Alkylene oxide polymer having a hydrophobic group, composition, method for producing the same, and detergent composition

Abstract

To provide an alkylene oxide polymer having a hydrophobic group which excels in cleaning level or re-contamination prevention ability, a composition containing the polymer, a method for producing the same, and a detergent composition containing the compound.SOLUTION: An alkylene oxide polymer comprises two types of hydrophobic groups derived from, respectively, C6-20 hydrocarbon groups comprising aromatic rings and C1-30 hydrocarbon groups. The alkylene oxide polymer comprises structural units derived from polyalkylene oxides.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to an alkylene oxide polymer having a hydrophobic group that has excellent detergency or anti-soil redeposition ability, a composition containing the polymer, a method for producing the same, and a detergent composition containing the compound. [Background technology]

[0002] It has been known that hydrophobic group-containing alkylene oxides obtained by addition reaction of alkylene oxides such as ethylene oxide with alcohols having hydrophobic groups, such as higher alcohols and benzyl alcohol, are useful in various detergent compositions.

[0003] For example, Patent Document 1 discloses a method for producing a surfactant by addition-polymerizing styrene oxide with an organic compound having 1 to 24 carbon atoms and containing one hydroxyl group or carboxyl group, and further addition-polymerizing a lower alkylene oxide in an amount of 1 to 45 moles per mole of the compound. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 49-49198 Summary of the Invention [Problem to be solved by the invention]

[0005] Meanwhile, through their investigations to date, the present inventors have found that the use of a polyalkylene oxide polymer having a hydrophobic group in a detergent composition improves the anti-soil redeposition ability.

[0006] However, the surfactant described in Patent Document 1, which is obtained by addition-polymerizing styrene oxide with an organic compound having 1 to 24 carbon atoms and containing one hydroxyl group or carboxyl group, and then addition-polymerizing 1 to 45 moles of lower alkylene oxide per mole of the compound, has a problem that there is room for improvement in cleaning power and anti-soil redeposition ability.

[0007] The present disclosure has been made in consideration of the above-mentioned drawbacks, and provides an alkylene oxide polymer having a hydrophobic group that has excellent cleaning ability or anti-soil redeposition ability, a composition containing the polymer, a method for producing the same, and a detergent composition containing the compound. [Means for solving the problem]

[0008] That is, the alkylene oxide polymer having a hydrophobic group according to the present disclosure is an alkylene oxide polymer having two types of hydrophobic groups, namely, a hydrocarbon group having 6 to 20 carbon atoms and containing an aromatic ring, and a hydrocarbon group having 1 to 30 carbon atoms, and having a structural unit derived from polyalkylene oxide. [Effects of the Invention]

[0009] According to the present disclosure, it is possible to provide an alkylene oxide polymer having a hydrophobic group that has excellent detergency or anti-soil redeposition ability, a composition containing the polymer, a method for producing the same, and a detergent composition containing the compound. DETAILED DESCRIPTION OF THE INVENTION

[0010]

[0023] The following detailed description of preferred embodiments of the present disclosure is merely exemplary in nature and is in no way intended to limit the present disclosure, its application, or its uses.

[0011] In the following description, unless otherwise specified, "%" means "% by mass", "parts" means "parts by mass", and the range "A to B" means A or more and B or less. In addition, in this disclosure, "(meth)acrylate" means "acrylate" or "methacrylate", and "(meth)acrylic" means "acrylic" or "methacrylic".

[0012] [Alkylene oxide polymer having a hydrophobic group according to the present disclosure] The alkylene oxide polymer having a hydrophobic group of the present disclosure can be represented by the following general formula (1).

[0013] [ka] (In general formula (1), Ar is a hydrocarbon group containing an aromatic ring and having 6 to 20 carbon atoms, R 1 represents a hydrocarbon group having 1 to 30 carbon atoms, R 2 represents a hydrocarbon group having 2 to 6 carbon atoms, R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. X 1 ,X 2 are the same or different and represent a direct bond, an oxygen atom, or a sulfur atom. However, X 1 base,X 2 The groups cannot simultaneously be direct bonds. Y 1 ,Y 2 are the same or different and represent a direct bond or a methylene group. However, Y 1 base,Y 2 The groups cannot simultaneously be direct bonds. n is an integer from 1 to 200.

[0014] The Ar group in general formula (1) is not particularly limited as long as it is a hydrocarbon group containing an aromatic ring and having 6 to 20 carbon atoms. The aromatic ring may be one or more. For example, it may have an aromatic ring such as benzene, naphthalene, biphenyl, or anthracene. These may have unsubstituted and / or substituted structures. The substituent may be a saturated and / or unsaturated hydrocarbon group having 1 to 14 carbon atoms. It may also be a linear and / or branched hydrocarbon group. Furthermore, it may be partially substituted with a halogen or the like. The Ar group is preferably a hydrocarbon group containing an aromatic ring and having 6 to 12 carbon atoms, and more preferably a hydrocarbon group having 6 carbon atoms. Alternatively, it is preferably a naphthyl group or a phenyl group, more preferably a phenyl group.

[0015] R in general formula (1) 1 There are no particular limitations on the group, as long as it is a hydrocarbon group having 1 to 30 carbon atoms. 1 The group may be a saturated and / or unsaturated hydrocarbon group, a linear and / or branched hydrocarbon group, or a group that may be partially substituted with a halogen or the like. R 1 The group is more preferably a hydrocarbon group having 6 to 24 carbon atoms, even more preferably a hydrocarbon group having 8 to 16 carbon atoms, and most preferably a hydrocarbon group having 10 to 14 carbon atoms. Specific examples of the alkenyl group include a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an icosyl group. Examples of the alkenyl group include a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, an octadecylene group, a nonadecylene group, and an icosylene group. Among these, R 1 is preferably an undecyl group, a dodecyl group, or a tridecyl group, and more preferably a dodecyl group.

[0016] R in general formula (1) 2 There are no particular limitations on the group, as long as it is a hydrocarbon group having 2 to 6 carbon atoms. 2 The group may be a linear and / or branched hydrocarbon group, more preferably a hydrocarbon group having 2 to 4 carbon atoms, even more preferably a hydrocarbon group having 2 to 3 carbon atoms, and most preferably a hydrocarbon group having 2 carbon atoms. Specific examples include an ethylene group, a propylene group, a butylene group, etc. Among these, at least one selected from an ethylene group and a propylene group is preferred because it can impart hydrophilicity to the alkylene oxide polymer having a hydrophobic group of the present disclosure. Similarly, from the viewpoint of imparting hydrophilicity to the alkylene oxide polymer having a hydrophobic group of the present disclosure, R 2 More preferably, the group is an ethylene group, which is a hydrocarbon group having two carbon atoms.

[0017] R in general formula (1) 3 The group is not particularly limited as long as it is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. R 3 When the group is a hydrocarbon group, it may be a saturated and / or unsaturated hydrocarbon group. It may also be a linear and / or branched hydrocarbon group. Furthermore, it may be partially substituted with halogen or the like. Specific examples include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, neopentyl, sec-butyl, tert-butyl, thexyl, and 2-ethylhexyl; and cyclic alkyl groups such as cyclopentyl and cyclohexyl. R 3 The group is more preferably one or more selected from a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms, and is further preferably a hydrogen atom and / or a methyl group.

[0018] X in general formula (1) 1 base,X2 There is no particular limitation as long as the X groups are the same or different and are a direct bond, an oxygen atom, or a sulfur atom. 1 base,X 2 The X group cannot simultaneously be a direct bond. 1 base,X 2 The groups are preferably each a combination of an oxygen atom and a direct bond.

[0019] Y in general formula (1) 1 base,Y 2 There is no particular limitation as long as the Y groups are the same or different and are a direct bond or a methylene group. 1 base,Y 2 The groups cannot simultaneously be direct bonds.

[0020] X in general formula (1) 1 base,Y 1 Base, Y 2 Group, X 2 When the groups are an oxygen atom, a methylene group, a direct bond, and a direct bond, respectively, they can be represented by the following general formula (1-1).

[0021] [ka] In the general formula (1-1), Ar, R 1 , R 2 , R 3 , n is the same as in the general formula (1).

[0022] In addition, X in general formula (1) 1 base,Y 1 Base, Y 2 Group, X 2 When the groups are an oxygen atom, a methylene group, a methylene group, and an oxygen atom, respectively, they can be represented by the following general formula (1-2).

[0023] [ka] In the general formula (1-2), Ar, R 1 , R 2 , R 3, n is the same as in the general formula (1).

[0024] In addition, X in general formula (1) 1 base,Y 1 Base, Y 2 Group, X 2 When the groups are a direct bond, a direct bond, a methylene group, and an oxygen atom, respectively, they can be represented by the following general formula (1-3).

[0025] [ka] In the general formula (1-3), Ar, R 1 , R 2 , R 3 , n is the same as in the general formula (1).

[0026] In general formula (1), n ​​is not particularly limited as long as it is an integer of 1 to 200. It is preferably 1 to 100, and more preferably 1 to 50. From the viewpoint of ensuring the cleanliness or anti-soil redeposition ability of the alkylene oxide polymer having a hydrophobic group of the present disclosure, the amount is preferably within the above-mentioned range.

[0027] The theoretical molecular weight of the polyalkylene oxide-containing compound of the present disclosure is not limited as long as it is 300 to 15,000. It is preferably 300 to 8,000, and more preferably 5,000 to 200,0000. From the viewpoint of ensuring the cleanliness or anti-soil redeposition ability of the alkylene oxide polymer having a hydrophobic group, the aforementioned range is preferred.

[0028] Compositions of the Present Disclosure An alkylene oxide polymer having a hydrophobic group represented by the general formula (1), and The compound may be a composition containing an alkylene oxide compound represented by the following general formula (2).

[0029] [ka] In general formula (2), R2 represents a hydrocarbon group having 2 to 6 carbon atoms, R 4 represents a hydrogen atom, Ar, or a hydrocarbon group having 1 to 30 carbon atoms. n is an integer from 1 to 200.

[0030] R in the general formula (2) 2 The group n is the same as in general formula (1). In addition, R in the general formula (2) 4 The group represents Ar or a hydrocarbon group having 1 to 30 carbon atoms. Ar is the same as the Ar group in the general formula (1). Furthermore, the hydrocarbon group having 1 to 30 carbon atoms is R 1 It is identical to the group.

[0031] When the alkylene oxide compound represented by the general formula (2) is contained in the composition of the present disclosure, the structure of the alkylene oxide compound represented by the general formula (2) contained as a by-product varies depending on the production methods (I) to (III) described below. The substituent with a different structure is R 4 It is the base. Specifically, in the case of the production method (I) and the production method (II) described later, R 4 The group is a hydrogen atom or an Ar group, and in the case of production method (III), it is a hydrocarbon group having 1 to 30 carbon atoms.

[0032] The composition of the present disclosure may contain the alkylene oxide compound represented by the general formula (2) in an amount of 20% by mass or less, preferably 10% by mass or less, and more preferably 4% by mass, based on 100% by mass of the total amount of the composition. Although there is no problem even if the alkylene oxide compound represented by the general formula (2) is contained at 0% by mass, it is usually contained at 0.1% by mass or more, or alternatively at 0.5% by mass or more. As will be described later, the alkylene oxide compound represented by the general formula (2) may be contained as an unreacted product when producing the alkylene oxide polymer having a hydrophobic group of the present disclosure.

[0033] [Manufacturing method of the present disclosure] The method (I) for producing an alkylene oxide polymer having a hydrophobic group according to the present disclosure can be produced by subjecting an alcohol compound having an aromatic ring to an addition reaction with an epoxy compound represented by the following general formula (3), and then subjecting an alkylene oxide compound to an addition reaction with the hydroxyl group produced by the addition reaction.

[0034] [ka] R 1 is R in the general formula (1). 1 The group is identical.

[0035] Specific examples of the aromatic alcohol include phenol, p-chlorophenol, 2,3,5-trichlorophenol, pentachlorophenol, pentabromophenol, p-bromophenol, o-methoxyphenol, p-methoxyphenol, p-benzylphenol, p-phenoxyphenol, o-phenylphenol, p-phenylphenol, p-ethoxyphenol, o-butoxyphenol, p-ethylphenol, m-ethylphenol, o-ethylphenol, p-butylphenol, p-nonylphenol, p-cyclohexylphenol, decylphenol, p-nitrophenol, p-cyanophenol, p-cresol, o-cresol, xylenol, diethylphenol, trime Phenols such as methylphenol, catechol, dihydroxybiphenyl, resorcinol, hydroquinone, phloroglucinol, α-naphthol, β-naphthol, dihydroxynaphthalene, bisphenol A, bisphenol F, and bisphenol S; benzyl alcohol, m- and p-nitrobenzyl alcohol, o-, m-, and p-methylbenzyl alcohol, m-hydroxybenzyl alcohol, p-ethylbenzyl alcohol, and 2,4-, 3,4-, and 3,5-dimethylbenzyl alcohol; and benzyl alcohols such as o-nitrobenzyl alcohol, o- and p-hydroxybenzyl alcohol, and 2,5-dimethylbenzyl alcohol; Benzyl alcohols are preferred, and benzyl alcohol is more preferred.

[0036] Specific examples of the epoxy compound represented by the general formula (3) include alkylene oxide compounds having an alkyl group, such as propylene oxide, butylene oxide, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxypentadecane, 1,2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,2-epoxyoctadecane, 1,2-epoxynonadecane, and 1,2-epoxyeicosane. 1,2-epoxytetradecane is preferred.

[0037] The conditions for reacting the aromatic alcohol with the epoxy compound represented by general formula (3) can be determined according to a conventional method using an alkali catalyst or the like. For example, the reaction temperature is preferably 50 to 200°C, more preferably 100 to 200°C. The reaction time is preferably 30 minutes to 5 hours, more preferably 40 minutes to 3 hours. When the reaction temperature and reaction time are within the above-mentioned ranges, the reaction proceeds almost quantitatively and improves, reducing the amount of unreacted raw materials, which tends to improve the cleanliness or anti-soil redeposition ability of the alkylene oxide polymer having a hydrophobic group of the present disclosure, which is preferable.

[0038] The reaction conditions for the addition reaction of the alkylene oxide compound in Production Method (I) can be the same as those of a conventional method. For example, the reaction can be carried out using a catalyst such as sodium hydroxide or potassium hydroxide, and, if necessary, using a pressure reactor such as an autoclave, at a reaction temperature of from room temperature to about 150° C. The reaction conditions for the addition reaction of the alkylene oxide compound in Production Method (II) and Production Method (III) described below are also the same.

[0039] In another production method (II), the compound can be produced by adding a glycidyl ether compound represented by the following general formula (4) to an alcohol compound having an aromatic ring, and then adding an alkylene oxide compound to the hydroxyl group generated by the addition reaction. The alcohol compound having an aromatic ring is the same as the compound used in the above production method (I).

[0040] [ka] R 1 is R in the general formula (1). 1 The group is identical.

[0041] Specific examples of the glycidyl ether compound represented by the general formula (4) include butyl glycidyl ether, alkyl glycidyl ethers having 8 to 10 carbon atoms, and alkyl glycidyl ethers having 12 to 14 carbon atoms. Examples include methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether (lauryl glycidyl ether), tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, heptadecyl glycidyl ether, octadecyl glycidyl ether, nonadecyl glycidyl ether, and icosyl glycidyl ether. Dodecyl glycidyl ether (lauryl glycidyl ether) is preferred.

[0042] The aromatic alcohol and the glycidyl ether compound represented by general formula (4) can be reacted under conditions such as using an alkali catalyst or the like according to a conventional method. For example, the reaction temperature is preferably 50 to 200°C, and more preferably 100 to 200°C. The reaction time is preferably 30 minutes to 5 hours, and more preferably 40 minutes to 3 hours. When the reaction temperature and reaction time are within the above-mentioned ranges, the reaction proceeds almost quantitatively and improves, reducing the amount of unreacted raw material, which tends to improve the cleanliness or anti-soil redeposition ability of the alkylene oxide polymer having a hydrophobic group of the present disclosure, which is preferable.

[0043] In addition, as another production method (III), the compound can be produced by adding an epoxy compound represented by the following general formula (5) to an alcohol compound having a hydrocarbon group having 1 to 30 carbon atoms, and then adding an alkylene oxide compound to the hydroxyl group generated by the addition reaction. The hydrocarbon group having 1 to 30 carbon atoms is R 1 It is the same as the base.

[0044] Specific examples of alcohol compounds having a hydrocarbon group having 1 to 30 carbon atoms include lower alcohols such as methanol, ethanol, propanol, and butyl alcohol; and aliphatic alcohols having 8 to 24 carbon atoms. Preferably, it is an aliphatic alcohol having 8 to 24 carbon atoms, more preferably an aliphatic alcohol having 10 to 18 carbon atoms, and most preferably an aliphatic alcohol having 12 to 14 carbon atoms. Specific examples include pentanol, hexanol, heptanol, octanol, nonanol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, and icosyl alcohol. Examples of alkenyl alcohols include pentenol, hexanal, heptenal, octenal, nonenal, decylene alcohol, undecylene alcohol, dodecylene alcohol, tridecylene alcohol, tetradecylene alcohol, pentadecylene alcohol, hexadecylene alcohol, heptadecylene alcohol, octadecylene alcohol, nonadecylene alcohol, and icosylene groups. Among these, undecyl alcohol, dodecyl alcohol, and tridecyl alcohol are preferred, and dodecyl alcohol is more preferred.

[0045] [ka] In general formula (5), Ar, Y 1 , X 1 is the same as the Ar group described in the general formula (1).

[0046] Specific examples of the epoxy compound having an aromatic ring represented by the general formula (5) include styrene oxide and phenyl glycidyl ether.

[0047] The conditions for reacting the alcohol compound having a hydrocarbon group of 1 to 30 carbon atoms with the epoxy compound represented by the general formula (5) can be determined according to a conventional method using an alkali catalyst or the like. For example, the reaction temperature is preferably 50 to 200°C, and more preferably 100 to 200°C. The reaction time is preferably 30 minutes to 5 hours, and more preferably 40 minutes to 3 hours. When the reaction temperature and reaction time are within the above-mentioned ranges, the reaction proceeds almost quantitatively and improves, reducing the amount of unreacted raw material, which tends to improve the cleanliness or anti-soil redeposition ability of the alkylene oxide polymer having a hydrophobic group of the present disclosure, which is preferable.

[0048] The production methods (I) to (III) include a step of reacting an alcohol compound (the aromatic alcohol and / or the alcohol compound having a hydrocarbon group of 1 to 30 carbon atoms) with an epoxy compound (the compound represented by the general formulas (3) to (5)). However, the reaction rate is not necessarily 100%, and therefore, there may be present by-products resulting from the reaction of an unreacted alcohol compound (the aromatic alcohol and / or the alcohol compound having a hydrocarbon group of 1 to 30 carbon atoms) with an unreacted epoxy compound (the compound represented by the general formulas (3) to (5)), or the unreacted epoxy compound (the compound represented by the general formulas (3) to (5)) with trace amounts of water or other impurities present in the reaction system and the unreacted epoxy compound.

[0049] The unreacted alcohol compound (the aromatic alcohol and / or the alcohol compound having a hydrocarbon group of 1 to 30 carbon atoms) and / or the unreacted epoxy compound (the compound represented by the general formulas (3) to (5)) may be contained in an amount of 20% by mass or less, preferably 10% by mass or less, and more preferably 4% by mass, when the total amount of the composition containing the alkylene oxide polymer having a hydrophobic group of the present disclosure is taken as 100% by mass. Although 0% by mass is acceptable, the amount is usually 0.1% by mass or more, or alternatively 0.5% by mass or more.

[0050] The by-products resulting from the reaction of the unreacted epoxy compound (the compound represented by the general formulas (3) to (5)) with water and other impurities present in trace amounts in the reaction system are: The composition containing the alkylene oxide polymer having a hydrophobic group of the present disclosure may contain 1 to 15% by mass, preferably 1 to 12% by mass, and more preferably 1 to 10% by mass, based on 100% by mass of the total amount of the composition.

[0051] [Uses of the alkylene oxide polymer having a hydrophobic group of the present disclosure] The alkylene oxide polymer having a hydrophobic group of the present disclosure can be suitably used in detergent builders, detergents, water treatment agents, dispersants, fiber treatment agents, scale inhibitors (scale inhibitors), cement additives, metal ion sequestering agents, thickeners, various binders, etc. In particular, it can be suitably used in detergent builders and detergents.

[0052] The present disclosure also relates to a detergent builder or detergent comprising, as an essential component, the alkylene oxide polymer having a hydrophobic group of the present disclosure or the alkylene oxide polymer having a hydrophobic group produced by the production method of the present disclosure.

[0053] <Detergent builders, detergent compositions> The detergent builder of the present disclosure acts to prevent soil from redepositing on clothes during washing. The copolymer of the present disclosure strongly disperses muddy soils due to the charge repulsion of the carboxyl groups, and also disperses detached muddy soils, preventing them from redepositing on clothes, thereby further enhancing the whiteness of white clothes and significantly increasing the added value of detergents. Furthermore, the copolymer has a high ability to disperse zeolites used in powder detergents, making it highly effective as a dispersant when producing detergent powders. The detergent builder of the present disclosure has excellent compatibility with surfactants, and the resulting detergent is a highly concentrated liquid detergent, making it suitable for use as a liquid detergent builder. The excellent compatibility with surfactants improves transparency when used in liquid detergents, preventing the separation problem of the liquid detergent caused by turbidity. Furthermore, the excellent compatibility allows for the production of highly concentrated liquid detergents, improving the cleaning ability of the liquid detergent. The detergent builder of the present disclosure exhibits an excellent thickening effect when incorporated into liquid detergents. Therefore, it is easy to handle because it suppresses dripping during use.

[0054] The detergent builder of the present disclosure has excellent anti-soil redeposition ability, and furthermore, is a detergent builder with extremely high quality agent performance and excellent stability, which is resistant to performance degradation when stored for a long period of time and resistant to impurity precipitation when kept at low temperatures.

[0055] The cleaning ability can be determined by the cleaning rate, which can be determined by the following method.

[0056] The cleaning rate (%) is calculated using the values ​​measured by the following method and the following formula. Cleaning power (%) = (Whiteness of artificially soiled cloth after washing - Whiteness of artificially soiled cloth before washing) ÷ (Whiteness of original white cloth (EMPA221) of artificially soiled cloth - Whiteness of artificially soiled cloth before washing) × 100 The present disclosure also provides a detergent builder, detergent, water treatment agent, or dispersant comprising a composition containing an alkylene oxide polymer having a hydrophobic group, wherein the detergent builder, detergent, water treatment agent, or dispersant has a detergent detergency of 7.3% or more when using EMPA164 or 17.4% or more when using EMPA106. Among such compositions containing an alkylene oxide polymer having a hydrophobic group, i.e., detergent builders and detergents, those that satisfy both of these characteristics, i.e., the detergent detergency when using EMPA164 and the detergent detergency when using EMPA106, are preferred. Furthermore, the detergent detergency when using EMPA164 is preferably 7.4% or more. The detergent detergency when using EMPA106 is preferably 17.5% or more, and more preferably 17.6% or more. The artificially soiled cloths EMPA164 and 106 used to measure the cleaning rate are standard samples for soiling tests, with certain soils attached to the cloth. EMPA164 is a white cotton cloth (EMPA221) with grass soiling attached, and EMPA106 is a white cotton cloth (EMPA221) with carbon black and mineral oil soiling attached.

[0057] As for the compositional components and blending ratios of the detergent builder other than the alkylene oxide polymer having a hydrophobic group, various components that can be used in conventionally known detergent builders can be used as appropriate based on the blending ratios thereof, within a range that does not impair the effects of the present disclosure.

[0058] The detergent may be either a powder detergent or a liquid detergent, but liquid detergents are preferred because the alkylene oxide polymer having a hydrophobic group has excellent solubility in liquid detergents. In addition to the alkylene oxide polymer having a hydrophobic group, additives typically used in detergents can be used in the detergent. Suitable additives include surfactants, alkali builders, chelating builders, anti-redeposition agents for preventing redeposition of contaminants such as sodium carboxymethylcellulose, soil inhibitors such as benzotriazole and ethylene-thiourea, soil release agents, color transfer inhibitors, fabric softeners, alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishing agents, disinfectants, bleaching agents, bleaching aids, enzymes, dyes, and solvents. In the case of powder detergents, it is also preferable to incorporate zeolite.

[0059] When used in the detergent, the alkylene oxide polymer having a hydrophobic group of the present disclosure is preferably added in an amount of 0.1 to 20% by mass relative to 100% by mass of the detergent. If the amount is less than 0.1% by mass, the detergency of the detergent may be insufficient, and if the amount is more than 20% by mass, the detergent may become uneconomical.

[0060] The detergents mentioned above include synthetic detergents for household use, detergents for textiles and other industrial uses, hard surface cleaners, as well as detergents used for specific purposes such as bleaching detergents that enhance the function of one of their components.

[0061] The surfactant is at least one selected from anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants, and these surfactants can be used alone or in combination. When two or more surfactants are used, the combined amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more relative to 100% by mass of all surfactants. More preferably, it is 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more.

[0062] Suitable anionic surfactants include alkylbenzenesulfonates, alkyl ether sulfates, alkenyl ether sulfates, alkyl sulfates, alkenyl sulfates, α-olefin sulfonates, α-sulfofatty acid or ester salts, alkanesulfonates, saturated fatty acid salts, unsaturated fatty acid salts, alkyl ether carboxylates, alkenyl ether carboxylates, amino acid surfactants, N-acylamino acid surfactants, alkyl phosphates or salts thereof, alkenyl phosphates or salts thereof, etc. The alkyl and alkenyl groups in the anionic surfactants may have a branched alkyl group such as a methyl group.

[0063] Suitable examples of the nonionic surfactant include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamides or their alkylene oxide adducts, sucrose fatty acid esters, alkyl glycoxides, fatty acid glycerin monoesters, alkylamine oxides, etc. The alkyl and alkenyl groups in the nonionic surfactants may have branched alkyl groups such as methyl groups. As the cationic surfactant, a quaternary ammonium salt or the like is suitable. Suitable amphoteric surfactants include carboxyl-type amphoteric surfactants and sulfobetaine-type amphoteric surfactants. The alkyl group and alkenyl group in the cationic surfactants and amphoteric surfactants may have a branched alkyl group such as a methyl group.

[0064] The surfactant content is preferably 10 to 60% by mass relative to 100% by mass of the liquid detergent. It is more preferably 15% to 50% by mass, even more preferably 20% to 45% by mass, and particularly preferably 25% to 40% by mass. If the surfactant content is less than 10% by mass, sufficient detergency may not be achieved, while if it exceeds 60% by mass, economic efficiency may be reduced.

[0065] The blending ratio of the liquid detergent builder is usually preferably 0.1 to 20% by mass relative to 100% by mass of the liquid detergent. More preferably, it is 0.2% by mass or more and 15% by mass or less, more preferably 0.3% by mass or more and 10% by mass or less, even more preferably 0.4% by mass or more and 8% by mass or less, and particularly preferably 0.5% by mass or more and 5% by mass or less. If the blending ratio of the liquid detergent builder is less than 0.1% by mass, the detergent performance may not be sufficient, and if it exceeds 20% by mass, the economical efficiency may decrease.

[0066] The amount of water contained in the liquid detergent is usually preferably 0.1 to 75% by mass relative to 100% by mass of the liquid detergent, more preferably 0.2% by mass or more and 70% by mass or less, even more preferably 0.5% by mass or more and 65% by mass or less, particularly preferably 0.7% by mass or more and 60% by mass or less, even more particularly preferably 1% by mass or more and 55% by mass or less, and most preferably 1.5% by mass or more and 50% by mass or less.

[0067] The liquid detergent preferably has a kaolin turbidity of 200 mg / L or less, more preferably 150 mg / L or less, even more preferably 120 mg / L or less, particularly preferably 100 mg / L or less, and most preferably 50 mg / L or less.

[0068] Furthermore, the change (difference) in kaolin turbidity between a liquid detergent containing the alkylene oxide polymer having a hydrophobic group of the present disclosure and a liquid detergent containing no alkylene oxide polymer is preferably 500 mg / L or less, more preferably 400 mg / L or less, even more preferably 300 mg / L or less, particularly preferably 200 mg / L or less, and most preferably 100 mg / L or less. Kaolin turbidity can be measured, for example, by the following method.

[0069] (Method for measuring kaolin turbidity) A uniformly stirred sample (liquid detergent) is placed in a 50 mm square cell with a thickness of 10 mm, and after removing air bubbles, the turbidity (kaolin turbidity: mg / L) at 25°C is measured using a turbidity meter NDH2000 (trade name, manufactured by Nippon Denshoku Co., Ltd.).

[0070] Suitable enzymes that can be incorporated into the detergent of the present disclosure include proteases, lipases, cellulases, etc. Among these, proteases, alkaline lipases, and alkaline cellulases, which are highly active in alkaline cleaning solutions, are preferred. The amount of the enzymes added is preferably 5% by mass or less relative to 100% by mass of the detergent. If the amount exceeds 5% by mass, no improvement in detergency will be observed, and economic efficiency may decrease.

[0071] Suitable alkali builders include silicates, carbonates, sulfates, etc. Suitable chelating builders include diglycolic acid, oxycarboxylic acids, EDTA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), citric acid, MGDA (methylglycinediacetic acid), HIDS (hydroxyiminodiacetic acid), etc. Water-soluble polycarboxylic acid polymers may also be used.

[0072] The detergent has excellent dispersibility and is highly stable with extremely high quality performance, being resistant to deterioration in performance when stored for a long period of time and resistant to precipitation of impurities when kept at low temperatures. [Example]

[0073] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."

[0074] <Evaluation test of cleaning power for complex soiling> (1) The L value, a value, and b value of the Lab color system of a 5cm x 5cm artificially soiled cloth PC-S-94 (manufactured by CFT) were measured using a reflectance meter (spectrophotometer, manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE6000). (2) 56.8 g of calcium chloride dihydrate and 26.1 g of magnesium chloride hexahydrate were mixed with pure water to prepare hard water mother liquor (i). (3) 11.6 g of linear alkylbenzenesulfonate sodium salt (Neopelex G-25 manufactured by Kao, hereinafter also referred to as LAS) was mixed with 88.4 g of pure water to prepare 100 g of a 3% LAS aqueous solution (ii). (4) 20 g of hard water mother liquor (i) and 54 g of 3% LAS aqueous solution (ii) were added to 4000 g of pure water and stirred to prepare a cleaning solution (iii). (5) For rinsing, 20 g of hard water mother liquor (i) was added to 4,000 g of pure water and stirred to prepare a rinsing liquid (iv). (6) 1000 g of cleaning solution (iii) was added to each pot in a Tergot-o-meter (manufactured by Daiei Scientific Co., Ltd., product name: TM-4), and 2.7 mL of a 1.5% solids aqueous solution of the evaluation sample was added to each pot and stirred. (7) The temperature inside the pot was adjusted to 25°C, and three sheets of PC-S-94 and 50 g of cotton cloth (5 cm x 5 cm Style #460, manufactured by Test Fabrics) for adjusting the bath ratio were placed in each pot, stirred, and then left to soak for 1 minute. (8) After soaking, the mixture was stirred at 150 rpm for 10 minutes. (9) The contaminated cloth was removed from each pot, the water was drained by hand, and 1000 g of the rinse solution (iv) was added to each pot. The temperature was adjusted to 25°C and the solution was stirred at 150 rpm for 5 minutes. (10) The procedure in (9) was repeated once more. (11) The soiled cloth was removed from each pot, the water was squeezed off by hand, and the cloth was allowed to dry at room temperature. The L value, a value, and b value of the soiled cloth were then measured again as reflectance using the above spectrocolorimeter. (10) From the above measurement results, the cleaning degree (cleaning power) was calculated using the following formula. TIFF0007763067000009.tif11144L before , L after are the L values ​​before and after cleaning, and a before , a after are the a values ​​before and after cleaning, and b before , b after indicates the b value before and after washing, respectively. The higher the value of the cleanliness, the better the cleaning power.

[0075] <Evaluation of carbon black re-soiling prevention> The following washing process, which involves washing, rinsing, and drying in this order, was repeated three times to measure the ability of carbon black to prevent redeposition of the fabric. Cleaning process: The following two types of cotton cloth were used as the items to be washed. Cotton cloth (1): Five 5cm x 5cm cotton knit cloths (manufactured by Tanigashira Shoten) were prepared as recontamination test cloths. Cotton cloth (2): Cotton cloth obtained from Testfabrics was prepared so that the total weight of the cotton cloth (2) and the cotton cloth (1) was 30 g. As surfactants, a 3% LAS aqueous solution and a 1.5% aqueous solution of each evaluation sample were prepared. Into a Tergot-o-meter (manufactured by Daiei Scientific Co., Ltd., product name: TM-4), 900 mL of 15°DH hard water (prepared from calcium chloride and magnesium chloride, Ca / Mg = 3 (mass ratio)) at 25°C, a contaminated solution prepared by mixing 7.5 g of the above 3% LAS aqueous solution with 0.05 g of carbon black (hereinafter also referred to as CB), 0.498 g of a 1.5% aqueous solution of the evaluation sample, and cotton cloths (1) and (2) were placed. Then, washing was carried out for 10 minutes at 25°C with a stirring speed of 120 rpm. Rinse step: After the washing process, the washed items and mud-stained fabrics were dehydrated for 1.5 minutes, and then rinsed in 900 mL of 15°DH hard water at 25°C for 3 minutes at 120 rpm and 25°C. This operation (dehydration and rinsing) was repeated twice. Drying process: After the rinsing step, the washed items and the mud-stained cloth were dehydrated for 1.5 minutes, and then only the cotton cloth (1) was taken out, sandwiched between two cotton cloths, and dried with an iron. The reflectance (Z value) of the cotton fabric (1) that had been washed 1 to 3 times as described above and the cotton fabric (1) before the washing treatment was measured using a reflectometer (spectrophotometric colorimeter, manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE6000), and the anti-redeposition rate was calculated using the following formula. Redeposition prevention rate = (Z value of cotton fabric (1) after 1 to 3 washings) / (Z value of cotton fabric (1) before washing) x 100

[0076] <Synthesis example of intermediate (1)> Synthesis of (1,2-epoxytetradecane-benzyl alcohol) A 300 mL glass four-necked recovery flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube was used. A reaction vessel was charged with 49.7 g (0.46 mol) of benzyl alcohol (manufactured by Fujifilm Wako Pure Chemical Industries, hereafter referred to as BnOH) and 2.58 g of potassium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, hereafter referred to as KOH), and nitrogen bubbling was performed at 100 mL / min for 1 hour at 120 °C. After the nitrogen flow rate was increased to 50 mL / min, 97.7 g (0.46 mol) of 1,2-epoxytetradecane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the reaction vessel using a dropping funnel over 60 minutes. The temperature was maintained for 3 hours under a nitrogen atmosphere to obtain a crude reaction product. The crude product was transferred to a 500 mL separatory funnel, and 150 g of pure water was added to separate the mixture. After recovering the organic layer, another 150 g of pure water was added to separate the mixture. The organic layer was then recovered, and the water contained in the organic layer was removed by evaporation to obtain an alkylene alcohol compound having an aromatic ring (hereafter referred to as intermediate (1)).

[0077] Example 1 A 1L stainless steel autoclave equipped with a thermometer, a stirrer, a raw material inlet pipe, and a nitrogen inlet pipe. In a reaction vessel, 89.7 g (0.28 mol) of intermediate (1) and potassium hydroxide as a catalyst were added. 0.224g (4.00mmol) was charged, and the atmosphere in the reaction vessel was replaced with nitrogen while stirring. The reaction vessel was heated to 130°C under atmospheric pressure. Then, the inside of the reaction vessel was evacuated to 1.8 kPa using a vacuum pump. The temperature was reduced to 100°C and the mixture was dehydrated for 1 hour under stirring. While maintaining the temperature, 160.4 g (3.64 mol) of ethylene oxide (EO) was introduced into the reactor over 2.5 hours, and the temperature was maintained for an additional 30 minutes. 92.6 g of an intermediate with a 13-mol EO adduct was then withdrawn from the reactor. 62.0 g (1.41 mol) of EO was again introduced into the reactor over 1 hour, and the temperature was maintained for an additional 30 minutes. 59.5 g of an intermediate with a 21-mol EO adduct was then withdrawn. 22.2 g (0.504 mol) of EO was again introduced into the reactor over 30 minutes, and the temperature was maintained for an additional 30 minutes. 87.9 g of an intermediate with a 25-mol EO adduct was then withdrawn. 41.8 g (0.95 mol) of EO was again introduced into the reactor over 20 minutes, and the temperature was maintained for an additional 30 minutes, after which the reactor was cooled to room temperature. In this way, a polyalkylene glycol compound (hereinafter referred to as PAG compound) (1) was obtained in which an average of 40 moles of EO was added to the intermediate (1).

[0078] Table 1 shows the results of the evaluation test of the detergency for the above complex soils for the PAG compound (1) obtained in Example 1, Newcol 2320 manufactured by Nippon Nyukazai Co., Ltd. as Comparative Example 1 (a compound in which an average of 20 moles of ethylene oxide are added to a primary alcohol having 12 to 13 carbon atoms, hereinafter also referred to as NC2320), and a compound in which 50 moles of EO are added to phenol as Comparative Example 2 (hereinafter also referred to as Phenol-EO50).

[0079] The results of the anti-redeposition evaluation for the PAG compound (1) obtained in Example 1 and the compound obtained by adding 25 moles of EO to 1-dodecanol (hereinafter also referred to as C12-EO25) as Comparative Example 3 are shown in Table 2. The PAG compound of Example 1 and C12-EO25 of Comparative Example 3 have similar HLB values.

[0080] [Table 1]

[0081] [Table 2]

Claims

1. An alkylene oxide polymer having a hydrophobic group represented by the following general formula (1): 【Chemical 0】 (In general formula (1), Ar is a hydrocarbon group containing an aromatic ring and having 6 to 20 carbon atoms; R １ represents a linear and / or branched hydrocarbon group having 10 to 14 carbon atoms, R ２ represents a hydrocarbon group having 2 carbon atoms, R ３ represents a hydrogen atom and / or a methyl group. X １ , X ２ are the same or different and represent a direct bond, an oxygen atom, or a sulfur atom. However, X １ Group, X ２ The groups cannot simultaneously be direct bonds. Y １ , Y ２ are the same or different and represent a direct bond or a methylene group. However, Y １ Base, Y ２ The groups cannot simultaneously be direct bonds. n is an integer from 1 to 50.

2. The alkylene oxide polymer having a hydrophobic group according to claim 1, wherein R 1 is one or more selected from a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, and a tetradecylene group.

3. An alkylene oxide polymer having a hydrophobic group represented by the following general formula (1), and 【Chemical 0】 (In general formula (1), Ar is a hydrocarbon group containing an aromatic ring and having 6 to 20 carbon atoms; R １ represents a linear and / or branched hydrocarbon group having 10 to 14 carbon atoms, R ２ represents a hydrocarbon group having 2 carbon atoms, R ３ represents a hydrogen atom and / or a methyl group. X １ , X ２ are the same or different and represent a direct bond, an oxygen atom, or a sulfur atom. However, X １ Group, X ２ The groups cannot simultaneously be direct bonds. Y １ , Y ２ are the same or different and represent a direct bond or a methylene group. However, Y １ Base, Y ２ The groups cannot simultaneously be direct bonds. n is an integer from 1 to 50. Contains an alkylene oxide compound represented by the following general formula (2): 【Chemical 0】 (In general formula (2), R ２ represents a hydrocarbon group having 2 carbon atoms, R 4 represents a hydrocarbon group such as a hydrogen atom and / or a methyl group. n is an integer from 1 to 50. composition.

4. The composition according to claim 3, wherein R 1 is one or more selected from a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, and a tetradecylene group.

5. The alkylene oxide compound represented by the general formula (2) is When the total amount of the composition is 100% by mass, the content is 1 to 20% by mass. The composition of claim 3.

6. A method for producing the composition of claim 3.

7. A detergent composition comprising the alkylene oxide polymer having a hydrophobic group according to claim 1.

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