KR20180074657A - Liquid cleaner - Google Patents

Abstract

A liquid detergent containing a propylene oxide adduct (A) of a trihydric alcohol and a surfactant (B).

Description

Liquid cleaner

The present invention relates to a liquid detergent.

The present application claims priority to U.S. Patent Application No. 2015-214548, filed on October 30, 2015, the contents of which are incorporated herein by reference.

Conventionally, a detergent excellent in detergency against stain-resistant contamination such as food spillage contamination, dirt pollution, sebum contamination on clothes sleeves, and lipstick contamination has been proposed.

For example, as a detergent excellent in detergency against oily pollution such as lipstick pollution, Patent Document 1 discloses a detergent comprising an alkyl sulfate-based surfactant and an anionic surfactant containing an alcohol ethoxylate surfactant Lt; RTI ID = 0.0 > a < / RTI > system. Patent Document 2 discloses a detergent composition comprising a specific amount of a hydrophilic main chain (main chain) and a cleaning polymer having at least one hydrophobic pendant group.

Japan Specification No. 2014-531506 Japan Specification No. 2008-540813

However, in the technologies of Patent Documents 1 and 2, the detergency against oily pollution was not sufficiently satisfactory. In particular, lipophilic properties, such as oil-based ink contamination, did not have sufficient detergency against stronger contamination.

In addition, providing a liquid detergent is required to have liquid stability, such as when the liquid detergent is solidified or precipitates are not formed, even when stored under an ambient temperature or a low temperature (for example, 5 to 35 DEG C).

In recent years, there has been an increase in the chance that a drum type washing machine is used when cleaning textile products such as medical care. In the drum type washing machine, cleaning is usually performed by tapping. At this time, if the amount of the foam is too large, the foam may become a cushion, resulting in that the cleaning effect due to the tapping may not be sufficiently obtained. Therefore, the liquid detergent may be required to have suppressing properties.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and aims to provide a liquid detergent excellent in detergency against oily pollution.

As a result of intensive studies, the present inventors have found that the following liquid cleansing agents can solve the above problems.

That is, the present invention has the following aspects.

[1] A liquid detergent containing a propylene oxide adduct (A) of a trivalent alcohol and a surfactant (B).

[2] The liquid detergent according to [1], wherein the mass ratio of the component (A) / the component (B) is 0.01 to 0.15.

[3] The liquid detergent according to [1] or [2], wherein the component (A) has a weight average molecular weight of 1,500 to 6,000.

[4] The liquid detergent according to any one of [1] to [3], wherein the component (A) is a propylene oxide adduct of glycerin.

[5] The composition according to any one of [1] to [5], wherein the content of the component (A) is 0.1 to 5% by mass with respect to the total mass of the liquid detergent and the content of the component (B) The liquid detergent according to any one of [1] to [4].

[6] The liquid detergent according to any one of [1] to [5], wherein the component (B) contains a nonionic surfactant and an anionic surfactant.

[7] The method according to any one of [1] to [6], wherein the mass ratio of the nonionic surfactant to the anionic surfactant is 0.1 to 20 in mass ratio represented by a nonionic surfactant / anionic surfactant Liquid detergent.

[8] The liquid detergent according to any one of [1] to [7], further comprising an alkylene oxide adduct (C) of a polyalkyleneamine.

[9] The liquid detergent according to any one of [1] to [8], wherein the component (B) is a bovine surfactant and a higher fatty acid or a salt thereof.

The liquid detergent of the present invention is superior in detergency against oily pollution.

The liquid detergent of the present invention is a composition containing a propylene oxide adduct of a trihydric alcohol (component (A)) and a surfactant (component (B)).

≪ Component (A) >

The component (A) is a propylene oxide adduct of a trivalent alcohol.

The liquid detergent of the present invention contains the component (A), thereby increasing the detergency against oily pollution. In addition, the suppression property is enhanced.

Oil-based ink contamination is contamination which is difficult to penetrate into fibers and remove by cleaning. The component (A) has high affinity for oil-based ink contamination and effectively works against oil-based ink contamination penetrating into the fibers. The liquid detergent of the present invention contains the component (A), thereby increasing the detergency against oily ink contamination.

Examples of the trivalent alcohol include a trivalent alcohol having 3 to 20 carbon atoms. The trivalent alcohol having 3 to 20 carbon atoms is preferably an aliphatic trivalent alcohol having 3 to 20 carbon atoms. The aliphatic group of the aliphatic trivalent alcohol may be interrupted by a nitrogen atom or the like.

Examples of the trivalent alcohol include glycerin, trimethylolethane, trimethylolpropane, trimethylol 7butane, trimethylolooctane, trimethylolone, 2-methyl-1,2,3-propanetriol, Butanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 1,2,3- Pentanetriol, 1,2,4-pentanetriol, 1,2,6-hexanetriol, 2,3,4-hexanetriol, 4-propyl- 4,5-heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, 3-methyl-1,3,5-pentanetriol, trialkanolamine and the like.

As the trivalent alcohol, glycerin and trimethylolpropane are preferable, and glycerin is more preferable.

The propylene oxide adduct of trihydric alcohol preferably has a weight average molecular weight of 1,500 to 6,000, more preferably 2,500 to 5,500, further preferably 3,000 to 5,000, and particularly preferably 3,500 to 4,500 .

If the weight average molecular weight is above the lower limit value, the detergency against oily pollution tends to become higher. If the weight average molecular weight is less than the upper limit, the liquid stability (solidification of the liquid detergent, or precipitation of the liquid detergent) tends to become higher.

The weight average molecular weight in the present specification is a value obtained from a molecular weight distribution obtained by GPC (gel permeation chromatography) using polypropylene glycol (weight average molecular weight: 800, 1200, 2000, 4000) as a standard.

As a propylene oxide adduct of a trihydric alcohol, a propylene oxide adduct of glycerin is preferable.

As the propylene oxide adduct of glycerin, a compound represented by the following general formula (I) is preferable.

[Chemical Formula 1]

In the formula (I), PO is an oxypropylene group. a, b and c each independently represents the average number of repeating units of PO and the weight average molecular weight of the compound represented by formula (I) is 1500 to 6000. The number of a, b, and c is preferably such that the weight average molecular weight of the compound represented by formula (I) is 2500 to 5500, more preferably 3000 to 5000, and particularly preferably 3500 to 4500.

(a + b + c), preferably 20 to 120, more preferably 50 to 100, still more preferably 55 to 90, 80 is particularly preferable.

The method for producing the component (A) can be produced by a method of addition polymerization of propylene oxide to a trihydric alcohol. By controlling the addition mole number of propylene oxide, propylene oxide having a desired weight average molecular weight Water can be produced.

The component (A) may be used singly or in combination of two or more.

The content of the component (A) in the liquid detergent is preferably from 0.1 to 5% by mass, more preferably from 0.5 to 3% by mass, and still more preferably from 0.6 to 2% by mass, based on the total mass of the liquid detergent. When the content of the component (A) is lower than the lower limit, the detergency against oily pollution tends to become higher. In addition, the suppression property tends to become higher. When the content of the component (A) is less than the upper limit, the liquid stability tends to be higher.

≪ Component (B) >

Component (B) is a surfactant. In the liquid detergent of the present invention, the component (B) functions as a cleaning component. Further, the liquid detergent of the present invention contains the component (B), so that the dispersion (dispersion) stability of the component (A) is enhanced.

As the component (B), known surfactants can be used.

Examples of the component (B) include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and semi-polar surfactants. From the standpoint of cleaning performance, anionic surfactants and nonionic surfactants are preferred. Further, a nonionic surfactant is preferable in that the dispersion stability of the component (A) becomes higher.

[Nonionic surfactant]

Examples of the nonionic surfactant include the following (1) to (8).

(1) an average of 3 to 30 mol, preferably 3 to 20 mol, of alkylene oxide having 2 to 4 carbon atoms per mol of monohydric aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, Is a polyoxyalkylene alkyl (or alkenyl) ether in which 5 to 20 moles is added. Of these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are suitable. Examples of the monovalent aliphatic alcohol used herein include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.

(2) polyoxyethylene alkyl (or alkenyl) phenyl ether.

(3) Fatty acid alkyl ester alkoxylates to which an alkylene oxide is added between ester bonds of a long chain fatty acid alkyl ester having 6 to 22 carbon atoms.

(4) Polyoxyethylene sorbitan fatty acid (having 6 to 22 carbon atoms) ester.

(5) Polyoxyethylene sorbit fatty acid esters having 6 to 22 carbon atoms.

(6) Polyoxyethylene fatty acid (having 6 to 22 carbon atoms) ester.

(7) Polyoxyethylene hardened castor oil.

(8) Glycerin fatty acid (having 6 to 22 carbon atoms) ester.

As the nonionic surfactant, those of the above-mentioned (1) or (3) are preferable, and those represented by the following general formula (II) or (III) are preferable.

R ² -C (═O) O - [(EO) _s / (PO) _t ] - (EO) _u -R ³ (II)

R ⁴ -O - [(EO) _v / (PO) _w ] - (EO) _x -H (III)

(Wherein R ² is a hydrocarbon group having 7 to ²² carbon atoms, R ³ is an alkyl group having 1 to 6 carbon atoms, s is an average number of repeating units of EO, is a number of 6 to 20, t is PO , U is an average number of repeating units of EO, 0 to 20, EO represents an oxyethylene group, and PO represents an oxypropylene group.

In the formula (III), R ⁴ is a hydrocarbon having ⁶ to ²² carbon atoms, v is an average number of repeating units of EO, is a number of 3 to 20, w is an average number of repeating units of PO, , x represents the average number of repeats of EO, 0 to 20, EO represents an oxyethylene group, and PO represents an oxypropylene group.)

In the formula (II), R ² is a hydrocarbon group having 7 to 22 carbon atoms. The carbon number of R ² is preferably 9 to 21, more preferably 11 to 21.

R ² is preferably an alkyl group or an alkenyl group.

R ² may be either straight chain or branched chain.

From the viewpoint of further improving the detergency, R ² is preferably a linear or branched alkyl group having 7 to 22 carbon atoms, or a linear or branched alkenyl group having 7 to 22 carbon atoms.

R ³ is an alkyl group having 1 to 6 carbon atoms, and may be a straight chain or a branched chain.

Among them, a methyl group and an ethyl group are preferable.

In the formula (II), s and u are independently numbers representing the average number of repeats of EO.

s + u is preferably 6 to 20, more preferably 6 to 18, and even more preferably 11 to 18. If it is more than the lower limit value, liquid stability tends to be improved more easily. If it is less than the upper limit value, the detergency is more easily improved.

In the formula (II), t is the number representing the average number of repetitions of PO.

t is a number of 0 to 6, preferably 0 to 3; When the content is less than the upper limit, liquid stability tends to be improved.

When t is 1 or more, in [(EO) _s / (PO) _t ], the oxyethylene group and the oxypropylene group may be bonded in a random phase or in a block state.

In the present specification, the average number of repeats can be measured by gas chromatography or the like.

In the formula (III), R ⁴ is a hydrocarbon group having ⁶ to ²² carbon atoms.

In the formula (III), the number of carbon atoms of R ⁴ is preferably 10 to 22, more preferably 10 to 20, and still more preferably 10 to 18 from the viewpoint of further improving the detergency.

R ⁴ may be straight-chain or branched.

Preferable examples of R ⁴ -O- include groups represented by the following general formula (IV).

(R < ¹⁰¹ >) (R < ¹⁰² >) CH- (IV)

(In the formula (IV), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or a chain hydrocarbon group, and the total number of carbon atoms of R ¹⁰¹ and R ¹⁰² is 5 to 21.)

The total number of carbon atoms of R ¹⁰¹ and R ¹⁰² is preferably 9 to 21, more preferably 9 to 19, and even more preferably 9 to 17.

R ¹⁰¹ and R ¹⁰² may be linear or branched.

As R ⁴ , specifically, an alkyl group derived from a secondary alcohol having 12 to 14 carbon atoms is preferable.

In the formula (III), v and x are each independently a number representing the average number of repeats of EO.

v + x is preferably from 3 to 20, more preferably from 5 to 18, still more preferably from 6 to 18, and particularly preferably from 11 to 18. If it is more than the lower limit value, liquid stability tends to be improved more easily. If it is less than the upper limit value, the detergency is more easily improved.

In the formula (III), w is the number representing the average number of repeats of PO.

w is a number of 0 to 6, preferably 0 to 3; When the content is less than the upper limit, liquid stability tends to be improved.

When w is 1 or more, the [(EO) _v / (PO) _w ] balkylene, oxyethylene group and oxypropylene group may be bonded in a random or block form.

The distribution of EO or PO in the formula (III) varies depending on the reaction method at the time of production. For example, when ethylene oxide or propylene oxide is added to a raw material by using sodium hydroxide, potassium hydroxide, or the like, which is a common alkali catalyst, the distribution of v or w is relatively wide. ^{3 +} Al, Ga ^{+ 3,} In ^3+, Tl ^{+ 3,} Co ^{+ 3,} Sc ^{+ 3,} La ^{+ 3,} Mn ^{+ 2,} etc. of the magnesium oxide was added to the metal ion as described in Japanese Patent Publication No. Hei-6-15038 , The distribution of v or w becomes relatively narrow when ethylene oxide or propylene oxide is added to the raw material.

A nonionic surfactant represented by the formula (II) (hereinafter also referred to as a "component (b1)") and a nonionic surfactant represented by the formula (hereinafter also referred to as a "component (b2)") Is preferably 20 mass% or more, and more preferably 25 mass% or more. The higher the elongation percentage is, the better the cleaning performance can be obtained. Further, when the elongation percentage is 20 mass% or more, particularly 25 mass% or more, it is easy to obtain a liquid detergent having a small amount of raw material odor of the surfactant.

When the component (b1) is prepared by a conventional method, the product may contain, together with the component (b1), a component which does not contribute to the cleaning power, for example, a fatty acid ester as a raw material of the component (b1) The ethylene oxide adduct having s of 1 or 2 of the nonionic surfactant to be coexisted, and the elongation percentage is lowered. Therefore, if the blowing rate is high, the coexisting components are sufficiently small, and the deterioration of the washing power and the problem of the odor of the raw material are less likely to occur. The same applies to the component (b2).

The upper limit of the elongation percentage is not particularly limited, but is preferably 80% by mass or less.

The elongation percentage is more preferably 20 to 50% by mass, and more preferably 20 to 40% by mass, since the liquid stability and solubility are improved.

Here, the "elongation percentage" in the present specification means the ratio of the distribution of ethylene oxide adducts in which the number of added moles of EO is different and is represented by the following formula (S).

[Equation 1]

[In the formula, P _max represents the number of moles of EO added to the ethylene oxide adduct which is the most abundant in the total ethylene oxide adduct. i represents the addition mole number of EO. Yi represents the ratio (mass%) of the ethylene oxide adduct having the addition mole number of EO present therein, which is present in the total ethylene oxide adduct.

The elongation percentage can be controlled by, for example, the method for producing the component (b1) or the component (b2). The method for producing the component (b1) is not particularly limited. For example, there is a method of addition polymerization of ethylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (Japanese Patent Laid-Open No. 2000-144179 ). ≪ / RTI > The component (b2) can be produced, for example, by a method in which a surface-modified composite metal oxide catalyst is used for addition polymerization of ethylene oxide to an alcohol having 6 to 22 carbon atoms.

Specific examples of the surface-modified composite metal oxide catalyst used in this method include metal ions (Al ^{3 +} , Ga ^{3 +} , In ³⁺ , Tl ^{3 +} , Co ^{3 +} , Sc ^{3 +} , La ^{3 +} , Mn ^{2 +,} and the like) or a hydrotalcite fired catalyst that is surface-modified with metal hydroxides and / or metal alkoxides .

In the surface modification using the composite metal oxide catalyst, it is preferable to use a composite metal oxide together with a metal hydroxide and / or a metal alkoxide. In this case, the ratio of metal hydroxide and / or metal alkoxide is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the composite metal oxide.

As the nonionic surfactant, a commercially available product or a product produced by a known synthesis method may be used. As a known production method, the component (b1) can be produced, for example, by a method of subjecting a fatty acid alkyl ester to addition polymerization of ethylene oxide and / or propylene oxide. The component (b2) can be produced, for example, by a method of subjecting an alcohol having 6 to 22 carbon atoms to addition polymerization of ethylene oxide and / or propylene oxide.

One type of nonionic surfactant may be used alone, or two or more types may be used in combination.

The nonionic surfactant is preferably a component (b1), more preferably a compound in which t in the formula (II) is 0 (i.e., a polyoxyethylene fatty acid alkyl ester), and more preferably a compound in which R ³ in the formula (II) Oxyethylene fatty acid methyl ester (hereinafter referred to as " MEE ") is particularly preferable in view of improving the detergency and the solubility of the liquid detergent.

Further, the liquid detergent of the present invention has a regular composition (concentration of surfactant in the liquid detergent, concentration of the surfactant in the liquid detergent) by setting the ultracentrifugation composition (surfactant concentration in the liquid detergent to 40 mass% or more with respect to the total mass of the liquid detergent) Is about 25% by mass with respect to the total mass of the liquid detergent), the compatibility with the ink contamination is enhanced and the cleaning power is increased. Particularly, the cleaning power is increased in the application cleaning (coating washing). Further, when MEE is used as the nonionic surfactant in the ultra-concentrated composition, the liquid stability of the liquid detergent tends to be higher. When the component (b1) and the component (b2) are used together as a nonionic surfactant, the cleaning power is further increased.

The mass ratio of the component (b1) to the component (b2) is preferably from 0.1 to 15, more preferably from 1 to 5, More preferably from 3 to 8 carbon atoms. If the b1 / b2 mass ratio is in the above preferable range, the detergency against oily pollution becomes higher.

The content of the component (b1) in the component (B) is preferably from 30% by mass to 90% by mass, more preferably from 40% by mass to 80% by mass relative to the total mass of the component (B) And more preferably not less than 70% by mass. When the content of the component (b1) is in the above-described preferable range, it is easy to obtain a liquid detergent excellent in cleaning ability against oily contamination and excellent in liquid stability.

The content of the nonionic surfactant in the component (B) is preferably from 30 to 90 mass%, more preferably from 40 to 80 mass%, still more preferably from 45 to 70 mass%, with respect to the total mass of the component (B) Do. If the content of the nonionic surfactant is within the above-mentioned preferable range, it is easy to obtain a liquid detergent excellent in cleaning ability against oily contamination and excellent in liquid stability.

Components other than the nonionic surfactant in component (B) include anionic surfactants, cationic surfactants, amphoteric surfactants and semi-polar surfactants described later.

The total of these surfactants does not exceed 100% by mass with respect to the total mass of the component (B).

[Anionic surfactant]

Examples of the anionic surfactant include the following (1) to (12).

(1) Methyl, ethyl or propyl ester salts of saturated or unsaturated? -Sulfo fatty acids having 8 to 20 carbon atoms.

(2) a linear or branched alkylbenzenesulfonic acid salt (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.

(3) An alkanesulfonate having 10 to 20 carbon atoms.

(4)? -Olefin sulfonic acid salts (AOS) having 10 to 20 carbon atoms.

(5) an alkylsulfate or alkenylsulfate (AS) having 10 to 20 carbon atoms.

(6) an alkylene oxide having 2 to 4 carbon atoms or an ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) ) A polyoxyalkylene alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms and an average of 0.5 to 10 moles per mole of ether.

(7) an alkylene oxide having 2 to 4 carbon atoms or an ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) (Or alkenyl) phenyl ether sulfates having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms and an average of 3 to 30 moles.

(8) an alkylene oxide having 2 to 4 carbon atoms or an ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) (Or alkenyl) ether carboxylate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms and an average of from 0.5 to 10 moles.

(9) An alkyl polyhydric alcohol ether sulfate such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms.

(10) long chain (having 8 to 20 carbon atoms) monoalkyl, dialkyl or sesquioalkyl phosphates.

(11) polyoxyethylene monoalkyl, dialkyl or sesquioalkyl phosphates.

(12) Higher fatty acids or salts thereof. A higher fatty acid or a salt thereof having an average carbon number of 10 to 20 (preferably 12 to 18).

Other anionic surfactants than those exemplified above may be used. For example, carboxylic anionic surfactants such as alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkylamide ether carboxylates or alkenylamide ether carboxylates, and acylaminocarboxylates; Phosphoric acid ester type anionic surfactants such as alkyl phosphate ester salts, polyoxyalkylene alkyl phosphate ester salts, polyoxyalkylene alkylphenyl phosphate ester salts and glycerin fatty acid ester monophosphate ester salts.

As the anionic surfactant, those of the above (2) or (6) are preferable.

The polyoxyalkylene alkyl ether sulfate of the formula (6) is specifically preferably a compound represented by the formula (V).

R ⁴⁰ -O - [(EO) _m / (PO) _n ] -SO ₃ ^- M ⁺ (V)

[In the formula (V), R ⁴⁰ is a linear or branched alkyl group having 8 to 20 carbon atoms. EO represents an oxyethylene group, and PO represents an oxypropylene group. m represents the average number of repetitions of EO and is a number of 1 or more. n represents the average number of repeats of PO, and is a number of 0 to 6. M ⁺ is a counterion. When n is more than 0, PO and EO in [(PO) _m (EO) _n ] may be arranged in a block or a random manner. PO and EO may be bonded to each other with PO "R ⁴⁰ -O-" and EO "R ⁴⁰ -O-".

As the polyoxyalkylene alkyl ether sulfate, it is preferable to have a linear or branched alkyl group having 10 to 20 carbon atoms, and to have an alkylene oxide added on an average of 1 to 5 moles per mole of the alkyl ether.

The number of carbon atoms of the alkyl group is preferably from 10 to 20, and more preferably from 12 to 14. Specific examples thereof include a dodecyl group, a tridecyl group and a tetradecyl group. Among them, a dodecyl group is preferable.

The average number of repeats of EO is preferably 1 to 5, more preferably 1 to 3.

The average number of repeats of PO is preferably 0 to 3.

The compound of m = 0 and n = 0 in the formula (V) is preferably contained in an amount of 35 to 55 mass% with respect to the total mass of the polyoxyalkylene alkyl ether sulfate represented by the formula (V).

Examples of the salt of the anionic surfactant include alkali metal salts such as sodium salt and potassium salt; Alkaline earth metal salts such as magnesium salts; Alkanolamine salts such as monoethanolamine salts and diethanolamine salts; Ammonium salts and the like. Among them, an alkali metal salt is preferable.

As a method for producing an anionic surfactant, for example, in the case of LAS, the alkylbenzene may be sulfonated with anhydrous sulfuric acid and neutralized with an alkali. For example, in the case of AES, the polyoxyalkylene alkyl ether can be produced by reacting anhydrous sulfuric acid or by reacting chlorosulfonic acid to sulfonate, and neutralizing with an alkali.

The anionic surfactants may be used singly or in combination of two or more.

The content of the anionic surfactant in the component (B) is preferably from 5 to 70 mass%, more preferably from 10 to 60 mass%, still more preferably from 10 to 50 mass%, based on the total mass of the component (B) , And particularly preferably from 20 to 40 mass%. When the content of the anionic surfactant is above the lower limit value, the detergency against oily pollution is more likely to be improved. When the content of the anionic surfactant is below the upper limit value, the liquid stability tends to further improve.

As the component (B), it is preferable that a nonionic surfactant and an anionic surfactant are used in combination. In this case, the mass ratio of the nonionic surfactant to the anionic surfactant (" mass ratio represented by nonionic surfactant / anionic surfactant ") is preferably 0.1 to 20, more preferably 0.3 to 9, More preferably from 1 to 8, and most preferably from 1.5 to 4. If the mass ratio is in the above-mentioned preferable range, the washing power becomes higher. Particularly, when the liquid detergent of the present invention is used for the application cleaning, the detergency against oil-based ink contamination becomes higher.

[Cationic surfactant]

Examples of the cationic surfactant include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, cationic surfactants such as alkylpyridinium salts, and the like. Examples of salts thereof include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, alkanolamine salts such as monoethanolamine and diethanolamine, and the like.

One cationic surfactant may be used singly or two or more thereof may be used in combination.

The content of the cationic surfactant in the component (B) is preferably 0 to 10 mass%, more preferably 0 to 5 mass%, based on the total mass of the component (A). When the content of the cationic surfactant is 0 mass%, it is said that the component (B) does not contain a cationic surfactant.

[Amphoteric surfactant]

Examples of the amphoteric surfactant include alkylbetaine, alkylamide beta-type, imidazoline, alkylaminosulfone, alkylaminocarboxylic acid, alkylamide carboxylic acid, amide amino acid, and phosphoric acid type amphoteric surfactant. .

One kind of amphoteric surfactant may be used alone, or two or more kinds thereof may be used in combination.

The content of the amphoteric surfactant in the component (B) is preferably 0 to 10 mass%, more preferably 0 to 5 mass%, based on the total mass of the component (B). When the content of the amphoteric surfactant is 0 mass%, it is said that the component (B) does not contain a positive surfactant.

The content of the component (B) in the liquid detergent is preferably from 15 mass% to 70 mass%, more preferably from 30 mass% to 60 mass%, and still more preferably from 35 mass% to 60 mass% with respect to the total mass of the liquid detergent Or less, more preferably 40 mass% or more and 60 mass% or less. If the content of the component (B) is lower than the lower limit value, the detergency against oily pollution becomes higher. Particularly, when the liquid detergent of the present invention is used for cleaning application, the detergency against oily ink contamination becomes higher.

When the content of the component (B) is lower than the upper limit, the liquid stability tends to be higher.

The component (B) is preferably used in combination with a non-saponified surfactant (B-1) and a higher fatty acid or a salt thereof (B-2).

The component (B-2) is a higher fatty acid or a salt thereof having 8 to 20 carbon atoms, preferably 12 to 14 carbon atoms. The carbon chain of the fatty acid may be linear or branched.

As the component (B-2), lauric acid (dodecanoic acid), tridecanoic acid, and myristic acid (tetradecanoic acid) are preferable.

The component (B-2) may be one kind or two kinds. Among them, coconut fatty acid including lauric acid and myristic acid is preferable.

The content of the component (B-2) in the medical liquid detergent is preferably 1 to 5 mass%, more preferably 1.5 to 3.5 mass%, further preferably 1.75 to 2 mass%, based on the total mass of the medical liquid detergent Do.

If the lower limit is above the lower limit, the effect of preventing re-contamination can be further improved. When the amount is less than the upper limit, the rinsing property is more easily improved.

The liquid detergent of the present invention preferably has a mass ratio of the component (A) and the component (B) [mass ratio represented by the component (A) / component (B), hereinafter also referred to as "A / B ratio") is 0.01 to 0.15 More preferably 0.01 to 0.06, and still more preferably 0.015 to 0.05. If the A / B ratio is not less than the lower limit value, the detergency against oily pollution becomes higher. In addition, the suppression property is higher. When the A / B ratio is lower than the upper limit value, liquid stability becomes higher.

≪ Component (C) >

The liquid detergent of the present invention preferably further contains an alkylene oxide adduct of polyalkyleneamine (component (C)). The liquid detergent of the present invention further contains the component (C), thereby improving the detergency against oily pollution such as ink.

Examples of the component (C) include the following components (c1) and (c2).

[Component (c1)] [

The component (c1) is an alkylene oxide adduct of a polyalkyleneimine.

The polyalkyleneimine which is the component (c1) is, for example, represented by the following general formula (VI).

NH ₂ -R ²¹ - (NA-R ²¹ ) _n -NH ₂ - (VI)

In the formula (VI), R ²¹ is independently an alkylene group having 2 to 6 carbon atoms, A represents a hydrogen atom or another polyamine chain formed by branching, and n is a number of 1 or more. Provided that A is not a hydrogen atom at all.

That is, the polyalkyleneimine represented by the formula (VI) has a polyamine chain branched in the structure.

R ²¹ is a straight chain alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms. R ²¹ is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 carbon atoms.

The polyalkyleneimine is obtained by polymerizing one or more alkyleneimines having 2 to 6 carbon atoms by a conventional method. Examples of the alkyleneimine having 2 to 6 carbon atoms include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine and 1,1-dimethylethyleneimine.

As the polyalkyleneimine, polyethyleneimine (PEI) and polypropyleneimine are preferable, and PEI is more preferable. PEI is obtained by polymerizing ethyleneimine and has a branched chain structure containing primary, secondary, and tertiary amine nitrogen atoms in its structure.

The weight average molecular weight of the polyalkyleneimine is preferably 200 to 2000, more preferably 300 to 1500, further preferably 400 to 1000, and particularly preferably 500 to 800.

The polyalkyleneimine preferably has 5 to 30 active hydrogen atoms per molecule, more preferably 7 to 25, and further preferably 10 to 20 active hydrogen atoms per molecule.

The component (c1) is obtained by adding an alkylene oxide to a polyalkyleneimine. As this method, an alkylene oxide such as ethylene oxide is added at 100 to 180 DEG C to the polyalkyleneimine as a starting material in the presence of an alkaline catalyst such as sodium hydroxide, potassium hydroxide, sodium methylate and the like And the like.

Examples of the alkylene oxide include alkylene oxides having 2 to 4 carbon atoms. Examples of the alkylene oxide include ethylene oxide, propylene oxide and butylene oxide. Ethylene oxide and propylene oxide are preferable, and ethylene oxide is more preferable.

Examples of the component (c1) include an ethylene oxide adduct of polyalkyleneimine, a propylene oxide adduct of polyalkyleneimine, and an ethylene oxide-propylene oxide adduct of polyalkyleneimine. The ethylene oxide-propylene oxide adduct of the polyalkyleneimine is obtained by adding ethylene oxide and propylene oxide to a polyalkyleneimine, and the ratio of ethylene oxide to propylene oxide to polyalkyleneimine The addition order and the additional form (block, random phase) are arbitrary.

As the component (c1), an ethylene oxide adduct of a polyalkyleneimine and an ethylene oxide-propylene oxide adduct of a polyalkyleneimine are preferable, and an ethylene oxide adduct of a polyalkyleneimine is more preferable.

As the component (c1), an average of from 5 to 40 alkylene oxides is preferably added to one active hydrogen atom of the raw material polyalkyleneimine, more preferably 10 to 30 alkylene oxides are added thereto Do. That is, it is preferable that an average of 5 to 40 moles of alkylene oxide is added per 1 mole of active hydrogen of the raw material polyalkyleneimine, more preferably 10 to 30 moles of alkylene oxide is added.

The mass average molecular weight of the component (c1) is preferably from 1,000 to 80,000, more preferably from 2,000 to 50,000, still more preferably from 5,000 to 30,000, and particularly preferably from 10,000 to 20,000.

The mass average molecular weight is a value obtained by converting a value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent on the basis of a calibration curve of PEG (polyethylene glycol) .

As the component (c1), for example, a compound represented by the formula (I-c) can be mentioned.

(2)

In the formula (Ic), R ²² is each independently an alkylene group having 2 to 6 carbon atoms, and m is independently at least one number.

R ²² is preferably an alkylene group having 2 or 3 carbon atoms, more preferably an alkylene group having 2 carbon atoms. m is the average number of repeats of (R ²² O), preferably 5 to 40, more preferably 10 to 30.

As the component (c1), a synthetic product may be used, or a commercially available product may be used.

Examples of commercially available products include Sokalan HP20, a product of BASF Corporation.

[Component (c2)] [

The component (c2) is an alkylene oxide adduct of a polyalkyleneamine represented by the following formula (VII).

NH ₂ (R ³¹ NH) ₁ H (VII)

In the formula (VII), R ³¹ is an alkylene group having 2 to 6 carbon atoms, and 1 is a number of 1 or more.

R ³¹ is a straight chain alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms. R ³¹ is preferably an alkylene group having 2 to 4 carbon atoms, and more preferably an alkylene group having 2 carbon atoms.

As the polyalkyleneamine, polyethyleneamine is preferable. Examples of the polyethylene amines include ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylpentanamine, pentaethylenehexaamine, and the like. These polyethyleneamines can be obtained by a known production method, for example, by reacting ammonia and ethylene dichloride.

The weight average molecular weight of the polyalkyleneamine is preferably 60 to 1800, more preferably 60 to 1,000, and still more preferably 60 to 800.

The polyalkyleneamine preferably has 6 to 30 active hydrogen atoms in one molecule thereof, and more preferably has 7 to 20 active hydrogen atoms in one molecule thereof.

The component (c2) is obtained by adding an alkylene oxide to a polyalkyleneamine. This reaction can be carried out in the same manner as the component (c1). Examples of the alkylene oxide include alkylene oxides having 2 to 4 carbon atoms. Examples of the alkylene oxide include ethylene oxide, propylene oxide and butylene oxide. Ethylene oxide and propylene oxide are preferable, and ethylene oxide is more preferable.

Examples of the component (c2) include an ethylene oxide adduct of a polyalkyleneamine, a propylene oxide adduct of a polyalkyleneamine, and an ethylene oxide-propylene oxide adduct of a polyalkyleneamine.

As the alkylene oxide adduct of the polyalkyleneamine, an ethylene oxide adduct of a polyalkyleneamine and an ethylene oxide-propylene oxide adduct of a polyalkyleneamine are preferable, and an ethylene oxide adduct of a polyalkyleneamine More preferable.

As the component (c2), an average of from 5 to 40 alkylene oxides is preferably added to one active hydrogen atom of the starting polyalkyleneamine, more preferably 10 to 30 alkylene oxides are added Do. That is, it is preferable that an average of 5 to 40 moles of alkylene oxide is added per 1 mole of active hydrogen of the raw material polyalkyleneamine, more preferably 10 to 30 moles of alkylene oxide is added.

The mass average molecular weight of the component (c2) is preferably from 1,000 to 80,000, more preferably from 2,000 to 50,000, still more preferably from 5,000 to 30,000, and particularly preferably from 10,000 to 20,000.

As the component (C), the component (c1) is preferable. Among the components (c1), the ethylene oxide adduct of polyethyleneimine represented by the formula (I-c) is particularly preferable.

With respect to the total mass of the liquid detergent of the present invention, the content of the component (C) is preferably from 0.01 to 5 mass%, more preferably from 0.05 to 3 mass%, and even more preferably from 0.1 to 2 mass%.

When the content of the component (C) is 0.01 mass% or more, the cleaning ability against oily pollution such as ink improves, and when the content is 5 mass% or less, the liquid stability is good.

In the liquid detergent of the present invention, the mass ratio (A / C) of the component (A) / the component (C) is preferably 0.1 to 4, more preferably 0.2 to 2.5, still more preferably 0.3 to 1.5.

When the mass ratio of the component (A) / component (C) is in the above range, the detergency against oily pollution such as ink is further improved.

The liquid detergent of the present invention contains the components (A) and (B) as essential components and the remaining components are optional components such as the component (C), water (water), and water-miscible organic solvent .

For example, the content of the component (A) is 0.1 to 5 mass% with respect to the total mass of the liquid detergent, the content of the component (B) is 15 to 70 mass% with respect to the total mass of the liquid detergent, ) Is 0.01 to 5% by mass with respect to the total mass of the liquid detergent, the content of water is 10 to 90% by mass with respect to the total mass of the liquid detergent, and the content of the optional components is And 0 to 30% by mass of the liquid detergent.

When the content of the optional component is 0 mass% with respect to the total mass of the liquid detergent, it is said that the liquid detergent does not contain any component.

<Water>

The liquid detergent of the present invention preferably contains water from the viewpoints of easiness in handling during production and solubility in water at the time of use.

The content of water in the liquid detergent is not particularly limited, but is preferably from 10 to 90 mass%, more preferably from 20 to 70 mass%, and still more preferably from 30 to 50 mass%, based on the total mass of the liquid detergent.

The total amount of the component (A), the component (B), the component (C) and water does not exceed 100 mass% with respect to the total mass of the liquid detergent.

<Optional ingredients>

The liquid detergent of the present invention may contain, in addition to the above components (A), (B) and (C), enzymes such as protease (for example, alcalase, corona etc.), water-miscible organic solvents such as ethanol, An antioxidant such as dibutylhydroxytoluene, an antiseptic such as sodium benzoate, an enzyme stabilizer such as calcium chloride and sodium lactate, a flavoring agent such as a flavoring agent, a coloring agent such as a coloring agent, and the like.

The liquid detergent of the present invention preferably contains a water-miscible organic solvent because of the improvement of the applied cleaning performance, the lowered viscosity and the improved usability.

Examples of the water-miscible organic solvent include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol and the like, glycols of propylene glycol (PG), butylene glycol and hexylene glycol, diethylene glycol, triethylene glycol , Polyethylene glycol having a weight average molecular weight of about 200 to 1000, polyglycols such as dipropylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol) , And alkyl ethers such as diethylene glycol dimethyl ether.

Of these, preferred are ethanol, propylene glycol, polyethylene glycol having a weight average molecular weight of about 200 to 1000, and diethylene glycol monobutyl ether (butyl carbitol) from the viewpoint of less odor, availability of the liquid, and fluidity of the liquid detergent Do.

The water-miscible organic solvent may be used singly or in combination of two or more kinds.

When the liquid detergent of the present invention contains a water-miscible organic solvent, the content of the water-miscible organic solvent is preferably from 0.1 to 30 mass%, more preferably from 0.1 to 15 mass%, based on the total mass of the liquid detergent.

In the present invention, the water-miscible organic solvent means an organic solvent which dissolves 50 g or more in 1 liter of ion-exchanged water at 25 占 폚.

Examples of the alkaline agent include monoethanolamine, diethanolamine, triethanolamine and the like.

When the liquid detergent of the present invention contains an alkaline agent, the content of the alkaline agent is preferably from 0.1 to 6% by mass based on the total mass of the liquid detergent.

The sum of components (A), (B), (C), water, and optional components does not exceed 100% by mass with respect to the total mass of the liquid detergent.

<pH>

The liquid detergent of the present invention preferably has a pH of 4 to 9 at 25 ° C, more preferably a pH of 6 to 9. When the pH is in this range, the liquid stability of the liquid detergent can be maintained satisfactorily.

The pH of the liquid detergent can be adjusted by adding a pH adjuster, if necessary. As the pH adjuster, sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine and the like are preferable as long as they do not impair the effect of the present invention.

The pH is a value measured at 25 占 폚 according to JIS Z8802: 2011.

<Manufacturing Method>

The liquid detergent of the present invention is produced by conventionally known production methods. For example, a method of adding the above components (A) and (B) to water as a solvent, adding optional components as needed, and mixing these components.

<Applications>

The liquid detergent of the present invention is used as a cleaning agent for various applications, but is excellent as a detergent against oil contamination, and therefore is suitable as a cleaning agent for oil contamination adhered to oil contamination. The liquid detergent of the present invention is suitable as a liquid detergent for textile products such as medical care, a liquid detergent for hard surfaces such as a window glass, a kitchen liquid cleaner such as a dishware and a cooking appliance. Among them, the liquid detergent of the present invention is suitable as a liquid detergent for fiber products such as medical care and the liquid surface cleaning liquid for windowpanes, etc., which are adhered with oil-based ink contamination, because of excellent cleaning ability against oily ink contamination. The liquid detergent of the present invention is particularly suitable as a liquid detergent for textile products because it has excellent washing power when applied and cleaned, particularly to a fiber product with oily ink contamination.

<How to use>

As a method for using the liquid detergent of the present invention, a usual method of use may be mentioned. When the liquid detergent of the present invention is used for cleaning a fiber product, for example, there is a method of cleaning a substrate with a washing machine using 5 to 30 ml of a liquid detergent added to 30 liters of water, And a method of immersing the article in water. Alternatively, the liquid detergent may be applied directly to the substrate and allowed to stand for a certain period of time, and thereafter, a method of performing normal washing (coating cleaning).

When the liquid detergent of the present invention is used for cleaning the hard surface, the liquid detergent may be applied to the light surface to be cleaned by spraying, and then rubbed with a cleaning tool such as a sponge.

When the liquid detergent of the present invention is used for cleaning a tableware or the like, there is a method of cleaning a dishwasher or the like by putting a liquid detergent into a sponge while keeping the liquid detergent in an undiluted solution, a method of preparing a diluted cleaning liquid by dissolving the liquid detergent in water, And rubbing with a sponge while immersing the back.

The liquid detergent of the present invention is preferably used for cleaning because it is excellent in cleaning ability against oily contamination. Particularly, when the oil-based ink contamination adhered to the fibers is applied and cleaned, the component (A) is more likely to act against the oil-based ink contamination, and the cleaning power against oil-based ink contamination becomes higher.

As described above, since the liquid detergent of the present invention contains the component (A) and the component (B), the liquid detergent is more excellent in detergency against oily pollution such as oil-based ink contamination. Further, it is excellent in liquid stability and suppressing properties.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the present embodiment, &quot;% &quot; indicates &quot; mass% &quot; unless otherwise specified.

The raw materials used in this embodiment are as follows.

&Lt; Component (A) >

A-1: polyoxypropylene glyceryl ether, Actcol T-1500 (trade name), manufactured by Mitsui Chemicals, Inc., weight average molecular weight 1500.

A-2: polyoxypropylene glyceryl ether, Actcall T-3000 (trade name), manufactured by Mitsui Chemicals, Inc., weight average molecular weight 3000.

A-3: polyoxypropylene glyceryl ether, Actcol T-4000 (trade name), manufactured by Mitsui Chemicals, Inc., weight average molecular weight 4,000.

A-4: polyoxypropylene glyceryl ether, Actcol T-5000 (trade name), manufactured by Mitsui Chemicals, Inc., weight average molecular weight 5000.

&Lt; Component (A '): Comparative component of component (A)

A'-1: polyoxypropylene ethylene glycol ether, Actcoll D-3000 (trade name), manufactured by Mitsui Chemicals, Inc., weight average molecular weight 3000.

A'-2: polyoxypropylene ethylene glycol ether, Actcall D-4000 (trade name), manufactured by Mitsui Chemicals, Inc., weight average molecular weight 4,000.

&Lt; Component (B) >

· B-1: Using an alkoxylation catalyst for MEE (polyoxyethylene fatty acid methyl ester) and coconut fatty acid methyl (mass ratio of methyl laurate / methyl myristate = 8/2) Of ethylene oxide added. In the general formula (II), R ² = an alkyl group having a carbon number of 11 and an alkyl group having a carbon number of 13, R ³ = a methyl group, s = 15, t = 0, u = 0. Synthesized by the following synthesis method.

[Synthesis example of B-1]

Synthesized according to the synthesis method described in Japanese Patent Application Laid-Open No. 2000-144179.

Alumina · magnesium hydroxide (Kyowado 300 (trade name), manufactured by Kyowa Chemical Industry Co., Ltd.) having a composition of 2.5 MgO · Al ₂ O ₃ · wH ₂ O was fired at 600 ° C. for 1 hour under a nitrogen atmosphere , And a calcined hydrous alumina-magnesium (unmodified) catalyst. 2.2 g of calcined hydrous alumina-magnesium (unmodified) catalyst, 2.9 ml of 0.5N potassium hydroxide ethanol solution, 280 g of methyl laurate and 70 g of methyl myristate were placed in a 4 L autoclave and the catalyst was reformed in an autoclave . Subsequently, the inside of the autoclave was replaced with nitrogen, and 1052 g of ethylene oxide was introduced while maintaining the temperature at 180 캜 and the pressure at 0.3 MPa, and the reaction was carried out with stirring.

The obtained reaction solution was cooled to 80 캜, and 15 g of water and 5 g of active white clay and diatomaceous earth were added as a filtration assistant, respectively, followed by mixing. The catalyst was filtered off to obtain B-1.

The elongation percentage of B-1 was 30 mass%.

B-2: Using an alkoxylation catalyst, 15 mole equivalent of MEE (polyoxyethylene fatty acid methyl ester) and coconut fatty acid methyl (mass ratio of methyl laurate / methyl myristate = 74/26) Of ethylene oxide added. In the general formula (II), R ² = an alkyl group having a carbon number of 11 and an alkyl group having a carbon number of 13, R ³ = a methyl group, s = 15, t = 0, u = 0.

[Synthesis example of B-2]

B-2 was synthesized according to the following synthesis method.

137 g of 2-ethylhexanol (first class reagent, manufactured by KANTO CHEMICAL Co., Ltd.) and 41.7 g of calcium acetate monohydrate (special grade reagent, manufactured by KANTO CHEMICAL Co., Ltd.) were placed in a 500 mL beaker, ) To obtain a dispersion (dispersion step). While stirring the dispersion, 20.9 g of sulfuric acid (special grade reagent, manufactured by Kanto Kagaku Co., Ltd.) was added thereto for 10 minutes by a dropping funnel and mixed (mixing step). In the mixing process, since heat is generated by addition of sulfuric acid, the beaker is cooled by water bath, and the reaction temperature is controlled at 30 to 50 캜. Sulfuric acid was added, and the mixture was further stirred for 2 hours while maintaining the temperature at 50 캜 (catalyst aging step) to obtain an alkoxylation catalyst.

12.5 g of the above alkoxylation catalyst, 462 g of methyl laurate (Pastel M12, manufactured by Lion Chemical Co., Ltd.) and 166 g of myristate methyl (pastel M14, manufactured by Lion Chemical Co.) were added to the autoclave and stirred. While the autoclave was purged with nitrogen with stirring, the autoclave was heated to 100 캜 and dehydrated for 30 minutes under a reduced pressure of 1.3 kPa or less. Subsequently, the temperature was raised to 160 캜, and 1876 g of ethylene oxide (15-fold mol of the total of methyl laurate and methyl myristate) was introduced under the conditions of 0.1 to 0.5 MPa and stirred (addition reaction step). Further, the mixture was stirred at an addition reaction temperature for 0.5 hours (aging step), and then cooled to 80 DEG C to obtain 2516 g of a reaction auxiliary (polyoxyethylene fatty acid methyl ester (MEE), average EO molar number = 15). The reaction mixture was filtered to remove the catalyst to obtain B-2.

The elongation percentage of B-2 was 30 mass%.

B-3: Sophotanol, a product obtained by adding ethylene oxide equivalent to 7 mol to a secondary alcohol having 12 to 14 carbon atoms, Sofotanol 70 (trade name), Nippon Catalysts Co., Ltd. In the general formula (III), R ⁴ = a branched chain alkyl group having 12 to 14 carbon atoms, v = 7, w = 0, x = 0.

B-4: Polyoxyethylene alkyl ether, a natural alcohol having 12 and 14 carbon atoms (primary alcohol) with 15 moles of ethylene oxide added. In the general formula (III), R ⁴ = a linear alkyl group having 12 to 14 carbon atoms, v = 15, w = 0, x = 0.

[Synthesis example of B-4]

224.4 g of CO-1214 (trade name, a natural alcohol having 12 and 14 carbon atoms) manufactured by Procter &amp; Co., Ltd. and 2.0 g of a 30 mass% aqueous sodium hydroxide solution were placed in a pressure-resistant reaction vessel and the inside of the reaction vessel was replaced with nitrogen. Next, after dehydration at a temperature of 100 ° C and a pressure of 2.0 kPa or less for 30 minutes, the temperature was raised to 160 ° C. Subsequently, while stirring the reaction solution, 760.6 g of ethylene oxide (gaseous state) was slowly added to the reaction solution. At this time, while adjusting the addition rate so that the reaction temperature did not exceed 180 占 폚, ethylene oxide was added via a blowing tube.

After completion of the addition of ethylene oxide, the reaction product was matured for 30 minutes at a temperature of 180 DEG C and a pressure of 0.3 MPa or lower. Thereafter, unreacted ethylene oxide was distilled off (distillation) for 10 minutes at a temperature of 180 deg. Respectively.

Next, after the temperature was cooled to 100 DEG C or lower, 70 mass% p-toluenesulfonic acid was added to neutralize the solution so that the pH of the 1 mass% aqueous solution of the reaction product became about 7 to obtain B-4.

B-5: 8 mole of ethylene oxide, 2 mole of propylene oxide, 2 mole of propylene oxide, 2 mole of propylene oxide, 2 mole of propylene oxide, And 8 moles of ethylene oxide in that order. In the general formula (III), R ⁴ = a linear alkyl group having 12 to 14 carbon atoms, v = 8, w = 2, x = 8.

B-6: AES, polyoxyalkylene alkyl ether sulfate (mixture of sodium polyoxyethylene lauryl ether sulfate and sodium polyoxyethylene myristyl ether sulfate, average molar number of added EO of 1), R in formula (V) ⁴⁰ = a straight chain alkyl group having 12 and 14 carbon atoms, m = 1.0, n = 0, M = sodium, m = 0 for all of B-6, 43% by mass of compounds with n = 0.

[Synthesis example of B-6]

In a 4 liter autoclave, 400 g of a product CO1270 alcohol (a mixture of a mixture of a C12 alcohol and a C14 alcohol in a mass ratio of 75/25) P & G as a starting alcohol, and 0.8 g of a potassium hydroxide catalyst as a reaction catalyst, The inside of the autoclave was replaced with nitrogen, and the temperature was raised with stirring. Subsequently, 91 g of ethylene oxide was introduced while maintaining the temperature at 180 캜 and the pressure at 0.3 MPa or lower, and reacted to obtain an alcohol ethoxylate.

Gas chromatographic mass spectrometer: GC-5890 manufactured by Hewlett-Packard, detector: hydrogen flame ionization type detector (FID), column: Ultra-1 (manufactured by HP, L 25 m x? 0.2 mm x T 0.11 탆). As a result, the obtained alcohol ethoxylate had an average addition mole number of ethylene oxide of 1.0. Further, the amount of the compound to which ethylene oxide was not added (finally, a compound of m = 0 and n = 0 in the general formula (V)) was 43 mass% with respect to the whole alcohol ethoxylate thus obtained.

Next, 237 g of the alcohol ethoxylate obtained above was taken in 500 ml of Frasco equipped with a stirrer and purged with nitrogen, and then 96 g of liquid sulfuric anhydride (sulphate) was slowly added dropwise while maintaining the reaction temperature at 40 캜. After completion of dropwise addition, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Subsequently, this was neutralized with an aqueous solution of sodium hydroxide to obtain B-6.

B-7: AEPS, monoethanolamine salt of polyoxyethylene polyoxypropane-1,2-diyl alkyl ether sulfuric acid ester. R ⁴⁰ in the general formula (V) = linear alkyl group having 12 carbon atoms, m = 2.0, n = 1.0, and M = monoethanolamine.

[Synthesis example of B-7]

640 g of a linear primary alcohol having a carbon number of 12 (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: 1-dodecanol molecular weight 186.33) having a purity of> 99%] was placed in an autoclave equipped with a stirrer, a temperature controller, And 1.0 g of potassium hydroxide were placed, and dehydration was carried out at 110 DEG C and 1.3 DEG C for 30 minutes. After the dehydration, the reaction solution was purged with nitrogen, and the temperature was raised to 120 ° C. Then 199 g of propane-1,2-diyl oxide was added. Subsequently, the mixture was subjected to an addition reaction and aging at 120 DEG C, and then the temperature was raised to 145 DEG C and 303 g of ethylene oxide was added. Subsequently, the mixture was subjected to addition reaction and aging at 145 占 폚, followed by cooling to 80 占 폚, and unreacted ethylene oxide was removed at 4.0 占.. After the removal of the unreacted ethylene oxide, 1.0 g of acetic acid was added to the autoclave, stirred at 80 캜 for 30 minutes and then taken out to obtain a polymer having an average addition mole number of the dodecyl group and PO of 1.0, To obtain an alkoxylate having an average addition mole number of 2.0.

The obtained alkoxylate was sulfated by a falling thin film reactor using sulfur trioxide gas. The obtained sulfur oxide was neutralized with monoethanolamine to obtain a composition containing a monoethanolamine salt (AEPS) of polyoxyethylene polyoxypropane-1,2-diyl alkyl ether sulfuric acid ester.

B-8: LAS, straight chain alkylbenzenesulfonic acid, Lyfon LH-200 (trade name), manufactured by Lion Corporation.

B-9: Coconut fatty acid, trade name "coconut fatty acid" manufactured by Nichiyu Co., Ltd.

B-10: Alkyl chloride (12 carbon atoms) trimethylammonium, Lion arc irradiation agent, trade name "Akado 12-37W".

B-11: Amide amine, trade name "KATTIAL PAS-R" manufactured by Toho Chemical Industry Co., Ltd.

&Lt; Component (C) >

HP-20: Ethylene oxide adduct of polyethyleneimine (manufactured by BASF, trade name "Sokalan HP20").

<Optional ingredients>

Coronase (enzyme), Novozymes Injection, trade name "Coronase48L".

· Alkaline (enzyme), novozine injection, product name "Alcalase2.5ℓ".

MEA: Monoethanolamine (alkaline agent), Nippon Catalyst Co., Ltd., trade name "monoethanolamine".

BHT: dibutylhydroxytoluene (antioxidant), SUMILZERBHT-R, manufactured by Sumitomo Chemical Co., Ltd.

3-methoxy-3-methylbutanol (trade name, "Solfit" manufactured by Kuraray Co., Ltd.).

PEG1000: polyethylene glycol, weight average molecular weight 1000 (water-miscible organic solvent), trade name "PEG # 1000-L60" manufactured by Lion Corporation.

Butyl carbitol, trade name &quot; butyldiglycol &quot;, manufactured by Nippon Oil &amp;

PG: Propylene glycol (water-miscible organic solvent), manufactured by BASF.

· Ethanol (water-miscible organic solvent), product of Nippon Alcohol Sales Co., Ltd., "Alcohol 95 specificity".

· Sodium benzoate (preservative), manufactured by DOWA SYNTHESIS CO., LTD., Product name "sodium benzoate".

Calcium chloride (enzyme stabilizer), Kanto Kagaku Co., Ltd., trade name "calcium chloride".

Sodium lactate (enzyme stabilizer), Kanto Kagaku Co., Ltd., trade name &quot; sodium lactate &quot;.

Flavor (Flavoring agent) The fragrance composition A. described in Tables 11 to 18 of JP-A-2002-146399.

· Coloring agent (coloring agent), trade name "Green No. 3" manufactured by Kishi Chemical Industry Co., Ltd.

Water (distilled water), manufactured by Kanto Kagaku Co., Ltd.

(Examples 1 to 21 and Comparative Examples 1 to 7)

The components (A), (B), (C), and optional components were added to and mixed with water according to the compositions shown in Tables 1 to 4 to obtain liquid cleaners of Examples 1 to 21.

Further, the liquid detergents of Comparative Examples 1, 2 and 5 were obtained in the same manner as in Examples 1 to 21 except that component (A) was not added. A liquid detergent of Comparative Examples 3, 4, 6 and 7 was obtained in the same manner as in Examples 1 to 21 except that component (A ') was used instead of component (A).

The compositions (mixing components, content (mass%)) of the obtained liquid cleaner of each example are shown in Tables 1 to 4.

In addition, unless otherwise indicated, mass% refers to net fractions.

In the table, when the blending component of the blank is present, the blending component is not blended.

In the table, the A / B ratios of Comparative Examples 3, 4, 6, and 7 show the mass ratios of the components (A ') and (B).

The liquid detergent of each of Examples 1 to 16 and Comparative Examples 1 to 4 was evaluated for cleaning power, liquid stability and rinsability as follows.

The evaluation results are shown in Tables 1 to 3.

&Lt; Evaluation of cleaning power &

A cloth made of a cotton cloth cut into 5 cm x 5 cm was used as an evaluation cloth and an ink of a milky ball pen (manufactured by ZEBRA, trade name: Clip-on-Slim oil-based ball pen) Ink cloth was produced. At this time, an oil-based ink was applied to the center of the cotton cloth to make a circle having a diameter of 2 cm.

This ink composition was washed in the following order.

0.05 ml of the liquid cleaner of each example was applied to the ink composition so that the oil-based ink stuck to the ink composition centered on the ink was allowed to stand for 3 minutes, and then 6 ml of each liquid cleaner Was washed with a washing solution having dissolved therein.

Terg-O-Tometer (manufactured by UNITED STATES TESTING) was used as a cleaning tester. Each of the above-mentioned ink compositions and the washing solution were put in a cleaning tester, and adjusted to a bath ratio of 30 times and rinsed at 120 rpm and 15 캜 for 10 minutes. Then, it was transferred to a two-piece washing machine (manufactured by Mitsubishi Electric Corporation, product number: CW-C30A1-H1), dehydrated for 1 minute, rinsed in 30 liters of tap water (15 DEG C, 4 DEG DH) for 3 minutes and air dried.

The reflectance was measured with a color difference meter (product name: SE200 type) manufactured by Nihon Furuso Co., Ltd., and the cleaning rate (%) was calculated by the following formula Respectively. The cleaning ratio (%) was calculated with respect to ten ink compositions, and the cleaning power against ink contamination was evaluated using the average value.

Washing rate (%) = 100 占 (K / S of ink ink before cleaning) - (K / S of ink ink after cleaning) / (K / S of ink ink before cleaning) 100.

(1 / R / 100) ² / (2R / 100) where R is the reflectance of the ink for the evaluation, )to be.

A cleaning rate of 30% or more was accepted.

<Evaluation of liquid stability>

100 ml of liquid cleaner of each example was filled in a transparent glass bottle (Hiroku standard bottle, PS-NO. 11), and the lid was closed and sealed. In this state, the mixture was allowed to stand in a thermostatic chamber at 5 DEG C or 25 DEG C for 7 days and stored.

After such preservation, the appearance of the liquid was visually observed, and the liquid stability of the liquid detergent was evaluated according to the following evaluation criteria.

(Evaluation standard)

?: No precipitating substance is recognized at the bottom of the glass bottle, and the liquid has fluidity.

?: Though a precipitate is observed at the bottom of the glass bottle, when the glass bottle is shaken gently, the precipitate disappears (dissolves).

X: Precipitated substances are recognized at the bottom of the glass bottle, and even if the glass bottle is gently shaken, the precipitate does not disappear, or gelation or clouding occurs immediately after the liquid cleaning agent is produced.

These evaluation results are shown in the columns of liquid stability (25 캜) and liquid stability (5 캜) of Tables 1 to 3, respectively.

&Lt; Evaluation of rinsability &

0.3 g of each medical liquid detergent was dissolved in 900 ml of 3 ° water at 25 ° C to prepare a cleaning liquid. 20 ml of this washing liquid was placed in a 100 ml capacity Eppendorf tube, and the tube was vibrated by shaking 20 times for 20 seconds and allowed to stand for 3 minutes. The height of the subsequent bubbles (the distance from the boundary between the bubbles and the rinsing liquid to the top surface of the bubbles) was measured. The height (unit: mm) of the measured foam is indicated in the table.

As the evaluation of the rinsability, the following ink-contaminated cleaning power and the effect of preventing re-contamination were evaluated. The evaluation of the rinsability was carried out in the same manner as in Examples 3, 15, 16, and Comparative Example (B-9) in order to confirm the effect on the presence or absence of the component (A), the presence of the component 1 &lt; / RTI &gt;

[Ink Contamination Cleaning Power]

(Cleaning power with sole-release effect by repeated washing treatment)

The cotton cloth was put into a fully automatic electric washing machine (AW-80VC, manufactured by TOSHIBA CO., LTD.), And the bath ratio was adjusted to 20 times. 12 g of the liquid cleansing agent of each example was added thereto, and a washing operation was performed to sequentially perform washing, rinsing and dehydration with a standard course. Regarding the washing time, rinsing, dehydration, and water amount (set to 36 liters), the standard setting of the washing machine was used without any adjustment. The temperature of the tap water used was 15 占 폚. This preliminary cleaning operation was repeated twice or five times. After two or five preliminary rinses were finished, the cotton cloth was laid flat and dried overnight, and the cotton cloth after the drying was cut to 5 x 5 cm.

The evaluation pouch was painted with an oil of a ballpoint pen (manufactured by ZEBRA, trade name "Clip-on-Slim oil-based ball pen") to prepare an ink composition with oil-based ink contamination. At this time, an oil-based ink was applied to the center of the cotton cloth to make a circle having a diameter of 2 cm.

This ink composition was washed in the following order.

0.05 ml of the liquid cleaner of each example was applied to the ink composition so that the oil-based ink stuck to the ink composition centered on the ink was allowed to stand for 3 minutes, and then 6 ml of each liquid cleaner Was washed with a washing solution having dissolved therein.

Terg-O-Tometer (manufactured by UNITED STATES TESTING) was used as a cleaning tester. Each of the above-mentioned ink compositions and the washing solution were placed in a cleaning tester, and the washing rate was adjusted to 30 times, followed by washing at 120 rpm and 15 캜 for 10 minutes. Then, it was transferred to a two-piece washing machine (manufactured by Mitsubishi Electric Corporation, product number: CW-C30A1-H1), dehydrated for 1 minute, rinsed in 30 l of tap water (15 캜, 4? DH) for 3 minutes and air dried.

The reflectance was measured with a color difference meter (product name: SE200 type) manufactured by Nippon Pure Optics, and the cleaning rate (%) was measured with respect to each of the following evaluations for the ink for evaluation, the ink for ink before cleaning and the ink for ink after cleaning Respectively. The cleaning rate (%) was calculated with respect to ten ink compositions, and the average value was used to evaluate the detergency against ink contamination based on the following criteria.

Washing rate (%) = 100 占 (K / S of ink ink before cleaning) - (K / S of ink ink after cleaning) / (K / S of ink ink before cleaning) 100.

(1 / R / 100) ² / (2R / 100) where R is the reflectance of the ink for the evaluation, )to be.

[Evaluation of effect of preventing re-contamination]

Using the liquid cleaner of each example, washing treatment was performed by repeating the cleaning process, the rinsing process, and the drying process shown below three times in this order.

Cleaning process: As the clothes, the following cotton cloth, polyester (PE) cloth, wet artificial cloth and undergarment shirt were used.

Cotton: 5 pieces of 5 cm × 5 cm cotton calyces (made by Tanikashira Store)

Polyester (PE) bag: 5 pieces of 5 cm x 5 cm of polyester tropic (made by Tanikashira Store)

Wet artificial contamination type: Ogupo (oleic acid 28.3%, triolein 15.6%, cholesterol oleate 12.2%, liquid paraffin 2.5%, squalene 2.5%, cholesterol 1.6%, gelatin 7.0%, mud ) 29.8%, and carbon black 0.5% (by mass ratio).

Shirt: A shirt (LL size, manufactured by DVD) finely cut (about 3 cm x 3 cm).

In a Terg-o-tometer (manufactured by UNITED STATES TESTING CO., LTD.), 900 ml of 3 ° DH water at 25 ° C was added, and 0.6 g of a liquid detergent was added thereto. Thereafter, 3 ° DH water was added to adjust the bath ratio to 20 times, and the plate was washed at 120 rpm and 25 ° C for 10 minutes.

Rinse process:

After cleaning, the substrate was dewatered for 1 minute, then 900 ml of 3 ° DH water at 25 ° C was added and rinsed at 120 rpm and 25 ° C for 3 minutes. This operation (dehydration and rinsing) was repeated twice. In the second cycle, a predetermined amount of a softening agent was added to 900 mL of 3 DEG DH water at 25 DEG C and rinsing was carried out. As the softening agent, Bomulim Sofuran (manufactured by Lion Corporation) was used.

Drying process:

After rinsed clothes were dehydrated for one minute, only the re-contamination determination cloth (cotton, PE cloth) was taken out, put on a filter paper, and dried with an iron.

The reflectance (Z value) of the re-contamination judgment blanks before and after the washing treatment was measured using a reflectance meter (spectral color sorter SE2000, manufactured by Nippon Seisakusho Kogyo Co., Ltd.), and? Z was calculated by the following formula.

DELTA Z = (Z value before washing) - (Z value after washing)

The average values of the five sheets were determined with respect to? Z in the respective re-contamination determination battens of cotton and PE battens. The effect of preventing recontamination of cotton cloth and PE cloth by the liquid detergent was evaluated according to the following criteria with the average value as an index. In the following criteria,? And? Were determined as acceptable. The evaluation results are shown in Tables 1 to 3.

<Acceptance criteria in cotton>

◎: ΔZ is less than 5.

○: ΔZ is 5 or more and less than 7.

?:? Z is 7 or more and less than 9.

×: ΔZ is 9 or more.

&Lt; Criteria in PE wrapping >

?:? Z is less than 3.

○: ΔZ is 3 or more and less than 4.

Δ: ΔZ is 4 or more and less than 5.

×: ΔZ is 5 or more.

[Table 1]

[Table 2]

[Table 3]

The liquid detergents of Examples 17 to 21 and Comparative Examples 5 to 7 were evaluated for their inhibition properties as follows. The evaluation results are shown in Table 4.

&Lt; Evaluation of suppression >

20 ml of an aqueous solution (concentration: 0.1% by mass) of the above liquid cleaning agent of each example was placed in a 100 ml Eppendorf tube, and the foam was vibrated 20 times for 20 seconds. After standing for 3 minutes, the height of the foam (the length from the boundary with the foam to the top of the foam to the top of the foam) was measured immediately. The height (unit: mm) of the measured foam is indicated in the table.

[Table 4]

From the results shown in Tables 1 to 3, it was confirmed that the liquid detergents of Examples 1 to 16 to which the present invention was applied were more excellent in detergency against oily pollution. In addition, it was confirmed that it was excellent in liquid stability. From the results shown in Table 4, it was confirmed that the liquid detergents of Examples 17 to 21 to which the present invention was applied were superior in the suppression property.

On the other hand, liquid detergents (Comparative Examples 1 and 2) which do not contain the component (A) and liquid detergents (Comparative Examples 3 and 4) containing the component (A ') instead of the component (A) The cleaning power was not sufficient. The liquid detergent (Comparative Example 4) containing the component (A'-2) instead of the component (A) had insufficient liquid stability at low temperature. The liquid detergent containing no component (A) (Comparative Example 5) and the liquid detergent containing the component (A ') (Comparative Examples 6 and 7) instead of the component (A)

From the above results, it can be confirmed that the liquid detergent to which the present invention is applied is superior in washing power against oily pollution.

[Industrial Availability]

The liquid detergent of the present invention is superior in detergency against oily pollution.

Claims (4)

A propylene oxide adduct of trivalent alcohol (A), and a surfactant (B). The method according to claim 1,
Wherein the mass ratio of the component (A) / (B) is 0.01 to 0.15. 3. The method according to claim 1 or 2,
Further, a liquid detergent characterized by containing an alkylene oxide adduct (C) of a polyalkyleneamine. 4. The method according to any one of claims 1 to 3,
Wherein the component (B) is a bovine surfactant, and a higher fatty acid or a salt thereof.