JP6783711B2 - Cleaning agent composition - Google Patents

Description

The present invention relates to a cleaning agent composition. More specifically, the present invention relates to a cleaning agent composition containing a cyclic polyether ester compound.

Conventionally, as household cleaning agents such as cleaning agents for clothing or tableware, cleaning agents containing nonionic surfactants such as ethylene oxide adducts of higher alcohols have been used. As a cleaning agent composition for clothing or tableware, which is required to have high detergency against oil and fat stains and good defoaming property, is excellent in detergency and defoaming property against oil and fat stains, and can further reduce the amount used. , A cleaning composition containing a specific nonionic surfactant is known (Patent Document 1). In addition, various biodegradable surfactants have been reported from the viewpoint of adverse effects on the environment and ecosystem (for example, Patent Document 2). However, the cleaning agent compositions described in Patent Documents 1 and 2 have a problem that the cleaning property is deteriorated by inorganic ions when used in hard water.

Japanese Unexamined Patent Publication No. 2013-12204 JP-A-2017-66394

An object of the present invention is to provide a cleaning agent composition having excellent cleaning properties even when a large amount of inorganic ions are contained in the cleaning liquid, such as cleaning in hard water. Furthermore, an object of the present invention is to provide a cleaning agent composition having biodegradability.

The present inventors have arrived at the present invention as a result of studies for achieving the above object. That is, the present invention is a cleaning agent composition containing a cyclic polyether ester compound represented by the general formula (1).

In the general formula (1), R ¹ is a divalent hydrocarbon group having 2 to 21 carbon atoms in which at least ^one of the hydrogen atoms may be substituted with a halogeno group, an acetyl group, an alkoxy group or a phenoxy group. ² is a divalent hydrocarbon group having 2 to 8 carbon atoms, m is an integer of 1 to 3, and n is a number of 1 to 500.

The cleaning agent composition of the present invention has excellent cleaning properties and biodegradability even when a large amount of inorganic ions are contained in the cleaning solution obtained by diluting the cleaning agent with hard water, such as cleaning in hard water.

The cleaning composition of the present invention contains the cyclic polyether ester compound (A) represented by the general formula (1).

In the general formula (1), R ¹ is a hydrocarbon group having 2 to 21 carbon atoms in which at least ^one of the hydrogen atoms may be substituted with a halogeno group, an acetyl group, an alkoxy group or a phenoxy group.

Examples of the hydrocarbon group having 2 to 21 carbon atoms include an alkylene group having 2 to 21 carbon atoms, an alkenylene group having 2 to 21 carbon atoms, an arylene group having 6 to 21 carbon atoms, and an aralkylene group having 7 to 21 carbon atoms. Be done.

Examples of the alkylene group having 2 to 21 carbon atoms include a linear alkylene group having 2 to 21 carbon atoms (ethylene group, trimethylene group, tetramethylene group, pentamethylene group and n-henicosanylene group) and a branched alkylene group having 3 to 21 carbon atoms. Groups (1-methylethylene group, 2-methylethylene group, 1-ethylethylene group, 2-ethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethyltrimethylene group, 1 -N-Butyl trimethylene group, 1-n-hexyl trimethylene group, 1-n-propyl trimethylene group, 1-n-heptilt methylene group, 1-n-octyl methylene group, 1-n-heptyltetra Methylene group and 1-n-octylethylene group, etc.) and cycloalkylene group having 4 to 21 carbon atoms (cyclobutylene group, cyclopentylene group, 2-methylcyclopentylene group, cyclohexylene group, 1,3-dimethylcyclohexi Silen group, cycloheptylene group, 1-ethylcyclopentylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, cycloundecylene group, cyclododecylene group, cyclotriderene group, cyclotetradecylene group, cyclopentadecylene group, cyclohexyl Sadecylene group, cycloheptadecylene group, cyclooctadecylene group, cyclononadesilene group, cycloeicocilene group, norbornylene group, dicyclopentylene group, isopropyridene dicyclohexylene group, cyclohexanedimethylene group, etc.) Can be mentioned.

Examples of the alkenylene group having 2 to 21 carbon atoms include a linear alkenylene group having 2 to 21 carbon atoms (ethenylene group, propenylene group, henicosenylene group, etc.) and a branched alkenylene group having 3 to 21 carbon atoms (1-ethylethenylene group, 1, 2-Dimethyl ethenylene group, 1-butyl ethenylene group, 1-hexyl ethenylene group, 1-octyl ethenylene group, etc.) and the like.

Examples of the arylene group having 6 to 21 carbon atoms include an o-, p- or m-phenylene group, a 2,4-naphthylene group, a biphenylene group, a terphenylene group, an anthrylene group, a phenylenelene group, a fluorenylene group and a pyrenylene group. Be done.

Examples of the aralkylene group having 7 to 21 carbon atoms include a phenylmethylene group, a diphenylmethine group, a 1-phenylethylene group, an o-phenylene ethyl group and a naphthylmethylene group.

Examples of the group in which at least one of the hydrogen atoms of these groups is substituted with a halogeno group, an acetyl group, an alkoxy group or a phenoxy group include a 1-bromo-trimethylene group, a 1-acetyl-trimethylene group and a 1-methoxy-trimethylene group. And 1-phenoxy-trimethylene group and the like.

Of these, R ¹ is preferably a linear or branched alkylene group having 3 to 16 carbon atoms, and is a trimethylene group, a tetramethylene group, a pentamethylene group, a tetradecamethylene group, a methylethylene group, 1-n−. Propyltrimethylene group, 1-n-heptil methylene group, 1-n-octyl methylene group, 1-n-heptyl tetramethylene group, 1-n-hexyl trimethylene group, 1-n-hexyl tetramethylene group, A 1-n-undecyl trimethylene group and a 1-n-undecyltetramethylene group are more preferred.

In the general formula (1), R ² is a divalent hydrocarbon group having 2 to 8 carbon atoms. Among the divalent hydrocarbon groups having 2 to 8 carbon atoms, preferred ones include a phenylethylene group and an alkylene group having 2 to 4 carbon atoms, and more preferably a linear alkylene group having 2 to 4 carbon atoms (ethylene). Groups, propylene groups, butylene groups, etc.) and branched alkylene groups having 3 or 4 carbon atoms (methylethylene group, ethylethylene group, methylpropylene group, 2-methylpropylene, etc.) are mentioned, and particularly preferably 2 to 4 carbon atoms. Is a linear alkylene group and a branched alkylene group having 3 to 4 carbon atoms, most preferably an ethylene group and a propylene group.

In the general formula (1), m is an integer of 1 to 3, preferably 1.
When m is 2 or 3, m R ¹ and m (OR ² ) _n may be the same or different.

In the general formula (1), n means the average number of moles of the oxyalkylene group represented by (OR ² ), and n is a number of 1 to 500, preferably 5 to 5 from the viewpoint of detergency and the like. It is a number of 200. The number of moles (n) of the oxyalkylene group added to the cyclic polyether ester compound (A) is adjusted according to the type of stain to be cleaned and the amount and type of surfactant component contained in the cleaning agent composition. can do.

In the general formula (1), when n has an average number of added moles of 1 to 500, R ² may be the same or different, and can be adjusted according to the type of dirt to be cleaned.
The value of n and the composition of R ² are described in Polymer. Chem., 2014, 5, 6905. It can be measured and analyzed by time-of-flight mass spectrometry (also referred to as MALDI-TOF MS) by the matrix-assisted laser desorption / ionization method described in 1.

As the cyclic polyether ester (A) compound contained in the cleaning agent composition of the present invention, if m is 1 to 3, the average number of moles of the oxyalkylene group represented by n in the general formula (1) is A cyclic polyether ester (A) having a specific value may be used, or a plurality of cyclic polyether ester (A) compounds having different values of n may be used in combination.
When a plurality of cyclic polyether esters (A) having different values (n) of the average number of moles of oxyalkylene groups represented by n in the general formula (1) are used in combination, the cyclic polyether ester compound (A) to be used is used. The value and ratio of the number of added moles of the oxyalkylene group of the above can be adjusted according to the type of dirt to be cleaned and the like.

The adjustment of the values of m and n in the general formula (1) and the adjustment of the content of the cyclic polyether ester compound (A) having n in a specific range have active hydrogen-containing groups used in the alkoxylation reaction described later. It can be carried out by adjusting the concentration ratio of the non-lactone and the alkylene oxide having 2 to 8 carbon atoms and changing the method of adding the alkylene oxide. Examples of the alkylene oxide addition method include a method of continuously or intermittently introducing an alkylene oxide.

The number average molecular weight (hereinafter abbreviated as Mn) of the cyclic polyether ester compound (A) contained in the cleaning agent composition of the present invention is adjusted according to the type of stain targeted by the cleaning agent composition of the present invention. From the viewpoint of cleanability and the like, 200 to 5000 is preferable, and the Mn of the cyclic polyether ester compound (A) can be set in a preferable range by adjusting the number of added moles of the oxyalkylene group and the like.

As the cyclic polyether ester compound (A) used in the cleaning agent composition of the present invention, preferably, R ¹ is a tetradecamethylene group, a hexamethylene group, and a propylene group, and R ² is an ethylene group and a propylene group. Examples thereof include cyclic polyether esters having m of 1 to 3 and an average addition molar number of 1 to 500.

The cyclic polyether ester compound (A) used in the cleaning agent composition of the present invention has the above-mentioned active hydrogen-containing group by using a lactone having no active hydrogen-containing group and an alkylene oxide having 2 to 8 carbon atoms. It can be obtained by carrying out a reaction (also referred to as an alkoxylation reaction) in which an oxyalkylene group is inserted between the carbonyl of the oxycarbonyl group of the non-lactone and the oxygen atom. In the alkoxylation reaction, a lactone having no active hydrogen-containing group and an alkylene oxide having 2 to 8 carbon atoms are used as a catalyst for the alkoxylation reaction, and a catalyst used for the ring-opening addition reaction and the alkoxylation reaction of the alkylene oxide is used as a catalyst for the alkoxylation reaction. You may use it.
The active hydrogen-containing group means a functional group to which an alkylene oxide can be ring-opened and added, and examples thereof include a hydroxyl group, a carboxyl group, a mercapto group and an amino group.

In the alkoxylation reaction, another cyclic polyether ester represented by the general formula (1) is inserted into the cyclic polyether ester compound (A) represented by the general formula (1) produced in the alkoxylation reaction. An additional side reaction occurs.
Therefore, in addition to the cyclic polyether ester (A) in which m = 1 in the general formula (1), the reaction product obtained in the alkoxylation reaction includes [R ¹ CO (OR ² ) in the general formula (1). ) _N O] contains a cyclic polyether ester having two units in one molecule (ie m = 2) and / or a cyclic polyether ester having three units (ie m = 3), and the reaction product , A polyether composition containing a cyclic polyether ester having 1 to 3 units represented by [R ¹ CO (OR ² ) _n O] in the general formula (1) as a main component.
The composition of the cyclic polyether contained in the reaction product is as follows: Polymer. Chem., 2014, 5, 6905. It can be analyzed and confirmed by the MALDI-TOF MS described in.

The reaction product of the alkoxylation reaction [that is, the mixture containing the cyclic polyether ester compound (A)] is further fractionated and purified by a known method such as a gel permeation method or silica gel column chromatography to obtain a specific m. A cyclic polyether ester (A) having and n can be obtained. As the cyclic polyether ester (A) contained in the cleaning agent composition of the present invention, the cyclic polyether obtained by fractionating and purifying the reaction product even if the reaction product of the alkoxylation reaction is used as it is. The ether ester compound (A) may be used.

The lactone having no active hydrogen-containing group used to obtain the cyclic polyether ester compound (A) is a carbon having one hydroxyl group and one carboxyl group and not having another active hydrogen-containing group. Cyclic esters obtained by intramolecular dehydration of hydroxyl groups and carboxyl groups for monohydroxycarboxylic acids of numbers 4 to 22 can be used. As a method for synthesizing a lactone by intramolecular dehydration, a method of heat dehydration by a known method, J.A. S. Nimitz, R.M. H. Wollemberg, Terahedron Lett. A known synthetic method can be used as described in 1978, 19, 3523, and a method using an enzyme such as lipase.

As a monohydroxycarboxylic acid having 4 to 22 carbon atoms which does not have an active hydrogen-containing group other than one hydroxyl group and one carboxyl group, a linear hydroxycarboxylic acid having 4 to 22 carbon atoms (3-hydroxy) Propanic acid, 4-hydroxybutyric acid, 5-hydroxypentanoic acid, 6-hydroxyhexanoic acid, 15-hydroxypentadecanoic acid, 16-hydroxyhexadecanoic acid, 4-hydroxy-2-butenoic acid, etc.) and branches with 3 to 22 carbon atoms. Hydroxycarboxylic acids (3-hydroxybutanoic acid, 5-hydroxytridecanoic acid, 2-methylene-4-hydroxybutyric acid, 4-phenyl-4-hydroxybutyric acid, 2,2-dimethyl-4-hydroxybutyric acid, 4-hexyl- 4-Hydroxybutyric acid, 4-hydroxy-2-methyl-2-butenoic acid, etc.) and the like.

As the lactone having no active hydrogen-containing group, at least one hydrogen atom among the hydrogen atoms bonded to the carbon atom of the monohydroxycarboxylic acid having 4 to 22 carbon atoms is a halogeno group, an acetyl group, an alkoxy group or a lactone. A lactone having a structure in which a hydroxycarboxylic acid substituted with a phenoxy group is intramolecularly dehydrated can also be used.
Among the monohydroxycarboxylic acids having 4 to 22 carbon atoms, examples of the hydroxycarboxylic acid in which at least one of the hydrogen atoms bonded to the carbon atom is replaced with a halogeno group include 2-bromo-4-hydroxybutyric acid, and acetyl. Examples of the hydroxycarboxylic acid substituted with a group include 2-acetyl-4-hydroxybutanoic acid, and examples of the hydroxycarboxylic acid substituted with an alkoxy group include 2-methoxy-4-hydroxybutyric acid. Examples of the hydroxycarboxylic acid substituted with a phenoxy group include 2-phenyl-4-hydroxybutyric acid.

As the lactone having no active hydrogen-containing group, β-lactone (β-propiolactone, β-butyrolactone, etc.), γ-lactone (γ-butyrolactone, etc.), δ-lactone (δ-valerolactone, etc.) are preferable. Etc.), ε-lactone (ε-caprolactone, etc.), lactone having a long-chain alkyl group (γ-enant lactone, γ-undecanolactone, γ-dodecalactone, δ-dodecanolactone, etc.), large cyclic lactone (15) −Pentadecanolactone), aromatic lactone (3,4-dihydrocmarin) and the like.
These lactones may be used alone or in combination of two or more.

Examples of the alkylene oxide having 2 to 8 carbon atoms (hereinafter, may be abbreviated as AO) used in the alkoxylation reaction include ethylene oxide, 1,2-propylene oxide, oxetane, 1,2-, 1,3-1, 1. , 4- or 2,3-butylene oxide, styrene oxide and the like, preferably alkylene oxides having 2 to 3 carbon atoms (ethylene oxide, 1,2-propylene oxide and oxetane), ethylene oxide and 1,2-propylene oxide. Oxides are more preferred.
The alkylene oxide may be used alone or in combination of two or more. When two or more types are used in combination, the binding form may be random, block, or both.
When two or more kinds of alkylene oxides are used in combination, the obtained cyclic polyether ester compound (A) is a cyclic polyether ester having a different kind of R ² corresponding to the kind of alkylene oxide used in the general formula (1). is there.

The average number of moles n of the cyclic polyether ester (A) added is 1 to 500, preferably 1 to 350, and more preferably 1 to 100 from the viewpoint of ease of handling.

The cyclic polyether ester compound (A) used in the cleaning agent composition of the present invention uses a lactone having no active hydrogen-containing group and an alkylene oxide having 2 to 8 carbon atoms and does not have an active hydrogen-containing group. It can be obtained by carrying out a reaction (also referred to as an alkoxylation reaction) in which an oxyalkylene group is inserted between the carbonyl of the oxycarbonyl group of the lactone and the oxygen atom. In the alkoxylation reaction, a lactone having no active hydrogen-containing group and an alkylene oxide having 2 to 8 carbon atoms are used as a catalyst for the alkoxylation reaction, and a catalyst used for the ring-opening addition reaction of the alkylene oxide and the alkoxylation reaction is used. You may go there.
The active hydrogen-containing group means a functional group to which an alkylene oxide can be ring-opened and added, and examples thereof include a hydroxyl group, a carboxyl group, a mercapto group and an amino group.

The alkoxylation reaction is preferably carried out in the presence of a catalyst.
As the catalyst used in the reaction step, hydroxides of metals (boron, tin, nickel, zinc, aluminum, etc.), inorganic acids (sulfuric acid, phosphoric acid, etc.), alkali metals (lithium, sodium, potassium, cesium, etc.) are hydroxylated. Two types of metals such as substances, amine compounds (diethylamine, triethylamine, etc.), phosphazene, complex metal cyanide complex catalysts (Japanese Patent Laid-Open No. 2005-53952, JP-A-2016-6203, etc.), zinc hexacyanocobaltate, etc. (Metal complex catalyst containing in the molecule, etc.), oxide composites described in JP-A-2000-354763, composite oxides of Al and Mg (C1), layered double hydroxides (C2), and them. It can be carried out by using the fired product (C3) of.

The layered double hydroxide used in the production method of the present invention is a divalent metal (Mg, Fe, Zn, Ca, Li, Ni, Co, Cu, etc.) and a trivalent metal (Al, Fe, Mn, etc.). It means an inorganic layered compound in which the above hydroxides are combined to form a laminated structure, and the general formula is [M 2 ⁺ _1-h M ^{3 +} _h (OH) ₂ ] [(W ^i- ) _{h / i} · jH. ₂ O] ^{[wherein, M 2+} is a divalent ^{metal, M 3+} is a trivalent ^{metal, W i-i-valent} anion _{^{(HCO 3 -, CO 3 2-}} , PO 4 3-, SO 4 2 ⁻ , Cl ⁻ , NO ₂ ⁻ and NO ₃ ^−, etc.), h, i and j are independent positive numbers. ], And includes hydrotalcite, motuchoreite, manaseito, stichtite, pyroaulite, tacobite, eardrite, meixenelite and the like. These layered double hydroxides are known as clay minerals and may be contained in naturally occurring minerals or synthetically obtained.

One type of catalyst may be used alone, or two or more types may be used in combination.
Of these, preferred from the viewpoint of reaction efficiency are a composite oxide of Al and Mg (C1), hydrotalcite having Al and Mg (C2-1), and a calcined product (C3) thereof.

The composite oxide (C1) used in the present invention is not particularly limited as long as it is an oxide having Al and Mg, but preferred composite oxides include compounds represented by the following general formula (2) or (3). Can be mentioned.
_{[AMgO · Al 2 O 3 · bH} 2 O ] (2)
_[Mg s _Al t _{O u]} (3)

In the general formula (2), a and b are independent positive numbers.
In the general formula (3), s, t and u are independent positive numbers.
From the viewpoint of reactivity, s / t is preferably 0.1 or more and less than 0.9.
Examples of the composite oxide (C1) include 2.5 MgO, Al ₂ O ₃ , bH ₂ O, Mg _0.7 Al _0.3 O _1.15, etc., respectively, and Kyowa Chemical Industry Co., Ltd. Manufactured by] and Kyoward 2000 [manufactured by Kyowa Chemical Industry Co., Ltd.], etc. can be obtained from the market.

Examples of the hydrotalcite (C2-1) used in the present invention include compounds represented by the following general formula (4).
[Mg _1-c Al _c (OH) ₂ ] ^{c +} [CO _{3c / 2} · dH ₂ O] ^c− (4)

Further, in the general formula (4), c is a number satisfying 0 <c ≦ 0.33, and d is a number satisfying 0 <d ≦ 1.0.

The hydrotalcite _{(C2-1), Mg 6 Al 2} (OH) 16 CO 3 · 4H 2 O and _{Mg 4.5 Al 2 (OH) 13} CO 3 · 3.5H 2 O and the like, respectively It can be obtained from the market as Kyoward 500 [manufactured by Kyowa Chemical Industry Co., Ltd.] and Kyoward 1000 [manufactured by Kyowa Chemical Industry Co., Ltd.].

As the hydrotalcite (C2-1) used in the present invention, in addition to the above compounds, known minerals described in West German Patent Publication No. 1592126 and European Patent Publication No. 0207811 can also be used.

As for (C1) and (C2-1), one type may be used alone, or two or more types may be used in combination.
Among these, preferred in view of reactivity is given to composite oxide (C1), more preferred _{2.5MgO · Al 2 O 3 · nH} 2 O (n is a positive number) and _Mg 0.7 Al _{0 .3} O _1.15 .

The calcined product of the composite oxide (C1) of Al and Mg or the calcined product of hydrotalcite (C2-1) having Al and Mg (C3) is the composite oxide (C1) of Al and Mg or Hydrotalcite (C2-1) can be obtained by heat treatment in an air atmosphere, preferably in a nitrogen stream, preferably at 400 to 1500 ° C. (more preferably 600 to 1000 ° C.) for 1 to 4 hours. it can.

In the reaction step of alkoxylation, the content of the catalyst is not particularly limited, but from the viewpoint of reaction rate and filtration efficiency, 0.0001 to 10% by weight is preferable, and more preferably 0.0001 to 10% by weight based on the total weight of the lactone and the alkylene oxide. It is 0.01 to 1.0% by weight.

Further, in the alkoxylation reaction step of the lactone, a solvent may be added in addition to the lactone, the alkylene oxide and the catalyst from the viewpoint of handling.
Solvents include toluene, xylene, benzene, dimethyl sulfoxide, diglyme, triglyme, 1,4-dioxane, cyclohexane, hexane, diethyl ether, tetrahydrofuran, dimethylformamide, carbon tetrachloride, N-methylpyrrolidone, 1,2-dimethoxyethane. , 1,2-Dichloroethane, chloroform and the like.
As the solvent, one type may be used alone, or two or more types may be used in combination.
Of these, toluene and xylene are preferable from the viewpoint of miscibility with lactones and alkylene oxides.
The weight of the solvent used in the alkoxylation reaction is preferably 0 to 99% by weight, more preferably 0 to 90% by weight, based on the total weight of the cyclic compound, the cyclic ether and the catalyst from the viewpoint of reaction rate and the like. ..

In the alkoxylation reaction, the temperature of the lactone and lactone, the alkylene oxide and, if necessary, the mixture of the catalyst and the solvent is preferably 90 to 250 ° C, more preferably 100 to 190 ° C.
The time for setting the above temperature is preferably 1 to 200 hours.

In the alkoxylation reaction, lactone, alkylene oxide, and if necessary, a catalyst and solvent are placed in the reaction apparatus, the inside of the system is replaced and sealed with an inert gas (nitrogen, argon, etc.), and the reaction temperature and reaction time are adjusted. This can be done by stirring and mixing.
As the reaction device, a known reaction device such as a mixing vessel (flask with stirrer, autoclave, etc.) to which a stirring device and a heating device are attached can be used.

In the production method of the present invention, the product obtained by the alkoxylation reaction [that is, the mixture containing the cyclic polyether ester compound (A)] is further filtered (the method described in JP-A-2011-213864, etc.) and gel. It may include a step of purifying by a known method such as a permeation method and silica gel column chromatography (hereinafter abbreviated as a purification step).
By the above purification step, only the cyclic polyether ester compound (A) having a specific structure can be extracted.

In addition to the cyclic polyether ester compound (A), the cleaning agent composition of the present invention comprises a cationic surfactant (B1), a betaine-type amphoteric surfactant (B2), and a nonionic surfactant from the viewpoint of improving detergency. It is preferable to contain the surfactant (B3) and the anionic surfactant (B4) because the detergency of the compound (A) in hard water is further improved.
From the viewpoint of biodegradability, it is more preferable to add a nonionic surfactant.

Examples of the cationic surfactant (B1) include a primary amine salt-type cationic surfactant, a secondary amine salt-type cationic surfactant, a tertiary amine salt-type cationic surfactant, and a quaternary amine salt-type cationic surfactant. Examples thereof include ammonium salt-type cationic surfactants, pyridinium salt-type quaternary ammonium salts, imidazoline-type cationic surfactants, and amine salt-type cationic surfactants. Surfactants having both functional groups of ammonium ion or iminium ion and anionic group are usually classified as amphoteric surfactant and are not included in the cationic surfactant used in the present invention. ..

As the primary amine salt type cationic surfactant, the primary amine is an inorganic acid (hydrogenic acid, nitrate, sulfuric acid, hydroiodic acid, etc.) or an organic acid (acetic acid, formic acid, oxalic acid, lactic acid, gluconic acid, etc.). Compounds obtained by neutralization with adipic acid, alkyl phosphate, etc.) can be used, and as primary amines, monoalkylamines having 2 to 21 carbon atoms (ethylamine, laurylamine, stearylamine, cetylamine and hen) can be used. Icosylamine, etc.) and the like.

As the secondary amine salt-type cationic surfactant, the secondary amine is an inorganic acid (hydrochloric acid, nitrate, sulfuric acid, hydroiodic acid, etc.) or an organic acid (acetic acid, formic acid, oxalic acid, lactic acid, gluconic acid, etc.). Compounds obtained by neutralizing with adipic acid, alkyl phosphoric acid, etc.) can be used, and as the secondary amine, an aliphatic secondary amine having 2 to 20 carbon atoms (dimethylamine, diethylamine, ethylpropylamine, methyl) can be used. (Pentylamine and ethyloctadecylamine) and monoalkylamines include amines in which an alkylene oxide is added to one hydrogen atom bonded to a nitrogen atom.

As the tertiary amine salt-type cationic surfactant, the tertiary amine is an inorganic acid (hydrochloric acid, nitrate, sulfuric acid, hydroiodic acid, etc.) or an organic acid (acetic acid, formic acid, oxalic acid, lactic acid, gluconic acid, etc.). Compounds obtained by neutralizing with adipic acid, alkyl phosphoric acid, etc.) can be used, and as tertiary amines, aliphatic tertiary amines having 6 to 20 carbon atoms (triethylamine, ethyldimethylamine and N, N, N', N'-tetramethylethylenediamine, etc.), alicyclic amines [N-methylpyrrolidin, N-methylpiperidin, N-methylhexamethyleneimine, N-methylmorpholin and 1,8-diazabicyclo (5,4,0) ) -7-Undecene, etc.], nitrogen-containing heterocyclic aromatic amines (4-dimethylaminopyridine, N-methylimidazole, 4,4'-dipyridyl, etc.), hydroxyl group-containing tertiary amines (triethanolamine monostearate, etc.) ) And amines in which an alkylene oxide is added to one hydrogen atom bonded to a nitrogen atom of a secondary amine.

As the quaternary ammonium salt type cationic surfactant, a quaternary agent known as a tertiary amine [alkyl halides (methyl chloride, methyl bromide, ethyl chloride, benzyl chloride, etc.), dimethyl sulfate, dimethyl carbonate and Examples of amines quaternized with [alkylene oxide, etc.] include lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide, stearyltrimethylammonium bromide, and lauryldimethylbenzylammonium chloride (benzalconium chloride). ), Cetylpyridinium chloride and polyoxyethylene trimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride, lanolin fatty acid ethyl sulfate fatty acid aminopropylethyldimethylammonium and the like.

In addition to the above, "Introduction to New Surfactants" [Takehiko Fujimoto, published by Sanyo Kasei Kogyo Co., Ltd. (1996), P70, as primary to tertiary amine salt-type cationic surfactants -74] can also be used, such as Solomin A-type cationic surfactant, Sapamine A-type surfactant, Arcobel A-type surfactant, and imidazoline-type surfactant, and quaternary ammonium salt-type cationic surfactant. In addition to the above, the agents include Solomin A-type quaternary ammonium salt and pyridinium salt described in "Introduction to New Surfactants" [Takehiko Fujimoto, published by Sanyo Kasei Kogyo Co., Ltd. (1996), P74-81]. Etc. can also be used.

Of these, a quaternary ammonium salt-type cationic surfactant is preferable, and polyoxyethylene (molecular weight: 120 to 1,200) didecylmethylammonium chloride and polyoxyethylene (molecular weight: 120 to 200) are more preferable. 1,200) Lauryldimethylammonium chloride, polyoxyethylene (molecular weight: 120 to 1,200) Lauryldimethylammonium methylsulfate, tripropylene glycol stearylammonium chloride, amine stearyl PG trimonium chloride and behenyl PG trimonium chloride, didecyl Examples thereof include dimethylammonium chloride.

The betaine-type amphoteric surfactant (B2) is an amphoteric surfactant having a cation moiety which is a quaternary ammonium salt and an anion moiety which is a carboxylate, and is a coconut oil fatty acid amide propyl dimethylamino acetate betaine and lauryl dimethyl amino. Examples thereof include betaine acetate, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, lauryl hydroxysulfobetaine and lauroylamide ethyl hydroxyethyl carboxymethyl betaine sodium hydroxypropyl phosphate. Of these, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine is preferred.

When the cleaning agent composition of the present invention contains a cationic surfactant (B1) and / or a betaine-type amphoteric surfactant (B2), the cyclic polyether ester compound is used in the cleaning agent composition from the viewpoint of detergency and the like. The ratio of the total number of ether bonds derived from (A) to the total number of nitrogen atoms derived from the cationic surfactant (B1) and the betaine-type amphoteric surfactant (B2) is 1: 1000 to 1000: 1. Is preferable.

When the cleaning agent composition of the present invention contains a cationic surfactant (B1) and / or a betaine-type amphoteric surfactant (B2), the cationic surfactant (B1) and betaine contained in the cleaning agent composition The ratio of the total number of nitrogen atoms contained in the type amphoteric surfactant (B2) to the total number of ether bonds contained in the cyclic polyether ester compound (A) is the ratio of the cyclic polyether ester compound contained in the cleaning agent composition. The weight of (A) and the weight of the cationic surfactant (B1) and / or the betaine-type amphoteric surfactant (B2) can be adjusted to a preferable range.

The cleaning agent composition of the present invention may contain the cyclic polyether ester compound (A), and the cyclic polyether ester compound (A) is 0.1 to 99. Based on the total weight of the cleaning agent composition. It is preferable to have 9% by weight.

When the cleaning agent composition of the present invention contains a cationic surfactant (B1) and / or a betaine-type amphoteric surfactant (B2), the cyclic polyether ester compound (A) contained in the cleaning agent composition of the present invention and The total weight of the cationic surfactant (B1) and the betaine-type amphoteric surfactant (B2) is preferably 0.1 to 99.9% by weight based on the total weight of the cleaning agent composition.

From the viewpoint of improving the detergency, the cleaning agent composition of the present invention preferably contains a cationic surfactant (B1) and / or a betaine-type amphoteric surfactant (B2). It is known that the quaternary nitrogen atom coordinates with the oxygen atom contained in the ether bond, and it is considered that the same thing occurs in the cleaning agent composition of the present invention.
When the nitrogen atom of the cationic surfactant (B1) and / or the betaine-type amphoteric surfactant (B2) is coordinated with the ether bond of the cyclic polyether ester compound (A), the parent of the cyclic polyether ester compound (A). It is presumed that the degree of oiliness and the solubility in water change, and the adsorptivity of the cleaning agent composition to stains and the dispersibility in the cleaning liquid are improved, and the cleaning property of the cleaning agent composition is improved. ..

Examples of the nonionic surfactant (B3) include an alkylene oxide-added nonionic surfactant and a polyhydric alcohol type nonionic surfactant.
Examples of the alkylene oxide-adducted nonionic surfactant include higher alcohol (10 to 18 carbon atoms) alkylene (2 to 4 carbon atoms, preferably 2 to 3 carbon atoms) oxide (1 to 50 adducts per active hydrogen). ) Adduct, alkyl (1 to 12 carbon atoms) phenol EO (1 to 30 added moles per active hydrogen) adduct, fatty acid (8 to 18 carbon atoms) EO (added moles per active hydrogen) 1-30) Adducts, polypropylene glycol (molecular weight 200-4000) EO (additional moles 1-50 per active hydrogen) adducts and polyoxyethylene (additional moles 3-30 per active hydrogen) Multivalent (2 to 8 valent) such as alkyl (6 to 20 carbon atoms) allyl ether, sorbitan monolaurate EO (additional moles 1 to 30) adduct, sorbitan monooleate EO (additional moles 1 to 30) adduct. Or more) Alcohol (2 to 30 carbon atoms) fatty acid (8 to 24 carbon atoms) ester EO adduct (1 to 30 adducts per active hydrogen) and the like.

Polyhydric alcohol type nonionic surfactants include polyhydric (2-8 valent or higher) alcohols (2 to 30 carbon atoms) such as glycerin monostearate, glycerin monooleate, sorbitan monolaurate, and sorbitan monoolate. ) Fatty acid (8 to 24 carbon atoms) ester, lauric acid monoethanolamide, fatty acid alkanolamide such as lauric acid diethanolamide, and the like.

As an alkylene oxide-added nonionic surfactant to be used in combination with the cleaning composition of the present invention, a higher alcohol (10 to 18 carbon atoms) alkylene (2 to 4 carbon atoms, preferably 2 to 3 carbon atoms) from the viewpoint of biodegradability. ) Oxide (additional number of moles 1 to 50 per active hydrogen) adduct is preferable. Specifically, ethylene oxide adducts of decyl alcohol, dodecyl alcohol, tetradecyl alcohol, or octadecyl alcohol, or copolymers of ethylene oxide and propylene oxide are more preferable.

Examples of the anionic surfactant (B4) include ether carboxylic acid (salt) having a hydrocarbon group having 8 to 24 carbon atoms [(poly) oxyethylene (repetition unit number 1 to 100) sodium lauryl ether acetate, etc.], carbon. Ether sulfate ester salt having a hydrocarbon group of 8 to 24 [(poly) oxyethylene (repetition unit number 1 to 100) sodium lauryl sulfate, etc.], sulfosuccinic acid ester salt having a hydrocarbon group of 8 to 24 carbons [ Mono or dialkyl sulfosuccinate di or monosodium, (poly) oxyethylene (repetition units 1 to 100) mono or dialkyl sulfosuccinate di or monosodium, etc.], (poly) oxyethylene (repetition units 1 to 100) palm oil Fatty acid monoethanolamide sodium sulfate, sulfonate having a hydrocarbon group of 8 to 24 carbon atoms (sodium dodecylbenzene sulfonate, etc.), phosphate ester salt having a hydrocarbon group of 8 to 24 carbon atoms [sodium lauryl phosphate] , (Poly) oxyethylene (number of repeating units 1 to 100) sodium lauryl ether phosphate, etc.], fatty acid salts (sodium laurate and triethanolamine laurate, etc.), acylated amino acid salts (coconut oil fatty acid methyl taurine sodium, palm) Oil fatty acid sarcosin sodium, coconut oil fatty acid sarcosin triethanolamine, N-palm oil fatty acid acyl-L-glutamate triethanolamine, N-palm oil fatty acid acyl-L-glutamate sodium, lauroylmethyl-β-alanine sodium, etc.) Can be mentioned.

The anionic surfactant to be used in combination with the cleaning composition of the present invention is an ether carboxylic acid (salt) having a hydrocarbon group having 8 to 24 carbon atoms [(poly) oxyethylene (repeatedly) from the viewpoint of biodegradability. Units 1 to 100) sodium lauryl ether acetate, etc.], ether sulfate ester salt having a hydrocarbon group having 8 to 24 carbon atoms [(poly) oxyethylene (repetition units 1 to 100) sodium lauryl sulfate, etc.], (poly) ) Oxyethylene (number of repeating units 1 to 100) Palm oil fatty acid monoethanolamide sodium sulfate, fatty acid salt (sodium laurate, triethanolamine laurate, etc.), acylated amino acid salt (palm oil fatty acid methyl taurine sodium, palm oil fatty acid) Sarcosin sodium, coconut oil fatty acid sarcosin triethanolamine, N-palm oil fatty acid acyl-L-glutamate triethanolamine, N-palm oil fatty acid acyl-L-glutamate sodium, lauroylmethyl-β-alanine sodium, etc.) are preferable.

The component contained in the cleaning composition of the present invention is not limited to the cyclic polyether ester compound (A), but water may be contained from the viewpoint of storage stability and environmental load. When the cleaning agent composition of the present invention contains water and / or an organic solvent, the content of water and the organic solvent is preferably 1 to 99% by weight based on the total weight of the cleaning agent composition.

Examples of the water that may be contained in the cleaning agent composition of the present invention include distilled water, reverse osmosis water, deionized water and the like.
Preferred organic solvents that may be included in the cleaning composition of the present invention are ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, glycerin, and diglycerin. , Polyglycerin, 3-methyl-1,3-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,2-hexanediol and other alcohols.

The cleaning agent composition of the present invention preferably has a viscosity of 10 to 30,000 mPa · s from the viewpoint of handleability and the like. The viscosity can be set in a preferable range by adjusting the amount of the cyclic polyether ester compound (A) contained in the cleaning agent composition, the amount of water and the organic solvent, and the like.

The cleaning composition of the present invention further comprises other known components, for example, a builder, a chelating agent, an enzyme, an antifoaming agent, a fluorescent whitening agent, a bleaching agent, and a softening agent described in JP-A-2004-27181. It may contain agents, disinfectants, fragrances, colorants and the like.

When other known components are contained, preferred other components include polycarboxylic acids (acrylic acid homopolymers, maleate homopolymers, etc.), polyvalent carboxylic acids (citric acid, malic acid, etc.) as builders. ), And alkaline builders (caustic soda, soda ash, ammonia, triethanolamine, sodium tripolyphosphate, sodium silicate, etc.), etc., as chelating agents include citrate, malate, ethylenediaminetetraacetic acid and sodium nitrilotriacetate. And the like, polyvalent carboxylates such as.

When the cleaning composition of the present invention contains surfactants (B1) to (B4) and other components, their content is based on the total weight of the liquid cleaning composition, and the cleaning property and foaming property. From the viewpoint of the above, it is preferably 80% by weight or less, more preferably 50% by weight or less, and the content of the chelating agent and the alkaline agent among the other components is preferably based on the total weight of the cleaning agent composition. Is 10% by weight or less. The content of the enzyme, disinfectant, fragrance and colorant is preferably 5% by weight or less based on the total weight of the cleaning composition.

The cleaning agent composition of the present invention can be obtained by uniformly mixing components other than the cyclic polyether ester compound (A) and the compound (A) with a known mixing device, and the order of mixing is not limited. For example, it can be obtained by stirring in a mixing tank equipped with a stirrer and a heating / cooling device at 10 to 50 ° C. until uniform.

When the cleaning agent composition of the present invention is used as a liquid cleaning agent composition for tableware or kitchen, the cleaning agent composition of the present invention is impregnated into a sponge or the like (preferably containing water) for tableware and food cooking. It can be applied to a method of directly contacting the sponge or the like with an instrument, a kitchen sink, a gas range, a ventilation fan or the like for cleaning, a method of spraying the cleaning agent composition of the present invention with a spray or the like for cleaning, and the like.

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto.
In addition, the part in an Example shows a part by weight.

<Manufacturing example 1>
"KYOWAAD 300" [Chemical _{Formula: 2.5MgO · Al 2 O 3 ·} nH 2 O (n is a positive number), Kyowa Chemical Industry Co., Ltd.] 24 hours of heat treatment under a nitrogen stream 900 ° C. in an electric furnace And the fired product was adjusted.

<Manufacturing example 2>
30 parts of 15-pentadecanolactone [manufactured by Tokyo Chemical Industry Co., Ltd.] and 1 part of the calcined product obtained in Production Example 1 were put into a stainless steel autoclave equipped with a stirrer and a temperature control function. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 27.5 parts of ethylene oxide was press-fitted at 150 ° C. over 10 hours. Then, it was aged for 10 hours to obtain a mixture (PA-1) containing the cyclic polyether ester compound (A).
The obtained mixture (PA-1) was cooled to 50 ° C., 100 parts of ethanol was added to adjust the temperature to 50 ° C., and then 5 parts of Radiolite # 700 [manufactured by Showa Chemical Co., Ltd.] as a filtration aid. And Kyoward 600 [manufactured by Kyowa Kagaku Kogyo Co., Ltd.] 5 parts were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic polyether ester compound (A-1).
The obtained cyclic polyether ester compound (A-1) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound was analyzed. In (A-1), in the general formula (1), R ¹ is a pentamethylene group, R ² is a methyl ethylene group, and n = 5, the cyclic polyether ester compound of the present invention, and further [R]. It was a mixture containing a cyclic polyether ester compound having two repeating units represented by ¹ CO (OR ² ) _n O] and a cyclic polyether ester compound having three repeating units.

<Manufacturing example 3>
5 parts of the cyclic polyether ester compound obtained in Production Example 2, 2 parts of the calcined product obtained in Production Example 1, and 25 parts of xylene were put into an autoclave made of stainless steel having a stirrer and a temperature control function. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 45.4 parts of ethylene oxide was press-fitted at 150 ° C. over 10 hours. Then, it was aged for 10 hours to obtain a mixture (PA-2) containing the cyclic compound (A).
The obtained mixture (PA-2) was cooled to 50 ° C., 100 parts of ethanol was added to adjust the temperature to 50 ° C., and then 5 parts of Radiolite # 700 [manufactured by Showa Chemical Co., Ltd.] as a filtration aid. And Kyoward 600 [manufactured by Kyowa Kagaku Kogyo Co., Ltd.] 5 parts were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic polyether ester compound (A-2).
The obtained cyclic polyether ester compound (A-2) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound was analyzed. (A-2) is the cyclic compound of the present invention in which R ¹ is a pentamethylene group, R ² is a methyl ethylene group, and n = 100 in the general formula (1), and further [R ¹ CO ( It was a mixture containing a cyclic compound having two repeating units represented by OR ² ) _n O] and a cyclic compound having three repeating units.

<Manufacturing example 4>
30 parts of the cyclic polyether ester compound (A-1) obtained in Production Example 2 and 1 part of the calcined product obtained in Production Example 1 were put into a stainless steel autoclave equipped with a stirrer and a temperature control function. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 28.7 parts of ethylene oxide was press-fitted at 150 ° C. over 10 hours. Then, it was aged for 10 hours to obtain a mixture (PA-3) containing a cyclic polyether ester compound.
The obtained mixture (PA-3) was cooled to 50 ° C., 100 parts of ethanol was added to adjust the temperature to 50 ° C., and then 5 parts of Radiolite # 700 [manufactured by Showa Chemical Co., Ltd.] as a filtration aid. And Kyoward 600 [manufactured by Kyowa Kagaku Kogyo Co., Ltd.] 5 parts were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic polyether ester compound (A-1).
The obtained cyclic polyether ester compound (A-3) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound was analyzed. In (A-3), in the general formula (1), R ¹ is a pentamethylene group, R ² is a methyl ethylene group, and n = 15, the cyclic polyether ester compound of the present invention, and further [R]. It was a mixture containing a cyclic polyether ester compound having two repeating units represented by ¹ CO (OR ² ) _n O] and a cyclic polyether ester compound having three repeating units.

<Manufacturing example 5>
10 parts of the cyclic polyether ester compound (A-2) obtained in Production Example 3 and 1 part of the fired product obtained in Production Example 1 were put into a stainless steel autoclave equipped with a stirrer and a temperature control function. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 37.9 parts of ethylene oxide was press-fitted at 150 ° C. over 10 hours. Then, it was aged for 10 hours to obtain a mixture (PA-4) containing a cyclic polyether ester compound.
The obtained mixture (PA-4) is cooled to 50 ° C., 100 parts of ethanol is added to adjust the temperature to 50 ° C., and then 5 parts of Radiolite # 700 [manufactured by Showa Chemical Co., Ltd.], which is a filtration aid. And Kyoward 600 [manufactured by Kyowa Kagaku Kogyo Co., Ltd.] 5 parts were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic polyether ester compound (A-1).
The obtained cyclic polyether ester compound (A-4) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound was analyzed. (A-4) is the cyclic polyether ester compound of the present invention in which R ¹ is a pentamethylene group, R ² is a methyl ethylene group, and n = 500 in the general formula (1), and further [R]. It was a mixture containing a cyclic polyether ester compound having two repeating units represented by ¹ CO (OR ² ) _n O] and a cyclic compound cyclic polyether ester compound having three.

<Manufacturing example 6>
20 parts of the cyclic polyether ester compound (A-3) obtained in Production Example 4 and 3 parts of the fired product obtained in Production Example 1 were put into a stainless steel autoclave equipped with a stirrer and a temperature control function. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 24.4 parts of ethylene oxide was press-fitted at 150 ° C. over 5 hours and then aged for 10 hours. Next, 12.8 parts of propylene oxide was press-fitted over 5 hours and then aged for 10 hours to obtain a mixture (PA-5) containing a cyclic polyether ester compound.
The obtained mixture (PA-5) was cooled to 50 ° C., 100 parts of ethanol was added to adjust the temperature to 50 ° C., and then 5 parts of Radiolite # 700 [manufactured by Showa Chemical Co., Ltd.] as a filtration aid. And Kyoward 600 [manufactured by Kyowa Kagaku Kogyo Co., Ltd.] 5 parts were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic polyether ester compound (A-5).
The obtained cyclic polyether ester compound (A-5) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound was analyzed. In the general formula (1), (A-5) is the cyclic polyether of the present invention in which R ¹ is a pentamethylene group, R ² is a methyl ethylene group, and n = 50 (EO 40 mol, PO 10 mol). It was a mixture containing an ester compound, a cyclic polyether ester compound having two repeating units represented by [R ¹ CO (OR ² ) _n O], and a cyclic polyether ester compound having three.

<Manufacturing example 7>
Twenty parts of 15-pentadecanolactone [manufactured by Tokyo Chemical Industry Co., Ltd.] and three parts of the calcined product obtained in Production Example 1 were put into a stainless steel autoclave equipped with a stirrer and a temperature control function. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 39 parts of the ethylene oxide / propylene oxide (molar ratio 4/1) mixture was press-fitted at 150 ° C. for 10 hours and then aged for 10 hours. Next, 41.0 parts of the reaction mixture was withdrawn from the autoclave, 52.9 parts of the ethylene oxide / propylene oxide (molar ratio 4/1) mixture was press-fitted over 10 hours, and then aged for 10 hours to contain the cyclic polyether ester compound. The mixture (PA-6) to be prepared was obtained.
The obtained mixture (PA-6) was cooled to 50 ° C., 100 parts of ethanol was added to adjust the temperature to 50 ° C., and then 5 parts of Radiolite # 700 [manufactured by Showa Chemical Co., Ltd.] as a filtration aid. And Kyoward 600 [manufactured by Kyowa Kagaku Kogyo Co., Ltd.] 5 parts were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic polyether ester compound (A-6).
The obtained cyclic polyether ester compound (A-6) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound was analyzed. In the general formula (1), (A-6) is the cyclic polyether of the present invention in which R ¹ is a pentamethylene group, R ² is a methyl ethylene group, and n = 50 (EO 40 mol, PO 10 mol). It was a mixture containing an ester compound, a cyclic polyether ester compound having two repeating units represented by [R ¹ CO (OR ² ) _n O], and a cyclic polyether ester compound having three.

<Manufacturing example 8>
20 parts of the cyclic polyether ester compound (A-3) obtained in Production Example 4 and 5 parts of the calcined product obtained in Production Example 1 were put into a stainless steel autoclave equipped with a stirrer and a temperature control function. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., 19.5 parts of ethylene oxide was press-fitted at 150 ° C. for 10 hours and then aged for 10 hours, and 25.7 parts of propylene oxide was press-fitted over 10 hours. After aging for 10 hours, 26.9 parts of the reaction mixture was withdrawn from the autoclave, and then 20.7 parts of ethylene oxide was press-fitted at 150 ° C. for 15 hours and then aged for 10 hours to obtain a cyclic polyether ester compound. The containing mixture (PA-7) was obtained.
The obtained mixture (PA-7) was cooled to 50 ° C., 100 parts of ethanol was added to adjust the temperature to 50 ° C., and then 5 parts of Radiolite # 700 [manufactured by Showa Chemical Co., Ltd.] as a filtration aid. And Kyoward 600 [manufactured by Kyowa Kagaku Kogyo Co., Ltd.] 5 parts were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic polyether ester compound (A-7).
The obtained cyclic polyether ester compound (A-7) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound was analyzed. In the general formula (1), (A-7) is a cyclic polyether of the present invention in which R ¹ is a pentamethylene group, R ² is a methyl ethylene group, and n = 90 (EO 70 mol, PO 20 mol). It was a mixture containing an ester compound, a cyclic polyether ester compound having two repeating units represented by [R ¹ CO (OR ² ) _n O], and a cyclic polyether ester compound having three.

<Manufacturing example 9>
30 parts of γ-butyrolactone [manufactured by Tokyo Chemical Industry Co., Ltd.] and 5 parts of the calcined product obtained in Production Example 1 were put into a stainless steel autoclave equipped with a stirrer and a temperature control function. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 50.5 parts of propylene oxide was press-fitted at 150 ° C. over 10 hours and then aged for 10 hours. Then, 54.1 parts of the reaction mixture was withdrawn from the autoclave, and then 43.5 parts of propylene oxide was press-fitted at 150 ° C. for 15 hours and then aged for 10 hours. Then, 34.2 parts of the reaction mixture is withdrawn from the autoclave, and then 55.2 parts of ethylene oxide is press-fitted at 150 ° C. for 15 hours and then aged for 10 hours to contain a mixture containing a cyclic polyether ester compound (PA). -8) was obtained.
The obtained mixture (PA-8) was cooled to 50 ° C., 100 parts of ethanol was added to adjust the temperature to 50 ° C., and then 5 parts of Radiolite # 700 [manufactured by Showa Chemical Co., Ltd.] as a filtration aid. And Kyoward 600 [manufactured by Kyowa Kagaku Kogyo Co., Ltd.] 5 parts were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic polyether ester compound (A-8).
The obtained cyclic polyether ester compound (A-8) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound was analyzed. In the general formula (1), (A-8) is a cyclic polyether of the present invention in which R ¹ is a pentamethylene group, R ² is a methyl ethylene group, and n = 55 (EO 40 mol, PO 15 mol). It was a mixture containing an ester compound, a cyclic polyether ester compound having two repeating units represented by [R ¹ CO (OR ² ) _n O], and a cyclic polyether ester compound having three.

<Manufacturing example 10>
30 parts of γ-butyrolactone [manufactured by Tokyo Chemical Industry Co., Ltd.] and 1 part of the calcined product obtained in Production Example 1 were put into a stainless steel autoclave equipped with a stirrer and a temperature control function. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 30.7 parts of ethylene oxide was press-fitted at 150 ° C. over 10 hours. Then, it was aged for 10 hours to obtain a mixture (PA-9) containing the cyclic polyether ester compound (A).
The obtained mixture (PA-9) was cooled to 50 ° C., 100 parts of ethanol was added to adjust the temperature to 50 ° C., and then 5 parts of Radiolite # 700 [manufactured by Showa Chemical Co., Ltd.] as a filtration aid. And Kyoward 600 [manufactured by Kyowa Kagaku Kogyo Co., Ltd.] 5 parts were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic compound (A-1).
The obtained cyclic polyether ester compound (A-9) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound was analyzed. (A-9) is the cyclic polyether ester compound of the present invention in which R ¹ is a pentamethylene group, R ² is a methyl ethylene group, and n = 2 in the general formula (1), and further [R]. It was a mixture containing a cyclic polyether ester compound having two repeating units represented by ¹ CO (OR ² ) _n O] and a cyclic polyether ester compound having three repeating units.

<Manufacturing example 11>
In a stainless steel autoclave with a stirrer and temperature control function, 240 parts (1 mol) of 15-pentadecanolactone, "Kyoward 500" [Kyowa Kagaku Kogyo Co., Ltd .: Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · _4H 2 O] 24.2 parts (0.04 mol) and aluminum perchlorate nonahydrate 1 parts (0.002 mole) after sealing put, 3 hours at 160 ° C. in vacuo It was heated and dehydrated. Next, the temperature was raised to 180 ° C., and 88 parts (2 mol) of ethylene oxide (hereinafter abbreviated as EO) was introduced into the autoclave while adjusting the gauge pressure to be within the range of 1 to 5 kgf / cm ² at 180 ° C. did. After introducing the total amount of EO, stirring was continued until the pressure reached 0.13 kgf / cm ² G. Then, 0.3 part of potassium hydroxide was added, and 176 parts (4 mol) of EO was further introduced at 180 ° C. so that the gauge pressure was 1 to 5 kgf / cm ² . After introducing the total amount of EO, stirring was continued until the pressure reached 0.13 kgf / cm ² G, and the reaction between 15-pentadecanolactone and EO was carried out. The total time required for the EO addition reaction was 8 hours. Then, the catalyst was filtered off from the reaction mixture obtained by the addition reaction of EO to obtain a cyclic polyether ester composition (A-10).
The obtained cyclic polyether ester compound (A-10) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound was analyzed. In the general formula (1), (A-10) is the cyclic polyether ester compound of the present invention in which R ¹ is a pentamethylene group, R ² is a methyl ethylene group, and n = 6, and further [R It was a mixture containing a cyclic polyether ester compound having two repeating units represented by ¹ CO (OR ² ) _n O] and a cyclic polyether ester compound having three repeating units.

<Manufacturing example 12>
240 parts (1 mol) of 15-pentadecanolactone, 24.2 parts (0.04 mol) of "Kyoward 500", and aluminum perchlorate in an autoclave made of stainless steel with a stirrer and temperature control function. After adding 1 part (0.002 mol) of hydrate and sealing, the mixture was heated at 160 ° C. for 3 hours under reduced pressure to dehydrate. Then, the temperature was adjusted to 150 ° C., and 61 parts (1.05 mol) of propylene oxide was introduced into the autoclave while adjusting the gauge pressure to 1 to 3 kgf / cm ² G at 150 ° C. After introducing the total amount of PO, stirring was continued until the pressure reached 0.13 kgf / cm ² G, and the reaction between 15-pentadecanolactone and PO was carried out. The time required for the addition reaction of PO was 12 hours. Then, the temperature was adjusted to 180 ° C., and 220 parts (5 mol) of ethylene oxide was introduced into the autoclave while adjusting the gauge pressure to 1 to 3 kgf / cm ² at 180 ° C. After introducing the total amount of EO, stirring was continued until the pressure became 0.13 kgf / cm ² G, and the EO reaction was carried out. The time required for the addition reaction of EO was 7 hours. The catalyst was filtered off from the reaction mixture obtained after completing the EO addition reaction to obtain a cyclic polyether ester composition (A-11).
The obtained cyclic polyether ester compound (A-11) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound was analyzed. In the general formula (1), (A-11) is the cyclic polyether of the present invention in which R ¹ is a pentamethylene group, R ² is a methyl ethylene group, and n = 6 (EO 5 mol, PO 1 mol). It was a mixture containing an ester compound, a cyclic polyether ester compound having two repeating units represented by [R ¹ CO (OR ² ) _n O], and a cyclic polyether ester compound having three.

<Manufacturing example 13>
In a stainless steel autoclave with a stirrer and temperature control function, 240 parts (1 mol) of 15-pentadecanolactone, "Kyoward 500" [Kyowa Kagaku Kogyo Co., Ltd .: Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · 4H ₂ O] 24.2 parts (0.04 mol) was sealed put, and heated 3 hours at 160 ° C. under reduced pressure and dehydrated. Then, the temperature was adjusted to 180 ° C., and 264 parts (6 mol) of EO was introduced into the autoclave while adjusting the gauge pressure to be within the range of 1 to 5 kgf / cm ² at 180 ° C. After the total amount of EO was added, stirring was continued until the pressure reached 0.13 kgf / cm ² G, and the reaction between 15-pentadecanolactone and EO was carried out. The time required for the addition reaction of EO was 10 hours. Then, the catalyst was filtered off from the reaction mixture obtained by the addition reaction of EO to obtain a cyclic polyether ester composition (A-12).
The obtained cyclic polyether ester compound (A-12) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound was analyzed. In (A-12), in the general formula (1), R ¹ is a pentamethylene group, R ² is a methyl ethylene group, and n = 6, the cyclic polyether ester compound of the present invention, and further [R]. It was a mixture containing a cyclic polyether ester compound having two repeating units represented by ¹ CO (OR ² ) _n O] and a cyclic polyether ester compound having three repeating units.

<Manufacturing example 14>
A nonionic surfactant (B3-1) used in a comparative cleaning composition in which ethylene oxide and propylene oxide are added to n-hexadecylamine in the same manner as in Production Example 1 of JP2013-12204. Obtained.

<Manufacturing example 15>
73.6 parts of 1-tetradecanol and 2.0 parts of potassium hydroxide were put into a stainless steel autoclave equipped with a stirrer and a temperature control function, and after nitrogen substitution, the mixture was sealed and the temperature was raised to 140 ° C. While adjusting the pressure to 0.5 MPa or less at 140 ° C. with stirring, 229.6 parts of propylene oxide was added dropwise over 10 hours, and after aging for 3 hours, 696.8 parts of ethylene oxide was added over 15 hours. 1-Tetradecanol propylene oxide / ethylene oxide adduct (B3-2) was obtained by dropping the mixture and aging for 5 hours.

<Examples 1 to 39, Comparative examples 1 to 5>
The raw materials constituting the cleaning agent composition are put into a mixing tank equipped with a stirrer and a temperature control function in the amounts shown in Table 1, and stirred at 20 to 30 ° C. for 10 minutes to clean the cleaning agent composition (Example). 1 to 39 and Comparative Examples 1 to 5) were prepared.
As the cationic surfactant (B1-1) shown in Table 1, didecyldimethylammonium chloride [manufactured by Sanyo Chemical Industries, Ltd.] was used, and as the betaine-type amphoteric surfactant (B2-1). , Levon 105 [manufactured by Sanyo Chemical Industries, Ltd., containing 34% by weight of 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine], Sanded as an anionic surfactant (B4-1) Polyoxyethylene alkyl ether sodium sulfate manufactured by Sanyo Chemical Industries, Ltd. was used.

The cleaning agent compositions of Examples 1 to 39 and Comparative Examples 1 to 5 were evaluated for their detergency in hard water by the following methods, and the results are shown in Table 1.

(Washability in hard water)
0.3 g of each of the cleaning agent compositions of Examples 1 to 39 and Comparative Examples 1 to 5 is dissolved in 999.7 g of hard water having a total hardness of 71 as measured by the method described in JIS K 0101: 1998 Industrial Water Test Method. To the solution, 10 wet artificially contaminated cloths manufactured by the Washing Science Association, which have the stain composition shown in Table 2, were put into the solution, and the following was used using a targotometer [manufactured by Daiei Scientific Seiki Seisakusho Co., Ltd.] After washing and rinsing under the conditions of (1), the cloth was taken out and dried at 70 ° C. for 60 minutes using a gear oven "GPS-222" [manufactured by Espec Co., Ltd.] to obtain a test cloth. Next, using a spectrophotometric color difference meter "SpectroPhotometer SD5000" [manufactured by Nippon Denshoku Kogyo Co., Ltd.], the reflectance of this test cloth at 540 nm was measured at two places on the front and back for each test cloth (total). (20 points) were measured, the average value was calculated, and the cleaning rate (%) was calculated by the following (calculation formula 1). The higher the cleaning rate, the better the cleaning property.
[Cleaning conditions]
Time: 10 minutes, temperature: 25 ° C, rotation speed: 85 rpm
[Rinse condition]
Time: 1 minute, temperature: 25 ° C, rotation speed: 85 rpm
Cleaning rate (%) = [(RW-RS) / (RI-RS)] x 100 (calculation formula 1)
In the above (calculation formula 1), RI indicates the reflectance of the cleaning cloth, RW indicates the reflectance of the cleaning cloth, and RS indicates the reflectance of the contaminated cloth. The artificially contaminated cloth used was a wet artificially contaminated cloth (reflectance at 540 nm: 40 ± 5%) manufactured by the Laundry Science Association, which has the stain composition shown in Table 2.

＜生分解性試験＞
実施例１〜１２及び比較例４の洗浄剤組成物それぞれ１ｇを水９９９ｇに溶解させた溶液について、生物化学的酸素消費量（ＢＯＤ）および化学的酸素消費量（ＣＯＤ）を測定した。生物化学的酸素消費量（ＢＯＤ）はＪＩＳ Ｋ０１０２−１７、化学的酸素消費量（ＣＯＤ）はＪＩＳ Ｋ０１０２−２１及び３２．２にそれぞれ従い求めた。生分解度を以下の式（５）により求め、生分解性を評価した。
生分解度（％）＝（ＢＯＤ／ＣＯＤ）×１００ （５）
表３には、生分解度６０％以上を○、６０％未満を×で表した。

<Biodegradability test>
Biochemical oxygen demand (BOD) and chemical oxygen demand (COD) were measured for solutions in which 1 g of each of the cleaning agent compositions of Examples 1 to 12 and Comparative Example 4 was dissolved in 999 g of water. The biochemical oxygen demand (BOD) was determined according to JIS K0102-17, and the chemical oxygen demand (COD) was determined according to JIS K0102-21 and 32.2, respectively. The degree of biodegradability was determined by the following formula (5), and the biodegradability was evaluated.
Biodegradation (%) = (BOD / COD) x 100 (5)
In Table 3, the degree of biodegradation of 60% or more is indicated by ◯, and the degree of biodegradation of less than 60% is indicated by ×.

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

Claims (2)

A cleaning agent composition containing the cyclic polyether ester compound (A) represented by the general formula (1).

[In the formula, R ¹ is a tetradecamethylene group or a trimethylene group , R ² is an ethylene group and / or a methylethylene group , m is an integer of 2 to 3, and n is a number of 1 to 500. .. ] A claim containing at least one selected from the group consisting of a cationic surfactant (B1), a betaine-type amphoteric surfactant (B2), a nonionic surfactant (B3) and an anionic surfactant (B4). Item 2. The detergent composition according to Item 1, wherein the cationic surfactant (B1) is didecyldimethylammonium chloride and the betaine-type amphoteric surfactant (B2) is 2-alkyl-N-carboxymethyl-N-. It is hydroxyethyl imidazolinium betaine, the nonionic surfactant (B3) is n-hexadecylamine with ethylene oxide and propylene oxide added, and the anionic surfactant (B4) is polyoxyethylene alkyl. Detergent composition which is ether sodium sulfate.