KR20190018406A - Detergent composition - Google Patents

Abstract

A detergent composition comprising a component (A) and a component (B), wherein the component (A) is a polymer having a specific constitutional unit, and the component (B) is an alkylene terephthalate unit and an alkylene isophthalate unit Is a water-soluble polymer having at least one repeating unit (b1) selected from the group consisting of an oxyalkylene unit and a polyoxyalkylene unit and at least one repeating unit (b2) selected from the group consisting of polyoxyalkylene units.

Description

Detergent composition

The present invention relates to detergent compositions.

The present application claims priority under Japanese Patent Application No. 2016-119315, filed on June 15, 2016, the contents of which are incorporated herein by reference.

The items to be cleaned such as clothing require a fluffy feeling of volume after washing.

Patent Document 1 proposes a detergent composition comprising a copolymer of dimethyldiallylammonium halide and acrylamide. According to the detergent composition of Reference 1, flexibility can be imparted to articles to be cleaned such as clothing.

However, in the detergent composition of Reference 1, when the raw material of the wiping treatment, which is made of polyester such as furis, is used as the object to be cleaned, it is impossible to sufficiently give a feeling of touch with a fluffy volume.

Japanese Patent Application Laid-Open No. 2-103291

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and aims to provide a detergent composition capable of imparting a tactile feel with a fluffy volume.

As a result of intensive studies, the present inventors have found that the following detergent composition can solve the above problems.

That is, the present invention has the following form.

[1] A detergent composition comprising the component (A) and the component (B)

The component (A) is a polymer having at least one repeating unit selected from the group consisting of a repeating unit represented by the following general formula (a-1) and a repeating unit represented by the following general formula (a-2) ,

Wherein the component (B) is at least one kind selected from the group consisting of an oxyalkylene unit and a polyoxyalkylene unit, at least one kind of repeating unit (b1) selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit And at least one kind of repeating unit (b2) selected.

Wherein R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms and X ^- is a counter ion.

Wherein R ³ and R ⁴ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms and X ^- is a counter ion.

[2] The detergent composition according to [1], wherein the component (A) further comprises a repeating unit represented by the following general formula (a-3).

Wherein R ⁵ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms and R ⁶ and R ⁷ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms.

[3] The detergent composition according to [1] or [2], further comprising at least one anionic surfactant selected from the group consisting of a sulfonic acid anionic surfactant and a sulfate anionic surfactant.

[4] The detergent composition according to any one of [1] to [3], further comprising a nonionic surfactant.

[5] at least one repeating unit selected from the group consisting of a repeating unit derived from a monomer represented by the following general formula (e-1) and a repeating unit derived from a monomer represented by the following general formula (e-2) 1 > to < 4 >

[In the formula (e-1), R ¹¹ is a hydrogen atom or a methyl group, and R ¹² is a hydrogen atom. In the formula (e-2), R ¹³ is a hydrogen atom or a methyl group, and R ¹⁴ is an alkyl group having 1 to 40 carbon atoms.

(Effects of the Invention)

According to the present invention, it is possible to provide a detergent composition capable of imparting a tactile feel with a fluffy volume.

The detergent composition of the present invention contains the following components (A) and (B).

<Component (A): a polymer having at least one repeating unit selected from the group consisting of repeating units represented by formula (a-1) and repeating units represented by formula (a-2)

(A) is a polymer having at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (a-1) and a repeating unit represented by the following formula (a-2) By containing the component (A) in the detergent composition of the present invention, it is possible to impart a tactile feeling with a fluffy volume to the object to be cleaned after washing.

Wherein R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and X ^- is a counter ion.

Wherein R ³ and R ⁴ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and X ^- is a counter ion.

The component (A) preferably further contains a repeating unit represented by the following formula (a-3).

Wherein R ⁵ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms and R ⁶ and R ⁷ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms.

The repeating unit represented by the general formula (a-1) and the repeating unit represented by the general formula (a-2) are derived from a dialkyldiallylammonium salt monomer represented by the following general formula (a-4) Lt; / RTI &gt;

Wherein R ⁸ and R ⁹ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms and X ^- is a counter ion.

The formula (a-1), (a -2) and (a-4) X in the ^- as the chlorine ion, an inorganic ion such as a halogen ion, sulfate ion, nitrate ion, sulfite ion such as a bromine ion, methyl And organic acid ions such as sulfuric acid ion, acetic acid ion and lactic acid ion.

The weight average molecular weight of the component (A) is usually 1,000 to 5,000,000, preferably 3,000 to 2,000,000, and more preferably 10,000 to 2,000,000. In the present specification, the weight average molecular weight means a value obtained by gel permeation chromatography (GPC) using polyethylene glycol as a standard substance.

The form of polymerization of the component (A) is not particularly limited, and any of block polymerization, random polymerization and graft polymerization may be used.

The content ratio of the repeating unit represented by (a-1), the repeating unit represented by (a-2) and the repeating unit represented by (a-3) in the component (A) is not particularly limited, (A-1), and a repeating unit represented by the formula (a-1), wherein the molar ratio of the repeating unit represented by (a-2) : The repeating unit represented by the formula (a-3)] is preferably 1: 9 to 7: 3, more preferably 2: 8 to 6: 4.

Examples of the polymer having at least one repeating unit selected from the group consisting of the repeating unit represented by the formula (a-1) and the repeating unit represented by the formula (a-2) include diallyldimethylammonium chloride Examples of commercially available products include trade name &quot; Makoto 100 &quot;, manufactured by Lubrizol Corporation.

At least one repeating unit selected from the group consisting of a repeating unit represented by the general formula (a-1) and a repeating unit represented by the general formula (a-2) Include diallyl dimethyl ammonium chloride acrylamide copolymer, diallyldimethyl ammonium chloride acrylamide, acrylic acid terpolymer, and the like.

As these polymers, synthetic products may be used, or commercial products may be used.

The polymer is not particularly limited, but can be produced by ordinary radical polymerization. For example, by polymerizing monomers constituting the component (A) such as diallyldimethylammonium chloride or acrylamide by a polymerization method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization. In polymerization, it is preferable to use a polymerization initiator used in ordinary radical polymerization, and examples thereof include peroxides such as benzoyl peroxide, potassium persulfate, azobisisobutyronitrile, azobiscyano valeric acid and the like Can be used.

Commercially available products of the above copolymers include, for example, trade names "Makoto 550", "Makoto 740", "Makoto 2200", "Noverite 300", and "Noverite 302" manufactured by Lubrizol Corporation.

Examples of commercial products of the terpolymer include trade names "Makoto 3330" and "Makoto 3940" manufactured by Lubrizol Corporation.

These components (A) may be used singly or in combination of two or more.

The content of the component (A) is preferably 0.1 to 5% by mass, more preferably 0.1 to 1.2% by mass, and still more preferably 0.1 to 0.6% by mass with respect to the total mass of the detergent composition. If the content of the component (A) is not more than the upper limit value, it is easy to impart a feeling of softness in volume. When the content of the component (A) is not less than the lower limit value, it is easy to impart a feeling of softness in volume.

<Component (B): At least one repeating unit (b1) selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit, an oxyalkylene unit, and a polyoxyalkylene unit Soluble polymer having at least one kind of repeating unit (b2) selected>

(Hereinafter also referred to as a "unit (b1)") constituting the water-soluble polymer of the component (B) and the "alkylene terephthalate unit and the alkylene isophthalate unit" The unit is a unit represented by the following formula (b1-1).

[Wherein R ²¹ is a lower alkylene group]

The carbon number of R ²¹ is 1 to 4, preferably 2 to 4.

Specific examples of the alkylene terephthalate unit include an ethylene terephthalate unit, an n-propylene terephthalate unit, an isopropylene terephthalate unit, an n-butylene terephthalate unit, an isobutylene terephthalate unit, a sec- A phthalate unit, and a tert-butylene terephthalate unit. Of these, isopropylene terephthalate units are preferred.

As the unit (b1), a single kind of alkylene terephthalate unit may be used singly or plural kinds of alkylene terephthalate units may be used in combination.

The alkylene isophthalate unit among the units (b1) constituting the water-soluble polymer is a unit represented by the following formula (b1-2).

Wherein R ²² is a lower alkylene group.

The carbon number of R ²² is 1 to 4, preferably 2 to 4.

Specific examples of the alkylene isophthalate unit include ethylene isophthalate unit, propylene isophthalate unit, n-butylene isophthalate unit, sec-butylene isophthalate unit and tert-butylene isophthalate unit. have. Of these, propylene isophthalate units are preferred.

As the unit (b1), a single kind of alkylene isophthalate unit may be used singly or plural kinds of alkylene isophthalate units may be used in combination.

The unit (b1) may be selected from the above-mentioned alkylene terephthalate units and alkylene isophthalate units, alone or in combination of two or more. That is, the unit (b1) may be composed of an alkylene terephthalate unit only, the alkylene isophthalate unit alone, or a mixture of an alkylene terephthalate unit and an alkylene isophthalate unit.

(Hereinafter also referred to as a (b2)) unit constituting the water-soluble polymer of the component (B) may be represented by the following formula (b- 2).

- (R &lt; ²³ &gt; O) _s- (b-2)

Wherein R ²³ is a lower alkylene group, and s is an integer of 1 to 100.

The carbon number of R ²³ is 1 to 4, preferably 2 to 4.

In the formula (b-2), when s is 1, it is an oxyalkylene unit, and when s is 2 or more, it is a polyoxyalkylene unit. s is an integer of 1 to 100, preferably 1 to 80, particularly preferably 1 to 50.

Specific examples of the unit (b2) include oxyethylene units and polyoxyethylene units; An oxypropylene unit, and a polyoxypropylene unit; And polyoxyethylene polyoxypropylene units. Of these, oxyethylene units and polyoxyethylene units are preferable.

The unit (b2) may be selected from the above-mentioned oxyalkylene units and polyoxyalkylene units, alone or in combination of two or more. That is, the unit (b2) may be composed of an oxyalkylene unit alone, or may consist of a polyoxyalkylene unit alone or a mixture of an oxyalkylene unit and a polyoxyalkylene unit.

The component (B) is preferably a polymer compound in which the above-mentioned units (b1) and (b2) are randomly or block-polymerized.

The B component may contain units other than the aforementioned units (b1) and (b2) (for example, a unit derived from a polymerization initiator or a polymerization terminator, or other copolymerizable units). In that case, it is preferable that 80 mol% or more, preferably 90 mol% or more of the component (B) is composed of the (b1) unit and the (b2) unit.

The "water-soluble polymer" in the component (B) refers to a polymer obtained by adding 10 g of the above polymer to 1000 g of water under the condition of 40 ° C. and stirring for 12 hours (200 rpm) in a stirrer (thickness: 8 mm, length: 50 mm, ) Is completely dissolved.

Specific examples of the component (B) include compounds represented by the following formula (b-3) or (b-4).

Wherein R ²⁴ , R ²⁵ and R ²⁶ each independently represent an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms X1 is 0 to 10, preferably 0.5 to 5, particularly preferably 0.5 to 2.5, y1 is 1 to 100, preferably 1 to 80, more preferably 1 to 50, still more preferably And z1 is 1 to 100, preferably 1 to 80, more preferably 1 to 50, more preferably 10 to 50, particularly preferably 20 to 30, 30.]

Wherein R ²⁷ , R ²⁸ and R ²⁹ each independently represent an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms , X2 is 0 to 10, preferably 0.5 to 5, particularly preferably 0.5 to 2.5, y2 is 1 to 100, preferably 1 to 80, more preferably 1 to 50, still more preferably And z2 is preferably 1 to 100, more preferably 1 to 80, more preferably 1 to 50, still more preferably 10 to 50, still more preferably 20 to 30, 30.]

In the formula (b-3), the ratio of x1 to y1 is preferably 1: 5 to 1:20, and more preferably 1: 8 to 1:18.

In the formula (b-4), the ratio of x2 and y2 is preferably 1: 5 to 1:20, and more preferably 1: 8 to 1:18.

The component (B) preferably has a weight average molecular weight of 500 to 8000. The weight average molecular weight refers to a value obtained by converting a value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent into a calibration curve of PEG (polyethylene glycol). The lower limit value of the weight average molecular weight is more preferably 800 or more, and particularly preferably 1000 or more. The upper limit of the weight average molecular weight is preferably 7000 or less, and particularly preferably 6000 or less. Therefore, the weight average molecular weight is preferably 800 to 7000, and particularly preferably 1000 to 6000.

The pH of the component (B) (5% aqueous solution at 20 캜) is preferably 3 to 7.

The melting point of the component (B) is preferably from 25 캜 to 60 캜.

(50 ° C) of the component (B) is preferably 100 to 1000 mPa · s. The viscosity is measured using a Brookfield viscometer with rotor No. 2.

(B) is a known substance and is easily available in the market. Also, synthetic methods disclosed in, for example, Journal of Polymer Science, Vol. 3, pp. 609 to 630 (1948), Journal of Polymer Science, Vol. 8, pp. 1-22 (1951) And can be produced by the method described in JP-A-61-218699.

Specific examples of the component (B) include commercially available products such as TexCare SRN-100 (manufactured by Kurarianto Co., weight average molecular weight: 2000 to 3000) or TexCare SRN-300 (Kurariant Co., weight average molecular weight: 7000) . Of these, TexCare SRN-100, which has high solubility in water and less deterioration in cleaning performance after storage, is preferable. Particularly preferably, a commercially available 70% aqueous solution of TexCare SRN-100 and marketed under the trade name TexCare SRN-170 (Kurarians) can be used.

These (B) components may be used alone, or two or more of them may be used in combination.

The content of the component (B) is preferably from 0.1 to 5% by mass, more preferably from 0.1 to 3% by mass, and still more preferably from 0.2 to 1% by mass with respect to the total mass of the detergent composition. When the content of the component (B) is not more than the upper limit value, it is easy to give a feeling of softness with a fluffy volume. If the content of the component (B) is less than the lower limit value, it is easy to give a feeling of softness with a fluffy volume.

The mass ratio (hereinafter also referred to as A / B ratio) expressed by the component (A) / (B) is preferably 0.02 to 50, more preferably 0.03 to 12,

By setting the A / B ratio within the above range, it is possible to impart a tactile feel with a fluffy volume.

<Optional ingredients>

The detergent composition of the present invention may contain other components than the above components (A) to (B), as long as the effect of the present invention is not impaired, and may be, for example, an anionic surfactant, A surfactant, a polymer other than the components (A) and (B), water, an organic solvent, a reducing agent and a solubilizing agent, a metal ion capturing agent (chelating agent), an antioxidant, A coloring agent, a coloring agent, an emulsifying agent, an antioxidant, an antioxidant, an antioxidant, a perfume, a perfume, a perfume, a perfume, a perfume, a perfume, a perfume, a perfume, a perfume, Extracts such as fragrances, insoluble particles, natural products and the like.

[Anionic surfactant]

The anionic surfactant in the present invention is a known substance and can be easily obtained in the market. Among them, at least one anionic surfactant selected from the group consisting of a sulfonic acid type anionic surfactant and a sulfuric acid ester type anionic surfactant (hereinafter also referred to as component (C)) is preferable. Here, the sulfonic acid type anionic surfactant is an anionic surfactant having -SO ₃ ^- M ⁺ in the molecule. The sulfate anionic surfactant is an anionic surfactant having -OSO ₃ ^- M ⁺ in the molecule. Where M ⁺ is the counter ion. Examples of the counter ion include a metal ion, a protonated amine, and ammonium.

Specific examples of the component (C) include straight chain alkylbenzenesulfonic acid salts; -olefin sulfonic acid salts; Straight-chain or branched-chain alkylsulfuric ester salts; Alkyl ether sulfuric acid ester salts or alkenyl ether sulfuric acid ester salts; An alkane sulfonate having an alkyl group; alpha -sulfo fatty acid ester salts, and the like.

Further, as the anionic surfactant, the following are preferable.

In the straight-chain alkylbenzenesulfonic acid salt, the number of carbon atoms of the straight-chain alkyl group is preferably 8 to 16, and particularly preferably 10 to 14 carbon atoms.

As the? -olefin sulfonic acid salt, those having 10 to 20 carbon atoms are preferable.

As the alkylsulfuric ester salt, those having 10 to 20 carbon atoms are preferable.

Examples of the alkyl ether sulfuric acid ester salt or alkenyl ether sulfuric acid ester salt include a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms and an average of 1 to 10 moles of ethylene oxide added (that is, a polyoxyethylene alkyl ether Sulfuric acid ester salt or polyoxyethylene alkenyl ether sulfuric acid ester salt) is preferable.

The alkanesulfonate salt has 10 to 20 carbon atoms, preferably 14 to 17 carbon atoms, and a secondary alkanesulfonate salt is particularly preferable.

As the? -sulfo fatty acid ester salt, a compound represented by the following formula (c-1) is preferable.

R ⁴³ CH (SO ₃ M) COOR ^{44 ...} (c-1)

(In the formula (c-1), R ⁴³ is a hydrocarbon group having 8 to 18 carbon atoms, R ⁴⁴ is a hydrocarbon group having 1 to 6 carbon atoms, and M is a counter ion.)

In the formula (c-1), the carbon number of the hydrocarbon group of R ⁴³ is 8 to 18. Namely, the carbon number of the fatty acid residue of the? -Sulfo fatty acid ester salt is 10-20.

The hydrocarbon group of R &lt; ⁴³ &gt; may be straight chain, branched chain or cyclic structure. The hydrocarbon group of R ⁴³ is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group or a linear or branched alkenyl group, more preferably a linear alkyl group or a straight chain alkenyl group.

In the formula (c-1), the carbon number of R ⁴⁴ is 1 to 6, preferably 1 to 3.

The hydrocarbon group of R &lt; ⁴⁴ &gt; may be a straight chain, branched chain or cyclic structure. The hydrocarbon group of R &lt; ⁴⁴ &gt; is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group or a linear or branched alkenyl group, more preferably a linear alkyl group or branched alkyl group.

As R ⁴⁴ , a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like are preferable, and a methyl group, an ethyl group and an n-propyl group are preferable, and a methyl group is particularly preferable.

In the formula (c-1), the counter ion of M is preferably capable of forming a water-soluble salt together with R ⁴³ CH (COOR ⁴⁴ ) SO ₃ ^-, and examples thereof include an alkali metal ion, a protonated amine, Ion and the like. Examples of the alkali metal that can be used as the counter ion include sodium and the like. Examples of the amine that can be a counter ion include primary, secondary, and tertiary amines. The total number of carbon atoms in the amine is preferably 1 to 6. Further, the amine may have a hydroxy group. The amine preferably has a hydroxyl group in that the solubility of the? -sulfo fatty acid ester salt in water is high. Examples of the amine having a hydroxyl group include an alkanolamine, and the number of carbon atoms of the alkanol group is preferably 1 to 3. Examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, and the like.

M is preferably an alkali metal ion, and sodium ion is particularly preferable because M is easily available and low-temperature stability of the liquid detergent tends to be higher.

As the? -sulfo fatty acid ester salt, the compound represented by the formula (c-1) wherein R ⁴³ is a linear or branched alkyl group having a carbon number of 14 to 16 or a straight chain or branched alkenyl group and R ⁴⁴ is a methyl group Is particularly preferable.

Among the above-mentioned specific examples, a straight-chain alkylbenzenesulfonic acid salt, an alkanesulfonic acid salt, a polyoxyethylene alkyl ether sulfate, and an -olefin sulfonic acid salt are preferable.

Examples of the salt include alkali metal salts such as sodium salt and potassium salt, alkane salts such as ammonium salt, monoethanolamine salt, diethanolamine salt, triethanolamine salt, 2-amino-2-methylpropanol salt, And basic amino acid salts such as allamine salts, lysine and arginine.

The above-mentioned component (C) can be mixed with a detergent composition in the form of an acid such as, for example, straight chain alkylbenzenesulfonic acid and neutralized with an alkali agent such as caustic soda or monoethanolamine to form a salt in the detergent composition.

These (C) components may be used alone, or two or more of them may be used in combination.

The content of the component (C) is preferably from 2 to 20 mass%, more preferably from 5 to 18 mass%, and even more preferably from 10 to 16 mass%, based on the total mass of the detergent composition. When the content of the component (C) is not more than the upper limit value, it is easy to give a feeling of softness with a fluffy volume. If the content of the component (C) is not less than the lower limit value, it is easy to impart a feeling of softness in volume.

The mass ratio (hereinafter also referred to as A / C ratio) expressed by the component (A) / (C) is preferably from 0.1 / 20 to 5/2, more preferably from 0.1 / 18 to 1.2 / 5.

By setting the A / C ratio within the above-mentioned range, it is possible to impart a tactile feeling with a fluffy volume.

Examples of the anionic surfactant other than the component (C) include carboxylates such as higher fatty acid salts, alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates and acylaminocarboxylates Phosphoric ester type anionic surfactants such as acid type, alkyl phosphoric acid ester salt, polyoxyalkylene alkyl phosphoric acid ester salt, polyoxyalkylene alkylphenyl phosphoric acid ester salt and glycerin fatty acid ester monophosphate ester salt.

(C) and a salt of a fatty acid having 8 to 22 carbon atoms (hereinafter also referred to as &quot; higher fatty acid &quot;) is preferably used in combination.

Examples of the higher fatty acids include salts of a single fatty acid such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, Palm oil fatty acid, and tallow fatty acid.

Examples of the salts of these higher fatty acids include alkali metal salts such as sodium salts and potassium salts, ammonium salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, 2-amino-2-methylpropanol salt, Alkanolamine salts such as diol, and basic amino acid salts such as lysine and arginine.

[Nonionic surfactant]

Examples of the nonionic surfactant (hereinafter also referred to as component (D)) include, but are not limited to, polyoxyalkylene type nonionic surfactants, alkylphenols, fatty acids having 8 to 22 carbon atoms or amines having 8 to 22 carbon atoms Polyalkylene oxide adducts, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or alkylene oxide adducts thereof, polyhydric alcohol fatty acid ethers, alkyl (or alkenyl) amines Oxides, alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, alkyl glycosides and the like. Any one of them may be used alone, or two or more of them may be used in combination.

As the component (D), a polyoxyalkylene-type nonionic surfactant is preferable (however, the component (F) is not included) from the viewpoint of improving the appearance stability while appropriately maintaining the viscosity of the liquid detergent.

Examples of the polyoxyalkylene type nonionic surfactant include compounds represented by the following general formula (d-1) (hereinafter referred to as "compound (d1)"), compounds represented by the following general formula (d-2) (Hereinafter referred to as &quot; compound (d2) &quot;). Any one of them may be used alone, or two or more of them may be used in combination.

_{^{R 51 -CO- (OR 52) m}} -OR 53 ... (d-1)

R ⁵⁴ -O - [(EO) _s / (PO) _t ] H ... (D-2)

In the formula (d-1), R ⁵¹ is a hydrocarbon group having 9 to 13 carbon atoms, R ⁵² is an alkylene group having 2 to 4 carbon atoms, and R ⁵³ is an alkyl group having 1 to 4 carbon atoms. m represents the average number of repeats of OR &lt; ⁵² &gt;

In the formula (d-2), R ⁵⁴ is a hydrocarbon group having 10 to 22 carbon atoms, EO is an oxyethylene group, and PO is an oxypropylene group. s represents the average number of repeats of EO, is a number from 5 to 20, t represents the average number of repeats of PO, and is a number from 0 to 4.

Compound (d1):

In the formula (d-1), the hydrocarbon group in R ⁵¹ may be straight chain, branched chain or cyclic structure.

The hydrocarbon group in R &lt; ⁵¹ &gt; is preferably an aliphatic hydrocarbon group, and a linear or branched alkyl group or a linear or branched alkenyl group is more preferable.

The carbon number of R ⁵¹ is 9 to 13, preferably 10 to 13, and more preferably 11 to 13 carbon atoms. If the carbon number of R &lt; ⁵¹ &^gt; is 9 or more, the washing power is higher. On the other hand, when the carbon number of R &lt; ⁵¹ &^gt; is 13 or less, storage stability is improved and gelation is particularly suppressed.

The compound (d1) may be a mixture of single chain lengths or a mixture of plural chain lengths. R ⁵¹ is derived from the fatty acid (R ⁵¹ -COOH) of the raw material.

In the formula (d-1), R ⁵³ is an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms. Specific examples of R ⁵³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group, and a methyl group and an ethyl group are preferable and a methyl group is more preferable. When R &lt; ⁵³ &gt; has 1 or more carbon atoms, precipitation at low temperature storage tends to be suppressed. On the other hand, if the carbon number of R &lt; ⁵³ &gt; is 4 or less, the solubility of the liquid detergent in water becomes higher.

In the formula (d-1), R ⁵² is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group.

The plurality of R ^{52 s} in the formula may be the same or different. That is, the alkylene group of R ⁵² may be a single species or a combination of two or more species. Among them, it is preferable that m OR ⁵² in the formula are all oxyethylene groups, or oxyethylene group and oxypropylene group are mixed in the point that bubbles occur at the time of cleaning and are inexpensive.

When two or more kinds of alkylene groups of R ⁵² are combined, the addition method of OR ⁵² is not particularly limited. For example, as an addition method when oxyethylene group and oxypropylene group are mixed, a random portion may be used, good. Examples of the method of block addition include a method of adding propylene oxide after addition of ethylene oxide, a method of adding ethylene oxide after addition of propylene oxide, a method of adding propylene oxide and further adding ethylene oxide after addition of ethylene oxide And the like.

In the formula (d-1), m represents the average number of repeats of OR ⁵² , and is a number of 5 to 25. If m is the lower limit value or more, the washing power, particularly the washing power against sebum dirt, is further improved. On the other hand, if m is not more than the upper limit, the solubility of the liquid detergent in water is further improved.

When OR ⁵² is an oxyethylene group, m is preferably from 5 to 20, and more preferably from 12 to 18.

When OR &lt; ⁵² &gt; is an oxyethylene group and an oxypropylene group are mixed, m is particularly preferably 12 to 21. Of these, the average number of repeating units of the oxypropylene group is preferably 5 or less, more preferably 4 or less, and still more preferably 3 or less. If the average number of repeating units of the oxypropylene group exceeds 5, there is a fear that the washing power and the storage stability (the fragrance, the stability with time, etc.) as the liquid detergent are lowered.

In the compound (d1), the narrowing ratio indicating the ratio of the distribution of the compounds having the repetition number of OR &lt; ⁵² &gt; is preferably 20 mass% or more. The upper limit value of the narrow rate is preferably substantially 80% by mass or less.

The low rate is more preferably from 20 to 50 mass%, and more preferably from 30 to 45 mass% from the viewpoints of storage stability and solubility in water.

A higher cleaning rate is more likely to be obtained as the narrow rate is higher. Further, when the above-mentioned line rate is preferably 20% by mass or more, particularly preferably 30% by mass or more, a liquid detergent having a low odor of raw material derived from the compound (d1) tends to be obtained. This is because, after the preparation of the compound (d1), the fatty acid ester which is a raw material of the compound (d1) coexisting with the compound (d1) and the alkylene oxide adduct in which m is 1 or 2 in the formula (d-1) to be.

The ratio of the total of the fatty acid ester as the raw material of the compound (d1) and the alkylene oxide adduct having m of 1 or 2 in the formula (d-1) among the compounds contained as the impurities in the compound (d1) Is preferably 0.5 mass% or less, and more preferably 0.2 mass% or less. If the ratio is 0.5% by mass or less, a liquid detergent with less odor of the raw material of the surfactant tends to be obtained.

In the present specification, the term "narrow rate" refers to a value represented by the following formula (S), which indicates the ratio of the distribution of alkylene oxide adducts in which the number of added moles of alkylene oxide is different.

In the above formula (S), m _max represents the number of repeating OR ⁵² (addition mole number) of the alkylene oxide adduct which is the most abundant in the entire compound (d1).

i represents the number of repetitions of OR ⁵² .

And Yi represents the proportion (% by mass) of the alkylene oxide adduct having the addition mole number of the alkylene oxide present in the entire compound (d1).

The narrow rate can be controlled by, for example, a method for producing the compound (d1).

The method for producing the compound (d1) is not particularly limited, and for example, a method of addition polymerization of an alkylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (Japanese Patent Laid-Open No. 2000-144179) Can be easily produced.

Preferable examples of such a surface-modified composite metal oxide catalyst include metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ^3+, , La ³⁺ , Mn ^2+, and the like), or a calcined catalyst of hydrotalcite surface-modified with metal hydroxide and / or metal alkoxide.

In addition, in the surface modification of the composite metal oxide catalyst, the mixing ratio of the composite metal oxide and the metal hydroxide and / or the metal alkoxide is preferably 0.5 to 0.5 part by mass of the metal hydroxide and / or the metal alkoxide, To 10 parts by mass, more preferably from 1 to 5 parts by mass.

As a method for producing the compound (d1), there is a method of adding an alkylene oxide to a fatty acid alkyl ester by an alkoxylation catalyst prepared from a mixture of an alkaline earth metal compound and an oxyacid. The alkoxylation catalyst is disclosed in, for example, Japanese Patent No. 04977609, International Publication No. 1993/004030, International Publication No. 2002/038269, International Publication No. 2012/028435, and the like, An alkoxylation catalyst prepared by mixing a metal salt and / or an alkaline earth metal salt of a hydroxycarboxylic acid with sulfuric acid or the like.

Compound (d2):

In the formula (d-2), the hydrocarbon group in R ⁵⁴ may be linear, branched or cyclic.

The hydrocarbon group in R ⁵⁴ is preferably an aliphatic hydrocarbon group, more preferably a straight chain or branched chain alkyl group or a straight chain or branched chain alkenyl group.

R ⁵⁴ has 10 to 20 carbon atoms, preferably 12 to 18 carbon atoms, and more preferably 12 to 14 carbon atoms. When the number of carbon atoms of R &lt; ⁵⁴ &gt; is 10 or more, the cleaning power is higher. On the other hand, when the carbon number of R ⁵⁴ is 20 or less, storage stability is improved and gelation is particularly suppressed.

The compound (d2) may be a mixture of single chain lengths or a mixture of plural chain lengths. R ⁵⁴ is derived from the alcohol (R ⁵⁴ -OH) of the raw material. Examples of the alcohol include alcohols derived from natural oils such as palm oil, palm oil, or tallow, and synthetic alcohols derived from petroleum.

In the formula (d-2), s represents the average number of repeating units of EO, and is a number of 5 to 20, preferably 12 to 18, and more preferably 12 to 16. When s is in the above range, the detergency of the liquid detergent, especially the detergency against sebum dirt, is further improved.

t represents the average number of repeats of PO, and is a number of 0 to 4, preferably 0 to 3, and particularly preferably 0. When t is within the above range, gelation of the liquid detergent is easily inhibited, and a good foam removing property is easily obtained at the time of rinsing.

In the above formula (d-2), EO and PO may be added in a block form or in a random form. As an addition method in the case where EO and PO are added in a block form, there are a method of adding propylene oxide after adding ethylene oxide, a method of adding ethylene oxide after adding propylene oxide, a method of adding propylene oxide And a method of adding ethylene oxide is also cited. Particularly, in view of better rinsability in washing in a fully automatic washing machine, a method in which propylene oxide is added after addition of ethylene oxide and ethylene oxide is added (terminal is -O-CH ₂ CH ₂ OH) .

In the compound (d2), the addition mole number distribution of the alkylene oxide (ethylene oxide, propylene oxide) is not particularly limited and can be controlled by the production method of the compound (d2). For example, when an alkylene oxide is added to a hydrophobic raw material by using a common alkali catalyst such as sodium hydroxide or potassium hydroxide, there is a tendency to have a relatively large added mole number distribution. In addition, metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , and Mn ³⁺ described in JP 6-15038 A When alkylene oxide is added to a hydrophobic raw material by using a specific alkoxylation catalyst such as magnesium oxide, there is a tendency that the addition molar number distribution is relatively narrow.

Specific examples of the compound (d2) include, for example, the following compounds.

(Such as a mixture of an alcohol having a carbon number of 12 and an alcohol having a carbon number of 14) or a trade name of Safol23 (a mixture of an alcohol having a carbon number of 12 and an alcohol having a carbon number of 13) manufactured by Lion Corporation To which 12 mol or 15 mol of EO is added.

A compound having 9 mol, 12 mol or 15 mol of EO added to a natural alcohol such as CO-1214 or CO-1270 by P &

(Nos. &Quot; SOFTANOL 90 &quot;, &quot; SOFTANOL 120 &quot;, &quot; SOFTANOL &quot;, &quot; 150 &quot;).

As the component (D), at least one member selected from the group consisting of the compound (d1) and the compound (d2) is particularly preferable in view of the cleaning power against sebum dirt and the difficulty of gelation in a high concentration region. Among them, it is more preferable to use a combination of the compound (d1) and the compound (d2) or the compound (d1).

As the compound (d1), a polyoxyethylene fatty acid alkyl ester in which R ⁵² is an ethylene group is preferable among the above, and a polyoxyethylene fatty acid methyl ester in which R ⁵³ is a methyl group (hereinafter referred to as "MEE" ) Is particularly preferable. Since they have a small gelation region even at a high concentration, gelation is unlikely to occur at a high mixing ratio.

Further, since the liquid detergent contains a polyoxyethylene fatty acid alkyl ester, the solubility in water becomes good and a high washing power tends to be easily obtained. In addition, even when a surfactant at a high concentration is contained, the concentration of the liquid detergent having a good flowability is hardly increased (gelation) remarkably. The reason for this is considered as follows.

Polyoxyethylene fatty acid alkyl esters, especially MEE, are highly concentrated and difficult to gelify because they are non-ionic surfactants having weak orientation of molecules in an aqueous system and unstable micelles, so that they can be compounded in a large amount in a liquid detergent alone . It is also presumed that the solubility in water is improved. It is also believed that this contributes to good fluidity at a high concentration. Therefore, when the polyoxyethylene fatty acid alkyl ester is put into water in a washing machine tank, the concentration of the polyoxyethylene fatty acid alkyl ester in the washing liquid rapidly becomes uniform and can be contacted with the object to be cleaned at a predetermined concentration from the beginning of cleaning, It is thought that the cleaning power is obtained.

As the compound (d2), a primary alcohol ethoxylate in which ethylene oxide is added to the primary alcohol among the above is particularly preferable.

The content of the component (D) is preferably from 10 to 50 mass%, more preferably from 10 to 40 mass%, and even more preferably from 15 to 30 mass%, based on the total mass of the detergent composition. When the content of the component (D) is 10% by mass or more, sufficient cleaning power is obtained. When the content is 50% by mass or less, the increase in viscosity is suppressed and the storage stability of the liquid detergent can be kept better.

[Cationic Surfactant]

Examples of the cationic surfactant include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and cationic surfactants such as alkylpyridinium salts.

Examples of the amphoteric surfactants include, but are not limited to, caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, Long-chain aliphatic amidoalkyl tertiary amines such as dimethylamino propylamide, hexanoic acid dimethylaminopropylamide and oleic acid dimethylaminopropylamide; Palmitic acid diethanol aminopropylamide, stearic acid diethanol aminopropylamide, and the like.

[Amphoteric surfactant]

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

[Polymers other than the components (A) and (B)] [

Examples of the polymer other than the components (A) and (B) include a repeating unit derived from a monomer represented by the following formula (e-1) and a repeating unit derived from a monomer represented by the following formula (e-2) (Hereinafter also referred to as a component (E)) containing at least one kind of repeating unit selected from the group consisting of Component (E) serves as a structuring agent. The detergent composition is structured by the liquid detergent containing component (E). Therefore, for example, when the liquid detergent contains insoluble particles, the insoluble particles can be uniformly dispersed in the liquid detergent, and the state can be maintained. In addition, the storage stability of the liquid detergent and the prevention of re-contamination are also enhanced.

[In the formula (e-1), R ¹¹ is a hydrogen atom or a methyl group, and R ¹² is a hydrogen atom. In the formula (e-2), R ¹³ is a hydrogen atom or a methyl group, and R ¹⁴ is an alkyl group having 1 to 40 carbon atoms.

The repeating unit derived from the monomer represented by the general formula (e-1) is preferably a repeating unit derived from the monomer represented by the general formula (e-1) when the monomer component containing the monomer represented by the general formula (e- Derived repeating unit.

Examples of the monomer represented by the general formula (e-1) include acrylic acid and methacrylic acid.

Any one of the monomers represented by the general formula (e-1) may be used alone, or two or more kinds thereof may be used in combination.

In the above formula (e-2), R ¹³ is a hydrogen atom or a methyl group, preferably a hydrogen atom.

In the formula (e-2), the alkyl group in R ¹⁴ may be straight chain, branched chain or cyclic structure.

The alkyl group in R ¹⁴ has 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.

The repeating unit derived from the monomer represented by the formula (e-2) is preferably a repeating unit derived from the monomer represented by the formula (e-2) when the monomer component containing the monomer represented by the formula (e- Derived repeating unit.

Examples of the monomer represented by formula (e-2) include acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, ; Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, decyl methacrylate, dodecyl methacrylate and eicosyl methacrylate .

Any one of the monomers represented by the general formula (e-2) may be used alone, or two or more kinds thereof may be used in combination.

The component (E) may be crosslinked or not crosslinked, but is preferably crosslinked.

Examples of the component (E) that is crosslinked include those crosslinked by a crosslinking agent (polymer crosslinked product).

As the crosslinking agent, for example, an allyl ether compound is preferably used.

Examples of the allyl ether compound include allyl ether, allyl ether of sugar, allyl ether of sugar alcohol and the like.

Examples of the sugar in the allyl ether of sugar include sucrose and the like.

Examples of sugar alcohols in allyl ether of sugar alcohols include pentaerythritol and the like.

Any one of the components (E) may be used alone, or two or more of them may be used in combination.

The component (E) is preferably a copolymer obtained by copolymerizing a repeating unit derived from a monomer represented by the general formula (e-1) and a repeating unit other than the repeating unit derived from a monomer represented by the general formula (e-2) .

Other repeating units include repeating units derived from other monomers.

The other monomer is not particularly limited as long as it can be copolymerized with the monomer represented by formula (e-1) and the monomer represented by formula (e-2), and at least one of them can be used.

Specific examples of the component (E) include the following trade names.

Commercially available products of the crosslinking type (E) include trade name "Carbopol Aqua 30", which is a crosslinking copolymer comprising two or more monomers selected from alkyl acrylates, alkyl methacrylates, acrylic acid and methacrylic acid manufactured by Lubrizol Corporation; Quot; Carbopol Aqua SF-1 &quot; which is a crosslinked copolymer composed of two or more monomers selected from alkyl acrylates (C1 to C4 and C8), alkyl methacrylates (C1 to C4 and C8) manufactured by Lubrizol, acrylic acid and methacrylic acid ; Quot; Carbopol EZ-4 &quot; which is a crosslinkable copolymer comprising two or more monomers selected from alkyl acrylates (C10 to C30), alkyl methacrylates (C10 to C30) and acrylic acid manufactured by Lubrizol, alkyl acrylate, Trade name &quot; ACUSOL 830 &quot; which is a crosslinkable copolymer made of acrylic acid or methacrylic acid, and the like.

Commercially available products of the non-crosslinkable type (E) component include, for example, trade names "Novethix HC200", which is a copolymer composed of two or more monomers selected from alkyl acrylates, alkyl methacrylates, acrylic acid and methacrylic acid manufactured by Lubrizol .

These (E) components may be used alone, or two or more of them may be used in combination.

The content of the component (E) is preferably from 0.1 to 5.0 mass%, more preferably from 0.5 to 2.5 mass%, based on the total mass of the detergent composition. When the content of the component (E) is within the above-mentioned numerical range, it is possible to structure the liquid detergent.

The mass ratio (hereinafter also referred to as A / E ratio) expressed by the component (A) / (E) is preferably 0.05 to 1.25, and more preferably 0.1 to 1.25.

When the A / E ratio is within the above-mentioned range, the liquid detergent is sufficiently structured and storage stability is improved.

[Organic solvents]

The detergent composition of the present invention may contain, for example, monohydric alcohols having 2 to 4 carbon atoms, polyhydric alcohols having 2 to 4 carbon atoms and the following formula (f-1), which may contain an organic solvent A glycol ether solvent represented by the following formula (f-2), and a solvent represented by the following formula (f-2).

R ³¹ - (OR ³² ) _m OH (F-1)

Wherein R ³¹ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ³² is an alkylene group having 2 to 4 carbon atoms, and m is an average addition mole number of 1 to 5.

CH ₃ OCR ³³ (CH ₃ ) CHR ³⁴ CHR ³⁵ OR ^{36 ...} (f-2)

Wherein R ³³ to R ³⁵ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ³⁶ is a hydrogen atom or an acetyl group.

Examples of the monohydric alcohol having 2 to 4 carbon atoms include ethanol, 1-propanol, 2-propanol, 1-butanol and the like.

Examples of the polyhydric alcohol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol, and glycerin.

Examples of the glycol ether solvent represented by the above formula (f-1) include ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol Monobutyl ether, and the like.

Examples of the solvent represented by the above formula (f-2) include 3-methoxy-3-methoxy-3-methylbutanol, 3-methoxy- Propanol butanol, 3-methoxy-1-methyl butanol, 3-methoxy-1-ethyl butanol, 3-methoxy- Methoxy-3-methylbutyl acetate, 3-methoxy-3-ethylbutyl acetate, 3-methoxy-3-propylbutyl acetate, 3-methoxybutyl acetate, Methoxy-2-ethylbutyl acetate, 3-methoxy-2-propylbutyl acetate, 3-methoxy-1-methylbutyl acetate, 3-methoxy- Ethyl butyl acetate, 3-methoxy-1-propyl butyl acetate, and the like.

Of these, ethanol, propylene glycol, diethylene glycol monobutyl ether, and 3-methoxy-3-methyl butanol are preferable because of their fluidity and smell as a liquid detergent, and ease of obtaining raw materials.

These (F) components may be used alone, or two or more of them may be used in combination.

The content of the component (F) is preferably 3 to 25 mass% with respect to the total mass of the detergent composition.

When the content of the component (F) is not more than the upper limit value, fluidity and liquid stability as a liquid detergent are easily imparted. When the content of the component (F) is at least the lower limit value, fluidity and liquid stability as a liquid detergent are easily imparted.

[Reductions agent and solubilizing agent]

Examples of the reducing agent and the solubilizing agent include triethylene glycol, tetraethylene glycol, polyethylene glycol having an average molecular weight of about 200, polyethylene glycol having an average molecular weight of about 400, polyethylene glycol having an average molecular weight of about 1000, glycols such as dipropylene glycol, Benzoate, and urea.

When the detergent composition of the present invention contains a scoring agent and a solubilizing agent, the content of the scoring agent and the solubilizing agent is preferably 0.01 to 15% by mass with respect to the total mass of the detergent composition.

[Metal ion capturing agent (chelating agent)]

Examples of the metal ion capturing agent (chelating agent) include malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, and citric acid.

When the detergent composition of the present invention contains a metal ion scavenger, the content of the metal ion scavenger is preferably 0.1 to 20 mass% with respect to the total mass of the detergent composition.

[Antioxidant]

Examples of the antioxidant include butylhydroxytoluene, cresol disilene, sodium sulfite, sodium hydrogen sulfite and the like.

When the detergent composition of the present invention contains an antioxidant, the content of the antioxidant is preferably 0.01 to 2% by mass based on the total mass of the detergent composition.

[antiseptic]

Examples of the preservative include "KSON CG" (trade name) manufactured by DOW CHEMICALS, "ACTISIDE MBS" (trade name) manufactured by SOUJI Japan, and "NIPACIDE BIT 20" (trade name) manufactured by Kurariant.

[coloring agent]

Examples of the colorant include Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, Red No. 106, Yellow No. 203, Turquoise P- And general pigments and pigments.

When the detergent composition of the present invention contains a colorant, the content of the colorant is preferably 0.00005 to 0.005 mass% with respect to the total mass of the detergent composition.

[Relieving Agent]

Examples of the emulsifying agent include a polystyrene emulsion and a polyvinyl acetate emulsion, and emulsions having a solid content of 30 to 50 mass% are exemplified. Specifically, a polystyrene emulsion (trade name, product of Siden Kagaku Co., Ltd.) Cyanol RPX-196 PE-3, solid content 40% by mass).

When the detergent composition of the present invention contains an emulsifying agent, the content of the emulsifying agent is preferably 0.01 to 0.5 mass% with respect to the total mass of the detergent composition.

[Spices]

Examples of the perfume include the perfume ingredients described in Japanese Patent Application Laid-Open No. 2002-146399.

When the detergent composition of the present invention contains a perfume, the content of the perfume is preferably 0.01 to 2% by mass relative to the total mass of the detergent composition.

[Insoluble Particles]

Insoluble particles are particles that are difficult to dissolve in the constituents of the liquid detergent.

Specific examples of the insoluble particles include capsule particles, beads or pearlescent agents for imparting unique product aesthetics, bentonite, carboxymethyl cellulose (CMC), and the like.

The capsule particle contains the active ingredient by the capsule wall formed of the polymer compound.

Capsule particles can be produced by a known method, and examples thereof include an interface polymerization method and an in-situ polymerization method.

Examples of the polymer compound forming the capsule wall include synthetic polymers such as polyacrylic acid type, polyvinyl type, polymethacrylic acid type, melamine type, and urethane type. Any one of them may be used alone, or two or more of them may be used in combination.

Examples of the effective ingredient include a perfume component, a sunscreen component (ultraviolet absorber, ultraviolet scattering agent, etc.), and the like.

Hereinafter, the capsule particle containing the perfume component by the capsule wall formed of the polymer compound is also referred to as &quot; capsule perfume &quot;.

Specific examples of the capsule perfume include the capsule perfume A, the capsule perfume B, and the capsule perfume C shown below, for example.

Capsule fragrance A:

The capsule perfume A includes the following perfume ingredients.

(0.40% by mass), cyclosiloxane (0.10% by mass), ethyl 2-methylbutyrate (3.50% by mass), triflall (5.00% Tricyclodecenyl acetate (19.00 mass%), belldox (18.00 mass%), necktalil (15.00 mass%), tetrahydrolinalool (14.00 mass% (0.50% by mass),? -Ionone (14.00% by mass) and dipropylene glycol (1.00% by mass).

Capsule flavor B:

The capsule perfume B includes the following perfume ingredients.

(10.00% by mass), isopropyl methyl-2-butylate (1.70% by mass), manzanate (2.00% by mass), triflic acid (2.40% (7.50 mass%),? -Decalactone (0.50 mass%),? -Undecaractone (7.50 mass%), Beldox (14.00 mass%), allyl amyl glycolate (2.00 mass%), allylcyclohexylpropionate ), α-damascone (0.25 mass%), nerol (0.20 mass%), hedione (5.00 mass%), lilial (12.00 mass%), linalool (23.00 mass%), pt- butylcyclohexyl acetate 0.20 mass%), vanillin (0.10 mass%), lime oxide (2.40 mass%) and dipropylene glycol (1.75 mass%).

Capsule flavor C:

The capsule perfume C includes the following perfume ingredients.

(3.49 mass%), ethyl 2-methylbutyrate (3.30 mass%), dihydrogenol (8.49 mass%), camphor (1.46 mass%) and 1,4-cineol (1.28 mass% (9.04 mass%),? -Nonaractone (0.84 mass%),? -Decactactone (2.58 mass%),? -Undecaractone (3.70 mass%), allyl caproate (7.47 mass% (0.80% by mass), hexyl acetate (1.27% by mass), geranyl propionate (6.38% by mass), prenyl acetate (1.52% by mass), allylphenoxyacetate (0.60% by mass), dimethylbenzylcarbylbutylate (11.53 mass%), cyclic aldehyde (3.05 mass%), amyl salicylate (1.39 mass%), isoiser (1.08 mass%), (0.34% by mass), anisaldehyde (8.46% by mass) and lime oxide (0.41% by mass).

When the detergent composition of the present invention contains insoluble particles, the content of insoluble particles is preferably 0.01 to 20% by mass relative to the total mass of the detergent composition.

[Extract of natural products]

Examples of the extracts of natural products include, but are not limited to, elk trees, bearberry leaves, echinacea, golden, yellowberry, chrysanthemum, allspice, oregano, painting trees, camomile, In the beginning of the month, there are many kinds of plants such as acerola, peony, ginger, seaweed, cherry tree, sage, mistletoe, pomegranate, thyme, clover, clove, citrus tree, tea tree, barberry, Eucalyptus, Lavender, Rose, Rosemary, Leaf, Cedar, Balsam Trees, Ringworm, Dewarri, Marigold, Relish, Maple tree, Leaves , Acanthopanax acacia L., Begonia vinegar, licorice, and Chinese cabbage herb.

When the detergent composition of the present invention contains an extract such as a natural product, the content of the extract in a natural product or the like is preferably 0 to 0.5 mass% with respect to the total mass of the detergent composition.

These components may be used alone, or two or more of them may be used in combination.

Further, it is also possible to use 2-ethylhexyl 2-ethylhexyl (2-ethylhexyl isooctylate), 2-ethylbutyl 2-ethylhexanoate, 2-ethyloctyl 2-ethylhexanoate And a foam removing agent. When the detergent composition of the present invention contains the agent having a defoaming effect, its content is preferably 0 to 2.0% by mass with respect to the total mass of the detergent composition.

The total amount of components constituting the detergent composition does not exceed 100% by mass.

The detergent composition of the present invention preferably has a pH of 4 to 10 at 25 ° C, more preferably 4 to 9, and more preferably 4 to 8. When the pH is in this range, the preservation stability of the detergent composition can be kept good.

The pH of the detergent composition can be adjusted, if necessary, by adding a pH adjuster.

As the pH adjuster, sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine and the like are preferable as long as the effect of the present invention is not impaired.

In the present specification, the pH means a value measured by a pH meter (product name: HM-30G, manufactured by DOKKAI K.K.) with an object to be measured at 25 캜.

The detergent composition of the present invention comprises a component (A) and a component (B), wherein the component (A) is a copolymer of dimethyldiallylammonium and acrylamide, and the component (B) b-4).

The detergent composition of the present invention comprises a component (A) and a component (B), wherein the component (A) is a copolymer of dimethyldiallylammonium and acrylamide, and the component (B) wherein the content of the component (A) is 0.1 to 5% by mass based on the total mass of the detergent composition, the content of the component (B) is 0.1 to 5% by mass with respect to the total mass of the detergent composition, .

The cleaning composition of the present invention comprises a component (A), a component (B), and a component (C), wherein the component (A) is a copolymer of dimethyldiallylammonium and acrylamide, -3) or (b-4), and the component (C) is a straight chain alkylbenzenesulfonic acid salt.

The cleaning composition of the present invention comprises a component (A), a component (B), and a component (C), wherein the component (A) is a copolymer of dimethyldiallylammonium and acrylamide, Wherein the component (C) is a linear alkylbenzenesulfonic acid salt, the content of the component (A) is 0.1 to 5% by mass with respect to the total mass of the detergent composition, and (B) ) Component is 0.1 to 5 mass% with respect to the total mass of the detergent composition, and the content of the component (C) is preferably 2 to 20 mass% with respect to the total mass of the detergent composition.

The detergent composition of the present invention comprises a component (A), a component (B), a component (C), and a component (D), wherein the component (A) is a copolymer of dimethyldiallylammonium and acrylamide, (D) is a compound represented by the formula (b-3) or (b-4), the component (C) is a straight chain alkylbenzenesulfonic acid salt, Is preferably a compound represented by the following formula.

The detergent composition of the present invention comprises a component (A), a component (B), a component (C), and a component (D), wherein the component (A) is a copolymer of dimethyldiallylammonium and acrylamide, (D) is a compound represented by the formula (b-3) or (b-4), the component (C) is a straight chain alkylbenzenesulfonic acid salt, Wherein the content of the component (A) is from 0.1 to 5 mass% based on the total mass of the detergent composition, the content of the component (B) is from 0.1 to 5 mass% with respect to the total mass of the detergent composition, The content of the component is preferably 2 to 20 mass% based on the total mass of the detergent composition, and the content of the component (D) is preferably 10 to 50 mass% with respect to the total mass of the detergent composition.

The detergent composition of the present invention comprises a component (A), a component (B), a component (C), a component (D) and a component (E), wherein the component (A) is a copolymer of dimethyldiallylammonium and acrylamide (B) is a compound represented by the formula (b-3) or (b-4), the component (C) is a straight chain alkylbenzenesulfonic acid salt and the component (D) d-2), and the component (E) is a crosslinking copolymer synthesized from two or more kinds of monomers selected from the group consisting of alkyl acrylates, alkyl methacrylates, acrylic acid, and methacrylic acid.

The detergent composition of the present invention comprises a component (A), a component (B), a component (C), a component (D) and a component (E), wherein the component (A) is a copolymer of dimethyldiallylammonium and acrylamide (B) is a compound represented by the formula (b-3) or (b-4), the component (C) is a straight chain alkylbenzenesulfonic acid salt and the component (D) wherein the component (E) is a crosslinked copolymer synthesized from at least two kinds of monomers selected from the group consisting of alkyl acrylates, alkyl methacrylates, acrylic acid, and methacrylic acid, and (A) ) Is 0.1 to 5% by mass based on the total mass of the detergent composition, the content of the component (B) is 0.1 to 5% by mass with respect to the total mass of the detergent composition, and the content of the component (C) Wherein the content of the component (D) is 10 to 50 mass% with respect to the total mass of the detergent composition, (E) The content of the component is preferably 0.1 to 5.0 mass% with respect to the total mass of the detergent composition.

The detergent composition of the present invention contains a component (A), a component (B), a component (C), a component (D), an component (E) and a component (F), wherein the component (A) (B) is a compound represented by the formula (b-3) or (b-4), the component (C) is a linear alkylbenzenesulfonic acid salt, the component (D) 1) or (d-2), and the component (E) is a crosslinking type copolymer which is synthesized from two or more kinds of monomers selected from the group consisting of alkyl acrylates, alkyl methacrylates, acrylic acid, and methacrylic acid And the component (F) is a monohydric alcohol having 2 to 4 carbon atoms or an organic solvent represented by the formula (f-1) or (f-2).

The detergent composition of the present invention contains a component (A), a component (B), a component (C), a component (D), an component (E) and a component (F), wherein the component (A) (B) is a compound represented by the formula (b-3) or (b-4), the component (C) is a linear alkylbenzenesulfonic acid salt, the component (D) 1) or (d-2), and the component (E) is a crosslinking type copolymer which is synthesized from two or more kinds of monomers selected from the group consisting of alkyl acrylates, alkyl methacrylates, acrylic acid, and methacrylic acid Wherein the component (F) is a monohydric alcohol having 2 to 4 carbon atoms or an organic solvent represented by the formula (f-1) or (f-2), and the content of the component (A) (B) is 0.1 to 5% by mass with respect to the total mass of the detergent composition, and the content of the component (C) is 0.1 to 5% by mass with respect to the total mass of the detergent composition , The content of the component (D) is 10 to 50 mass% with respect to the total mass of the detergent composition, the content of the component (E) is 0.1 to 5.0 mass% with respect to the total mass of the detergent composition, The content of the component (F) is preferably 3 to 25 mass% with respect to the total mass of the detergent composition.

The detergent composition of the present invention is produced by a conventionally known method for producing a detergent.

When the detergent composition is a liquid, for example, there can be mentioned a method of adding (A) to (B) components to water as a solvent, and optional components as required, and mixing them.

When the detergent composition is in the form of powder, for example, dry blending method in which each raw material is powder-mixed, dry-type granulation method in which powder material is flowed, stirring agitation method in which a liquid binder is sprayed while flowing the powder raw material An extrusion granulation method in which a raw material is kneaded and extruded by an extruder, a pulverizing granulation method in which a raw material is kneaded and pulverized, and a spray drying method in which a slurry containing a raw material is spray dried.

As a method of using the detergent composition of the present invention, for example, when the detergent composition is used for cleaning a textile product, a method of applying the detergent composition to the water together with the laundry at the time of washing, a method of directly applying the detergent composition to the soil or sebum dirt A method in which the detergent composition is previously dissolved in water to immerse the clothes, and the like. It is also preferable to apply the detergent composition to the laundry, then allow it to stand properly, and then perform normal washing using a normal washing liquid.

Examples of the object to be cleaned include textile products such as clothes, cloths, sheets, curtains and rugs.

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.

(Raw materials used)

&Lt; Component (A) >

A-1: Dimethyldiallylammonium acrylamide copolymer, trade name "Noverite 300", manufactured by Lubrizol Corporation.

&Lt; Component (B) >

(5 mass% aqueous solution at 20 占 폚) = 4, viscosity (20 占 폚) = 300 mPa (viscosity at 20 占 폚), B-1: water-soluble polymer, trade name "TexCare SRN-170C", Kurariant Japan Co., · S, and the polymer represented by the formula (b-4).

<Optional ingredients>

[Component (C)] [

C'-1: straight-chain alkyl (having 10 to 14 carbon atoms) benzenesulfonic acid, trade name "LYONON LH-200", average molecular weight: 322, manufactured by Lion Corporation, Sulfonate (C-1) (average molecular weight: 383).

[Component (D)] [

D-1: polyoxyethylene alkyl ether (natural alcohol CO-1270 (product name, produced by PROCUTTA & GAMBLE Co., Ltd.) with an average of 15 moles of ethylene oxide added).

D-2: mixture of 8/2 by mass ratio of C ₁₁ H ₂₃ CO (OCH ₂ CH ₂ ) _m OCH ₃ and C ₁₃ H ₂₇ CO (OCH ₂ CH ₂ ) _m OCH ₃ , m = average 15, Yield: 33% by mass.

[Component (E)] [

(E-1) Crosslinked copolymers synthesized from two or more kinds of monomers selected from the group consisting of alkyl acrylates, alkyl methacrylates, acrylic acid and methacrylic acid, trade name "Carbopol Aqua 30", manufactured by Lubrizol.

[Component (F)] [

F-1: Ethanol, trade name &quot; Specific alcohol 95 degree synthesis &quot;, manufactured by Nippon Alcohol Co., Ltd.

F-2: diethylene glycol monobutyl ether, trade name "butyldiglycol", manufactured by Nippon Yuka Co., Ltd.

F-3: 3-methoxy-3-methylbutanol, trade name "Solfit", manufactured by Kuraray Co., Ltd.

[Common component a]

Polyethylene glycol: trade name &quot; PEG # 1000-60L &quot;, manufactured by Lion Corporation) 2% by mass.

· Palm oil fatty acid: made by Nichiyu Kogyo Co., Ltd. 4% by mass.

· Sodium benzoate: Product name "Sodium benzoate", Doagose ... 0.5% by mass.

· Citric acid: "liquid citric acid", manufactured by Ipposha Yushi Kogyo Co., Ltd. 0.5% by mass.

· Dibutylhydroxytoluene: SUMILZER BHT-R, manufactured by Sumitomo Chemical Co., Ltd .; 0.05% by mass.

· Flavor: Flavor component based on Japanese Patent Laid-Open No. 2009-108248 a ... 0.8% by mass.

· Capsule flavor: Capsule flavor A ... 0.1% by mass.

· Green No. 3 (coloring): Product name "Green No. 3", made by Kishi Kasei Co., Ltd. ... 0.0002% by mass.

[Common component b]

Polyethylene glycol: trade name &quot; PEG # 1000-60L &quot;, manufactured by Lion Corporation) 2% by mass.

· Palm oil fatty acid: made by Nichiyu Kogyo Co., Ltd. 4% by mass.

· Sodium benzoate: Product name "Sodium benzoate", Doagose ... 0.5% by mass.

· Citric acid: "liquid citric acid", manufactured by Ipposha Yushi Kogyo Co., Ltd. 0.5% by mass.

· Dibutylhydroxytoluene: SUMILZER BHT-R, manufactured by Sumitomo Chemical Co., Ltd .; 0.05% by mass.

· Flavor: Flavor component based on Japanese Patent Laid-Open No. 2009-108248 a ... 0.8% by mass.

· Capsule flavor: Capsule flavor A ... 0.1% by mass.

· Green No. 3 (coloring): Product name "Green No. 3", made by Kishi Kasei Co., Ltd. ... 0.0002% by mass.

2-ethylhexyl 2-ethylhexanoate: trade name "2-ethylhexyl isooctylate", manufactured by Lion Specialty Chemicals Co., Ltd. 0.8 mass%

[pH adjusting agent]

· Monoethanolamine: Nippon Shokubai now available ... Amount to pH7.

<Preparation of detergent composition>

A detergent composition having the composition shown in Table 1 was prepared in the following procedure.

Polyethylene glycol, the component (C), the component (D), the component (F), the coconut fatty acid, the pH adjuster (monoethanolamine) and water were placed in a 500 mL beaker and sufficiently stirred with a magnet stirrer (manufactured by MITAMURA KOGYO INC.) . Subsequently, the other components (A), (E), sodium benzoate, citric acid and water were added and stirred. After confirming that the pH at 25 ° C was around 7, the components (B) Dibutylhydroxytoluene was previously dissolved), and a capsule perfume was added to obtain a detergent composition.

In Table 1, the unit of the blending amount of each component is &quot; mass% &quot;.

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

The content of water &quot; balance &quot; is an amount necessary to make 100% by mass in the entire detergent composition.

In the table, the ratio (A / C ratio) of the blending amounts of the components (A) and (C) in the detergent composition is indicated.

The following evaluations were performed on the obtained detergent composition. The results are shown in Table 1.

&Lt; Evaluation of feeling of fluffy volume &

Three pieces of a fleece garment (UNIQLO Furisu pull-up jacket, polyester 100%) and a commercial cotton towel (100% cotton) were put in a fully automatic electric washing machine (JW-Z23A made by Haier) Was adjusted so that the total fabric mass was about 1 kg). To this was added 12.5 mL of a detergent composition, and a cleaning operation was performed to sequentially perform cleaning, rinsing, and dehydration. The standard course setting of the washing machine was used without adjusting any of the cleaning time, rinsing, dehydration and water quantity. After the laundry was finished, the furris clothing was dried, and the feel was compared with the clothes before washing (new articles of the same clothes), and the furries were evaluated according to the following criteria.

«Criteria»

1 point: Very uncomfortable finishing touch (no volume feeling finish) which is not softer than the contrasting fabric.

2 points: Uncomfortable finish (no volume feeling) that is not softer than the contrast fabric.

3 points: Finish feeling about the same as the contrast fabric.

4 points: Good finishing touch (finishing with a sense of volume) compared to the contrast fabric.

5 points: Very good finishing touch (compared to the contrast fabric).

From the average value of the scoring results of five panelists, the finish feeling was evaluated according to the following criteria.

«Evaluation Criteria»

◎: 4 points or more.

○: 3.5 points or more and less than 4 points.

△: 3 points or more and less than 3.5 points.

X: Less than 3 points.

From the results shown in Table 1, the detergent compositions of Examples 1 to 11 to which the present invention was applied were able to impart a tactile feel with a puffy volume.

On the other hand, in Comparative Example 1 which does not contain the component (A), it was impossible to impart a feeling of softness with a soft volume.

In Comparative Example 2 which did not contain the component (B), it was impossible to give a feeling of softness with a fluffy volume.

From the above results, it can be confirmed that the detergent composition to which the present invention is applied can impart a tactile feel with a puffy volume.

(Industrial availability)

According to the present invention, it is possible to provide a detergent composition capable of imparting a tactile feel with a fluffy volume.

Claims (5)

(A), and a component (B)
The component (A) is a polymer having at least one repeating unit selected from the group consisting of a repeating unit represented by the following general formula (a-1) and a repeating unit represented by the following general formula (a-2) ,
Wherein the component (B) is at least one kind selected from the group consisting of an oxyalkylene unit and a polyoxyalkylene unit, at least one kind of repeating unit (b1) selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit And at least one kind of repeating unit (b2) selected.

Wherein R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms and X ^- is a counter ion.

Wherein R ³ and R ⁴ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms and X ^- is a counter ion. The method according to claim 1,
Wherein the component (A) further comprises a repeating unit represented by the following general formula (a-3).

Wherein R ⁵ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms and R ⁶ and R ⁷ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms. 3. The method according to claim 1 or 2,
At least one anionic surfactant selected from the group consisting of anionic surfactants, sulfonic acid anionic surfactants, and sulfuric acid ester anionic surfactants. 4. The method according to any one of claims 1 to 3,
A detergent composition further comprising a nonionic surfactant. 5. The method according to any one of claims 1 to 4,
Having at least one repeating unit selected from the group consisting of a repeating unit derived from a monomer represented by the following general formula (e-1) and a repeating unit derived from a monomer represented by the following general formula (e-2) &Lt; / RTI &gt; further comprising a polymer.

[In the formula (e-1), R ¹¹ is a hydrogen atom or a methyl group, and R ¹² is a hydrogen atom. In the formula (e-2), R ¹³ is a hydrogen atom or a methyl group, and R ¹⁴ is an alkyl group having 1 to 40 carbon atoms.