JP2003041290A - Detergent composition for dry cleaning - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent composition for dry cleaning that can be used together with a silicone-based solvent or a mixed solvent of a fluorine- based solvent and a silicone-based solvent and can exhibit excellent effects. SOLUTION: The detergent composition for dry cleaning comprises (A) 2-50 wt.% one or more selected from the group consisting of a carboxy-modified silicone represented by formula [1] and a salt of the carboxy-modified silicone and an alkylene oxide adduct of an amine, (B) 8-60 wt.% anionic surfactant as a non-silicone surfactant wherein the non-silicone surfactant is an anionic surfactant capable of dissolving in a silicone solvent at the same time and (C) 10-90 wt.% silicone-based solvent or mixed solvent of a fluorine-based solvent and a silicone-based solvent (wherein in formula [1], Z each independently denotes a methyl group or -RCOOH (wherein R denotes a 2-14C alkylene group) and x and y are each independently an integer satisfying the relationship: x+y=200 to 1,000; and the carboxy-modified silicone has a carboxy equivalent of 500-10,000).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cleaning composition for dry cleaning. More specifically, the present invention relates to a cleaning composition for dry cleaning, which has excellent effects and can be used in a silicone solvent or a mixed solvent of a fluorine solvent and a silicone solvent.

[0002]

2. Description of the Related Art Conventionally, there is a dry cleaning method for washing clothes and the like. In recent years, silicone solvents have been attracting attention as a solvent for dry cleaning from the viewpoint of safety.
Used in some cleaning facilities. Further, since such a silicone solvent has high safety but is flammable, a fluorine-based solvent (for example, hydrofluorocarbon, hydrofluoroether, hydrochlorofluorocarbon, etc.) is mixed for the purpose of flame retardancy or nonflammability. Is being used.

However, as for the surfactant used together with the silicone solvent and the fluorine-based solvent mixed therewith, most of the hydrocarbon-based surfactants which have hitherto been mainly used as a detergent composition are sufficient. There is a problem that it cannot be used because it does not have solubility, or there is a problem that even if a specific surfactant that partially dissolves is used, it does not have sufficient detergency (JP-A-2000).
No. 290689, JP 2000-319694).

Therefore, even if it is used by adding it to a silicone-based solvent which does not have such a problem or a silicone-based mixed solvent containing a fluorine-based solvent, it can be diluted sufficiently stably and has excellent cleaning properties and prevention of recontamination. , A cleaning composition for dry cleaning, which has properties, flexibility with respect to an object to be washed, and smoothness and antistatic property, is strongly demanded.

[0005]

The present invention is capable of sufficiently stable dilution even when used by adding to a silicone solvent or a silicone mixed solvent containing a fluorine solvent.
Another object of the present invention is to provide a cleaning composition for dry cleaning, which has excellent cleaning properties, anti-soil redeposition properties, flexibility with respect to an object to be washed, and smoothness and antistatic properties.

[0006]

As a result of intensive studies, the present inventors have carried out carboxyl modification as a surfactant for use with a silicone solvent or a mixed solvent of an incombustible fluorine solvent and a silicone solvent. The present invention has been completed by discovering that a surfactant comprising a combination of a silicone-based surfactant and a non-silicone-based surfactant and an anionic surfactant which is soluble in a silicone-based solvent solves the above problems. .

That is, the detergent composition for dry cleaning according to the present invention is characterized in that the novel combination of the surfactants is contained in an appropriate amount in a silicone solvent or a mixed solvent containing a fluorine solvent and a silicone solvent. And

In the present invention, a silicone solvent characterized by using a cleaning composition for dry cleaning,
Alternatively, a dry cleaning method using a mixed solvent containing a fluorine solvent and a silicone solvent is also included.

More specifically, the present invention is selected from the group consisting of a carboxyl-modified silicone represented by the following general formula [1] as the component (A), and a salt of the carboxyl-modified silicone and an alkylene oxide adduct of amine. 2 to 50% by weight of at least one kind, and 8 to 60% by weight of a non-silicone type anionic surfactant as the component (B).
And a silicone solvent as component (C) or a mixed solvent of a fluorine solvent and a silicone solvent in an amount of 10 to 90% by weight, the present invention relates to a cleaning composition for dry cleaning. .

[0010]

[Chemical 4]

In the formula, Z's each independently represent a methyl group or --RCOOH (R represents an alkylene group having 2 to 14 carbon atoms), x and y are integers satisfying x + y = 200 to 1000, Carboxyl equivalent is 500-100
00.

In the present invention, the cleaning for dry cleaning is characterized in that the amine is at least one selected from the group consisting of amines represented by the following general formulas [2], [3] and [4]. Agent composition.

[0013]

[Chemical 5]

Where R¹, R²Each independently water
Elementary atom, alkyl group having 1 to 18 carbon atoms, 2 to 18 carbon atoms
Alkenyl group, hydroxyalkyl having 1 to 18 carbon atoms
Group, cyclohexyl group, benzyl group or phenethyl group
Represent, R³Represents an alkyl group having 1 to 14 carbon atoms, R^FourIs
Represents an alkylene group having 2 to 6 carbon atoms, R^Five, R⁶Is that
Independently hydrogen atom, alkyl group having 1 to 18 carbon atoms, carbon
C2-C18 alkenyl group, C1-C18 hydroxy
Cyalkyl group, cyclohexyl group, benzyl group or phenyl group
Represents a netyl group, R⁷Is an alkylene having 1 to 10 carbon atoms
Group, -C₂H_FourOC₂H_Four-, -C₂H_FourOC₂H_FourOC₂H
_Four-, -C₃H₆OCH₂C (CH₃)₂CH₂OC ₃H₆-Or
-C₃H₆O (C₂H_FourO)_kC₃H₆-(Where k is 1-6
It represents an integer).

Further, the present invention relates to a dry cleaning detergent composition, wherein the alkylene oxide is at least one selected from ethylene oxide, propylene oxide and butylene oxide.

The present invention also relates to a cleaning composition for dry cleaning, wherein the non-silicone anionic surfactant is a compound represented by the following general formula [5].

R ⁸ O (R ⁹ O) _m (CH ₂ ) _n COOX [5] In the formula, R ⁸ represents an alkyl group or an alkenyl group having 6 to 18 carbon atoms, and R ⁹ has 2 carbon atoms or 3 represents an alkylene group, m is an integer of 0 to 10, n is 1 or 2, and X represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an alkanolamine.

Further, in the present invention, the above-mentioned silicone solvent is highly safe, and the cyclic silicone represented by the following general formula [6] and / or the boiling point of which has substantially no emission regulation is 13
The present invention relates to a cleaning composition for dry cleaning, which is a linear silicone at 0 to 250 ° C.

[0019]

[Chemical 6] Here, p represents an integer of 4 to 6.

The present invention also relates to a cleaning composition for dry cleaning, wherein the fluorine-based solvent is at least one selected from the group consisting of hydrofluorocarbons, hydrofluoroethers and hydrochlorofluorocarbons. .

Furthermore, the present invention relates to a dry cleaning method using such a cleaning composition for dry cleaning in a silicone solvent or a mixed solvent of a fluorine solvent and a silicone solvent.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The cleaning composition for dry cleaning of the present invention can be sufficiently and stably diluted when used by adding it to a silicone solvent or a silicone mixed solvent containing a fluorine solvent. In addition, a novel combination of a carboxyl-modified silicone-based surfactant and a non-silicone-based surfactant and an anionic surfactant that dissolves in a silicone-based solvent provides superior cleaning properties and recontamination prevention. And imparts excellent flexibility, smoothness and antistatic property to the object to be washed. The cleaning composition for dry cleaning of the present invention adopted for exhibiting such comprehensively excellent performance is a novel composition of a silicone surfactant having a specific structure and a non-silicone surfactant having a specific structure. It is characterized by containing a surfactant component according to the combination. By using the component (A), it becomes possible to enhance the cleaning property and the anti-redeposition property, and to give the article to be washed a smooth and flexible texture, and also a silicone solvent or a fluorine solvent. Solubility in a solvent such as a mixed solvent of a silicone-based solvent and the like can be enhanced.

Particularly, the silicone surfactant as the component (A) is preferably a carboxyl-modified silicone surfactant. The surfactant is not particularly limited as long as it is a silicone-based surfactant having a carboxyl group introduced, but in the present invention, a carboxyl-modified silicone represented by the following general formula [1], or an alkylene oxide adduct of the carboxyl-modified silicone and an amine is particularly preferable. And a salt thereof or any combination thereof are preferable.

[0024]

[Chemical 7]

Particularly, Z is independently a methyl group or --R.
It is preferably COOH. In addition, R has 2 to 1 carbon atoms
4, preferably an alkylene group having 2 to 12 carbon atoms, which may be linear or branched. It is preferable that x and y are integers satisfying x + y = 200 to 1000, preferably 300 to 800.
Further, the carboxyl equivalent of the carboxy-modified silicone is preferably 500 to 10,000.

In the present invention, the carboxyl-modified silicone represented by the above general formula [1] is preferably a salt of an amine with an alkylene oxide adduct. Here, the amine is at least one selected from the group consisting of amines represented by the following general formulas [2], [3] and [4], particularly amines represented by the general formulas [2] and [3]. Preferably. The alkylene oxide is preferably at least one selected from ethylene oxide, propylene oxide and butylene oxide. Further, the number of added moles of alkylene oxide is preferably 4 or less.

[0027]

[Chemical 8]

Here, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a hydroxyalkyl group having 1 to 18 carbon atoms,
It represents a cyclohexyl group, a benzyl group or a phenethyl group, and it is more preferred that either R ¹ or R ² is an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 12 carbon atoms or a cyclohexyl group. In the general formula [2], the alkyl group, alkenyl group and hydroxyalkyl group represented by R ¹ and R ² may be linear or branched.

The alkoxyamine represented by the general formula [3] is

[Chemical 9] Is. Here, R ³ represents an alkyl group having 1 to 14 carbon atoms, R ⁴ represents an alkylene group having 2 to 6 carbon atoms, and these alkyl group and alkylene group may be linear or branched. It may be. In the general formula [3], R ³
More preferably has 1 to 10 carbon atoms and R ⁴ has 2 to ⁴ carbon atoms.

The amine represented by the general formula [4] is

[Chemical 10] Is. Where R^Five, R⁶Are each independently a hydrogen atom,
C1-C18 alkyl group, C2-C18 alkene
Nyl group, hydroxyalkyl group having 1 to 18 carbon atoms, cycl
Rohexyl group, benzyl group or phenethyl group is preferred.
, These alkyl groups, alkenyl groups and hydroxy
The alkyl group may be linear or branched.
Yes. R⁷Is a linear or branched C1-C10 al.
Xylene group, -C₂H_FourOC₂H_Four-, -C₂H_FourOC₂H_FourOC
₂H_Four-, -C₃H₆OCH₂C (CH₃)₂CH ₂OC₃H₆-Also
Is -C₃H₆O (C₂H_FourO)_kC₃H₆-(Where k is 1-6
Represents an integer of). Also the general formula
In [4], R^Five, R⁶Either one has 1 to 1 carbon atoms
An alkyl group of 8 and R⁷Is an alkyle having 2 to 6 carbon atoms
More preferably, it is a phenyl group.

As the carboxyl-modified silicone, a commercially available product can be used as it is. In addition, it is also possible to synthesize by a well-known method (for example, "Handbook of Silicone Materials, Toray Dow Corning Silicone Co., Ltd. (edited / issued) (1993)", "Organic Synthetic Chemistry Journal, No. 40"). Vol., P. 575 (1982) "). The salt of the amine with an alkylene oxide adduct is also generally known, for example, by adding 1 equivalent of an amine of an alkylene oxide adduct of an amine to 1 equivalent of a carboxyl of a carboxyl-modified silicone at room temperature to 5%.
It can be obtained as a neutralized salt by mixing at a temperature of 0 ° C. As the alkylene oxide adduct of amine used here, a commercially available product can be used, or it can be synthesized by a commonly known method (for example, “New surfactant, Hiroshi Horiguchi, Sankyo Publishing (stock) ), P. 638 (1975) "
Can be referred to).

There is no limitation on the non-silicone type anionic surfactant which is the component (B) used in combination with the component (A) described above, and in particular, the silicone type solvent or the fluorine type solvent which is the component (C). Those which are soluble in a mixed solvent of a silicone solvent and a silicone-based solvent can be selected and used, for example, higher fatty acids (eg caproic acid, lauric acid) and tertiary amines (eg dimethyllaurylamine, dioleyl) Examples thereof include salts with methylamine) and alkyl ether carboxylates. In the present invention, an alkyl ether carboxylate represented by the following general formula [5] is particularly preferable.

R ⁸ O (R ⁹ O) _m (CH ₂ ) _n COOX [5] Here, in the general formula [5], R ⁸ is an alkyl group or an alkenyl group having 6 to 18 carbon atoms and has a straight chain structure. May be a branched chain, R ⁹ is preferably an alkylene group having 2 or 3 carbon atoms, m is an integer of 0-10,
It is preferable that n is 1 or 2. Further, X is preferably a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an alkanolamine. In particular, it is preferable that R ⁸ is an alkyl group having 8 to 14 carbon atoms, m is 2 to 5 and X is a sodium atom.

The component (B), particularly the compound represented by the general formula [5], may be a commercially available product as it is or may be produced by a conventionally known method (for example, “Fat and fat Vol. 45, No. 7,
p.76 (1992) ”).

The cleaning composition for dry cleaning of the present invention comprises the component (A) and the component (B) described above, and a silicone-based solvent or a fluorine-based solvent and a silicone-based solvent as the component (C). It is contained in a mixed solvent. The silicone solvent usable in the present invention is not particularly limited, but a cyclic silicone represented by the following general formula [6] and / or a linear silicone having a boiling point of 130 to 250 ° C. is preferable.

[0036]

[Chemical 11]

Here, in the general formula [6], p is preferably 4 to 6, and particularly preferably p. The fluorine-based solvent of the present invention is not particularly limited as long as it is nonflammable, but HFC-43-10mee, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, and HFC-365mfc are preferable. The content of such a fluorine-based solvent is 5 to 30 of the component (C).
It is preferably% by volume.

The cleaning composition for dry cleaning of the present invention may contain various additives in addition to the components (A), (B) and (C) described above, if necessary. For example, higher alcohol having 10 to 20 carbon atoms; higher alcohol fatty acid ester such as polyoxyalkylene alkyl ether, methyl laurate and oleyl oleate; dimethylpolysiloxane, epoxy modified silicone, alkylaralkyl modified silicone, phenol modified silicone, alkyl modified silicone, Silicone compounds such as polyether-modified silicone; dissolution aids such as petroleum-based solvents and alcohol-based solvents, rust preventives, and the like can be appropriately added within a range that does not impair the effects of the present invention.

It is easy to appropriately determine the mixing ratio of the above-mentioned three components according to the usage conditions,
It is preferable to contain 2 to 50% by weight of the component (A), 8 to 60% by weight of the component (B) and 10 to 90% by weight of the component (C). In this case, if the content of the component (A) is less than 2% by weight, the detergency, recontamination resistance, etc. may be deteriorated, while if it exceeds 50% by weight, the viscosity of the cleaning composition for dry cleaning is high. However, there is a tendency that the stability decreases, the usability deteriorates, and the like. Further, if the content of the component (B) is less than 8% by weight, the antistatic property may be deteriorated, which is not preferable.

The cleaning composition for dry cleaning of the present invention can be easily obtained by uniformly mixing the components described above.

The detergent composition for dry cleaning of the present invention can be used as it is, but it can be used by adding and dissolving it in a solvent for dry cleaning so as to be 0.2 to 5% by volume. As the dry cleaning solvent, it is preferable to use a silicone solvent used as the component (C) or a mixed solvent of a fluorine solvent and a silicone solvent. The cleaning composition for dry cleaning of the present invention is obtained as a stable diluted solution.

[0042]

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. The evaluation of Examples and Comparative Examples was carried out by the following methods.

Dilution stability (1% by volume) 1 ml of a cleaning agent for dry cleaning was added to decamethylcyclopentasiloxane, and decamethylcyclopentasiloxane: methylperfluorobutylether (volume ratio 9:
Mixture 1) (hereinafter abbreviated as "silicone mixture") 1
Add it to 00 ml and visually check the dissolution state after stirring as described below.
Graded. ○: transparent △: uniform turbidity ×: separated

Cleaning Rate and Recontamination Rate Using a stainless pot having a capacity of 500 ml, 0.5 ml of a cleaning agent for dry cleaning was added to 100 ml of the silicone mixed solution.
A washing solution was prepared by adding and dissolving so as to be a volume%. Round O Meter [Daei Kagaku Seiki Co., Ltd., L
-20], a 40 cm cotton broad cloth, wool muslin, and acrylic knitted white cloth measuring 4 cm × 8 cm and a contaminated cloth prepared according to the Japan Oil Chemistry Society method are washed with a washing liquid at 20 ° C. for 10 minutes. Washed. Then, using a centrifugal dehydrator [Eiko Sangyo Co., Ltd., H-120A], it was drained for 1 minute and air dried for 8 hours. For white cloth and contaminated cloth before and after washing, the reflectance at 550 nm was measured using a colorimeter [Murakami Color Research Laboratory, Clean Master CM-53D], and the washing rate and redeposition rate were calculated according to the following formulas. did.

Cleaning rate (%) = {(S2-S1) / (W1
-S1)} × 100 Redeposition rate (%) = {(W1-W2) / W1} × 100 where S1: the reflectance of the contaminated cloth before cleaning, S2: the reflectance of the contaminated cloth after cleaning, W1: before the cleaning White cloth reflectance, W2: White cloth reflectance after washing. The higher the cleaning rate is, the better the cleaning property is, and the lower the redeposition rate is, the higher the anti-redeposition property is.

Flexibility Using a stainless steel pot having a capacity of 500 ml, a cleaning solution for dry cleaning was added and dissolved in 200 ml of a silicone mixed solution so as to be 1% by volume to prepare a treatment liquid. round·
Oh Meter [Daei Kagaku Seiki Co., Ltd., L-20]
20 cm of cotton knit and acrylic knit using
Test cloths each having a size of 20 cm were treated with the treatment liquid at 20 ° C. for 10 minutes. Then, using a centrifugal dehydrator [Eikoh Sangyo Co., Ltd., H-120A], the liquid was deliquored for 1 minute and dried at a hot air circulation dryer kept at 80 ° C for 30 minutes, and then left to stand in the room for 2 hours, followed by a touch method. The flexibility was evaluated according to the following 5 grades. 1 (coarse hard), 2 (somewhat hard), 3 (soft), 4
(Quite soft), 5 (extremely soft) Here, the softer it is, the less wrinkles are generated, the better the finish, and the better the feeling of wearing.

Antistatic property Using a stainless pot having a capacity of 500 ml, a cleaning solution for dry cleaning was added and dissolved in 200 ml of a silicone mixed solution so as to be 1% by volume to prepare a treatment liquid. Round O Meter [Daei Kagaku Seiki Co., Ltd., L-2
0] was used to treat acrylic knitted fabric and polyester jersey test cloths each having a size of 20 cm × 20 cm with a treatment solution at 20 ° C. for 10 minutes. Then, using a centrifugal dehydrator [Eikoh Sangyo Co., Ltd., H-120A], the liquid was deliquored for 1 minute and dried with a hot air circulation dryer kept at 80 ° C for 30 minutes, and a constant temperature and humidity of 20 ° C and a humidity of 40%. In the room, the insulation meter [Toa Denpa's SUPER MEGOHMMETER SM
-5E], the surface resistance value was measured and evaluated in the following three stages. ○ (10 ¹⁰ Ω), △ (10 ¹¹ Ω), × (10 ¹² Ω)

Examples and Comparative Examples The components shown in Tables 1 and 3 below were mixed together until the components became uniform, to give a dry cleaning detergent. Here, compounds 1 to 13 are as follows.

Compound 1: SF-8418 (carboxyl
Modified silicone, carboxyl equivalent is 3500, Toray
Dow Corning Silicone Co., Ltd.) Compound 2: BY-16-880 (carboxyl modified silicone
Corn, carboxyl equivalent is 3500, Toray Dowko
Ning Silicone Co., Ltd. Compound 3: BY-16-750 (carboxyl modified silic
Corn, carboxyl equivalent is 750, Toray Dowconi
Silicone Co., Ltd.) Compound 4: X-22-3710 (carboxyl modified silyl
Corn, carboxyl equivalent 1250, Shin-Etsu Silicone
(Made by Co., Ltd.) Compound 5: the above carboxyl-modified silicone SF-8
418 (Compound 1) and 3-ethoxypropylamine
2 mol of ethylene oxide adduct (C₂H_FiveOC ₃H₆N
(C₂H_FourOH)₂) With salt Pre-dehydrated 3-ethoxypropylamine is autoclaved
In a reaction vessel of a tube and stir with nitrogen gas while stirring.
It was replaced and placed under a nitrogen atmosphere. 120 while stirring this
After heating to ℃, 1 mol of 3-ethoxypropylamine
2mol ethylene oxide is weighed against
Start and stir in the temperature range of 120-130 ℃ with stirring.
Add lenoxide over 2 to 3 hours to react
It was At the end of the reaction, the pressure in the reaction
It was judged to be helpful. After that, cool to 100 ° C
After removing the volatile components present in the reaction vessel under reduced pressure,
It was cooled, then returned to room temperature and taken out. Obtained 3-D
Addition of 2 mol of ethylene oxide to toxypropylamine
1 mol of the compound and carboxyl-modified silicone SF-84
1 carboxyl equivalent of 18 was mixed at about 30 ° C. and salt
Got

Compound 6: Carboxyl-modified silicone BY-15-880 (Compound 2) and a 1-mole propylene oxide adduct of dibutylamine ((C ₄ H ₉ ) NC)
₍₃ H ₆ OH) salt and pre-dehydrated dibutylamine were charged into a reaction vessel of an autoclave, and the atmosphere was replaced with nitrogen gas while stirring and under a nitrogen atmosphere. After heating this to 120 ° C. with stirring, 1 mol of propylene oxide was weighed to 1 mol of dibutylamine and the addition was started.
Propylene oxide at about 2 to about 140 ° C.
It was added and reacted for 3 hours. The completion of the reaction was judged by the pressure in the reaction vessel decreasing and reaching a constant pressure. Then, the mixture was cooled to 100 ° C., the volatile components existing in the reaction vessel were removed under reduced pressure, then cooled, returned to room temperature and taken out. About 30 moles of the obtained dibutylamine of 1 mole of propylene oxide adduct and 1 mole of the carboxyl of the carboxyl-modified silicone BY-16-880 was added.
Mix at ℃ to obtain the salt.

Compound 7: Carboxyl-modified silicone B
Y- 16-750 (Compound 3) and dimethylaminoethylamine 2 mol ethylene oxide adduct ((CH ₃ ) ₂
Salt with NC ₂ H ₄ N (C ₂ H ₄ OH) ₂ ) Preliminarily dehydrated dimethylaminoethylamine was charged into a reaction vessel of an autoclave, and the atmosphere was replaced with nitrogen gas while stirring and under a nitrogen atmosphere. 100 ° C while stirring this
After heating up to 1 mol of dimethylaminoethylamine, 2 mol of ethylene oxide is weighed and the addition is started. While stirring, ethylene oxide is added in a temperature range of 100 to 110 ° C. over about 2 to 3 hours, It was made to react. The completion of the reaction was judged by the pressure in the reaction vessel decreasing and reaching a constant pressure. Then cool to 100 ° C,
The volatile components present in the reaction vessel were removed under reduced pressure, cooled, returned to room temperature and taken out. The resulting dimethylaminoethylamine ethylene oxide 2 mol addition product was added to
5 mol and carboxy-modified silicone BY-16-75
One equivalent of 0 carboxyl was mixed at about 30 ° C. to give the salt.

Compound 8: TSF-4460 (polyether-modified silicone, manufactured by GE Toshiba Silicone Co., Ltd.) Compound 9: TSF-4452 (polyether-modified silicone, manufactured by GE Toshiba Silicone Co., Ltd.) Compound 10: ETC-3NEX ( Polyoxyethylene (3) sodium tridodecyl ether acetate, manufactured by Nikko Chemicals Co., Ltd.), and the number in parentheses is the number of moles of ethylene oxide added.

Compound 11: TSF-4450 (polyether-modified silicone, manufactured by GE Toshiba Silicone Co., Ltd.) Compositions of the dry cleaning detergents obtained in Examples 1 to 3 and Comparative Examples 1 to 6 and 1% by volume solution Table 1 for dilution stability
Table 2 shows the evaluation results of the cleaning rate, recontamination rate and flexibility.
Shown in.

[0054]

[Table 1]

[0055]

[Table 2]

Comparing the same fiber materials from the results of Table 2, the cleaning ratios of Examples 1 to 3 in which the carboxyl-modified silicone surfactant and the anionic surfactant were used in combination were not ionic. Compared with Comparative Examples 1 and 2 using the modified silicone and Comparative Examples 3 and 4 using only the conventional anionic surfactant, the overall value is higher, especially for wool, it is 5% or more higher. It can be seen that the cleaning detergent composition has excellent detergency.

The recontamination rate was lower in the Examples using the cleaning agent for dry cleaning of the invention than in the Comparative Examples.
It can be seen that the cleaning composition for dry cleaning of the present invention has an excellent anti-redeposition property.

One of the cleaning agents for dry cleaning of the embodiment
The volume% solution was uniformly dissolved and had good dilution stability, but Comparative Example 2 was cloudy. It can be seen that this Comparative Example 2 is inferior in the cleaning property and the anti-redeposition property to the Comparative Examples 5 and 6 in which only the solvent is used.

Regarding the flexibility, the examples are much superior to the comparative examples, and it can be seen that the cleaning composition for dry cleaning of the present invention has excellent flexibility.

Next, Table 3 shows Examples 4 to 6 and Comparative Examples 7-1.
The results of evaluation of the composition of the cleaning agent for dry cleaning of No. 1, the dilution stability of the 1% by volume solution, the antistatic property and the flexibility are shown.

[0061]

[Table 3]

Comparing the results of Table 3 with respect to the same fiber material, as for the antistatic property, the examples using the dry cleaning detergent of the present invention showed the salt of carboxyl-modified silicone and alkylene oxide adduct of amine. It is superior to Comparative Example 7 used, Comparative Examples 8 and 9 using polyether-modified silicone, and Comparative Example 11 using only a solvent. It can be seen that the flexibility of the example is higher than that of the comparative example.

Therefore, it can be seen that the dry cleaning detergent composition of the present invention is excellent in all properties of dilution stability, detergency, recontamination resistance, flexibility and antistatic property.

[0064]

EFFECTS OF THE INVENTION The detergent composition for dry cleaning of the present invention comprises a surfactant component relating to a novel combination of a silicone surfactant having a specific structure and a non-silicone surfactant having a specific structure. And a silicone-based solvent (or a silicone-based mixed solvent containing a fluorine-based solvent) having such a constitution.
It can be diluted in a sufficiently stable manner when it is added to, and is further modified with a carboxyl-modified silicone-based surfactant and a non-silicone-based surfactant, and an anionic surfactant soluble in a silicone-based solvent. The surfactant of the novel combination of (1) gives excellent cleaning properties and anti-soil redeposition property, and also provides excellent flexibility, smoothness and antistatic property to the object to be washed.

Claims (6)

[Claims] 1. 2-50 at least one selected from the group consisting of (A) a carboxyl-modified silicone represented by the following general formula [1] and a salt of the carboxyl-modified silicone and an alkylene oxide adduct of an amine. weight%,
(B) A non-silicone type anionic surfactant is added in an amount of 8 to 60.
10% to 90% by weight, and (C) a silicone-based solvent or a mixed solvent of a fluorine-based solvent and a silicone-based solvent.
A cleaning composition for dry cleaning containing: [Chemical 1] (In the formula, Z is independently a methyl group or -RCOOH.
(R represents an alkylene group having 2 to 14 carbon atoms),
x and y are integers satisfying x + y = 200 to 1000, and the carboxyl equivalent is 500 to 10,000. ) 2. The amine has the following general formula [2]:
The cleaning composition for dry cleaning according to claim 1, which is at least one selected from the group consisting of amines represented by [3] and [4]. [Chemical 2] [In the formula, R ¹ and R ² are each independently a hydrogen atom and a carbon number of 1
~ 18 alkyl group, C2-18 alkenyl group,
A hydroxyalkyl group having 1 to 18 carbon atoms, a cyclohexyl group, a benzyl group or a phenethyl group is represented, R ³ is an alkyl group having 1 to 14 carbon atoms, R ⁴ is an alkylene group having 2 to 6 carbon atoms, R ⁵ , R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a hydroxyalkyl group having 1 to 18 carbon atoms,
It represents a cyclohexyl group, a benzyl group or a phenethyl group, R ⁷ is an alkylene group having 1 to 10 carbon atoms, —C ₂ H ₄ O
_{C 2 H 4 -, - C} 2 H 4 OC 2 H 4 OC 2 H 4 -, - C 3 H 6 OC
_{H 2 C (CH 3) 2} CH 2 OC 3 H 6 - or _{-C 3 H 6 O (C 2} H 4
_{O) k C 3 H 6 -} ( a, where k is an integer of 1-6). ] 3. The alkylene oxide is at least one selected from ethylene oxide, propylene oxide and butylene oxide.
The dry cleaning detergent composition according to item 1. 4. The cleaning composition for dry cleaning according to claim 1, wherein the non-silicone anionic surfactant is a compound represented by the following general formula [5]. ^{R 8 O (R 9 O)} m (CH 2) n COOX [5] ( wherein, R ⁸ represents an alkyl or alkenyl group having 6 to 18 carbon atoms, R ⁹ is an alkylene group having 2 or 3 carbon atoms Represents, m is an integer of 0 to 10, n is 1 or 2, and X represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an alkanolamine.) 5. The cyclic silicone represented by the following general formula [6] and / or the boiling point of the silicone solvent is 13:
A linear silicone having a temperature of 0 to 250 ° C. 5.
The cleaning composition for dry cleaning according to any one of 1. [Chemical 3] (In the formula, p represents an integer of 4 to 6.) 6. The cleaning composition for dry cleaning according to claim 1, wherein the fluorine-based solvent is at least one selected from the group consisting of hydrofluorocarbons, hydrofluoroethers and hydrochlorofluorocarbons.