JPH1121586A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition having excellent detergency by incorporating a compound obtained by a reaction of acrylic acid or the like with 1,2- dihydroxy-3-(meth)allyloxypropane or the like and having specified structural units. SOLUTION: There is provided a detergent composition containing 0.1-20 wt.% compound having structural units represented by formula I and structural units represented by formula II, 0.5-90 wt.% alkali metal hydroxide, 0.1-20 wt.% polycarboxylic acid or its salt and 0.5-40 wt.% metal scavenger such as ethylenediaminetetraacetic acid. The compound which can give a structural unit represented by formula I is exemplified by acrylic acid, maleic acid or itaconic acid, and the compound which can give a structural units represented by formula II is exemplified by 1,2-dihydroxy-3-(meth)allyloxypropane. In the formula, R<1> to R<4> are each H, a hydrocarbon group, -COOM<1> or the like; R<5> is an alkylene; m is 1 or greater; R<6> is H or methyl; X is H or -OH; Y is -OH, -SO3 M<2> or the like; M<1> and M<2> are each H, a metal atom or the like; and n is 1 or greater.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a detergent composition suitable for use as a detergent for automatic dishwashers.

[0002]

2. Description of the Related Art In recent years, automatic dishwashers used in kitchens such as hotels and restaurants have been rapidly developed for the purpose of mechanizing or automating the washing of dishes and containers, saving labor, improving the working environment, and improving sanitary management. It is widespread. There are various types of detergents for automatic dishwashers used in the above automatic dishwashers. For example, a slurry-like alkaline detergent composition comprising sodium hydroxide, potassium hydroxide, sodium tripolyphosphate, silicate, a copolymer of isoamylene and maleic anhydride, polyacrylic acid and water (JP-B-63-37838); Hard surface cleaning composition comprising sodium or potassium hydroxide, 2-hydroxyethyl iminodiacetic acid salt and a copolymer of isoamylene and maleic anhydride (Japanese Patent Publication No. 2-273)
No. 97), sodium or potassium hydroxide, an alkali metal nitrilotriacetic acid salt and a hard surface cleaning composition comprising a copolymer of isoamylene and maleic anhydride (Japanese Patent Publication No. 3-60358), potassium tripolyphosphate, tripolyphosphoric acid Liquid detergent composition comprising sodium, potassium silicate, alkali hypochlorite and water
No. 50399), a liquid detergent composition for an automatic dishwasher comprising sodium hydroxide or potassium hydroxide, a polyacrylate and water having a specific conductivity (JP-A-4-152).
No. 99), a detergent composition for an automatic dishwasher containing a nonionic surfactant, a calcium ion-trapping chelating agent and an enzyme (JP-A-4-72397, JP-A-4-723).
No. 98).

[0003]

However, the conventional cleaning agents as described above, when used as a cleaning agent for an automatic dishwasher, (1) only remove the dirt adhering to dishes and containers with the cleaning agent. However, there are problems such as (2) when a dirt component is mixed into the cleaning liquid, the cleaning ability is extremely reduced, and (3) scale adhesion to the cleaning machine.

Accordingly, it is an object of the present invention to provide a detergent composition which has excellent detergency and anti-redeposition performance, and is particularly preferably used as a detergent for automatic dishwashers.

[0005]

In view of the above problems, the present inventors have found that by using a compound having a specific structure, dirt adhering to dishes and containers can be completely eliminated. When used as a cleaning agent for automatic dishwashers, it can exhibit excellent cleaning performance even when contaminants are mixed in the cleaning solution, and have excellent scale adhesion control capability. We have invented a detergent composition that is suitable for use as a detergent for automatic dishwashers.

That is, the present invention provides, as a component (A), the following general formula (1):

Embedded image (Wherein, R ^{1 to} R ⁴ are a hydrogen atom, a hydroxyl group, a hydrocarbon group, a hydrocarbon group containing an oxygen atom, —COOM ¹ or —R ⁵ —CO
OM ¹ , R ⁵ represents an alkylene group, M ¹ represents a hydrogen atom, a metal atom or ammonium, and m represents a number of 1 or more. ) And the following general formula (2)

Embedded image (Wherein, R ⁶ represents a hydrogen atom or a methyl group, X represents a hydrogen atom or a hydroxyl group, Y represents a hydroxyl group, —SO ₃ M ² or —PO ₃ M ³ M ⁴ , and M ^{2 to} M ⁴ represent A cleaning composition containing a compound having a structural unit represented by a hydrogen atom, a metal atom or ammonium, and n represents a number of 1 or more. Further, the present invention is a detergent composition further containing an alkali metal hydroxide as the component (B). Further, the present invention is a detergent composition further comprising a polycarboxylic acid or a salt thereof as a component (C).
Further, the present invention is a detergent composition further comprising a sequestering agent as a component (D). Further, the present invention is a detergent composition for an automatic dishwasher comprising the above detergent composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) of the present invention is a compound having a structural unit represented by the general formulas (1) and (2). In the general formula (1), R ^{1 to} R ⁴ represent a hydrogen atom,
Represents a hydroxyl group or a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, and a cycloalkenyl group.

Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Tert-butyl, tert-butyl, pentyl, isopentyl, neopentyl, secondary pentyl, tert-pentyl, hexyl, secondary hexyl, heptyl, secondary heptyl, octyl, 2-ethylhexyl, secondary octyl, nonyl, secondary nonyl, decyl , 2nd grade decyl, undecyl,
Secondary undecyl, dodecyl, secondary dodecyl, tridecyl, isotridecyl, secondary tridecyl, tetradecyl,
Secondary tetradecyl, hexadecyl, stearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-octyldodecyl, 2-dodecylhexadecyl, 2-tetradecyloctadecyl, monomethyl-branched-isostearyl and the like can be mentioned.

Examples of the alkenyl group include vinyl, allyl, propenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like.

The aryl group includes, for example, phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octyl Phenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl,
Examples include phenylphenyl, benzylphenyl, styrenated phenyl, p-cumylphenyl, α-naphthyl and β-naphthyl groups.

Examples of the cycloalkyl group and cycloalkenyl group include, for example, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, methylcyclohepenyl And a thenyl group.

R ^{1 to} R ⁴ are -COOM ¹ or -R ^5-
The group represented by COOM ¹ may be used. R ⁵ represents an alkylene group; M ¹ represents a hydrogen atom, a metal atom or ammonium. Examples of the alkylene group include methylene, ethylene, propylene and the like. Examples of the metal atom or ammonium include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium and calcium (although alkaline earth metals are usually divalent, １ ／), ammonia and methylamine. , Dimethylamine, ethylamine, diethylamine, (iso)
Propylamine, di (iso) propylamine, ethanolamine, methylethanolamine, ethylethanolamine, diethanolamine, triethanolamine,
And ammonium such as propanolamine, dipropanolamine, and tripropanolamine. Accordingly, a group represented by -COOM ¹ or -R ⁵ -COOM ¹ represents carboxy, methylene carboxylate, ethylene carboxylate, or a salt thereof.

Further, R ^{1 to} R ⁴ may be a hydrocarbon group having an oxygen atom. For example, an alkoxy group or an allyloxy group represented by —O—R ⁷ (R ⁷ represents the hydrocarbon group exemplified above), —O— (C ＝ O) —R ⁸ (R ⁸ is exemplified above. An ester group represented by a hydrocarbon group),-(C = O) -OR ⁹ (R ⁹ represents the hydrocarbon group exemplified above), and a hydrocarbyloxycarbonyl group.

Specifically, examples of the alkoxy group or allyloxy group include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, undecyloxy, dodecyl Oxy, phenoxy, toluyloxy and the like can be mentioned.

Examples of the ester group include acetyl, propionyl, butyroyl, isobutyroyl, valeroyl, isovaleryl, pivaloyl, lauroyl, myristoyl, palmitoyl, stearoyl and the like.
Examples of the hydrocarbyloxycarbonyl group include, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, Undecyloxycarbonyl, dodecyloxycarbonyl, phenoxycarbonyl, toluyloxycarbonyl and the like can be mentioned.

[0016] Among each of these substituents, preferably all of R ¹ to R ⁴ is not simultaneously hydrogen atoms, R ¹ ~
At least one of R ⁴ is —COOM ¹ or —R ⁵ —COOM ¹
Is more preferably a group represented by

The compound giving the structural unit represented by the general formula (1) is a compound having a polymerizable carbon-carbon double bond. For example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, and seracoleic acid, or metal salts or ammonium salts thereof, methyl (meth) acrylate, (meth) acrylate Ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, (meth) acryl 2-ethylhexyl acid, (meth)
Nonyl acrylate, decyl (meth) acrylate, phenyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, dimethyl maleate (or fumarate) Carboxylic acid esters such as monomethyl maleate (or fumarate), diethyl maleate (or fumarate), monoethyl maleate (or fumarate), methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, pentyl vinyl ether , Hexyl vinyl ether, heptyl vinyl ether, octyl vinyl ether, vinyl ethers such as phenyl vinyl ether, vinyl acetate, vinyl esters such as vinyl propionate,
Ethylene, propylene, 1-butene, 1-pentene, 1
-Hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-
Olefins such as tridecene, 1-tetradecene, 1-octadecene, isobutylene, isoprene and the like can be mentioned.

In the general formula (2), R ⁶ represents a hydrogen atom or a methyl group, X represents a hydrogen atom or a hydroxyl group, Y represents a hydroxyl group, —SO ₃ M ² or —PO ₃ M ³ M ⁴ . Express. M ^{2 to} M ⁴ represent a hydrogen atom, a metal atom or ammonium. Examples of M ^{2 to} M ⁴ include, for example, alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium and calcium, ammonia, methylamine, dimethylamine, ethylamine, diethylamine, and the like.
(Iso) propylamine, di (iso) propylamine,
Ethanolamine, methylethanolamine, ethylethanolamine, diethanolamine, triethanolamine, propanolamine, dipropanolamine,
Ammonium such as tripropanolamine.

Compounds providing the structural unit represented by the general formula (2) include, for example, 1,2-dihydroxy-3- (meth) allyloxypropane, 1-hydroxy-3- (meth) allyloxypropane, 3- ( (Meth) allyloxy-1-propanesulfonic acid (salt), 2-hydroxy-3
-(Meth) allyloxy-1-propanesulfonic acid (salt), 3- (meth) allyloxy-1-propanephosphonic acid (salt), 2-hydroxy-3- (meth) allyloxy-1-propanephosphonic acid (salt) And the like.

The compound of the component (A) of the present invention can be obtained by copolymerizing a compound giving the structural unit represented by the above general formula (1) and a compound giving the structural unit represented by the general formula (2). be able to. m and n each represent a number of 1 or more, and the ratio (molar ratio) of m to n is m: n = 1: 9 to
9: 1 is preferable, and 3: 7 to 7: 3 is more preferable.
Further, the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2)
The bonding mode of the structural unit represented by is not particularly limited, and may be a block copolymer, a random copolymer, a block / random copolymer, or the like. The average molecular weight of the component (A) compound is preferably from 500 to 100,000, preferably 1,000.
-10,000 is more preferable.

The compounding amount of the component (A) of the present invention is not particularly limited, but is preferably 0.1 to 20% by weight based on the total amount of the composition in order to exhibit a particularly excellent effect of preventing reattachment of stains. 0.5 to 15% by weight is more preferable, and 1 to 10% by weight.
% By weight is more preferred.

In the cleaning composition of the present invention,
When the alkali metal hydroxide (B) is further added to the component (A), excellent detergency is exerted especially on the oil component. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide.

The blending amount of the component (B) of the present invention is not particularly limited, but in order to exhibit a particularly excellent cleaning effect,
It is preferably 0.5 to 90% by weight based on the total amount of the composition, and 1
0 to 50% by weight is more preferable, and 25 to 45% by weight is further preferable.

The detergent composition of the present invention exhibits excellent detergency and anti-stain reattachment performance even with the components (A) and (B) alone, and further comprises the polycarboxylic acid or a salt thereof as the component (C). , A more excellent effect of preventing re-adhesion of stains is exhibited by a synergistic effect with the component (A). Examples of the polycarboxylic acid or a salt thereof include a polymer of the unsaturated carboxylic acid or unsaturated carboxylic acid ester exemplified as the compound giving the structural unit represented by the general formula (1) of the component (A), or an unsaturated carboxylic acid. Copolymers of acids or unsaturated carboxylic esters with other polymerizable compounds, or salts thereof. As the polycarboxylic acid or a salt thereof, specifically, for example, polyacrylic acid,
Polymaleic acid, acrylic acid / maleic acid copolymer, acrylic acid / methacrylic acid copolymer, acrylic acid / itaconic acid copolymer, acrylic acid / acrylic acid ester copolymer, acrylic acid / methyl vinyl ether copolymer, acrylic Examples thereof include acid / olefin copolymers, maleic acid / styrene sulfonic acid copolymers, and salts thereof.

Examples of the salt include salts of alkali metals such as lithium, sodium and potassium, salts of alkaline earth metals such as magnesium and calcium, ammonia, methylamine, dimethylamine, ethylamine, diethylamine, (iso) propylamine, and the like. Examples thereof include ammonium salts such as di (iso) propylamine, ethanolamine, methylethanolamine, ethylethanolamine, diethanolamine, triethanolamine, propanolamine, dipropanolamine, and tripropanolamine.

The average molecular weight of the polycarboxylic acid or a salt thereof is not particularly limited, but is preferably from 500 to 50,000, more preferably from 1,000 to 20,000.

The amount of the component (C) of the present invention is not particularly limited, but is preferably 0.1 to 20% by weight based on the total amount of the composition in order to exhibit an excellent effect of preventing reattachment of stains. 0.5-15% by weight is more preferable, and 1-10% by weight is even more preferable.

The cleaning composition of the present invention comprises (A) and (B)
And (C) alone provide excellent detergency and anti-soil re-adhesion performance, but when a sequestering agent (D) is further added, it acts to block calcium ions and magnesium ions in water. Demonstrates superior cleaning power and dirt re-adhesion prevention performance. As the sequestering agent, for example, condensed phosphoric acid such as tripolyphosphoric acid,
Aminocarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), N-hydroxyethyliminodiacetic acid or salts thereof, citric acid, glucone Oxycarboxylic acids such as acid, glycolic acid, tartaric acid, and salts thereof, and the like.

The amount of the component (D) of the present invention is not particularly limited. However, in order to exhibit particularly excellent sequestering performance, it is preferably 0.5 to 40% by weight based on the total amount of the composition. -35 wt% is more preferable, and 5-40 wt% is still more preferable.

The cleaning composition of the present invention can contain other components. For example, alcohol ether type,
Nonionic surfactants such as esters and amides, anionic surfactants such as alkylbenzene sulfonic acid, alkyl ether sulfate, alkyl sulfate and alkyl sulfonic acid, cationic surfactants, carbobetaine and sulfobetaine And a foaming agent such as amine oxide.

In addition, the detergent composition of the present invention may contain, if necessary, an inorganic salt, a recontamination inhibitor, an enzyme, a chlorine scavenger, a bleach, a solubilizer, a defoamer, an enzyme activator, an antioxidant. Agent,
Preservatives, dyes, fragrances and the like can be added.

Examples of the inorganic salts include sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium sulfate, potassium sulfate and the like. Examples of the anti-redeposition agent include polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose and the like. Examples of the enzyme include cellulase, protease, amylase, lipase, hemicellulase, glycosidase, glucose oxidase, and cholesterol oxidase. Examples of the chlorine scavenger include ammonium sulfate, urea, guanidine hydrochloride, guanidine carbonate, guanidine sulfamate, thiourea dioxide, monoethanolamine, diethanolamine, and triethanolamine. Examples of the bleaching agent include percarbonate, perborate, sulfonated phthalocyanine salt, hydrogen peroxide and the like. Examples of the solubilizer include ethanol, propanol, 2-propanol, ethylene glycol, propylene glycol, lower alkyl ethoxylate, benzenesulfonate, and paratoluenesulfonate. Examples of the antifoaming agent include a polyoxyethylene polyoxypropylene copolymer.

The properties of the detergent composition of the present invention are not particularly limited, and may be any properties such as liquid, solid, paste, flake, granule, powder and the like. Although the specific use of the detergent of the present invention is not particularly limited, a compound having a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2) is used as the component (A). Therefore, it is preferably used as a detergent for automatic dishwashers. When the detergent composition of the present invention is used as a detergent for automatic dishwashers, it exerts an excellent cleaning effect on strong stains attached to dishes and food containers, and stains derived from dishes and the like in the washing liquid. When contamination is present, the stains do not re-adhere to the dishes and the like to be washed, and also exhibit an excellent effect of suppressing the adhesion of scale. These effects are unique to the present invention using a compound having the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) as the component (A).

[0034]

EXAMPLES The present invention will be described more specifically with reference to the following examples. In the following examples, parts and percentages are by weight unless otherwise specified. (Example 1: Cleaning performance) 2 g using a 1-door type automatic dishwasher (made by IHI, Model D-6) as a washing machine.
Were washed under the following conditions, dried, and visually determined according to the following criteria. <Washing conditions> Washing temperature: 60 ° C Detergent concentration: 0.1% (amount of water in tank) Washing time: 40 seconds Rinse concentration: 80 ° C Rinse time: 12 seconds Dirt in washing tank: Yes (based on water amount in tank) 0.1
% Of lard mixed. ) And none <Determination criteria> ：: Dirt was completely removed ：: Dirt was almost removed △: Dirt was not sufficiently removed ×: Dirt was hardly removed

(Example 2: Anti-redeposition performance) As a washing machine, a one-door type automatic dishwashing machine for business use (IHI, D-6)
0.1% lard based on the amount of water in the tank is mixed into the washing tank, washed under the following conditions and dried, and the degree of reattachment of dirt to the cleaning dish is determined as follows. It was visually determined by reference. <Washing conditions> Washing temperature: 60 ° C Detergent concentration: 0.1% (amount of water in tank) Washing time: 40 seconds Rinse concentration: 80 ° C Rinsing time: 12 seconds <Criterion> ◎: No dirt on the cleaning dish ○: Dirt was scarcely adhered to the cleaning dish △: Dirt was adhered to the cleaning dish ×: Dirt was considerably adhered to the cleaning dish

(Example 3: Scale adhesion inhibiting performance) Using tap water (hardness: 50 ppm in terms of calcium ion), a detergent concentration (0.01 to 0.1%) similar to that of a normal automatic dishwasher rinsing step. 001%) in the cleaning solution
Test panel made of S304 (size: 2.5 cm x 7.5)
cm) was immersed and shaken for 1 week with a shaker, washed with ion-exchanged water, and the amount of scale was visually determined according to the following criteria. <Judgment Criteria> A: There was no scale adhering. A: There was almost no scale adhering. B: There was scale adhering. X: The scale adhered remarkably. The above test results are shown in the following table. The unit of the numerical value of each component in the table is%.

[0037]

[Table 1]

[0038]

[Table 2]

The compounds used as component (A) in the above table are as follows.

[Table 3]

The compounds used as component (C) in the above table are as follows.

[Table 4]

As is clear from the above embodiment, (A)
It can be seen that the present invention products 1 to 12 containing the component have better cleaning performance, anti-redeposition performance and scale adhesion prevention performance than the comparative products 1 to 6 not containing the component (A). In addition, the products 11 and 12 of the present invention do not contain the component (C), so that the anti-redeposition performance and the like are slightly inferior to those of the products 1 to 10 of the present invention, but are superior to the comparative products. On the other hand, comparative product 1
6 are inferior to the products of the present invention 1 to 12 in all the performances, and in particular, the detergency in the case where there is dirt in the tank is inferior to the products of the present invention.

[0042]

The effect of the present invention is to provide a novel detergent composition. The detergent composition of the present invention exhibits superior detergency and prevention of soil reattachment as compared with conventional detergents, and is particularly preferably used as a detergent for automatic dishwashers.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kohei Nimura 7-35 Higashiogu, Arakawa-ku, Tokyo Asahi Denka Chemical Industry Co., Ltd.

Claims (5)

[Claims] 1. Component (A) represented by the following general formula (1): (Wherein, R ^{1 to} R ⁴ are a hydrogen atom, a hydroxyl group, a hydrocarbon group, a hydrocarbon group containing an oxygen atom, —COOM ¹ or —R ⁵ —CO
OM ¹ , R ⁵ represents an alkylene group, M ¹ represents a hydrogen atom, a metal atom or ammonium, and m represents a number of 1 or more. And a structural unit represented by the following general formula (2): (Wherein, R ⁶ represents a hydrogen atom or a methyl group, X represents a hydrogen atom or a hydroxyl group, Y represents a hydroxyl group, —SO ₃ M ² or —PO ₃ M ³ M ⁴ , and M ^{2 to} M ⁴ represent A hydrogen atom, a metal atom or an ammonium, and n represents a number of 1 or more.) 2. The cleaning composition according to claim 1, further comprising an alkali metal hydroxide as the component (B). 3. The cleaning composition according to claim 1, further comprising a polycarboxylic acid or a salt thereof as the component (C). 4. The cleaning composition according to claim 1, further comprising a sequestering agent as the component (D). 5. A cleaning composition for an automatic dishwasher, comprising the cleaning composition according to claim 1. Description: