JPS63162797A - Detergent for automatic tableware washer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to cleaning agents used in automatic dishwashers.

[Prior art]

Automatic dishwashers are not only used for commercial purposes such as restaurants, hospitals, and schools, but have also rapidly become popular for general household use in recent years.

By the way, in such an automatic dishwasher, if water, especially hard water, is used in the rinsing process after washing with a detergent, spots or streaks of water-insoluble dirt may appear on the surface of the dishes after drying. Since so-called water spots occur and significantly deteriorate the finish of tableware such as glass cups and plates, improvements in this regard are strongly desired.

As a method to eliminate these drawbacks, a method using polyoxyethylene polypropylene alkyl allyl ether as the main component of a cleaning composition (Japanese Unexamined Patent Publication No. 15209/1989)
8) Those using carboxymethyl cellulose (
! FiI (1982-34900) or gelatin (Japanese Patent Laid-open No. 52-86410) have been proposed, but although these methods have the effect of overcoming the above-mentioned drawbacks to some extent, If the amount is not increased, sufficient effects cannot be achieved, and once rinsed, the effects are significantly reduced.

〔the purpose〕

The present invention not only has good cleaning power, but also provides an excellent finish without water-insoluble spots or streaks on the surface of tableware after rinsing, even when using highly hard washing water. To provide a detergent for automatic dishwashers that does not disappear even when washed.

〔composition〕

According to the present invention, there is provided a detergent for automatic dishwashers characterized by containing chitosan or a modified product thereof.

The present inventors have discovered that it is possible to suppress the formation of water-insoluble spots and streaks, so-called water spots, that form on the surface of dishes washed and dried by an automatic dishwasher, and that the suppression effect can be improved by rinsing and washing. As a result of intensive research into cleaning agents for automatic dishwashers that do not deteriorate
It was surprisingly discovered that a cleaning agent containing chitosan or a modified product thereof is suitable for the above purpose, and the present invention was completed.

The present invention will be explained in more detail below.

Chitosan used in the present invention is a compound derived from chitin.

In chitin, N-acetyl-D-glucosamine is β-1 as shown in the general formula (1).
, 4, and chitosan is its deacetylated product, which can be expressed as in general formula (2).

In the present invention, chitosan is defined as having a deacetylation rate of 40% or more. As chitosan, oligomers that have been depolymerized to have a lower molecular weight can also be used.

High molecular weight water-insoluble polymers or oligomers (n>3
5), and low-molecular water-soluble oligomers (2≦n≦35
) or monomers can be used.

An average molecular weight of about 500 to 100,000 is used, but from the viewpoint of smoothness, one of 1000 to 70,000 is more suitable.

As chitosan modified products, various modified products such as salts of chitosan and organic acids or inorganic acids, N-substituted products, and O-substituted products of chitosan can also be used in the present invention. Specific examples of these modified products were formed into salts.

Alternatively, the following examples are exemplified together with the general formula showing a glucosamine unit into which a substituent has been introduced.

(A) A salt of chitosan and an organic or inorganic acid (in the formula,
represents an anionic residue of an organic or inorganic acid. ) Organic acids include acetic acid, propionic acid, butyric acid, lactic acid, malonic acid, succinic acid, citric acid, malic acid, tartaric acid, maleic acid, fumaric acid, α- and β-alanine, glutamic acid, and those having 12 to 18 carbon atoms. Various amino acids such as acylglutamic acid and glycine, alkylbenzene sulfonic acids with 0 to 10 carbon atoms, aliphatic olefin sulfonic acids with 10 to 20 carbon atoms, alkyl phosphoric acid esters with 10 to 20 carbon atoms, etc. Examples include hydrochloric acid, sulfuric acid, and phosphoric acid. Among these, lactic acid, succinic acid, and malic acid.

Carboxylic acids such as citric acid and tartaric acid, toluene sulfonates, and alkyl phosphates have excellent effects,
Moreover, it is particularly preferable because it is easily available. This chitosan salt is particularly suitable for the present invention because of its excellent dispersibility in detergents.

(B) 0-hydroxyalkyl chitosan (in the formula, m is 1
~4) (C) 0-Carboxyalkyl chitosan or a salt thereof [wherein zo is -CIl, C00M, -CH2-CI,
C00M.

-CH2-CH, -CH2C00M (M represents hydrogen or a salt such as an alkali metal salt or an organic ammonium salt)
and Z2 is H or Zl. ] (D) N-acyl chitosan [R□ is an alkylcarbonyl group such as formyl, propionyl, butyryl, stearoyl, alkenylcarbonyl group such as oleyl, chloroacetyl (-COCH, C
Q), glycyl, succinyl (-COCH2CH2C0
(E) N-alkylidene or N-allylidene chitosan (wherein R2 is 11, an alkyl group such as -CH3, -C,H, - C,11s, -C,1(4No, ,
-CsH,F, -C,H4CQ.

-CGl(40CI+3.-CG11.OR,-C,H
, (OCll, ), etc. ) (F) 0-acyl chitosan (in the formula, R represents an acyl group such as -COCH, -COC, Hs, etc., and R4 is 11 or 10 OCR) (G) sulfated chitosan or the like salt (in the formula,
zl represents SoIM, Z2 represents H, or zl represents hydrogen or a salt such as an alkali metal or organic ammonium salt;
'represents ■ or -SO3M,) (H) Salt of phosphorylated chitosan 0M (In the formula, Zl represents -p=o, Z2 represents H or zl.

Police station 01’l.

Ml and M2 represent hydrogen or a salt such as an alkali metal or organic ammonium salt. ) Among the above derivatives, (A), (B), (C
), (G) and (H) are water-soluble, (D),
(E) and CF) are water-insoluble.

As mentioned above, the chitosan modified product referred to in the present invention means a derivative that retains the characteristics of chitosan itself, and in the glucosamine unit contained in chitosan salt and chitosan, the OH group or NH group is This includes those denatured by reagents.

In the present invention, the chitosan or its modified product is contained in the entire cleaning composition in an amount of o,oos to 0.5% by weight, preferably o,oos to 0.2% by weight.

If the amount is less than o, oos weight percent, not only is it insufficient to suppress the formation of water spots, but also the water spots after rinsing are significantly inferior.

Moreover, if it exceeds 0.5% by weight, the surface of the item to be washed will feel "slimy" and lose its luster, which is undesirable.

In addition, this chitosan or its modified product is added to the cleaning solution at 1
It is preferable to use it in an amount of ppm or more, preferably 5 ρρm, but of course it can be used in an amount greater than that, for example in the range of 10 to 15 ppn+.

The detergent for automatic dishwashers of the present invention contains chitosan or its modified product as an essential ingredient, but it also contains conventionally known nonionic surfactants, anionic surfactants, and amphoteric surfactants as other active ingredients. These surfactants can be applied singly or as a mixture of two or more.

The surfactants used in the present invention are illustrated below.

Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene polypropylene glycol, polyoxyethylene alkyl phenyl ether,
These include polyoxyethylene fatty acid ester, polyoxyethylene polypropylene alkyl ether, fatty acid alkanolamide, etc. As anionic surfactants, α-
Olefin sulfonate salt fatty acid salt, alkylbenzene sulfonate, polyoxyethylene alkyl ether sulfate salt, alkyl ether sulfate.

These include alkenyl succinates and alkyl phosphates. Further, examples of amphoteric surfactants include amidoamine type, betaine type, imidacilline type, alanine type, etc., but these are only examples, and the exemplified ones are not intended to be limiting.

There is no particular limit to the amount of these surfactants to be used, but from the perspective of the development of effects, the amount of surfactants used should be 1 to 30
The amount is preferably 5 to 20% by weight.

The automatic dishwasher detergent composition of the present invention contains the above-mentioned chitosan or a modified product thereof as an essential component,
If desired, various auxiliary ingredients customary in cleaning compositions of this type include, for example, fragrances, dyes, bleaching agents,
It is possible to add a bactericidal agent and the like, and it is also possible to contain general hydrotropes such as ethanol, propylene glycol, polyethylene glycol, and toluene sulfonate. It can also contain citrate, CMC, gluconate, water-soluble polymers, and chelating agents and enzymes such as amylase and protease.

The cleaning composition of the present invention can be applied to all commonly used tableware such as glass tableware, ceramics, plastic, aluminum, stainless steel, and copper tableware, and is a cleaning agent for industrial or household automatic dishwashers. Widely used as

〔effect〕

Since the automatic dishwasher detergent of the present invention contains chitosan or its modified product as an essential ingredient, it has excellent cleaning power and does not form water spots on the surface of dishes even if the cleaning water is hard. Since the water spot suppressing effect does not deteriorate even after rinsing or washing, its commercial value is extremely high.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Examples 1-10. Comparative Examples 1 to 4 Various automatic dishwasher detergents having the compositions shown in Table 1 were prepared and their detergency was investigated. The results are shown in Table-1.

The test method and evaluation method were as follows.

Four clean porcelain plates each with 0.5 g of beef tallow on each plate, and 4 plastic plates with 0.5 g of butter on each plate.
Two plastic plates with no dirt attached were placed in the dishwasher and washed with a detergent concentration of 0.2% under the following conditions, and then evaluated based on the following evaluation method.

(i) Washing conditions ■) Dishwasher: A fully automatic dishwasher in which a detergent solution is sprayed from a rotating nozzle to wash dishes placed on the spray trajectory.

2) Cleaning temperature: Automatically supplied tap water (15℃) is gradually heated by a heater during cleaning, and when cleaning is finished, the temperature is gradually raised by a heater, and the cleaning liquid temperature at the end of cleaning is 60℃.
It is ℃.

3) Washing time: 20 minutes 4) Rinsing: After supplying water, rinse for 1 minute and drain the water three times, then heat rinse once while raising the temperature to 60°C.
Let's go around.

5) Drying: After rinsing, set the temperature inside the dishwasher to 80℃.
Dry for 1 hour while gradually raising the temperature to .

(ii) Evaluation of Water Spots Water spots adhering to the dried dishes were evaluated according to the criteria shown below.

1: Those with 10 or more water spots+;
7 to 9 items±;
4 to 6 items 1; 0 to 3 items Table 1 also lists the drying properties of the tableware and the glossiness of the surface of the tableware.

(iii) Evaluation of glossiness 0: Good gloss on the surface of the item to be washed.

Δ; There is uneven gloss.

X; Lack of luster.

Examples 11 to 19, Comparative Examples 5 to 9 Various automatic dishwasher detergents having the compositions shown in Table 2 were prepared, and their detergency was evaluated by the same test method as in the Examples.

The results are shown in Table-2.

Claims (4)

[Claims] (1) A detergent for automatic dishwashers characterized by containing chitosan or a modified product thereof. (2) The detergent for automatic dishwashers according to claim 1, wherein the active ingredient of the detergent for automatic dishwashers is one or more of nonionic surfactants and anionic surfactants. (3) The automatic dishwasher detergent according to claim 1 or 2, wherein the chitosan modified product is a chitosan carboxylate. (4) The automatic dishwasher detergent according to claim 1 or 2, wherein the chitosan modified product is a chitosan alkylbenzene sulfonate or a chitosan alkyl phosphate.