JP5211374B2 - Liquid detergent composition for clothing - Google Patents

Description

  The present invention relates to a liquid detergent composition suitable for textile products such as clothing. Specifically, the present invention relates to a liquid detergent composition in which a textile product is hardly yellowed even after repeated washing.

“Welding” occurs in clothing and the like while repeatedly washing and using textile products such as clothing in daily life. Yellowing is caused by deterioration of sebum remaining in the fiber product, iron in tap water adsorbed on the fiber product, or fluorescent whitening agent remaining in the fiber product decomposed by ultraviolet rays, etc. It is thought to be due to various factors.
On the other hand, liquid detergent compositions for clothing are generally known so far, in which an anionic surfactant or a nonionic surfactant is the main component and an alcohol, a chelating agent, or a fragrance is combined with this (for example, , See Patent Document 1).

JP 2000-282099 A

  Therefore, an object of the present invention is to provide a liquid detergent composition that prevents yellowing of a textile product even after repeated washing.

As a result of intensive studies by the present inventors, it has been found that the above object can be achieved by using a specific plant extract in combination with a nonionic surfactant and a long-chain tertiary alkylamine.
That is, the present invention provides (A) a nonionic surfactant,
(B) a long chain aliphatic alkylamine, and
(C) Group consisting of γ-oryzanol, tannic acid, hornon extract, horsetail extract, hop extract, pine extract, lemon extract, rosemary extract, asparagus lineaaris extract, oolong tea extract, hypericum extract, button extract, eucalyptus extract and sage extract A liquid detergent composition comprising at least one plant extract selected from

  According to the present invention, it is possible to effectively prevent the textile product from being yellowed even after repeated washing. According to the present invention, it is also possible to impart flexibility, impart antistatic properties, and suppress sebum odor.

(A) Nonionic surfactant The nonionic surfactant (A) is a component mainly responsible for the cleaning function of the liquid detergent composition, and may be used alone or in combination of two or more.
The nonionic surfactant (A) used in the present invention is not particularly limited. For example, a polyoxyalkylene type nonionic surfactant represented by the following formula (I) is preferably used.
R1-Y- (EO) s (PO) t-R2 (I)
In the formula (I), R1 is a hydrocarbon group having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms. The hydrocarbon group is preferably an alkyl group or an alkenyl group, which may be linear or branched. Examples of the hydrocarbon group raw material include primary or secondary higher alcohols, higher fatty acids, higher fatty acid amides, and the like.

When R1 is branched, the branching ratio is 25% by mass or more, preferably 40% by mass or more, and preferably 80% by mass or less. Of these branched alkyl or alkenyl groups, the intermediate chain branching ratio is 40% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more. When the branching ratio is in such a range, the detergency against oil is improved, which is preferable. A higher intermediate chain branching ratio is more preferable because the detergency against oil becomes higher.
Here, “branch ratio” and “intermediate chain branch ratio” will be described by taking, as an example, a primary higher alcohol which is a raw material of the component (A) represented by formula (I). The higher alcohol is, for example, a mixture of a branched higher alcohol represented by the following formulas (1) to (2) and a linear higher alcohol represented by the formula (3).

In the formulas (1) to (3), R21, R23, and R31 are linear alkyl groups having 1 or more carbon atoms, R32 and R22 are alkyls having 2 or more carbon atoms, p is 1, q is And r is an integer of 1 or more, and the total number of carbon atoms in each formula is equal to the carbon number of R ¹ in formula (I).
The “branch rate” is the mass of the branched alkyl group in the compounds represented by the above formulas (1) to (2) with respect to the total mass of the hydrocarbon moiety in the compounds represented by the above formulas (1) to (3). Represents a percentage.
“Intermediate chain branching ratio” represents the ratio of the mass of the compound represented by the above formula (2) to the total mass of the hydrocarbon moiety in the compounds represented by the above formulas (1) to (2).

The branching rate and the intermediate chain branching rate can be measured under the following conditions using GC / MS.
<Measurement conditions for GC / MS>
Column: Ultra Alloy PY-1
Temperature: Oven; Temperature rising rate 10 ° C / min 50 → 310 ° C
Inlet; 310 ° C
Detector: 310 ° C
Carrier gas: He
Table 1 shows the results of measuring the branching rate and the intermediate chain branching rate using Sasol 23 of Sasol.

R2 is a hydrogen atom or an alkyl or alkenyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or 1 to 3 carbon atoms, and more preferably a hydrogen atom.
-Y- is a linking group, preferably -O-, -COO-, or -CONH-, more preferably -O-.
EO is ethylene oxide and PO is propylene oxide. s and t represent the average added moles of EO and PO, respectively. s is 3-20, Preferably it is 5-18, More preferably, it is a number of 5-15. t is 0-6, preferably 0-3.
By setting the average added mole number s of EO to 20 or less, it is possible to suppress a decrease in cleaning function due to disadvantageous cleaning of sebum due to an excessively high HLB value, and an average added mole number s of EO of 3 By making the average addition mole number t of PO 6 or less as described above, it is possible to suppress a decrease in storage stability of the composition at high temperature.

  The added mole number distribution of EO or PO varies depending on the reaction method during the production of the nonionic surfactant (A). For example, the addition mole number distribution of EO or PO is relatively wide when ethylene oxide or propylene oxide is added to a hydrophobic group raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide. Then, ethylene oxide or oxidation using a specific alkoxylation catalyst such as magnesium oxide added with metal ions such as Al3 +, Ga3 +, In3 +, Tl3 +, Co3 +, Sc3 +, La3 +, Mn2 +, etc. described in JP-B-615038 When propylene is added to the hydrophobic group raw material, it tends to have a relatively narrow distribution.

As a specific example of the nonionic surfactant (A) represented by the above formula (I),
(I) For example, manufactured by Mitsubishi Chemical Co., Ltd .: Trade name Diadol (C13 (showing carbon number 13). Similarly, “Cn” (n is an integer) indicates that the carbon number is n. )),
Made by Sasol: A product obtained by adding 12 moles of ethylene oxide to a synthetic alcohol obtained by the oxo method such as trade name Safol23 (C12 / C13 mixture) (ii) P & G Co., Ltd .: trade name CO-1214 (C12 / C14 mixture), made by Eco Green Oleochemicals: a product obtained by adding 12 moles of ethylene oxide to a natural alcohol such as the brand name Ecolor (C12 / C14 mixture), and further manufactured by Shin Nippon Rika Co., Ltd .: A product obtained by adding 9 moles of ethylene oxide to a natural alcohol such as the trade name Conol (C12),
(Iii) A C12 alkene obtained by trimerizing butene is added to 7 moles or 10 moles of ethylene oxide with respect to 1 mole of C13 alcohol obtained by subjecting it to the oxo process (for example, manufactured by BASF: commercial products) Names Lutensol TO7, Lutensol TO10),
(Iv) 15 moles of ethylene oxide added to lauric acid methyl ester,
(V) 10 mol equivalent of ethylene oxide added to 1 mol of C12 alcohol obtained by subjecting hexanol to garvet reaction (for example, manufactured by CONDEA: trade name ISOFOL12-10EO),
(Vi) 15 mol equivalent of ethylene oxide added to a C12-14 secondary alcohol (for example, Nippon Shokubai Co., Ltd .: trade name Softanol 150),
(Vii) A compound obtained by adding 15 moles of ethylene oxide and 3 moles of propylene oxide to methyl laurate using an alkoxylation catalyst.

Other suitable nonionic surfactants include, for example, polyoxyethylene (EO addition mole number 1 to 20) sorbitan fatty acid (C10-22) ester, polyoxyethylene (EO addition mole number 1 to 20) sorbite fatty acid (C10 -22) ester, polyoxyethylene (EO addition mole number 1-20) glycol fatty acid (C10-22) ester, glycerin fatty acid (C10-22) ester, alkyl (C10-22) glycoside and the like.
In the present invention, the blend amount of the nonionic surfactant (A) (when two or more types are used in combination, it means the total amount. The same applies to other components described later). 10-50 mass% is preferable in a composition, and 10-40 mass% is especially preferable from the point of the color tone change prevention of a colored fiber product. When the blending amount of the nonionic surfactant (A) is 10% by mass or more, the detergency is improved, and when it is 50% by mass or less, the viscosity of the composition is prevented from being excessively increased and the handling becomes easy.

(B) Long-Chain Aliphatic Alkylamine The alkyl part of the long-chain aliphatic alkylamine contained in the detergent composition of the present invention may be linear or branched, and may be saturated or not. It may be saturated, may further have a substituent, and may have a linking group in the chain. The number of carbon atoms is 7 to 28 (the number of carbons here includes the substituent and the linking group). A tertiary amine containing 1 to 3 hydrocarbon groups and / or a salt thereof. In particular, tertiary amines containing 1 to 3, preferably 1 to 2 hydrocarbon groups having 7 to 25 carbon atoms and / or salts thereof are included.
Here, the “substituent” specifically includes a hydroxy group, an amino group, and the like. Specific examples of the “linking group” include an amide group, an ester group, and an ether group.
The long chain aliphatic alkylamine may be in the form of a salt. Examples of the amine salt include acid neutralized acid salts. Examples of the acid used for neutralization include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, glycolic acid, lactic acid, citric acid, polyacrylic acid, paratoluenesulfonic acid, cumenesulfonic acid, and the like. Two or more types may be used in combination.
As the long-chain aliphatic alkylamine, a tertiary amine represented by the following formula (II) and / or a salt thereof is particularly suitable.

In the above formula (II), R3 is a hydrocarbon group having 7 to 28 carbon atoms, which may be linear or branched, saturated or unsaturated, It may contain a substituent. R3 may have a linking group such as an amide group, an ester group or an ether group in its chain, and an amide group or an ester group is preferably used as the linking group. In addition, when R3 contains a substituent or a linking group, the carbon number in the substituent and the linking group is not included in the carbon number of R3.
Among them, -R3 is "-R6-W" (wherein R6 is a linear or branched alkylene group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms. -W is -NHCO-R7 or -OOC-R8, R7 is a hydrocarbon group having 7 to 23 carbon atoms, preferably 7 to 21, more preferably 9 to 19, and R8 is a hydrocarbon group having 11 to 23 carbon atoms, preferably 12 to 20 carbon atoms. R7 and R8 may be linear or branched and may be saturated or unsaturated.). R7 and R8 are preferably linear. R7 and R8 are preferably saturated.
R4 is a hydrocarbon group having 1 to 25 carbon atoms. R4 may be linear or branched, may be saturated or unsaturated, and may further contain a substituent. R4 may have a linking group such as an amide group, an ester group or an ether group in the chain. Of these, a linear or branched alkyl group having 1 to 4 carbon atoms and a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms are preferably used.
R5 is any one of a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms, and a polyoxyethylene group having 1 to 3 EO addition moles. Yes, a linear or branched alkyl group having 1 to 4 carbon atoms or a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms is preferably used.
Among the above formulas (II), tertiary amines represented by the following formula (III) and / or salts thereof are more preferable.

In formula (III), R10 and R11 are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms.
R12 is a linear or branched alkylene group having 1 to 4 carbon atoms.
Z- is a group represented by the following formula (IV) or (V).

In the formula (IV), R13 is a hydrocarbon group having 7 to 23 carbon atoms, preferably 7 to 21 carbon atoms. In the formula (V), R14 has 11 to 23 carbon atoms, preferably 12 to 20 carbon atoms. It is a hydrogen group, and R13 and R14 may be linear or branched, and may be saturated or unsaturated.
Preferable specific examples of (B) include caprylic amidopropyl dimethylamine, capric amidopropyl dimethylamine, lauric amidopropyl dimethylamine, myristic amidopropyl dimethylamine, palmitic acid amidopropyl dimethylamine, stearic acid amidopropyl. Long chain aliphatic amide alkyl tertiary amines such as dimethylamine, amidopropyl dimethylamine behenate, amidopropyl dimethylamine oleate or salts thereof; aliphatic ester alkyls such as palmitate ester propyldimethylamine, stearate ester propyldimethylamine Tertiary amine or a salt thereof; palmitic acid amidopropyl diethanolamine, stearic acid amidopropyl diethanolamine and the like.
Among them, caprylic amidopropyl dimethylamine, capric amidopropyl dimethylamine, lauric amidopropyl dimethylamine, myristic amidopropyl dimethylamine, palmitic amidopropyl dimethylamine, stearic acid amidopropyl dimethylamine, behenic acid amidopropyl dimethylamine Particularly preferred is amidepropyldimethylamine oleate or a salt thereof.

The “long-chain aliphatic amidoalkyl tertiary amine” in the above examples is a condensation of a fatty acid or a fatty acid derivative such as a fatty acid lower alkyl ester or animal / vegetable oil and fat with a dialkyl (or alkanol) aminoalkylamine. After the reaction, unreacted dialkyl (or alkanol) aminoalkylamine is obtained by distilling off under reduced pressure or nitrogen blowing.
On the other hand, the “aliphatic ester alkyl tertiary amine” is obtained, for example, by an esterification reaction in which a fatty acid or a fatty acid lower alkyl ester, a fatty acid derivative such as animal or vegetable oil and fat, and a dialkylamino alcohol are condensed.
Here, as the fatty acid or fatty acid derivative, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, 12-hydroxystearic acid, coconut oil fatty acid, cottonseed oil fatty acid, Specific examples include corn oil fatty acid, beef tallow fatty acid, palm kernel oil fatty acid, soybean oil fatty acid, flaxseed oil fatty acid, castor oil fatty acid, olive oil fatty acid and other vegetable oils or animal oil fatty acids, or their methyl esters, ethyl esters, glycerides, etc. Among them, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like are particularly preferable.
These fatty acids or fatty acid derivatives may be used alone or in combination of two or more.

Specific examples of the “dialkyl (or alkanol) aminoalkylamine” include dimethylaminopropylamine, dimethylaminoethylamine, diethylaminopropylamine, diethylaminoethylamine, etc. Among them, dimethylaminopropylamine is particularly preferable.
Examples of “dialkylamino alcohol” include dimethylaminoethanol, diethylaminoalcohol and the like. As the diethylamino alcohol, diethylaminoethanol is preferable. Among these, dimethylaminoethanol is particularly preferable.
In addition, the amount of dialkyl (or alkanol) aminoalkylamine used in the production of the long-chain aliphatic amidoalkyl tertiary amine is preferably 0.9 to 2.0 moles relative to the fatty acid or derivative thereof. 0 to 1.5 times mole is particularly preferable.
The reaction temperature is usually 100 to 220 ° C, preferably 150 to 200 ° C. If the reaction temperature is less than 100 ° C., the reaction is too slow, and if it exceeds 220 ° C., the resulting tertiary amine may be markedly colored, which is not preferable.

As for the usage-amount of the dialkylamino alcohol in esterification reaction at the time of manufacturing aliphatic ester alkyl tertiary amine, 0.1-5.0 times mole is preferable with respect to a fatty acid or its derivative (s), and 0.3-3. 0 times mole is more preferable, 0.9-2.0 times mole is further more preferable, and 1.0-1.5 times mole is especially preferable.
The reaction temperature is usually 100 to 220 ° C, preferably 120 to 180 ° C. In this range, an appropriate reaction rate can be maintained, and excessive coloration of the resulting tertiary amine can be prevented.
The production conditions of the long-chain aliphatic amidoalkyl tertiary amine and aliphatic ester alkyl tertiary amine other than those described above are the same, and the pressure during the reaction may be normal pressure or reduced pressure, and an inert gas such as nitrogen is blown during the reaction. It is also possible to introduce it.
Also, when using fatty acids, acid catalysts such as sulfuric acid and p-toluenesulfonic acid, and when using fatty acid derivatives, alkaline catalysts such as sodium methylate, caustic potash and caustic soda can be used for a short time at a low reaction temperature. The reaction can proceed efficiently.
Further, when the obtained tertiary amine is a long-chain amine having a high melting point, it is preferably molded into a flake shape or a pellet shape after the reaction in order to improve handling properties, or in an organic solvent such as ethanol. It is preferable to dissolve and make it liquid.

Other preferred specific examples of (B) include lauryl dimethylamine, myristyl dimethylamine, palm alkyl dimethylamine, palmityl dimethylamine, beef tallow alkyl dimethylamine, cured beef tallow alkyl dimethylamine, stearyl dimethylamine, stearyl diethanolamine, poly Examples thereof include oxyethylene-cured beef tallow alkylamine (trade name: ETHOMEEN HT / 14 manufactured by Lion Akzo Co., Ltd.) or a salt thereof.
(B) may be used alone or in combination of two or more.
In this invention, 0.1-10 mass% is preferable in a cleaning composition, and, as for the compounding quantity of (B), 0.5-5 mass% is especially preferable. A favorable yellowing prevention effect is obtained by setting the blending amount of the component (B) to 0.1% by mass or more. On the other hand, when the blending amount of the component (B) is 10% by mass or less, the stability of the composition is improved and it is economically advantageous.

(C) Plant extract The plant extract is an ethanol solution containing ethanol, propylene glycol, diethylene glycol, 1,3-butylene glycol, glycerin, and 0.5 to 3% urea as an extraction solvent from a specific plant described later. Obtained by extraction using a hydrophilic organic solvent selected from the group consisting of 1,3-butylene glycol solution containing 0.5 to 3% urea and a mixture thereof, water, or a mixture of hydrophilic solvent and water. It is done.
γ-Oryzanol can be obtained from the seed coat of rice Oryza sativa Linne (Gramineae) using n-hexane as an extraction solvent or by a critical extraction method using carbon dioxide. It consists mainly of ferulic acid ester of triterpene alcohol. The dried product contains 95.0% or more of cycloartenyl ferulate when quantified. Specific examples of commercially available products of γ-oryzanol of 0.5% or less as the ignition residue include Oriza Gamma V, Oriza Gamma Milky, etc. from Oriza Oil Chemical Co., Ltd.
Tannic acid is obtained from pentaploid and gallic. Extracted with a mixture of ether and ethanol, and further extracted with water from the leachate. Specific examples of commercial products of tannic acid include Lexode P of Ichimaru Falcos Co., Ltd.

Ougon extract is obtained from the roots excluding the pericarp of Scutellaria baicalensis Georgi (Labiatae). A preferred extraction solvent is water, ethanol, 1,3-butylene glycol or a mixture thereof. Specific examples of commercially available products of Ogon Extract include Ougon Falcos Ougon Extract Powder, Ogon Liquid B, Ogon Liquid SE, Maruzen Pharmaceutical Ougon Extract-J, Ougon Extract-BG-JC, Ogon Extract SQ, Ogon Extract BG-50 from Koei Kogyo Co., Ltd.
Horsetail extract is obtained from the whole plant of Horsetail Equisetum arvense Linne (Equisetaceae). A preferred extraction solvent is water, ethanol, propylene glycol, 1,3-butylene glycol or a mixture thereof, or a 1% urea-containing ethanol solution or a 1% urea-containing 1,3-butylene glycol solution. Specific examples of commercial products of Sugina extract include Falco Rex Sugina B, Falco Rex BX46, Falco Rex BX 50, Ichimaru Falcos Co., Ltd., Sugina Extract, Sugina Extract BG, Sugina Extract LA, Maruzen Pharmaceutical Co., Ltd. Koei Kogyo Co., Ltd. too much extract, mixed plant extract (1), mixed plant extract (11), mixed plant extract (13), mixed plant extract (15), mixed plant extract (21 ), Mixed plant extract (22) and the like.

The hop extract is obtained from female spikelets of hops Humulus lupulus Linne (Moraceae). Preferred extraction solvents are water, ethanol, propylene glycol, 1,3-butylene glycol or a mixture thereof. Specific examples of commercial hop extract products include Ichimaru Falcos' Hop Liquid, Falco Rex BX46, Falco Rex BX 52, Maruzen Pharmaceutical's Hop Extract, Hop Extract BG-JN, and Koei Kogyo Co., Ltd. ) Hop extract, hop extract HS, and the like.
Pine extract is obtained from the cone of Pinus sylvestris Linne (Pinaceae). Preferable extraction solvents are water, propylene glycol, 1,3-butylene glycol, glycerin or a mixture thereof, 1% urea-containing ethanol solution, 1% urea-containing 1,3-butylene glycol solution. Specific examples of commercially available pine extract include Falco Rex Pine B, Falco Rex BX32, Falco Rex BX46, mixed plant extract (2) from Koei Kogyo Co., Ltd., etc.
Lemon extract is obtained from the fruit (raw) or fruit juice of lemon Citrus limon Burmann fil (Rutaceae). Preferred extraction solvents are water, propylene glycol, 1,3-butylene glycol, glycerin or a mixture thereof. Specific examples of lemon extract commercial products include Lemon Extra Liquid from Ichimaru Falcos, Falco Rex BX46, Falco Rex BX47, Falco Rex BX52, Lemon Extract BG-J from Maruzen Pharmaceutical Co., Ltd., Koei Kogyo ( Lemon extract, mixed plant extract (5) and the like.

Rosemary extract is obtained from leaves or leaves and flowers of Mannen Rosmarinus officinalis Linne (Labiatae). A preferable extraction solvent is water, ethanol, propylene glycol, 1,3-butylene glycol or a mixture thereof, 1% urea-containing ethanol solution or 1% urea-containing 1,3-butylene glycol solution. Specific examples of commercially available rosemary extract include Falco Rex Rosemary B, Falco Rex Rosemary E, Falco Rex BX46, Falco Rex BX32, Ichimaru Falcos Co., Ltd. Rosemary Extract-J from Maruzen Pharmaceutical Co., Ltd. , Rosemary Extract BG-J, Rosemary Extract LA, Rosemary Extract SQ, Organic Rosemary Extract BG-50 from Koei Kogyo Co., Ltd., Mannen Extract, Mannen Extract HS, Rose Examples include Marie extract S, mixed plant extract (2), and mixed plant extract (13).
The Asparagus Linea Aris extract is obtained from the whole plant of Aspalathus linearis (NLBurm.) R. Dahlgren (Leguminosae). A preferred extraction solvent is 1,3-butylene glycol. As a specific example of a commercially available product of Asparasas rinealis extract, there is Falco Rex Robos B (N) from Ichimaru Falcos Co., Ltd.
Oolong tea extract is obtained from leaves of the tea tree Thea sinensis Linne (Theaceae). A preferred extraction solvent is ethanol. Specific examples of commercially available oolong tea extract include Falco Rex Oolong E from Ichimaru Falcos Co., Ltd., Oolong Tea Extract from Maruzen Pharmaceutical Co., Ltd., and Oolong Tea Extract BG.

Hypericum extract is obtained from the above-ground part of Hypericum perforatum Linne or Hypericum erectum Thunberg (Guttiferae). Preferred extraction solvents are water, ethanol, propylene glycol, 1,3-butylene glycol, diethylene glycol or a mixture thereof. Specific examples of commercially available hypericum extract include Falco Rex Hypericum B, Falco Rex Hypericum E, Falco Rex BX43, Falco Rex BX44, Falco Rex BX52, and Hypericum Extract from Maruzen Pharmaceutical Co., Ltd.-J , Hypericum extract-BG, Hypericum extract of Koei Kogyo Co., Ltd., mixed plant extract (3), mixed plant extract (6), mixed plant extract (21), mixed plant extract (22), etc. Is mentioned.
The button extract is obtained from the root bark of the button Paeonia suffruticosa Andrews (Paeonia moutan Sims) (Paeoniaceae). A preferred extraction solvent is ethanol. An extract showing 0.5 w / v% or less as an ignition residue. Specific examples of commercially available button extracts include Falco Rex Buttonpi B, Falcolex Buttonpi E, Falcolex HGL, Falcolex PSP, Phyto desensitizer ABBA, Phyto Blend TIPS, Maruzen Pharmaceutical Co., Ltd. And button pi extract from Koei Kogyo Co., Ltd.

Eucalyptus extract is obtained from leaves of Eucalyptus globules Labillardiere or other related plants (Myrtaceae). Preferred extraction solvents are water, ethanol, propylene glycol, 1,3-butylene glycol or a mixture thereof. Specific examples of commercially available eucalyptus extracts include Falco Rex Eucalyptus B from Ichimaru Falcos, Falco Rex Eucalyptus E, Eucalyptus Extract BG from Maruzen Pharmaceutical Co., Ltd., Eucalyptus Extract BG, Eucalyptus from Koei Kogyo Co., Ltd. An extract, Eucalyptus extract S, etc. are mentioned.
Sage extract is obtained from flowers, leaves or whole grass of sage Salvia officinalis Linne (Labiatae). A preferred extraction solvent is water, ethanol, propylene glycol, 1,3-butylene glycol or a mixture thereof, 1% urea-containing ethanol solution, or 1% urea-containing 1,3-butylene glycol solution. Specific examples of commercially available sage extracts include Falco Rex Sage B, Falco Rex Sage E, Falco Rex BX47, Falco Rex BX 52 from Ichimaru Falcos, Organic Sage Extract BG-50 from Koei Kogyo Co., Ltd., and Salvia Extract, Salvia extract HS, mixed plant extract (5), mixed plant extract (11), mixed plant extract (13), mixed plant extract (21), mixed plant extract (22), etc. It is done.

(C) is preferably γ-oryzanol or tannic acid.
(C) is preferably blended in the composition in an amount of 0.001 to 1% by weight.

In the detergent composition after the addition of the plant extract agent of the present invention, a pH of 4 or more is preferable from the viewpoint of maintaining a good yellowing prevention effect and maintaining a good stability when the composition is stored for a long period of time. It is preferable to set it to 8 or less from the point which keeps the yellowing prevention effect favorable.
What is necessary is just to mix | blend a pH adjuster suitably in order to adjust pH to 8 or less. As a pH adjuster, as long as the effect of the present invention is not impaired, sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine and the like are preferable from the viewpoint of blending stability.
The preparation method of the liquid detergent composition to which the plant extract of the present invention is added is not particularly limited, and the components (A) to (C) are prepared in accordance with conventional methods in the same manner as ordinary liquid detergent compositions. ), The above-mentioned optional components, and water as appropriate, and can be prepared by mixing them.
Moreover, the liquid detergent composition to which the plant extract of the present invention is added can be used after being filled in a resin-made container. The method for using the liquid detergent composition is not particularly limited, and may be washing by hand or washing by a washing machine. For example, in the case of washing with a normal washing machine, after the article to be washed is put into the washing machine, the washing machine tub is filled with water, and the composition of the present invention is added to an appropriate concentration and dissolved. Thus, the washing liquid can be obtained, and thereby the washing object can be washed.

<Optional component>
The cleaning composition of the present invention may contain other optional components as necessary as long as the effects of the present invention are not impaired.

  The cleaning composition of the present invention can contain a polyether-modified silicone. Specifically, CF1188HV, SH3748, SH3749, SH3772M, SH3775M, SF8410, SH8700, BY22-008, BY22-012, SILWET L-7001, SILWET L-7602, SILWET L-7602 manufactured by Toray Dow Corning Co., Ltd. , SILWET L-7604, SILWET FZ-2104, SILWET FZ-2120, SILWET FZ-2161, SILWET FZ-2162, SILWET FZ-2164, SILWET FZ-2171, ABN SILWET FZ-F1F09-IL, AB1-009-01, AB1-009-01 F1-009-02, ABN SILWET FZ-F1-009-03, ABN SILWET FZ-F1-009-05, ABN S LWET FZ-F1-009-09, ABN SILWET FZ-F1-009-11, ABN SILWET FZ-F1-009-13, ABN SILWET FZ-F1-009-54, ABN SILWET FZ-22-22, Shin-Etsu Chemical Examples include polyether-modified silicones such as X-20-8010B, KF352A, KF6008, KF615A, KF6012, KF6016, KF6017, and TSF4450, TSF4452, and TSF4445 (trade names) manufactured by GE Toshiba Silicone. It is done. For example, 0.01 to 10% by mass of the polyether-modified silicone can be contained based on the total amount of the composition.

Polyacrylic acid; polymaleic acid; carboxymethylcellulose; polyethylene glycol; copolymers of maleic acid and olefins such as maleic anhydride-diisobutylene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-isobutylene copolymer A recontamination inhibitor or dispersant such as a polymer and a maleic anhydride-vinyl acetate copolymer can be contained in an amount of, for example, 0.1 to 10% by mass based on the total amount of the composition.
A preservative such as Rohm and House's Caisson CG (trade name) can be contained, for example, in an amount of 0.001 to 1% by mass based on the total amount of the composition.

  In addition to the nonionic surfactant (A), the liquid detergent composition of the present invention may also contain the following surfactants: anionic surfactants (alkyl carboxylates, alkylsulfonates, alkyls) Sulfate ester, alkyl phosphate ester salt), cationic surfactant (alkylamine salt, alkyl quaternary ammonium salt), amphoteric surfactant: carboxylic acid type amphoteric surfactant (amino type, betaine type), sulfate type Amphoteric surfactants, sulfonic acid type amphoteric surfactants, phosphate ester type amphoteric surfactants, other surfactants (natural surfactants, derivatives of protein hydrolysates, polymeric surfactants, titanium and silicon Including surfactants and fluorocarbon surfactants).

  Other ingredients that can be blended include, for example, enzymes (proteases, lipases, cellulases, etc.), stabilizers (sodium benzoate, citric acid, sodium citrate, Monohydric alcohol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, polyethylene polypropylene glycol alkyl ether, polyethylene (propylene) glycol phenyl ether, polypropylene glycol phenyl ether, polyethylene polypropylene glycol phenyl ether, etc.), thickener (long chain fatty acid alkylamide, etc.) ), Texture improvers, pH adjusters, preservatives, hydrotropes, fluorescent agents, dye transfer inhibitors, pearl agents, antioxidants, soil release agents, and the like.

In addition, a coloring agent, a flavoring agent, an emulsifying agent, etc. can also be mix | blended for the purpose of the added value improvement of goods, etc. As colorants, Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Turquoise PG
General-purpose dyes and pigments such as R (both are trade names) can be used, and a preferable blending amount is about 0.00005 to 0.0005% by mass based on the total amount of the composition.
As the flavoring agent, for example, perfume compositions A, B, C and D described in Tables 11 to 18 of JP-A-2002-146399 can be used, and the preferred blending amount is 0.1 based on the total amount of the composition. ˜1% by mass.
Examples of the emulsifying agent include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is suitably used. Specific examples include polystyrene emulsion (Saiden Chemical Co., Ltd. (trade name) Cybinol RPX-196 PE-3, solid content 40% by mass) and the like, and the preferred blending amount is 0.01 based on the total amount of the composition. It is -0.5 mass%.

[Preparation of liquid detergent composition]
The components used to prepare the liquid detergent compositions of Examples and Comparative Examples are shown below.
As component (A),
(A-1): CnH2n + 1O (EO) 15H (n = 12/13 mixture (mass ratio 55/45)), synthetic product.
(A-2): C13H27O (EO) 7H (C chain length: branched type), manufactured by BASF (trade name) Lutensol TO7
It was used.
In addition, the manufacturing method of (a-1) is as follows.
Sasol (trade name) Safol 23 alcohol (branch rate 50%) 224.4 g and 30% by mass NaOH aqueous solution 2.0 g were collected in a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen.
Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. While stirring the alcohol, 763.6 g of ethylene oxide (gaseous) was gradually added to the alcohol liquid. At this time, it added, adjusting the addition rate so that reaction temperature might not exceed 180 degreeC using the blowing tube.
After completion of the addition of ethylene oxide, aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature to 100 ° C. or less, 70% by mass p-toluenesulfonic acid is added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product becomes about 7, (a-1) Got.

As component (B),
(B-1): CnH2n + 1CONH (CH2) 3N (CH3) 2 (n = 15/17 mixture (mass ratio 3/7)), manufactured by Toho Chemical Co., Ltd. (trade name) Katchinal MPAS-R
(B-2): C16H33N (CH3) 2, manufactured by Lion Akzo Co., Ltd. (trade name) Armin DM16D.
(B-3): C11H23CONH (CH2) 3N (CH3) 2, a synthetic product.
It was used.
In addition, the manufacturing method of (b-3) is as follows.
In a 1 liter four-necked flask, 261 g of lauric acid was charged, and nitrogen substitution was performed twice at 80 ° C. The temperature was raised to 170 ° C., and 173 g of dimethylaminopropylamine was added dropwise over 2 hours while distilling off by-product water.
After completion of dropping, the mixture was kept at 170 to 180 ° C. and aged for 7 hours. The conversion rate of lauric acid calculated from the acid value was 98%. After aging, the pressure was reduced to remove unreacted amine and water to obtain (b-3).

As component (C),
(C-1): manufactured by Oriza Oil Chemical Co., Ltd., Oriza Gamma V (contains 100% as oryzanol)
(C-2): Ichimaru Falcos, Lexode P (100% tannic acid)
(C-3): Made by Ichimaru Falcos, Ogon Liquid SE (contains 1.69% as Ougon extract)
(C-4): Ichimaru Falcos Co., Ltd., Falco Rex Sugina B (contains 1.0% as Sugina extract)
(C-5): Ichimaru Falcos, Hop Liquid (1.5% hop extract)
(C-6): Ichimaru Falcos Co., Ltd., Falco Rex Pine B (contains 0.64% as pine cone extract or pine extract)
(C-7): Ichimaru Falcos Co., Ltd. Lemon Extra Liquid (containing 0.65% as a lemon extract or lemon fruit extract)
(C-8): Ichimaru Falcos Co., Ltd., Falco Rex Rosemary B (0.6% rosemary extract)
(C-9): Ichimaru Falcos Co., Ltd., Falco Rex Rooibos B (N) (0.5% as rooibos extract)
(C-10): Ichimaru Falcos Co., Ltd., Falco Rex Oolong E (contains 2.56% as Oolong tea extract)
(C-11): Ichimaru Falcos Co., Ltd., Falco Rex Hypericum E (contains 0.86% as Hypericum Extract)
(C-12): Ichimaru Falcos Co., Ltd., Falco Rex Buttonpi E (contains 1.1% as a button extract)
(C-13): Ichimaru Falcos Co., Ltd., Falco Rex Eucalyptus E (containing 0.59% as eucalyptus extract or eucalyptus leaf extract)
(C-14): manufactured by Ichimaru Falcos, Falco Rex Sage E (contains 0.85% as sage extract or sage leaf extract)
It was used.
In addition, in Table 1 and Table 2, the compounding quantity (mass%) of a component (C) represents the density | concentration as an extract.

Details of each component included in the “common components” in the table are as follows.
POE-modified silicone: polyether-modified silicone, manufactured by Toray Dow Corning Silicone Co., Ltd. (trade name) SH3775M.
Olefin / maleic acid copolymer sodium salt: BASF Corporation (trade name) Sokalan CP9.
Sodium benzoate: Toagosei (trade name) sodium benzoate.
Trisodium citrate: Made by Miles (USA) (trade name) sodium citrate.
Para-toluenesulfonic acid: Kyowa Hakko Kogyo Co., Ltd. (trade name) PTS acid.
Isothiazolone solution: Rohm and Haas (trade name) Caisson CG (5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one / magnesium salt / water mixture liquid).
Dye (acid red 138): Sumitomo Chemical Co., Ltd. (trade name) Suminol Milling Brilliant Red BS
Fragrance | flavor: The fragrance | flavor composition A of Tables 11-18 of Unexamined-Japanese-Patent No. 2002-146399.
pH adjuster: sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine, etc.

Liquid detergent compositions of Examples and Comparative Examples were prepared as follows using the components shown above and the compositions shown in Tables 1 and 2.
(1) Put ethanol, the component (A), and the POE-modified silicone in the following common components into a 300 mL beaker and stir well with a magnetic stirrer (MITAMURA KOGYO INC.).
(2) After the water in the common component at 40 ° C. is added to (1), the component (B) previously dissolved in ethanol is added and sufficiently dissolved.
(3) Add the remaining common components to (2) and stir well, and adjust the pH to 7 with a small amount of sodium hydroxide aqueous solution.
(4) Add component (C) and stir well to obtain a liquid cleaning composition for clothing.
The yellowing prevention effect of the liquid detergent composition thus obtained was evaluated as follows. The results are shown in Tables 1 and 2.

[Evaluation of yellowing prevention effect]
1. Preparation of dirt cloth Squalene was used as sebum. Squalene dissolved in a solvent (toluene) was added to a cotton cloth (5 cm × 5 cm) so that the concentration was 0.5% owf, and the mixture was allowed to stand at room temperature and dried.
2. Evaluation in washing system 1kg of the soiled cloth created above is put into a fully automatic washing machine (AW-F80HVP) made by Toshiba, and each liquid detergent composition is used at a rate of 40ml in 30L of tap water and washed with a weak water flow. The washing operation was performed with 6 minutes for time, 1 minute for dehydration, then rinse (repeated twice, 4 minutes each), and 1 minute for dehydration. The tap water used was adjusted to 25 ° C.
After washing treatment, it was air-dried, and the soiled cloth was allowed to stand at 100 ° C. for 24 hours to promote yellowing.

3. Yellowness Evaluation Method Using a dirty cloth before and after yellowing acceleration, b value was measured according to JIS Z 8729 according to the CIE L * a * b * color system. For measurement of b value, Spectro Color Meter SE2000 of Nippon Denshoku Industries Co., Ltd. was used. The b value is a parameter belonging to the L * a * b * (Elster Aster Baster) color system, and the yellow becomes stronger as it goes in the positive direction, and the blue becomes stronger as it goes in the negative direction. The difference in b value of the soiled cloth before and after yellowing acceleration was taken and evaluated according to the following criteria. ○ If it is above, it shall have yellowing suppression effect.
<Evaluation criteria>
◎◎: Less than Δ1 (no yellowing was observed)
◎: More than Δ1 and less than Δ2 (Slight yellowing change was observed compared to pre-deteriorated clothing, but there is virtually no problem)
○: Δ2 or more and less than Δ4 (Although a slight yellowing change was observed compared to pre-deteriorated clothing, there was virtually no problem)
×: Δ4 or more (a significant change in yellowing was observed compared to pre-deteriorated clothing)

Claims (5)

(A) As a nonionic surfactant , 10-40 mass% of nonionic surfactants represented by the following formula (I):
R1-Y- (EO) s (PO) t-R2 (I )
(In Formula (I), R1 is a hydrocarbon group having 8 to 22 carbon atoms. -Y- is a linking group, and is -O-, -COO-, -CONH-. EO is ethylene oxide, PO represents propylene oxide, s and t represent the average added moles of EO and PO, respectively, s is a number of 3 to 20, t is a number of 0 to 6. R2 is a hydrogen atom or a carbon number of 1 to 6 linear or branched alkyl groups or alkenyl groups) ,
(B) Long-chain aliphatic alkylamines include caprylic amidopropyl dimethylamine, capric amidopropyl dimethylamine, lauric amidopropyl dimethylamine, myristic amidopropyl dimethylamine, palmitic amidopropyl dimethylamine, stearic acid amidopropyl One or more selected from dimethylamine, amidopropyldimethylamine behenate, amidopropyldimethylamine oleate or a salt thereof , and
(C) As a plant extract, γ-oryzanol or tannic acid 0.1-1% by mass
A liquid detergent composition comprising: ( A) The liquid detergent composition according to claim 1, wherein the nonionic surfactant is the following (a-1) or (a-2) .
_{(A-1): C n} H 2n + 1 O (EO) 15 H (n = 12/13 mixture (weight ratio 55/45))
(A -2): C ₁₃ H ₂₇ O (EO) ₇ H (C chain length: branched type) ( B) The liquid detergent composition according to claim 1 or 2, wherein the long-chain aliphatic alkylamine is one or more selected from the following (b-1) to (b-3) .
_{(B-1): C n} H 2n + 1 CONH (CH 2) 3 N (CH 3) 2 (n = 15/17 mixture (weight ratio 3/7))
( B-2): C ₁₆ H ₃₃ N (CH ₃ ) ₂
( B-3): C ₁₁ H ₂₃ CONH (CH ₂ ) ₃ N (CH ₃ ) ₂ ( C) The γ-oryzanol is one obtained by extracting n-hexane as an extraction solvent, or one obtained by a critical extraction method using carbon dioxide. Liquid detergent composition . The liquid detergent composition according to any one of claims 1 to 3, wherein ( C) tannic acid is extracted with a mixture of ether and ethanol and further extracted with water from the leachate .