WO2000034428A1

WO2000034428A1 - Builder for detergents and detergent

Info

Publication number: WO2000034428A1
Application number: PCT/JP1999/006637
Authority: WO
Inventors: Koji Kawaguchi; Hiroshi Itayama
Original assignee: Sanyo Chemical Industries, Ltd.; Matsushita Electric Industrial Co., Ltd.
Priority date: 1998-12-09
Filing date: 1999-11-26
Publication date: 2000-06-15
Also published as: CN1290293A; CN1197945C; TWI230197B; KR20010040783A; MY132557A

Abstract

A detergent comprising a builder (A) consisting of an organic amine or quaternary ammonium salt of a carboxyl polymer and a nonionic surfactant (B) represented by the general formula: RO-(A1O)p-H (wherein R is C8-C18 aliphatic hydrocarbyl; p is an integer of 1 to 30; and A1 is C2-C4 alkylene). The builder is excellent in compatibility with the surfactant and the detergent is useful in washing clothes and particularly excellent in the detergency against mud soil.

Description

Specification

Builders and detergents for cleaning agents

The present invention relates to a detergent builder and a detergent. More specifically, the present invention relates to a detergent builder and a detergent excellent in cleaning mud and dirt. Background art

Conventionally, metal salts of alkali metal such as polyacrylic acid / polyitaconic acid, and copolymers of acrylic acid and maleic acid have been known as a builder for detergents. In addition, detergents used for household clothing generally include alkyl benzene sulfonic acid, alkyl sulfates, fatty acid amides, alkali metal salts of inorganic acids, polyoxyalkylated higher alcohols and alkyl phenols. Such a surfactant is blended.

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

The present inventors have conducted intensive studies to obtain a detergent having excellent compatibility with a surfactant and an excellent detergency including mud stains. The present invention was found to be effective for the purpose of the present invention, and reached the present invention. Disclosure of the invention

That is, the present invention provides a builder for a detergent comprising an organic amine salt or a quaternary ammonium salt (A) of a carboxyl group-containing polymer; a detergent comprising the builder and a nonionic surfactant (B); It is produced by adding an alkylene oxide (bl) to an aliphatic alcohol (a1). A cleaning agent containing a nonionic surfactant (B) that fills the skin; and a cation surfactant (C) and an organic amine salt or a quaternary ammonium salt of Z or a low molecular weight polycarboxylic acid ( D).

(1) Ratio between weight average molecular weight (Mw) and number average molecular weight (Mn): MwZMn satisfies the following relational expression (3) or (4).

M w / M n ≤ 0.030 L n (v) + 1.010 (where v く 10) (3) M w / M n ≤-0.026 L n (v) + 1.139 (where v ≥ 1 0) (4) {where, v represents the average number of moles of alkylene oxide (bl) added per mole of aliphatic alcohol (a1). }

② The distribution constant c obtained from the following equation (5) is 2.0 or less.

c = (V + no / no o-1) / [Ln (n. Zn.) + n. Zn. . — 1] (5) {where V is the same as equation (3) or (4), n ». Is the number of moles of the aliphatic alcohol (a1) used in the reaction, n. Indicates the number of moles of the unreacted aliphatic alcohol (a 1). } Detailed disclosure of the invention

Examples of the carboxyl group-containing polymer in the present invention include polymers having an α, -unsaturated carboxylic acid as an essential constituent unit.

a, ι3—Examples of unsaturated carboxylic acids include monocarboxylic acids (eg, (meth) acrylic acid, etc.), dicarboxylic acids (eg, maleic acid, fumaric acid, itaconic acid, and citraconic acid). Acid), dicarboxylic anhydrides (e.g., anhydrous maleic acid, itaconic anhydride, citraconic anhydride, etc.) and dicarboxylic acid half esters (dicarboxylic acid and alkano having 2 to 16 carbon atoms) Half ester with carboxylic acid, carbitol or cellosolve, for example, maleic acid half ester (monobutyl maleate ester, monoethyl maleate carbitol ester, etc.), fumaric acid half ester (monobutyl fumarate) Beauty treatment , Monoethyl carbitol fumarate, etc.)}, and combinations thereof. Of these, acrylic acid is preferred.

As the polymer, other copolymerizable monomers can be used as constituent units. Other monomers include, but are not limited to, the following:

(a) Aromatic ethylenically unsaturated monomer:

Styrenes, α-methylstyrene, styrenes such as vinyl toluene and hydroxystyrene, halogen-substituted styrenes such as dichlorostyrene, vinyl naphthylene, etc .;

(b) an aliphatic ethylenically unsaturated monomer having 2 to 20 carbon atoms:

Ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, olefins such as dodecene and octadecene, butenes such as butadiene and isoprene;

(c) an alicyclic ethylenically unsaturated monomer having 5 to 15 carbon atoms:

Cycopene Gen, Pinnen, Limonen, Indene, Biscopene Gen, Etiri Dennorbornen, etc .;

(d) Alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate Acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate Rate

, Hep Yu decyl (meta) acrylate, eicosyl (meta) acrylate, etc .;

(e) an ethylenically unsaturated monomer having a hydroxyl group or a (poly) oxyalkylene group (molecular weight: 44 to 200) Esters of carboxylic acid):

Hydroxyalkyl (C2-C6) (meta) acrylate, poly (hydroxyalkyl) such as hydroxypropyl (meta) acrylate and hydroxypropyl (methyl) acrylate Ethylene glycol (molecular weight 300) mono (meth) acrylate, propylene glycol (molecular weight 500) mono (meth) acrylate, methyl alcohol ethylene oxide 100 Mole adduct

(Poly) oxyalkylene groups such as (meth) acrylate and lauryl alcohol ethylene oxide 30 mol adduct (meth) acrylate

(Methyl) having a (molecular weight of 44 to 200, carbon number of alkylene group of 2 to 4) and the corresponding (meth) methyl other than the corresponding (meth) acrylate. β monounsaturated carboxylic acid ester;

(f) Amide-containing ethylenically unsaturated monomer:

(Meta) acrylamide, N-methylol (meth) acrylamide, etc .;

(g) Sulfonate or sulfate ester-containing monomer:

Vinyl sulfonic acid, (meth) aryl sulfonic acid, 2 — hydroxy 3 —

(Met) acryloxyprononsulfonic acid, styrenesulfonic acid, monomethylstyrenesulfonic acid, sulfopropyl (meth) acrylate, 2-hydroxy-3— (meth) acryloxyprononsulfonic acid, 2 — (Meth) acryloylamino 2,2 — dimethyl ethane sulfonic acid and 21 (meth) acryloyloxy ethane sulfonic acid, etc., monomer containing a sulfone group, polyoxyalkylene mono (meta) lactone Sulfated ester of relay (The oxyalkylene is a mixture of one or more of oxyalkylenes having 2 to 4 carbon atoms, and in the case of a mixture of two or more, random or brominated. And the number of moles to be added is usually 1 to 30).

In the polymer, the content of the / 3 -unsaturated carboxylic acid as a structural unit is usually 50 to 100 mol%, preferably 70 to 100 mol%. In addition, the content of the other monomer is usually 0 to 50 mol%, preferably 0 to 30 mol%.

The polymer can be obtained by subjecting the above monomer to radical polymerization, and in this case, a radical polymerization initiator can be used.

Examples of the radical polymerization initiator include 2,2′-azobisisobutyl nitrile, 2,2′-azobis (2,4—dimethylvaleronitrile), and 2,2′-azobis (2-methylbutyroni) 2,2'-azobis (2,4,4-trimethylpentane), dimethyl 2,2'-azobis (2-methylprobionate), 2,2'-azobis [2— (hydro Azo compounds such as loxymethyl) propionitol] and 1,1'-azobis (1-acetoxy-111-phenylethane); dibenzoylperoxide, dicumylperoxide, bis (4-t-butylbutyl) Rohexyl) Organic peroxides such as peroxide, benzoyl peroxide, lauroyl peroxide, and persuccinic acid; persulfates, perboric acid And inorganic peroxides such as hydrogen peroxide can be used. Also, a redox-based initiator in which these are combined with a reducing agent can be used.

Examples of the reducing agent used in the redox initiator include ascorbic acid (salt), longarite, hypophosphorous acid (salt), sulfite (salt), bisulfite (salt), and bisulfite (salt). Iron salts and the like. Two or more radical polymerization initiators may be used in combination.

The amount of the radical polymerization initiator is usually from 0.01 to 20% by weight, preferably from 0.05 to 5% by weight, based on the total weight of the α,) 3 -unsaturated carboxylic acid and Ζ or other monomer. It is preferably 10% by weight, particularly preferably 0.1 to 2% by weight.

In addition, a chain transfer agent can be used when the above monomers are subjected to radical polymerization. Examples of the chain transfer agent include lauryl mercaptan, thioglycolic acid, mercaptoethanol, and triol. Ethylene glycol coal dimercap evening Can be used.

The amount of chain transfer agent is usually from 0.01 mol% to 10 mol%, preferably from 0 mol% to 10 mol%, based on the total moles of α, | 3-unsaturated carboxylic acid and / or other monomer. 0 5 to 3 mol%.

The radical polymerization may be any of bulk polymerization, emulsion polymerization, suspension polymerization and solution polymerization. Preference is given to solution polymerization.

The polymerization temperature is from 50 to 300 ° C, preferably from 60 to 250 ° C. In the case of solution polymerization, the polymerization temperature may be any temperature below the boiling point of the polymerization solvent or above the boiling point. Preferably, the temperature is equal to or higher 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 determined by gel permeation chromatography (hereinafter abbreviated as GPC) is usually from 1,000 to 100,000, and is preferably. Is 3, 000 to 300, 000. The weight average molecular weight Mw by GPC is usually 1,100 to 110,000, preferably 3,300 to 330,000.

The acid value of the polymer is usually from 200 to 1,400, preferably from 300 to 1,000.

When the organic amine is converted into an organic amine salt of the polymer, the organic amine may be an aliphatic amine, an alicyclic amine, a heterocyclic amine, or an alkanolamine, or an organic amine. Alkylene oxide adducts and the like can be mentioned.

Aliphatic amines include hexylamine, octylamine, methylhexylamine, methyloctylamine, dimethylhexylamine, dimethylethyloctylamine, dimethylrawylamine, dimethylcetylamine, and the like. Mono-, di- and trialkylamines having 1 to 18 carbon atoms in the alkyl group are exemplified.

Examples of alicyclic amines include cyclobutylamine and cyclohexylamine. Cycloalkylamines having 4 to 12 carbon atoms such as cycloalkylamines, cyclopentylamine, cyclooctylamine, N—methylcyclohexylamine and N—ethylcyclohexylamine; Formulas 1 to 6) Substituents are exemplified.

Heterocyclic amines include those having 4 to 10 carbon atoms, such as morpholine, and alkanolamines include monoethanolamine, diethanolamine and triarylamine. Mono-, di- and tri-hydroxyalkylamines having 2 to 8 carbon atoms in the hydroxyalkyl group such as ethanolamine.

Examples of the alkylene oxide of these alkylene oxide adducts include ethylene oxide, propylene oxide and butylene oxide. Preferably it is ethylene oxide. The molar number of these additions is usually 1 to 5 mol, preferably 1 to 2 mol per active hydrogen. These alkylene oxide adducts include, for example, dihydroxyshethylhexylamine, hydroxyshethylmethylhexylamine and the like.

In the quaternary ammonium salt of the polymer, quaternary ammonium cations include, for example, trimethylethylammonium, triethylmethylammonium, trimethylhexylammonium, trimethyloctylammonium, Alkyl groups such as triptyoctylammonium, trimethyldecylammonium, trimethyltetradecylammonium, trimethylcetylammonium and monomethyltrioctylammonium have 1 to 18 carbon atoms. N, N—Dimethylcyclohexylammonium and N, N—Jetylcyclohexylammonium and other cycloalkyl groups having 4 to 12 carbon atoms and carbon atoms of the alkyl groups Alkyl dialkyl ammonium with a number of 1 to 6 Pum Trihydroxyalkylalkyl ammonium having 2 to 8 carbon atoms in an alkylalkyl group and 1 to 6 carbon atoms in an alkyl group, such as trihydroxyshetylhexylammonium; .

Among these salts (A), preferred are salts derived from aliphatic or cycloaliphatic amines or alkylene oxide adducts thereof, more preferred. These are the quaternary ammonium salts. More preferably, a salt comprising a quaternary ammonium cation having an alkyl group having 2 to 12 carbon atoms, particularly preferably triethylmethylammonium salt, triethyloctylammonium salt, or These are trimethyldecylammonium salt, trimethylhexylammonium salt and trimethyloctylammonium salt.

The organic amine salt of the polymer can be synthesized by neutralizing the polymer with an organic amine, and in this case, it can be neutralized in a solution using a solvent. Solvents include water, alcohols (methanol, ethanol, isopropyl alcohol, etc.), ketones (aceton, methyl isoptyl ketone, etc.), and ethers (getyl ether, tetraethyl). Etc.), aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (toluene, xylene, etc.) and mixtures thereof. When a nonionic surfactant (B) is used, the polymer may be neutralized with an organic amine and then mixed with the nonionic surfactant (B). After mixing with the nonionic surfactant (B), the mixture may be neutralized with an organic amine. The neutrality is usually from 30 to L 0%, preferably from 60 to 100%.

The quaternary ammonium salt of the polymer can be prepared in a conventional manner, for example, by using a tertiary amine and an alkyl halide or an aryl halide (for example, a compound having 1 carbon atom such as methyl chloride, ethyl bromide and bromobenzene). ~ 10 halides) to form a quaternary ammonium halide. Reacting with an alkali hydroxide (eg, sodium hydroxide, potassium hydroxide) to obtain a quaternary ammonium salt hydroxide, and then neutralizing the polymer with this; The quaternary ammonium carbonate is reacted with a dialkyl (C1-6) carbonate (for example, dimethyl carbonate, getyl carbonate) to obtain a quaternary ammonium carbonate. It can be obtained by a method such as exchanging a polymer by anion. Neutralization or anion exchange can be carried out in solution using the same solvent as in the case of organic amine neutralization, or when using a nonionic surfactant or in the case of organic amines. As with, the nonionic surfactant can be mixed either before or after neutralization or anion exchange.

As a concrete method of exchanging the polymer with a quaternary ammonium carbonate, for example, in the case of a salt of polyacrylic acid and trimethyloctyl ammonium, dimethyl ester is used. Trimethyl octyl ammonium is prepared by charging 1 mol of dimethylamine and dimethyl carbonate and methanol in an equimolar amount or more in a pressure vessel and reacting under a pressure of about 5 kg / cm ² at about 120.ゥ Obtain a methanol solution of mucarbonate. Next, 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 added. Evaporate to obtain an aqueous solution of trimethyl octyl ammonium salt of polyacrylic acid.

The degree of neutralization or anion exchange is usually between 30 and 100%, preferably between 60 and 100%.

The solubility parameter (hereinafter referred to as the SP value) of the organic amine salt or quaternary ammonium salt (A) of the polymer is usually from 8.0 to 8.0 from the viewpoint of solubility in a detergent. 12.0, preferably 8.5 to 11.5. When it is in the range of 8.0 to 12.0, the detergency becomes better, and the Dissolution stability is better. The SP value can be expressed by the general formula (6). General formula δ = (ΔΗ / ν) ^1/2 (6)

Where (5 is the SΡ value, ΔΗ is the molar heat of evaporation (ca 1), and V is the molar volume (cm ³ ).

Here, the SP value is determined by the atom described in “POL YM ERENGINEERINGANDFEBRUARY, 1974, Vol. 14, No. 2, ROBERTF. FEDORS.” (Pages 151 to 153). Can be calculated from the sum of the molar evaporation heat of the group (sum of Ae (ΔΗ) and sum of mole volume (Avi) (V)

The detergent of the present invention comprises a detergent builder comprising an organic amine salt or a quaternary ammonium salt (A) of the polymer and a nonionic surfactant (B).

Examples of the non-ionic surfactant (B) include alkylene oxide-added non-ionic surfactants (b-1) and polyhydric alcohol-type non-ionic surfactants

(b-2).

(b-1) is a higher alcohol (8 to 18 carbon atoms) alkylene

(C 2-4) Oxide (Additional moles per active hydrogen 1-30) Adduct, alkyl (C 1-12) phenol ethylene oxide (1 active hydrogen Addition mole per 1 to 30) Adduct, fatty acid (8 to 18 carbon atoms) Ethylene oxide (1 to 30 addition mole per active hydrogen) Adduct, propylene glycol Cole (molecular weight: 200 to 400) Ethylene oxide (addition moles per active hydrogen: 1 to 50) Adducts and polyoxyethylene (addition per active hydrogen) 1 to 30 moles) Alkyl (1 to 20 carbons) aryl ether, sorbitan monolaurate ethylene oxide (1 to 30 moles added), adduct, sorbitan monooleate ethylene oxide Id (number of moles added: 1 to 30) Polyhydric (2 to 8 or more) alcohols (2 to 30 carbon atoms) fatty acids (8 to 24 carbon atoms) Ester ethylene oxide adducts (addition moles per active hydrogen Numerals 1 to 30) and the like.

(b-2) includes polyhydric (2 to 8 or more) alcohols such as glycerin monostearate, glycerin monolate, sorbitan monolaurate, and sorbitan monolate. Fatty acid (C2-C30) fatty acid (C2-C24) esters, fatty acid alcohols such as monoethanolamide laurate, diethanolamide laurate, and the like.

Of these, preferred is (b-1), more preferred is a compound represented by the following general formula (1), and particularly preferred is a compound represented by the following general formula (2) It is a compound shown.

RO-(A ¹ O) H (1)

R0- [(C ₂ H ₄ 0)-(A ² 0) _m ]-(C 2H4 O) _q- (A ² 0) -H (2)

In the above general formula (1) or (2), R is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, preferably an aliphatic hydrocarbon group having 10 to 18 carbon atoms. is there. When the number of carbon atoms is in the range of 8 to 18, good cleaning power 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, and 1,1-dimethyloctyl group An unsaturated aliphatic hydrocarbon group such as an octenyl group, a decenyl group, a dodecenyl group, a tridecenyl group, a pendecenyl group, an oleyl group, a linoleyl group, etc. (alkenyl group, alkadienyl group, alkatrienyl group); And cycloalkyl groups); cyclic aliphatic hydrocarbon groups such as ethylcyclohexyl group, propylcyclohexyl group, octylcyclohexyl group, and nonylcyclohexyl group. You. These aliphatic hydrocarbon groups may be linear or branched.

In the general formula (1), Α ′ represents an alkylene group having 2 to 4 carbon atoms, and specifically includes an ethylene group, a propylene group and a butylene group. (Α 'Ο) If the unit is 2 or more, it can be alone, random, or block. Ρ is an integer of 1 to 30 and is preferably 6 to 20. When ρ is in the range of 1 to 30, a better detergency can be obtained. In the general formula (2), A ² is an alkyler group having 3 or 4 carbon atoms, and n is 0 or an integer of 1 to 12 and preferably 1 to 10. Q is an integer of 1 to 16 and is preferably 2 to 12. When n is 0 or in the range of 1 to 8, more favorable detergency is obtained when the Q force is in the range of 1 to 16.

M is 0 or an integer of 1 to 6, and preferably 1 to 4. R is 0 or an integer of 1 to 15, and preferably 1 to 8. When m is 0 or in the range of 1 to 6, when r is 0 or in the range of 1 to 15, the fluidity of the cleaning agent is further improved.

(M + n + q) is an integer from 1 to 30, preferably from 6 to 20. When (m + n + q) is in the range of 1 to 30, better cleaning power can be obtained.

(Η + ΐί ΐίιη + η + οι + ΐ ") is from 0.5 to 1.0, and preferably from 0.7 to 0.9. Within this range, even better detergency can be obtained.

Of the compounds represented by the general formula (2), they are produced by adding alkylene oxide (bl) to an aliphatic alcohol (a1), and have a weight average molecular weight (Mw) by GPC and a number average molecular weight (Gw by GPC) Compounds whose ratio (MwZ M n) to M n) satisfies the following relational expression (3) or (4) and whose distribution constant c obtained from the following general formula (5) is 2.0 or less are particularly preferable. Like New

M w / M n ≤ 0.030 L n (v) + 1.010 (however, v 1 10) (3) M w / M n ≤-0.026 L n (v) + 1.139 (however, v ≥ 10) (4) In the formulas (3) and (4), v represents the average number of moles of the alkylene oxide (b 1) added per mole of the aliphatic alcohol (a 1). L n (V) indicates the natural logarithm of V.

As the aliphatic alcohol (a1), an alcohol having an aliphatic hydrocarbon group having 8 to 18 carbon atoms can be used. a l is preferably an alcohol having an aliphatic hydrocarbon group having 10 to 18 carbon atoms. Specific examples include alcohols having an aliphatic hydrocarbon group exemplified in the description of R in the general formula (1) or (2). Ethylene oxide, propylene oxide and butylene oxide can be used as the alkylenoxide (b1), and it may be in any of a single form, a random form, a block form or a combination thereof.

c = (v + noZnoo—l) / [Ln (n./n.) + n. Zn. . — L] (5) where, in equation (5), V is the same as equation (3) or (4), n ». Is the number of moles of the aliphatic alcohol (a1) used in the reaction, n. Represents the number of moles of unreacted aliphatic alcohol (al). More preferably, c is less than 1.0. When c is 2.0 or less, the content of the unreacted aliphatic alcohol becomes extremely small, and a better surface activity can be obtained.

The alkylene oxide addition type nonionic surfactant (b-1) can be produced by using a usual alkylene oxide addition reaction, and is carried out in a reaction catalyst at 70 to 200. It can be produced by adding ethylene oxide, propylene oxide, and butylene oxide to alcohols at a specific temperature.

For example, a higher alcohol having 8 to 18 carbon atoms may be replaced with an alkali (eg, K OH, etc.) or an acid (e.g., BF _3, etc.) under a nitrogen atmosphere was added a catalyst, ethylene emissions Okishi de and professional Pirenokishi de mixture was random addition of, then E Chirenokishi de Bro Tsu and click added, followed pro Pi Renokishi Can be manufactured by adding blocks.

As the aliphatic hydrocarbon alcohol having 8 to 18 carbon atoms, a saturated or unsaturated primary, secondary or tertiary alcohol can be used. Preferred among these are saturated aliphatic primary alcohols. The number of carbon atoms is preferably from 10 to 18. The aliphatic hydrocarbon alcohol may be one kind or a mixture of two or more kinds.

Specific examples of the saturated aliphatic primary alcohol include decyl alcohol, lauryl alcohol, stearyl alcohol, and alcohol synthesized using a Ziegler catalyst [for example, trade name: ALFOL 1214 (manufactured by CONDEA)] Etc.), alcohols produced by oxo synthesis [for example, Dovanol 23, 25, 45 (trade name) (manufactured by Mitsubishi Yuka), tridecanol (manufactured by Kyowa Hakko), oxocol 1 2 1 3, 1 215, 1415 (manufactured by Nissan Chemical), diamond 1115 — L, 115H, 135 (manufactured by Mitsubishi Chemical)], and the like.

As saturated aliphatic secondary alcohols, those obtained by an oxidation method using n-paraffin as a raw material, Oil Chemistry, Vol. 21, No. 5, pp. 233-242 (1) 972).

Examples of unsaturated aliphatic alcohols include oleyl alcohol, alcohols obtained by a reduction method [for example, brand names HYCOL 40, 60 (manufactured by Kyowa Yushi), Angecol 50A (New Japan) Rika)] and the like. A method for producing a compound that satisfies the above formula (3) or (4) and has a distribution constant c of 2.0 or less obtained from the above formula (5) is as follows. Alkali gold such as tritium, calcium or cesium Alkylene oxides to aliphatic alcohols using a catalyst that can narrow the molecular weight distribution compared to basic hydroxides or carbonates or basic catalysts such as amine compounds). (2) A method of adding 1 to 3 moles of alkylene oxide to aliphatic alcohol using a general catalyst, removing unreacted alcohol by distillation or the like, and then adding the alkylene oxide using a general catalyst. And the like. Preferably, it is the production method of (1).

Examples of the catalyst for narrowing the molecular weight distribution include a calcined magnesium oxide-containing compound (Japanese Patent Application Laid-Open No. Hei 11-64437) and a calcined hide-mouth talc stone (Japanese Patent Application Laid-Open No. Heisei 2-71841). Gazette), perchlorates (U.S. Pat. No. 4,112,231), perhalic acid (salt), sulfuric acid (salt), nitric acid (salt) and divalent or trivalent metal alcohols Examples include catalysts selected from the rattle. Examples of the cationic surfactant (C) include quaternary ammonium salt-type or ammonium salt-type cationic surfactants.

The quaternary ammonium salt type cationic surfactants include tertiary amines and quaternizing agents (alkyl halides such as methyl chloride, methyl bromide, ethyl chloride and benzyl chloride, etc.). Compounds obtained by reaction with dimethyl sulfate, dimethyl carbonate, ethylene oxide, etc.) can be used. For example, lauryl trimethyl ammonium chloride, didecyl dimethyl ammonium chloride , Dioctyl dimethyl ammonium chloride, stearyl trimethyl ammonium chloride, lauryl dimethyl pendanol ammonium chloride (benzal konium chloride), cetyl pyridinium chloride, polyoxyethylene Trimethylammonium chloride, stearamidethyl Getyl methyl ammonium sulfate.

As amine salt type cationic surfactants, primary to tertiary amines are used as inorganic surfactants. It can be obtained by neutralization with an acid (such as hydrochloric acid, nitric acid, sulfuric acid, or hydroiodic acid) or an organic acid (such as acetic acid, formic acid, oxalic acid, lactic acid, dalonic acid, adipic acid, or alkyl phosphoric acid). Compounds can be used. Examples of the primary amine salt type include aliphatic higher amines (such as laurylamine, stearylamine, cetylamine, hardened tallowamine, and rosinamine). Inorganic acid salts or organic acid salts of amines; higher fatty acid (stearic acid, oleic acid, etc.) salts of lower amines.

Examples of the secondary amine salt type include an inorganic acid salt or an organic acid salt such as an ethylene oxide adduct of an aliphatic amine. Examples of the tertiary amine salt type include, for example, aliphatic amines (triethylamine, ethyldimethylamine, N, N, N′′N ′) Methylethylenediamine, etc.), alicyclic amines (N-methylpyrrolidine, N-methylpiperidine, N-methylhexamethyleneimine, N-methylmorpholine, 1,8-diazabicyclo (5 , 4,0) -17 -Indene, etc.), and nitrogen-containing heterocyclic aromatic amines (4 -dimethylaminopyridin, N -methylimidazole, 4,4'-dipyridyl, etc.) inorganic acids Salts or organic acid salts; inorganic or organic acid salts of tertiary amines such as triethanolamine monostearate and stearamide ethylethylmethylethanolamine.

One or a mixture of two or more of these can be used as the cationic surfactant (C), and is preferably selected from the group consisting of compounds represented by formulas (6) to (9). One or more compounds.

X (6)

R

No

However, in the formulas (6) to (9), R ¹ , R ² and R ³ represent a hydrogen atom or an alkyl group having 1 to 24 carbon atoms, an alkenyl group or a —hydroxyalkyl group, preferably 1 carbon atom. To 18 alkyl groups or alkenyl groups. Specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, and an isodecyl group. Group, undecyl group, isopendecyl group, dodecyl group, isododecyl group, tridecyl group, isotridecyl group, tetradecyl group, isotetradecyl group, pendecyl group, isopendyl group Sil group, hexadecyl group, isohexadecyl group, octadecyl group, Examples of the alkenyl group include octenyl groups, decenyl groups, dodecenyl groups, tetradecenyl groups, hexadecenyl groups, and octenyl decenyl groups. In addition, examples of the / 3-hydroxyalkyl group include a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 2-hydroxybutyl group, and the like.

R ⁴ and R ⁵ represent an alkyl group having 1 to 24 carbon atoms, a hydroxyalkyl group, a benzyl group or a compound represented by the formula: 1 (A′〇) -Z {where A ¹ represents an alkylene having 2 to 4 carbon atoms; A group (for example, an ethylene group, a propylene group or a butylene group), Z is a hydrogen atom or an acyl group, n is an integer of 1 to 50, preferably an integer of 5 to 30}. And preferably an alkyl group having 1 to 4 carbon atoms or a benzyl group. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isopropyl group, and a sec-butyl group.

R ⁶ is an alkyl group having 1 to 36 carbon atoms, an alkenyl group, or a) 3-hydroxyalkyl group, preferably an alkyl group having 8 to 24 carbon atoms or an alkenyl group. Specifically, R ', in addition to the same groups as R ² and R ^3, Ei co sill group, Lee Soei co sills group, Aye Koseniru group and the like.

Y represents an alkyl group or alkenyl group having 1 to 36 carbon atoms; a 3-hydroxyalkyl group; and a formula: R ⁴ C〇 ₂ CH ₂ — (where R ⁴ is the same as described above). Or a group represented by the formula: R ⁴ OCH ₂ — (where R ⁴ is the same as described above), and preferably an alkyl group or an alkenyl group having 1 to 18 carbon atoms. Specifically, it is the same group as RR ² and R ³ .

X— is a counter ion, and is a halogen ion (F—, CI—, Br—, I—), a hydroxy ion, an ester carbonate ion having an alkyl group having 1 to 4 carbon atoms, or a sulfate ion. And carboxylic and sulfonic acids having an alkyl or alkenyl group having 1 to 24 carbon atoms. One or more anions selected from the group consisting of

The compound represented by the formula (6) has, for example, (1) an alkyl group having 1 to 24 carbon atoms such as laurylamin and stearylamine, an alkenyl group or a 3-hydroxyalkyl group. Secondary amido having a C1-C24 alkyl, alkenyl, or / 3-hydroxyalkyl group such as primary amine, dilaurylamine, distearylamine, etc. Or a tertiary group having an alkyl, alkenyl, or) 3-hydroxyalkyl group having 1 to 24 carbon atoms such as trimethylamine, lauryldimethylamine, dimethylstealylamine, etc. The amine is converted to a halogenic acid such as hydrochloric acid, bromic acid or iodic acid, or a carboxylic acid having 1 to 24 carbon atoms such as formic acid, acetic acid, propionic acid, lauric acid and stearic acid. Those who neutralize with etc. Possible to get at is Ru can.

Also, (ii) tertiary amines having an alkyl group having 1 to 24 carbon atoms, such as trimethylamine, lauryldimethylamine, and dimethylstearylamine, having an alkyl group or a 3 / 3-hydroxyalkyl group. Min can be obtained by a method in which an alkylating agent such as methyl chloride, benzyl chloride, dimethyl carbonate, getyl carbonate, or dimethyl sulfate is heated under pressure and reacted.

Also, (iii) a primary or dilaurylamine having an alkyl, alkenyl, or i3-hydroxyalkyl group having 1 to 24 carbon atoms such as laurylamine or stearylamine. Ethylene oxide is added to a secondary amine having an alkyl, alkenyl, or / 3-hydroxyalkyl group having 1 to 24 carbon atoms, such as distearylamine, under alkaline conditions. The resulting tertiary amine is converted into a halogenic acid such as hydrochloric acid, bromic acid or iodic acid, or a formic acid, acetic acid, propionic acid, rauric acid, stearic acid or the like. It can be obtained by a method such as neutralization with a carboxylic acid having 1 to 24 carbon atoms. You.

The compound represented by the formula (7) is, for example, a compound having 1 to 24 carbon atoms such as methyl chloride, octyl chloride, stearyl chloride, oleyl bromide, or hydroxyxyl chloride in pyridine. This alkylating agent can be obtained by heating and reacting under pressure.

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

The compound represented by the formula (9) can be obtained, for example, by subjecting a fatty acid having 1 to 36 carbon atoms, such as lauric acid and stearic acid, to heat condensation with N, N getylethylenediamine. Neutralizing amide tertiary amine with hydrochloric acid, acetic acid or other acid, and adding methyl chloride, dimethyl carbonate and dimethyl sulfate to the amide tertiary amine. It can be obtained by a method of reacting by heating under pressure.

In order to make the ion X of the formulas (6) to (9) a hydroxyion, a compound in which X is a halogen ion, and silver hydroxide is added thereto and heated. I can get it.

The low molecular weight polycarboxylic acid constituting the organic amine salt or the quaternary ammonium salt (D) of the low molecular weight polycarboxylic acid has a molecular weight of usually not more than 700, preferably not more than 500. When the number is 0 or less, an aliphatic polycarboxylic acid and an aromatic polycarboxylic acid in which the number of carboxyl groups in one molecule is usually 2 to 8 are exemplified. It may contain a hydroxyl group or an amino group as a group other than the carboxyl group. Specific examples of low molecular weight polycarboxylic acids include: Acids, malonic acid, succinic acid, butanetricarboxylic acid, adipic acid, maleic acid, fumaric acid, itaconic acid, aconitic acid, fumaric acid, trimellitic acid, citric acid Linoleic acid, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and aspartic acid. In addition, when the low molecular weight polyvalent carboxylic acid organic amine salt is used as the organic amine, the above-mentioned aliphatic amine, alicyclic amine or alkanolamine is used as the organic amine. And their alkylene oxide adducts. In the above-mentioned quaternary ammonium cation of low molecular weight polyvalent carboxylic acid, the quaternary ammonium cation includes the above-mentioned quaternary ammonium cation.

The content of (A) in the cleaning agent of the present invention is usually 0 or 1 to 30% by mass, preferably 0 or 2 to 20% by mass, and further based on the total mass of the cleaning agent. It is preferably 0 or 3 to 15% by mass.

The content of (B) is usually 10 to 95% by mass, preferably 20 to 80% by mass, and more preferably 30 to 90% by mass, based on the total mass of the detergent. 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). 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), and particularly preferably, the content of the compound represented by the general formula (2) is The content of the compound that satisfies the relational expressions (3) and (4) and the distribution constant c obtained from the general expression (5) is 2.0 or less is based on the content of (B). % By mass or more.

The content of (C) is usually 0 or 0.01 to 10% by mass, and 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 0.1 to 20% by mass, preferably 0 or 1 to 15% by mass, based on the total mass of the detergent. The water content is usually from 2 to 80% by mass, preferably from 10 to 60% by mass, based on the total mass of the detergent. Also, if necessary,

In addition to (A), (B), (C) and water, other components can be contained in an amount of 0 to 50% by mass based on the total mass of the detergent.

Other components include anionic surfactants {alkyl (1 to 20 carbon atoms) ether sulfate, and aliphatic (1 to 20 carbon atoms) alcohol ethylene oxide adducts (addition moles 1 to 30) Sulfated or carboxymethylated compound) is 0 to 15% by mass, and other builders (alkaline builders such as caustic soda, soda ash, ammonia, triethanolamine, sodium tripolyphosphate). 0 to 5% by mass, fluorescent agents, bleaching agents, softeners, enzymes, bactericides, fragrances, coloring agents, etc. 0 to 5% by mass, hydrophilic solvents (methanol, ethanol, isopropyl alcohol) , Ethylene glycol, propylene glycol, etc.) in an amount of 0 to 20% by mass, and an antifoaming agent (silicone antifoaming agent, pull nick type or polyoxyarylene type antifoaming agent, mineral oil type antifoaming agent) Etc.) can and this contains 0-5% by weight.

The cleaning agent of the present invention is particularly useful for cleaning natural fibers, synthetic fibers, and blended and woven fibers thereof. Natural fibers include cotton, hemp, wool, etc. Synthetic fibers include regenerated cellulose fibers such as rayon and acetate, polyester, polyamide fibers, acryl, spandex, etc. Synthetic fibers. These blended and woven fibers include cotton and hemp and other fibers (such as wool, polyester, polyamide, and acryl), and wool and other fibers (polyester, polyamide, and acryl). ), Polyester fibers and other fibers (rayon, acetate, polyamide, acryl, spandex, etc.), polyamide fibers and other fibers (rayon, acetate, acryl) , Spandex, etc.).

The cleaning agents of the present invention are typically used in concentrations ranging from 0.001 g / L to 5 g / L. used.

The bath ratio is not particularly limited, but is usually 1: 4 to 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, 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, a cleaning agent for textiles and a soaping agent.

In the case of washing using the detergent of the present invention, there is no particular limitation on the washing method. In the home, hand washing and washing machines, and in industrial use, batch processing by a liquid jet dyeing machine, and continuous processing by a continuous purification device. Can be used for such. Among them, it is suitable as a washing agent for washing using a washing machine of a type such as a centrifugal washing type that causes less damage to the laundry. The centrifugal washing method is a novel washing method in which a water flow is created by “centrifugal force” by rotating the washing machine tub itself, and dirt is removed by the force of water passing through the laundry. For example, a centrifugal washing machine NA-800P manufactured by Matsushita Electric Industrial Co., Ltd. may be mentioned. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. Hereinafter, parts and% mean parts by mass and% by mass, respectively.

The conditions for measuring the molecular weight of the carboxyl group-containing polymer by GPC are as follows.

Model: Waters 501 (made by Nippon Waters Ltd.) Column: TSK gel G 500 pwXL TSK gel G 3 0 0 0 p wX L

(All manufactured by Tosoh Corporation)

Column temperature: 40 ° C

Detector: R I

Solvent: 0.5% sodium acetate / water / methanol (volume ratio: 70 Z30) Flow rate: 1.0 m1 min

Sample concentration: 0.25%

Injection volume: 200 ^ 1

Standard: Polyoxyethylene glycol

(Manufactured by TOSHI CORPORATION; T S K S T A N D A R D P O L Y E T H Y L E N E O X ID E

Data processor: SC-8100 (manufactured by Tosoichi Co., Ltd.) The conditions for measuring the molecular weight of the nonionic surfactant (B) by GPC are as follows.

GPC measurement conditions>

Model: H L C— 8 1 2 0 (Tosoichi Co., Ltd.)

Column: T S K g e l S up e r H 4 0 0 0

: T S K g e l S Sup e r H 3 0 0 0

: T S K g e l S up e r H 2 0 0 0

(All manufactured by Tosoh Corporation)

Column temperature: 40 ° C

Detector: R I

Solvent: tetrahydrofuran

Flow velocity: 0.6 ml min

Sample concentration: 0.25% Injection volume: 1 0 ^ 1

Standard: Polyoxyethylene glycol

(Manufactured by TOSHI CORPORATION; T S K S T A N D A R D P O L Y E T H Y L E N E O X I D E)

Data processor: SC-8200 (manufactured by Tosoichi Co., Ltd.) Gas chromatograph (hereinafter abbreviated as GC) used for measuring the concentration of unreacted aliphatic alcohol of nonionic surfactant Is as follows.

G C measurement conditions>

Model: Gas chromatograph G C—14 B (manufactured by Shimadzu Corporation) Detection ^ r F ID

Column Glass column (inner diameter = approx. 3 mm, length = approx. 2 m) Column filler Silicone G E S E-30 5%

The temperature was raised from 90 at column temperature to 280 at column temperature. Heating rate = 4 minutes Carrier gas

Sample 50% acetate solution

Injection volume

Quantitation: 2 or more carbon atoms depending on the aliphatic alcohol used

Quantification was performed using three less aliphatic alcohols as internal standard substances. Example 1

A pressure-resistant reaction vessel was charged with 420 parts of isopropyl alcohol and 120 parts of water, replaced with nitrogen, sealed, and heated to 100 ° C. With stirring, 778 parts of acrylic acid were added over 3 hours, 228 parts of acrylic acid, 4 parts of a chain transfer agent (triethylene glycol dimercaptane), and sodium hypophosphite. 2 parts of dihydrate and A homogenous mixture of 0.7 parts of ferrous chloride tetrahydrate was added dropwise over 2 hours, and 50 parts of a 6% aqueous solution of sodium persulfate was added dropwise over 3.5 hours. After completion of the dropwise addition, 3 parts of a 35% aqueous hydrogen peroxide solution was added thereto, and the mixture was stirred at 100 ° C for 1 hour to obtain a polymer (a) having a conversion of 99.9%. Its weight average molecular weight by GPC was 10,000 and its number average molecular weight by GPC was 7,800.

Another pressure vessel was charged with 195 parts of methanol and 586 parts of dimethyl carbonate, replaced with nitrogen, sealed, and heated to 120 ° C. Under stirring, 219 parts of triethylamine are added dropwise, and the mixture is stirred at 120 for 2 hours to obtain a methanol solution of triethylmethylammonium methyl carbonate (b). After mixing 707 parts of a 60% methanol solution of (b) obtained above with 400 parts of the polymer (a) (100% neutralization), isopropanol was added. , Methanol and dimethyl carbonate were distilled off at 100 ° C under normal pressure, and 580 parts of water was added to obtain a 45% aqueous solution of triethylmethylammonium polyacrylate. Was.

This was combined with the nonionic surfactant (B) shown in Table 2, triethanolamine citrate, propylene glycol, 2.5 L of alcohol, and water to obtain the formulation shown in Table 4. The detergent was made by volume. Examples 2, 3, 9 to 24

Tables 4-6 were prepared in the same manner as in Example 1 except that the poly (trimethylmethylammonium acrylate) salt of Example 1 was used and the nonionic surfactant (B) was changed as shown in Table 2. Detergents were prepared in the stated amounts. Examples 4, 5, 6, 7

Table 1 shows the neutralized salt and degree of neutralization using the polymer (a) obtained in Example 1. A detergent was prepared in the same manner as in Example 1 except that the nonionic surfactant (B) was replaced as shown in Table 2 in the same manner as in Example 1. Example 8

The polymer (a) obtained in Example 1 was neutralized with dimethylhexylamine. Using this together with the nonionic surfactant (B), triethylmethylammonium citrate, propylene glycol, 2.5 L of alcohol and water shown in Table 2, The detergent was prepared with the compounding amount described in the above section. Example 2 5

In a pressure-resistant reaction vessel, 370 parts of isopropyl alcohol and 170 parts of water were charged, sealed after replacement with nitrogen, and heated to 100 ° C. 24.9 parts of acrylic acid with stirring, 40.1 parts of 2-acrylamide 2-methylpropanesulfonic acid, and 80 parts of a 4% aqueous solution of sodium persulfate were separately added. The solution was dropped from each container over 3 hours (dropping was started simultaneously). After completion of the dropwise addition, 3 parts of a 35% aqueous hydrogen peroxide solution was added thereto, and the mixture was stirred at 100 ° C for 1 hour to obtain a copolymer (c) having a conversion of 99.9%. Its weight average molecular weight by GPC was 8,000 and its number average molecular weight was 5,600.

A mixture of 707 parts of a 60% methanol solution of triethylmethylammonium methyl carbonate (b) obtained in Example 1 and 174 parts of the copolymer (c) was mixed (10%). (0% neutralized), isopropanol, methanol and dimethyl carbonate are distilled off at 100 ° C under normal pressure at 100 ° C, and triethyl methylammonium poly (vinyl acrylate) is removed. Was obtained.

Using this together with the nonionic surfactant (B) shown in Table 2, triethyl methylammonium salt, propylene glycol, 2.5 L of alcohol, and water, the results are shown in Table 6. A detergent was prepared with the compounding amount. Example 26

Table 6 was prepared in the same manner as in Example 25 except that the polyacrylic acid trimethylmethylammonium salt of Example 5 was used and the nonionic surfactant (B) was changed as shown in Table 2. The detergent was prepared with the compounding amount of. Example 2 7

The same procedures as in Example 25 were carried out except that the poly (methyl octylammonium acrylate) salt of Example 6 was used, and the nonionic surfactant (B) was changed as shown in Table 2. Thus, detergents were prepared in the amounts shown in Table 6. Example 2 8 to 30

Polyacrylic acid trimethyldecyl ammonium salt of Example 7, nonionic surfactant (B) described in Table 2, citric acid, trimethyloctyl ammonium salt, propylene glycol, alcalase 2 Using 5 L and water, detergents were prepared in the amounts shown in Table 6. Example 3 1

Steer Riruami emissions is reacted with Mechiruku b lie de with cationic surfactant (c 1, in the formula (6), R '= R 2 = R 3 = H, R 4 = CH 37, X- = CI -) a Obtained.

Using the cationic surfactant (c1) and the polyacrylic acid triethyl methylammonium salt of Example 1, the nonionic surfactant (B) shown in Table 2 and citrate triethanolamine salt were used. , Propylene glycol, 2.5 L of alcohol and water were used to prepare detergents in the amounts shown in Table 7. Example 3 2

Dimethyl steer Li Ruami down by reacting dimethyl carbonate with a cationic surfactant (c 2, in the formula (6), R '= C ' 8 H 37, R 2 = R 3 = R 4 = CH 3, X- = CH ₃ CO ₃ ) was obtained.

Using the cationic surfactant (c 2) and the polyacrylic acid triethyl methylammonium salt of Example 1, the nonionic surfactant (B) shown in Table 2 and the triethanolamine citrate were used. Detergents were prepared using the salt, propylene glycol, 2.5 L of alcohol and water in the amounts shown in Table 7. Example 3 3

The pyridinium Jin by reacting Okuchiruku b lie de with cationic surfactant (c 3, in formula _{(7), Y = C 8} H 17, X- = C 1 -) was obtained.

Using the cationic surfactant (c 3) and the polyacrylic acid triethyl methylammonium salt of Example 1, the nonionic surfactant (B) shown in Table 2 and triethanol amine citrate were used. Detergents were prepared using the salt, propylene glycol, 2.5 L of alcohol and water in the amounts shown in Table 7 using water. Example 3 4

After the force pre-le acid by reacting Application Benefits et evening Noruami down, by reacting dimethyl carbonate with a cationic surfactant (c 4, in the formula ^{(8), R 5 = CH} 3, R 6 = C τΗ ■ XCH a C Ο ³ ").

Using the cationic surfactant (c 4) and the polyacrylic acid triethyl methylammonium salt of Example 1, the nonionic surfactant (Β) shown in Table 2 was used. A detergent was prepared using triethanolamine salt of citrate, propylene glycol, 2.5 L of alcohol, and water in the amounts shown in Table 7 using water. Example 3 5

Jirau Li Rumechiruami in to reacting the Mechiruku b Lai de cations boundary surface active agent (c 5, in the formula ^{(6), R 1 = R} 2 = C, 8 H 3 7, R 3 = R 4 = CH, X _ = C 1).

Using a cationic surfactant (c5), a nonionic surfactant (B) listed in Table 2, triethanolamine citrate, propylene glycol, 2.5 L of alcoholase and water A detergent was prepared with the compounding amount described in 7. Example 3 6

By reacting triethylamine with getyl sulfate, the cationic surfactant (c 6, in formula (6), R ′ = R ² = R ³ = R ⁴ = C ₂ H ₅ , X— = C ₂ HSO ₄ " ).

Using a cationic surfactant (c6), the nonionic surfactant (B) described in Table 2, triethanolamine citrate, propylene glycol, 2.5 L of alcoholase and water, A detergent was prepared with the compounding amount described in 7. Example 3 7

The pyridinium Jin by reacting Echiruku b lie de with cationic surfactant (c 7, in equation _{(7), Y = C 2} H 5, X- = C 1) was obtained.

Cationic surfactant (c7) and nonionic surfactants listed in Table 2 (B), triethanolamine salt of citrate, propylene glycol, 2.5 L of alcoholase and water were used to prepare detergents in the amounts shown in Table 7. Example 3 8

After steer Li Ruami in to N, by reacting N oxygenate chill ethylenedioxy § Mi emissions, dimethyl sulfate reacted with the cationic surfactant (c 8, Oite the equation ^{(9), R 5 = CH} 3, R ⁶ = CH ₅ , X— = CH ₃ S 〇 ₄ ). Cationic surfactant (c8) and nonionic surfactants listed in Table 2

(B), triethanolamine salt of citrate, propylene glycol, 2.5 L of alcoholase and water were used to prepare detergents in the amounts shown in Table 7. Comparative Examples 1 and 2

Nonionic surfactants listed in Table 3, triethanolamine amine salt, propylene glycol, alcohol 2.5 L and water, sodium dodecylbenzene sulfonic acid sodium or dodecyl ether Using sodium sulfate, detergents were prepared in the amounts shown in Table 7. Comparative Example 3

The polymer (a) obtained in Example 1 was neutralized with aqueous ammonia. The detergent was used in combination with the nonionic surfactant shown in Table 3, triethanolamine citrate, propylene glycol, 2.5 L of alcalase, and water in the amounts shown in Table 7. Created. Comparative Examples 4 and 5 The polymer (a) obtained in Example 1 was neutralized with sodium hydroxide. This was used in combination with the nonionic surfactants listed in Table 3, triethanolamine citrate, propylene glycol, 2.5 L of alcalase, and water to obtain the detergent in the amounts shown in Table 7. It was created. Comparative Example 6

The polymer (a) obtained in Example 1 was neutralized with sodium hydroxide. Using this, a nonionic surfactant described in Table 3, 2.5 L of alcalase and water, a detergent was prepared in the blending amounts shown in Table 7. Comparative Example 7

The polymer (a) obtained in Example 1 was neutralized with sodium hydroxide. Using this, the nonionic surfactant shown in Table 3, propylene glycol, 2.5 L of allylase and water, a detergent was prepared with the blending amounts shown in Table 7. Comparative Example 8

Polyvinyl alcohol {trade name: PVA-105 (manufactured by Kuraray Co., Ltd.), weight-average molecular weight by GPC: 22,200}, a nonionic surfactant listed in Table 3 and tricarboxylic acid trioxide Detergents were prepared using ethanolamine salt, propylene glycol, 2.5 L of alcalase and water in the amounts shown in Table 7. Comparative Example 9

Sodium polystyrenesulfonate {trade name: Chemistat SA-9 (manufactured by Sanyo Chemical Industries, Ltd.), weight average molecular weight by GPC: 40,0 0 0} and the nonionic surfactants listed in Table 3, triethanolamine citrate, propylene glycol, 2.5 L of alcalase and water, and the detergents in the amounts shown in Table 7 It was created. table 1

Table showing the structures of nonionic surfactants used in Examples and Comparative Examples

2 and Table 3. EO indicates an oxyethylene group, PO indicates an oxypropylene group, EOZP〇 indicates random addition, and E〇-PO indicates block addition. M w M n (actual measurement) is the actual measurement by GPC. M w M n (calculated value) is a calculated value calculated from the relational expression (3) or (4). The distribution constant c is a value obtained by measuring the amount of unreacted alcohol by GC and calculating from the relational expression (5).

table

Three

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

Table 4

* Alcalase 2.5 L: Protease (Novo Nordisk Enzyme) Table 6

* Alcalase 2.5 L: Protea'-ze (Novo Nordisk Enzyme) Table 7

* Alcalase 2.5 L: Protease (Novo Nordisk enzyme) 8

* Alcalase 2.5 L: Proteases (enzymes from Novo Nordisk)

Cleansing power test>

Detergency: Using a centrifugal washing machine “NA-F800P” manufactured by Matsushita Electric Industrial Co., Ltd., artificial contaminated cloth (cotton pearl) is used in a water volume of 50, and the bath ratio is 30 times, and the cleaning agent is used. Was washed for 10 minutes under the conditions of the use amount of 25 g and the water temperature of 25 ° C. Then, rinsing was performed twice for 3 minutes, and the detergency was calculated by the following formula and evaluated.

Detergency (%) = {(R w - R s) / (R, - R s)} XI 0 0

In addition, R and R indicate the reflectance of the cleaning cloth, R w indicates the reflectance of the cleaning cloth, and R s indicates the reflection rate of the contaminated cloth, respectively, and a multi-source spectrophotometer (manufactured by Suga Test Instruments) was used. The reflectivity at nm was measured.

The artificially stained cloth used was a wet artificially stained cloth (reflectivity at 540 nm: 40%, 5%) manufactured by the Japan Society for Laundry Sciences with the soil composition shown in Table 9. Table 9 Component name content (%) Oleic acid 28.3

Oil Trio Rein 15.6

Fatty Cholesterolate 1.2.2

Liquid paraffin 2.5

Component Squalene 2.5

Cholesterol 1.6

Minute protein Gelatin 7.0

Inorganic component mud 29.8

Carbon black 0.5 As evaluation criteria, the cleaning power is 40% or more ◎, the cleaning power is 32% or more and less than 40%, Δ is 20% or more and less than 32%, and X is less than 20%. I expressed it.

Gathering foaming test>

Using 1.5 L of a 0.1% aqueous solution of the detergent, the foaming power at 25 ° C was evaluated with a high-pressure jet liquid foaming tester (manufactured by Tsujii Dyeing Machinery Co., Ltd.).

As evaluation criteria, those with a foaming height of 20 mm or less are represented by 〇, those having a foaming height of 20 to 50 mm are represented by △, and those having a foaming height of 50 mm or more are represented by X.

The stability of the detergent was allowed to stand at 25 ° C. for 24 hours, and the appearance was visually observed, and evaluated according to the following criteria.

As evaluation criteria, those with no separation of the cleaning agent were denoted by 〇, and those with separation of the cleaning agent were denoted by X. Industrial applicability

INDUSTRIAL APPLICABILITY The cleaning agent builder according to the present invention has an effect of having good compatibility with a surfactant, excellent washing property of laundry, particularly excellent in cleaning mud stains, and low foaming. Further, the detergent of the present invention exerts an extremely excellent effect as a detergent for a washing machine of a type with less damage to laundry, especially for a centrifugal washing machine.

Claims

The scope of the claims

1. A detergent builder comprising a carboxyl group-containing polymer organic amine salt or a quaternary ammonium salt (A).

2. The builder for a cleaning agent according to claim 1, wherein the solubility parameter of (A) is 8.0 to 12.0.

3. The builder according to claim 1 or 2, wherein (A) is a salt derived from an aliphatic or alicyclic amine or an alkylene oxide adduct thereof.

4. The builder according to any one of claims 1 to 3, wherein the carboxyl group-containing polymer is polyacrylic acid.

5. A cleaning agent comprising the builder according to any one of claims 1 to 4 and a nonionic surfactant (B).

6. The cleaning agent according to claim 5, wherein (B) is a compound represented by the following general formula (1).

General formula

R O-(A 'O) p— H (1)

(In the formula, R is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, p is an integer having 1 to 30 carbon atoms, and A ¹ is an alkylene group having 2 to 4 carbon atoms.)

7. The method according to claim 6, wherein (B) is a compound represented by the following general formula (2). The cleaning agent as described.

General formula

R0- [(C 2H4 O) · (A ² 0) _m ]-(C 2H4 O) _q- (A ² 0) -H (2)

{Wherein, R represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms, A ² represents 3 carbon atoms or

An alkylene group of 4, n is an integer of 0 or 2, m is 0 or an integer of 1 to 6, Q is an integer of 1 to 16, r is an integer of 0 or ~ 15, and (m + n + q) is 1-3 integer 0, indicating the ^{(n + q) / / (} m + n + q + r) is from 0.5 to 1.0. [(C ₂ H ₄ 〇) _η · (A ² 〇) _m ] indicates random addition or block addition.

8. The detergent according to claim 6 or 7, wherein (B) is a compound produced by adding an alkylene oxide (b1) to an aliphatic alcohol (a1) and satisfying the following (1) and (2).

M w / M n ≤ 0.030 L n (v) + 1.010 (however, v 1 10) (3) Mw / M n ≤-0.026 L n (v) + 1.139 (however, v ≥ 10) (4) {where, v represents the average number of moles of alkylene oxide (bl) added per mole of aliphatic alcohol (a1). }

c = (ν + ηο / η ο ο — Ι) / [L n (n. .zn.) + n. / n. . — L] 5) {where V is the same as equation (3) or (4), n. . Represents the number of moles of the aliphatic alcohol (a1) used in the reaction, and nD represents the number of moles of the unreacted aliphatic alcohol (a1). }

9. The cleaning agent according to any one of claims 5 to 8, further comprising a cationic surfactant (C).

A nonionic surfactant (B) and a cationic surfactant (C) which are produced by adding an alkylene oxide (b1) to a 10-aliphatic alcohol (a1) and satisfy the following conditions (1) and (2): A cleaning agent containing.

(1) Ratio between weight average molecular weight (Mw) and number average molecular weight (Mn): Mw / Mn satisfies the following relational expression (3) or (4).

M w / M n ≤ 0.030 L n (v) + 1.010 (however, v 1 10) (3) M w / M n ≤-0.026 L n (v) + 1.139 (however, v ≥ 10) (4) {where, v represents the average number of moles of alkylene oxide (bl) added per mole of aliphatic alcohol (a1). }

(2) The distribution constant c obtained from the following equation (5) is 2.0 or less.

c = (v + n. / n.—l) / [Ln (n.zn.) + n. z n. . — 1] (5) {where, V is the same as equation (3) or (4), η ». Is the number of moles of the aliphatic alcohol (a1) used in the reaction, n. Indicates the number of moles of the unreacted aliphatic alcohol (a 1). }

11. The detergent according to claim 9 or 10, wherein (C) is at least one compound selected from the group consisting of compounds represented by the following general formulas (6) to (9).

However, in the formulas (6) to (9), R ′, R ² and R ³ represent a hydrogen atom or an alkyl group having 1 to 24 carbon atoms, an alkenyl group, or a | 3-hydroxyalkyl group, R ⁴ and R ⁵ is an alkyl group having 1 to 24 carbon atoms, a hydroxyalkyl group, a benzyl group or a formula: — (A ¹ ^) n-Z (where A ¹ is an alkylene group having 2 to 4 carbon atoms, and Z is hydrogen An atom or an acyl group, n is an integer of 1 to 50.), R ⁶ is an alkyl group having 1 to 36 carbon atoms, an alkenyl group or a / 3-hydroxyalkyl group, Y is an alkyl group, § alkenyl group of from 1 to 3 6 carbon atoms, | 3 - arsenide de Rokishiarukiru group of the formula: R ⁴ C_〇 ₂ CH ₂ - (Note, R ⁴ is as defined above.) is represented by Group or formula: R ⁴ （CH ₂ — (wherein R ⁴ is the same as described above), and a pair of ions X_ is octalogion, hydroxy ion Carbonic acid ester having an alkyl group having 1 to 4 carbon atoms And at least one anion selected from the group consisting of a carboxylate ion and a sulfonate ion having an alkyl group or an alkenyl group having 1 to 24 carbon atoms.

12. The cleaning agent according to any one of claims 5 to 11, comprising an organic amine salt or a quaternary ammonium salt (D) of a low molecular weight polycarboxylic acid.

Claims of amendment

[Apr. 28, 2000 (28.04.00) Accepted by the International Bureau:

Claims 11-9 and 12 have been amended; other claims remain unchanged. (Page 6)]

1. (After correction) Washing in which the quaternary ammonium salt (A) of a carboxyl group-containing polymer is contained as a detergent builder and the water content is 10 to 80% by mass. Agent.

2. (After correction) The detergent according to claim 1, wherein the solubility parameter of (A) is 8.0 to 12.0.

3. (After correction) The cleaning agent according to claim 1 or 2, wherein the carboxyl group-containing polymer is polyacrylic acid.

4. (After correction) The cleaning agent according to any one of claims 1 to 3, further comprising a nonionic surfactant (B).

5. The cleaning agent according to claim 4, wherein (after correction) (B) is a compound represented by the following general formula (1).

General formula

R O-(A 'O) n-H (1)

(In the formula, R is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, p is an integer of 1 to 30 and A ¹ is an alkylene group having 2 to 4 carbon atoms.)

6. The cleaning agent according to claim 5, wherein (after correction) (B) is a compound represented by the following general formula (2).

General formula

Paper that has been corrected (Article 2 of the Convention) RO- [(. C 2 H O ) n - (A 2 O) m] -. (C 2 HO) q (A ^ O) r -H (2)

(Wherein, R represents an aliphatic hydrocarbon group having 8 to 1-8 carbon atoms, lambda ² is the number 3 or 4 alkylene group with a carbon, n represents 0 or 1 to 1 2 integer, m is 0 or 1-6 , Q is an integer from 1 to 16, r is 0 or an integer from 1 to 15, (m + n + q) is an integer from 1 to 30, (n + q) / (m + n + q + r) represents 0.5 to 1.0, and [(C ₂ H ₄ O) π · (A ² O) _m ] represents random addition or block addition.

7. The washing according to claim 6 or 7, wherein (after correction) (B) is a compound produced by adding an alkylene oxide (bl) to an aliphatic alcohol (a1) and satisfying the following (1) and (2). Agent.

M w / M n ≤ 0.030 L n (v) + 1.010 (where v く 10) (3) M w / M n ≤-0.026 L n (v) + 1.139 (where v ≥ 10) (4 (Where v represents the average number of moles of alkylene oxide (bl) added per mole of aliphatic alcohol (a1).) )

c = (V + no / n0 0—1) / L Ln (no / n.) + n. / n. . 1 1] (5) {where, v is the same as in formula (3) or (4), and n is . Is the number of moles of the aliphatic alcohol (a1) used in the reaction, n. Represents the number of moles of the unreacted aliphatic alcohol (a 1). )

8. (After correction) The organic amine salt or quaternary ammonium salt (A) of the carboxyl group-containing polymer is contained as a builder, and the aliphatic alcohol

Amended paper (Article 19 of the Convention) A cleaning agent which is produced by adding an alkylene oxide (bl) to a polymer (al) and contains a compound (B) satisfying the following (1) and (2).

M w / M n ≤ 0.030 L n (v) + 1.010 (where v 1 1 0) (3) M w / M n ≤-0.026 L n (v) + 1.139 (where v ≥ 10) (4 ) {Where, v represents the average number of moles of alkylene oxide (b 1) added per mole of aliphatic alcohol (a 1). }

c = (V + n o / n .- 1) Z [L n n. . Z n. ) + n. n. . I 1] (5) {where, v is the same as equation (3) or (4), n. . Is the number of moles of the aliphatic alcohol (a1) used in the reaction, n. Represents the number of moles of the unreacted aliphatic alcohol (a 1). }

Paper captured (Article 19 of the Convention)

9. The cleansing agent according to any one of claims 18 to 18, which comprises (after correction) a cationic surfactant (C).

10. A nonionic surfactant (B) and a cationic surfactant (C) which are produced by adding an alkylene oxide (b1) to an aliphatic alcohol (a1) and satisfy the following (1) and (2). Cleaning agent contained.

w / M n ≤ 0.030 L n (v) + 1.010 (however, v 10) (3) M w / M n ≤-0.026 L n (v) + 1.139 (where v ≥ 10) (4) {Where, v represents the average number of moles of alkylene oxide (bl) added per mole of aliphatic alcohol (a1). }

c = v + n z n 00 — 1) / [L n / no + no / no o — 1], 5)

{Where v is the same as equation (3) or (4), n. . Is the number of moles of the aliphatic alcohol (a1) used in the reaction, n. Represents the number of moles of the unreacted aliphatic alcohol (a 1). }

11. The detergent according to claim 9 or 10, wherein (C) is at least one compound selected from the group consisting of compounds represented by the following general formulas (6) and (9).

Paper captured (Article 19 of the Convention)

However, in the formulas (6) to (9), RR ² and R ³ are a hydrogen atom or an alkyl group or an alkenyl group having 1 to 24 carbon atoms, or) 3 -hydroxyalkyl group, and R ⁴ and R are carbon atoms. 1-2 4 alkyl, human de Rokishiarukiru group, benzyl group, or the formula: a (a 'O) - Z (Note, a ¹ is § alkylene group having 2 to 4 carbon atoms, Z is a hydrogen atom or a Ashiru group , N is an integer of 1 to 50.), R ⁶ is an alkyl group having 1 to 36 carbon atoms, an alkenyl group or a] 3-hydroxyalkyl group, and Y is a group having 1 to 50 carbon atoms. 36 alkyl group, alkenyl group, | 3-hydroxyalkyl group, formula: R′CO ₂ CH ₂ (where R ⁴ is the same as described above) or formula: R ⁴ OCH ₂ — (wherein R ⁴ is the same as above), and the ion X is a halogen, a hydroxyion, a carbon atom 1 Carbonic ester having up to 4 alkyl groups

Paper (Article 19 of the Convention) O 00/34428-selected from the group consisting of ionic or sulphate ion and carboxylic or sulphonic acid ions having an alkyl or alkenyl group having 1 to 24 carbon atoms Indicates more than one kind of anion.

1 2. (After correction) The cleaning agent according to any one of claims 4 to 11, which comprises an organic amine salt or a quaternary ammonium salt (D) of a low molecular weight polycarboxylic acid.

Hesitated paper (Article 5 of the Convention) No description of the quaternary ammonium salt of the invention of the present application is found in the description based on Article 19 (1) of the Convention, References JP, 1-132692, JP, 7-18689, JP, 3-254828 and JP, 3-128997. . The reference JP, 6-346097 and JP, 3-215600 differ from the present invention in the water content.