JP2011195811A - Detergent for dishwasher - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent for a dishwasher, which has excellent detergency and is small in foaming even when used in the dishwasher.SOLUTION: The detergent for the dishwasher contains an alkylene oxide adduct (A) of aliphatic amine expressed by general formula (1) and an alkylene oxide adduct (B) of aliphatic alcohol expressed by general formula (2) or an alkylene oxide adduct (C) of aliphatic amine expressed by general formula (3), wherein it is preferable that the content of oxyethylene group in (A) is 20-40 wt.% on a basis of the weight of (A), the content of oxyethylene group in (B) is 60-95 wt.% on a basis of the weight of (B) and the content of oxyethylene group in (C) is 45-95 wt.%. on a basis of the weight of (C).

Description

  The present invention relates to a cleaning agent. More specifically, the present invention relates to a detergent for dishwashers.

In the dishwashers currently in widespread use, the dishwashing water is sprayed on the dishes to wash the dishes, and the used detergent solution is circulated and reused. Accordingly, it is essential that the dishwasher detergent has a low foaming property, and at present, inorganic alkaline agents (such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide) that have less foaming are mainly used. Ingredients are the mainstream.
However, cleaning agents based on inorganic alkaline agents have strong irritation to the skin and mucous membranes,
There is a problem with safety. Further, such waste water of the cleaning agent is not preferable because it adversely affects the environment. Therefore, from the viewpoints of safety, reduction of environmental burden, etc., recently, there has been a strong demand for weakly alkaline or neutralized detergents used in dishwashers.

However, if the detergent is weakly alkalized or neutralized, there is a problem that the detergency is reduced. In order to supplement the detergency, various surfactants having high detergency against oil and dirt are washed. Although what was mix | blended with the agent (patent documents 1 and 2) is proposed, all have a problem that cleaning power is insufficient and foaming at the time of washing is intense.

JP-A-11-61180 JP 2001-64698 A

  An object of this invention is to provide the washing | cleaning agent for dishwashers which is excellent in detergency and has few foaming even if it uses it with a dishwasher.

式中、Ｒ^１は炭素数１０〜２０の炭化水素基；Ｒ^２及びＲ^３はそれぞれ独立に水素原子又は炭素数１〜４の炭化水素基；ｈ＋ｊは１０〜５０の数；ｉ＋ｋは１５〜７０の数；[(Ｃ_２Ｈ_４Ｏ)_ｈ ／ (Ｃ_３Ｈ_６Ｏ)_ｉ]及び[(Ｃ_２Ｈ_４Ｏ)_ｊ ／ (Ｃ_３Ｈ_６Ｏ)_ｋ]は、それぞれブロック付加又はランダム付加を表す。

式中、Ｒ^４は炭素数１０〜２０の炭化水素基；ｐは１０〜１００の数；ｑは０〜２０の数；[(Ｃ_２Ｈ_４Ｏ)_ｐ ／ (Ｃ_３Ｈ_６Ｏ)_ｑ]はブロック付加又はランダム付加を表す。

式中、Ｒ^５は炭素数１０〜２０の炭化水素基；ｒ＋ｔは３〜１００の数；ｓ＋ｕは０〜１４の数；[(Ｃ_２Ｈ_４Ｏ)_ｒ ／ (Ｃ_３Ｈ_６Ｏ)_ｓ]及び[(Ｃ_２Ｈ_４Ｏ)_ｔ ／ (Ｃ_３Ｈ_６Ｏ)_ｕ]は、それぞれブロック付加又はランダム付加を表す。 The inventors of the present invention have arrived at the present invention as a result of studies to achieve the above object. That is, the present invention includes an alkylene oxide adduct (A) of an aliphatic amine represented by the general formula (1) and an alkylene oxide adduct (B) of an aliphatic alcohol represented by the general formula (2). A detergent for a dishwasher comprising an alkylene oxide adduct (C) of an aliphatic amine represented by the formula (3).

In the formula, R ¹ is a hydrocarbon group having 10 to 20 carbon atoms; R ² and R ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; h + j is a number having 10 to 50; i + k is 15 to 15 [(C ₂ H ₄ O) _h / (C ₃ H ₆ O) _i ] and [(C ₂ H ₄ O) _j / (C ₃ H ₆ O) _k ] are respectively block addition or random Represents an addition.

In the formula, R ⁴ is a hydrocarbon group having 10 to 20 carbon atoms; p is a number of 10 to 100; q is a number of 0 to 20; [(C ₂ H ₄ O) _p / (C ₃ H ₆ O) _q ] Represents block addition or random addition.

In the formula, R ⁵ is a hydrocarbon group having 10 to 20 carbon atoms; r + t is a number from 3 to 100; s + u is a number from 0 to 14; [(C ₂ H ₄ O) _r / (C ₃ H ₆ O) _s ] And [(C ₂ H ₄ O) _t / (C ₃ H ₆ O) _u ] represent block addition or random addition, respectively.

  The dishwasher cleaning agent of the present invention has a high detergency against oils and fats as compared with conventional dishwasher cleaners, and has the effect of having less foaming even when used in an automatic dishwasher.

  The detergent for dishwashers of the present invention includes an alkylene oxide adduct (A) of an aliphatic amine represented by the general formula (1) and an alkylene oxide adduct of an aliphatic alcohol represented by the general formula (2). It is characterized by containing an alkylene oxide adduct (C) of an aliphatic alcohol represented by (B) or general formula (3).

R ¹ in the general formula (1) is a hydrocarbon group having 10 to 20 carbon atoms, and may be a linear, branched or cyclic hydrocarbon group, or a saturated or unsaturated hydrocarbon group. Examples of the hydrocarbon group having 10 to 20 carbon atoms include n-decyl group, isodecyl group, 1-cyclohexyl-n-butyl group, decenyl group, n-dodecyl group, isododecyl group, dodecenyl group, n-tridecyl group, isotridecyl group. N-tetradecyl group, iso-tetradecyl group, tetradecenyl group, n-hexadecyl group, isohexadecyl group, hexadecenyl group, n-octadecyl group, isooctadecyl group, n-nonadecyl group and n-eicosyl group. Among these, a hydrocarbon group having 12 to 18 carbon atoms is preferable from the viewpoint of detergency, and a hydrocarbon group having 14 to 18 carbon atoms is more preferable.

R ² and R ³ in the general formula (1) are each independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and the hydrocarbon group having 1 to 4 carbon atoms may be a linear or branched hydrocarbon group. It may be a saturated or unsaturated hydrocarbon group. Examples of the hydrocarbon group having 1 to 4 carbon atoms include methyl group, ethyl group, vinyl group, n-propyl group, isopropyl group, propenyl group, allyl group, n-butyl group, isobutyl group, t-butyl group, and butenyl group. Etc. Among these, a hydrogen atom and a hydrocarbon group having 1 or 2 carbon atoms are preferable from the viewpoint of detergency.

  H + j in the general formula (1) is a number of 10 to 50, preferably 12 to 30, and more preferably 12 to 25. When h + j is less than 10, detergency deteriorates, and when h + j exceeds 50, foaming becomes severe, which is not preferable. In addition, since h and j each represent the average addition mole number of an oxyethylene group, h + j is not necessarily an integer and may be a decimal.

  I + k in General formula (1) is a number of 15-70, Preferably it is 17-65, More preferably, it is 20-60. When i + k is less than 15, foaming becomes intense, and when i + k exceeds 70, the cleaning properties are deteriorated. In addition, since h and j each represent the average addition mole number of an oxypropylene group, i + k is not necessarily an integer and may be a decimal.

[(C ₂ H ₄ O) _h / (C ₃ H ₆ O) _i ] and [(C ₂ H ₄ O) _j / (C ₃ H ₆ O) _k ] in the general formula (1) are block additions, respectively. Or it represents a random addition. In addition, in the case of block addition, it is preferable to add in order of the oxyethylene group and the oxypropylene group to the nitrogen atom in General formula (1) from a low foaming viewpoint.

  The content of oxyethylene groups in the alkylene oxide adduct (A) of an aliphatic amine is preferably 20 to 40% by weight, more preferably 30 to 40% by weight, based on the weight of (A). If the content of the oxyethylene group is 20% by weight or more, the detergency is improved, and if it is 40% by weight or less, foaming is less preferable.

The alkylene oxide adduct (A) of an aliphatic amine in the present invention can be produced by a known method, and examples thereof include the following methods.
A primary amine represented by R ¹ —NH ₂ is charged into a pressurized reaction vessel, and ethylene oxide (hereinafter abbreviated as EO) and / or propylene oxide (hereinafter abbreviated as PO) in the presence of no catalyst or catalyst. The reaction is carried out in one or more stages. The reaction temperature is preferably 60 to 200 ° C, more preferably 70 to 140 ° C. The reaction pressure is preferably −0.1 to 0.5 MPa. The reaction time is preferably 2 to 24 hours, more preferably 3 to 10 hours. Catalysts include alkali catalysts (such as sodium hydroxide and potassium hydroxide), ammonium salt catalysts [quaternary ammonium salts of lower alkyl (carbon number of 1 to 4), etc.] and Lewis acid catalysts (boron trifluoride and tin tetrachloride). Etc.). The amount of the catalyst used is preferably 0.01 to 5% by weight, more preferably 0.1 to 0.5% by weight, based on the weight of (A). After completion of the reaction, the catalyst may be left in (A) as it is, or a method of adsorbing, filtering and removing using an adsorbent, a method of neutralizing with an acid or alkali and inactivating the catalyst, and heating. It can be processed by a method of decomposing and removing under reduced pressure. After completion of the addition reaction of alkylene oxide, R ¹ —NH _{2 is} subjected to R ¹ -NH ₂ in the presence of 1.1 to 3 molar equivalents of an alkali catalyst (for example, lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide). It was added dropwise ¹ -NH ₂ with respect to 1 to 2 molar equivalents of an alkylating agent (e.g., alkyl sulfate having 1 to 4 alkyl halide and carbon atoms from 1 to 4 carbon atoms, etc.) performing the alkylation reaction. The reaction temperature is preferably 20 to 100 ° C., the reaction pressure is preferably −0.1 to 0.2 MPa, and the reaction time is preferably 2 to 30 hours. After completion of the reaction, the unreacted alkylating agent is distilled off under reduced pressure at 50 to 150 ° C., the alkali catalyst is neutralized with an acid, the salt formed is filtered or treated with an adsorbent, and then the adsorbent is filtered. An alkylene oxide adduct (A) of an aliphatic amine can be obtained.

Specific examples of the aliphatic oxide alkylene oxide adduct (A) include decylamine EO 10 mol / PO15 mol block adduct, undecylamine EO 10 mol / PO15 mol block adduct, dodecylamine EO 12 mol / PO15 mol random Adduct, EO 25 mol / PO 32 mol block adduct of dodecylamine, methyl etherified product of tridecylamine EO15 mol / PO15 mol block adduct, tetradecylamine EO20 mol / PO20 mol block adduct, pentadecylamine EO20 Mol / PO 30 mol block adduct, hexadecylamine EO 20 mol / PO 25 mol block adduct, heptadecylamine EO 20 mol / PO 35 mol block adduct, octadecylamine EO 17 mol / PO25 Rulundum adduct, EO 40 mol / PO 60 mol random adduct of octadecylamine, EO 25 mol / PO 32 mol block adduct of oleylamine, n-butyl etherified product of nonadecylamine EO 30 mol / PO 35 mol block adduct and eicosylamine EO 45 mol / PO60 mole block adduct and the like. (A) may be a combination of two or more of these.

R ⁴ in the general formula (2) is the same group as R ¹ in the general formula (1), and the preferred range is also the same.

P in General formula (2) is a number of 10-100, Preferably it is 10-50, More preferably, it is 15-40. If p is less than 10, the detergency deteriorates, and if p exceeds 100, it is not preferable because the bubble breakage deteriorates. In addition, since p represents the average added mole number of an oxyethylene group, it is not necessarily an integer and may be a decimal number.

Q in General formula (2) is a number of 0-20, Preferably it is 0-10, More preferably, it is 0-5. If q exceeds 20, it is not preferable because detergency deteriorates. In addition, since q represents the average addition mole number of an oxypropylene group, it is not necessarily an integer and may be a decimal.

[(C ₂ H ₄ O) _p / (C ₃ H ₆ O) _q ] in the general formula (2) represents block addition or random addition, respectively.

  The content of the oxyethylene group in the alkylene oxide adduct (B) of the aliphatic alcohol is preferably 60 to 95% by weight, more preferably 70 to 80% by weight, based on the weight of (B). If the content of the oxyethylene group is 60% by weight or more, the detergency is improved, and if it is 95% by weight or less, foaming is less preferable.

  The alkylene oxide adduct (B) of an aliphatic alcohol in the present invention can be produced by a known method. For example, addition of an alkylene oxide in the production method of an alkylene oxide adduct (A) of an aliphatic amine described above. The method similar to reaction is mentioned.

Specific examples of the alkylene oxide adduct (B) of the aliphatic alcohol of the present invention include decyl alcohol PO 2 mol / EO 10 mol block adduct, undecyl alcohol EO 15 mol adduct, dodecyl alcohol EO 20 mol adduct, tri EO 30 mol adduct of decyl alcohol, EO 45 mol adduct of tetradecyl alcohol, EO 50 mol / PO 5 mol block adduct of pentadecyl alcohol, EO 50 mol / PO 10 mol block adduct of hexadecyl alcohol, EO 25 mol addition of heptadecyl alcohol , EO 25 mol adduct of octadecyl alcohol, EO 20 mol adduct of oleyl alcohol, EO 50 mol / PO 8 mol random adduct of nonadecyl alcohol and EO 70 mol / PO 1 of eicosyl alcohol Mole adducts. (B) may be a combination of two or more of these.

R ⁵ in the general formula (3) is the same group as R 1 in the general formula (1), and the preferred range is also the same.

  R + t in General formula (3) is a number of 3-100, Preferably it is 5-70, More preferably, it is 10-50. When r + t is less than 3, detergency deteriorates, and when r + t exceeds 100, foaming becomes violent. In addition, since r and t each represent the average addition mole number of an oxyethylene group, r + t is not necessarily an integer and may be a decimal.

  In the general formula (3), s + u is a number from 0 to 14, preferably 0 to 13, and more preferably 0 to 12. If s + u exceeds 14, detergency deteriorates, which is not preferable. In addition, since s and u represent the average added mole number of an oxypropylene group, respectively, s + u is not necessarily an integer and may be a decimal.

[(C ₂ H ₄ O) _r / (C ₃ H ₆ O) _s ] and [(C ₂ H ₄ O) _t / (C ₃ H ₆ O) _u ] in the general formula (3) are block additions, respectively. Or it represents a random addition.

  The content of the oxyethylene group in the alkylene oxide adduct (C) of the aliphatic amine is preferably 45 to 95% by weight, more preferably 60 to 80% by weight, based on the weight of (C). If the content of the oxyethylene group is 45% by weight or more, the detergency is improved.

  The alkylene oxide adduct (C) of the aliphatic amine in the present invention can be produced by a known method. For example, the addition of the alkylene oxide in the production method of the alkylene oxide adduct (A) of the aliphatic amine described above. The method similar to reaction is mentioned.

Specific examples of the aliphatic amine alkylene oxide adduct (C) of the present invention include decylamine EO 3 mol adduct, undecylamine EO 10 mol adduct, dodecylamine EO 40 mol / PO5 mol random adduct, tridecyl EO 30 mol adduct of amine, EO 30 mol adduct of tetradecylamine, EO 50 mol adduct of pentadecylamine, EO 60 mol adduct of hexadecylamine, EO2 mol of hexadecylamine / (EO 40 mol / PO12 mol random addition) / EO 12 mol adduct, heptadecylamine EO 25 mol adduct, octadecylamine EO 20 mol adduct, oleylamine EO 2 mol / (EO 50 mol / PO14 mol random addition) / EO 10 mol adduct, nonadecylamine EO 40 mol adduct and D EO70 mol adduct of Koshiruamin like. (C) may be a combination of two or more of these.

In the present invention, the weight ratio [(A) / (B)] of the alkylene oxide adduct (A) of the aliphatic amine and the alkylene oxide adduct (B) of the aliphatic alcohol is preferably 95/5 to 70/30. More preferably, it is 90 / 10-80 / 20. If [(A) / (B)] is 70/30 or more, foaming is less, and if it is 95/5 or less, the detergency is improved, which is preferable.

The weight ratio [(A) / (C)] of the aliphatic amine alkylene oxide adduct (A) to the aliphatic amine alkylene oxide adduct (C) in the present invention is preferably 95/5 to 30/70. More preferably, it is 90/10 to 40/60. If [(A) / (C)] is 30/70 or more, foaming is less, and if it is 95/5 or less, the cleaning properties are improved.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents “parts by weight”.

<Production Example 1> [Synthesis of dodecylamine EO 12 mol / PO 25 mol random adduct (A-1)]
Dodecylamine 185 was added to a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a dropping cylinder.
Part (1 mol part) and 4 parts of potassium hydroxide were added, sealed with nitrogen, sealed and heated to 130 ° C. A mixture of 528 parts (12 parts by mole) of EO and 1,450 parts (25 parts by mole) of PO was added dropwise over 10 hours while adjusting the pressure to 0.5 MPa or less, and then at 130 ° C. for 2 hours. Aged. Next, after cooling to 90 ° C., 20 parts of an adsorption treatment agent “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd.) is added and stirred for 1 hour at 90 ° C. to adsorb potassium hydroxide, followed by adsorption treatment agent. Was obtained to obtain a random adduct (A-1) of EO 12 mol / PO 25 mol of dodecylamine {(A-1) is R ¹ in the general formula (1), R ² and R ³ are hydrogen. Atom, h + j is 12, i + k is 25, [(C ₂ H ₄ O) _h / (C ₃ H ₆ O) _i ] and [(C ₂ H ₄ O) _j / (C ₃ H ₆ O) _k ] are , Compounds that are each a random addition}.

<Production Example 2> [Synthesis of dodecylamine EO 25 mol / PO 32 mol block adduct (A-2)]
In a pressure-resistant reaction vessel similar to Production Example 1, 185 parts (1 mole part) of dodecylamine and 4 parts of potassium hydroxide were added, sealed with nitrogen, and heated to 130 ° C. While stirring, 1,100 parts (25 mole parts) of EO was added dropwise over 4 hours while adjusting the pressure to 0.5 MPa or less, and then aged at 130 ° C. for 2 hours. Next, 1,856 parts (32 mole parts) of PO were added dropwise over 8 hours while adjusting the pressure to be 130 MPa at a pressure of 0.5 MPa or less, and then aged at 130 ° C. for 2 hours. After cooling to 90 ° C., 20 parts of an adsorption treatment agent “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at 90 ° C. for 1 hour to adsorb potassium hydroxide. Filtration yielded an EO 25 mol / PO 32 mol block adduct (A-2) of dodecylamine {(A-2) is a general formula (1) wherein R ¹ is a dodecyl group, R ² and R ³ are hydrogen atoms , h + j is 25, i + k is _{32, [(C 2 H 4} O) h / (C 3 H 6 O) i] and _{[(C 2 H 4 O)} j / (C 3 H 6 O) k] is Each compound is a block addition}.

<Production Example 3> [Synthesis of octadecylamine EO 17 mol / PO 25 mol random adduct (A-3)]
A mixture of 185 parts of dodecylamine with 269 parts (1 mole part) of octadecylamine, 528 parts (12 mole parts) of EO and 1,450 parts (25 mole parts) of PO, 748 parts of EO (17 mole parts) and 1,450 parts of PO Except having changed to what mixed (25 mol part), it carried out similarly to manufacture example 1, and obtained EO17 mol / PO25 mol random adduct (A-3) of octadecylamine {(A-3) is general In formula (1), R ¹ is an octadecyl group, R ² and R ³ are hydrogen atoms, h + j is 17, i + k is 25, [(C ₂ H ₄ O) _h / (C ₃ H ₆ O) _i ] and [( C ₂ H ₄ O) _j / (C ₃ H ₆ O) _k ] is a random addition, respectively}.

<Production Example 4> [Synthesis of octadecylamine EO 40 mol / PO 60 mol random adduct (A-4)]
185 parts of dodecylamine mixed with 269 parts (1 mole part) of octadecylamine, 528 parts (12 mole parts) of EO and 1,450 parts (25 mole parts) of PO, 760 parts of EO (40 mole parts) and PO3 Except having changed into what mixed 480 parts (60 mol part), it carried out similarly to manufacture example 1, and obtained EO40 mol / PO60 mol random adduct (A-4) of octadecylamine {(A-4) is In the general formula (1), R ¹ is an octadecyl group, R ² and R ³ are hydrogen atoms, h + j is 40, i + k is 60, [(C ₂ H ₄ O) _h / (C ₃ H ₆ O) _i ] and [(C ₂ H ₄ O) _j / (C ₃ H ₆ O) _k ] is a compound in which each is a random addition}.

<Production Example 5> [Synthesis of dodecylamine EO 12 mol / PO 75 mol random adduct (A′-1)]
A mixture of 528 parts (12 moles) of EO and 1,450 parts (25 moles) of PO
EO12 mol / PO75 mol random adduct (A′-1) of dodecylamine in the same manner as in Production Example 1 except that O528 part (12 mol part) and PO4, 350 part (75 mol part) were mixed. {(A′-1) is obtained in the general formula (1), R ¹ is a dodecyl group, R ² and R ³ are hydrogen atoms, h + j is 12, i + k is 75, [(C ₂ H ₄ O) _{h / (C 3 H 6 O} ) i] and _{[(C 2 H 4 O)} j / (C 3 H 6 O) k] , the compound is a random addition, respectively}.

<Production Example 6> [Synthesis of dodecylamine EO 25 mol / PO 5 mol block adduct (A′-2)]
Except that the number of parts of PO was changed from 1,856 parts to 290 parts (5 mole parts), EO25 mole / PO5 mole block adduct (A′-2) of dodecylamine was obtained in the same manner as in Production Example 2 {( In A′-2), R ¹ in the general formula (1) is a dodecyl group, R ² and R ³ are hydrogen atoms, h + j is 25, i + k is 5, [(C ₂ H ₄ O) _h / (C ₃ H ₆ O) _i] and _{[(C 2 H 4 O)} j / (C 3 H 6 O) k] , the compound are each block addition}.

<Production Example 7> [Synthesis of EO 20 mol adduct of dodecyl alcohol (B-1)]
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a dropping cylinder, dodecyl alcohol 1
86 parts (1 mol part) and 2 parts of potassium hydroxide were added, sealed with nitrogen, and heated to 160 ° C. While stirring, 880 parts (20 mol parts) of EO was added dropwise over 4 hours while adjusting the pressure to 0.5 MPa or less, and then aged at 160 ° C. for 2 hours. Next, after cooling to 90 ° C., 20 parts of an adsorption treatment agent “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd.) is added and stirred for 1 hour at 90 ° C. to adsorb potassium hydroxide, followed by adsorption treatment agent. To obtain an EO20 molar adduct (B-1) of dodecyl alcohol [(B-1) is a compound in which R ⁴ in the general formula (2) is a dodecyl group, p is 20, and q is 0] .

<Production Example 8> [Synthesis of heptadecyl alcohol EO 25 mol adduct (B-2)]
186 parts of dodecyl alcohol to 256 parts (1 mole part) of heptadecyl alcohol, EO
The EO 25 mol adduct (B-2) of heptadecyl alcohol was obtained in the same manner as in Production Example 7 except that 880 parts of the above were changed to 1,100 parts (25 mol parts) [(B-2) In the general formula (2), R ⁴ is a heptadecyl group, p is 25, and q is 0].

<Production Example 9> [Synthesis of hexadecyl alcohol EO 50 mol / PO 10 mol block adduct (B-3)]
185 parts of dodecylamine to 242 parts (1 mole part) of hexadecyl alcohol, 1,100 parts of EO to 2,200 parts (50 mole parts), and 1,856 parts of PO to 580 parts (10 mole parts) ) Was obtained in the same manner as in Production Example 2, except that hexadecyl alcohol EO 50 mol / PO 10 mol block adduct (B-3) was obtained {(B-3) is R ⁴ in the general formula (2). Is a hexadecyl group, p is 50, q is 10, and [(C ₂ H ₄ O) _p / (C ₃ H ₆ O) _q ] is a block addition compound}.

<Production Example 10> [Synthesis of oleyl alcohol EO 20 mol adduct (B-4)]
Except for changing 186 parts of dodecyl alcohol to 268 parts (1 mole part) of oleyl alcohol, the same procedure as in Production Example 7 was carried out to obtain an EO20 mole adduct (B-4) of oleyl alcohol [(B-4) Compound in which R ⁴ in general formula (2) is an oleyl group, p is 20, and q is 0].

<Production Example 11> [Synthesis of oleyl alcohol EO 5 mol adduct (B′-1)]
EO 5 mol adduct of oleyl alcohol in the same manner as in Production Example 7 except that 186 parts of dodecyl alcohol was changed to 268 parts (1 mol part) of oleyl alcohol and 880 parts of EO was changed to 220 parts (5 mol part). B′-1) was obtained {(B′-1) is a compound in which R ⁴ in the general formula (2) is an oleyl group, p is 5, and q is 0}.

<Production Example 12> [Synthesis of Octadecylamine EO 20-Mole Adduct (C-1)]
Except having changed 186 parts of dodecyl alcohol into 270 parts (1 mol part) of octadecylamine, it carried out similarly to manufacture example 7, and obtained the EO20 mol adduct (C-1) of octadecylamine [(C-1). Compound in which R ⁵ in general formula (3) is an octadecyl group, r + t is 20, and s + u is 0].

<Production Example 13> [Synthesis of tetradecylamine EO 30 mol adduct (C-2)]
EO30 of tetradecylamine in the same manner as in Production Example 7 except that 186 parts of dodecyl alcohol was changed to 214 parts (1 mole part) of tetradecylamine and 880 parts of EO were changed to 1,320 parts (30 mole parts). A molar adduct (C-2) was obtained [(C-2) is a compound in which R ⁵ in the general formula (3) is a tetradecyl group, r + t is 30, and s + u is 0].

<Production Example 14> [Synthesis of dodecylamine EO 40 mol / PO 5 mol random adduct (C-3)]
A mixture of 528 parts (12 moles) of EO and 1,450 parts (25 moles) of PO
EO 40 mol / PO 5 mol random adduct (C-3) of dodecylamine in the same manner as in Production Example 1 except that O1, 760 parts (40 mol parts) and PO 290 parts (5 mol parts) were mixed. {(C-3) is a compound of the general formula (3) wherein R ⁵ is a dodecyl group, r + t is 40, s + u is 5, [(C ₂ H ₄ O) _r / (C ₃ H ₆ O) _s ] And [(C ₂ H ₄ O) _t / (C ₃ H ₆ O) _u ] are each a random addition}.

<Production Example 15> [Synthesis of hexadecylamine EO 2 mol / (EO 40 mol / PO 12 mol random addition) / EO 12 mol adduct (C-4)]
In a pressure-resistant reaction vessel similar to Production Example 1, 241 parts (1 mol part) of hexadecylamine was charged, sealed with nitrogen, and heated to 130 ° C. While stirring, 88 parts (2 mole parts) of EO was added dropwise over 4 hours while adjusting the pressure to 0.5 MPa or less, and then aged at 130 ° C. for 2 hours. After cooling to 90 ° C., 4 parts of potassium hydroxide was added, and EO 1,760 parts (40 mole parts) and PO696 parts (12 mole parts) were mixed so that the pressure would be 0.5 MPa or less at 130 ° C. While adjusting, the solution was added dropwise over 8 hours and aged at 130 ° C. for 2 hours. Subsequently, 528 parts (12 mol parts) of EO was added dropwise over 4 hours while adjusting the pressure to be 130 MPa at a pressure of 0.5 MPa or less, and then aged at 130 ° C. for 2 hours. After cooling to 90 ° C., 20 parts of an adsorption treatment agent “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at 90 ° C. for 1 hour to adsorb potassium hydroxide. Filtration gave hexadecylamine EO 2 mol / (EO 40 mol / PO 12 mol random addition) / EO 12 mol adduct (C-4) {(C-4) is R ⁵ in general formula (3) is hexadecyl Group, r + t is 54, s + u is 12, [(C ₂ H ₄ O) _r / (C ₃ H ₆ O) _s ] and [(C ₂ H ₄ O) _t / (C ₃ H ₆ O) _u ] are , Compounds each being a block-random-block addition}.

<Production Example 16> [Synthesis of octadecylamine EO2 molar adduct (C′-1)]
Production Example 7 except that 186 parts of dodecyl alcohol was changed to 270 parts (1 mol part) of octadecylamine, 2 parts of potassium hydroxide were changed to 0 part, and 880 parts of EO were changed to 88 parts (2 mol parts). Similarly, an EO2 molar adduct (C′-1) of octadecylamine was obtained [(C′-1): R ⁵ in the general formula (3) is an octadecyl group, r + t is 2, and s + u is 0. Compound].

<Examples 1-8, Comparative Examples 1-7>
The raw materials for the dishwasher cleaning agent in the number of parts listed in Table 1 are put into a mixing tank equipped with a stirrer and a temperature control function, and stirred at 20 to 70 ° C. for 10 minutes. Examples 1 to 8 and Comparative Examples 1 to 7) were produced.

  About the washing | cleaning agent for Examples 1-8 and Comparative Examples 1-7, the washability and the low foaming property were evaluated with the following method. The results are shown in Table 1.

<Evaluation method for detergency>
1 g of beef tallow [manufactured by Wako Pure Chemical Industries, Ltd.] was uniformly applied to a porcelain dish having a diameter of 25 cm to obtain a contaminated dish. These 5 dishes were loaded into an automatic dishwasher “NP-60SS6” (manufactured by Panasonic Corporation), and 1 g each of the detergent for the dishwasher (Examples 1-8, Comparative Examples 1-7) was used. "Speedy course cleaning" was performed, and the cleaning performance was evaluated according to the following evaluation criteria.
○: No beef tallow remains and no stickiness is felt even when the dish is touched △: Beef tallow residue is not visually recognized, but touches the dish and feels some sliminess x: Tallow Residue is visually observed

<Low foaming evaluation method>
Into the above automatic dishwasher / dryer, 2 g of dishwasher cleaning agents (Examples 1 to 8 and Comparative Examples 1 to 7) are added, and “speed course cleaning” is started. The operation was stopped 10 minutes after the start, and the state of the foam in the automatic dishwasher 10 seconds after the stop was visually observed and evaluated according to the following evaluation criteria.
◎: No bubbles are observed on the liquid surface. ○: A very small amount of bubbles are observed on the liquid surface. △: The liquid surface is covered with a thin foam layer. Covered with a layer, the liquid level is not visible at all XX: The liquid level is covered with a thick foam layer, and the liquid level is not visible at all

  As is clear from Table 1, the dishwasher cleaning agent of the present invention (Examples 1 to 8) is superior in cleaning properties to the dishwasher cleaning agents of Comparative Examples 1 to 7, and has low foaming. It is sex.

The cleaning agent for dishwashers of the present invention is suitable as a cleaning agent for dishwashers because of its excellent detergency and low foaming properties. Moreover, it can be used not only in tableware washing, but also in washing processes that require high detergency and low foaming in bioprocesses, food production processes, pulp production processes, paper making processes, fiber processing, metal processing, and the like.

Claims (6)

An alkylene oxide adduct (A) of an aliphatic amine represented by the general formula (1) and an alkylene oxide adduct (B) of an aliphatic alcohol represented by the general formula (2) or the general formula (3) A detergent for dishwashers comprising an alkylene oxide adduct (C) of an aliphatic amine.

[Wherein R ¹ is a hydrocarbon group having 10 to 20 carbon atoms; R ² and R ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; h + j is a number having 10 to 50; i + k is 15 the number of _{~70; [(C 2 H 4} O) h / (C 3 H 6 O) i] and _{[(C 2 H 4 O)} j / (C 3 H 6 O)] , respectively block addition or random Represents an addition. ]

[Wherein R ⁴ is a hydrocarbon group having 10 to 20 carbon atoms; p is a number of 10 to 100; q is a number of 0 to 20; [(C ₂ H ₄ O) _p / (C ₃ H ₆ O) _q ] represents block addition or random addition. ]

[Wherein R ⁵ is a hydrocarbon group having 10 to 20 carbon atoms; r + t is a number of 3 to 100; s + u is 0;
The number of ˜14; [(C ₂ H ₄ O) _r / (C ₃ H ₆ O) _s ] and [(C ₂ H ₄ O) _t / (C ₃ H ₆ O) _u ] are respectively block addition or Represents random addition. ]   The cleaning agent for dishwashers according to claim 1, wherein the content of the oxyethylene group in (A) is 20 to 40% by weight based on the weight of (A).   The cleaning agent for dishwashers according to claim 1 or 2, wherein the content of the oxyethylene group in (B) is 60 to 95% by weight based on the weight of (B).   The cleaning agent for dishwashers according to claim 1 or 2, wherein the content of the oxyethylene group in (C) is 45 to 95% by weight based on the weight of (C).   The detergent for tableware washing machines in any one of Claims 1-3 whose weight ratio [(A) / (B)] of said (A) and (B) is 95 / 5-70 / 30. The washing | cleaning agent for tableware washing machines of Claim 1, 2, or 4 whose weight ratio [(A) / (C)] of said (A) and (C) is 95 / 5-30 / 70.