JP2011256365A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent composition which excels in detergency over oil and fat staining, rinse aid nature, and flowability, and can reduce the quantity consumed.SOLUTION: The detergent composition comprises a nonionic surfactant (A) expressed by general formula (1). In the formula, Rdenotes a 8-24C alkyl group or alkenyl group; AO and AO each independently denote an oxyethylene group and/or an oxypropylene group; EO denotes an oxyethylene group; PO denotes an oxypropylene group; a, b, c, d, e, f, g and h denote numbers which satisfy a+b=0-10, c+d=5-50, e+f=1-20, g+h=0-40; and [(EO)/(PO)] and [(EO)/(PO)] denote a group in which EO and PO have carried out random addition and/or block addition.

Description

  The present invention relates to a cleaning composition. More specifically, the present invention relates to a cleaning composition used for cleaning a knitted fabric or a fabric.

2. Description of the Related Art Conventionally, nonionic surfactants such as higher alcohol ethylene oxide adducts are generally blended in household or dishwashing detergents used at home. However, ethylene oxide adducts of higher alcohols cannot be said to have sufficient detergency against fat and oil stains and have poor foaming properties. Moreover, since fluidity | liquidity is bad, when mix | blended with a liquid cleaning composition, the viscosity of the liquid cleaning composition rose and there existed a subject that handling property fell.
Then, in order to improve the subject which the ethylene oxide adduct of a higher alcohol has, it has been proposed to use an ethylene oxide / propylene oxide adduct of a higher alcohol as a cleaning composition (Patent Document 1). However, the ethylene oxide / propylene oxide adduct of higher alcohol described in Patent Document 1 has good fluidity and excellent foaming properties, but is not sufficiently cleanable against oil stains. Therefore, there is a demand for a detergent composition that is excellent in cleaning properties, fluidity, and foam resistance against oil and fat stains.

JP-A-10-130690

  An object of the present invention is to provide a cleaning composition that is excellent in detergency, bubbling and fluidity with respect to fat and oil stains, and can reduce the amount used.

式（１）中、Ｒ^１は炭素数８〜２４のアルキル基又はアルケニル基；Ａ^１Ｏ及びＡ^２Ｏはそれぞれ独立にオキシエチレン基及び／又はオキシプロピレン基：ＥＯはオキシエチレン基；ＰＯはオキシプロピレン基；ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ及びｈは、ａ＋ｂ＝０〜１０、ｃ＋ｄ＝５〜５０、ｅ＋ｆ＝１〜２０、ｇ＋ｈ＝０〜４０を満たす数；[（ＥＯ）_ｃ／（ＰＯ）_ｅ] 及び[（ＥＯ）_ｄ／（ＰＯ）_ｆ]は、ＥＯとＰＯがランダム付加及び／又はブロック付加した基；を表す。 The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention is a cleaning composition comprising a nonionic surfactant (A) represented by the following general formula (1).

In formula (1), R ¹ is an alkyl group or alkenyl group having 8 to 24 carbon atoms; A ¹ O and A ² O are each independently an oxyethylene group and / or oxypropylene group: EO is an oxyethylene group; PO is Oxypropylene group; a, b, c, d, e, f, g, and h are numbers satisfying a + b = 0 to 10, c + d = 5 to 50, e + f = 1 to 20, and g + h = 0 to 40; EO) _c / (PO) _e ] and [(EO) _d / (PO) _f ] represent groups obtained by random addition and / or block addition of EO and PO.

  The cleaning composition of the present invention has an effect that it is excellent in detergency against oil and fat stains, foam removal and fluidity.

The cleaning composition of the present invention contains a nonionic surfactant (A) represented by the general formula (1).
R ¹ in the general formula (1) represents an alkyl group or alkenyl group having 8 to 24 carbon atoms. Examples of the alkyl group having 8 to 24 carbon atoms include linear or branched alkyl groups or cycloalkyl groups, and specifically, n- or isooctyl group, 2-ethylhexyl group, n- or isononyl group, n- or Isodecyl group, n- or isododecyl group, n- or isotridecyl group, n- or isotetradecyl group, n- or isohexadecyl group, n- or isooctadecyl group, n- or isononadecyl group, n- or isoeicosyl group and Examples thereof include an n- or isotetracosyl group.
Examples of the alkenyl group having 8 to 24 carbon atoms include linear or branched alkenyl groups, and specifically, n- or isooctenyl group, n- or isodecenyl group, n- or isoundecenyl group, n- or isododecenyl group, Examples thereof include an n- or isotetradecenyl group, an n- or isohexadecenyl group, an n- or isooctadecenyl group, and an n- or isogadoleyl group.

Of R ¹ , alkyl groups and alkenyl groups having 12 to 20 carbon atoms are preferable from the viewpoint of detergency, and alkyl groups and alkenyl groups having 14 to 20 carbon atoms are more preferable.

In the general formula (1), EO represents an oxyethylene group, and PO represents an oxypropylene group. A ¹ O and A ² O each independently represent an oxyethylene group and / or an oxypropylene group, and preferably an oxyethylene group alone from the viewpoint of detergency. A, b, c, d, e, f, g and h in the general formula (1) are numbers satisfying a + b = 0 to 10, c + d = 5 to 50, e + f = 1 to 20, and g + h = 0 to 40. From the viewpoints of detergency and fluidity, it is preferably a number satisfying a + b = 1-8, c + d = 10-40, e + f = 2-18, g + h = 2-30, and more preferably a + b = 2-6. , C + d = 15 to 35, e + f = 4 to 16, and g + h = 5 to 25. In addition, since a, b, c, d, e, f, g, and h represent the average added mole number of oxyethylene group and / or oxypropylene group, a + b, c + d, e + f, and g + h are integers. Not always, but sometimes decimal.
[(EO) _c / (PO) _e ] and [(EO) _d / (PO) _f ] represent groups in which EO and PO are randomly added and / or block-added, and are preferably random from the viewpoint of fluidity. It is addition.

The content of EO in the groups represented by [(EO) _c / (PO) _e ] and [(EO) _d / (PO) _f ] in the general formula (1) is [(EO) _c / (PO) _e ] and [(EO) _d / (PO) _f ] based on the weight of foam and fluidity, preferably 50 to 95% by weight, more preferably 55 to 90% by weight, especially Preferably it is 60 to 80 weight%.

  If necessary, the detergent composition of the present invention comprises a nonionic surfactant (B) other than (A), an anionic surfactant (C), a cationic surfactant (D) and an amphoteric surfactant (E ) Or the like may be contained.

Examples of the nonionic surfactant (B) other than (A) include alkylene oxide addition type nonionic surfactants and polyhydric alcohol type nonionic surfactants.
Alkylene oxide addition type nonionic surfactants include higher alcohols (8 to 24 carbon atoms) alkylene (2 to 4 carbon atoms, preferably 2) oxide adducts (1 to 1 added moles per active hydrogen). 80), alkyl (carbon number 1 to 12) phenol ethylene oxide adduct (addition mole number 1 to 80), fatty acid (carbon number 8 to 24) ethylene oxide adduct (addition mole number per active hydrogen 1 to 80) ), Polypropylene glycol (number average molecular weight 200 to 4,000) ethylene oxide adduct (1 to 50 moles added per active hydrogen) and polyoxyethylene (3 to 30 repeating units) alkyl (6 to 6 carbon atoms) 20) Allyl ether and the like.
Examples of the polyhydric alcohol type nonionic surfactant include polyvalent (2 to 8 or more) alcohols (2 to 30 carbon atoms) such as glycerol monostearate, glycerol monooleate, sorbitan monolaurate and sorbitan monooleate. ) Fatty acid (carbon number 8-24) ester, fatty acid (carbon number 10-18) alkanolamide such as lauric acid monoethanolamide and lauric acid diethanolamide.

  Examples of the anionic surfactant (C) include ether carboxylic acids (salts) having a hydrocarbon group having 8 to 24 carbon atoms [(poly) oxyethylene (having 1 to 100 repeating units) sodium lauryl ether acetate, etc.], carbon Ether sulfate ester salt having a hydrocarbon group of 8 to 24 [(poly) oxyethylene (repeating unit number 1 to 100) sodium lauryl sulfate, etc.], Sulfosuccinate ester salt having a hydrocarbon group of 8 to 24 carbon atoms [ Mono- or dialkylsulfosuccinic acid ester di or monosodium, (poly) oxyethylene (repeating unit number 1 to 100) mono or dialkylsulfosuccinic acid ester di or monosodium], (poly) oxyethylene (repeating unit number 1 to 100) coconut oil Fatty acid monoethanolamide sodium sulfate, carbon number 8-2 A sulfonate having a hydrocarbon group (sodium dodecylbenzenesulfonate, etc.), a phosphate ester salt having a hydrocarbon group having 8 to 24 carbon atoms [sodium lauryl phosphate, (poly) oxyethylene (a number of repeating units 1 to 100) Sodium lauryl ether phosphate, etc.], fatty acid salts (such as sodium laurate and triethanolamine laurate), acylated amino acid salts (coconut oil fatty acid methyl taurine sodium, coconut oil fatty acid sarcosine sodium, coconut oil fatty acid sarcosine triethanolamine) N-coconut oil fatty acid acyl-L-glutamic acid triethanolamine, N-coconut oil fatty acid acyl-L-glutamic acid sodium, lauroylmethyl-β-alanine sodium, etc.).

Examples of the cationic surfactant (D) include quaternary ammonium salt type or amine salt type cationic surfactants.
Quaternary ammonium salt type cationic surfactants include tertiary amines and quaternizing agents [alkyl halides (methyl chloride, methyl bromide, ethyl chloride, benzyl chloride, etc.), dimethyl sulfate, dimethyl carbonate, ethylene oxide, etc.] Can be used, such as lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide, stearyltrimethylammonium bromide, lauryldimethylbenzylammonium chloride (benzalkonium chloride), cetylpyridinium chloride, Examples include polyoxyethylene trimethyl ammonium chloride and stearamide ethyl diethyl methyl ammonium methosulfate. It is.
As amine salt type cationic surfactants, primary to tertiary amines are inorganic acids (hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid, etc.) or organic acids (acetic acid, formic acid, oxalic acid, lactic acid, gluconic acid, adipic acid. And a compound obtained by neutralization with an alkylphosphoric acid), for example, as a primary amine salt type, higher aliphatic amines (laurylamine, stearylamine, cetylamine, hardened tallow amine, rosinamine, etc.) Inorganic acid salts or organic acid salts of these, higher fatty acid (such as stearic acid and oleic acid) salts of lower amines and the like. Examples of the secondary amine salt type include inorganic acid salts or organic acid salts such as ethylene oxide adducts of aliphatic amines.

  Amphoteric surfactants (E) include betaine-type amphoteric surfactants (coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine. And lauryl hydroxysulfobetaine and lauroylamidoethyl hydroxyethylcarboxymethylbetaine hydroxypropyl sodium phosphate), amino acid type amphoteric surfactants (such as sodium β-laurylaminopropionate) and the like.

  If necessary, the cleaning composition of the present invention may contain water or other known components such as builders, chelating agents, enzymes, hydrophilic solvents, antifoaming agents, and fluorescent whitening agents described in JP-A-2004-27181. , Bleaching agents, softening agents, disinfecting agents, perfumes and coloring agents may be contained.

  Builders include polycarboxylates (such as acrylate and maleate homopolymers), polyvalent carboxylates (such as citric acid and malic acid), and alkali builders (caustic soda, soda ash, ammonia, triethanol, etc.) Amine, sodium tripolyphosphate and sodium silicate). Examples of the chelating agent include EDTA and NTA. Examples of the enzyme include protease, lipase, amylase, and cellulase. Examples of the hydrophilic solvent include methanol, ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol, and propylene glycol. Examples of antifoaming agents include silicone-based antifoaming agents, polyoxyalkylene-based antifoaming agents, and mineral oil-based antifoaming agents.

The content rates of the nonionic surfactant (A), the known surfactant, water and other components in the cleaning composition of the present invention are as follows.
The content of the nonionic surfactant (A) is preferably 5 to 100% by weight, more preferably 10 to 100% by weight, particularly preferably based on the weight of the detergent composition, from the viewpoint of detergency. Is 20 to 100% by weight.
The content of the known surfactant is preferably 0 to 80% by weight, more preferably 0 to 50% by weight, particularly preferably 0 to 30% from the viewpoint of detergency based on the weight of the detergent composition. % By weight.
The water content is preferably 0 to 80% by weight, more preferably 10 to 60% by weight, based on the total weight of the cleaning composition and water.
Among the other components, the content of the builder and the chelating agent is preferably 10% by weight or less, and more preferably 5% by weight or less, based on the weight of the cleaning composition. The content of fluorescent brightener, bleach, softener, enzyme, disinfectant, fragrance, colorant and antifoaming agent is preferably 5% by weight or less based on the weight of the detergent composition, Preferably it is 2 weight% or less. The content of the hydrophilic solvent is preferably 20% by weight or less, more preferably 10% by weight or less, based on the weight of the cleaning composition.

  The property of the cleaning composition of the present invention is not particularly limited, and examples thereof include a liquid shape, a paste shape, a powder shape, a flake shape, and a block shape. Of these, liquid is preferred from the viewpoint of ease of handling.

The cleaning composition of the present invention can be produced by selecting the following method depending on the difference in properties.
(1) When the property of the cleaning composition is liquid or pasty In a mixing tank equipped with a stirrer and a heating / cooling device, a nonionic surfactant (A) and, if necessary, a known surfactant, A method in which water and other components are added to the charging order without any particular limitation and stirred at 10 to 50 ° C. until uniform.
(2) When the property of the cleaning composition is powdery In a mixing tank equipped with a stirrer and a heating / cooling device, a nonionic surfactant (A) and, if necessary, a known surfactant, water and others Are added to the charging order without any particular limitation, and stirred at 10 to 50 ° C. until uniform, followed by a spray dryer (for example, a pressure spray nozzle type spray dryer, a two-fluid spray nozzle type spray dryer, and a rotary disk type) Spray drying with a spray dryer or the like).
(3) When the properties of the detergent composition are powder, flake and block, in a mixing tank equipped with a stirrer and a heating / cooling device, if necessary, a nonionic surfactant (A) and, if necessary, a known interface The activator and other components are added to the charging order without any particular restrictions, and after stirring at 10 to 50 ° C. until uniform, the melt is taken out on a release paper and cooled to room temperature, and the resulting solidified product is pulverized. A method of pulverizing to an appropriate size (powder, flake or block) with a mill (for example, a mill mixer, a ball mill, a jet mill, a colloid mill, or a homogenizer).

  The cleaning composition of the present invention can be used as a cleaning agent for clothing, a cleaning agent for dishwashing, and an industrial cleaning agent (for example, a cleaning agent such as a fiber refining agent and a metal degreasing agent). As a knitted or woven fabric containing cellulose fibers, synthetic fibers, wool, silk or acetate fibers.

  The amount used when the cleaning composition of the present invention is used as a cleaning agent for clothing is arbitrarily selected according to the degree of soiling of the clothing to be cleaned, etc., preferably 1 to 30 g per 1 kg of clothing to be cleaned, More preferably, it is 5-20g, Most preferably, it is 10-15g.

  The amount of water used for washing (washing) clothes using the cleaning composition of the present invention is about 1 to 30 L per kg of clothes.

  The washing temperature can be arbitrarily selected depending on the type of fiber to be applied, but is preferably 5 to 80 ° C, more preferably 15 to 50 ° C.

  There are no particular restrictions on the cleaning method, and hand washing and washing machines can be used at home, and batch processing using a liquid flow dyeing machine and continuous processing using a continuous refining apparatus can be applied in industry (for business use).

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

<Production Example 1>
In a pressure-resistant reaction vessel equipped with a thermometer, a heating / cooling device, a stirrer, and a dropping cylinder, 241 parts of n-hexadecylamine was charged, sealed after nitrogen substitution, and heated to 140 ° C. While stirring at 140 ° C., adjusting the pressure to be 0.5 MPa or less, 88 parts of ethylene oxide was added dropwise over 5 hours and then aged at the same temperature for 3 hours, cooled to 60 ° C. and cooled to n-hexadecylamine. Ethylene oxide 2-mole adduct (x-1) was obtained. Next, 3 parts of potassium hydroxide was added, and after replacing with nitrogen, it was sealed and heated to 140 ° C. A mixture of 1320 parts of ethylene oxide and 696 parts of propylene oxide was added dropwise over 5 hours while adjusting the pressure at 140 ° C. with stirring so that the pressure was 0.5 MPa or less, and then aged at the same temperature for 3 hours. Further, 440 parts of ethylene oxide was added dropwise over 5 hours while adjusting the pressure so that the pressure became 0.5 MPa or less at 140 ° C. with stirring, and then aged at the same temperature for 3 hours to obtain ethylene oxide / propylene of n-hexadecylamine. oxide adduct (a-1) was obtained [(a-1) has the general formula (1) in ^{which R 1} is n- hexadecyl group, ^{a 1} O and ^{a 2} O is an oxyethylene group, a + b = 2 , C + d = 30, e + f = 12, g + h = 10, [(EO) _c / (PO) _e ] and [(EO) _d / (PO) _f ] are groups obtained by random addition of EO and PO Surfactant].

<Production Example 2>
In a reaction vessel similar to Production Example 1, 329 parts of (x-1) obtained in Production Example 1 and 3 parts of potassium hydroxide were charged, sealed with nitrogen, and heated to 140 ° C. A mixture of 660 parts of ethylene oxide and 290 parts of propylene oxide was added dropwise over 5 hours and aged at the same temperature for 3 hours at 140 ° C. with stirring while adjusting the pressure to 0.5 MPa or less. Further, 440 parts of ethylene oxide was added dropwise over 5 hours and then aged at the same temperature for 3 hours at 140 ° C. under stirring while adjusting the pressure to be 0.5 MPa or less, and the ethylene oxide / n-hexadecylamine / Propylene oxide adduct (A-2) was obtained [(A-2) is a compound in which R ¹ in the general formula (1) is an n-hexadecyl group, A ¹ O and A ² O are oxyethylene groups, and a + b = 2, c + d = 15, e + f = 5, g + h = 10, [(EO) _c / (PO) _e ] and [(EO) _d / (PO) _f ] are groups in which EO and PO are randomly added. Ionic surfactant].

<Production Example 3>
In a reaction vessel similar to Production Example 1, 185 parts of n-dodecylamine and 4 parts of potassium hydroxide were charged, sealed after nitrogen substitution, and heated to 140 ° C. While stirring at 140 ° C. and adjusting the pressure to 0.5 MPa or less, a mixture of 2,220 parts of ethylene oxide and 1,160 parts of propylene oxide was dropped over 5 hours and then aged at the same temperature for 3 hours, An ethylene oxide / propylene oxide adduct (A-3) of n-dodecylamine was obtained [(A-3): R ¹ in the general formula (1) is an n-dodecyl group, and A ¹ O is an oxyethylene group. Yes, a + b = 0, c + d = 50, e + f = 20, g + h = 0, [(EO) _c / (PO) _e ] and [(EO) _d / (PO) _f ] are randomly added by EO and PO Nonionic surfactant which is a group].

<Production Example 4>
In a reaction vessel similar to Production Example 1, 269 parts of n-octadecylamine and 4 parts of potassium hydroxide were charged, sealed after nitrogen substitution, and heated to 140 ° C. While adjusting the pressure at 140 ° C. with stirring so that the pressure is 0.5 MPa or less, 440 parts of ethylene oxide was added dropwise over 5 hours and then aged at the same temperature for 3 hours. Furthermore, a mixture of 220 parts of ethylene oxide and 58 parts of propylene oxide was added dropwise over 5 hours and aged at the same temperature for 3 hours at 140 ° C. under stirring while adjusting the pressure to be 0.5 MPa or less. Further, 1,320 parts of ethylene oxide was added dropwise over 5 hours while adjusting the pressure at 140 ° C. with stirring so that the pressure was 0.5 MPa or less, followed by aging at the same temperature for 3 hours. Next, 580 parts of propylene oxide was added dropwise over 5 hours while adjusting the pressure so that the pressure became 0.5 MPa or less at 140 ° C. with stirring, followed by aging at the same temperature for 3 hours, and ethylene oxide / propylene of n-octadecylamine. Oxide adduct (A-4) was obtained [(A-4), wherein R ¹ in the general formula (1) is an n-octadecyl group, A ¹ O is an oxyethylene group, and A ² O is an oxyethylene group. Is added to the oxypropylene group, and a + b = 10, c + d = 5, e + f = 1, g + h = 40 (of 40, the oxyethylene group is 30, the oxypropylene group is 10), [(EO _C / (PO) _e ] and [(EO) _d / (PO) _f ] are groups obtained by random addition of EO and PO].

<Production Example 5>
In Production Example 1, 2-ethylhexylamine ethylene oxide / propylene oxide adduct (A-5) was prepared in the same manner as in Production Example 1, except that 241 parts of n-hexadecylamine was changed to 129 parts of 2-ethylhexylamine. In the obtained [(A-5), R ¹ in the general formula (1) is a 2-ethylhexyl group, A ¹ O and A ² O are oxyethylene groups, a + b = 2, c + d = 30, e + f = 12, g + h = 10, [(EO) _c / (PO) _e ] and [(EO) _d / (PO) _f ] are nonionic surfactants in which EO and PO are randomly added)].

<Production Example 6>
In Production Example 1, n-tetracosylamine ethylene oxide / propylene oxide adduct (A-6) was prepared in the same manner as in Production Example 1 except that 241 parts of n-hexadecylamine was changed to 353 parts of n-tetracosylamine. In the general formula (1), R ¹ is an n-tetracosyl group, A ¹ O and A ² O are oxyethylene groups, and a + b = 2, c + d = 30, e + f = 12, g + h = 10, [(EO) _c / (PO) _e ] and [(EO) _d / (PO) _f ] are nonionic surfactants in which EO and PO are randomly added)].

<Production Example 7>
In a reaction vessel similar to Production Example 1, 329 parts of (x-1) obtained in Production Example 1 and 3 parts of potassium hydroxide were charged, sealed with nitrogen, and heated to 140 ° C. While adjusting the pressure at 140 ° C. with stirring so that the pressure was 0.5 MPa or less, 1320 parts of ethylene oxide was added dropwise over 3 hours and then aged at the same temperature for 3 hours. Next, 696 parts of propylene oxide was added dropwise over 2 hours at 140 ° C. with stirring so that the pressure was adjusted to 0.5 MPa or less, and then aged at the same temperature for 3 hours. Further, 440 parts of ethylene oxide was added dropwise over 5 hours while adjusting the pressure so that the pressure became 0.5 MPa or less at 140 ° C. with stirring, and then aged at the same temperature for 3 hours to obtain ethylene oxide / propylene of n-hexadecylamine. Oxide adduct (A-7) was obtained [(A-7), wherein R ¹ in the general formula (1) is an n-hexadecyl group, A ¹ O and A ² O are oxyethylene groups, and a + b = 2 , C + d = 30, e + f = 12, g + h = 10, [(EO) _c / (PO) _e ] and [(EO) _d / (PO) _f ] are nonionic groups in which EO and PO are blocked. Surfactant].

<Production Example 8>
In a reaction vessel similar to Production Example 1, 186 parts of n-dodecyl alcohol and 0.2 part of potassium hydroxide were added, sealed after nitrogen substitution, and heated to 140 ° C. While adjusting the pressure at 140 ° C. with stirring so that the pressure is 0.5 MPa or less, 440 parts of ethylene oxide was added dropwise over 5 hours and then aged at the same temperature for 3 hours to give an ethylene oxide adduct of n-dodecyl alcohol (B -1) was obtained [(B-1) is a nonionic surfactant in which R ² in the general formula (2) is an n-dodecyl group, m = 10, n = 0].

<Production Example 9>
In a reaction vessel similar to Production Example 1, 186 parts of n-dodecyl alcohol and 0.2 part of potassium hydroxide were added, sealed after nitrogen substitution, and heated to 140 ° C. A mixture of 660 parts of ethylene oxide and 174 parts of propylene oxide was added dropwise over 5 hours and aged at the same temperature for 3 hours at 140 ° C. with stirring so that the pressure would be 0.5 MPa or less, and n-dodecyl alcohol The ethylene oxide / propylene oxide adduct (B-2) of [(B-2) was obtained by the general formula in which R ² in (2) is an n-dodecyl group, m = 15, n = 3, [(EO _{^{) m / (A 3 O)}} n] is a nonionic surfactant which is a group of EO and PO is randomly added.

<Production Example 10>
In a reaction container similar to Production Example 1, 242 parts of n-hexadecyl alcohol and potassium hydroxide part were charged, sealed with nitrogen, and heated to 140 ° C. While stirring at 140 ° C. and adjusting the pressure to 0.5 MPa or less, a mixture of 1,320 parts of ethylene oxide and 580 parts of propylene oxide was added dropwise over 5 hours and then aged at the same temperature for 3 hours. An ethylene oxide / propylene oxide adduct (B-3) of hexadecyl alcohol was obtained [(B-3), wherein R ² in the general formula (2) is an n-hexadecyl group, m = 30, n = 10, [ (EO) _m / (A ³ O) _n ] is a nonionic surfactant in which EO and PO are randomly added groups.

<Production Example 11>
In a reaction vessel similar to Production Example 1, 270 parts of n-octadecyl alcohol and 1.3 parts of potassium hydroxide were charged, sealed with nitrogen, and then heated to 140 ° C. While stirring at 140 ° C. and adjusting the pressure to 0.5 MPa or less, a mixture of 2,220 parts of ethylene oxide and 1,160 parts of propylene oxide was dropped over 5 hours and then aged at the same temperature for 3 hours, An ethylene oxide / propylene oxide adduct (B-4) of n-octadecyl alcohol was obtained [(B-4), wherein R ² in (2) is an n-octadecyl group, m = 50, n = 20. , [(EO) _m / (A ³ O) _n ] is a nonionic surfactant in which EO and PO are randomly added].

<Production Example 12>
In a reaction vessel similar to Production Example 1, 241 parts of n-hexadecylamine and 1 part of potassium hydroxide were charged, sealed after nitrogen substitution, and heated to 140 ° C. While adjusting the pressure at 140 ° C. with stirring so that the pressure is 0.5 MPa or less, 880 parts of ethylene oxide was added dropwise over 5 hours and then aged at the same temperature for 3 hours to give an ethylene oxide adduct of n-hexadecylamine ( A′-1) was obtained.

<Examples 1-12, Comparative Examples 1-4>
Each raw material of the number of parts of the liquid detergent composition described in Table 1 was put into a mixing tank equipped with a stirrer and a temperature control function, and stirred at 20 to 30 ° C. for 10 minutes to give a liquid detergent composition (Example) 1-12 and Comparative Examples 1-4) were produced. As the protease in Table 1, “Alcalase 2.5L” (manufactured by Novo Nordisk) was used.

  About the liquid detergent composition of Examples 1-12 and Comparative Examples 1-4, the detergency, foaming property, and fluidity | liquidity were evaluated with the following method. The results are shown in Table 1.

<Detergency test>
Wet artificial contamination made by the Laundry Science Association, which has the soil composition shown in Table 2, in a solution obtained by dissolving 0.3 g of each of the cleaning agents of Examples 1 to 12 and Comparative Examples 1 to 4 in 999.7 g of water 10 sheets of cloth were put in, and after washing and rinsing under the following conditions using a targotometer (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.), the cloth was taken out and the gear oven “GPS-222” [Espec Corp. The product was dried at 70 ° C. for 60 minutes to obtain a test cloth. Next, using a spectroscopic color difference meter “SpectroPhotometer SD5000” (manufactured by Nippon Denshoku Industries Co., Ltd.), the reflectance of 540 nm of this test cloth was measured in two places, one on the front and one back on each test cloth (test A total of 20 places with 10 cloths) were measured, the average value was obtained, and the washing rate (%) was calculated by the following formula (3). A higher cleaning rate indicates better cleaning properties.
[Cleaning conditions]
Time: 10 minutes, temperature: 25 ° C., rotation speed: 85 rpm
[Rinsing conditions]
Time: 1 minute, temperature: 25 ° C., rotation speed: 85 rpm
Cleaning rate (%) = [(R _W −R _S ) / (R _I −R _S )] × 100 (3)
In formula (3), R _I represents the reflectance of the cleaning cloth, R _W represents the reflectance of the cleaning cloth, and R _S represents the reflectance of the contaminated cloth. Moreover, the used artificially contaminated cloth is a wet artificially stained cloth (reflectance at 540 nm of 40 ± 5%) manufactured by the Japan Laundry Science Association having the dirt composition shown in Table 2.

<Bubble-out test>
Using 10 g of each of the liquid detergent compositions of Examples 1 to 12 and Comparative Examples 1 to 4, an uncontaminated test cloth (2 kg) was washed with a washing machine “NA-FD8005S” [manufactured by Panasonic Corporation] at a medium water level course. The first and second drains were rinsed. 20 ml of rinse water was placed in a 100 ml stoppered graduated cylinder and the height of the foam immediately after shaking 20 times by hand was measured. It shows that it is excellent in foaming property, so that the height of foam is low.

<Fluidity test>
The viscosities at 0 ° C. and 25 ° C. of the liquid detergent compositions of Examples 1 to 12 and Comparative Examples 1 to 4 were measured using a B-type viscometer, and the fluidity was evaluated according to the following evaluation criteria.
A: The viscosity of the liquid detergent composition is less than 500 mPa · s. O: The viscosity of the liquid detergent composition is 500 mPa · s or more and less than 3000 mPa · s. Δ: The viscosity of the liquid detergent composition is 3000 mPa · s or more and less than 10,000 mPa · s. X: The viscosity of the liquid detergent composition is 10,000 mPa · s or more

  As is clear from the results in Table 1, the liquid detergent composition of the present invention was all cleanable, foam-free, and flowable at 0 ° C. and 25 ° C. compared to the liquid detergent composition of the comparative example. Excellent in properties.

The cleaning composition of the present invention can be used as a cleaning agent for clothes, a cleaning agent for dishwashing, an industrial cleaning agent (for example, a cleaning agent such as a fiber refining agent and a metal degreasing agent), and the like. Among them, as a cleaning agent for clothing, it is particularly useful for cleaning a knitted fabric or a fabric containing cellulose fiber, synthetic fiber, wool, silk or acetate fiber.

Claims (7)

A cleaning composition comprising a nonionic surfactant (A) represented by the following general formula (1).

{In Formula (1), R ¹ is an alkyl group or alkenyl group having 8 to 24 carbon atoms; A ¹ O and A ² O are each independently an oxyethylene group and / or oxypropylene group: EO is an oxyethylene group; PO is an oxypropylene group; a, b, c, d, e, f, g and h are numbers satisfying a + b = 0 to 10, c + d = 5 to 50, e + f = 1 to 20, and g + h = 0 to 40; [(EO) _c / (PO) _e ] and [(EO) _d / (PO) _f ] represent groups obtained by random addition and / or block addition of EO and PO. } The content of EO in the groups represented by [(EO) _c / (PO) _e ] and [(EO) _d / (PO) _f ] in the general formula (1) is [(EO) _c / (PO) The cleaning composition according to claim 1, which is 50 to 95% by weight based on the weight of _e ] and [(EO) _d / (PO) _f ]. The cleaning agent according to claim 1 or 2, wherein [(EO) _c / (PO) _e ] and [(EO) _d / (PO) _f ] in the general formula (1) are groups in which EO and PO are randomly added. Composition. The cleaning composition according to any one of claims 1 to 3, wherein A ¹ O in the general formula (1) is an oxyethylene group, and a and b are numbers satisfying a + b = 2 to 10. The cleaning composition according to any one of claims 1 to 4, wherein A ² O in the general formula (1) is an oxyethylene group, and g and h are numbers satisfying g + h = 2 to 40.   The cleaning composition according to any one of claims 1 to 5, which is used for washing a knitted or woven fabric containing cellulose fiber, synthetic fiber, wool, silk or acetate fiber. The property is liquid, The cleaning composition according to any one of claims 1 to 6.