JP4969844B2 - Cleaning method for textile products - Google Patents

Description

  The present invention relates to a cleaning aid that can provide excellent detergency even when packed and washed, and can reduce wrinkles after drying, a cleaning composition containing the same, and a cleaning method using the same.

Conventionally, techniques for blending polyether-modified silicone or amino-modified silicone with a detergent composition are known. For example, Patent Documents 1, 2, and 3 disclose a detergent composition containing polyether-modified silicone that prevents shrinkage of a fiber product or imparts flexibility. Patent Documents 4 and 5 disclose a detergent composition containing an amino-modified silicone and imparting a good texture.
JP 11-293299 A Japanese Patent Laid-Open No. 2-145862 JP 11-293297 A JP-A-10-140183 Japanese Patent Laid-Open No. 10-60480

  In the above-mentioned patent document, there is a problem when stuffed and washed with a small amount of washing water relative to the weight of the textile product, that is, a sufficient cleaning power cannot be obtained, and the clothes are liable to get entangled. A technique for solving the problem of causing wrinkles is not disclosed.

  An object of the present invention is to provide a cleaning aid that provides excellent cleaning power even when stuffed and washed, and that can reduce wrinkles after drying, a cleaning composition containing the same, and a cleaning method using the same. is there.

  The present invention includes a cleaning aid containing at least one modified silicone (hereinafter referred to as component (a)) selected from modified silicones represented by the following general formula (1) or (2), and the cleaning aid. And a method for cleaning textiles using the cleaning aid or cleaning composition.

[Wherein R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ² represents either R ¹ or A. Table A is -R ³ -Z (wherein represents a divalent hydrocarbon group, Z is primary to tertiary amino group-containing group or an ammonium group-containing group R ³ is a direct bond or a 1 to 20 carbon atoms) Represents a group. a represents an integer of 2 or more, b represents an integer of 1 or more, c represents a number of 4 or more, n represents an integer of 2 to 4, and c (C _n H _2n O) may be the same or different. d represents an integer of 2 or more. Y represents a divalent organic group bonded to an adjacent silicon atom via a carbon-silicon bond and to a polyoxyalkylene chain via an oxygen atom. The polysiloxane block accounts for 45 to 85% by weight of the total modified silicone. These groups are selected so that the weight average molecular weight of the modified silicone is 8000 to 500,000. ]

[Wherein, X represents —R ⁶ , —O—R ⁶ or —OH, and R ⁶ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms. R ⁴ independently represents a hydrogen atom, —OH, or a monovalent hydrocarbon having 1 to 6 carbon atoms. R ⁵ represents R ⁴ , B or C. B and C are -R ⁷ -Q [wherein R ⁷ represents a divalent hydrocarbon group of direct bond or a C 1 to 20, Q is-containing primary to tertiary amino group containing no polyoxyalkylene group group or ammonium group-containing group, or _{-O (C m H 2m O)} i R 8 (m is an integer of 2 to 4, i is a number from 1 to 200, the i-number (C _m H _2m O ) May be the same or different, R ⁸ represents a monovalent hydrocarbon group or a hydrogen atom)], or —NR ¹⁰ —R ⁹ —O (C _m H _2m O) _i R ⁸ (R ⁹ represents A direct bond, a divalent hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group in which a part of hydrogen atoms is substituted with a hydroxyl group, R ¹⁰ is a hydrogen atom or —R ⁹ —O (C _m H _2m O) _i R ⁸ , m, i and R ⁸ are the same as defined above. B and C may be the same or different, but Q in both B and C is not an amino group-containing group or an ammonium group-containing group that does not contain a polyoxyalkylene group. e, f, and g are integers of 1 or more. These groups are selected such that the kinematic viscosity at 25 ° C. of the modified silicone is 9000 mm ² / s or more. ]

  When the cleaning aid and the cleaning composition of the present invention are used for cleaning textile products, for example, even when shampooing such that the bath ratio [amount of washing water (L) / weight of textile products (kg)] is 12 or less is performed. Excellent detergency can be given and wrinkles after drying can be reduced.

  The modified silicone which is the component (a) of the present invention has high wet lubricity, and therefore prevents entanglement of the textile during washing, and the mechanical force of the pulsator and drum rotation is uniformly transmitted to the textile. Can improve the cleaning power. In addition, since it prevents entanglement of the textile product during washing, there are few dewatering creases, and during drying (hanging drying, drying with a dryer), the yarns can slide well and wrinkles can be stretched to reduce wrinkles.

[Cleaning aid]
The cleaning aid of the present invention contains at least one modified silicone selected from the modified silicones represented by the above general formula (1) or (2).

  In the modified silicone of the above general formula (1), the polysiloxane block accounts for 45 to 85% by weight of the whole modified silicone, and the weight average molecular weight of the modified silicone is 8000 to 500,000, preferably 15,000 to 400,000, more preferably Is 25000 or more and 350,000 or less.

  In the modified silicone represented by the general formula (1), the weight average molecular weight of each polysiloxane block is preferably 600 to 5000, and the weight average molecular weight of each polyoxyalkylene block is preferably 500 to 3000.

  In the present invention, the weight average molecular weight is a value measured by a conventional method using gel permeation chromatography and using chloroform as an eluent and polystyrene as a standard substance.

The siloxane block refers to a siloxane having two R ¹ groups represented by — [Si (R ¹ ) ₂ —O] _a — and —Si (R ¹ ) ₂ —O—. The ratio means the ratio of the molecular weight of the siloxane block to the molecular weight of the modified silicone of the general formula (1) expressed in weight%. The above weight percentages are modified silicone was diluted in methanol -d ₄ solution, a ¹ H-NMR was measured, determined by the peaks of the spectrum.

Further, the modified silicone represented by the general formula (1) preferably has a kinematic viscosity at 25 ° C. of 500 mm ² / s or more, further 10000 mm ² / s or more, particularly 20000 mm ² / s or more. This viscosity is measured with a B-type viscometer under the condition of 25 ° C.

  In addition, the modified silicone represented by the general formula (1) preferably has an amino equivalent of 500 to 8000 g / mol, more preferably 800 to 4500 g / mol. The amino equivalent is a molecular weight per nitrogen atom, and is determined by amino equivalent = molecular weight / number of nitrogen atoms. The molecular weight is a value determined by gel permeation chromatography using polystyrene as a standard, and the number of nitrogen atoms can be determined by elemental analysis or the like.

In the modified silicone represented by the general formula (2), B and C each represent a group represented by —R ⁷ —Q or —NR ¹⁰ —R ⁹ —O (C _m H _2m O) _i R ^8. , B and C are not both an amino group-containing group or an ammonium group-containing group that does not contain a polyoxyalkylene group.

Modified silicone of the general formula (2), the kinematic viscosity at 25 ° C. and at 9000 mm ² / s or more, preferably 15000 ² / s or more. The weight average molecular weight is preferably 10,000 or more and 500,000 or less, more preferably 15,000 or more and 400,000 or less, and particularly preferably 25,000 or more and 350,000 or less. The methods for measuring these kinematic viscosities and weight average molecular weights are as described above. The modified silicone represented by the general formula (2) has an amino equivalent of 500 to 8000 g / mol, more preferably 800 to 4500 g / mol.

  The cleaning aid of the present invention preferably contains a surfactant from the viewpoint of blending such as emulsification, dispersion and stability of the component (a). Suitable surfactants include nonionic surfactants, cationic surfactants, and amphoteric surfactants. Nonionic surfactants and cationic surfactants are preferred, and nonionic surfactants are more preferred. Nonionic surfactants include higher alcohol ethylene oxide (hereinafter referred to as “EO”) adducts or EO / propylene oxide (hereinafter referred to as “PO”) adducts, especially EO average of alcohols having 8 to 16 carbon atoms. ˜15 mol adduct is preferred from the viewpoint of blending stability of component (a).

  The content of the component (a) in the cleaning aid of the present invention is preferably 1 to 50% by weight, more preferably 3 to 25% by weight. Moreover, 0.5-50 weight% is preferable and, as for content of surfactant, 1-25 weight% is still more preferable.

  The cleaning aid of the present invention may be used in combination with a powder or liquid detergent in advance, or the washing aid of the present invention may be used together with the detergent during washing.

[Cleaning composition]
The cleaning composition of the present invention contains the cleaning aid of the present invention. The content of the cleaning aid of the present invention in the cleaning composition is preferably 0.5 to 20% by weight, more preferably 1.5 to 10% by weight, as the content of the component (a).

  The cleaning composition of the present invention may be in the form of powder or liquid. When blending the cleaning aid of the present invention in a powder cleaning composition, for example, the method of mixing the cleaning aid of the present invention and a quaternary ammonium salt, pulverizing after cooling, and blending into the cleaning composition, the present invention A method of forming a capsule-like agent containing a cleaning aid and a zeolite carrier and blending it into the cleaning composition, mixing the cleaning aid of the present invention and a nonionic surfactant, and then making the mixture oil-absorbing Examples thereof include a method of blending in a cleaning composition by supporting it on a carrier, and a method of blending in a cleaning composition by spraying the cleaning aid of the present invention diluted with an organic solvent such as ethanol onto a powder cleaning agent. When the cleaning aid of the present invention is blended in the liquid cleaning composition, the cleaning aid of the present invention and other components may be mixed.

  In the case where the cleaning composition of the present invention is a powder cleaning composition, in addition to the cleaning aid of the present invention, components to be blended with conventional powder cleaning compositions such as surfactants, builders, alkaline agents, bleaching components, etc. Can be contained. In addition, when the cleaning composition of the present invention is a liquid cleaning composition, in addition to the cleaning aid of the present invention, it contains components blended in the conventional liquid cleaning composition such as surfactants and alcohols. be able to.

  The content of the surfactant in the cleaning composition of the present invention is not particularly limited, but is preferably 5 to 60% by weight, and more preferably 15 to 50% by weight.

  Examples of the builder used in the cleaning composition of the present invention include an inorganic builder such as crystalline aluminosilicate, amorphous aluminosilicate, crystalline sodium silicate, sodium tripolyphosphate, sodium pyrophosphate, formula (3)

[Wherein, R ¹² represents a group represented by — (CH ₂ ) _h —E, E represents a hydrogen atom, a hydroxyl group or —COOM ¹ ; M ¹ represents a hydrogen atom, an alkali metal (preferably Na, K ) Or ammonium, and h is a number from 0 to 3. ]
Organic builder such as aminopolycarboxylic acid represented by Although content of the builder in the cleaning composition of this invention is not specifically limited, 10 to 50 weight% is preferable and 15 to 40 weight% is still more preferable.

  Examples of the alkaline agent used in the cleaning composition of the present invention include carbonates, silicates, amines (alkylamines, alkanolamines, etc.), and carbonates and silicates are more preferable. The content of the alkaline agent in the cleaning composition of the present invention is not particularly limited, but is preferably 5 to 50% by weight, and more preferably 10 to 40% by weight.

  Examples of the bleaching component used in the cleaning composition of the present invention include substances that release hydrogen peroxide in aqueous solutions (hereinafter referred to as hydrogen peroxide releasing substances) and bleach activators. The content of the hydrogen peroxide releasing substance in the cleaning composition of the present invention is not particularly limited, but is preferably 0.1 to 80% by weight, and more preferably 0.5 to 70% by weight.

  Examples of the bleach activator used in the cleaning composition of the present invention include compounds represented by formula (4) or (5).

[Wherein R ¹³ is an alkyl group having 4 to ¹³ carbon atoms, preferably 10 to 13 carbon atoms, R ¹⁴ is an alkyl group having 5 to ¹³ carbon atoms, preferably 7 to 11 carbon atoms, M ² is a hydrogen atom or an alkali metal, an alkali Indicates earth metal, ammonium or alkanolamine. ]
The content of the bleach activator in the cleaning composition of the present invention is not particularly limited, but is preferably 0.05 to 20% by weight, and more preferably 0.1 to 10% by weight.

[How to wash textile products]
The textile product cleaning method of the present invention is either a method of cleaning a textile product using the cleaning aid of the present invention together with a conventional cleaning agent, or a method of cleaning a textile product using the cleaning composition of the present invention. But it ’s okay.

  In the cleaning method of the present invention, the concentration of the component (a) in the cleaning bath is preferably 0.02 to 0.5% by weight, more preferably 0.03 to 0.3% by weight, based on the weight of the fiber product.

The method of cleaning the invention, washing stuffing washing water is small relative to the textile weight, in particular bath ratio, i.e. the ratio of the wash濯水of textile laundering and washing water (L) / laundered textiles Weight (kg) This is effective when stuffing and washing is performed with a value of 12 or less .

Example 1
Cleaning aids having the compositions shown in Table 1 were prepared using the ingredients shown below. About the obtained washing | cleaning adjuvant, the cleaning power and wrinkle determination were performed with the following method. These results are shown in Table 1.

<Blending ingredients>
Component (a) of the present invention (a) -1: Modified silicone represented by the formula (1-1) [weight average molecular weight 14000, polysiloxane block weight average molecular weight 2700, polyoxyalkylene block weight average molecular weight 530 , Ratio of polysiloxane block to the whole modified silicone 70% by weight, viscosity 3000 mm ² / s (25 ° C.)], amino equivalent 850 g / mol

(A) -2: Modified silicone represented by the formula (1-2) [weight average molecular weight 32000, polysiloxane block weight average molecular weight 4300, polyoxyalkylene block weight average molecular weight 900, polysiloxane block modified silicone as a whole % By weight, viscosity 50000 mm ² / s (25 ° C.)], amino equivalent 1350 g / mol

(A) -3: Modified silicone represented by the formula (2-1) [weight average molecular weight 27000, viscosity 43000 mm ² / s (25 ° C.)], amino equivalent 1900 g / mol

(A) -4: Modified silicone represented by formula (2-2) [weight average molecular weight 31,000, viscosity 44000 mm ² / s (25 ° C.)], amino equivalent 5200 g / mol

Comparative modified silicone (a ′)-1: KF615A Polyether-modified silicone manufactured by Shin-Etsu Chemical Co., Ltd. [viscosity 1250 mm ² / s (25 ° C.), HLB = 14]
Surfactant Nonionic surfactant a: polyoxyethylene alkyl ether (average of 13.1 mol of EO added to a linear primary alcohol having 12 carbon atoms)
Nonionic surfactant b: polyoxyethylene alkyl ether (average of 2.9 mol of EO added to linear primary alcohol having 12 carbon atoms)
<Determination method of cleaning power and wrinkles>
Cotton knitted fabric was cut into 11 × 20 cm, and the cloth was fixed across the folds of the heels of clothes such as work clothes, and the clothes were worn for 3 days. The cloth was removed from the clothes, and a pair of cloth pieces (9 × 6 cm) were cut out so as to be evenly soiled and used as test cloths, which were sewn to the underwear. A total of 4.0 kg of 18 underwear (100% cotton), 3 polo shirts (100% cotton), 2 polo shirts (polyester / cotton blend) and 5 T-shirts (100% cotton) were washed as follows. .

  As a washing machine, we use a fully automatic washing machine National NA-F70PX5 (water volume 48L, bath ratio 12) manufactured by Matsushita Electric Industrial Co., Ltd. Washing was performed on a standard course by adding 53 g of powder detergent “Attack” manufactured by Co., Ltd. and 53 ml of a cleaning aid.

  After washing, the clothes were taken out, shaped while tapping, hung on a hanger, hung indoors (20 ° C., 65% RH) and dried. After drying, the test cloth was removed, and 10 panelists used the comparative product 1 as a control product, and visually determined the cleaning power according to the following criteria. Similarly, ten panelists visually judged the wrinkles of the T-shirt after drying according to the following criteria. Table 1 shows the average values of 10 panelists.

・ Detergent criteria 5: Less soiling than the control product 4: Slightly less soiling than the control product 3: Equivalent to the control product 2: Slightly less contamination in the control product 1: Less contamination in the control product Criterion 5: No wrinkles 4: Wrinkles are considerably reduced 3: Some wrinkles remain 2: Corresponding wrinkles remain 1: Wrinkles remain remarkably

Example 2
Using the same component (a) of the present invention as in Example 1 and comparative modified silicone, these modified silicones were dissolved in ethanol to prepare a 5 wt% ethanol solution of the modified silicone. Separately, an index detergent (powder) for determining cleaning power described in JIS K3362 is prepared, and the 5% ethanol solution of the modified silicone is added thereto so that the modified silicone content in the cleaning composition is 5% by weight. Spraying to obtain a powder detergent composition.

  About the obtained powder cleaning composition, the cleaning power and wrinkle determination were performed by the following method. These results are shown in Table 2.

<Determination method of cleaning power and wrinkles>
The same test cloth and apparel as in Example 1 were used, and washing was performed in the same manner as in Example 1 except that 67 g of the powder detergent composition prepared above was used instead of “Attack” and the cleaning aid. Wrinkles were determined. In addition, the cleaning power and the determination of wrinkles were performed using the comparative product 3 as a control product.

Example 3
A liquid detergent composition having the composition shown in Table 3 was prepared using the same component (a) of the present invention as in Example 1, a comparative modified silicone, and the nonionic surfactant described below. In addition, the component (a) of the present invention and the comparative modified silicone were mixed with a nonionic surfactant in advance so as to be easily dispersed and then mixed with other components.

  About the obtained liquid detergent composition, the cleaning power and wrinkle determination were performed by the following method. These results are shown in Table 3.

Nonionic surfactant Nonionic surfactant c: Polyoxyethylene alkyl ether (average of 7 mol of EO added to a linear primary alcohol having 10 to 14 carbon atoms)
Nonionic surfactant d: polyoxyethylene alkyl ether (average of 7 mol of EO added to a linear secondary alcohol having 10 to 14 carbon atoms)
<Determination method of cleaning power and wrinkles>
The same test cloth and apparel as in Example 1 were used, and washing was performed in the same manner as in Example 1 except that 67 ml of the liquid detergent composition prepared above was used instead of “Attack” and the cleaning aid. Wrinkles were determined. In addition, the cleaning power and wrinkle determination were performed using the comparative product 5 as a control product.

Claims (3)

Using washing water containing a cleaning aid and a cleaning agent containing at least one modified silicone (hereinafter referred to as component (a)) selected from modified silicones represented by the following general formula (1) or (2) A method for cleaning a textile product, wherein the concentration of the component (a) in the wash water is 0.03 to 0.3% by weight based on the weight of the textile product.

[Wherein R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ² represents either R ¹ or A. Table A is -R ³ -Z (wherein represents a divalent hydrocarbon group, Z is primary to tertiary amino group-containing group or an ammonium group-containing group R ³ is a direct bond or a 1 to 20 carbon atoms) Represents a group. a represents an integer of 2 or more, b represents an integer of 1 or more, c represents a number of 4 or more, n represents an integer of 2 to 4, and c (C _n H _2n O) may be the same or different. d represents an integer of 2 or more. Y represents a divalent organic group bonded to an adjacent silicon atom via a carbon-silicon bond and to a polyoxyalkylene chain via an oxygen atom. The polysiloxane block accounts for 45 to 85% by weight of the total modified silicone. These groups are selected so that the weight average molecular weight of the modified silicone is 8000 to 500,000. ]

[Wherein, X represents —R ⁶ , —O—R ⁶ or —OH, and R ⁶ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms. R ⁴ independently represents a hydrogen atom, —OH, or a monovalent hydrocarbon having 1 to 6 carbon atoms. R ⁵ represents R ⁴ , B or C. B and C are -R ⁷ -Q [wherein R ⁷ represents a divalent hydrocarbon group of direct bond or a C 1 to 20, Q is-containing primary to tertiary amino group containing no polyoxyalkylene group group or ammonium group-containing group, or _{-O (C m H 2m O)} i R 8 (m is an integer of 2 to 4, i is a number from 1 to 200, the i-number (C _m H _2m O ) May be the same or different, R ⁸ represents a monovalent hydrocarbon group or a hydrogen atom)], or —NR ¹⁰ —R ⁹ —O (C _m H _2m O) _i R ⁸ (R ⁹ represents A direct bond, a divalent hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group in which a part of hydrogen atoms is substituted with a hydroxyl group, R ¹⁰ is a hydrogen atom or —R ⁹ —O (C _m H _2m O) _i R ⁸ , m, i and R ⁸ are the same as defined above. B and C may be the same or different, but Q in both B and C is not an amino group-containing group or an ammonium group-containing group that does not contain a polyoxyalkylene group. e, f, and g are integers of 1 or more. These groups are selected such that the kinematic viscosity at 25 ° C. of the modified silicone is 9000 mm ² / s or more. ] The method for washing textile products according to claim 1, wherein the washing ratio between the amount of washing water and the textile product to be washed is 12 or less in terms of the amount of washing water (L) / weight of the textile product to be washed (kg). The said washing | cleaning adjuvant contains 3-25 weight% of (a) component, and 1-25 weight% of ethylene oxide average 1-15 mol adduct of C8-C16 alcohol. How to wash textile products.