JP3085986B2 - Laundry stain treatment composition and treatment method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a soiling composition for laundry. Laundry can be treated by applying the composition to the soiled area before or after the normal washing process to at least partially release the soil and facilitate soil removal. .

It is known that a solvent-water based emulsion is effective as a soil pretreatment composition for both hydrophobic soil and hydrophilic soil.

UK Patent Application No. A-2 published March 9, 1988
194 547 discloses a mixture of n-dodecane with a short chain nonionic surfactant (Neodol 19-6) and a long chain nonionic surfactant (Neodol 45-1). These compositions are in the form of liquid solutions, water-in-oil or oil-in-water microemulsions, or gels. However, this application does not disclose a composition comprising an alkaline substance.

U.S. Patent No. 4,093,418 issued June 6, 1978
No. and U.S. Pat.No. 4,178,
No. 262 discloses combinations of isoparaffins (C ₁₁ -C ₁₄ ) and long-chain (C ₁₀ -C ₁₈ ) nonionic surfactants.

The present invention relates to cleaning compositions, the detergent composition, non-aqueous hydrophobic solvent, anion or nonionic primary surfactant having a can C ₁₁ or less alkyl chain length, and the length Is an oil-in-water or water-in-oil emulsion, or solution, comprising an anionic or nonionic secondary surfactant having an alkyl chain of C ₁₂ or higher.

It is an object of the present invention to provide fatty dirt, especially including cosmetics and food dirt such as creams, milks and sauces.
Alternatively, it is to improve the cleaning performance of the soil treatment composition against oil and fat soil.

It is another object of the present invention to improve the removal of bleachable soils by applying the composition of the present invention and by applying a bleaching compound, preferably a peroxide compound.

SUMMARY OF THE INVENTION The object of the present invention is achieved by providing a cleaning composition having a pH higher than 8, thereby increasing the cleaning performance on both fatty soils and bleachable soils. The pH is preferably higher than 9, and more preferably higher than 10.

Preferably, the cleaning composition comprises 5-95% by weight of the composition of water.

The present invention also relates to a method for treating stains and stains on a woven fabric using the cleaning composition of the present invention.

DETAILED DESCRIPTION OF THE INVENTION Hydrophobic solvents are an essential feature of the compositions of the present invention. Preferred hydrophobic solvents are determined by Hansen parameters. The hydrophobic solvent defined in the present invention is a Hansen hydrogen bonding force parameter dH of 18 (joule / c).
m ³ ) It is considered that the solvent is less than ^0.5 . Preferred hydrophobic solvents are those having a Hansen hydrogen bonding parameter dH of 12
(Joule / cm ³ ) is less than ^0.5 and the Hansen polarity parameter dP is less than 8 (Joule / cm ³ ) ^0.5 .

A preferred solvent to be used has a flash point of 70 ° C or higher, an initial boiling point of 130 ° C or higher, preferably 145 ° C or higher, and a hydrocarbon having a freezing point of 20 ° C or lower, and an aliphatic fatty acid ester. A mixture is included. More preferred solvents are alkanes or alkenes having a chain length exceeding C7, especially alkanes or alkenes having an average of 8 to 20 carbon atoms. Particularly preferred hydrophobic solvents are deodorized kerosene, solvent naphtha, chlorinated hydrocarbons, and terpenes. Even more preferred are paraffins, isoparaffins, naphthenes, aromatic hydrocarbons, olefins, 1,1,1-trichloroethaneperchloroethylene, methylene chloride, trade name Shellsol SS mixture (S8-C11 isoparaffin + aliphatic C7 ester 5). %), D-limonene, and the trade name Grid Safe supplied by Grid Sol. The solvent is added to the detergent composition of the present invention in an amount of 3 to 90% by weight of the detergent composition, more preferably 4 to 45% by weight, most preferably 5 to 90% by weight.
Used at a level of 25% by weight.

Hansen parameter dH is 18 (joules / cm ³ ) ^0.5
Other solvents less than include glycol ethers, more preferably glycol ethers based on ethylene oxide, propylene oxide, or mixtures thereof. Particularly preferred are ethylene glycol monoethyl ether, propylene glycol monomethyl ether, 2-butoxyethanol, butyl diethylene glycol ether ethanol, butoxytriglycol, butylene glycol, hexylene glycol, and propylpropanol. Such a solvent is used in combination with a mixture of a short-chain surfactant and a long-chain surfactant.

In the present invention, "short chain" refers to a hydrophobic portion.
It refers to a surfactant comprising a C ₆ -C ₁₁ alkyl chains. Accordingly, such short-chain surfactants, which are conventionally used in this field, have a short alkyl chain and may be of any type. Therefore, the short-chain surfactants suitable for use in the present invention, alkyl sulfate (C ₆ -C ₁₁ in C ₆ -C ₁₁ SO
₄ ), alkyl ether sulfate (C ₆ -C ₁₁ (OCH ₂ CH
₂ ) eSO ₄ ), alkyl sulfonate (C ₆ -C ₁₁ SO ₃ ), alkyl succinate (C ₆ -C ₁₁ OOCH ₂ CH ₂ COOZ), alkyl carboxylate (C ₆ -C ₁₁ COOM), alkyl ether carboxy Rate (C ₆ -C ₁₁ (OCH ₂ CH ₂ ) eCOOM), alkyl sarcosinate (C ₆ -C ₁₁ CON (CH ₃ ) R), alkyl sulfosuccinate (C ₆ -C ₁₁ OOCCH (SO ₃ M) CH ₂ COO
Z), amine oxides (C ₆ ~C ₁₁ RR'NO), glucose amides _{(C 6 ~C 11 CONR "X} ), alkyl pyrrolidones (C ₆ -C
₁₁ (C ₄ H ₆ ON), alkyl polysaccharide (C _{6 to} C ₁₁ OGg), alkyl alkoxylate (C _{6 to} C ₁₁ (COH ₂ CH ₂ ) e (OCH ₂ CH ₂ C)
H ₂ ) pOH) and betaine (C ₆ -C ₁₁ N + (CH ₃ ) ₂ CH ₂ COO
-) Is included. In the formulas in parentheses, e and p are independently 0 to
20 with e + p> 0, Z is M or R, and M is H or any such as those known in the art including Na, K, Li, NH ₄ , amines X is a polyhydroxyhydrocarbyl having at least three hydroxyls and a linear hydrocarbyl chain directly attached to the chain, or an alkoxylated derivative thereof, wherein R, R ′ and R ″ are C ₁ -C a ₅ alkyl group, optionally are functionalized with hydroxyl radical, R and R 'are preferably C ₁ -C _3, and most preferably methyl, R "is preferably 2-hydroxy Ethyl or 2-hydroxypropyl;
Is a saccharide, preferably glucose, and g is 1.5-8. All of these surfactants are well known in the art. A more complete disclosure of conventional glucose amides can be found, for example, in WO 92-06154, and a more complete disclosure of conventional alkyl polysaccharides is, for example, U.S. Patent No. 4,536,319. It can be found in the description. Compositions according to the present invention can include any one of the above surfactants, or any combination thereof.

Preferred short chain nonionic surfactants for use in the present invention are alkyl alkoxylates of the formula _{C 6 ~C 11 (OCH 2 CH} 2) e (OCH 2 CH 2 CH 2) pOH. In the formula, e and p representing the degree of ethoxylation and the degree of propoxylation are independently 0.
2020 and e + p> 0. Most preferred short chain nonionic surfactants for use in the present invention are those wherein e and p are e + p = 3-10, especially those wherein p is 0 and e is 3-8. The most preferred short-chain nonionic surfactant for use in the present invention is that the short chain has 7 to 11 carbon atoms.
Are hydrocarbons. The short chain nonionic surfactants preferred for use in the present invention can be prepared by methods well known to those skilled in the art, such as condensation of the corresponding alcohol with an alkylene oxide,
Such short-chain surfactants are more conveniently
For example, from Sidbre under the brand name Martar C ₄ (C8EO4), and from Kolb under Inventin AG / 810/050 and AG / 8
10/080 under the trade name (respectively C8～10EO5, and C8~10EO8) B, Dobanol shell 91-2.5 (C ₉ ~C ₁₁ EO2.
5), Dovanol 91-6 (C ₉ -C ₁₁ EO6), Dovanol 91
It is commercially available from Vista Chemicals under the trade name Vista 1012-52 and from Exxon under the trade name Asopol 91-4.6.

Another preferred type of short chain nonionic surfactant is a secondary alcohol ethoxylate of the formula:

In the formula, (X + Y) is 2 to 10, and n indicating the number of ethoxylate groups is 1 to 7. Examples of commercially available surfactants of this type include Union Carbide Targitol S series.

Preferred short chain anionic surfactants for use in the present invention, C ₆ -C ₁₁ alkyl sulfates, C ₆ -C ₁₁ alkyl sulfonates, C ₆ -C ₁₁ betaines, C ₆ -C ₁₁ amine oxides, and mixtures thereof It is. Most preferred is C ₆
~C is ₈ alkyl sulfates and sulfonates. Such short-chain anionic surfactants can be prepared by well-known methods, such as neutralization after sulfation or sulfonation, but the short-chain anionic surfactants are more convenient. The good news is that it is commercially available, for example, from Rhone Poulin under the trade name Rhodapon OLS or from Waco under the trade name Witconate.

Any alkaline material is suitable for use in the present invention. Preferred as alkaline substances are from the group consisting of potassium hydroxide, sodium hydroxide, ammonium hydroxide, ammonium silicate, sodium bicarbonate, borax, monoethanolamine borate, monoethanolamine, triethanolamine, and mixtures thereof. It is the choice. Usually, the soil treatment composition comprises 0.1 to 10% by weight, preferably 0.5 to 3% by weight of an alkaline substance. The pH is preferably higher than 8, more preferably higher than 9, and most preferably higher than 10. Nick's portable pH meter (Portameth 752) for undiluted compositions
Was measured.

In the present invention, "long chain" means a surfactant having an alkyl chain having 12 or more carbon atoms.

Non-limiting examples of useful long chain surfactants in the present invention, conventional C ₁₂ -C ₁₈ alkyl benzene sulfonates ( "LAS"), first branch-chain random C ₁₂ -C ₂₀ alkyl sulfates ( "AS"), the formula _{CH 3 (CH 2) x (} CHOSO 3 - M +) C
H _3, and _{CH 3 (CH 2) y (} CHOSO 3 - M +) CH 2 CH 3 ( wherein, x
And (y + 1) is least about 7, preferably at least about 9 integer, and M is C ₁₂ -C ₁₈ secondary (2,3) alkyl sulfate represented by a water-solubilizing cation, especially sodium) unsaturated sulfates such as oleyl sulfate, C ₁₂ -C ₁₈ alkyl alkoxy sulfates ( "AE _x S", especially EO1~7 ethoxysulfate), C ₁₂ -C ₁₈ alkyl alkoxy carboxylates (especially EO1~5 ethoxy carboxylates ), C ₁₂ ~C ₁₈
Glycerol ethers, C ₁₂ -C ₁₈ alkyl polyglycosides and sulfated polyglycosides and their corresponding, C ₁₂ -C ₁₈
Includes alpha-sulfonated fatty acid ester methyl ester sulfonate (MES), and oleyl sarcosinate. C ₁₂ -C ₁₈ alkyl ethoxylates ( "A
Typical nonionic and amphoteric surfactants, particularly preferably C ₁₂ -C ₁₆ fatty alcohol polyglycol ethers, or EO2~7 ethoxylated primary alcohol (especially ethoxylates, and ethoxylated / propoxylated mixtures such as E ")) , C ₁₂ -C ₁₈ betaines, C ₁₂ -C ₁₈ sulfobetaine ( "sultaines"), C ₁₂ -C ₁₈ amine oxides, etc. can also be included in the overall compositions. C ₁₂ -C ₁₈ N-alkyl polyhydroxy fatty acid amides can also be used. Examples of typical, C ₁₂ ~C ₁₈ N- methyl glucamides and the like. See International Patent No. 9,206,154. Surfactants derived from other sugars, C ₁₂ ~C ₁₈ N-
N-alkoxy polyhydroxy fatty acid amides, such as (3-methoxypropyl) glucamide, are included. N
- N- hexyl C ₁₂ -C ₁₈ glucamides propyl it can be used for low sudsing. Usual C ₁₂ -C ₂₀ soaps can also be used. If high foaming properties are desired, branched C
It may be used ₁₂ -C ₁₆ soaps. Mixtures of anionic and nonionic surfactants are particularly useful. Other commonly useful surfactants are described in standard textbooks. Particularly preferred in the composition according to the invention are:
A mixed nonionic surfactant system comprising a short-chain first nonionic surfactant and a long-chain second nonionic surfactant is contained in an amount of 5 to 50% by weight. More preferably, the composition comprises from 10 to 40% by weight of the mixed nonionic surfactant, most preferably from 15 to 30% by weight. The total HLB value of the nonionic surfactant system is preferably 2-16, more preferably 8-14, most preferably 9-10. Further, the ratio of the first surfactant and the second surfactant is preferably 1:10 to 10: 1, more preferably 1: 3 to 3: 1,
Most preferably about 1: 1.

Bleaching agents are also useful in the method of the present invention for treating bleachable soils. The bleaching agent may be incorporated into the above composition or may be added as a separate bleaching composition. Peroxide bleach is most preferred.

The detergent composition of the present invention can be used for various known ordinary washing methods. However, preferred washing methods include applying the detergent composition to stains and stains, placing an absorbent layer adjacent to the stains and stains of the fabric, and applying heat to the stains and stains of the fabric. Applying pressure or heat and pressure to cause some or all of the dirt and stains to be absorbed by the absorbent layer. An even more preferred washing method comprises the following steps (a) and (b).

(A) to apply the detergent composition to the stains and stains and to transfer the absorbent layer adjacent to the stains and stains of the woven fabric and some or all of the stains and stains to the absorbent layer; (B) applying a hydrophilic solvent or water to the stained or stained portion of the woven fabric to remove the stain on the woven fabric; A process in which an absorbent layer is placed adjacent to a stained portion and heat is applied to the stained or stained portion of the woven fabric. Heat or pressure, or both, can be applied by any means, but most preferably with a hand-held tool such as an airo. Conventional irons having a solid hot plate in the body are highly preferred as hand-held tools. The hot plate is most commonly heated by electrical means and may have means for adjusting the temperature. Iron or water or steam may be supplied. Most preferably, the absorbent layer is placed on a flat surface, such as an ironing board, and the soiled or stained fabric is spread flat over the absorbent layer in contact with the absorbent layer. By doing so, the iron can be easily applied to the stained or stained portions of the textile, and the stains or stains can be completely or substantially completely transferred to the absorbent layer.

Ironing is preferably carried out at a temperature of 40-200 ° C, more preferably 40-180 ° C.

Another tool for applying heat or pressure is a heat roller or any other heat applicator. The roller or applicator may be equipped with a detergent composition supply means.

Suitable applicators include European Patent Application A
Includes a steam iron with a suction brush as disclosed in US Pat. No. 0 493 348, and a thermoelectric applicator as disclosed in US Patent Application No. A-0 552 397. Steam irons with atomizers, such as those disclosed in EP-A-0 629 736, are also suitable. According to this specification, the detergent composition may be stored in an iron and delivered directly to the fabric by a sprayer.

While not wishing to be bound by theory, it is believed that hydrophobic dirt may first become hydrophilic by applying the detergent composition while gently rubbing in some cases. Grease stains containing hydroxyl groups are deprotonated at high pH, and therefore more readily solubilized in detergent solutions. High pH
This also causes sol peptization of certain food stains. Dirt is effectively destroyed and easier to remove. High
The benefit of pH can be particularly observed when another composition containing bleaching species is applied to the soil before or after application of the detergent composition. In fact, conventional peroxide bleaching techniques increase reactivity with pH. Thereafter, water is applied again to the dirt while rubbing lightly in some cases. By placing the soiled woven fabric adjacent to the absorbent layer, the soil is removed. The stain rendered hydrophilic by this treatment moves to the absorbent layer.

A woven fabric is any loose object made from fabric, including clothing such as shirts, blouses, socks, skirts, pants, jackets, underwear, and the like, and tablecloths, towels, curtains, and the like. The definition of woven fabric used in the present invention does not include carpets and similar floor coverings.

The knitted fabric used in the present invention is usually made by weaving or knitting. Synthetic fibers (eg, polyester, polyamide, etc.), and natural fibers from plants (eg, cotton, hemp) and natural fibers from animals (eg, wool, Many different fibers can be used, including angora, silk). A mixture of various fibers is also commonly used.

Examples Example 1 Example 2 Example 3 Example 4 Shersol 20 20 20 20 Dovanol 25EO3 5.55-Alkyl Sulfate C8AS 5-55 Dehydrol C8EO4-5-5 Sodium hydroxide 11 1--Monoethanolamine--33 Water 69 69 67 67 In the examples, Shelsol was 5% aliphatic C7 ester.
A mixture of C8-C11 isoparaffins.

Dehydrol is a fatty alcohol polyglycol ether octyl with an average degree of ethoxylation of 4 sold by Henkel.

Dovananol R is an ethoxylated primary alcohol with an average degree of ethoxylation of 3 sold by Shell.

C8AS, which is an alkyl sulfate, has an average of 8 carbon atoms in the alkyl chain.

These emulsions were prepared by mixing the components in the following order. First, Dovanol 25E3 and Schelsol solvent were mixed. Thereafter, a short-chain surfactant (alkyl sulfate or dehydrol) was added, followed by an aqueous solution of sodium hydroxide. Mixing was continued until a stable oil-in-water emulsion was formed.

Example 5 Example 6 Example 7 Limonene 18.3 18.3 23.5 HLAS 10.5--Dehydrol C8EO4 6 16.5-Alkyl sulfate C8A5--7.8 Monoethanolamine 3 35.8 Butyl carbitol 10 10 11.7 Oleic acid--6 Water Remaining Remaining Remaining Remaining Example 8 Example 9 Example 10 Example 11 Dodecane 22 48.2 − − Hexadecane − − 10 − Tridecane − − − 20 C14 to 15EO1 5.5 14.8 10 − C12 to 15EO3 − − − 5 C9 to 11EO6 22 34.2 7.5 − C8EO4 − − 5 Sodium hydroxide 1 1 1 1 butyl carbitol - 0.8 - - with water balance balance balance balance example 11, a grid tetrazole is tridecane, Isopar K, a mixture of terpene hydrocarbons Guridokku a C ₁₀ -C ₁₂ isoparaffin hydrocarbons exon 66-2, Griddol 100, a mixture of Gridock's terpene hydrocarbons, and Dow's emulsion, an emulsion of terpene citrate and water Over door 2000, in was replaced.

Example 12 Example 13 Shersol 20 20 Dovanol 25-3 (C12EO3) 0.2 5.2 C8 alkyl sulfate 55 C10 alkyl sulfate 0.2 0.2 Dehydrol 04 (C8EO4) 5-Sodium hydroxide 0.3 0.3 DTPMP 0.04 0.04 Dovanol 90 0.3 0.3 Hydrogen peroxide 1.4 1.4 Water Remainder Remainder PH = 9 PH = 9 DTPMP is Monsanto's quest 2060 (diethylenetriaminepentamethylenephosphoric acid).

A set of polycotton cloth (50 mm square) was soiled with makeup cosmetics, chocolate sauce, and tomato sauce. Remove this dirt from normal room temperature (about 20 ° C, 60%
RH) for a day. Each stained cloth was washed in the following manner.

1. The soiled area was placed directly on the absorbent paper (the paper used was the absorbent core of the diaper).

2. 1 ml of the composition of Example 1 was applied to the soiled portion.

3. Brush the stained area with a regular electric toothbrush for 10 seconds (toothbrush used, brown dental d3
Was for normal use in daily tooth care).

4. Steps 2 and 3 were repeated once.

5. 1 ml of distilled water was applied to the stained area, and pressure and heat were applied for 10 seconds using an iron set at a temperature of 120 ° C. Common ironing pressures, commonly used to smooth fabric wrinkles, were used.

6. Step 5 was repeated using another 2 ml of distilled water.

7. The cloth was dried and stretched.

Using the compositions of Examples 2 to 13 instead of the composition of Example 1,
This cleaning procedure was repeated on the soiled cloth.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-7-310099 (JP, A) JP-A-7-292392 (JP, A) JP-A-7-292390 (JP, A) JP-A-5-292390 194990 (JP, A) Table 7-507094 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 17/08 C11D 1/37 C11D 1/825 C11D 1/83 C11D 3/43 WPIDS (STN)

Claims (12)

(57) [Claims] 1. A cleaning composition which is an oil-in-water or water-in-oil emulsion or solution, comprising: (i) a non-aqueous hydrophobic solvent; and (ii) a C6-C11 alkyl chain in length. (Iii) one anionic or nonionic surfactant, (iii) a second anionic or nonionic surfactant having an alkyl chain of C12 or longer, (iv) potassium hydroxide, sodium hydroxide, hydroxide Ammonium, ammonium silicate, sodium bicarbonate,
0.1 to 10% by weight of an alkali substance selected from the group consisting of borax, monoethanolamine borate, monoethanolamine, triethanolamine, and a mixture thereof
And a pH of at least 8. 2. The cleaning composition according to claim 1, further comprising 5 to 95% by weight of water. 3. The cleaning composition according to claim 1, wherein the pH of the 1% solution obtained by dissolving in distilled water is at least 9, preferably at least 10. 4. The hydrogen bond parameter dH of Hansen is 18
2. A non-aqueous hydrophobic solvent having a (joule / cm < ³ >) less than ^0.5 and a Hansen polarity parameter dP of less than 8 (joule / cm < ³ >) ^{0.5, comprising 3} to 90% by weight.
3. The cleaning composition according to item 1. 5. The cleaning composition according to claim 4, wherein the solvent comprises a hydrocarbon having a flash point of 70 ° C. or higher, an initial boiling point higher than 145 ° C., and a freezing point lower than 20 ° C. . 6. The cleaning composition according to claim 5, wherein the solvent is selected from the group consisting of C ₁₀ -C ₁₈ linear or branched alkanes, terpenes, and mixtures thereof. 7. The second surfactant is a C ₁₂ -C ₁₆ fatty alcohol polyglycol ether and has an ethoxylation degree of 2
The cleaning composition according to claim 1, wherein the cleaning composition is selected from the group consisting of ethoxylated primary alcohols of Nos. 1 to 7. 8. A nonionic surfactant system comprising a first surfactant and a second surfactant and having a total HLB value of 2 to 16 comprising 5 to 50% by weight. 3. The cleaning composition according to item 1. 9. The cleaning composition according to claim 8, wherein the molar ratio of the first surfactant to the second surfactant is from 1:10 to 10: 1. 10. A method for treating stains and stains on a woven fabric, comprising the following steps. The detergent composition according to any one of the preceding claims,
Applying dirt and stains, placing an absorbent layer adjacent to the stains and stains on the woven fabric, and applying heat, pressure, or heat and pressure to the stains and stains on the textiles The process of absorbing some or all of the stains into the absorbent layer. 11. The method according to claim 10, comprising the following steps (a) and (b). (A) to apply the detergent composition to the stains and stains and to transfer the absorbent layer adjacent to the stains and stains of the woven fabric and some or all of the stains and stains to the absorbent layer; And (b) applying a hydrophilic solvent or water to the stained or stained portion of the woven fabric, and forming an absorbent layer adjacent to the stained or stained portion of the woven fabric. And placing a second means to transfer some or all of the dirt and stains to the absorbent layer. 12. A second means for transferring some or all of the stains and stains to the absorbent layer, using a hand-held iron to apply heat to the stains and stains of the fabric. 12. The method of claim 11, comprising the step of applying.