCA mixed solution) was added and left at 30 ° C. for 30 minutes. After standing, the obtained aqueous solution was filtered, and 5 ml of a 0.55 M Na ₂ CO ₃ solution and 1 ml of 3-fold diluted Folin reagent were added to 1 ml of this filtrate and reacted at 30 ° C. for 30 minutes. Using a spectrophotometer (SHIMADZU UV-1200), the absorbance at 660 nm of the obtained reaction solution is measured, and the whole reaction solution is given a coloration degree represented by 1γ L-tyrosine at 30 ° C. for 1 minute. The titer was determined with the protease activity as one unit. From this titer, the residual value of the protease activity after storage for 90 days at 40 ° C. was determined with the initial value of the protease activity in the detergent as 100.

<Protease activity evaluation criteria>
A: 90% or more of the initial activity value remains.
○: 70% to 90% remaining of initial activity value Δ: 60% to 70% remaining of initial activity ×: 60% or less of initial activity

  From the above, the detergent composition for dishwashing in the present invention has stable enzyme retention in the detergent for a long period of time, effectively removes starch and protein stains, and has a sufficient antifoaming effect. It is understood that is possible.

In addition, the detail of the nonionic surfactant used in the said Example is as follows.
<Synthesis Method of Nonionic Surfactant 1>
In a 3 liter autoclave equipped with a stirrer, a thermometer and a nitrogen gas introduction tube, 107 g (0.5 mol) of tetradecyl alcohol and 114 g (0.5 mol) of pentadecyl alcohol and 1.5 g of sodium hydroxide as a catalyst were added. After charging and heating up to 100 ° C., dehydration under reduced pressure at 2 kPa for 1 hour was performed. Thereafter, the pressure in the system is raised to normal pressure with nitrogen, the temperature in the system is raised to 120 ° C., 660 g (15 moles) of ethylene oxide is introduced into the system over 2 hours, and the reaction temperature is 120 ° C., and the mixture is aged for 1 hour. Was completely reacted. Thereafter, 580 g (10 mol) of propylene oxide was introduced into the system over the course of 2 hours while maintaining the same reaction temperature, followed by further aging for 1 hour. After completion of the reaction, the temperature in the system is cooled to 100 ° C., 5 g of synthetic aluminum silicate (trade name Kyoward 700, manufactured by Kyowa Chemical Co., Ltd.) is added as an inorganic adsorbent, and the mixture is stirred at 100 ° C. for 1 hour. Sodium oxide was adsorbed, the inorganic adsorbent was removed by filtration, and nonionic surfactant 1 was obtained.
Nonionic surfactant _{^{1: R 3 -O- (C 2}} H 4 O) 15 - (C 3 H 6 O) 10 -H
(R ³ is a one-to-one mixture of branched alkyl groups having 14 and 15 carbon atoms)

<Synthesis Method of Nonionic Surfactant 2>
In the same reactor and reaction method as Nonionic Surfactant 1, 33.5 g (0.25 mol) of trimethylolpropane was substituted for tetradecyl alcohol and pentadecyl alcohol, and the catalyst was 16 g of potassium hydroxide instead of sodium hydroxide. And 238 g (5.4 mol) of ethylene oxide were reacted, and then 1351 g (23.3 mol) of propylene oxide were reacted to block ethylene oxide (15% by mass) of propylene oxide (85% by mass) of trimethylolpropane. A copolymer was obtained.
Nonionic surfactant 2: block copolymer of trimethylolpropane ethylene oxide (15% by mass) propylene oxide (85% by mass)

<Synthesis Method of Nonionic Surfactant 3>
In the same reaction apparatus and reaction method as nonionic surfactant 1, instead of tetradecyl alcohol and pentadecyl alcohol, 186 g (1.0 mol) of dodecyl alcohol, 440 g (10 mol) of ethylene oxide, and 232 g (4 mol) of propylene oxide were used. It was made to react and the nonionic surfactant 3 was obtained.
Nonionic surfactant _{3: C 12 H 25 -O- (} C 2 H 4 O) 10 - (C 3 H 6 O) 4 -H

Claims (8)

A dishwashing detergent composition comprising (A) a nonionic surfactant, (B) protease , (C) glycine, (D1) a boron-containing compound, (D2) a calcium-containing compound, and (D3) a polyhydric alcohol. The (D1) boron-containing compound is one or more selected from hydrates of sodium borate, potassium borate, disodium tetraborate and disodium tetraborate, (D2) the calcium-containing compound is calcium formate, One or more selected from calcium acetate, calcium propionate and calcium citrate, and the (D3) polyhydric alcohol is ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, isoprene Glycol (3-methyl-1,3-butanediol), 1,2-hexanediol, 1,6-hexanediol, glycerin, 1,2,3-butanetriol, 1,2,4-butanetriol, 2- Methyl-1,2,3-propanetriol, 1,2,3-pentanetriol, 1,2,4-pentanetriol, 1,3,5-pentanetriol, 2,3,4-pentanetriol, 2-methyl -2,3,4-butanetriol, trimethylolethane, 2,3,4-hexanetriol, 2-ethyl-1,2,3-butanetriol, trimethylolpropane, 4-propyl-3,4,5- Heptanetriol, pentamethylglycerin (2,4-dimethyl-2,3,4-pentanetriol), triethanolamine, triisopropa Nolamine, pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,3,4,5-hexane Tetrol, diglycerin, ditrimethylolpropane, sorbitan, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxyethyl) ethylenediamine, The dishwashing detergent composition, which is one or more selected from adonitol, arabitol, xylitol, triglycerin, dipentaerythritol, sorbitol, mannitol, iditol, inositol, dulcitol, talose and allose. (A) is the following general formula (1)

(R ¹ represents an aliphatic hydrocarbon group having 10 to 18 carbon atoms, m represents a number of 5 to 30, n represents a number of 3 to 20, and m is larger than n). The detergent composition for tableware washing | cleaning of Claim 1 characterized by these. (A) is the following general formula (2)

(R ² represents a residue obtained by removing a hydroxyl group from an r-valent alcohol having 3 to 10 carbon atoms, p represents a number of 2 to 15, q represents a number of 15 to 60, q is larger than p, r represents a number of 3 to 6.)
The cleaning composition for dishwashing according to claim 1 or 2, further comprising: The cleaning composition for dishwashing according to any one of claims 1 to 3, wherein the (D1) boron-containing compound is selected from sodium borate or potassium borate . The cleaning composition for dishwashing according to any one of claims 1 to 3, wherein the (D2) calcium-containing compound is selected from calcium formate or calcium acetate . The (D3) polyhydric alcohol is ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, isoprene glycol ( 3-methyl-1,3-butanediol), 1,2-hexanediol, 1,6-hexanediol, glycerin, 1,2,3-butanetriol, 1,2,4-butanetriol and 2-methyl- The cleaning composition for tableware washing | cleaning as described in any one of Claims 1-3 which is 1 type, or 2 or more types selected from 1,2, 3- propanetriol. The (D1) boron-containing compound is selected from sodium borate or potassium borate, the (D2) calcium-containing compound is selected from calcium formate or calcium acetate, and the (D3) polyhydric alcohol is selected from propylene glycol or glycerin. The cleaning composition for dishwashing of Claim 1 selected. A cleaning composition for pre-cleaning, comprising the cleaning composition for tableware cleaning according to any one of claims 1 to 7 .