JP5537826B2 - Anti-contamination agent for clothes cleaner and clothes cleaner - Google Patents

Description

  The present invention relates to a recontamination inhibitor for garment cleaning agents. More particularly, the present invention relates to a recontamination inhibitor for liquid detergents for clothing and a liquid detergent containing the same.

  In recent years, liquid clothing cleaning agents are frequently used as clothing cleaning agents used for washing clothes. Liquid clothing cleaners are superior to powder clothing cleaners in that they have good solubility in water, do not flake, and can be applied directly to dirt to provide a high cleaning effect. Conventionally, as a recontamination preventing agent used for powder liquid clothing detergents, polymers obtained by graft polymerization of an ethylenically unsaturated monomer such as (meth) acrylic acid to polyether (see Patent Document 1), unsaturated Polymers obtained by polymerizing monomers such as carboxylic acids and (meth) acrylic acid esters (see Patent Document 2) are known, and attempts to use them as anti-contamination agents for liquid clothing detergents It has been. However, the conventional anti-contamination agent for powder clothing detergents has a problem that the blending amount cannot be increased because the blending stability when blended with a liquid clothing detergent is poor. In recent years, drum-type washing machines have come to be used from the viewpoints of water saving and energy saving. However, the amount of water during washing is less than that of conventional vertical aquarium washing machines, and conventional liquid clothing detergents. The recontamination preventive agent has a problem that the recontamination prevention performance is insufficient and recontamination occurs remarkably.

JP-A-7-53993 JP-A-11-140488

  An object of the present invention is to provide a recontamination preventing agent for a garment cleaning agent that has good blending stability in a liquid garment cleaning agent and is excellent in recontamination prevention performance even when the amount of water during washing is small.

（式中、Ｒ¹ は、炭素数１〜２０のアルキレン基又は芳香環を有する炭素数６〜２４の２価の有機基であり、Ｒ ² は一般式（２）で表される基；ＯＡ¹は炭素数２及び／又は３のオキシアルキレン基；ＯＡ²及びＯＡ³はそれぞれ独立して炭素数２〜４のオキシアルキレン基；ａは３０〜５００の数；ｂ及びｃはそれぞれ独立して０〜１０の数；ｄは１〜１２０の数である。）

（式中、Ｘ ¹ 及びＸ ² はそれぞれ独立して水素又は炭素数１〜３のアルキル基である。） The inventor of the present invention has arrived at the present invention as a result of intensive studies to achieve the above object. That is, the present invention is a recontamination preventive for clothing detergents comprising a polymer (P) having a number average molecular weight of 2,000 to 30,000 represented by the general formula (1).

(In the formula, R ¹ is an alkylene group having 1 to 20 carbon atoms or a divalent organic group having 6 to 24 carbon atoms having an aromatic ring , and R ² is a group represented by the general formula (2) ; OA; ¹ is an oxyalkylene group having 2 and / or 3 carbon atoms; OA ² and OA ³ are each independently an oxyalkylene group having 2 to 4 carbon atoms; a is a number from 30 to 500; b and c are each independently A number from 0 to 10; d is a number from 1 to 120.)

(In the formula, X ¹ and X ² are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms.)

  The anti-contamination agent for clothing detergents of the present invention has good blending stability with liquid clothing detergents. Moreover, the liquid clothing cleaning agent containing the anti-contamination agent of the present invention has good anti-contamination properties, and particularly exhibits excellent anti-contamination properties even when washed with a small amount of water.

In the general formula (1) representing the polymer (P) in the present invention, R ¹ and R ² are each independently an alkylene group having 1 to 20 carbon atoms and a divalent organic group having 6 to 24 carbon atoms having an aromatic ring. It is.

Examples of the alkylene group having 1 to 20 carbon atoms include methylene group, ethylene group, butylene group, hexamethylene group, 2-ethylhexylene group, decylene group, dodecylene group, tetradecylene group, hexadecylene group, octadecylene group and icosylene group. Can be mentioned.
Examples of the divalent organic group having 6 to 24 carbon atoms having an aromatic ring include a phenylene group, a biphenylene group, a naphthylene group, and a phenylalkylene group having 1 to 6 carbon atoms in an alkylene group (for example, a phenylmethylene group and 1-phenylethylene). Group, 2-phenylpropylene group, 1-phenylbutylene group, 1-phenylpentylene group and 2-phenylhexylene group), alkylphenylene groups having 1 to 6 carbon atoms (for example, methylphenylene group, ethyl group) A phenylene group, a propylphenylene group, a butylphenylene group, a pentylphenylene group, a hexylphenylene group, etc.) and a group represented by the following general formula (2).

In the formula, X ¹ and X ² are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and a methyl group is preferable.

Among R ¹ , the alkylene group having 1 to 20 carbon atoms, the phenylene group, the biphenylene group, and the phenyl alkylene group having 1 to 6 carbon atoms of the alkylene group are more preferable from the viewpoint of preventing recontamination. Is an alkylene group having 2 to 12 carbon atoms, a phenylene group, and a phenylalkylene group having 1 to 6 carbon atoms in the alkylene group.

Among R ² , an alkylene group having 4 to 12 carbon atoms and a divalent organic group having 6 to 24 carbon atoms having an aromatic ring are preferable from the viewpoint of preventing recontamination, and carbon is more preferable. An alkylene group having 6 to 12 carbon atoms, a phenylene group, a biphenylene group, and a group represented by the general formula (2), particularly preferably an alkylene group having 6 to 12 carbon atoms and the group represented by the general formula (2). It is a group.

OA ¹ in the general formula (1) is an oxyalkylene group having 2 and / or 3 carbon atoms, and examples thereof include an oxyethylene group and an oxypropylene group. OA ¹ may be a combination of an oxyethylene group and an oxypropylene group. Of these, from the standpoint of preventing recontamination, the use of an oxyethylene group alone and the combined use of an oxyethylene group and an oxypropylene group are more preferred, and the use of an oxyethylene group alone is more preferred.
When the oxyethylene group and the oxypropylene group are used in combination, the molar ratio of oxyethylene group / oxypropylene group is preferably from 99/1 to 60/40, more preferably from 9/60, from the viewpoint of recontamination prevention. 10-70 / 30.

OA ² and OA ³ are each independently an oxyalkylene group having 2 to 4 carbon atoms, and examples thereof include an oxyethylene group, an oxypropylene group, and an oxybutylene group. Of these, oxyethylene groups and oxypropylene groups are preferable from the viewpoint of preventing recontamination, and oxyethylene groups are more preferable. OA ² and OA ³ may be a combination of two or more oxyalkylene groups. When two or more oxyalkylene groups are used in combination, a combination of an oxyethylene group and an oxypropylene group is preferred. When the oxyethylene group and the oxypropylene group are used in combination, the molar ratio of oxyethylene group / oxypropylene group is preferably from 99/1 to 60/40, more preferably from 90/40, from the viewpoint of recontamination prevention. 10-70 / 30.

A in the general formula (1) is a number of 10 to 500, preferably 20 to 400, and more preferably 30 to 300 from the viewpoint of recontamination prevention.
b and c are each independently a number of 0 to 10, preferably 1 to 8 and more preferably 1 to 5 from the viewpoint of recontamination prevention.
d is a number of 1 to 120, preferably 2 to 100, more preferably 3 to 50 from the viewpoint of preventing recontamination.
Since (OA ¹ ) _a , (OA ² ) _b and (OA ³ ) _c are usually produced by a ring-opening addition reaction of alkylene oxide, a, b and c are the average number of added moles of alkylene oxide. And not necessarily an integer. D is the average number of repeating units in the (poly) ester produced by the esterification reaction of the dicarboxylic acid having R ¹ and the diol having R ² , and is not necessarily an integer.

  The number average molecular weight (hereinafter abbreviated as Mn) of the polymer (P) is preferably 1,000 to 30,000, more preferably 2,000 to 20,000, from the viewpoint of recontamination prevention. Particularly preferred are 3,000 to 10,000. Mn can be measured by gel permeation chromatography using polyethylene glycol as a standard substance.

  The polymer (P) can be obtained by an esterification reaction between the carboxyl group-containing compound (A) represented by the general formula (3) and the polyether (B) represented by the general formula (4).

In the general formula (3), are the same groups corresponding to R ^1, wherein R ^2, OA ² and OA ³ are each formula in (1) R ^1, R ^2, OA ² and OA ^3, b, c and Each d is the same number corresponding to b, c and d in the general formula (1).

H- (OA ¹ ) a-OH (4)
In the formula, OA ¹ is the same group as OA ^{1 in the} general formula (1), and a is the same as a in the general formula (1).

The polymer (P) in the present invention can be obtained by an esterification reaction between the carboxyl group-containing compound (A) and the polyether (B). As the esterification reaction, for example, a carboxyl group-containing compound (A) and a polyether (B) are charged into a reaction vessel and produced by an ester reaction with stirring at a reaction temperature of 100 to 250 ° C. and a pressure of −0.1 to 1.2 MPa. A method of esterifying water (hereinafter abbreviated as produced water) while distilling out of the reaction system. The charged molar ratio [(A) / (B)] of the carboxyl group-containing compound (A) and the polyether (B) is preferably 0.1 to 1.0, more preferably from the viewpoint of re-contamination prevention. Is from 0.2 to 0.5. Moreover, in order to accelerate | stimulate reaction, it is preferable to use a 0.05 to 0.5 weight% catalyst based on the weight of a polymer (P). Catalysts include inorganic acids (such as sulfuric acid and hydrochloric acid), organic sulfonic acids (such as methane sulfonic acid, paratoluene sulfonic acid, xylene sulfonic acid, and naphthalene sulfonic acid) and organic metal compounds (such as dibutyltin oxide, tetraisopropoxy titanate). Bistriethanolamine titanate and potassium oxalate titanate). When a catalyst is used, the catalyst can be neutralized as necessary after completion of the esterification reaction and treated with an adsorbent to remove and purify the catalyst. Examples of the method for distilling the produced water out of the reaction system include the following methods.
(1) Using an organic solvent incompatible with water (for example, toluene, xylene, cyclohexane, etc.), the organic solvent and the generated water are azeotroped under reflux, and only the generated water is distilled out of the reaction system. Method (2) A method in which a carrier gas (for example, air, nitrogen, helium, argon, carbon dioxide, etc.) is blown into the reaction system, and produced water is distilled out of the reaction system together with the carrier gas. (3) The pressure in the reaction system is reduced. In the case where an organic solvent is used in the method (1), the organic solvent can be distilled by reducing the pressure in the reaction system after completion of the esterification reaction. .

  The carboxyl group-containing compound (A) is a (poly) ester of the dicarboxylic acid (a) represented by the general formula (5) or the anhydride of the dicarboxylic acid and the diol (b) represented by the general formula (6). It can be obtained by a chemical reaction. About (poly) esterification reaction, the method similar to the method of obtaining polymer (P) by esterification reaction of (A) and (B) is mentioned.

HOOC-R ¹ -COOH (5)
In the formula, R ¹ is the same group as the group in the general formula (3).

^{H- (OA 2) b-O} -R 2 - (OA 3) c-OH (6)
In the formula, R ² , OA ² , OA ³ , b and c are the same as those in the general formula (3).

  Examples of the dicarboxylic acid (a) represented by the general formula (5) and its anhydride include linear or branched chain saturated dicarboxylic acids having 3 to 22 carbon atoms (for example, malonic acid, succinic acid, glutaric acid, methyl succinic acid). , Ethyl succinic acid, dimethyl malonic acid, α-methyl glutaric acid, β-methyl glutaric acid, 2,4-diethyl glutaric acid, isopropyl malonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid , Undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid and dodecylsuccinic acid), and aromatic dicarboxylic acids having 8 to 26 carbon atoms (for example, terephthalic acid) , Isophthalic acid, phthalic acid, phenylmalon Acid, phenylsuccinic acid, β-phenylglutaric acid, α-phenyladipic acid, β-phenyladipic acid, biphenyl-2,2′- and 4,4′-dicarboxylic acid and naphthalenedicarboxylic acid).

  Examples of dicarboxylic acid anhydrides include the above dicarboxylic acid anhydrides such as succinic anhydride and phthalic anhydride.

  The dicarboxylic acid and its anhydride may be used alone or in combination of two or more. Of these, aromatic dicarboxylic acids are preferable from the viewpoint of preventing recontamination, and fumaric acid, terephthalic acid, isophthalic acid and phthalic acid are more preferable.

  As the diol (b) represented by the general formula (6), an alkylene oxide (hereinafter abbreviated as AO) adduct of an alkanediol having 1 to 20 carbon atoms and a carbon having an aromatic ring. Examples thereof include AO adducts of compounds having two hydroxyl groups of formulas 6 to 24.

  Examples of the alkanediol having 1 to 20 carbon atoms include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol and decanediol. Examples of the AO adduct of alkanediol include compounds obtained by adding AO having 2 to 4 carbon atoms to the diol. As AO having 2 to 4 carbon atoms, ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,2-butylene oxide and 1,4-butylene. And oxide (hereinafter abbreviated as BO). Two or more kinds of these AOs may be used in combination, and the combination mode in the case of using two or more kinds may be any of block addition, random addition, and combination thereof. The number of moles of AO added per molecule of alkanediol is usually 2 to 20 moles.

  Examples of the compound having two hydroxyl groups in the AO adduct of a compound having two hydroxyl groups having 6 to 24 carbon atoms having an aromatic ring include bisphenol A, cresol, hydroxymethylphenol, and hydroxyethylphenol.

  Of the diols (b) represented by the general formula (6), an AO adduct of a compound having two hydroxyl groups having 6 to 24 carbon atoms and having an aromatic ring is preferable from the viewpoint of preventing recontamination. More preferred is the AO adduct of bisphenol A.

Specific examples of the polymer (P) represented by the general formula (1) include the following.
(1): [In the general formula (1), OA1, OA2 and OA3 = oxyethylene group, R1 = phenylene group, a = 45, b and c = 1, d = 7.5, R2 is the general formula (2) A compound represented by the formula: wherein X1 and X2 are methyl groups]
(2): [In the general formula (1), OA1, OA2 and OA3 = oxyethylene group, R1 = phenylene group, a = 91, b and c = 1, d = 7.5, R2 is the general formula (2) A compound represented by the formula: wherein X1 and X2 are methyl groups]
(3): [in the general formula (1), OA1 = combination of oxyethylene groups and oxypropylene groups, OA2 and OA ³ = oxyethylene group, R1 = phenylene group, a = 91, b and c = 1, d = 7.5, a compound in which R2 is a group represented by the general formula (2), and X1 and X2 are methyl groups]
(4): [In the general formula (1), OA1, OA2 and OA3 = oxyethylene group, R1 = phenylene group, a = 91, b and c = 2, d = 7.5, R2 is the general formula (2) A compound represented by the formula: wherein X1 and X2 are methyl groups]
(5): [In the general formula (1), OA1, OA2 and OA3 = oxyethylene group, R1 = hexamethylene group, a = 91, b and c = 1, d = 7.5, R2 is represented by the general formula (2 And a compound represented by X1 and X2 = methyl group]
(6): [In the general formula (1), OA1, OA2 and OA3 = oxyethylene group, R1 = phenylene group, a = 91, b and c = 1, d = 7.5, R2 = hexamethylene group. Compound]
(7): [In the general formula (1), OA1 = oxyethylene group, OA2 and OA3 = oxypropylene group, R1 = octadecylene group, a = 300, b and c = 10, d = 100, R2 = phenylene group Some compounds]
(8): [In the general formula (1), OA1 = combination of oxyethylene group and oxypropylene group, OA2 and OA3 = oxyethylene group, R1 = 2-phenylpropylene group, a = 30, b and c = 8, Compound in which d = 100 and R2 = dodecylene group]
(9): [In the general formula (1), OA1 = combination of oxyethylene group and oxypropylene group, OA2 and OA3 = oxyethylene group, R1 = 2-phenylpropylene group, a = 450, b and c = 3, Compound in which d = 50, R2 is a group represented by the general formula (2), and X1 and X2 are hydrogen atoms]

The anti-contamination agent for clothing detergents of the present invention may contain a solvent and / or a known anti-contamination agent as necessary. Examples of the solvent include water, monohydric alcohols (for example, methanol, ethanol and isopropyl alcohol), dihydric alcohols (for example, ethylene glycol, propylene glycol and the like) and the like. Among these, water is preferable from the viewpoint of solubility. The content of the solvent is preferably 5 to 300% by weight based on the total weight of the polymer (P).
Known recontamination inhibitors include polycarboxylates [eg, polymers such as acrylic acid, methacrylic acid and itaconic acid (Mn = 1,000-100,000) and alkalis (eg, sodium hydroxide, potassium hydroxide, Salt with ammonia, triethanolamine, diethanolamine, monoethanolamine, etc.]], carboxymethylcellulose (Mn = 10,000-100,000), polyethylene glycol (Mn = 1,000-100,000) and polyvinyl alcohol (Mn) = 1,000 to 100,000).
The content of the known anti-staining agent is preferably 5 to 300% by weight, based on the total weight of the polymer (P).

  Although the property of the anti-staining agent for clothing detergents of the present invention is not particularly limited, examples thereof include liquid, paste, powder, flake and block. Among these, liquid is preferable from the viewpoint of easy handling.

In the case of containing only the polymer (P), the anti-fouling agent for garment cleaning agents of the present invention synthesizes the polymer (P) and then pulverizers (for example, a mill mixer, a ball mill, a jet pulverizer, a colloid mill, and a homogenizer). Etc.) and an appropriate size (powder, flake, block, etc.).
In the case of containing a solvent, the polymer (P) can be synthesized by a method in which the polymer (P) is synthesized and then dissolved in the solvent.
When a known recontamination inhibitor is contained, the polymer (P) [or the polymer (P) solution (suspension or emulsion)] and a known recontamination inhibitor {or a known recontamination inhibitor solution ( Suspension or emulsion)}.

  The anti-contamination agent for clothing cleaners of the present invention can also be used as a constituent of the clothing cleaner of the present invention, but is not blended with the clothing cleaner, and separately from the clothing cleaner. It is also possible to add to the washing water of clothing.

  The clothing cleaning agent of the present invention is a clothing cleaning agent containing the anti-staining agent for clothing cleaning agents of the present invention. In addition to the anti-staining agent of the present invention, it contains a known nonionic, anionic, amphoteric or cationic surfactant (described in JP-A-2004-27181). Among these surfactants, nonionic surfactant (C) and anionic surfactant (D) are preferable from the viewpoint of detergency.

  Examples of the nonionic surfactant (C) include an alkylene oxide addition type nonionic surfactant (C1) and a polyhydric alcohol type nonionic surfactant (C2).

  (C1) includes higher alcohol (8 to 18 carbon atoms) alkylene (2 to 4 carbon atoms, preferably 2) oxide adduct (1 to 30 moles added per active hydrogen), alkyl (carbon number) 1-12) Phenol EO adduct (addition mole number 1-30), higher amine (8-22 carbon atoms) alkylene (2-4 carbon atoms, preferably 2) oxide adduct (addition per active hydrogen) 1-40 moles), fatty acid (8-18 carbon atoms) EO adduct (1-60 added moles per active hydrogen), polypropylene glycol (molecular weight 200-4000) EO adduct (per active hydrogen) 1 to 50), polyoxyethylene (3 to 30 repeating units) alkyl (6 to 20 carbon atoms) allyl ether and sorbitan monolaurate EO adduct (active water) Polyhydric (2 to 8 or more) alcohols (2 carbon atoms) such as 1 to 30 moles added per 1) and sorbitan monooleate EO adduct (1 to 30 moles added per active hydrogen) To 30) fatty acid (carbon number 8 to 24) ester EO adduct (number of added moles per active hydrogen 1 to 30) and the like.

  As (C2), fatty acid (carbon number 8) of polyhydric (2 to 8 or more) alcohol (carbon number 2 to 30) such as glycerol monostearate, glycerol monooleate, sorbitan monolaurate and sorbitan monooleate -24) Esters and fatty acid alkanolamides such as lauric acid monoethanolamide and lauric acid diethanolamide.

  Among the nonionic surfactants (C), higher alcohols (8 to 18 carbon atoms) alkylene (2 to 4 carbon atoms, preferably 2) oxide adduct (active hydrogen 1) are preferred from the viewpoint of detergency. 1 to 30 addition moles per unit) and higher amines (8 to 22 carbon atoms) alkylene (2 to 4 carbons, preferably 2) oxide adduct (1 to 40 addition moles per active hydrogen) It is.

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

  Of the anionic surfactants (D), ether carboxylic acids (salts) having a hydrocarbon group having 8 to 24 carbon atoms and ethers having a hydrocarbon group having 8 to 24 carbon atoms are preferable from the viewpoint of detergency. It is a sulfonate having a sulfate ester salt and a hydrocarbon group having 8 to 24 carbon atoms.

  The clothing cleaning agent of the present invention may contain water as necessary in order to make the properties liquid or pasty.

  The clothing cleaning agent of the present invention may contain other known components as necessary, for example, builders, chelating agents, enzymes, hydrophilic solvents, antifoaming agents, fluorescent whitening agents, bleaching agents described in JP-A-2004-27181. , Softeners, disinfectants, fragrances and colorants may be included.

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

The content of the anti-contamination agent for detergents of the present invention, a surfactant, water and other components in the clothes detergent of the present invention is as follows.
The content of the anti-recontamination agent for clothing detergents of the present invention is preferably 0.1 to 5% by weight, more preferably from the viewpoint of anti-staining properties, based on the total weight of the clothing detergent. It is 0.5 to 5% by weight, particularly preferably 1 to 5% by weight.
The content of the surfactant is preferably 95 to 99.9% by weight, more preferably 95 to 99.5% by weight based on the total weight of the cleaning agent, and more preferably 95 to 99.5% by weight. Preferred is 95 to 99% by weight.
The water content is preferably 1,000% by weight or less, more preferably 500% by weight or less, and particularly preferably 100% by weight or less, based on the total weight of the clothing detergent.
Among the other components, the content of the builder and the chelating agent is preferably 10% by weight or less, and more preferably 5% by weight or less, based on the total weight of the clothing detergent. The content of the optical brightener, bleach, softener, enzyme, disinfectant, fragrance, colorant and antifoaming agent is preferably 5% by weight or less based on the total weight of the clothing detergent, More preferred is 2% by weight or less. The content of the hydrophilic solvent is preferably 20% by weight or less, and more preferably 10% by weight or less, based on the total weight of the clothes detergent.

  Although the property of the clothes washing | cleaning agent of this invention is not specifically limited, Liquid state, paste shape, powder shape, flake shape, block shape, etc. are mentioned. Among these, liquid is preferable from the viewpoint of easy handling.

The clothing cleaning agent of the present invention can be produced by selecting the following method depending on the difference in properties of the clothing cleaning agent.
(1) When the clothes cleaning agent is in a liquid or paste state In the mixing tank equipped with a stirrer and a temperature control function, the anti-contamination agent and surfactant for the clothes cleaning agent of the present invention, and if necessary, water and A method in which other components are charged in the order of addition without particular limitation and stirred at 10 to 50 ° C. until uniform.
(2) When the clothes cleaning agent is in powder form In the mixing tank equipped with a stirrer and a temperature control function, the anti-contamination agent and surfactant for the clothes cleaning agent of the present invention, and if necessary, water and / or The other components are charged without any particular restriction in the order of addition and stirred until uniform at 10 to 50 ° C., and then a spray dryer (for example, a pressure spray nozzle type spray dryer, a two-fluid spray nozzle type spray dryer and a rotating disk type) Spray drying with a spray dryer or the like).
(3) When the clothes cleaning agent is in the form of powder, flakes, or blocks, the mixing tank equipped with a stirrer and a temperature control function, and the anti-contamination agent and surfactant for the clothes cleaning agent of the present invention are further required. Then, the other components are charged to the charging order without any particular restriction, and stirred until it is uniformly melted at 30 to 100 ° C., then the melt is taken out on the release paper and cooled to room temperature, and the resulting solidified product is pulverized. (For example, a mill mixer, a ball mill, a jet mill, a colloid mill, and a homogenizer) A method of pulverizing to an appropriate size (powder, flake or block).

  The anti-recontamination agent for garment cleaning agents and the garment cleaning agent containing the same according to the present invention are useful for water cleaning natural fibers, synthetic fiber, and mixed / knitted / woven fabric fibers.

  The amount of use of the antifouling agent for clothes cleaning agent of the present invention is arbitrarily selected according to the degree of soiling of clothes to be cleaned, etc., but preferably 0.2 mg to 2 g, more preferably 1 kg of clothes to be cleaned. Is 0.9 mg to 1.5 g, particularly preferably 7 mg to 1.2 g.

  Although the usage-amount of the clothes cleaning agent of this invention is arbitrarily selected according to the grade etc. of the clothes to wash | clean, 1-30g is preferable per 1 kg of clothes to wash | clean, More preferably, it is 5-20g. Particularly preferred is 10 to 15 g.

  The amount of water used for washing (washing) the clothing using the anti-recontamination agent for clothing cleaning of the present invention or the clothing cleaning agent containing the same is about 1 to 30 L per 1 kg of clothing. is there.

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

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

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

Mn was measured by GPC under the following conditions.
Model: HLC-8220GPC [Tosoh Corporation liquid chromatograph]
Column: TSK gel Super H4000
+ TSK gel Super H3000
+ TSK gel Super H2000
[Both made by Tosoh Corporation]
Column temperature: 40 ° C
Detector: RI (Refractive Index)
Solvent: Tetrahydrofuran Flow rate: 0.6 ml / min Sample concentration: 0.25% by weight
Injection volume: 10 μl
Standard: Polystyrene
[TSK STANDARD POLYSTYRENE; manufactured by Tosoh Corporation]

<Production Example 1> [Synthesis of polymer (P-1)]
In a glass reaction vessel equipped with a stirrer, a heating / cooling device, a nitrogen vent pipe and a water diversion pipe, an EO2 molar adduct “New Paul BPE-20” [manufactured by Sanyo Chemical Industries, Ltd .: hereinafter referred to as BPE-20] Abbreviated. ] 300 parts, 120 parts of terephthalic acid (BPE-20 / terephthalic acid = 1.28 / 1 molar ratio) and 1.2 parts of bistriethanolamine titanate were added for 10 hours while distilling off water at 200 ° C. under nitrogen flow. Reacted. After cooling to 180 ° C., 840 parts of polyoxyethylene glycol “PEG2000” (manufactured by Sanyo Chemical Industries Co., Ltd.) was added, and the mixture was allowed to react for 5 hours while distilling off water at 180 ° C. under a nitrogen stream. Polymer (P1) 1285 Part (Mn = 5500) was obtained. [(P-1) is OA1, OA2 and OA3 = oxyethylene group, R1 = phenylene group, a = 45, b and c = 1, d in the general formula (1). = 7.5, a compound in which R2 is a group represented by the general formula (2), and X1 and X2 are methyl groups.

<Production Example 2> [Synthesis of polymer (P-2)]
In the same manner as in Production Example 1, except that 840 parts of “PEG2000” was changed to 1325 parts of polyoxyethylene glycol “PEG4000” (manufactured by Sanyo Chemical Industries, Ltd.), 1725 parts of polymer (P2) (Mn = 7600) were obtained. [(P-2) is general formula (1), OA1, OA2 and OA3 = oxyethylene group, R1 = phenylene group, a = 91, b and c = 1, d = 7.5, R2 is general Compound represented by formula (2), wherein X1 and X2 = methyl group].

<Production Example 3> [Synthesis of polymer (P-3)]
1840 parts of polymer (P3) in the same manner as in Production Example 1, except that 840 parts of “PEG2000” was changed to 1435 parts of EO adduct “New Pole PE-74” (manufactured by Sanyo Chemical Industries, Ltd.) of polyoxypropylene (Mn = 7800) was obtained [(P-3) in the general formula (1), OA1 = oxyethylene group and oxypropylene group in combination, OA2 and OA3 = oxyethylene group, R1 = phenylene group, a = 91, b and c = 1, d = 7.5, a compound in which R2 is a group represented by the general formula (2), and X1 and X2 = methyl group].

<Production Example 4> [Synthesis of polymer (P-4)]
In a glass reaction vessel equipped with a stirrer, a heating / cooling device, a nitrogen ventilation pipe and a water diversion pipe, an EO4 mol adduct “New Pole BPE-40” [manufactured by Sanyo Chemical Industries, Ltd .: hereinafter referred to as BPE-40 Abbreviated. ] 180 parts, 60 parts of terephthalic acid (BPE-40 / terephthalic acid = 1.28 / 1 molar ratio) and 0.6 parts of bistriethanolamine titanate were added for 10 hours while distilling off water at 200 ° C. under nitrogen flow. Reacted. After cooling to 180 ° C., 650 parts of polyoxyethylene glycol “PEG 4000” (manufactured by Sanyo Chemical Industries Co., Ltd.) was added and reacted at 180 ° C. for 5 hours to obtain 877 parts of polymer (P4) (Mn = 8200). (P-4) is represented by the general formula (1) in which OA1, OA2 and OA3 = oxyethylene group, R1 = phenylene group, a = 91, b and c = 2, d = 7.5, R2 is represented by the general formula ( A compound represented by 2), wherein X1 and X2 are methyl groups.

<Production Example 5> [Synthesis of polymer (P-5)]
Polymer (P5) 1730 parts (Mn = 7600) was obtained in the same manner as in Production Example 1 except that 120 parts of terephthalic acid was changed to 124 parts of adipic acid and 840 parts of “PEG2000” were changed to 1325 parts of “PEG4000”. (P-5) is represented by the general formula (1), OA1, OA2 and OA3 = oxyethylene group, R1 = tetramethylene group, a = 91, b and c = 1, d = 7.5, and R2 is the general formula A compound represented by (2), wherein X1 and X2 = methyl group].

<Production Example 6> Synthesis of polymer (P-6)]
Polymer (P6) was prepared in the same manner as in Production Example 1 except that 300 parts of “BPE-20” was changed to 187 parts of EO2 molar adduct of 1,6 hexanediol and 840 parts of “PEG2000” were changed to 1325 parts of “PEG4000”. 1615 parts (Mn = 7600) were obtained. [(P-6) is a compound represented by the following formula (1): OA1, OA2 and OA3 = oxyethylene group, R1 = phenylene group, a = 91, b and c = 1, Compound in which d = 7.5 and R2 = hexamethylene group].

<Production Example 7> [Synthesis of Nonionic Surfactant (C-1)]
A pressurized reaction vessel equipped with a stirrer, a heating / cooling device and a dropping cylinder is charged with 109 parts of stearylamine and 0.2 parts of potassium hydroxide, and after nitrogen substitution, dehydration is performed at 120 ° C. for 1 hour under reduced pressure (20 mmHg). went. Next, the temperature was raised to 130 ° C., 267 parts of EO was added dropwise over 2 hours while adjusting the pressure so that it did not exceed 0.5 MPa, and further aged for 3 hours at the same temperature to obtain the nonionic surfactant (A1) [ Stearylamine- (EO) ₁₅ adduct], 376 parts.

<Production Example 8> [Synthesis of Anionic Surfactant (D-1)]
A glass reaction vessel equipped with a stirrer, a heating / cooling device, and a dropping funnel was charged with 100 parts of dodecylbenzenesulfonic acid “Taika Power L-121” [solid content concentration 20 wt%, manufactured by Teika Co., Ltd.] and stirred. At 20 to 30 ° C., 3.7 parts of monoethanolamine was added dropwise over 1 hour, and the mixture was further stirred at the same temperature for 1 hour. The anionic surfactant (D-1) [dodecylbenzenesulfonic acid monoethanolamine salt ( Degree of neutralization: 100 mol%, solid content concentration 22.9 wt%)] was obtained.

<Examples 1-11 and Comparative Examples 1-3>
The raw materials for the number of parts of the garment detergent listed in Table 1 were charged into a mixing tank equipped with a stirrer and a temperature control function, and stirred at 20 to 30 ° C. for 1 hour to garment detergent (Examples 1 to 11 and comparison) Examples 1 to 3) were prepared. The resulting clothing detergent was evaluated for blending stability, detergency and anti-recontamination property by the following methods, and the results are shown in Table 1.
In addition, the following were used for each raw material described in Table 1.
Sodium polyacrylate (Mn = 10,000): Carribbon L-400 [manufactured by Sanyo Chemical Industries, Ltd.]
Enzyme: Protease “Alcalase 2.5L” [Novo Nordisk Pharma Co., Ltd.]

<Compounding stability>
The clothing detergents of Examples 1 to 11 and Comparative Examples 1 to 3 were allowed to stand in a constant temperature bath at 40 ° C. for one month, and then the appearance was visually observed and evaluated according to the following criteria.
(Evaluation criteria)
○: Uniform transparent liquid △: Slightly hazy ×: Completely separated into two layers

<Cleanability>
Wet artificial contamination cloth having the soil composition shown in Table 2 in an aqueous solution prepared by dissolving 0.6 g of the clothing detergent of any of Examples 1 to 11 and Comparative Examples 1 to 999.4 g of water (Laundry Science Foundation) 10 pieces), and after washing and rinsing under the following conditions using a targotometer [manufactured by Daiei Chemical Co., Ltd.], the cloth is taken out and the gear oven “GPS-222” [Espec Corp. The product was dried at 70 ° C. for 60 minutes to obtain a test cloth. Then, using a spectroscopic color difference meter “SpectroPhotometer SD5000” (manufactured by Nippon Denshoku Industries Co., Ltd.), the reflectance of 540 nm of the test cloth is measured in two places, one on each side of the test cloth (test cloth 10). A total of 20 spots were measured, and the average value of the obtained reflectances was obtained, and the cleaning rate (%) was calculated by the following equation (7).
(Cleaning conditions)
Time: 10 minutes, temperature: 25 ° C., rotation speed: 85 rpm
(Rinsing conditions)
Time: 1 minute, temperature: 25 ° C., rotation speed: 85 rpm
Cleaning rate (%) = {(R _W −R _S ) / (R _I −R _S )} × 100 (7)
In the formula (7), R _I is the reflectance of the cleaning cloth (cloth having no soil composition before the cleaning test), R _W is the reflectance of the cleaning cloth (cloth having the soil composition after the cleaning test), R _S represents the reflectance of a contaminated cloth (a cloth having a dirt composition before the cleaning test).
Moreover, the used artificially contaminated cloth is a wet artificially stained cloth having a dirt composition shown in Table 2 (reflectance at 540 nm is 40 ± 5%, manufactured by the Laundry Science Association).

<Recontamination prevention>
In an aqueous solution obtained by dissolving 0.3 g of the garment cleaning agent of any of Examples 1 to 11 and Comparative Examples 1 to 439.7 g in water, a cloth [cotton width 3 ( JIS L0803-1980)] was cut into 10 cm × 10 cm, and 0.04 g of carbon black (manufactured by the Laundry Science Association) designated by the Japan Oil Chemistry Association was added to the targotometer [Daiei Chemical Co., Ltd.] After washing and rinsing under the following conditions, the cloth was taken out and dried at 70 ° C. for 60 minutes using a gear oven “GPS-222” [manufactured by ESPEC Corporation] to obtain a test cloth. . Subsequently, using a spectroscopic color difference meter [SpectroPhotometer SD5000] [manufactured by Nippon Denshoku Industries Co., Ltd.], the reflectance at 540 nm of the test cloth was measured at two places on each side of the test cloth, a total of four places (test cloth 20). A total of 80 spots were measured, and the average value of the obtained reflectances was obtained, and the recontamination prevention rate (%) was calculated by the following equation (8).
(Cleaning conditions)
Time: 10 minutes, temperature: 25 ° C., rotation speed: 120 rpm
(Rinsing conditions)
Time: 1 minute, temperature: 25 ° C., rotation speed: 120 rpm
Recontamination prevention rate (%) = 100 − [(R _I −R _S ) / R _I ] × 100 (8)
In formula (8), R _I represents the reflectance of the clean cloth (cloth before the cleaning test), and R _S represents the reflectance of the test cloth (cloth after the cleaning test).

  As shown in Table 1, the clothes detergent (Examples 1-11) of this invention was the result which was excellent in mixing | blending stability, cleaning property, and recontamination prevention property compared with Comparative Examples 1-3.

  The anti-recontamination agent for garment cleaning agents of the present invention and the garment cleaning agent containing the same have good blending stability with liquid garment cleaning agents and are excellent in anti-staining and decontamination properties. It is useful for water washing of synthetic fiber and these mixed spun woven fabric fibers, and is not only used for conventional vertical aquarium washing machines, but also has a drum type in which the amount of water during washing is relatively small compared to the amount of fibers. It is useful for washing machines such as washing machines.

Claims (3)

A recontamination preventive for clothing detergents comprising a polymer (P) having a number average molecular weight of 2,000 to 30,000 represented by the general formula (1).

(In the formula, R ¹ is an alkylene group having 1 to 20 carbon atoms or a divalent organic group having 6 to 24 carbon atoms having an aromatic ring , and R ² is a group represented by the general formula (2) ; OA; ¹ is an oxyalkylene group having 2 and / or 3 carbon atoms; OA ² and OA ³ are each independently an oxyalkylene group having 2 to 4 carbon atoms; a is a number from 30 to 500; b and c are each independently A number from 0 to 10; d is a number from 1 to 120.)

(In the formula, X ¹ and X ² are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms.) The polymer (P) is a polymer obtained by an esterification reaction between a carboxyl group-containing compound (A) represented by the general formula (3) and a polyether (B) represented by the general formula (4). The anti-recontamination agent for clothing cleaners according to claim 1.

(In the formula, R ¹ is an alkylene group having 1 to 20 carbon atoms or a divalent organic group having 6 to 24 carbon atoms having an aromatic ring , and R ² is a group represented by the general formula (2) ; OA; ² and OA ³ are each independently an oxyalkylene group having 2 to 4 carbon atoms; b and c are each independently a number from 0 to 10; d is a number from 1 to 120.)
^{H- (OA 1) a -OH (} 4)
(In the formula, OA ¹ is an oxyalkylene group having 2 and / or 3 carbon atoms; a is a number of 30 to 500.) A clothing detergent comprising 0.1 to 5% by weight of the antifouling agent for clothing detergent according to claim 1 or 2 based on the weight of the detergent.