JP3364608B2 - Builders and cleaners for cleaning agents - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a builder for detergents.
And cleaning agents. More specifically, it relates to a builder for detergents and a detergent which are excellent in cleaning mud stains.

[0002]

2. Description of the Related Art Alkali metal salts such as polyacrylic acid, polyitaconic acid and copolymers of acrylic acid and maleic acid have been known as builders for detergents. In addition, cleaning agents used for home clothing are generally mainly
Alkylbenzene sulfonic acid, alkyl sulfate,
Surfactants such as fatty acid amides, alkali metal salts of inorganic acids, polyoxyalkylated higher alcohols and alkylphenols are blended.

[0003]

However, the alkali metal salt of polycarboxylic acid has a problem that although it has improved detergency, it has poor compatibility with a surfactant.

[0004]

The present inventors have SUMMARY OF THE INVENTION is excellent in compatibility with the surfactant, the results so diligent studies to obtain a detergent with excellent clay soil detergency against including dirt, the The inventors of the present invention have found that the builder for detergents and detergents of the present invention are effective for these purposes, and arrived at the present invention. That is, the present invention is Ri Tona quaternary ammonium salt of a carboxyl group-containing polymer (A), the content of water 10-80
Containing the builder, detergent containing chromatic amount of water is 10 to 80 wt%; builder is for weight percent of the detergent of the carboxyl group-containing polymer It is composed of a quaternary ammonium salt (A) and has a solubility parameter of 8.0.
2 to 30% by mass of the builder, which is ˜12.0, and water
Detergent further contains the nonionic surfactant (B);;-containing organic amount is 10 to 80 wt% detergent carboxyl group-containing polymer A detergent containing a quaternary ammonium salt (A) as a builder, produced by adding an alkylene oxide (b1) to an aliphatic alcohol (a1), and containing a nonionic surfactant (B) satisfying the following and . Weight average molecular weight (Mw) and number average molecular weight (M
Ratio with n: Mw / Mn satisfies the following relational expression (3) or (4).

[Equation 7]   Mw / Mn ≦ 0.030 Ln (v) +1.010 (provided that v <10) (3)

## EQU00008 ## Mw / Mn.ltoreq.-0.026Ln (v) +1.139 (where v.gtoreq.10) (4) {where v is an alkylene oxide (b1) added per mol of the aliphatic alcohol (a1). The average number of added moles of is shown. } The distribution constant c obtained from the following equation (5)
Is 2.0 or less.

## EQU9 ## c = (v + n ₀ / n ₀₀ -1) / [Ln (n
₀₀ / n ₀ ) + n ₀ / n ₀₀ -1] (5) {where v is the same as in formula (3) or (4), n ₀₀ is the number of moles of the aliphatic alcohol (a1) used in the reaction, and n ₀ represents the number of moles of the unreacted aliphatic alcohol (a1). }

Examples of the carboxyl group-containing polymer in the present invention include polymers having α, β-unsaturated carboxylic acids as an essential constituent unit. Examples of the α, β-unsaturated carboxylic acids include monocarboxylic acids (eg (meth) acrylic acid etc.), dicarboxylic acids (eg maleic acid, fumaric acid, itaconic acid, citraconic acid etc.), dicarboxylic anhydrides (eg , Maleic anhydride, itaconic anhydride, citraconic anhydride, etc.) and dicarboxylic acid half-esters {half-esters of dicarboxylic acid and alkanol having 2 to 16 carbon atoms, carbitol or cellosolv, for example, maleic acid half-ester (maleic acid monoester Butyl ester, maleic acid monoethyl carbitol ester, etc.), fumaric acid half ester (fumaric acid monobutyl ester, fumaric acid monoethyl carbitol ester, etc.)}, and combinations thereof. Of these, preferred is acrylic acid.

Other copolymerizable monomers can be used as the structural unit in the polymer. Examples of the other monomer include, but are not limited to, the followings. (A) Aromatic ethylenically unsaturated monomer: styrene, α-
Styrenes such as methylstyrene, vinyltoluene and hydroxystyrene, halogen-substituted styrenes such as dichlorostyrene, vinylnaphthalene, etc .; (b) Aliphatic ethylenically unsaturated monomer having 2 to 20 carbon atoms: ethylene , Propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, olefins such as dodecene and octadecene, dienes such as butadiene and isoprene; (c) alicyclic ethylenically unsaturated monomers having 5 to 15 carbon atoms: Cyclopentadiene, pinene, limonene, indene, bicyclopentadiene, ethylidene norbornene, etc .; (d) alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms: methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate, etc. (E) an ester of an ethylenically unsaturated monomer having the hydroxyl group or the (poly) oxyalkylene group (molecular weight 44 to 2000) (the above α, β-unsaturated carboxylic acid):
Hydroxyalkyl (C2-6) (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate, polyethylene glycol (molecular weight 300) mono (meth) acrylate, polypropylene glycol (molecular weight 500) mono (meth ) (Poly) oxyalkylene groups such as acrylate, methyl alcohol ethylene oxide 10 mol adduct (meth) acrylate and lauryl alcohol ethylene oxide 30 mol adduct (meth) acrylate (molecular weight 44 to 2000, alkylene group having 2 to 4 carbon atoms). (Meth) acrylates having) and corresponding α, β-unsaturated carboxylic acid esters other than the corresponding (meth) acrylates; (f) amide-containing ethylenically unsaturated monomer: (meth) acrylic Amide, N-methylol (meth) acrylamide, etc .; (g) Sulfone group- or sulfate ester group-containing monomer: vinylsulfonic acid, (meth) allylsulfonic acid, 2-hydroxy-3- (meth) allyloxypropanesulfonic acid ,
Styrene sulfonic acid, α-methyl styrene sulfonic acid,
Sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropanesulfonic acid, 2-
Sulfonate-containing monomers such as (meth) acryloylamino-2,2-dimethylethanesulfonic acid and 2- (meth) acryloyloxyethanesulfonic acid, and sulfuric acid esterified products of polyoxyalkylene mono (meth) acrylate (the oxyalkylene Is a mixture of two or more kinds of oxyalkylene having 2 to 4 carbon atoms, and in the case of a mixture of two or more kinds, it may be random or block, and the number of added moles is usually 1 to 30).

In the polymer, as a constitutional unit,
The content of α, β-unsaturated carboxylic acid is usually 50 to 10
0 mol%, preferably 70 to 100 mol%, and the content of other monomers is usually 0 to 50 mol%, preferably 0.
~ 30 mol%.

The polymer can be obtained by radically polymerizing the above-mentioned monomer, and a radical polymerization initiator can be used in this case. Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) and 2,2′-azobis (2-methylbutyronitrile). 2,2'-azobis (2,4,4-trimethylpentane), dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis [2- (hydroxymethyl) propionitrile ], Azo compounds such as 1,1′-azobis (1-acetoxy-1-phenylethane); dibenzoyl peroxide, dicumyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, benzoyl peroxide , Lauroyl peroxide, organic peroxides such as persuccinic acid; Inorganic peroxides such as persulfate, perborate and hydrogen peroxide are used. it can. Further, a redox type initiator in combination with these and a reducing agent can be used. Examples of the reducing agent used for the redox type initiator include ascorbic acid (salt), rongalite, hypophosphorous acid (salt), sulfurous acid (salt), bisulfite (salt), ferrous salt and the like. Two or more radical polymerization initiators may be used in combination.
The amount of the radical polymerization initiator is usually 0.01 based on the total mass of the α, β-unsaturated carboxylic acid and / or other monomer.
-20% by mass, preferably 0.05-10% by mass, particularly preferably 0.1-2% by mass.

A chain transfer agent can be used when radically polymerizing the above-mentioned monomer.
For example, lauryl mercaptan, thioglycolic acid, mercaptoethanol, triethylene glycol dimercaptan and the like can be used. The amount of chain transfer agent is
It is usually 0.01 mol% to 10 mol%, preferably 0.05 to 3 mol% based on the total number of moles of the α, β-unsaturated carboxylic acid and / or other monomer.

The radical polymerization may be any of bulk polymerization, emulsion polymerization, suspension polymerization and solution polymerization.
Solution polymerization is preferred.

The polymerization temperature is 50 to 300 ° C, preferably 60 to 250 ° C. In the case of solution polymerization, the polymerization temperature may be a temperature below the boiling point of the polymerization solvent or above the boiling point. The temperature is preferably not lower than the boiling point of the polymerization solvent. Here, the boiling point means the boiling point at normal pressure.

The number average molecular weight Mn of the polymer by gel permeation chromatography (hereinafter abbreviated as GPC) is usually 1,000 to 100,000, preferably 3,000 to 30,000. The weight average molecular weight Mw by GPC is usually 1,10
0 to 110,000, preferably 3,300 to 3
It is 3,000. The acid value of the polymer is usually 200 to
It is 1,400, preferably 300 to 1,000.

[0013]

In the quaternary ammonium salt of the polymer, examples of the quaternary ammonium cation include trimethylethylammonium, triethylmethylammonium, trimethylhexylammonium, trimethyloctylammonium, tributyloctylammonium, trimethyldecylammonium and trimethyltetradecylammonium. , A tetraalkylammonium having 1 to 18 carbon atoms in the alkyl group such as trimethylcetylammonium and monomethyltrioctylammonium; a cycloalkyl group such as N, N-dimethylcyclohexylammonium and N, N-diethylcyclohexylammonium Cycloalkyldialkylammonium having 4 to 12 carbon atoms and 1 to 6 carbon atoms of the alkyl group; trihydroxy Carbon number of 2 to 8 and an alkyl group carbon number of hydroxyalkyl groups such as hexyl ammonium to chill include trihydroxy alkyl alkylammonium 1-6.

Of these salts (A), preferred are:
Salts composed of quaternary ammonium cations having an alkyl group having 2 to 12 carbon atoms, particularly preferably triethylmethylammonium salt, triethyloctylammonium salt, trimethyldecylammonium salt, trimethylhexylammonium salt and trimethyloctylammonium salt.

[0016]

The quaternary ammonium salt of the polymer is prepared by a conventional method, for example, a tertiary amine and an alkyl halide or an aryl halide (for example, a halide having 1 to 10 carbon atoms such as methyl chloride, ethyl bromide and brombenzene). To give a quaternary ammonium halide, which is then reacted with an alkali hydroxide (eg sodium hydroxide, potassium hydroxide) to give a quaternary ammonium salt hydroxide, which is then used to neutralize the polymer. Method: A method in which a tertiary amine is reacted with a dialkyl (C 1-6) carbonate (for example, dimethyl carbonate, diethyl carbonate) to obtain a quaternary ammonium carbonate, and then the polymer is anion-exchanged. Obtainable. Neutralization or anion exchange can be carried out in solution using the same solvent as in the case of neutralization of organic amines, and when a nonionic surfactant is used, as in the case of organic amines, The nonionic surfactant can be mixed either before or after neutralization or anion exchange. As a specific method for anion-exchanging the polymer with a quaternary ammonium carbonate, for example, in the case of a salt of polyacrylic acid and trimethyloctylammonium, a pressure-resistant container containing at least 1 mol of dimethyloctylamine and at least 1 mol of dimethyl carbonate and methanol. And a reaction solution at about 120 ° C. under a pressure of about 5 kg / cm ² to obtain a methanol solution of trimethyloctyl ammonium carbonate. Then, a methanol solution of trimethyloctylmethyl carbonate is gradually added to the aqueous solution of polyacrylic acid at 80 to 90 ° C., and the generated carbon dioxide and methanol are distilled off to obtain an aqueous solution of trimethyloctyl ammonium salt of polyacrylic acid. The degree of neutralization or anion exchange is usually 3
It is 0 to 100%, preferably 60 to 100%.

Of the polymer The solubility parameter of the quaternary ammonium salt (A) (hereinafter referred to as SP value) is
From the viewpoint of solubility in the detergent, it is usually 8.0 to 12.
It is 0, preferably 8.5 to 11.5. 8.0-1
When it is in the range of 2.0, the detergency becomes better, and the dissolution stability in the detergent becomes better. The SP value can be expressed by the general formula (6). General formula δ = (ΔH / V) ^1/2 (6) However, in the formula (6), δ is the SP value, ΔH is the heat of molar evaporation (cal), and V is the molar volume (cm ³ ). here,
The SP value is "POLYMER ENGINEERING
ANDFEBRUARY, 1974, Vol. 1
4, No. 2, ROBERT F. FEDORS. (1
51-153) ”, the heat of molar evaporation of the atomic groups (Δe
_i ) total (ΔH) and molar volume (Δv _i ) total (V)
Can be calculated from

[0019]

Examples of the nonionic surfactant (B) include alkylene oxide addition type nonionic surfactant (b-1) and polyhydric alcohol type nonionic surfactant (b-2). Examples of (b-1) include higher alcohols (having 8 to 18 carbon atoms) alkylene (having 2 to 4 carbon atoms) oxides (having 1 to 30 moles of addition per active hydrogen), and alkyls (having 1 to 12 carbon atoms). ) Phenol ethylene oxide (additional mol number of 1 to 30 per active hydrogen)
Addition product, fatty acid (C8 to C18) ethylene oxide (addition mol number per active hydrogen 1 to 30) adduct,
Polypropylene glycol (molecular weight 200-4000)
Ethylene oxide (1 to 50 moles added per active hydrogen) adduct, and polyoxyethylene (1 to 30 moles added per active hydrogen) alkyl (1 to 20 carbon atoms) allyl ether, sorbitan mono Multivalent (2 to 8 valent or higher) alcohols (2 to 30 carbon atoms) such as laurate ethylene oxide (addition mole number 1 to 30) adduct and sorbitan monooleate ethylene oxide (addition mole number 1 to 30) adduct. ) Fatty acids (8 carbon atoms
.About.24) ester ethylene oxide adduct (addition mole number per active hydrogen 1 to 30) and the like.
Examples of (b-2) include fatty acids (carbons having 2 to 30 carbon atoms) of polyvalent (2 to 8 valent or higher) alcohols such as glycerin monostearate, glycerin monooleate, sorbitan monolaurate and sorbitan monooleate. Number 8
~ 24) ester, lauric acid monoethanolamide,
Examples thereof include fatty acid alkanolamides such as lauric acid diethanolamide.

Of these, the compound (b-1) is preferable, the compound represented by the following general formula (1) is more preferable, and the compound represented by the following general formula (2) is particularly preferable. _{^{RO- (A 1 O) p -H}} (1)

[Chemical 2]

In the above general formula (1) or (2),
R is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, and preferably an aliphatic hydrocarbon group having 10 to 18 carbon atoms. When the carbon number is in the range of 8 to 18, better detergency can be obtained. Specifically, saturated aliphatic hydrocarbon groups such as octyl group, 2-ethylhexyl group, decyl group, lauryl group, myristyl group, palmityl group, stearyl group, 1,1-dimethyloctyl group; octenyl group, decenyl group, Unsaturated aliphatic hydrocarbon groups such as dodecenyl group, tridecenyl group, pentadecenyl group, oleyl group and linoleyl group (alkenyl group, alkadienyl group, alkatrienyl group and alkapolyenyl group); ethylcyclohexyl group, propylcyclohexyl group, octyl group Examples thereof include cycloaliphatic hydrocarbon groups such as cyclohexyl group and nonylcyclohexyl group. These aliphatic hydrocarbon groups may be linear or branched.

In the general formula (1), A ¹ has 2 carbon atoms.
4 represents an alkylene group, specifically, an ethylene group,
A propylene group and a butylene group are mentioned. (A
^{When the number of 1} O) units is 2 or more, it may be single, random or block. Moreover, p is an integer of 1 to 30, and preferably 6 to 20. When p is in the range of 1 to 30, better detergency can be obtained.

In the general formula (2), A ² is an alkylyl group having 3 or 4 carbon atoms, and n is 0 or an integer of 1 to 12, preferably 1 to 10. Also, q is 1 to
It is an integer of 16, and preferably 2 to 12. n is 0
Alternatively, when it is in the range of 1 to 8, and when q is in the range of 1 to 16, further good detergency can be obtained. Also, m
Is 0 or an integer of 1 to 6, and preferably 1 to 4. In addition, r is 0 or an integer of 1 to 15, preferably 1 to 8. When m is 0 or in the range of 1 to 6, and when r is 0 or in the range of 1 to 15, the fluidity of the detergent is further improved. Also, (m + n + q)
Is an integer of 1 to 30, preferably 6 to 20. (M
When + n + q) is in the range of 1 to 30, better detergency can be obtained. Also, (n + q) / (m + n + q + r)
Is 0.5 to 1.0, preferably 0.7 to 0.9
Is. If it is in the range of 0.5 to 1.0, even better detergency can be obtained.

Of the compounds represented by the general formula (2), the alkylene oxide (b1) is added to the aliphatic alcohol (a1).
Produced by adding GPC to the weight average molecular weight (M
w) and the number average molecular weight (Mn) by GPC (Mw)
/ Mn) satisfies the following relational expression (3) or (4), and the distribution constant c obtained from the following general expression (5) is 2.
A compound of 0 or less is particularly preferable.

[Equation 13] Mw / Mn ≦ 0.030 Ln (v) +1.010 (provided that v <10) (3)

Mw / Mn ≦ −0.026Ln (v) +1.139 (where v ≧ 10) (4) However, in the formulas (3) and (4), v is an aliphatic alcohol (a1). The average number of moles of added alkylene oxide (b1) per mole is shown. Also, Ln
(V) shows the natural logarithm of v. Aliphatic alcohol (a
As 1), an alcohol having an aliphatic hydrocarbon group having 8 to 18 carbon atoms can be used. Al is preferably an alcohol having an aliphatic hydrocarbon group having 10 to 18 carbon atoms. Specific examples thereof include alcohols having an aliphatic hydrocarbon group exemplified in the description of R in the general formula (1) or (2). Also, as the alkylene oxide (b1),
Ethylene oxide, propylene oxide and butylene oxide may be used and may be in the form of addition alone, random, block or combinations thereof.

[0026]

## EQU15 ## c = (v + n ₀ / n ₀₀ -1) / [Ln (n ₀₀ / n ₀ ) + n ₀ / n ₀₀ -1] (5) However, in the expression (5), v is the expression (3). ) Or (4), n ₀₀ represents the number of moles of the aliphatic alcohol (a1) used in the reaction, and n ₀ represents the number of moles of the unreacted aliphatic alcohol (a1). More preferably, c is 1.0 or less. When c is 2.0 or less, the content of unreacted aliphatic alcohol is extremely small, and more favorable surfactant activity can be obtained.

The above alkylene oxide addition type nonionic surfactant (b-1) can be produced by using a usual alkylene oxide addition reaction, and is 70 to 70% under a reaction catalyst.
It can be produced by adding ethylene oxide, propylene oxide or butylene oxide to alcohol at 200 ° C. by a specific addition method. For example, an alkali (eg, KOH) or acid (eg, BF ₃ etc.) catalyst is added to a higher alcohol having 8 to 18 carbon atoms, a mixture of ethylene oxide and propylene oxide is randomly added under a nitrogen atmosphere, and then ethylene oxide is blocked. It can be prepared by addition followed by block addition of propylene oxide.

As the aliphatic hydrocarbon alcohol having 8 to 18 carbon atoms, saturated or unsaturated primary, secondary or tertiary alcohol can be used. Of these, preferred is a saturated aliphatic primary alcohol. 10 to 18 carbon atoms
Is preferred. 1 or 2 aliphatic hydrocarbon alcohols
Any mixture of at least one species may be used.

Specific examples of the saturated aliphatic primary alcohol include decyl alcohol, lauryl alcohol, stearyl alcohol, and alcohols synthesized by using a Ziegler catalyst [eg, trade name ALFOL 1214 (CON.
DEA) and the like], alcohols produced by oxo synthesis [for example, trade names Dobanol 23, 25, 45 (manufactured by Mitsubishi Yuka), tridecanol (manufactured by Kyowa Hakko), Oxochol 1213, 1215, 1415 (manufactured by Nissan Kagaku). , Diadol 115-L, 115H, 135 (manufactured by Mitsubishi Chemical)] and the like. As the saturated aliphatic secondary alcohol, those obtained by an oxidation method using n-paraffin as a raw material, Oil Chemistry Vol. 21, No. 5, pp. 233-242 (1
972) and the like. Examples of the unsaturated aliphatic alcohols include oleyl alcohol, alcohols obtained by a reduction method [eg, trade name Hicol 40, 60 (manufactured by Kyowa Yushi Co., Ltd.)
(Manufactured by New Japan Rika)] and the like.

As a method for producing a compound satisfying the above formula (3) or (4) and having a distribution constant c determined from the above formula (5) of 2.0 or less, a general catalyst (lithium, sodium, A method of adding an alkylene oxide to an aliphatic alcohol using a catalyst capable of narrowing the molecular weight distribution compared with a hydroxide or carbonate of an alkali metal such as potassium or cesium, or a basic catalyst such as an amine compound. Examples include a method of adding 1 to 3 mol of alkylene oxide to an aliphatic alcohol using a general catalyst, removing unreacted alcohol by distillation or the like, and then adding an alkylene oxide using a general catalyst. The production method is preferred. As a catalyst for narrowing the molecular weight distribution, a calcined magnesium oxide-containing compound (JP-A-1-164437), a calcined hydrotalcite (JP-A-2-71841), a perchlorate (US Pat. No. 4,112). , 231),
Examples thereof include a catalyst selected from perhalogen acid (salt), sulfuric acid (salt), nitric acid (salt), and divalent or trivalent metal alcoholate.

As the cationic surfactant (C), the fourth
Examples thereof include a quaternary ammonium salt type or amine salt type cationic surfactant. Examples of the quaternary ammonium salt type cationic surfactant include tertiary amines and quaternizing agents (alkyl halides such as methyl chloride, methyl bromide, ethyl chloride and benzyl chloride, dimethyl sulfate, dimethyl carbonate, ethylene oxide). )
Compounds and the like obtained by the reaction with can be used, for example, lauryl trimethyl ammonium chloride, didecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium bromide, stearyl trimethyl ammonium bromide, lauryl dimethyl benzyl ammonium chloride (benzalkonium chloride), cetyl pyridinium chloride , Polyoxyethylene trimethyl ammonium chloride, stearamidoethyl diethyl methyl ammonium methosulfate and the like.

As the amine salt type cationic surfactant,
Neutralize primary to tertiary amines with inorganic acids (hydrochloric acid, nitric acid, sulfuric acid, hydriodic acid, etc.) or organic acids (acetic acid, formic acid, oxalic acid, lactic acid, gluconic acid, adipic acid, alkylphosphoric acid, etc.) The compound obtained by can be used, for example,
Examples of the primary amine salt type include aliphatic higher amines (laurylamine, stearylamine, cetylamine,
Inorganic or organic acid salts of hardened tallow amine, higher amines such as rosin amine; higher fatty acid (stearic acid, oleic acid, etc.) salts of lower amines, and the like. Examples of the secondary amine salt type include inorganic acid salts or organic acid salts such as ethylene oxide adducts of aliphatic amines. Further, examples of the tertiary amine salt type include, for example, aliphatic amines (triethylamine,
Ethyldimethylamine, N, N, N ′, N′-tetramethylethylenediamine, etc.), alicyclic amine (N-methylpyrrolidine, N-methylpiperidine, N-methylhexamethyleneimine, N-methylmorpholine, 1,8 -Diazabicyclo (5,4,0) -7-undecene etc.),
Inorganic or organic acid salts of nitrogen-containing heterocyclic aromatic amines (4-dimethylaminopyridine, N-methylimidazole, 4,4'-dipyridyl, etc.); triethanolamine monostearate, stearamidoethyldiethylmethylethanolamine Examples thereof include inorganic acid salts or organic acid salts of tertiary amines. As the cationic surfactant (C), one kind or a mixture of two or more kinds thereof can be used, and preferably one or more kinds of compounds selected from the group consisting of the compounds represented by the formulas (6) to (9). is there.

[0033]

[Chemical 3]

[0034]

[Chemical 4]

[0035]

[Chemical 5]

[0036]

[Chemical 6]

However, in the formulas (6) to (9), R ¹ , R ² and R ³ are a hydrogen atom or an alkyl group having 1 to 24 carbon atoms,
An alkenyl group or a β-hydroxyalkyl group, preferably an alkyl group or alkenyl group having 1 to 18 carbon atoms. Specifically, as the alkyl group, methyl group, ethyl group, propyl group, hexyl group, octyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, isoundecyl group, dodecyl group. Group, isododecyl group, tridecyl group, isotridecyl group, tetradecyl group, isotetradecyl group, pentadecyl group, isopentadecyl group, hexadecyl group, isohexadecyl group, octadecyl group, isooctadecyl group, and the alkenyl group, Examples thereof include an octenyl group, a decenyl group, a dodecenyl group, a tetradecenyl group, a hexadecenyl group and an octadecenyl group. Further, as the β-hydroxyalkyl group, a 2-hydroxyethyl group,
Examples thereof include 2-hydroxypropyl group and 2-hydroxybutyl group.

R ⁴ and R ⁵ are alkyl groups having 1 to 24 carbon atoms, hydroxyalkyl groups, benzyl groups or formula:
(A ¹ O) _n -Z {where A ¹ is an alkylene group having 2 to 4 carbon atoms (for example, ethylene group, propylene group, butylene group), Z is a hydrogen atom or an acyl group, and n is an integer of 1 to 50. , Preferably an integer of 5 to 30},
Preferred is an alkyl group having 1 to 4 carbon atoms or a benzyl group. Specifically, a methyl group, an ethyl group, a propyl group,
Examples thereof include an isopropyl group, a butyl group, an isobutyl group and a sec-butyl group.

R ⁶ is an alkyl group having 1 to 36 carbon atoms, an alkenyl group or a β-hydroxyalkyl group, preferably an alkyl group or alkenyl group having 8 to 24 carbon atoms. Specific examples thereof include an eicosyl group, an isoeicosyl group, and an eicosenyl group, in addition to the groups similar to R ¹ , R ² and R ³ .

Y is an alkyl group having 1 to 36 carbon atoms,
Alkenyl group, β-hydroxyalkyl group, formula: R ⁴ C
A group represented by O ₂ CH ₂ — (wherein R ⁴ is the same as above) or a group represented by the formula: R ⁴ OCH ₂ — (wherein R ⁴ is the same as above), preferably It is an alkyl group or an alkenyl group having 1 to 18 carbon atoms. Specifically, R ¹ and R ²
And R3 are the same groups.

X ⁻ is a counter ion and is a halogen ion (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), a hydroxy ion, a carbonate or sulfate ester ion having an alkyl group having 1 to 4 carbon atoms, and a carbon atom. One or more anions selected from the group consisting of a carboxylate ion and a sulfonate ion having an alkyl group or an alkenyl group of the formulas 1 to 24 can be mentioned.

The compound represented by the formula (6) is, for example,
1-2 carbon atoms such as laurylamine and stearylamine
Primary amine having 4 alkyl group, alkenyl group or β-hydroxyalkyl group, dilaurylamine,
A secondary amine having an alkyl group having 1 to 24 carbon atoms such as distearylamine, an alkenyl group or a β-hydroxyalkyl group, or an alkyl group having 1 to 24 carbon atoms such as trimethylamine, lauryldimethylamine, dimethylstearylamine, A tertiary amine having an alkenyl group or a β-hydroxyalkyl group is converted to a halogen acid such as hydrochloric acid, bromic acid or iodic acid, or formic acid, acetic acid,
1 carbon atom such as propionic acid, lauric acid, stearic acid
It can be obtained by a method of neutralizing with a carboxylic acid of -24 or the like.

Further, trimethylamine, lauryldimethylamine, dimethylstearylamine and the like have 1 to 1 carbon atoms.
24 alkyl groups, tertiary amine having an alkyl group or β-hydroxyalkyl group is methyl chloride,
It can be obtained by a method in which an alkylating agent such as benzyl chloride, dimethyl carbonate, diethyl carbonate or dimethyl sulfate is heated and reacted under pressure.

Further, primary amines having an alkyl group, an alkenyl group or a β-hydroxyalkyl group having 1 to 24 carbon atoms such as lauryl amine and stearyl amine, or 1 to 24 carbon atoms such as dilauryl amine and distearyl amine. Of a secondary amine having an alkyl group, an alkenyl group or a β-hydroxyalkyl group under alkaline conditions with a tertiary amine obtained by adding ethylene oxide to a halogen acid such as hydrochloric acid, bromic acid or iodic acid, or It can be obtained by a method of neutralizing with a carboxylic acid having 1 to 24 carbon atoms such as formic acid, acetic acid, propionic acid, lauric acid and stearic acid.

The compound represented by the formula (7) is obtained by heating pyridine with an alkylating agent having 1 to 24 carbon atoms such as methyl chloride, octyl chloride, stearyl chloride, oleyl bromide and hydroxyethyl bromide under pressure. It can be obtained by reacting.

The compound represented by the formula (8) is obtained by, for example, heating and condensing a fatty acid having 1 to 36 carbon atoms such as lauric acid and stearic acid with triethanolamine to form an ester type tertiary amine. It can be obtained by a method of neutralizing with an acid such as hydrochloric acid or acetic acid, or a method of reacting the above ester type tertiary amine by heating methyl chloride, dimethyl carbonate or dimethyl sulfuric acid under pressure.

The compound represented by the formula (9) is, for example, an amide-type third compound obtained by heat-condensing a fatty acid having 1 to 36 carbon atoms such as lauric acid and stearic acid with N, N-diethylethylenediamine. It can be obtained by a method of neutralizing a primary amine with an acid such as hydrochloric acid or acetic acid, a method of reacting the above amide type tertiary amine with methyl chloride, dimethyl carbonate or dimethyl sulfuric acid under heating under pressure. In addition, in order to make the counter ion X ⁻ of formulas (6) to (9) a hydroxy ion, a compound in which X ⁻ is a halogen ion is prepared,
It can be obtained by adding silver hydroxide to this and heating.

The low molecular weight polyvalent carboxylic acid constituting the organic amine salt or quaternary ammonium salt (D) of the low molecular weight polyvalent carboxylic acid has a molecular weight of usually 700 or less, preferably 500 or less, and one molecule. Examples thereof include aliphatic polycarboxylic acids and aromatic polycarboxylic acids having usually 2 to 8 carboxyl groups. A hydroxyl group and an amino group may be contained as groups other than the carboxyl group. Specific examples of low molecular weight polycarboxylic acids include oxalic acid, malonic acid, succinic acid, butanetricarboxylic acid, adipic acid, maleic acid, fumaric acid, itaconic acid, aconitic acid, phthalic acid, trimellitic acid, citric acid. , Malic acid, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NT
A), aspartic acid and the like. In addition, examples of the organic amine in the case of forming the organic amine salt of the low molecular weight polyvalent carboxylic acid include the above-mentioned aliphatic amine, alicyclic amine or alkanolamine, or alkylene oxide adducts thereof. In the quaternary ammonium salt of the low molecular weight polyvalent carboxylic acid, examples of the quaternary ammonium cation include the above-mentioned quaternary ammonium cations.

The content of (A) in the detergent in the present invention is usually 0 or 1 to 30 based on the total weight of the detergent.
%, Preferably 0 or 2 to 20% by mass, more preferably 0 or 3 to 15% by mass. Also, (B)
The content of is usually 10 to 9 based on the total mass of the detergent.
It is 5% by mass, preferably 20 to 80% by mass, more preferably 30 to 60% by mass. Of the content of (B),
The content of the compound represented by the general formula (1) or (2) is preferably 85% by mass or more based on the content of (B), and more preferably the content of the compound represented by the general formula (2) is ( 85% by mass or more based on the content of B), particularly preferably the distribution constants satisfying the relational expressions (3) and (4) among the compounds represented by the general formula (2) and obtained from the general formula (5) The content of the compound in which c is 2.0 or less is 85% by mass or more based on the content of (B).

The content of (C) is usually 0 or 0.01 to 10% by mass, preferably 0 or 0.05 to 5% by mass, based on the total mass of the detergent. The content of (D) is usually 0 or 0. 0 based on the total mass of the detergent.
It is 1 to 20% by mass, preferably 0 or 1 to 15% by mass.

The content of water is usually 2 to 80% by mass, preferably 10 to 60% by mass, based on the total mass of the detergent. In addition, (A), (B),
In addition to (C) and water, other components can be contained in an amount of 0 to 50 mass% based on the total mass of the detergent.

As other components, anionic surfactants {alkyl (C1-20) ether sulfates,
0 to 15% by mass of a sulfated or carboxymethylated product of an ethylene oxide adduct of an aliphatic (carbon number 1 to 20) alcohol (additional mole number 1 to 30), other builder (caustic soda, soda ash, ammonia, 0 to 5% by mass of alkali builder such as triethanolamine and sodium tripolyphosphate, fluorescent agent, bleaching agent, softening agent, enzyme,
0-5% by weight of germicide, fragrance, colorant, etc., hydrophilic solvent (methanol, ethanol, isopropyl alcohol,
Ethylene glycol, propylene glycol, etc.)
˜20% by mass, and 0 to 5% by mass of an antifoaming agent (silicone antifoaming agent, pluronic or polyoxyarlene antifoaming agent, mineral oil antifoaming agent, etc.) can be contained.

The cleaning agent of the present invention is particularly useful for cleaning natural fibers, synthetic fiber and mixed spun and knitted fibers thereof. Examples of the natural fiber include cotton, hemp, and wool. Examples of the synthetic fiber include regenerated cellulose fiber such as rayon and acetate, polyester, polyamide fiber, synthetic fiber such as acrylic and spandex. These mixed-spun mixed woven fibers include cotton and hemp and other fibers (wool, polyester, polyamide, acrylic, etc.), wool and other fibers (polyester, polyamide, acrylic, etc.), polyester fibers and other fibers (rayon, Acetate, polyamide, acrylic, spandex, etc.), polyamide fiber and other fibers (rayon, acetate, acrylic, spandex, etc.).

The cleaning agent of the present invention is usually 0.001 g / L.
Used at concentrations ranging from ˜5 g / L.

The bath ratio is not particularly limited, but is usually 1: 4 to.
It is 1:40, preferably 1: 6 to 1:30.

The washing temperature can be arbitrarily selected depending on the type of fiber to be applied, but is usually 5 to 80 ° C, preferably 20 to 50 ° C.

The cleaning agent of the present invention can be used not only as a cleaning agent for clothing but also as an industrial cleaning agent, for example, as a cleaning agent for fiber refining agents, soaping agents and the like.

When the cleaning agent of the present invention is used for cleaning, there is no particular limitation on the cleaning method.
In the washing machine and industrial use, it can be used for batch treatment with a jet dyeing machine, continuous treatment with a continuous refining device, and the like. Among them, it is suitable as a cleaning agent for washing using a washing machine of a method such as a centrifugal washing method which causes little damage to the laundry. The centrifugal washing method is a new washing method in which a "water flow" is created by "centrifugal force" by rotating the tub itself of a washing machine, and stains are removed by the force of water passing through laundry. For example,
Matsushita Electric Industrial Co., Ltd. “Centrifugal washing machine NA-800
P ”.

[0059]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. In addition, below, a part and% show a mass part and mass%. The conditions for measuring the molecular weight of the carboxyl group-containing polymer by GPC are as follows. <GPC measurement conditions> Model: Waters 510 (manufactured by Japan Waters Limited) Column: TSK gel G5000pwXL TSK gel G3000pwXL (both manufactured by Tosoh Corporation) Column temperature: 40 ° C Detector: RI Solvent: 0.5% sodium acetate・ Water / methanol (volume ratio 70/30) Flow rate: 1.0 ml / min Sample concentration: 0.25% Injection volume: 200 μl Standard: Polyoxyethylene glycol (manufactured by Tosoh Corporation; TSK STANDARD POLYETHYLENE OXIDE) Data processing Device: SC-8010 (manufactured by Tosoh Corporation)

The conditions for measuring the molecular weight of the nonionic surfactant (B) by GPC are as follows. <GPC measurement conditions> Model: HLC-8120 (manufactured by Tosoh Corporation) Column TSK gel SuperH4000 TSK gel SuperH3000 TSK gel SuperH2000 (both manufactured by Tosoh Corporation) Column temperature: 40 ° C Detector: RI solvent: Tetrahydrofuran Flow rate: 0 .6 ml / min Sample concentration: 0.25% Injection volume: 10 μl Standard: Polyoxyethylene glycol (manufactured by Tosoh Corporation; TSK STANDARD POLYETHYLENE OXIDE) Data processing device: SC-8020 (manufactured by Tosoh Corporation)

The gas chromatography (hereinafter abbreviated as GC) measurement conditions used for measuring the concentration of the unreacted aliphatic alcohol of the nonionic surfactant are as follows. <GC measurement conditions> Model: Gas chromatograph GC-14B (manufactured by Shimadzu Corporation) Detector: FID column: Glass column (inner diameter = about 3 mm, length = about 2 m) Column packing material: Silicone GE SE-30 5% column Temperature: Raised from 90 ° C to 280 ° C. Temperature rising rate = 4 ° C / min Carrier gas: Nitrogen Sample: 50% acetone solution Injection volume: 1 μl Quantification: Aliphatic alcohol having 2 or 3 less carbon atoms than the aliphatic alcohol used was used as an internal standard substance. It was quantified.

Example 1 420 parts of isopropyl alcohol and 1 part of water were placed in a pressure resistant reactor.
20 parts were charged, the atmosphere was replaced with nitrogen, the vessel was sealed, and the temperature was raised to 100 ° C. 77 parts of acrylic acid with stirring for 3 hours, 228 parts of acrylic acid, 4 parts of chain transfer agent (triethylene glycol dimercaptan), 2 parts of sodium hypophosphite dihydrate and ferrous chloride tetrahydrate 0.7 parts of the homogeneous mixture was added dropwise over 2 hours, and 50 parts of sodium persulfate 6% aqueous solution was added dropwise over 3.5 hours (simultaneously started under appropriate conditions). After the completion of dropping, add 3 parts of 35% hydrogen peroxide aqueous solution to 100 ° C.
After stirring for 1 hour, a polymer (a) having a polymerization rate of 99.9% was obtained. The weight average molecular weight of this product by GPC is 10,
000, the number average molecular weight by GPC was 7,800. In another pressure-resistant container, 195 parts of methanol and 586 parts of dimethyl carbonate were charged, the atmosphere was replaced with nitrogen, and the container was sealed.
The temperature was raised to ° C. With stirring, 219 parts of triethylamine was added dropwise, and the mixture was stirred at 120 ° C. for 2 hours to obtain a methanol solution of triethylmethylammonium methyl carbonate (b). 60% methanol solution of (b) obtained here 7
07 parts and 400 parts of polymer (a) are mixed (100% neutralization)
After that, isopropyl alcohol, methanol and dimethyl carbonate are distilled off at 100 ° C. under normal pressure to remove water 58
0 part was added to obtain a 45% aqueous solution of polyacrylic acid triethylmethylammonium salt. This, nonionic surfactant (B) shown in Table 2, triethanolamine citrate, propylene glycol, alcalase 2.5L
A cleaning agent was prepared with the compounding amounts shown in Table 4 using water and water.

Examples 2, 3, 9 to 24 Same as Example 1 except that the polyacrylic acid triethylmethylammonium salt of Example 1 was used and the nonionic surfactant (B) was changed as shown in Table 2. Then, a cleaning agent was prepared with the compounding amounts shown in Tables 4 to 6.

Examples 4, 5, 6, 7 Using the polymer (a) obtained in Example 1, the neutralization salt and the degree of neutralization were changed as shown in Table 1, and the nonionic surfactant (B )
In the same manner as in Example 1 except that was changed as shown in Table 2, a detergent was prepared with the compounding amounts shown in Table 4.

Example 8 The polymer (a) obtained in Example 1 was neutralized with dimethylhexylamine. In addition to this, the nonionic surfactant (B) described in Table 2, triethylmethylammonium citrate salt,
A cleaning agent was prepared with propylene glycol, 2.5 L of Alcalase and water in the compounding amounts shown in Table 4.

Example 25 370 parts of isopropyl alcohol and 1 part of water in a pressure resistant reactor.
70 parts were charged, the atmosphere was replaced with nitrogen, the vessel was sealed, and the temperature was raised to 100 ° C. With stirring, 264.9 parts of acrylic acid, 40.1 parts of 2-acrylamido-2-methylpropanesulfonic acid, and 80 parts of a 4% aqueous solution of sodium persulfate were added dropwise from separate containers over 3 hours (at the same time). Start dripping). After the dropping was completed, 3 parts of 35% hydrogen peroxide aqueous solution was added, and 10
The mixture was stirred at 0 ° C for 1 hour to obtain a copolymer (c) having a polymerization rate of 99.9%. The weight average molecular weight of this product by GPC was 8,000 and the number average molecular weight was 5,600. After mixing 707 parts of a 60% methanol solution of triethylmethylammonium methyl carbonate (b) obtained in Example 1 and 174 parts of copolymer (c) (100% neutralization),
Isopropyl alcohol, methanol, and dimethyl carbonate were distilled off at 100 ° C. under normal pressure to obtain an aqueous solution of polyacrylic acid triethylmethyl ammonium salt. Using this, the nonionic surfactant (B) described in Table 2, triethylmethylammonium citrate salt, propylene glycol, 2.5 L of alcalase and water, a cleaning agent was prepared in a compounding amount described in Table 6.

Example 26 As described in Table 6 except that the polyacrylic acid triethylmethylammonium salt of Example 5 was used and the nonionic surfactant (B) was changed as shown in Table 2, A cleaning agent was prepared with the compounding amount of.

Example 27 As described in Example 6 except that the polyacrylic acid trimethyloctyl ammonium salt of Example 6 was used and the nonionic surfactant (B) was changed as shown in Table 2, A cleaning agent was prepared with the compounding amount of.

Examples 28 to 30 Polyacrylic acid trimethyldecyl ammonium salt of Example 7, nonionic surfactant (B) shown in Table 2, citric acid, trimethyloctyl ammonium salt, propylene glycol, alcalase 2.5 L and A cleaning agent was prepared using water and the compounding amount shown in Table 6.

Example 31 Stearylamine was reacted with methyl chloride to give a cationic surfactant (c1, in the formula (6), R ¹ = R ² =
^{R 3 = H, R 4 =} C 18 H 37, X - = Cl -) was obtained. Using the cationic surfactant (c1) and the polyacrylic acid triethylmethylammonium salt of Example 1, the nonionic surfactant (B) shown in Table 2, citric acid triethanolamine salt, propylene glycol, 2.5 L of alcalase and A cleaning agent was prepared using water and the compounding amounts shown in Table 7.

Example 32 Dimethyl stearylamine was reacted with dimethyl carbonic acid to give a cationic surfactant (c2, in the formula (6), R ¹ =
^{_{C 18 H 37, R 2 =}} R 3 = R 4 = CH 3, X - = CH 3 CO 3 -)
Got Using the cationic surfactant (c2) and the polyacrylic acid triethylmethylammonium salt of Example 1, the nonionic surfactant (B) described in Table 2, triethanolamine citrate salt, propylene glycol, alcalase 2.5 L and A cleaning agent was prepared using water and the compounding amounts shown in Table 7.

Example 33 Pyridine was reacted with octyl chloride to give a cationic surfactant (c3, in the formula (7), Y = C ₈ H ₁₇ , X ^−).
= Cl ^-) was obtained. Using the cationic surfactant (c3) and the polyacrylic acid triethylmethylammonium salt of Example 1, the nonionic surfactant (B) shown in Table 2, citric acid triethanolamine salt, propylene glycol, alcalase 2.5 L and A cleaning agent was prepared using water and the compounding amounts shown in Table 7.

Example 34 Caprylic acid was reacted with triethanolamine and then reacted with dimethyl carbonate to obtain a cationic surfactant (c4, in the formula (8), R ⁵ = CH ₃ , R ⁶ = C ₇ H ₁₅ , ^X - = C
H3CO3 ⁻ ) was obtained. Using the cationic surfactant (c4) and the polyacrylic acid triethylmethylammonium salt of Example 1, the nonionic surfactant (B) shown in Table 2, citric acid triethanolamine salt, propylene glycol, 2.5 L of alcalase and A cleaning agent was prepared using water and the compounding amounts shown in Table 7.

Example 35 Reaction of dilaurylmethylamine with methyl chloride
And a cationic surfactant (c5, in the formula (6), R¹
= R²= C₁₈H₃₇, R³= R^Four= CH₃, X^-= Cl ^-) Got
It was Cationic surfactant (c5) and nonionics listed in Table 2
Surfactant (B), triethanolamine citrate salt,
Propylene glycol, alcalase 2.5L and water
And was used to prepare a cleaning agent in the blending amount shown in Table 7.

Example 36 Triethylamine was reacted with diethyl sulfate to prepare a cationic surfactant (c6, in the formula (6), R ¹ = R ² = R ^{3
_{= R 4 = C 2 H 5}} , X - = C 2 H 5 SO 4 -) was obtained. Washing with the cationic surfactant (c6), the nonionic surfactant (B) shown in Table 2, triethanolamine citrate, propylene glycol, 2.5 L of alcalase and water at the blending amount shown in Table 7. The agent was created.

Example 37 Pyridine was reacted with ethyl chloride to give a cationic surfactant (c7, in the formula (7), Y = C ₂ H ₅ , X ⁻ =).
Cl ⁻ ) was obtained. 1. Cationic surfactant (c7), nonionic surfactant (B) listed in Table 2, triethanolamine citrate salt, propylene glycol, alcalase 2.
A cleaning agent was prepared with 5 L and water in the compounding amounts shown in Table 7.

Example 38 Stearylamine was reacted with N, N-diethylethylenediamine and then reacted with dimethylsulfate to obtain a cationic surfactant (c8, in the formula (9), R ⁵ = CH ₃ , R ⁶
= C ₁₇ H ₃₅ , X ⁻ = CH ₃ SO ₄ ⁻ ) was obtained. Washing with the cationic surfactant (c8), the nonionic surfactant (B) listed in Table 2, triethanolamine citrate, propylene glycol, 2.5 L of alcalase and water at the blending amount shown in Table 7. The agent was created.

Comparative Examples 1 and 2 Nonionic surfactants listed in Table 3, triethanolamine citrate salt, propylene glycol, alcalase 2.
Table 5 using 5 L and water and sodium dodecylbenzene sulfonate or sodium dodecyl ether sulfate.
A cleaning agent was prepared in the stated blending amount.

Comparative Example 3 The polymer (a) obtained in Example 1 was neutralized with aqueous ammonia. Using this, the nonionic surfactant described in Table 3, the triethanolamine citrate salt, propylene glycol, 2.5 L of alcalase, and water, a cleaning agent was prepared in the compounding amount described in Table 7.

Comparative Examples 4 and 5 The polymer (a) obtained in Example 1 was neutralized with sodium hydroxide. Using this, the nonionic surfactant described in Table 3, the triethanolamine citrate salt, propylene glycol, 2.5 L of alcalase, and water, a cleaning agent was prepared in the compounding amount described in Table 7.

Comparative Example 6 The polymer (a) obtained in Example 1 was neutralized with sodium hydroxide. Using this, the nonionic surfactant described in Table 3, 2.5 L of alcalase and water, a cleaning agent was prepared in the compounding amount described in Table 7. Comparative Example 7 The polymer (a) obtained in Example 1 was neutralized with sodium hydroxide. Using this, the nonionic surfactant described in Table 3, propylene glycol, 2.5 L of Alcalase and water, a cleaning agent was prepared in the compounding amount described in Table 7.

Comparative Example 8 Polyvinyl alcohol {trade name: PVA-105 (manufactured by Kuraray Co., Ltd.), weight average molecular weight by GPC: 22,
000} and the nonionic surfactant described in Table 3, the triethanolamine citrate salt, propylene glycol, 2.5 L of alcalase and water were used to prepare a cleaning agent in the compounding amount described in Table 7.

Comparative Example 9 Sodium polystyrene sulfonate {trade name: Chemistat SA-9 (manufactured by Sanyo Chemical Industry Co., Ltd.), weight average molecular weight by GPC: 40,000} and nonionic surfactants listed in Table 3, citric acid A cleaning agent was prepared using triethanolamine salt, propylene glycol, 2.5 L of alcalase and water in the compounding amounts shown in Table 7.

[0084]

[Table 1]

The structures of the nonionic surfactants used in Examples and Comparative Examples are shown in Tables 2 and 3. EO is an oxyethylene group, PO is an oxypropylene group,
EO / PO indicates random addition, and EO-PO indicates block addition. Mw / Mn (measured value) is a measured value by GPC. Mw / Mn (calculated value) is a calculated value calculated from the relational expression (3) or (4). The distribution constant c is GC
The amount of unreacted alcohol is measured by, and the value calculated from the relational expression (5) is shown.

[0086]

[Table 2]

[0087]

[Table 3]

The cleaning agents prepared in Examples 1 to 38 and Comparative Examples 1 to 9 were tested for detergency, foaming ability and detergent stability. The results are shown in Tables 4-8. The test method is as described below.

[0089]

[Table 4]

[0090]

[Table 5]

[0091]

[Table 6]

[0092]

[Table 7]

[0093]

[Table 8]

<Detergency test> For the detergency, a centrifugal washing machine "NA-F800P" manufactured by Matsushita Electric Industrial Co., Ltd. was used.
50L of artificially contaminated cloth (cotton knitting), bath ratio 30 times,
Washing was carried out for 10 minutes under the condition that the amount of the cleaning agent used was 25 g and the water temperature was 25 ° C., then rinsing was performed twice for 3 minutes, and the washing power was calculated by the following formula and evaluated. Detergency _{(%) = {(R W} -R S) / (R I -R S)} × 10
0 Note that R _I is the reflectance of the cleaning cloth, R _W is the reflectance of the cleaning cloth, and R
_S represents the reflectance of the contaminated cloth, and the reflectance at 540 nm was measured using a multi-source spectrophotometer (manufactured by Suga Test Instruments). In addition, the artificially contaminated cloth used was a wet artificially contaminated cloth (540
The reflectance in nm is 40 ± 5%).

[0095]

[Table 9]

As the evaluation criteria, a cleaning power of 40% or more is represented by ⊚, a cleaning power of 32% or more and less than 40% is represented by O, 20% or more and less than 32% is represented by Δ, and less than 20% is represented by X.

<Foaming power test> Using 1.5 L of a 0.1% aqueous solution of the detergent, a high pressure jet type liquid flow foaming tester (manufactured by Tsujii Dye Machinery Co., Ltd.) was used to measure the foaming power at 25 ° C. evaluated.

As the evaluation criteria, those having a foaming height of 20 mm or less are represented by O, those having a foaming height of 20 to 50 mm are represented by Δ, and those having a foaming height of 50 mm or more are represented by X.

<Stability of Cleaning Agent> The stability of cleaning agent is 2
After leaving still at 5 ° C. for 24 hours, the appearance was visually observed and evaluated according to the following criteria.

As evaluation criteria, those without separation of the cleaning agent are represented by O, and those with separation of the cleaning agent are represented by X.

[0101]

EFFECT OF THE INVENTION The detergent builder of the present invention has good compatibility with a surfactant, and has excellent effects of washing mud stains particularly when laundering clothes and having low foaming. Further, the cleaning agent of the present invention exerts an extremely excellent effect as a cleaning agent for a washing machine with little damage to the laundry, particularly a centrifugal washing machine.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C11D 10/02 C11D 10/02 (56) Reference JP-A-7-278597 (JP, A) JP-A-9-24266 (JP , A) JP-A-9-187638 (JP, A) JP-A-7-308563 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C11D 1/72 C11D 1/722 C11D 3/20 C11D 3/26 C11D 3/37 C11D 10/02 CA (STN) REGISTRY (STN) JISC file (JOIS)

Claims (12)

(57) [Claims] 1. A Ri quaternary ammonium salt (A) Tona carboxyl group-containing polymer, the content of water 10-80
Builders are for mass% of detergent. 2. The solubility parameter of (A) is 8.0 to
12.0 according to claim 1. builder. 3. The number average molecular weight of (A) is 3,000 to 3.
The amount according to claim 1 or 2 builder. 4. The carboxyl group-containing polymer is polyacrylic acid, according to claim 1. builder. 5. contain builder according to any one of claims 1 to 4, the detergent containing chromatic amount of water is 10 to 80 mass%. 6. A carboxyl group-containing polymer Consists quaternary ammonium salt (A), the solubility parameter contains 2 to 30 wt% of builder is 8.0 to 12.0, containing organic content of water is 10 to 80% by weight of (A) Washing soap. 7. The cleaning agent according to claim 5, further comprising a nonionic surfactant (B). 8. The cleaning agent according to claim 7, wherein (B) is a compound represented by the following general formula (1). Formula _{^{RO- (A 1 O) p -H}} (1) ( wherein, R represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms, p is from 1 to 30 integer, ^{A 1} is C2-4 Indicates an alkylene group.) 9. The cleaning agent according to claim 7, wherein (B) is a compound represented by the following general formula (2). General formula [Chemical formula 1] {In the formula, R is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, A ²
Is an alkylene group having 3 or 4 carbon atoms, n is 0 or 1-
12 is an integer, m is 0 or an integer of 1 to 6, q is 1 to 16
, R is 0 or an integer of 1 to 15, (m + n + q)
Represents an integer of 1 to 30, and (n + q) / (m + n + q + r) represents 0.5 to 1.0. [(C ₂ H ₄ O) _n · (A
² O) _m ] indicates random addition or block addition. } 10. The cleaning agent according to claim 8 or 9, wherein (B) is a nonionic surfactant produced by adding an alkylene oxide (b1) to the aliphatic alcohol (a1) and satisfying the following. The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn): Mw / Mn satisfies the following relational expression (3) or (4). Mw / Mn ≦ 0.030Ln (v) +1.010 (where v <10) (3) Mw / Mn ≦ −0.026Ln (v) +1.139 (where v ≧ 10) (4) {however, v represents the average number of moles of the alkylene oxide (b1) added per mole of the aliphatic alcohol (a1). } The distribution constant c obtained from the following equation (5) is 2.0 or less. ## EQU3 ## c = (v + n ₀ / n ₀₀ -1) / [Ln (n
₀₀ / n ₀ ) + n ₀ / n ₀₀ -1] (5) {where v is the same as in formula (3) or (4), n ₀₀ is the number of moles of the aliphatic alcohol (a1) used in the reaction, and n ₀ represents the number of moles of the unreacted aliphatic alcohol (a1). } 11. A polymer containing a carboxyl group It contains a quaternary ammonium salt (A) as a builder, and contains an alkylene oxide (b1) in the aliphatic alcohol (a1).
A detergent containing a nonionic surfactant (B), which is produced by adding the following: The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn): Mw / Mn satisfies the following relational expression (3) or (4). Mw / Mn ≦ 0.030Ln (v) +1.010 (where v <10) (3) Mw / Mn ≦ −0.026Ln (v) +1.139 (where v ≧ 10) (4) {however, v represents the average number of moles of the alkylene oxide (b1) added per mole of the aliphatic alcohol (a1). } The distribution constant c obtained from the following equation (5) is 2.0 or less. ## EQU6 ## c = (v + n ₀ / n ₀₀ -1) / [Ln (n
₀₀ / n ₀ ) + n ₀ / n ₀₀ −1] (5) {where v is the same as in formula (3) or (4), n ₀₀ is the number of moles of the aliphatic alcohol (a1) used in the reaction, and n ₀ represents the number of moles of the unreacted aliphatic alcohol (a1). } 12. The cleaning agent according to claim 5, which further contains a cationic surfactant (C).