JPS5850639B2 - Liquid detergent composition containing cationically modified starch - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel liquid cleaning composition, more specifically, a method for cleaning tableware made of glass, ceramic, metal, plastic, etc.
The present invention relates to a novel liquid detergent composition which can easily remove food stains, does not leave a film or water spots on dishes after washing, and gives a natural gloss.

When used tableware is washed with detergent, rinsed with water, and dried, it is often seen that spots and films called water spots are left 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 rinse 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 important challenges in the dishwashing detergent manufacturing industry has been to provide detergents that do not leave such water spots or films after normal washing operations.

Until now, detergents for the purpose of preventing water spots have been prepared by adding specific gelatin (JP-A-49-94701, JP-A-50-46709).
(Japanese Patent Application Laid-open No. 72908/1983), a compound consisting of quaternary ammonium, a polyethylene oxide-polypropylene oxide condensate, and a water-soluble compound with a special structure (Japanese Patent Application Laid-open No. 72908/1983), an anionic surfactant and a polypropylene having a specific molecular weight. Cleansers containing peptides (Japanese Unexamined Patent Publication No. 50-157404) and abrasives (Japanese Unexamined Patent Publication No. 5070411)
Publication No. 2), etc. have 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.

In order to meet these demands (as a result of extensive research), the present inventors have found that a cationically modified starch or its derivative with a quaternary nitrogen content of 0.01 to 5% by weight and an anionic surfactant are combined in a predetermined manner. It was discovered that a liquid detergent contained in a concentration range does not leave water spots or a film on the surface of tableware after drying, and based on this finding, the present invention was developed.

That is, the present invention provides a cationically modified starch or a derivative thereof having a quaternary nitrogen content of 0.01 to 5% by weight.
5% by weight of anionic surfactant, 16-35% by weight of anionic surfactant, and the balance conventional ingredients.

The cationically modified starch used in the present invention can be obtained, for example, by reacting starch with a glycidyl trialkylammonium salt or a 3-halogeno-2-hydroxypropyl triplekylammonium salt.

Cation-modified starch derivatives include, for example, hydroxyalkyl starch obtained by adding alkylene oxide such as ethylene oxide or propylene oxide to starch, and glycidyltrialkylammonium salt or 3-halogeno-2-hydroxypropyltrialkylammonium salt. It can be produced by the reaction of

Starches that can be used as raw materials for cationically modified starch or its derivatives include Japanese starch, potato starch, wheat starch, corn starch, rice starch,
Any starch such as tapioca starch can be used.

These are commercially available products that are used as they are or after being purified to a necessary degree.

In addition, soluble starch (acid-treated starch) obtained by hydrolyzing starch with an inorganic or organic acid can also be used as the raw material starch.

As the starch derivative, one obtained by adding alkylene oxide to the above-mentioned starch at an average ratio of 0.1 to 2 moles per glucose unit is preferably used.

Examples of glycidyltrialkylammonium salts include glycidyltrimethylammonium chloride, glycidyltriethylammonium chloride, glycidyldimethylethylammonium chloride, glycidylmethyldimethylammonium chloride, glycidyltripropylammonium chloride, glycidylmethylethylpropylammonium chloride, and corresponding bromides. and yoshito.

Examples of 3-halogeno-2-hydroxypropyltrialkylammonium salts include 3chloro-2-hydroxypropyltrimethylammonium chloride 1.3
-Chloro-2-hydroxypropyltriethylammonium chloride, 3chloro-2-hydroxypropyldimethylethylammonium chloride, 3-chloro-2-hydroxyfurobylmethyldiethylammonium chloride, 3-chloro-2-hydroxypropyltripropylammonium chloride , 3-chloro-2hydroxypropylmethylethylpropylammonium chloride and corresponding bromides and iosites.

The reaction of starch with a glycidyltrialkylammonium salt or a 3-halogeno-2-hydroxypropyltrialkylammonium salt can be carried out by adding a glycidyltrialkylammonium salt or a 3-halogeno-2-hydroxypropyltrialkylammonium salt to a dispersion of starch in the presence of an alkaline catalyst such as sodium hydroxide. ~Halogeno-2
-Hydroxypropyl trialkylammonium salt solution is added, the reaction is heated, and the reaction mixture is then neutralized with an acid such as hydrochloric acid.

To separate the cationically modified starch from the reaction mixture thus obtained, a hydrophilic solvent such as methanol is added to precipitate the cationically modified starch, which is then separated by Sawabetsu,
dry.

The reaction between starch and alkylene oxide, such as ethylene oxide, can be carried out by adding a mixture of an organic solvent and an aqueous alkaline solution to starch to produce alkaline starch, and then adding the alkylene oxide to the mixture.

The hydroxylalkyl starch thus obtained,
The reaction with the glycidyltrialkylammonium salt or the 3-halogeno-2-hydrohexpropyltrialkylammonium salt can be carried out in the same manner as in the case of the cationically modified starch described above.

The cationically modified starch used in the present invention has a quaternary nitrogen content of 0.01 to 5% by weight, preferably 0.02% by weight.
~3% by weight and 0.0% for cationically modified starch derivatives.
0.01 to 5% by weight, preferably 0.012 to 3% by weight.

Therefore, in the above-mentioned reaction, it is necessary to select the ratio of raw materials to be used so as to obtain a quaternary nitrogen content within such a range.

When the quaternary nitrogen content of the cationically modified starch or its derivative is lower than the above-mentioned amount, no effect of suppressing the formation of water spots is observed.

Furthermore, even if the amount is increased above the above-mentioned amount, no improvement in the effect of suppressing the formation of water spots will be observed, and the economic burden will only increase.

Next, the amount of cationically modified starch or its derivative used in the present invention is 0.05 to 0.05 to
It is selected within a range of 5% by weight.

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 it will also affect the stamina of the foam and the solubilization. Sexuality decreases.

Normally, if the amount of this cation-modified starch or its derivative exceeds 1.0% by weight, it may give an unpleasant slimy feeling when used, but amphoteric surfactants such as imidacillin-type amphoteric surfactants, alkyl betaines, etc. Discomfort can be eliminated by adding at least 05% by weight of an amphoteric surfactant, an amidoamine type amphoteric surfactant, etc. based on the total amount.

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 has 8 carbon atoms.
Those having ~15 long-chain alkyl groups are preferred, and higher alkyl polyoxyethylene ether sulfates have alkyl groups having 8 to 16 carbon atoms, particularly 11 to 14 carbon atoms, and the average number of moles of ethylene oxide added is 1. -4 are preferred.

In addition, higher α-olefin sulfonate has 10 carbon atoms.
~20, preferably 14 to 16 carbon atoms, such as those having 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 lowered, and if it is larger, the transparency of the liquid will be lowered, which is not preferable.

In addition, these anionic surfactants should be added in an amount of 1
It is necessary to use concentrations in the range of 6-35% by weight.

In the composition of the present invention, the cationically modified starch or its derivative 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 agent showed an effect of inhibiting 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.

That is, when an anionic surfactant and a cationically modified starch or its derivative form a polymer complex, a new hydrophilic part and a hydrophobic part are generated, which exhibits the performance as an active agent and also makes the polymer complex or cationically modified starch or its derivative The derivative functions to protect the surface of tableware and prevents the formation of water spots.

As mentioned above, it is necessary to use an anionic surfactant in the present invention, and nonionic surfactants and cationic surfactants do not provide the desired effect at all.

The components in the composition of the present invention other than the cationically modified starch or its derivative and the anionic surfactant are those commonly used in common liquid detergents.

Most of these solvents are water, but other solvents include lower alcohols such as ethanol and isopropanol, polyhydric alcohols such as ethylene glycol and glycerin, hydrotropes such as urea and benzoates, 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.

■ Number of water spots Apply 0.5 fI of butter to the inside of the glass tip, and after air drying, scrub the inside 5 times and the outside 4 times using a sponge in a detergent solution (detergent concentration: 0.15%).

After rinsing the washed glass tip three times with tap water and immersing it in the blue dye aqueous solution,
Dry at 05°C for 4 minutes.

The number of water spots remaining inside the tip after cooling was counted visually.

The same operation was performed on four glass chips, and the average amount of water spots 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.

501 rLl of detergent solution and 100 ml of yellow OB are collected in an Erlenmeyer flask with a solubilization capacity of 200 TLl, shaken in a constant temperature bath at 25°C for 24 hours, filtered, and the solubilized amount is determined from the absorbance of the p solution.

■ Number of dishes to wash (foam stamina test) Wash the surface of dishes (0.5P/1 piece) soiled with butter in a vat with a diameter of 30 crfL using a washing liquid with a capacity of 31, a concentration of 0.15%, and a liquid temperature of 25°C. The number of dishes that could be washed by scrubbing the back side three times with a sponge until the foam height of the washing liquid was 1 meter.

■Appearance After blending, leave indoors for 1 day and visually judge Example 1 30g of barley starch was dispersed in 150P of a 50% by weight aqueous isopropanol solution, and 9.9P of a 15% by weight sodium hydroxide aqueous solution (relative to starch). 0.2 times the mole) was added thereto, and the mixture was heat-treated at 45°C for 1 hour.

Next, active ingredient 14. Of (0.5 times mole of starch)
An aqueous solution of glycidyltrimethylammonium chloride was added thereto, and the mixture was heated and reacted at 50°C for 3 hours.

After the reaction was completed, 4.2 P of concentrated hydrochloric acid (1.1 times the mole of sodium hydroxide charged) was diluted with 150 fI of a 50% by weight aqueous solution of isopropanol and used for neutralization.

After neutralizing for 1 hour at room temperature, the reaction solution is poured into 30 oz of methanol to precipitate the reaction product, and then sent to each house.

The obtained precipitate is washed with methanol 3001.

After repeating such washing and purification three times, the reaction product is dried under reduced pressure.

The nitrogen content of the cationically modified starch thus obtained was 2.63%, and the ionic chlorine content was 6.6%.
It was 67%.

This cationically modified starch was used in combination with the anionic surfactant described below.

Linear alkylbenzene sulfonic acid magnesium salt (however, the alkyl group is linear and has 11 to 14 carbon atoms, hereinafter referred to as component A) is mixed with alkyl polyoxyethylene ether (however, the alkyl group has 9 to 13 carbon atoms, average 11
The average number of moles of ethylene oxide added is 10 moles, hereinafter referred to as component B), and an imidacillin-type amphoteric surfactant (manufactured by Lion Oil Co., Ltd., trade name: Enadicol CN5J).
, hereinafter referred to as component C), and the above-mentioned cationically modified starch having a quaternary nitrogen content of 2.63% (hereinafter referred to as component C).

), and ethanol and urea as additives in the parts by weight shown in Table 1, respectively, and water was added until the total amount became 100 parts by weight to prepare a liquid cleaning composition.

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

The results are shown in Table 4 (however, the concentration of detergent used; 0.1 5%).

As is clear from this table, the cleaning agents (Experiment Nos. 1 to 4) having compositions within the range of the present invention have good water spot generation suppressing ability and cleaning ability.

On the other hand, cleaning agents having compositions outside the scope of the present invention (Experiment Nos. 5 to 8) had low ability to suppress water spot formation, and were inferior in cleaning ability and transparency.

Example 2 The same alkyl polyoxyethylene ether (component B) used in Example 1, an imidacillin-type amphoteric surfactant ("
Enadicol CN5J, component C) and cation-modified starch (component D) were combined with linear alkylbenzenesulfonic acid sodium salt (however, the alkyl group is linear and has 11 to 11 carbon atoms).
14, hereinafter referred to as component E), was added to the sodium salt of alkyl polyoxyethylene ether sulfate (however, the number of carbon atoms in the alkyl group is 9 to 15, on average 13, and the average number of moles of ethylene oxide added is 2 moles). (hereinafter referred to as component F), alpha-olefin sulfonic acid sodium salt (with 12 to 18 carbon atoms, hereinafter referred to as component G),
Then, ethanol and urea were mixed as additives in the parts by weight shown in Table 2, and water was added until the total amount became 100 parts by weight to prepare a liquid cleaning composition.

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

The results are shown in Table 2 (however, detergent concentration: 0.
15%, and the symbols for appearance and comprehensive evaluation in the table have the same meanings as in Example 1).

As is clear from this table, the cleaning agents (Experiment Nos. 9 to 13) having compositions within the range of the present invention have good water spot generation suppressing ability and cleaning ability.

Example 3 The same linear alkylbenzenesulfonic acid magnesium salt (hereinafter abbreviated as LASMg) used in Examples 1 and 2,
Linear alkylbenzenesulfonic acid sodium salt (LAS
-Na), alkyl polyoxyethylene ether sodium sulfate salt (hereinafter abbreviated as AES-Na), imidacillin type amphoteric surfactant (hereinafter abbreviated as amphoteric), alkyl polyoxyethylene ether (hereinafter abbreviated as nonion).

), cationically modified starch (hereinafter abbreviated as Ct-8tr)
A detergent having the composition shown in Table 3 was prepared by adding additives commonly used in detergents.

Detergent I, ■ is a lotion type, detergent ■ is a transparent colored type, and detergent ■ is a transparent uncolored type kitchen detergent.

All of these were found to be superior to conventional ones in terms of cleaning performance, water spot prevention effect, etc.

Claims (1)

[Scope of Claims] 1. From 0.05 to 5% by weight of a cationically modified starch or its derivative with a quaternary nitrogen content of 0.01 to 5% by weight, 16 to 35% by weight of an anionic surfactant, and the balance of conventional ingredients. A liquid detergent composition containing cationically modified starch. 2. The liquid detergent composition according to claim 1, wherein the cationic starch is a reaction product of starch and a glycidyl triplekylammonium salt or a 3-halogeno-2-hydroxypropyl triplekylammonium salt. 3. Claim 4, wherein the cationically modified starch derivative is a reaction product of a hydroxyalkyl starch and a glycidyltrialkylammonium salt or a 3-halogeno-2-hydroxypropyltrialkylammonium salt.
The liquid cleaning composition described in Section 1. 4. The liquid detergent composition according to claim 3, wherein the hydroxyalkyl starch is hydroxyethyl starch or hydroxypropyl starch. 5. The liquid cleaning composition according to claim 1, wherein the anionic surfactant is a higher alkylbenzene sulfonate. 6. The liquid cleaning composition according to claim 1, wherein the anionic surfactant is a higher alkyl polyoxyethylene ether sulfate. 7. The liquid cleaning composition according to claim 1, wherein the anionic surfactant is a higher α-olefin sulfonate. 8. The liquid detergent composition according to claim 1, wherein the anionic surfactant is a higher alcohol sulfate.