KR20140076745A - Liquid Detergent Composition - Google Patents

Abstract

The present invention relates to a liquid detergent composition which comprises at least one kin selected from zinc sulfate and glycine-N,N-diacetic acid derivatives and a non-ionic surfactant as a main component. According to the present invention, provided is the liquid detergent composition with an improved odor removal effect after the washing of laundry.

Description

[0001] Liquid detergent composition [0002]

The present invention relates to a liquid detergent composition, and more particularly, to a liquid detergent composition having an excellent odor removal effect after washing of a malodorous laundry.

Recently, the laundry detergent market is rapidly changing from a powder form to a liquid form due to changes in the laundry environment, ease of use, and rapid spread of the drum washing machine.

That is, the importance of washing power, which is a function of washing detergent in the laundry environment, is gradually reduced, and convenience of use and provision of various functions are demanded.

However, the liquid laundry detergent has a problem that it is difficult to formulate an enzyme, a bleaching agent, and the like due to the characteristics of the liquid laundry detergent.

Disclosure of Invention Technical Problem [8] In order to cope with such changes in the laundry environment, the present invention provides a detergent composition which is excellent in phase stability and provides a functional advantage, Environment.

There are various kinds of odor of laundry such as mold odor, foul smell, smell like fish smell, and smell from dirty clothes. Examples of the cause of such smell include aldehydes of medium carbon chain, ketones, medium carbon chain Alcohols, fatty acids of short carbon chains, amines, and sulfur compounds.

In addition, it is known that such odor-causing substances occur at each stage of the washing cycle such as washing, drying, storage, use, and laundry treatment.

Conventionally, as a technique for eliminating the odor of such laundry, WO10 / 103833 discloses a granular detergent containing zinc oxide, zinc aluminosilicate and carboxymethylcellulose as a granular detergent for suppressing odor generation during drying of laundries Of detergent compositions are known.

Accordingly, a problem to be solved by the present invention is to provide a liquid detergent composition for removing odor of laundries by using zinc sulfate and glycine-N, N-diacetic acid derivatives while maintaining excellent detergency by using a nonionic surfactant To do

In order to achieve the above technical object, in the present invention,

(One) Odor removal component

A) at least one kind of zinc sulfate and glycine-N, N-diacetic acid derivative, and zinc sulfate at 0.1% by weight to 5% by weight,

The glycine-N, N-diacetic acid derivative may be used in an amount of 0.1 wt% to 5 wt%.

Particularly preferably, they are used in the form of a complex salt in combination. When used in combination, the equivalent ratio of zinc sulfate to glycine-N, N-diacetic acid derivative is preferably 0.5 to 2.0.

Zinc sulphate, which can be used in accordance with the present invention, is commercially available in the form of a hydrate, and may be in powder or granular form.

In the present invention, it is particularly preferable to be in the form of a monohydrate.

Zinc sulfate monohydrate is easy to dissolve in water and is commercially available.

The zinc sulfate monohydrate is acidic in pH and has a disadvantage in that the solution becomes cloudy in the pH range of the liquid detergent composition of the present invention.

The present invention provides a composition having excellent stability using a solubilizing agent.

Suitable glycine-N, N-diacetic acid derivatives which may be used in accordance with the present invention are compounds of formula (I)

[Chemical Formula 1]

Wherein,

R is C1-C12alkyl,

M is an alkali metal.

In the compounds of formula (I), M is an alkali metal, preferably sodium or potassium, more preferably sodium.

R is a C1-12 alkyl radical, preferably a C1-6 alkyl radical, more preferably a methyl or ethyl radical. Ingredients used

(b) is preferably an alkali metal salt of methylglycinediacetic acid (MGDA). Very particular preference is given to using trisodium salts of methylglycine diacetic acid.

(2) Nonionic surfactant

In the present invention, a surfactant is included to provide excellent cleaning power, and in the present invention, a nonionic surfactant is used as the main cleaning component.

Any nonionic surfactant contemplated may be any that is known to be useful as a detergent for cleaning contaminated fabrics. Suitable nonionic surfactants are commercially available and are derived from the condensation of ethylene oxide or a corresponding reactant and a reactive-hydrogen-hydrophobic compound. The hydrophobic organic compound may be an aliphatic, aromatic or heterocyclic compound, but a mixture of aliphatic and aromatic compounds is preferred.

Preferred types of hydrophobic compounds are higher aliphatic alcohols and alkylphenols, but other compounds such as carboxylic acids, carboxamides, mercaptans, sulfonamides and the like may also be used.

Kylen condensates for oxidation with higher alkyl phenols or higher fatty alcohols are the preferred type of nonionic compounds.

Usually the hydrophobic component should contain at least about 6, preferably at least about 8 carbon atoms, with a preferred carbon number range of from about 8 to 22, in particular 10 to 18 carbon atoms for aliphatic alcohols, Lt; / RTI > may contain from 12 to 20 carbon atoms. The amount of alkylene oxide may vary considerably with hydrophobic components, but as a general guideline and rule at least about 3 to 200 moles, preferably about 5 to 50 moles, of alkylene oxide per mole of hydrophobic component will provide the desired solubility and cleaning performance Or < / RTI > compatibility with other components.

A preferred type of nonionic surfactant may be represented by the following formula (2) or (3).

(2)

R1O (CH2CH2O) mH

(Wherein R1 is primary or secondary alkyl having about 8 to 22 carbon atoms and m is an integer from 5 to 50)

In the compound of Formula 2, R 1 represents a primary or secondary alkyl having about 8 to 22 carbon atoms, preferably a primary or secondary alkyl having 10 to 18 carbon atoms, and is preferably a primary or secondary More preferred are alkyl and mixtures thereof.

Examples of preferred alcohols from which the compound of Formula 2 can be prepared include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol and oleyl alcohol, and mixtures thereof.

A typical example of the nonionic surfactant of Formula 2 is 5 to 11 moles of ethylene oxide and condensed lauryl alcohol.

(3)

(6)

(6)

(Wherein R2 is primary or secondary alkyl having 4 to 12 carbon atoms and n is an integer of 5 to 50)

In the compound of Formula 3, R 2 represents a primary or secondary alkyl having 4 to 12 carbon atoms, preferably primary or secondary alkyl having 8 to 12 carbon atoms, and octyl, isooctyl and nonyl Is more preferable.

A typical example of the nonionic surfactant of Formula 3 is iso-octylphenol or nonylphenol condensed with 3 to 8 moles of ethylene oxide.

[ Formula 4 ]

R3 (CH2CH2O) m / (CH2CH (CH3) n) H

Wherein R3 is primary or secondary alkyl having about 8 to 22 carbon atoms and m is an average addition mole number of ethylene oxide and is an integer of 3 to 20, preferably 5 to 20. [

n represents an average addition mole number of propylene oxide, and is 1 to 6, preferably 1 to 3)

When m exceeds 6, the foamability becomes too high to deteriorate the washing performance and the rinsability. When n exceeds 6, the stability of the composition tends to deteriorate. The sum of m and n is preferably 3 to 10. If the sum of m and n is less than 3, the effect of removing oil stains is lowered. If the sum of m and n is more than 10, the foamability is increased and detergency and rinsing properties are deteriorated.

[ Formula 5 ]

R4-CO (OR5) mOR6

(Wherein R 4 represents a linear or branched alkyl group or an alkenyl group having 9 to 21, preferably 11 to 21, R 5 is an alkylene group having 2 to 4 carbon atoms, and R 6 is an alkylene group having 1 to 3 carbon atoms

Alkyl group, m is an average addition mole number and is 5 to 25)

Typical examples of the nonionic surfactant of Formula 5 are fatty acid methyl ester ethoxylate, adduct of ethylene oxide and propylene oxide of fatty acid methyl ester, and esters of ethyl lactate methyl ethoxylate, myristyl methyl ester ethoxylate Late, coconut fatty acid methyl ester ethoxylate is more preferred. Here, the average addition mole number of the alkylene oxide is preferably 15.

Other examples of nonionic surfactants that can be used include polyoxyalkylene esters such as those derived from organic acids such as higher fatty acids, rosin acids, tall fatty acids, and petroleum oxidation products. These esters generally contain from about 3 to about 40 moles of ethylene oxide or its counterpart and from about 10 to about 22 carbon atoms in acidic solution.

Other surfactants are alkylene oxide condensates with higher fatty acid amides. The fatty acid groups generally contain from about 8 to 22 carbon atoms and can be condensed with about 3 to 40 moles of ethylene oxide as a preferred example. The corresponding carboxamides and sulfonamides can also be used as substantial compatibilizers.

In the present invention, the nonionic surfactant may be used singly or in combination, and 10 to 40% by weight may be used based on the total mass of the liquid detergent composition.

(3) Solubilizing agent

In the liquid detergent composition of the present invention, a solubilizing agent may be used for phase stability, and as the solubilizing agent, alcohol such as ethanol, ethylene glycol, propylene glycol, sodium xylene sulfonate, urea, or the like may be used.

As another stabilizer in the present invention, polyethylene glycol may be included. In particular, it may contain a compound having a molecular weight of 100 to 10000, more preferably 200 to 8000.

These may be used singly or as a mixture, and may be used in the range of 1 to 15% by weight.

(4) Viscosity adjusting agent

The liquid detergent composition of the present invention preferably has a viscosity at 25 ° C of 40 to 150 mPa-s, more preferably 50 to 130 mPa-s.

Especially when the metering cap is small, it is not easy to measure the liquid detergent in the desired amount if it does not have proper viscosity. However, if the viscosity is more than 40 mPa-s,

The usability is good and it becomes easy to measure an appropriate amount. On the other hand, when the viscosity is 150 mPa-s or less, gelling can be suppressed particularly when the liquid detergent composition is put into the detergent inlet of the washing machine at low temperature.

Further, in the present invention, a viscosity adjusting agent may be used for maintaining a proper viscosity of a product.

In the present invention, it is preferable to use carboxymethyl cellulose, xanthan gum or the like, and the content thereof is preferably 0.2 to 3.0% by weight.

As another viscosity modifier, an acrylic polymer latex can be used. Acusol 820, 823 and the like are available as Acusol series from HASE.

The content thereof is preferably 0.1 to 15% by weight.

(5) pH Modulator

The liquid detergent composition of the present invention preferably has a pH of 4 to 9 at 25 ° C, more preferably 4 to 8. If the pH is within the above range, stability over time can be maintained particularly even if the liquid detergent composition is stored for a long period of time.

The pH of the liquid detergent composition of the present invention can be adjusted by a pH adjuster. Examples of the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as hydroxycarboxylic acids; and sodium hydroxide, potassium hydroxide, alkanolamine and ammonia. Among them, sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamine are preferable from the viewpoint of stability with time of the liquid detergent composition. These pH adjusting agents may be used alone or in combination of two or more.

In addition, an inorganic acid (preferably hydrochloric acid, sulfuric acid), potassium hydroxide or the like may be added again for fine adjustment of the pH of the liquid detergent composition.

(6) Other ingredients

The auxiliary component of the liquid detergent composition of the present invention is not particularly limited as long as it is generally used in a liquid detergent. Specific examples include enzymes, coloring matters, fragrances, preservatives, fluorescent whitening agents and the like

The auxiliary component used in the present invention is preferably 10% by weight or less, more preferably 5% by weight or less

Since the liquid detergent composition of the present invention excellently removes the odor generated in each cycle of the laundry, it is possible to provide a liquid detergent excellent in not only the conventional detergency but also the malodor.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example  One. Liquid detergent  Preparation of composition

ingredient Detergent I Detergent II Detergent Ⅲ Detergent IV Propylene glycol 7 7 7 7 PEG-1000 5 5 5 5 Sodium citrate 4 4 4 4 Zinc sulfate 0.4 0.4 0.4 0.4 Glycine-N, N-diacetic acid 0.7 0.7 0.7 0.7 Acusol 823 2 2 2 2 AE nonionic surfactant 1) 30 10 EO / EO nonionic surfactant 2) 30 10 FMEE nonionic surfactant 3) 30 10 Purified water Balance adjustment Balance adjustment Balance adjustment Balance adjustment

ingredient Detergent V Detergent VI Detergent VII Detergent VIII Propylene glycol 7 7 7 7 PEG-1000 5 5 5 5 Sodium citrate 4 4 4 4 Zinc sulfate 0.7 0.7 1.0 0.7 Glycine-N, N-diacetic acid 0.7 0.4 0.7 1.0 Acusol 823 2 2 2 2 AE nonionic surfactant 1) 15 15 10 EO / EO nonionic surfactant 2) 15 15 10 FMEE nonionic surfactant 3) 15 15 10 Purified water Balance adjustment Balance adjustment Balance adjustment Balance adjustment

Specific examples of the components used in the examples of the present invention are as follows.

AE nonionic surfactant 1): polyoxyethylene lauryl ether (average molar number of ethylene oxide added is 7 moles) Monopol-LE1017 (manufactured by Dongnam Chemical Co., Ltd.)

EO / PO nonionic surfactant 2): M-RPE1293 (manufactured by Dongnam Chemical Co., Ltd.)

MEE nonionic surfactant 3) A synthetic product was supplied from Lion Corporation of Japan as a mixture of C11H23CO (OCH2CH2) 15OCH3 and 8/2 by mass ratio of C13H27CO (OCH2CH2) 15OCH3.

PEG 1000: polyethylene glycol having an average addition mole number of ethylene oxide of 1000

A liquid detergent composition for the following comparison was prepared for the odor removal effect test on the liquid detergent composition prepared in Example 1).

Comparative Example  One

ingredient Comparative detergent I Comparative detergent II Comparative detergent Ⅲ Comparative detergent IV Propylene glycol 7 7 7 7 PEG-1000 5 5 5 5 Sodium citrate 4 4 4 4 Zinc sulfate 0.4 0.7 1.0 0 Glycine-N, N-diacetic acid 0 0 0 0.4 Acusol 823 2 2 2 2 AE nonionic surfactant 1) 10 10 EO / EO nonionic surfactant 2) 20 10 FMEE nonionic surfactant 3) 20 10 30 10

ingredient Comparative detergent V Comparative detergent VI Comparative detergent VII Propylene glycol 7 7 7 PEG-1000 5 5 5 Sodium citrate 4 4 4 Zinc sulfate 0 0 0 Glycine-N, N-diacetic acid 0.7 1.0 0 Acusol 823 2 2 2 AE nonionic surfactant 1) 15 EO / EO nonionic surfactant 2) 15 FMEE nonionic surfactant 3) 15 15 30

The liquid detergent composition obtained in the above Example 1) and Comparative Example 1) was subjected to the following test method to examine the effect of removing odor.

(One) Test odor removal effect

1. Laboratory instruments and reagents

1) Plastic centrifuge tube 50ml (Falcon Co.)

2) Triethylamine (Shinjeong Chemical Co., Ltd.)

3) Hexanoic acid (Aldrich)

4) Water bath water bath

   2. Preparation of sample

1) Triethylamine solution

Add 98.8 μmol of triethylamine as a cause of odor to 20 ml of deionized water and use it as a smell sample.

2) Hexanoic acid solution

8.6 μmol of hexanoic acid as the odor causing substance is put into 20 ml of deionized water and used as a smell sample.

3) Manufacture of detergent solution

1 g of the liquid detergent composition prepared in Example 1) and Comparative Example 1 was added to 100 ml of water, respectively.

3. Experimental Method

20 ml of each of the triethylamine solution of the previously prepared sample solution 1), the hexanoic acid solution of 2) and the detergent solution of 3) was taken and placed in a centrifuge tube 50 ml (Falcon Co.) , And reacted for 1 hour.

After one hour, the reaction product was terminated and three panelists of the following panel were comparatively evaluated as follows, and their average values were determined.

The degree of odor (odor) is determined as follows.

5 point: Very strong smell (odor).

4 points: strong smell (stink).

3 points: It smells (stinks).

2 points: It smells weakly (stink).

One point: I smell weak (odor) so I can not feel well.

0 point: No smell (odor) is felt at all.

Odor removal (triethylamine) test results Detergent II Detergent I Detergent II Detergent Ⅲ Detergent IV score 1.3 2.1 2.3 1.5 1.6 Detergent V Detergent VI Detergent VII Detergent VIII Detergent V score 2.2 2.0 2.0 1.8 2.2 Comparative detergent I Comparative detergent II Comparative detergent Ⅲ Comparative detergent IV score 4.1 3.5 4.1 3.9 Comparative detergent V Comparative detergent VI Comparative detergent VII score 3.5 4.0 5

Odor elimination (hexanoic acid) test result Detergent II Detergent I Detergent II Detergent Ⅲ Detergent IV score 1.7 1.5 0.5 1.4 1.3 Detergent V Detergent VI Detergent VII Detergent VIII Detergent V score 2.1 1.4 1.6 1.4 2.1 Comparative detergent I Comparative detergent II Comparative detergent Ⅲ Comparative detergent IV score 3.3 3.3 3.8 2.2 Comparative detergent V Comparative detergent VI Comparative detergent VII score 3.3 3.8 4.5

As shown in Tables 5 and 6, it can be seen that the liquid detergent compositions using both zinc sulfate and glycine-N, N-diacetic acid are superior to the liquid detergent compositions used singly.

Further, the use of an actual washing cycle for the liquid detergent composition obtained in Example 1) and Comparative Example 1)

In order to test the effect of eliminating the odor actually generated in the process and drying process, the following test method was carried out to test the effect of the odor removal.

(One) Cotton towel  Test odor removal effect

1) Pretreatment of Cotton Towel

- The towels purchased on the market were allowed to use for one week at home for one week and then they were wet-dried for 72 hours in the clothes drying room under the condition of constant temperature and humidity at 28 ° C and 80% RH.

2) Washing treatment

- The liquid compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were washed at a concentration of 1 g / 1 L in a washing machine in a standard course and dried in a clothes dryer at 28 ° C and 80% RH under a constant temperature and humidity condition for 72 hours Respectively.

  This wet-dried cotton towel is then worn by three professional panelists

The degree of the smell (odor) was determined as follows, and the average value thereof was shown by the following results.

5 point: Very strong smell (odor).

4 points: strong smell (stink).

3 points: It smells (stinks).

2 points: It smells weakly (stink).

One point: I smell weak (odor) so I can not feel well.

0 point: No smell (odor) is felt at all.

Test results of odor level of cotton towel Detergent II Detergent I Detergent II Detergent Ⅲ Detergent IV score 1.2 1.2 1.5 1.8 1.2 Detergent V Detergent VI Detergent VII Detergent VIII Detergent V score 1.6 1.4 1.4 1.8 1.8 Comparative detergent I Comparative detergent II Comparative detergent Ⅲ Comparative detergent IV score 2.8 2.8 3.0 3.0 Comparative detergent V Comparative detergent VI Comparative detergent VII score 3.2 3.2 4.0

As shown in Table 7, the liquid detergent compositions using both zinc sulfate and glycine-N, N-diacetic acid showed better odor removal effect than the liquid detergent composition used alone, .

Claims (5)

A) a liquid detergent composition containing at least one of zinc sulfate and glycine-N, N-diacetic acid derivatives as main cleaning components and b) a nonionic surfactant; The method according to claim 1, wherein a) the zinc sulfate is 0.1 wt.% To 5 wt.%, The glycine-N, N-diacetic acid derivative is 0.1 wt.% To 5 wt.%, , Wherein the equivalence ratio of zinc sulfate to glycine-N, N-diacetic acid derivative is 0.5 to 2.0. The liquid detergent composition according to claim 1, wherein b) the nonionic surfactant is represented by the following formula (2) and (3, 4, 5).
(2)
R1O (CH2CH2O) mH wherein R1 is primary or secondary alkyl having 8 to 22 carbon atoms, m is an integer of 5 to 50,
(3)

(Wherein R2 is primary or secondary alkyl having 4 to 12 carbon atoms and n is an integer of 5 to 50)
[Chemical Formula 4]
Wherein R3 is primary or secondary alkyl having from about 8 to 22 carbon atoms, m is an integer from 3 to 20, and n is from 1 to 6, wherein R3 is (CH2CH2O) m / (CH2CH (CH3)
[Chemical Formula 5]
Wherein R 4 is a linear or branched alkyl group or alkenyl group having 9 to 21 carbon atoms and R 5 is an alkylene group having 2 to 4 carbon atoms and R 6 is an alkyl group having 1 to 3 carbon atoms, m is from 5 to 25) The nonaqueous surfactant according to claim 1, wherein the nonionic surfactant is 10 to 40% by weight based on the total mass of the liquid detergent composition. The liquid detergent composition according to claim 1, wherein the composition comprises other components such as a solubilizing agent, a pH adjusting agent, a viscosity adjusting agent and an enzyme, a perfume, a fluorescent whitening agent,