JPS595238B2 - Liquid detergent composition for dishwashing - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel liquid detergent composition for dishwashing, and more specifically, food stains can be easily removed from tableware such as glass, ceramic, metal, and Plus 15 chips. The present invention relates to a novel liquid cleaning composition that leaves no film or water spots on dishes after cleaning and gives them a natural shine.

When used tableware is washed with detergent, rinsed with water, and dried (20), it is often seen that spots and films called water spots remain behind, detracting from the original luster of the tableware. This is thought to be due to insufficient cleaning as well as the high hardness of the rinsing water. That is, when rinsing with hard water, the salt contained therein adheres to and remains on the surface of the tableware, resulting in the formation of water spots or a film on the surface. Even though the dirt has been completely removed, water spots and localized films formed on the surface give the appearance that dirt still exists. Therefore, one of the major challenges in the dishwashing detergent manufacturing industry has become to provide detergents that do not leave such water spots or films after normal cleaning operations. Until now, detergents for the purpose of preventing water spots have been prepared by adding a specific gelatin (Japanese Patent Laid-Open Publication No. 4
9-94701, JP-A-50-46709), those consisting of quaternary ammonium, polyethylene oxide-polypropylene oxide condensates, and water-soluble compounds with special structures (JP-A-50-72908),
one consisting of an anionic surfactant and a polypeptide having a specific molecular weight (Japanese Unexamined Patent Publication No. 157404/1983);
A cleanser containing an abrasive (Japanese Unexamined Patent Publication No. 50-70411) has been proposed.

However, the effectiveness of these cleaning agents in preventing water spots is still not sufficient, and there has been a demand for cleaning agents with even improved properties. As a result of extensive research in order to meet these demands, the present inventors have found that the quaternary nitrogen content is 2 to 5% by weight. We discovered the fact that a liquid detergent containing a cationic denatured protein hydrolyzate and an anionic surfactant in a predetermined concentration range does not leave water spots or films on the surface of tableware after drying. The present invention was made based on this.

That is, the present invention uses anionic surfactants 16 to 35
weight? In a liquid cleaning agent which does not contain a builder component and contains conventional ingredients, a cationically modified protein hydrolyzate having a quaternary nitrogen content of 2 to 5% by weight and a quaternary nitrogen content of 0.05 to 5% by weight is used as a water spot prevention component. The present invention provides a liquid dishwashing detergent composition characterized by containing:

The cationically modified protein hydrolyzate used in the present invention is obtained by hydrolyzing natural proteins such as collagen, keratin, fiproin, and casein with an enzyme, acid, or alkali, and has a molecular weight of 100 to 50.0.
00 oligopeptide or polypeptide, glycidyl trialkylammonium salt or 3-halogeno-2-
It can be produced by reacting a hydroxypropyl trialkylammonium salt.

Examples of glycidyl trialkylammonium salts used in this case include glycidyl trimethyl ammonium chloride, glycidyl triethylammonium chloride,
Examples include glycidyldimethylethylammonium chloride, glycidylmethyldiethylammonium taloride, glycidyltripropylammonium chloride, glycidylmethylethylpropylammonium chloride, and corresponding bromides and iodides.

Examples of 3-halogeno-2-hydroxypropyltrialkylammonium salts include 3-chloro-2-hydroxypropyltrimethylammonium chloride, 3-halogeno-2-hydroxypropyltrialkylammonium salt,
-Talolo-2-hydroxypropyltriethinogenmonium chloride, 3-chloro-2-hydroxypropyldimethylethylammonium chloride, 3-chloro-2-
Examples include hydroxypropylmethyldiethylammonium chloride, 3-chloro-2-hydroxypropyltripropylammonium talolide, 3-talolo-2-hydroxypropylmethylethylpropylammonium chloride, and corresponding bromides and iodides.
The reaction of the protein hydrolyzate with the glycidyl trialkylammonium salt or the 3-halogeno-12-hydroxypropyl trialkylammonium salt can be carried out using a solution or suspension of the protein hydrolyzate in the presence of an alkaline catalyst such as sodium hydroxide. It is carried out by adding a solution of a glycidyltrialkylammonium salt or a 3-halogeno-12-hydroxypropyltrialkylammonium salt to a cloudy solution, causing a heating reaction, and then neutralizing the reaction mixture with an acid such as hydrochloric acid. .

To separate the cationically modified protein hydrolyzate from the reaction mixture obtained in this way, a hydrophilic solvent such as acetone is added to it to precipitate the target substance as a white solid, which is then dried separately. . The cationically modified protein hydrolyzate used in the present invention needs to have a quaternary nitrogen content in the range of 2 to 5% by weight.

If it is less than 2% by weight, the effect of suppressing the formation of water and subots will not be recognized, and if it is more than 5% by weight, there will be no increase in the suppressing effect and the economic burden will simply increase. . Therefore, when reacting a protein hydrolyzate with a glycidyltrialkylammonium salt or a 3-halogeno-12-hydroxypropyltrialkylammonium salt, the quaternary nitrogen content of the reaction product should be within the above range. It is necessary to determine the amount of raw material components to be used in appropriate proportions. Next, the amount of cationically modified protein hydrolyzate used in the present invention is selected within the range of 0.05 to 5% by weight based on the total amount of the composition.

If this amount is less than 0.05% by weight, the effect of suppressing the formation of water spots will not be observed, and if it is more than 5% by weight, it will cause the cleaning agent to become cloudy, and the stamina of the foam may deteriorate. Solubility decreases. Normally, if the amount of this cationic denatured protein hydrolyzate is 1.0% by weight or more, it may give an unpleasant slimy feel when used.
At least 0.5% by weight of an amphoteric surfactant, such as an imidazoline type amphoteric surfactant, an alkylbetaine type amphoteric surfactant, an amidoamine type amphoteric surfactant, etc.
By adding it, discomfort can be removed. Therefore, the addition of such an amphoteric surfactant is very advantageous since it will greatly improve the effectiveness of the liquid cleaning agent of the present invention. On the other hand, the anionic surfactants used in the present invention include alkali metal salts, alkaline earth metal salts, and alkanols of higher alkylbenzene sulfonic acids, higher alkyl polyoxyethylene ether sulfuric acids, higher α-olefin sulfonic acids, and higher alcohol sulfuric acids. Mention may be made of amine salts.

These may be used alone or as a mixture of two or more. The above-mentioned higher alkylbenzene sulfonate preferably has a long-chain alkyl group having 8 to 15 carbon atoms, and the higher alkyl polyoxyethylene ether sulfonate preferably has an alkyl group having 8 to 16 carbon atoms, particularly 11 to 14 carbon atoms. A compound having an average number of added moles of ethylene oxide of 1 to 4 is preferable.

In addition, higher α-olefin sulfonate has 10 carbon atoms.
to 20, preferably 14 to 16 carbon atoms, for example, 10 to 20 carbon atoms obtained by the wax cracking method, the ethylene polymerization method using a Ziegler catalyst, or an improved method thereof.
α-olefin is formed into a thin film, and after sulfonation reaction with gaseous anhydrous sulfuric acid diluted with an inert gas, neutralization is performed with an inorganic base such as an alkali metal or alkaline earth metal hydroxide or an organic base such as an alkanolamine. , and those produced by hydrolysis. In these surfactants, if the number of carbon atoms in each alkyl group is smaller than the above-mentioned range, the cleaning power and cleaning speed will be significantly reduced, and if it is larger, the transparency of the liquid will be reduced, which is not preferable. Moreover, these aniosodic surfactants need to be used at a concentration in the range of 16 to 35% by weight based on the total amount. In the composition of the present invention, the cationically modified protein hydrolyzate exhibits the effect of suppressing the formation of water spots without impairing the performance of the anionic surfactant described above. Until now, it was generally thought that anionic surfactants and cationic surfactants form a complex and lose their respective properties. It was completely unexpected that the active agent exhibited an inhibitory effect on the formation of water spots without impairing its performance. This is thought to be because when one of the components is a polymer compound, as in the composition of the present invention, the resulting polymer complex behaves differently from a normal low-molecular complex. In other words, when an anionic surfactant and a cationically modified protein hydrolyzate form a polymer complex, a new hydrophilic part and a hydrophobic part are generated, which exhibits performance as an active agent and also forms a polymer complex or a cationically modified protein. The hydrolyzate exerts its surface protection function on tableware, preventing the formation of water stains and spots.

As described above, in the present invention, it is necessary to use an anionic surfactant, and nonionic surfactants and cationic surfactants will not achieve the desired effect at all. In addition to the cationically modified protein hydrolyzate and the anionic surfactant, the composition of the present invention contains moieties conventionally used in liquid dishwashing detergents, but not normally used in liquid dishwashing detergents, e.g. Contains no builder, alkaline agent, anti-redeposition agent, etc.

Among the ingredients commonly used in liquid dishwashing detergents, most of them are solvents such as water, but they also include ethanol, lower alcohols such as isopropanol, polyhydric alcohols such as ethylene glycol and glycerin, urea, benzoates, etc. These include hydrodrobe agents, fragrances, and pigments.
Next, the present invention will be explained in more detail with reference to Examples.

The results of the characteristic tests shown in each example were evaluated as follows.

I Water/Spot Number Apply 0.59% butter to the inside of the glass tip, and after air drying, use a sponge to scrub the inside 5 times and the outside 4 times in a detergent solution (detergent concentration: 0.15%). .

After washing the glass tip with tap water and overflowing it three times, and then immersing it in a blue dye aqueous solution,
Dry for 4 minutes at 05°C. After cooling, the number of water spots remaining inside the cup was counted with the naked eye. The same operation was performed on four glass chips, and the average value per glass was taken as the number of water spots.

In practice, if there are more than 30 water spots,
The glass tip was rated as having poor transparency after cleaning.
H A detergent solution of 50WLI and Yellow-0B of 100~ were collected in an Erlenmeyer flask with a solubilization capacity of 200ml, and incubated in a thermostatic bath at 25℃ for 2 hours.
After shaking for 4 hours, the solution was filtered, and the amount of solubilization was determined from the absorbance of the filtered solution.

Number of dishes washed (foam stamina test) Volume 311 Concentration 0.15%, liquid temperature 25℃ washing liquid with diameter 3
In the vat of 0CTfL, a plate dirty with butter (0.59
/1 dish) The number of dishes that could be washed by scrubbing the front side 5 times and the back side 3 times with a sponge until the foam height of the washing liquid reached 171&m.

Appearance After blending, leave indoors for 1 day and visually judge Example 1 Protein hydrolyzate (manufactured by Croda, trade name "Crotein A") 100.59 was dispersed and dissolved in water 1009,
To this, 15% by weight aqueous sodium hydroxide solution 13.39
was added, and further 150.09 g of glycidyltrimethylammonium chloride dissolved in water was added.

Next, it was heated to 50°C, and once it reached 50°C, it was maintained at this temperature for 5 hours to cause a reaction. After the reaction is complete, add 2.
39 was added to neutralize the mixture, and after keeping it at room temperature for 1 hour, acetone was added to cause reprecipitation, and the mixture was dried individually to obtain a powder of cationic denatured protein hydrolyzate. The nitrogen content of this material is 12.35%, the chlorine content is 12.31%,
The quaternary nitrogen content calculated from the nitrogen content of the raw material is 3.
It was 91%. The cationically modified protein hydrolyzate thus obtained was used in combination with the anionic surfactant described below.

Linear alkylbenzene sulfonic acid magnesium salt (Tataru, the alkyl group is linear and has 11 to 14 carbon atoms, hereinafter referred to as component A) is mixed with alkyl polyoxyethylene ether (Tataru, the alkyl group has 9 carbon atoms). ~13, average 11
The average number of moles of ethylene oxide added is 10 moles, hereinafter referred to as component B), and an imidazoline type amphoteric surfactant (Lion Oil Co., Ltd., trade name "Enadicol CNS"),
This is hereinafter referred to as component C), the above-mentioned cationically modified protein hydrolyzate with a quaternary nitrogen content of 3.91% (hereinafter referred to as component D), and ethanol and urea as additives. The parts by weight shown in Table 1 were mixed, and water was added until the total amount became 100 parts by weight to prepare a liquid cleaning composition.

Regarding these, water quantity, number of subbots, solubilization ability,
The number of dishes washed, viscosity, and appearance were evaluated.

The results are shown in Table 1 (however, detergent concentration: 0.
15%). As is clear from this table, all of the cleaning agents prepared within the formulation range of the present invention (Experiment Nos. 1 to 4) have excellent water and spot suppression ability and cleaning ability; The cleaning agents outside the scope of the invention (experiment numbers 5 to 8) had low water and spot suppression effects;
The cleaning effect and transparency are also low. Example 2 The same alkyl polyoxyethylene ether used in Example 1 (component B), an imidazoline type amphoteric surfactant (“Enazicoil CNS”, component C), and a cation A denatured protein hydrolyzate (component D), a linear alkylbenzenesulfonic acid sodium salt (however, the alkyl group is linear and has 11 to 14 carbon atoms, hereinafter referred to as component E), and alkyl polyoxyethylene ether sulfuric acid. Sodium salt (however, the number of carbon atoms in the alkyl group is 9 to 15, average 1
3, the average number of moles of ethylene oxide added is 2 moles, hereinafter referred to as component F), α-olefin sulfonic acid sodium salt (with 12 to 18 carbon atoms, hereinafter referred to as component G), and As additives, ethanol and urea were mixed in the parts by weight shown in Table 2, and the total amount was 100%.
Water was added up to parts by weight to prepare a liquid cleaning composition.

Regarding these, water quantity, number of spots, solubilization ability,
The number of dishes washed, viscosity, and appearance were evaluated.

The results are shown in Table 2 (however, detergent concentration: 0.
The appearance and overall evaluation symbols in the table are those of Example 1.
As is clear from this table, all of the cleaning agents within the scope of the present invention (Experiment Nos. 9 to 13) exhibit excellent water-spot suppression and cleaning abilities; The samples (experiment numbers 14 to 17) were inferior in water spot suppression ability, cleaning ability, and transparency.

Example 3 The same linear alkylbenzenesulfonic acid magnesium salt used in Examples 1 and 2 (hereinafter abbreviated as LAS-Mg)
, linear alkylbenzenesulfonic acid sodium salt (hereinafter abbreviated as LAS-Na), alkyl polyoxyethylene ether sulfate sodium salt (hereinafter abbreviated as AES-Na),
Imidazoline-type amphoteric surfactants (hereinafter abbreviated as amphoteric), alkyl polyoxyethylene ethers (hereinafter abbreviated as nonions), power thion-modified protein hydrolysates (hereinafter abbreviated as Ct-
Pep) and additives commonly used in detergents were added thereto to prepare detergents having the compositions shown in Table 3.

Detergent I is lotion type, cleaning is transparent colored type,
The detergent is a transparent, uncolored kitchen detergent.

Claims (1)

[Scope of Claims] 1. A liquid detergent comprising 16 to 35% by weight of an anionic surfactant and conventional ingredients and containing no pilder component, with a quaternary nitrogen content of 2 to 5% by weight as a water spot prevention component. A liquid dishwashing detergent composition, characterized in that it contains 0.05-5% by weight of a cationically modified protein hydrolyzate. 2. The liquid detergent composition for dishwashing according to claim 1, wherein the cationically modified protein hydrolyzate is a reaction product of a protein hydrolyzate and a glycidyl trialkylammonium salt. 3. The liquid detergent composition for dishwashing according to claim 1, wherein the cationically modified protein hydrolyzate is a protein hydrolyzate and a 3-halogeno-2-hydroxypropyl trialkylammonium salt. 4. The liquid dishwashing detergent composition according to claim 1, wherein the anionic surfactant is a higher alkylbenzene sulfonate. 5. The liquid dishwashing detergent composition according to claim 1, wherein the anionic surfactant is a higher alkyl polyoxyethylene ether sulfate. 6. The liquid dishwashing detergent composition according to claim 1, wherein the anionic surfactant is a higher α-olefin sulfonate. 7. The liquid dishwashing detergent composition according to claim 1, wherein the anionic surfactant is a higher alcohol sulfate.