JPH10324900A - Detergent composition for hard surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent compsn. excellent in low-temp. detergency by incorporating at least one kind of a nonionic surfactant selected from among specific three kinds of nonionic surfactants, an alkali agent, and a chelating agent each in a specified amt. into the same. SOLUTION: This compsn. compsn. contains 0.01-20 wt.% at least one nonionic surfactant selected from among nonionic surfactants represented by formulas I, II, and III, 0.1-50 wt.% alkali agent, and 0.01-20 wt.% chelating agent. In these formulas, R<1> to R<3> are each 6-24C alkyl, etc.; EO is oxyethylene; PO is oxypropylene; x1 +x2 >=4; x3 +x4 >=4; x5 +x6 +x7 +x8 >=4; x6 +x7 >=1; x1 to x85 and x8 are each 2 or higher; 0<y2 <x3 +x4 ; y3 +y5 >=1; y3 to y5 are each 0 or higher; y3 +y4 +y5 <x5 +x6 +x7 +x8 ; [ ] means random polyaddition; and () means block polyaddition. Potassium hydroxide, sodium orthosilicate, sodium pyrophosphate, etc., are used as the alkali agent. Sodium gluconate, sodium ethylenediaminetetraacetate, etc., are used as the chelating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hard surface cleaning composition used for cleaning hard surfaces of metals, glasses, ceramics, plastics and the like, and more particularly to a hard surface cleaning composition having a good cleaning power even at low temperatures. The present invention relates to an alkaline cleaning composition.

[0002]

2. Description of the Related Art Conventionally, alkaline cleaning agents have been widely used for cleaning hard surfaces such as metals, glasses, ceramics, and plastics. In the field where an alkaline cleaning agent is used, cleaning is often performed at a higher cleaning temperature than room temperature in order to improve the cleaning performance. For example, when a steel plate (steel strip) is continuously cleaned at an ironworks or the like, the temperature of the cleaning liquid is generally 70 to
80 ° C. Further, when washing glass, porcelain, plastics, etc. using an automatic dishwasher in the restaurant industry or the like, the washing temperature is generally 60 to 70 ° C. However, from the viewpoint of cleaning cost, there has been a demand for a cleaning agent having good cleaning properties even when the cleaning temperature is lowered.

Hitherto, alkaline cleaning agents for hard surfaces having excellent low-temperature cleaning ability include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene alkyl. Detergent compositions containing a nonionic surfactant such as phenyl ether (JP-A-55-141577, JP-A-57-67699, JP-A-61-60892, Japanese Patent Publication No. 4-18000, JP-A-6-1808000) -116768) and the like. Especially. Polyoxyethylene polyoxypropylene alkyl ether is disclosed in
No. 141577, JP-A-61-60892,
A type in which the raw material alcohol is first reacted with ethylene oxide and then reacted with propylene oxide, and conversely, a type in which the raw material alcohol is first reacted with propylene oxide and then reacted with ethylene oxide, is disclosed. The ability of the composition to clean at low temperatures is also not satisfactory.

Accordingly, an object of the present invention is to provide a metal, glass,
In cleaning hard surfaces such as ceramics and plastics,
An object of the present invention is to provide an alkaline cleaning composition having a sufficient cleaning performance at a low temperature (50 ° C. or lower).

[0005]

Means for Solving the Problems The present inventors have found that a detergent composition containing a specific nonionic surfactant and an alkaline agent can solve the above problems, and have completed the present invention.

That is, the present invention is characterized by containing (A) one or more nonionic surfactants represented by the following general formulas (I) to (III) and (B) an alkali agent. The present invention provides a hard surface cleaning composition.

R ¹ O- (EO) x _1- (PO) y _1- (EO) x ₂ -H (I) R ² O- [EOx ₃ / POy ₂ ]-(EO) x ₄ -H (II ^{) R 3 O- (EO) x} 5 - [EOx 6 / POy 3] - (PO) y 4 - [EOx 7 / POy 5] - (EO) 8 -H (III) wherein x, R ^1, R ² and R ^{3 each} represent a linear or branched alkyl or alkenyl group having 6 to 24 carbon atoms, EO represents an oxyethylene group, and PO represents an oxypropylene group. x ₁ , x ₂ , x ₃ ,
x ₄ , x ₅ , x ₆ , x ₇ and x ₈ are numbers indicating the average number of moles of ethylene oxide added, and x ₁ , x ₂ , x ₃ , x ₄ , x ₅ and x ₈ are each a number of 1 or more , X ₁ + x ₂ ≧ 4, x ₃ + x ₄ ≧ 4, x ₅ + x ₆ + x ₇ +
x ₈ ≧ 4, is x ₆ + x ₇ ≧ 1. y ₁ , y ₂ , y ₃ , y ₄ and y ₅ are numbers indicating the average number of moles of propylene oxide added, and 0 <
y ₁ <x ₁ + x ₂ , 0 <y ₂ <x ₃ + x ₄ , y ₃ + y ₅ ≧ 1, y ₃ ≧ 0, y ₄
≧ 0, y ₅ ≧ 0, y ₃ + y ₄ + y ₅ <x ₅ + x ₆ + x ₇ + x ₈ The portion enclosed by [] indicates random addition, and the portion enclosed by () indicates block addition. Further, the present invention provides a hard surface cleaning composition characterized by further comprising (C) a chelating agent in addition to the component (A) nonionic surfactant and the component (B) alkali agent. Is provided.

[0008] By containing the chelating agent of the component (C), the cleaning performance is synergistic in combination with at least one of the specific nonionic surfactants represented by the general formulas (I) to (III). There is an advantage to improve.

The cleaning composition of the present invention has a low temperature (50 ° C. or lower).
In, although having sufficient washing performance, even when washed at a temperature higher than 50 ° C. using the detergent composition of the present invention,
Needless to say, it shows better performance than the above-mentioned cleaning agents containing a known nonionic surfactant.

[0010]

Embodiments of the present invention will be described below in detail.

The nonionic surfactant (A) used in the present invention is represented by the above general formulas (I) to (III).
In the general formulas (I) to (III), R ¹ , R ² and R ³ are a straight-chain or branched-chain alkyl or alkenyl group having 6 to 24 carbon atoms, preferably a straight-chain having 8 to 20 carbon atoms. Or a branched-chain alkyl or alkenyl group, more preferably a straight-chain or branched-chain alkyl or alkenyl group having 10 to 18 carbon atoms, particularly preferably a straight-chain or branched-chain having 10 to 16 carbon atoms. It is an alkyl group or an alkenyl group. If the carbon number of R ¹ , R ² , and R ³ is less than 6 or 25 or more, the cleaning performance is undesirably reduced.

Specific examples of the raw material alcohol before addition of ethylene oxide or propylene oxide used for obtaining the nonionic surfactants represented by the general formulas (I) to (III) include decyl alcohol and lauryl. Linear alcohols such as alcohol and myristyl alcohol (manufactured by Kao Corporation, trade names "Calcol 1095", "Calcol 20")
98 "and" Calcol 4098 "), a mixed alcohol having a carbon number of 6 to 24 (Kao Co., Ltd., trade name" Calcol 2474 ", etc.), synthesized using the oxo method or the Ziegler method. Alcohols having 6 to 24 carbon atoms with branches (manufactured by Kyowa Hakko Co., Ltd., trade name "Oxocol 900",
“Oxocol 1213”, “Decanol” and “Tridecanol”, manufactured by Mitsubishi Chemical Corporation, trade name “Dovanol 2”
3 "," Dovanol 25 "and" Diadoll 115H ",
"Neo Doll 23", "Neo Doll 25", "Neo Doll 1" and "Lineball 911" manufactured by Shell Chemical Co., Ltd.
Etc.).

As a method for adding an alkylene oxide to these alcohols, a known alkoxylation method may be used. The catalyst used for this alkoxylation may be either an acid catalyst or a base catalyst,
Further, MgO-Zn described in JP-A-7-227540.
O, MgO-SnO, MgO- TiO 2, MgO-Sb
Narrow alkylene oxide addition distribution such as O (narrow rang
The synthesis can also be carried out using a catalyst which gives e), or a catalyst which gives a selectively narrow alkylene oxide addition distribution, such as a similar Mg-based catalyst described in JP-A-1-164439. These catalysts are preferably neutralized after completion of the reaction or removed by adsorption treatment from the viewpoint of product stability. The neutralizing agent for the alkali catalyst is preferably a low molecular weight organic acid such as acetic acid, glycolic acid, lactic acid, levulinic acid and the like.

[0014] In a non-ionic surfactant represented by the general formula (I) of the present invention, x ₁ and x ₂ represents an average molar number of addition of ethylene oxide is a number of 1 or more, respectively, x ₁ and
the sum of x ₂ is the number of 4 or more. When the sum of x ₁ and x ₂ is less than 4, compatibility with the nonionic surfactant and water, represented by the general formula (I) is deteriorated. Although the sum of x ₁ and x ₂ does not change even cleaning performance beyond 20, since there is a possibility that the waste water treatment and foaming such problems, the sum of x ₁ and x ₂ is preferably 20 or less And more preferably 6 to 15.

Further, the average addition mole number y ₁ of propylene oxide of the nonionic surfactant represented by the general formula (I) is larger than 0, and the sum of x ₁ and x ₂ which are the average addition mole number of ethylene oxide. A smaller number, preferably 0.5 to
6, more preferably 1-5. and cleanability y ₁ is equal to or greater than the sum of x ₁ and x _2, is not preferable because the biodegradability and the like is deteriorated.

[0016] In a non-ionic surfactant represented by the general formula (II) of the present invention, x ₃ and x ₄ represents an average molar number of addition of ethylene oxide is a number of 1 or more, respectively, x ₃ and x ₄
Is a number of 4 or more. When the sum of x ₃ and x ₄ is less than 4, compatibility with the nonionic surfactant and water, represented by the general formula (II) is deteriorated. Although the sum of x ₃ and x ₄ does not change even cleaning performance beyond 20, since there is a possibility that the waste water treatment and foaming such problems, the sum of x ₃ and x ₄ is preferably 20 or less And more preferably 6 to 15.

The average addition mole number y ₂ of propylene oxide of the nonionic surfactant represented by the general formula (II) is 0.
Larger, a x ₃ and the sum is smaller than the number of x ₄ is an average number of added moles of ethylene oxide, preferably 0.5 to
6, more preferably 1-5. and cleanability y ₂ is equal to or greater than the sum of x ₃ and x _4, undesirably biodegradability, etc. is deteriorated.

[0018] In a non-ionic surfactant represented by the general formula (III) of the present invention, x ₅ and x ₈ shows the average addition mole number of ethylene oxide is a number of 1 or more, respectively, and x ₆
the sum of x ₇ is a number of 1 or more, the sum of x ₅ and x ₆ and x ₇ and x ₈ is a number of 4 or more. When the sum of x ₅ and x ₆ and x ₇ and x ₈ are less than 4, the general formula
The compatibility between the nonionic surfactant represented by the formula (III) and water deteriorates. In order sum of x ₅ and x _6, x ₇ and x ₈ are, but does not change the cleaning performance beyond 20, there is a possibility that the waste water treatment and foaming such problems, x ₅ and x ₆ and x the sum of ₇ and x ₈ are preferably a number of 20 or less, more preferably a number from 6 to 15.

The average addition mole number y ₃ of propylene oxide of the nonionic surfactant represented by the general formula (III)
y ₄ and y ₅ are each 0 or more, and y ₃ + y ₅ ≧ 1. y ₃
The sum of y ₄ and y ₅ is the sum is smaller than the number of x ₅ and x ₆ and x ₇ and x ₈ are the average number of added moles of ethylene oxide, preferably 0.5 to 6, more preferably from 1 to 5 Is a number. y ₃ and y ₄
The sum of y ₅ is x ₅ and x ₆ and x ₇ and the cleaning property becomes greater than or equal to the sum of x _8, undesirably biodegradability, etc. is deteriorated.

In the present invention, as the alkali agent used as the component (B), any water-soluble alkali agent can be used. Specific examples include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide,
Sodium orthosilicate, sodium metasilicate, sodium sesquisilicate, silicates such as No. 1 sodium silicate, No. 2 sodium silicate, No. 3 sodium silicate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, pyrophosphoric acid Phosphates such as sodium, sodium tripolyphosphate and sodium hexametaphosphate; carbonates such as disodium carbonate, sodium hydrogencarbonate, dipotassium carbonate and potassium hydrogencarbonate; borates such as sodium borate; Two or more water-soluble alkali agents may be used in combination. Of these alkali agents, preferred are sodium hydroxide, potassium hydroxide, sodium orthosilicate and sodium metasilicate, and more preferred are sodium hydroxide and potassium hydroxide.

In the present invention, the chelating agent used as the component (C) includes alkali metal salts or lower amine salts of aldonic acids such as glyceric acid, tetronic acid, pentonic acid, hexonic acid and heptonic acid, nitrilotriacetic acid, Alkali metal salts or lower amine salts of aminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenediaminediacetic acid, and tetraethylenetetraminehexaacetic acid; alkali metal salts or lower amine salts of oxycarboxylic acids such as citric acid and malic acid; aminotrimethylene phosphone Acid, hydroxyethylidenediphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, etc., alkali metal salts or lower amine salts of phosphonic acids such as ethanolamine, diethanolamine, triethanolamine Alkanolamines such as ethanolamine are exemplified. Of these chelating agents, gluconic acid, glucoheptonic acid, ethylenediaminetetraacetic acid, citric acid, malic acid, alkali metal salts or lower amine salts of hydroxyethylidene diphosphonic acid, particularly preferably sodium gluconate,
Sodium glucoheptonate, sodium ethylenediaminetetraacetate, sodium citrate, and sodium hydroxyethylidene diphosphonate.

The content of the nonionic surfactant (A) in the detergent composition of the present invention is preferably 0.01 to 20% by weight, and the content of the alkaline agent (B) is preferably 0.1 to 50% by weight. . Also
When the chelating agent of the component (C) is blended, its content is preferably 0.01 to 20% by weight.

When the detergent composition of the present invention is used for washing as it is, the amount of the nonionic surfactant (A) is preferably 0.01 to 5% by weight, more preferably 0.05 to 3% by weight.
Is more preferred. Sufficient cleaning performance can be obtained by adding 0.01% by weight or more, and if more than 5% by weight, the cleaning performance is saturated, which is economically disadvantageous. The amount of the alkali agent (B) is preferably 0.1 to 10% by weight,
-8% by weight is more preferred. Sufficient cleaning performance can be obtained by adding 0.1% by weight or more, and if more than 10% by weight, the cleaning performance is saturated, which is economically disadvantageous.
(C) The compounding amount of the chelating agent is preferably from 0.01 to 5% by weight, more preferably from 0.05 to 2% by weight, from the viewpoints of detergency and economy.

The detergent composition of the present invention has the surfactants represented by the above general formulas (I) to (III) which are generally used in detergent compositions for the purpose of improving the detergency. A nonionic surfactant other than the agent, an anionic surfactant, an amphoteric surfactant and the like can be blended in consideration of an increase in COD and cost.

A hard surface cleaning agent is commercially available as a concentrated product, and is diluted with a water-soluble medium such as water during cleaning.
It is generally used. The composition of the present invention is a solubilizing agent for suppressing the separation of the detergent as necessary, and the form of a concentrated detergent composition produced using a slurrying agent that makes the appearance of the detergent a white suspension state. You can also.

Examples of the solubilizer used in the present invention include compounds represented by the following general formulas (IV) to (VI).

R ⁴ -X- (CH ₂ ) _m COOM ¹ (IV) R ⁵ COOM ² (V) R ⁶ SO ₃ M ³ (VI) wherein R ⁴ , R ⁵ and R ⁶ each have a carbon number A saturated or unsaturated linear or branched aliphatic hydrocarbon group having 3 to 22 carbon atoms or an aromatic hydrocarbon group having 5 to 18 carbon atoms, wherein X is a group> N
H,> N (CH ₂ ) _n COOM ¹ or> CHCOOM ¹ ; M ¹ , M ² and
M ³ represents respectively a hydrogen atom, an alkali metal, an aliphatic amine having 1 to 4 carbon atoms, ammonia or an alkanolamine, m and n indicate integers of 1 to 3. Examples of the compound represented by the general formula (IV) include alkenyl succinic acids having 6 to 18 carbon atoms and salts thereof, and compounds represented by the following formula.

[0028]

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The compound represented by the general formula (V) includes
Examples include caproic acid, enanthic acid, caprylic acid, capric acid, lauric acid, butyric acid, valeric acid, isobutyric acid, 2-ethylhexanoic acid, and salts thereof. Examples of the compound represented by the general formula (VI) include a compound in which the carboxyl group of the fatty acid represented by the general formula (V) is changed to a sulfonic acid group.

In the above general formulas (IV) to (VI), M ¹ , M ² and
Specific examples of M ^3, methylamine, ethylamine, propylamine, butylamine, ethylenediamine, diethylenetriamine, ammonia, monoethanolamine, diethanolamine, triethanolamine, other carbon atoms 2-10 alkanolamine, potassium, sodium, hydrogen Atoms and the like.

As the slurrying agent used in the present invention, a water-soluble polymer carboxylic acid represented by the following general formula (VII):
Alternatively, naphthalenedicarboxylic acid, naphthalenedisulfonic acid or phthalic acid and alkali metal salts or amine salts thereof may be mentioned.

[0032]

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[Wherein R ^{7 to} R ¹² represent a hydrogen atom and a carbon atom of 1
Alkyl group of 5 to 5, alkoxyl group of 1 to 5 carbon atoms, CO
It is either OM or OH, and may be the same or different. M is a hydrogen atom, an alkali metal, an alkylamine having 1 to 4 carbon atoms, or an alkanolamine having 1 to 6 carbon atoms. The both terminals of the general formula (VII) are not particularly limited, but include a hydrogen atom, OH, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, SO ₃ M (M has the above-mentioned meaning) and the like. And may be the same or different. p and q each indicate the number of moles of the monomer in parentheses, and p may be 0. When p is 0, the polymer is a homopolymer of a monomer whose molar number is represented by q.
The copolymerization molar ratio p / q of p and q is 0/10 to 10/1,
The weight average molecular weight (Mw) is 1,000 to 100,000, preferably 3,
000-50,000, more preferably 5,000-20,000. The polymerization form may be block or random. Specific examples of the water-soluble polymer carboxylic acid represented by the general formula (VII) include acrylic acid homopolymer, acrylic acid-maleic acid copolymer, α-hydroxyacrylic acid homopolymer, and C ₅ olefin-maleic acid. Copolymers, isobutylene-maleic acid copolymers, and the like, and alkali metal salts or amine salts thereof. Preferred are acrylic acid homopolymer and acrylic acid-maleic acid copolymer. Specific product names include Kao Corporation's Poise 540, Poise 530, Poise 521, Poise 520, Nippon Peroxide Co., Ltd. Pale Plaque 250, Pale Plaque 1200, Pale Plaque 5000, Nippon Zeon Co., Ltd. 540, quinflow 542, quinflow 54
3, Quinflow 560, Quinflow 640, Quinflow 750, Alon T-40 (M) manufactured by Toagosei Co., Ltd., Isoban 06, Isoban 04, Isoban 600 manufactured by Kuraray Co., Ltd. No. Two or more water-soluble polymer carboxylic acids may be used in combination.

When the detergent composition of the present invention is provided in the form of a concentrated detergent, the composition is not particularly limited,
Preferably the non-ionic surfactant of component (A) is preferably
0.1 to 20% by weight, more preferably 0.5 to 5% by weight, the alkali agent of the component (B) is 1 to 50% by weight, more preferably 15 to 45% by weight, and the solubilizing agent or the slurrying agent is , Preferably 0.05 to 40% by weight, more preferably
0.1 to 10% by weight. When the chelating agent (C) is contained, the content is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight. If the detergent composition is stable, a solubilizing agent or a slurrying agent may not be used.

Further, the cleaning composition of the present invention includes an antifoaming agent for suppressing foams generated in the cleaning step, for example, silicone-based, higher alcohol-based, higher fatty acids and salts thereof, pluronic copolymers, tetranics A type copolymer, polyethylene glycol, polypropylene glycol, or the like can also be blended.

The hard surface cleaning composition of the present invention comprises a metal,
It is effective when cleaning glass, porcelain, plastics and the like at a low temperature, and is particularly effective in continuous cleaning of steel plates at steelworks, that is, immersion cleaning, spray cleaning, brush cleaning, electrolytic cleaning, and the like.

[0037]

EXAMPLES Examples are shown below, in which percentages are by weight unless otherwise specified. The average molecular weight of the nonionic surfactant was measured by the following method. That is, the hydroxyl value of the synthesized nonionic surfactant was determined by a neutralization titration method according to JIS K0070, and the average molecular weight was determined from the obtained hydroxyl value according to the following equation.

[0038]

(Equation 1)

[0039] Synthesis Example 1 Formula _{C 12 H 25 O- (EO)} 5 - (PO) 4 - (EO) with a two metering tanks for ₅ and for the synthesis of ethylene oxide of the compound represented by -H propylene oxide Lauryl alcohol (trade name: Calcol 209) was placed in a 5-liter rotary stirring autoclave.
8 ”, manufactured by Kao Corporation), 500 g, and potassium hydroxide 3.0
g, purge with nitrogen, then raise to 110 ° C, 40 torr
For 1 hour. Next, the temperature was raised to 150 ° C., 592 g of ethylene oxide was introduced into the autoclave at a pressure of 3.5 kg / cm ² , and the reaction was continued until the pressure was reduced to a constant level. After cooling to 120 ° C., 624 g of propylene oxide was added. Was introduced into the autoclave at a pressure of 3.5 kg / cm ² , and the reaction was continued until the pressure decreased and became constant as in the case of ethylene oxide. Thereafter, the temperature was raised again to 150 ° C., 592 g of ethylene oxide was introduced, and the reaction was continued until the pressure dropped and became constant. After completion of the reaction, the temperature was lowered to extract a synthesized sample to obtain about 2.3 kg of the target polyalkylene glycol lauryl ether (average molecular weight: 860).

Synthesis Example 2 Synthesis of Compound Represented by Formula C ₁₂ H ₂₅ O- (EO) _3- (PO) _2- (EO) ₃ -H The same amounts of lauryl alcohol and catalyst as in Synthesis Example 1 were charged. Ethylene oxide was prepared by the same procedure as in Synthesis Example 1.
355 g, 312 g of propylene oxide, and 355 g of ethylene oxide are reacted, and about 1.5 kg of the target polyalkylene glycol lauryl ether (average molecular weight: 566)
) Got.

Synthesis Example 3 Synthesis of compound represented by the formula (C ₁₂ H ₂₅ , C ₁₄ H ₂₉ ) O- (EO) _5- (PO) _2- (EO) ₅ -H Instead, a mixed alcohol of lauryl alcohol (72% by weight) and myristyl alcohol (28% by weight) (trade name: Calcol 2474, manufactured by Kao Corporation) was used, and 572 g of ethylene oxide was prepared in the same procedure as in Synthesis Example 1. 302 g of propylene oxide and 572 g of ethylene oxide were sequentially reacted to obtain about 2.0 kg of the target polyalkylene glycol lauryl myristyl ether (average molecular weight: 756).

Synthesis Example 4 Synthesis of Compound Represented by Formula C ₁₂ H ₂₅ O— [EO ₃ / PO ₂ ] — (EO) ₄ —H Using the same apparatus as in Synthesis Example 1, the same as in Synthesis Example 1 After lauryl alcohol (500 g) and potassium hydroxide (3.0 g) were charged, the atmosphere was replaced with nitrogen, the temperature was raised to 110 ° C., and dehydration was performed at 40 torr for 1 hour. Then, the temperature was raised to 150 ° C., and the EO / PO mixture (molar ratio =
3/2) 667 g was introduced into the autoclave and reacted until the pressure became constant. Finally, 474 g of EO was introduced into the reaction system and reacted until the pressure became constant. After completion of the reaction, the temperature was lowered to remove the reactants, and the catalyst was neutralized with acetic acid.
6 kg of the title nonionic surfactant were obtained.

Synthesis Example 5 Synthesis of compound obtained by successively adding 5 mol of EO, 2 mol of PO and 5 mol of EO to C ₁₂ H ₂₅ OH, using the same apparatus as in Synthesis Example 1, lauryl alcohol 500
g, and 3.0 g of potassium hydroxide, and after the dehydration and the temperature were raised in the same manner as in Synthesis Example 1, 591 g of EO was charged and the reaction was carried out. As soon as all the EO has been introduced into the system, it is switched to the PO measuring tank, and the PO 3 remains unreacted in the system.
The reaction is carried out by introducing 12 g. Immediately after the introduction of PO, it was switched to EO again, 591 g of EO was introduced, and the reaction was continued until the pressure was lowered and became constant. After completion of the reaction, the same operation as in Synthesis Example 4 was performed, and 2.
0 kg of the title nonionic surfactant was obtained.

Synthesis Example 6 Synthesis of a compound represented by the formula RO- (EO) _2- [EO ₄ / PO ₄ ]-(EO) ₄ -H (RO is an oxo alcohol residue having 12 or 13 carbon atoms) Using the same apparatus as in Example 1, 500 g of oxo alcohol having 12 or 13 carbon atoms (linear ratio 0.64, trade name “Oxocol 1213”, average molecular weight 194, manufactured by Kyowa Hakko Co., Ltd.) and 3.0 g of potassium hydroxide were charged. After replacing with nitrogen, the temperature was raised to 110 ° C.
Dehydration was performed for 1 hour at 40 torr. Next, the temperature is raised to 150 ° C and EO
At a pressure of 3.5 kg / cm ^{2 into} a 227 g autoclave,
After the reaction was continued until the pressure decreased and became constant, 1051 g of an EO / PO mixture (molar ratio = 4/4) was introduced into the autoclave, and the reaction was likewise continued until the pressure became constant. Finally
454 g of EO was introduced into the reaction system and reacted until the pressure became constant. After completion of the reaction, the same operation as in Synthesis Example 4 was performed,
2.2 kg of the title nonionic surfactant were obtained.

Examples 1 to 18 and Comparative Examples 1 to 17 Preparations of the present invention and comparative cleaning compositions (balance amount is deionized water) having the compositions shown in Tables 1 and 2 were prepared.
A cleaning test of the steel sheet was performed by the following method, and the amount of residual oil adhering was measured. The results are shown in Tables 1 and 2.

<Steel Sheet Washing Test> (1) Steel Sheet to be Washed As the steel sheet to be washed, a steel sheet cold-rolled with tallow-based rolling oil was cut into a size of 25 mm × 50 mm.

(2) Washing test procedure All washing tests were performed in the following procedure. That is, the steel sheet to be cleaned is immersed in the cleaning composition for 1 second, and then the current density is continuously measured.
Electrolytic cleaning was performed by switching the potential of the steel sheet from negative to positive at 10 A / dm ² for 0.5 seconds each, rinsed with water, and dried. The washing was performed at 40 ° C. unless otherwise specified.

(3) Method for Measuring the Amount of Remaining Adhered Oil The amount of oil adhering to the surface of the steel sheet after the cleaning test was all measured using a steel sheet adhering oil content measuring device EMIA-111 (manufactured by HORIBA, Ltd.). The measured value is an average of five measurements. As a criterion for determining the detergency, the residual oil content of 20 mg / m ² or more was evaluated as poor, 10 mg / m ² or more and less than 20 mg / m ² as good, and less than 10 mg / m ² as excellent.

[0049]

[Table 1]

[0050]

[Table 2]

As is clear from Tables 1 and 2, the detergent composition containing a nonionic surfactant according to the present invention exhibits good cleaning performance, whereas the detergent composition containing no nonionic surfactant. The composition and the detergent composition containing a nonionic surfactant other than the nonionic surfactant according to the present invention have a higher residual adhering oil content compared to the detergent composition of the present invention and have poor cleaning performance. ing.

Examples 19 to 26 As shown in Table 3, detergent compositions having various compositions in which the amount of the nonionic surfactant was varied were prepared (the balance was deionized water). A cleaning test of the steel sheet was performed in the same manner as in Example 1, and the amount of residual oil adhering was measured. Table 3 shows the results.

[0053]

[Table 3]

As is apparent from Table 3, good detergency is exhibited when the amount of the nonionic surfactant is 0.01% or more, and saturation of the detergency is observed when the content is 5.0% or more.

Examples 27 to 60 As shown in Tables 4 to 6, detergent compositions having various compositions in which the amounts of the alkali agent and the chelating agent were variously changed (balance amount is deionized water) were prepared. Example 1
A cleaning test of the steel sheet was performed in the same manner as described above, and the amount of residual oil adhering was measured. The results are shown in Tables 4 to 6.

[0056]

[Table 4]

[0057]

[Table 5]

[0058]

[Table 6]

As is clear from Tables 4 to 6, good detergency was exhibited when the concentration of the alkali agent was 0.1% or more. Further, when the concentration of the chelating agent was lowered, the detergency tended to be lowered.

Examples 61 to 102 A concentrated detergent composition having a composition as shown in Tables 7 to 10 (balance amount is deionized water) was prepared and diluted 5 to 20 times with water. A cleaning test of the steel sheet was performed in the same manner as in Example 1, and the amount of residual oil adhering was measured. Table 7 to Table
See Figure 10.

[0061]

[Table 7]

[0062]

[Table 8]

[0063]

[Table 9]

[0064]

[Table 10]

[0065]

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[0066]

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As is clear from Tables 7 to 10, good cleaning performance is exhibited even when the concentrated detergent composition is diluted 5 to 20 times with water.

Examples 103 to 105 A cleaning composition of the present invention (balance amount is deionized water) having a composition shown in Table 11 was prepared, and a cleaning test of a steel sheet was carried out in the same manner as in Example 1. The adhering oil content was measured. Table 11 shows the results.

[0069]

[Table 11]

As is clear from Table 11, the cleaning composition containing the nonionic surfactant according to the present invention shows good cleaning performance.

[0071]

The hard surface cleaning composition of the present invention has an excellent degreasing effect at low temperatures and can lower the cleaning temperature.

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Claims (5)

[Claims] 1. A hard surface cleaner comprising (A) one or more nonionic surfactants represented by the following general formulas (I) to (III) and (B) an alkali agent. Composition. R ¹ O- (EO) x _1- (PO) y _1- (EO) x ₂ -H (I) R ² O- [EOx ₃ / POy ₂ ]-(EO) x ₄ -H (II) R ³ _{O- (EO) x 5 - [} EOx 6 / POy 3] - (PO) y 4 - [EOx 7 / POy 5] - (EO) x 8 -H (III) wherein, R ^1, R ² and R ³ represents a linear or branched alkyl or alkenyl group having 6 to 24 carbon atoms, EO represents an oxyethylene group, and PO represents an oxypropylene group. x ₁ , x ₂ , x ₃ ,
x ₄ , x ₅ , x ₆ , x ₇ and x ₈ are numbers indicating the average number of moles of ethylene oxide added, and x ₁ , x ₂ , x ₃ , x ₄ , x ₅ and x ₈ are each a number of 1 or more , X ₁ + x ₂ ≧ 4, x ₃ + x ₄ ≧ 4, x ₅ + x ₆ + x ₇ +
x ₈ ≧ 4, is x ₆ + x ₇ ≧ 1. y ₁ , y ₂ , y ₃ , y ₄ and y ₅ are numbers indicating the average number of moles of propylene oxide added, and 0 <
y ₁ <x ₁ + x ₂ , 0 <y ₂ <x ₃ + x ₄ , y ₃ + y ₅ ≧ 1, y ₃ ≧ 0, y ₄
≧ 0, y ₅ ≧ 0, y ₃ + y ₄ + y ₅ <x ₅ + x ₆ + x ₇ + x ₈ The portion enclosed by [] indicates random addition, and the portion enclosed by () indicates block addition. ] 2. The hard surface cleaning composition according to claim 1, further comprising (C) a chelating agent. 3. The composition according to claim 1, wherein the content of the nonionic surfactant (A) is 0.01 to 20% by weight, and the content of the alkaline agent (B) is 0.1 to 50% by weight. Or the hard surface cleaning composition according to 2. 4. The hard surface cleaning composition according to claim 2, wherein the content of the chelating agent of the component (C) in the composition is 0.01 to 20% by weight. 5. The cleaning composition according to claim 1, which is used for cleaning a steel sheet.