CN100540644C - Anti-soiling detergent composition - Google Patents

Abstract

The invention provides a kind of fabulous detergency that has, give the clean surface with the anti-effect of staining, keep effectively and anti-stain effect, have fabulous package stability, and can be used in toilet, pond, bathing pool or other humidities, hard lip-deep anti-soiling detergent composition.This anti-soiling detergent composition comprises polyetheramides modification organopolysiloxane and/or the amino modified organopolysiloxane of (A) 0.05% mass ratio to 10% mass ratio, (B) 0.1% mass ratio is to the special surface promoting agent of 30% mass ratio, (C) 0.1% mass ratio is to the metal chelator of 20% mass ratio, and (D) water.

Description

Anti-soiling detergent composition

Technical field

The present invention relates to a kind ofly except showing good detergency, also have fabulous package stability and on the clean surface, keep the anti-anti-soiling detergent composition of effect that stains.

Domain background

According to the difference in the place of using, dissimilar dirts is deposited on the rigid surface in bathroom, wash stand, toilet and other moist places.For example, the dirt in the bathroom comprises protein and other nitrogenous compounds, fatty acid metal salt or its analogue; Dirt in the toilet comprise urinary calculi throw out, dirt, urine and other types based on ight soil movement, or the like.In addition, these rigid surfaces have experienced repeatedly dry after continuing to touch tap water, and silicate scale that is come by tap water or carbonate deposit are by the localized rich precipitation that contracts like this, and generation is commonly referred to as the dirt of " water stain " or " water dirt ".Especially, water closet pan, washbowl and other ceramic equipment, and the glass surface in mirror and other zones, toilet all is hydrophilic, so often covered by the water dirt.

If the continuous accumulation of these water dirts surpasses the long time, the water dirt will be firmly bonded on the hard surface, not only can make to remove and become more and more difficult, and the one-tenth branch of water dirt becomes the breeding ground of the dirt of fungi and bacterium and other types gradually, will occur the problem of health aspect then.Initial water dirt can be removed relatively like a cork by careful cleaning, but present situation is because the cleaning operation mode of flowing water type makes that the frequency of cleaning is tending towards reducing.

Consider these situations, will there be the demand that has the sanitising agent of the sedimentary ability of dirt (the anti-effect of staining) that reduces water dirt and other types to a kind of, and, when cleaning, give the cleaning rear surface with anti-soiled effect, begun development to prevent the sanitising agent that the water dirt sticks on the rigid surface securely.Proposed on the surface after the cleaning, to form film and provide the sanitising agent of anti-soiled ability to stain the product of effect and give sanitising agent as having to resist like this by special organopolysiloxane is attached in the cleanser compositions.

The anti-example that stains effect and comprise the sanitising agent of such organopolysiloxane that is combined with that has been disclosed comprises: comprise amino modified organopolysiloxane and nonionogenic tenside and be applicable to the cleaning bathtub; suppress the sedimentary redeposition that water forms; and the composition (reference that the material of bathtub is had provide protection; as; Japanese Unexamined Patent Publication No S51-83608); and comprise special organopolysiloxane and the cleanser compositions (reference of delustring and surface protection is provided for bathroom fittings; as, Japanese Unexamined Patent Publication No H3-197596).Decontamination that is applicable to rigid surface that is disclosed equally and antimicrobial clean cleanser compositions and comprise special cats product, the cation radical sterilant, with hydrophilic organopolysiloxane and have anti-stain effect and antibacterial effect (with reference to, as, Japanese Unexamined Patent Publication No 2000-198999)

The cleanser compositions that Japanese Patent Application Publication is disclosed for S51-83608 number and H3-197596 number has fabulous anti-effect and the soil release characteristics of staining for precipitation that is formed by water and dirt, but it does not relate to the anti-effect of staining to the water dirt, also stain effect and package stability without any disclosing to relate to keep to resist, these in fact all are very important.Dirt has the good anti-effect of staining to the cleanser compositions that Japanese Patent Application Publication is disclosed for 2000-198999 number for water.

The description of invention

Do not disclose or recognize demand in the prior art for the details of package stability or detergency, and satisfy simultaneously and relate to the enhanced detergency, the good anti-effect of staining, and the sanitising agent of all demands of suitable package stability is still waiting further research and development.

Therefore just exist the demand of a kind of sanitising agent of exploitation, even this sanitising agent except in toilet, washroom, bathroom with other places of repeating to contact tap water all show good detergency, also show good anti-effect and the package stability of staining.

One object of the present invention is to provide except good detergency is arranged, and also makes the surface after the cleaning possess the good anti-effect of staining, and keeps this and anti-ly stains effect, and show the cleanser compositions of good storing stability.Clearer and more definite, its objective is be to provide a kind of can be at those for example plastics, stainless steel, porcelain, ceramic tile, glasswork, ceramic, grouan/terrazzo, and other help cleaning and anti-soiled on the rigid surface of the moist local lithotome of toilet, washroom, bathroom and other etc.; Especially, be used for cleaning and resist and stain those for example anti-soiled cleanser compositions of the water dirt on the rigid surfaces such as ceramic tile, glass and ceramic of toilet and washroom.

The contriver has been found that, except good detergency is arranged, also on the surface after the cleaning, have anti-effect, this anti-effect of staining of maintenance of staining, and show the anti-soiling detergent composition of good storing stability, can pass through polyetheramides modification organopolysiloxane and/or amino modified organopolysiloxane, tensio-active agent, metal chelator and water mix and obtain.The present invention is perfect on the basis of this discovery.

Particularly, anti-soiling detergent composition provided by the invention comprises:

(A) 0.05% mass ratio is to the polyetheramides modification organopolysiloxane and/or the amino modified organopolysiloxane of 10% mass ratio;

(B) 0.1% mass ratio is at least a tensio-active agent of choosing from nonionogenic tenside, amphoterics and cats product of 30% mass ratio;

(C) 0.1% mass ratio is to the metal chelator of 20% mass ratio; And

(D) water.

Of the present invention resisting dyed the thing cleanser compositions except comprising from (A) to (D) composition, can also comprise the thickening material of (E) 0.01% mass ratio to 5% mass ratio.

Of the present invention resisting dyed the thing cleanser compositions except comprising composition recited above, can further include the water-soluble solvent of (F) 0.1% mass ratio to 20% mass ratio.

Of the present inventionly anti-dye the thing cleanser compositions and comprise component (A), (B), (C) with (D) as its basal component.

Employed in the present invention composition (A) is polyetheramides modification organopolysiloxane and/or amino modified organopolysiloxane, and the purpose of adding it is in order to give surface after the cleaning with anti-soiled effect.

Polyetheramides modification organopolysiloxane among the present invention in the employed composition (A) can be a band polyoxyethylene group and by the organopolysiloxane of the represented amido of an average group accepted way of doing sth (1).

R ¹ _aR ² _bQ ¹ _cQ ² _dSiO _{(4-a-b-c-d)/2} (1)

In an average group accepted way of doing sth (1), a and d are 0 or positive number; B and c are positive numbers, make 1.9≤a+b+c+d≤2.2; R ¹Be hydrogen atom, hydroxyl, or that replace or unsubstituted monovalence alkyl with 1 to 6 carbon atom.The particular example of such monovalence alkyl comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl and other alkyl; Phenyl, tolyl, xylyl and other aryl; Phenmethyl, styroyl and other aralkyl; And the 3-chloropropyl, 3,3,3-trifluoro propyl and other halo alkyl.

In formula (1), R ²Be the monovalence alkyl with 1 to 6 carbon atom, the particular example of such monovalence alkyl comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, vinyl, and phenyl.

In formula (1), Q ¹It is the divalent organic group that contains by the represented amido in general formula (2) or (3).

[chemical formula 4]

In general formula (2) and (3), R ³And R ⁵Be the bivalent hydrocarbon radical that has 2 to 18 carbon atoms, the particular example of such bivalent hydrocarbon radical comprises vinyl, propenyl, butenyl, isobutenyl, pentamethylene base, octamethylene, decamethylene, dodecyl, and cyclohexyl.In the formula, R ⁴And R ⁶Be hydrogen atom or the monovalence alkyl that has 1 to 6 carbon atom, the particular example of such monovalence alkyl comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl and other alkyl; Phenyl, tolyl, xylyl and other aryl; Phenmethyl, styroyl and other aralkyl; And the 3-chloropropyl, 3,3,3-trifluoro propyl and other halo alkyl.

In general formula (2) and (3), X is any monovalent organic radical group by general formula 4 expressions,

-R ⁷ _eO _f-(C ₂H ₄O) _g-(R ⁸O) _h-Y (4)

Wherein e and f respectively do for oneself 0 or 1, and g and h be zero or 1 or than 1 bigger positive integer.R ⁷Be the bivalent hydrocarbon radical that has 2 to 18 carbon atoms, the particular example of such bivalent hydrocarbon radical comprises vinyl, propenyl, butenyl, isobutenyl, pentamethylene base, octamethylene, decamethylene, dodecyl, and cyclohexyl.R ⁸Be the bivalent hydrocarbon radical that has 3 to 10 carbon atoms, the particular example of such bivalent hydrocarbon radical comprises propenyl, sec.-propyl, butenyl, and isobutenyl.Y is selected from hydrogen atom, alkyl, and acyl group, and the group among the isocyanato, wherein, alkyl is the monovalence alkyl that has 1 to 18 carbon atom, the example comprises methyl, ethyl, propyl group, ethanoyl, and propionyl.

In formula (1), Q ²Be to contain by the represented any monovalent organic radical group of containing polyoxyalkylenes of general formula (5)

-R ⁹ _iO _j-(C ₂H ₄O) _k-(R ¹⁰O) _m-Z (5)

Wherein i and j respectively do for oneself 0 or 1; K be 1 or than 1 bigger positive integer; M be zero or 1 or than 1 bigger positive number; R ⁹Be the bivalent hydrocarbon radical that has 2 to 18 carbon atoms, the particular example of such bivalent hydrocarbon radical comprises vinyl, propenyl, butenyl, isobutenyl, pentamethylene base, octamethylene, decamethylene, dodecyl, and cyclohexyl.R ¹⁰Be the bivalent hydrocarbon radical that has 3 to 10 carbon atoms, the particular example of such bivalent hydrocarbon radical comprises propenyl, sec.-propyl, butenyl, and isobutenyl.Z is selected from hydrogen atom, alkyl, and acyl group, and the group among the isocyanato, wherein, alkyl is the monovalence alkyl that has 1 to 18 carbon atom, and the example comprises methyl, and ethyl, propyl group, ethanoyl, and propionyl, d and g can not be zero simultaneously.

The molecular structural formula of polyetheramides modification organopolysiloxane not only can be linear, also can be side chain, and is ring-like, or netted.

The such amido and the polyoxyethylene groups of polyetheramides modification organopolysiloxane can be, for example, and by the expressed compound of following general formula.

[chemical formula 5]

(R in the formula, ¹¹For-(CH ₂) ₃NHCO (CH ₂) _qO (CH ₂CH ₂O) _r(CH ₂) _sH, wherein, n is 10 to 1000, and p is 1 to 100, and q is 1 to 100, and r is 2 to 20, s is 0 to 20.)

[chemical formula 6]

(R in the formula, ¹²For-(CH ₂) ₃NH (CH ₂) ₂NHCO (CH ₂) _wH, R ¹³For-(CH ₂) ₃O (CH ₂CH ₂O) _x(CH ₂CHCH ₃O) _y(CH ₂) _zH, t are 10 to 1000, and u is 1 to 100, and v is 1 to 100, and w is 1 to 20, and x is 2 to 20, and y is 0 to 20, and z is 0 to 20.)

[chemical formula 7]

(R in the formula, ^C1For-(CH ₂) ₃NHCO (CH ₂) _M4O _M5(CH ₂CH ₂O) _M6(CH ₂CHCH ₃O) _M7(CH ₂) _M8H; R ^C2For-(CH ₂) ₃O (CH ₂CH ₂O) _M9(CH ₂CHCH ₃O) _M10(CH ₂) _M11D ¹E ¹And E ²That can be the same or different is R ^C1, R ^C2,-OH, or (CH ₂) _P1H, preferably-CH ₃D ¹For-H or-COCH ₃M1 is 10 to 1000; M2 is 1 to 100; M3 is 0 to 100; M4 is 1 to 100; M5 is 0 or 1; M6 is 0 to 20; M7 is 0 to 20; M8 is 0 to 20; M9 is 2 to 20; M10 is 0 to 20; M11 is 0 to 20; P1 is 0 to 20; And m3 and m6 can not be 0 simultaneously.)

[chemical formula 8]

(R in the formula, ^C3For-(CH ₂) ₃NH (CH ₂) ₂NHCO (CH ₂) _M15O _M16(CH ₂CH ₂O) _M17(CH ₂CHCH ₃O) _M18(CH ₂) _M19H; R ^C4For-(CH ₂) ₃O (CH ₂CH ₃O) _M20(CH ₂CHCH ₃O) _M21(CH ₂) _M22D ²E ³And E ⁴That can be the same or different is R ^C3, R ^C4,-OH, or (CH ₂) _P2H, preferably-CH ₃D ²For-H or-COCH ₃M12 is 10 to 1000; M13 is 1 to 100; M14 is 0 to 100; M15 is 1 to 100; M16 is 0 or 1; M17 is 0 to 20; M18 is 0 to 20; M19 is 0 to 20; M20 is 2 to 20; M21 is 0 to 20; M22 is 0 to 20; P2 is 0 to 20; And m14 and m17 can not be 0 simultaneously.)

Can be used as special example and be cited just like the compound of the chemical formula shown in following.

[chemical formula 9]

(G in the formula, ¹Be (CH ₂) ₃NHCOCH ₂O (CH ₂CH ₂O) ₄C ₁₂H ₂₅)

[Chemical formula 1 0]

(G in the formula, ²Be (CH ₂) ₃NH (CH ₂) ₂NHCO (CH ₂) ₃O (CH ₂CH ₂O) ₁₀C ₁₂H ₂₅)

[Chemical formula 1 1]

(G in the formula, ³Be (CH ₂) ₃O (CH ₂CH ₂O) ₁₀(CH ₂CHCH ₃O) ₁₀H, G ⁴Be (CH ₂) ₃NHCO (CH ₂) ₃O (CH ₂CH ₂O) ₆C ₁₀H ₂₁)

[Chemical formula 1 2]

(G in the formula, ⁵Be (CH ₂) ₃O (CH ₂CH ₂O) ₁₀COCH ₃, G ⁶Be (CH ₂) ₃NH (CH ₂) ₂NHCOC ₁₆H ₃₃)

Polyetheramides modification organopolysiloxane in the employed in the present invention component (A) also can be to have amino, polyoxyethylene groups and by the organopolysiloxane of the represented amido of an average group accepted way of doing sth (6).

R ¹ _aR ² _bQ ¹ _cQ ² _dQ ³ _e1SiO _{(4-a-b-c-d-e1)/2} (6)

In formula (6), a and b are zero or positive number; B, c and e1 are positive number, make 1.9≤a+b+c+d+e1≤2.2; R ¹Be hydrogen atom, hydroxyl, or that replace or unsubstituted monovalence alkyl with 1 to 6 carbon atom.The particular example of such monovalence alkyl comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl and other alkyl; Phenyl, tolyl, xylyl and other aryl; Phenmethyl, styroyl and other aralkyl; And the 3-chloropropyl, 3,3,3-trifluoro propyl and other halo alkyl.

In formula (6), R ²Be the monovalence alkyl with 1 to 6 carbon atom, the particular example of such monovalence alkyl comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, vinyl, and phenyl.

In formula (6), Q ¹It is the divalent organic group that contains by the represented amido in general formula (2) or (3).

[Chemical formula 1 3]

In general formula (2) and (3), R ³And R ⁵Be the bivalent hydrocarbon radical that has 2 to 18 carbon atoms, the particular example of such bivalent hydrocarbon radical comprises vinyl, propenyl, butenyl, isobutenyl, pentamethylene base, octamethylene, decamethylene, dodecyl, and cyclohexyl.In the formula, R ⁴And R ⁶Be hydrogen atom or the monovalence alkyl that has 1 to 6 carbon atom, the particular example of such monovalence alkyl comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl and other alkyl; Phenyl, tolyl, xylyl and other aryl; Phenmethyl, styroyl and other aralkyl; And the 3-chloropropyl, 3,3,3-trifluoro propyl and other halo alkyl.

In general formula (2) and (3), X is any monovalent organic radical group by general formula 4 expressions,

-R ⁷ _eO _f-(C ₂H ₄O) _g-(R ⁸O) _h-Y (4)

Wherein, e and f respectively do for oneself 0 or 1, g and h be zero or 1 or than 1 bigger positive integer.R ⁷Be the bivalent hydrocarbon radical that has 2 to 18 carbon atoms, the particular example of such bivalent hydrocarbon radical comprises vinyl, propenyl, butenyl, isobutenyl, pentamethylene base, octamethylene, decamethylene, dodecyl, and cyclohexyl.R ⁸Be the bivalent hydrocarbon radical that has 3 to 10 carbon atoms, the particular example of such bivalent hydrocarbon radical comprises propenyl, sec.-propyl, butenyl, and isobutenyl.Y is selected from hydrogen atom, alkyl, and acyl group, and the group among the isocyano-, the example comprises methyl, ethyl, propyl group, ethanoyl, and propionyl.

In formula (6), Q ²Be to contain by the represented any monovalent organic radical group of containing polyoxyalkylenes of general formula (5)

-R ⁹ _iO _j-(C ₂H ₄O) _k-(R ¹⁰O) _m-Z (5)

Wherein, i and j respectively do for oneself 0 or 1; K be 1 or than 1 bigger positive integer; M be zero or 1 or than 1 bigger positive integer; R ⁹Be the bivalent hydrocarbon radical that has 2 to 18 carbon atoms, the particular example of such bivalent hydrocarbon radical comprises vinyl, propenyl, butenyl, isobutenyl, pentamethylene base, octamethylene, decamethylene, dodecyl, and cyclohexyl.R ¹⁰Be the bivalent hydrocarbon radical that has 3 to 10 carbon atoms, the particular example of such bivalent hydrocarbon radical comprises propenyl, sec.-propyl, butenyl, and isobutenyl; Z is selected from hydrogen atom, alkyl, and acyl group, and the group among the isocyano-, the example comprises methyl, ethyl, propyl group, ethanoyl, and propionyl.

In formula (6), Q ³It is the divalent organic group that contains by the represented amino in general formula (7) or (8).

[Chemical formula 1 4]

In general formula (7) and (8), from R ³To R ⁶All with above-described the same.

Owing to consider to relate to and anti-ly stain the continuous capability of effect, the relatively more suitable scope of total amount that is included in general formula (7) in the polyetheramides modification organopolysiloxane molecule or first and second amino in (8) be from 0.15% (quality) to 0.45% (quality).When total content of first and second amino is less than 0.15% (quality), the anti-effect of staining will be because of on the surface that lacks after polyetheramides modification organopolysiloxane is adsorbed in cleaning and make that to keep ability relatively poor, otherwise, when total content of first and second amino during greater than 0.45% (quality), the storage capacity of said composition will be relatively poor.

The molecular structure of polyetheramides modification organopolysiloxane not only can be linear, also can be side chain, and is ring-like, or netted.

Such amido of polyetheramides modification organopolysiloxane, polyoxyethylene groups and and amino can be, for example, by the expressed compound of following general formula.

[Chemical formula 1 5]

(R in the formula, ¹⁴For-(CH ₂) ₃O (CH ₂CH ₂O) _N5(CH ₂CHCH ₃O) _N6(CH ₂) _N7D ³R ¹⁵For-(CH ₂) ₃NH ₂R ¹⁶For-(CH ₂) ₃NHCO (CH ₂) _N8O _N9(CH ₂CH ₂O) _N10(CH ₂CHCH ₃O) _N11(CH ₂) _N12H; E ⁵And E ⁶Can identical or also can be inequality be R ¹⁴, R ¹⁵, R ¹⁶,-OH, or-(CH ₂) _P3H, and comparative optimization is-CH ₃D ³For-H or-COCH ₃N1 is 10 to 1000; N2 is 0 to 100; N3 is 1 to 100; N4 is 1 to 100; N5 is 2 or 20; N6 is 0 to 20; N7 is 0 to 20; N8 is 1 to 100; N9 is 0 or 1; N10 is 0 to 20; N11 is 0 to 20; N12 is 0 to 20; P3 is 0 to 20; And n2 and n10 can not be 0 simultaneously.)

[Chemical formula 1 6]

(R in the formula, ¹⁷For-(CH ₂) ₃O (CH ₂CH ₂O) _N17(CH ₂CHCH ₃O) _N18(CH ₂) _N19D ⁴R ¹⁸For-(CH ₂) ₃NH (CH ₂) ₂NH ₂R ¹⁹For-(CH ₂) ₃NH (CH ₂) ₂NHCO (CH ₂) _N20O _N21(CH ₂CH ₂O) _N22(CH ₂CHCH ₃O) _N23(CH ₂) _N24H; E ⁷And E ⁸Can identical or also can be inequality be R ¹⁷, R ¹⁸, R ¹⁹,-OH, or-(CH ₂) _P4H, and comparative optimization is-CH ₃D ⁴For-H or-COCH ₃N13 is 10 to 1000; N14 is 0 to 100; N15 is 1 to 100; N16 is 1 to 100; N17 is 2 or 20; N18 is 0 to 20; N19 is 0 to 20; N20 is 1 or 100; N21 is 0 or 1; N22 is 0 to 20; N23 is 0 to 20; N24 is 0 to 20; P4 is 0 to 20; And n14 and n22 can not be 0 simultaneously.)

Can be used as special example and be cited just like the compound of the chemical formula shown in following.

[Chemical formula 1 7]

(G in the formula, ¹⁴For-(CH ₂) ₃O (CH ₂CH ₂O) ₅C ₁₂H ₂₅, G ¹⁵For-(CH ₂) ₃NH ₂, G ¹⁶For-(CH ₂) ₃NHCOCH ₂O (CH ₂CH ₂O) ₅C ₁₂H ₂₅)

[Chemical formula 1 8]

(G in the formula, ¹⁷For-(CH ₂) ₃O (CH ₂CH ₂O) ₁₀C ₁₀H ₂₁, G ¹⁸For-(CH ₂) ₃NH (CH ₂) ₂NH ₂, G ¹⁹For-(CH ₂) ₃NH (CH ₂) ₂NHCOCH ₂O (CH ₂CH ₂O) ₄C ₁₀H ₂₁)

Amino modified organopolysiloxane in the employed in the present invention component (A) is everybody commercial available amino modified organopolysiloxane known to general.It might be, for example, some methyl in the polydimethylsiloxane are selected to carry amino or the amino organic group that has replaced, as aminomethyl, aminoethyl, aminopropyl, ammonia butyl and other aminoalkyls, and the modified amido product of the organopolysiloxane that group replaced of at least one type in the aminoalkyl (substituting group that also can comprise other) that replaced of the aminopropyl that replaced of aminomethyl and other aminoalkyls.

In these, stain effect, preferably use by the represented compound of following general formula owing to consider relevant resisting.

[Chemical formula 1 9]

(in the formula, R ' and R " be bivalent hydrocarbon radical with 1 to 10 carbon atom, a1 be zero or 1 or than 1 bigger positive number, b1 be 1 or than 1 bigger positive number.)

In the superincumbent general formula, identical as described above group can be used as with the example of the bivalent hydrocarbon radical of 1 to 10 carbon atom and quotes.As component (A), is very suitable selection from the angle of package stability with polyetheramides modification organopolysiloxane.

The interpolation quantity of component (A) is selected between 0.05% to 10% in the mass percent scope with respect to the said composition total mass.If being less than 0.005% mass ratio, this quantity will produce the relatively poor anti-effect of staining; Economic benefit in fact can become very little and if addition is greater than 10% mass ratio will make the degree that anti-enhancing of staining effect will reach capacity.Owing to considering the reason of staining effect and package stability about anti-, the interpolation quantitative range of preferred ingredients (A) at 0.1% mass ratio between 8% mass ratio, owing to the problem of considering economic benefit make preferred scope at 0.1% mass ratio between 5% mass ratio.Component (A) can be separately or is used with the form of the binding substances of two or more compositions.

Among the present invention the interpolation of employed surface active agent composition (B) be for removing stick to cleaning on the rear surface dirt and solubilising as the polyetheramides modification organopolysiloxane of component (A) and/or the purpose of amino modified organopolysiloxane.

Has one type the tensio-active agent that tensio-active agent in nonionogenic tenside, amphoterics and the cats product is used as component (B) that is selected from least, this is to stain effect because consider relevant resisting, and this effect is controlled by component (A).

The example of such nonionogenic tenside comprises polyoxyalkylene alkyl, polyoxyalkylene alkenyl ether, polyoxyalkylene alkane phenyl ether, alkyl polyglucoside, fatty acid polyglycerol ester, sucrose fatty acid ester, and Marlamid.In the present invention, because consider the problem of relevant detergency, polyoxyalkylene alkyl preferably in these nonionogenic tensides, alkyl polyglucoside, and Marlamid, and when considering the problem of relevant economic benefit, polyoxyalkylene alkyl and alkyl polyglucoside become and are more preferably.

The example of amphoterics comprises the alkyl carboxyl trimethyl-glycine, the alkylthio trimethyl-glycine, the alkyl hydroxy thetine, the alkylamidoalkyl trimethyl-glycine, imidazolinium betaine, alkyl diamino ethyl glycine, dialkyl group diamino ethyl glycine, alkyl amine oxide, alkyl oxide amine oxide, and oxidized nicotinamide/amine.In the present invention, because consider the reason of relevant detergency, alkyl carboxyl trimethyl-glycine preferably in these amphotericses, alkylthio trimethyl-glycine, alkyl hydroxy thetine, the alkylamidoalkyl trimethyl-glycine, alkyl amine oxide, alkyl oxide amine oxide, and oxidized nicotinamide/amine, and considering under the situation that relates to economic benefit that alkylamidoalkyl trimethyl-glycine and alkyl amine oxide are more preferably.

The example of cats product comprises alkyltrimethylammonium salt, dialkyl group diformazan ammonium salt, alkyltrimethylammonium salt, alkyl-dimethyl ammonium hexanodioic acid, phenylmethane ammonium salt, benzethonium salts, pyridine (salt), imidazoline salt, and biguanide compound.The counter ion of these cats products are halide-ionss etc.In the present invention, because consider the reason of relevant sterilization idiocratic and economic benefit, preferably dialkyl group diformazan ammonium salt, alkyl-dimethyl ammonium hexanodioic acid, phenylmethane ammonium salt, benzethonium salts and biguanide compound in these cats products, and considering relevant anti-staining under the situation of effect, chlorination benzalkonium and chlorination dialkyl group dimethylammonium are more preferably.

These tensio-active agents can be separately or are used with the form of the binding substances of two or more compositions, and can be according to for the detergency of dirt, foam characteristic, cleaning characteristics, to the mildness of skin, the infringement of material, difficulty or ease and other performance quality of wiping are come appropriate selection and use.

The interpolation quantity of component (B) be selected from respect to the mass percent scope of said composition 0.1% to 30% between.If this quantity is less than 0.1% mass ratio, the detergency of component (A) and anti-stain effect and will be restricted; If add quantity greater than 30% mass ratio and be somebody's turn to do, the degree that the enhancing of detergency will reach capacity, and economic benefit will descend gradually.Owing to consider and relate to detergency, the interpolation quantitative range of preferred surfactants based on 1% mass ratio of the total mass of said composition between 30% mass ratio; After considering the reason that relates to economic benefit, preferred scope at 1% mass ratio between 15% mass ratio.

The example of sequestrant that is used for the present invention's component (C) comprises hydroxycarboxylic acid, aminocarboxylic acid, phosphoric acid, the acid of seeing, phosphono-carboxylic acids, water-soluble macromolecule polymkeric substance and their salt, and other compounds that can be dissolved in water and have sequestering power.They can be separately or use with the form of the binding substances of two or more compounds.The purpose of adding metal chelator is in order to obtain better detergency.

The example of hydroxycarboxylic acid comprises acetate, lipid acid, monochloracetic acid, oxalic acid, Succinic Acid, oxidation Succinic Acid, the carboxymethyl Succinic Acid, carboxymethyl oxidation Succinic Acid, oxyacetic acid, two sweet acid, lactic acid, tartrate, carboxymethyl tartrate, citric acid, oxysuccinic acid, glyconic acid, and their salt.

The example of aminocarboxylic acid comprises nitrilotriacetic acid(NTA), inferior nitrogen base oxalic acid, ethylenediamine tetraacetic acid (EDTA), diethylene triaminepentaacetic acid(DTPA), N-hydroxyethyl-ethylenediamine acetate, ethylenediamine tetrapropionic acid(EDTP) acetate, the methyl aminoacetic acid etheric acid, triethylenetetraaminehexaacetic acid, ethylene glycol bisthioglycolate ether diamine tetraacethyl, hydroxyethyliminodiacetic acid, hexanaphthene-1, the 2-ethylenediamine tetraacetic acid (EDTA), djenkolic acid, and their salt.

The example of phosphoric acid comprises ortho-phosphoric acid, tetra-sodium, tripolyphosphate, metaphosphoric acid, six poly-metaphosphoric acids, phytinic acid and other condensed phosphoric acids, and their salt.

The example of acid of seeing comprises ethyl-1, Jiao's 1-acid of seeing, ethyl-1,1,2-tripolyphosphate, 1-hydroxyethyl-1, Jiao's 1-acid of seeing, with and derivative, 1-hydroxyethyl-1,1,2-ethyl tripolyphosphate, ethyl-1,2-dicarboxyl-1, Jiao's 2-acid of seeing, the acid of seeing of ethyl hydroxyl, amino trimethylene methyl see acid and their salt.

The example of phosphono-carboxylic acids comprises 2-phosphono propyl group-1,2-dicarboxylic acid, 1-phosphono propyl group-2,3,4-tricarboxylic acid, Alpha-Methyl phosphonosuccinic acid, and their salt.

The example of water-soluble macromolecule polymkeric substance comprises polyacrylic acid, polymaleic acid, the multipolymer of vinylformic acid and toxilic acid, poly-equisetic acid, poly-Alpha-hydroxy vinylformic acid, polymethyl acrylic acid, and their salt.

These metal chelators can use with acid or the form that partly or entirely becomes salt.The example of such salt comprises the salt of potassium, sodium and other alkali metal; Monoethanolamine MEA BASF, diethanolamine, trolamine and other alkanol amine salts; And ammonium salt.

Since consider the influence that relates to environment, in these metal chelators, hydroxycarboxylic acid, aminocarboxylic acid and their an alkali metal salt, and alkanol amine salt is preferred; And when considering relevant economic benefit, more preferably hydroxycarboxylic acid, aminocarboxylic acid and their sodium salt.

The interpolation quantity of component (C) is selected in the scope of 20% mass ratio at 0.1% mass ratio with respect to said composition.If this amount is less than the effect of improving that 0.1% mass ratio will limit detergency; And if addition is greater than 20% mass ratio, the improving effect and will reach capacity of detergency, the package stability of composition will be very poor, and economic benefit will be lower.Owing to consider the problem of relevant detergency, the interpolation quantitative range of preferred metal chelator based on 1% mass ratio of the total mass of said composition between 20% mass ratio; And since consider the problem of relevant economic benefit after, preferred scope at 1% mass ratio between 15% mass ratio.

Purify waste water, deionized water, soft water, distilled water and tap water can be used as the example that is used for water of the present invention or component (D).The water of these types can be separately or is used with the form of the binding substances of two or more compositions.In these dissimilar centres,, preferably use tap water and deionized water owing to consider the factor of relevant economic benefit and package stability.

Refer to the summation of the extraneous water that is provided at this employed term " water ", and this water comprises the aqueous solution or the crystal water that derives from the composition of forming anti-soiling detergent composition of the present invention.The interpolation of this water makes the composition of whole anti-soiling detergent composition reach 100%.

In the present invention, also can add thickening material as component (E) to basal component (A) to (D) as required.Adding component (E) share more for anti-soiling detergent synthetics of the present invention is become by thickening effect; Especially, improve its operability at use spraying cleaning way or when on non-level surface, cleaning, and therefore improve the detergency on non-horizontal surface.

The example that can be used as the thickening material of component (E) use among the present invention comprises xanthan gum, carrageenin (carageenan), guar gum, Sudan Gum-arabic, Viscogum BE, alginate, the saccharan of carboxymethyl cellulose and other multiviscosisty, and carboxy vinyl polymer, cross linked polyacrylate, and their salt.In the present invention, owing to consider the problem of the stability of relevant composition, xanthan gum in the above-mentioned example and carboxy vinyl polymer are preferred.

The addition of component (E) is selected in the scope of 5% mass ratio at 0.01% mass ratio with respect to said composition.If this addition is less than 0.01% mass ratio, will produce the relatively poor anti-effect of staining; If this addition is greater than 5% mass ratio, composition will produce undue thickness, be difficult to handle, and economic benefit also can be very poor.Owing to consider the complexity that relates to operation, the addition scope of preferred thickening with respect to 0.05% mass ratio of said composition total mass between 2% mass ratio; After considering economic benefit, preferred addition scope at 0.05% mass ratio between 1% mass ratio.

In the present invention, also can in (D), add water miscible solvent to basal component (A) as required as component (F).The effect of component (F) is further to strengthen detergency, especially, and the detergency relevant with organic dirt.

Be water-soluble solvent below, or perhaps the example of component (F):

(1) alcohol is as ethanol, propyl alcohol, Virahol, butanols and other MHAs; Ethylene glycol, glycol ether, isoprene alcohol, propylene glycol and other alkyl alcohol; And glycerol, Polyglycerine, 1,3 butylene glycol and other polyhydroxy-alcohols

(2) glycol ether is as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, Glycol Monomethyl ether, the propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol one phenyl ether, the Diethylene Glycol monomethyl ether, Diethylene Glycol monoethyl ether, Diethylene Glycol monobutyl ether, the dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, triglycol monobutyl ether, tripropylene diethylene glycol dimethyl ether and other inferior hydrocarbyl ethers (, two) alkyl oxide

(3) Limonene, sobrerone, terpinolene, myrcene, terpinene, phenanthrene and other terpene base hydrocarbon solvents

These water miscible solvents can be separately or are used with the form of the binding substances of two or more compositions, and can be according to detergency to dirt, to the damage of material, the complexity of scouring, and the requirement of other aspect of performances comes appropriate selection and use.

In these water miscible solvents, owing to consider relevant detergency, preferably with the lower alcohol of 1 to 5 carbon atom, glycol ether and terpene base hydrocarbon solvent; And for considering relevant detergency, stability and water miscible reason, following solvent can be preferred: with the lower alcohol of 1 to 5 carbon atom, glycol ether, with terpene base hydrocarbon solvent, Glycol Monomethyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, and Limonene.

The interpolation quantity of component (F) is selected in the scope of 20% mass ratio at 0.1% mass ratio with respect to said composition.If this addition is less than 0.1% mass ratio, detergency will be restricted; If this addition is greater than 20% mass ratio, the enhancing of detergency will reach capacity, and economic benefit will descend, and the package stability of said composition will can be not satisfactory yet.Owing to consider and relate to detergency and package stability, the addition scope of preferred water-soluble solvent with respect to 1% mass ratio of said composition total mass between 15% mass ratio; After considering economic benefit, preferred addition scope with respect to 1% mass ratio of said composition total mass between 10% mass ratio.

The pH value that is suitable for the liquid storage of anti-soiling detergent composition of the present invention is adjusted between 5 to 9, considers without any disadvantageous effect at the material of cleaning of objects, and the security on biology and the environment, preferred pH value is 6 to 8.This pH value can be used the material that shows as alkalescence and show as the tart material and regulate

The examples of substances that can be used for regulating the alkalescence of pH value comprises sodium hydroxide, potassium hydroxide and other alkaline hydrated oxides; Yellow soda ash, salt of wormwood and other carbonate; Water glass, potassium silicate and other silicate; Monoethanolamine, diethanolamine and other amine; And ammonia.The tart examples of substances that can be used for regulating the pH value comprises hydrochloric acid, sulfuric acid and other mineral acid, and citric acid, acetic acid and other organic acid.

If be used as pH value conditioning agent with the corresponding organic acid of component (C), must consider that the interpolation ratio of component (C) can not exceed 0.1% mass ratio outside the scope of 20% mass ratio.

Only however entail dangers to object of the present invention, spices, dyestuff, pigment, sterilant, sanitas, or the like, also can be used as necessity product except above-mentioned component, be added in the anti-soiling detergent composition of the present invention.

Anti-soiling detergent synthetics of the present invention can be used for promoting in the cleaning and the decontamination that repeat to contact and be easy to form with tap water on the rigid surface of water dirt; Especially, on the rigid surface in toilet, toilet rack, bathroom or the like.The material of these clean surface comprises plastics, stainless steel, porcelain, ceramic tile, glasswork, ceramic, grouan/terrazzo, and other lithotomes.

Anti-soiling detergent synthetics of the present invention can be used as liquid storage or use in the degree of making dirty water or warm water dilution back according to clean surface.Staining under the situation of effect based on considering relevant detergency and resisting, the degree of dilution can be up to 50 times.

Use the example of the method that anti-soiling detergent synthetics of the present invention cleans as follows.

(1), is used for wiping and wash away hard surface then with anti-soiling detergent composition saturated sponge shape thing of the present invention or other similar things.

(2) on the clean surface, spray anti-soiling detergent synthetics of the present invention, clean flushing then with sponge or other similar things.

(3) on the clean surface, spray anti-soiling detergent synthetics of the present invention, allow to keep for some time, then flushing.

(4) under the situation of vertical surface, soak into anti-soiling detergent composition of the present invention with nonwoven fabric or other similar things, be attached on its surface, allow to keep for some time, then flushing.

(5) soak into this present invention's anti-soiling detergent composition with towel or duster, rub off the dirt, the surface is with wiping in the wet hair then.

To the present invention be carried out further detailed description by example and the comparative example relevant now, but the present invention is not limited to this with anti-soiling detergent synthetics of the present invention.

Example 1 to 28, comparative example 1 to 18

Different tests is carried out in anti-soiling detergent synthetics and the preparation of preparation as shown in form 1 to 8.The numerical value of relevant component refers to the mass percentage content of each component in the form.The pH value is by means of regulating on demand as pH value conditioning agents such as acetate, sulfuric acid or sodium hydroxide, and component (A) is to (F), pH value conditioning agent, and the summation of any constituent adds up to 100% mass ratio.In form 1 to 8, indicate the case of having used pH value conditioning agent with the circle symbol.

Thus obtained anti-soiling detergent synthetics by testing method and according to the hierarchy system that describes below come to as pH value, detergency, anti-ly stain effect, anti-ly stain the ability of keeping of effect and the test parameter of package stability is assessed, the result is as shown in form 1 to 8.

(1) pH value

PH value meter (pH value meter F-12, Horiba makes) is used to according to JIS Z-8808:1984 25 ℃ of pH values of measuring prepared anti-soiling detergent synthetics liquid storage down

(2) the detergency test 1: simulation toilet dirt

[preparing mimic toilet dirt]

0.5 gram lanolin is dissolved in 5 milliliters the chloroform, and the ethanol that adds 495 milliliters obtains ready ethanolic soln thus as dilution.Be dissolved in by ferric oxide and add this synthetic solution then in 500 milliliters the water and in ethanolic soln, obtain preparation 10 grams.Preparation is spread upon ceramic tile (SPKC-100/LOO with accurate 1 milliliter quantity; White; 10 centimetres x10 centimetre; INAX makes) on, sand paper (No. 12 have been used on the surface of this ceramic tile in advance; Scribble abrasive, Nippon produces) on vertical and horizontal rub back and forth ten times and change 20 circles with the formation circle roughening processing treatment mistake.The ceramic tile of smearing was toasted 1 hour down at 145 ℃, and cool to room temperature obtains test sample then.

[test method]

The liquid storage of each component is dropwise added on the test sample for 5 milliliters, under the help of detergency testing apparatus (making), wipe back and forth 15 times, finish the detergency test by trier Sangyo with sponge (4 centimetres x8 centimetre).Then test, test sample washed for 10 seconds with a certain amount of tap water, and is at room temperature dry then.The white content of experiment with measuring before and after test sample is determined the cleaning ratio with the formula shown in following.Use colour-difference meter (the CR-331 type is made by Minolta) to measure white content.

Cleaning ratio (%)=(white content before the white content one after the cleaning cleans)/(the post-depositional white content of presedimentary white content one dirt of dirt) x100

Use these cleaning rate values to finish evaluation thus based on following hierarchy system.

[hierarchy system]

⊙: 80% or higher cleaning ratio

Zero: 60% or higher cleaning ratio

△: 40% or higher cleaning ratio

*: the cleaning ratio is lower than 40%

(3) the detergency test 2: simulation soap dirt dirt

[preparing simulation soap dirt dirt]

By with 2.5 gram oleic acid, 2.5 gram trioleins, 0.25 gram white protein and 4.75 gram calcium stearates join in the chloroforms of 60 grams and obtain preparation.The exact quantity of preparation with 1 milliliter spread upon on the glass slide (7.6 centimetres x2.6 centimetre) equably.This glass slide at room temperature after the dried overnight as test sample.

[test method]

The liquid storage of each component dropwise is added on the test sample, and the Conradi rod scrub test sample of using tissue paper (Kim thieving paper, Crecia makes) to twine is then cleaned back and forth and is carried out the detergency test for 15 times.Then test, test sample washed for 10 seconds with a certain amount of tap water, and is at room temperature dry then.The quality of experiment with measuring before and after test sample, the cleaning ratio is determined by following formula.

Cleaning ratio (%)=(quality of sedimentary dirt before the quality of the dirt that the detergency test is disposed/detergency test) x100

Use these cleaning rate values to finish evaluation thus based on following hierarchy system.

[hierarchy system]

⊙: 80% or higher cleaning ratio

Zero: 60% or higher cleaning ratio

△: 40% or higher cleaning ratio

*: the cleaning ratio is lower than 40%

(4) the anti-effect test that stains

[test method]

Sponge (4 centimetres x8 centimetre) cleaning ceramic tile (SPKC-100/L00 with the liquid storage that contains 2 milliliters of each components; White; 10 centimetres x10 centimetre; INAX makes), washed for 20 seconds with a certain amount of tap water, at room temperature dry then, obtain test sample.With minim pipette five are dissolved in the 100 gram water by 1 gram ferric oxide and the drips of solution that obtains on the stain on the test sample, then with test sample at 105 ℃ of bakings 3 hours down, cool to room temperature then.Rub off the dirt from test sample with wet tissue paper (Kim thieving paper, Crecia makes), direct viewing is estimated clean effect.

[hierarchy system]

⊙: on five all positions, dab and remove dirt

Zero: on five all positions, firmly wipe dirt

△: on four positions, firmly wipe dirt

*: although firmly wiping, still residual on two or more positions have a dirt

(5) anti-test 1 of staining the effect continuous capability

[test method]

Test to determine to resist and stain the degree that effect can be kept in the application of reality, be included in the urinal that cleaned the shared toilet of men and women once in a day, water closet (Japanese type and west type), and lavatory basin.

In first day test, dip in the liquid storage of each component with sponge and clean urinal, water closet and lavatory basin, then the surface of cleaning with the flowing water flushing.Began not use in lasting six days any sanitising agent at second day, clean then only flushing from the teeth outwards with wet sponge.When the 7th day cleans, using the liquid storage of each composition with first day identical method, and the surface water flushing then that sponges down.

Use each composition liquid storage to clean one month (four cycles) by this way weekly continuously, after this on-test, direct viewing is by soiled regional one month (four cycles), based on the evaluation result of following hierarchy system.

[hierarchy system]

⊙: the clean surface was former as one month, few dirt deposition, and cleaning time reduces

Zero: a clean surface and a relatively not variation in the past in month, but a spot of dirt deposition is arranged once in a while

△: dirt was in the past more than one month

*: dirt was howed a lot than one month in the past

(6) anti-test 2 of staining the effect continuous capability

[test method]

Test to determine to resist and stain the degree that effect can be kept in the application of reality, be included in the urinal that cleaned the shared toilet of men and women once in a day, water closet (Japanese type and west type), and lavatory basin.

In first day test, dip in the liquid storage of each component with sponge and clean urinal, water closet and lavatory basin, then the surface of cleaning with the flowing water flushing.Began not use in lasting 13 days any sanitising agent at second day, clean then only flushing from the teeth outwards with wet sponge.When the 14th day cleans, using the liquid storage of each composition with first day identical method, and the surface water flushing then that sponges down.

Use the cleaning of each composition liquid storage whenever biweekly to carry out continuously one month (two cycles) by this way, after this test of beginning, one month (two cycles) of the scope that direct viewing is made dirty is based on the evaluation result of following hierarchy system.

[hierarchy system]

⊙: the clean surface was former as one month, few dirt deposition, and cleaning time reduces

Zero: a clean surface and a relatively not variation in the past in month, but a spot of dirt deposition is arranged once in a while

△: dirt was in the past more than one month

*: dirt was howed a lot than one month in the past

(7) storage stability test 1: high-temperature stability

[test method]

Each composition all is allowed to be placed on temperature and is set at 50 ℃ thermostat container (IS82 type; Yamato Scientific makes) in three months, directly observation whether precipitate, the appearance of colour-change or fractionation phenomenon.Based on estimating of following hierarchy system.

[hierarchy system]

⊙: in composition, do not have precipitation, colour-change or fractionation phenomenon to occur fully

Zero: in composition, have slight precipitation, colour-change or fractionation phenomenon to occur

△: in composition, can clearly see the appearance of precipitation, colour-change or fractionation phenomenon

*: in composition, observe significant precipitation, colour-change or fractionation phenomenon

(8) storage stability test 2: high-temperature stability

[test method]

Each composition all is placed on temperature and is set at-15 ℃ thermostat container (HRF-90P type; The Hoshizaki manufacturing) spends the night in, permit condensing, at room temperature make it then to thaw.With this process recirculation five times, from beginning to melt the situation of continuous eight hours direct viewing compositions.Based on estimating of following hierarchy system.

[hierarchy system]

⊙: after the condensing of 5 cycles/thaw cycle, in composition, observe the appearance of precipitation, colour-change or fractionation phenomenon

Zero: after the condensing of 4 cycles/thaw cycle, in composition, observe the appearance of precipitation, colour-change or fractionation phenomenon, but observe some precipitation, colour-change or fractionation phenomenon the 5th cycle period

△: after the condensing of 3 cycles/thaw cycle, in composition, observe the appearance of precipitation, colour-change or fractionation phenomenon, but observe some precipitation, colour-change or fractionation phenomenon the 4th cycle period

*: before the condensing of 3 cycles/thaw cycle, in composition, observe the appearance of precipitation, colour-change or fractionation phenomenon

The detail file of the composition of table 1 below to the table 8 are as follows.

* organopolysiloxane 1: polyetheramides modification organopolysiloxane is by following chemical formulation

[Chemical formula 2 0]

(in this chemical formula, G ⁷Be (CH ₂) ₃NHCOCH ₂O (CH ₂CH ₂O) ₄C ₁₂H ₂₅)

* organopolysiloxane 2: polyetheramides modification organopolysiloxane is by following chemical formulation

[Chemical formula 2 1]

(in this chemical formula, G ⁸Be (CH ₂) ₃NHCOCH ₂O (CH ₂CH ₂O) ₅C ₁₂H ₂₅)

* organopolysiloxane 3: polyetheramides modification organopolysiloxane is by following chemical formulation

[Chemical formula 2 2]

(in this chemical formula, G ⁹Be (CH ₂) ₃O (CH ₂CH ₂O) ₁₀C ₁₂H ₂₅, G ¹⁰Be (CH ₂) ₃NH ₂, G ¹¹Be (CH ₂) ₃NHCOCH ₂O (CH ₂CH ₂O) ₅C ₁₂H ₂₅)

* organopolysiloxane 4: polyetheramides modification organopolysiloxane is by following chemical formulation

[Chemical formula 2 3]

(in this chemical formula, G ¹²Be (CH ₂) ₃O (CH ₂CH ₂O) ₈C ₁₂H ₂₅, G ¹³Be (CH ₂) ₃NHCOCH ₂O (CH ₂CH ₂O) ₄C ₁₂H ₂₅)

* organopolysiloxane 5: amino modified organopolysiloxane

(the registrar name of an article: SF8417, Toray Dow Corning Silicone produces)

* organopolysiloxane 6: the modified polyether organopolysiloxane

(the registrar name of an article: KF-6011, Shin-Etsu Silicones produces)

* organopolysiloxane 7: polydimethylsiloxane

(the registrar name of an article: BY22-007, Toray Dow Corning Silicone produces)

* nonionogenic tenside 1: alkyl polyglucoside

(the registrar name of an article: 215CSUP, Japanese Cognis produces)

* nonionogenic tenside 2: Voranol EP 2001

(the registrar name of an article: Naroakty-ID70, Sanyo Chemical Manufacture)

* nonionogenic tenside 3: Voranol EP 2001

(the registrar name of an article: Lutensol TO8, BASF produces)

* amphoterics 1: alkyl amine group propane trimethyl-glycine

(the registrar name of an article: TegoBetain L10S, Goldschmidt produces)

* amphoterics 2: the alkyl amine group oxide compound

(the registrar name of an article: Barlox 12, Lonza produces)

* cats product 1: the benzalkonium muriate

(the registrar name of an article: Cation G-50, Sanyo Chemical Manufacture)

* cats product 2: didecyl dimethyl amine muriate

(the registrar name of an article: Bardac 2280, Lonza produces)

* anion surfactant 1: the alkyl oxide sodium sulfonate

(the registrar name of an article: Alscoap TH-330, Toho Chemical Manufacture)

* anion surfactant 2: sodium alkyl benzene sulfonate

(the registrar name of an article: Taycapower LN2450, Tayca produces)

* thickening material 1: carboxy vinyl polymer

(the registrar name of an article: Hiviswako 105, Wako purifying worker produces)

* thickening material 2: xanthan gum

(the registrar name of an article: Kelzan, Kelco produces)

[table 1]

[table 2]

[table 3]

[table 4]

[table 5]

[table 6]

[table 7]

[table 8]

Based on above result, the composition that can find example 1 to 28 is showing satisfied performance as detergency, anti-staining on the test subjects such as effect, the anti-ability of keeping of staining effect and package stability.By contrast, the composition of comparative example 1 to 6 lacks the polyetheramides modification organopolysiloxane and/or the amino modified organopolysiloxane of component (A), the content of component in the composition of comparative example 7 (A) is too low, shows the relatively poor and insufficient anti-effect of staining of keeping.The amount of the component (A) that comparative example 8 and 9 composition add shows relatively poor package stability greater than 10% mass ratio.

The tensio-active agent that lacks component (B) in the comparative example 10, the addition of the tensio-active agent of component in the comparative example 11 (B) very little, the low detergency that all shows, the relatively poor anti-effect of staining are kept ability and relatively poor package stability.The amount of the component of adding in the composition of comparative example 12 (B) is greater than 30% mass ratio, shows relatively poor package stability and low and insufficiently anti-ly stains effect and keep ability.In comparative example 13 and 14 the composition with anion surfactant as component (B), low and insufficiently anti-ly stain effect and keep ability.

Lack the metal chelator as component (C) in comparative example 15 and 16 the composition, the component of adding in the composition of comparative example 17 (C) shows relatively poor detergency very little.Find also that simultaneously the component of adding in the composition of comparative example 18 (C) shows relatively poor package stability greater than 20% mass ratio.

Example 7 to 11,12, and 26 to 28 composition with stain effect and keep mode identical in the ability test anti-, be used to clean the mirror in toilet, toilet rack and shop, office, shelter or the like the place, find that it shows enough detergencies and is also obtaining satisfied result aspect the anti-ability of keeping of staining effect.

Claims (22)

1. anti-soiling detergent composition comprises:

(A) 0.05% mass ratio is to the polyetheramides modification organopolysiloxane of 10% mass ratio;

(B) 0.1% mass ratio is to the tensio-active agent of at least a type of selecting from nonionogenic tenside, amphoterics and cats product of 30% mass ratio;

(C) 0.1% mass ratio is to the metal chelator of 20% mass ratio; And

(D) water.

2. according to the anti-soiling detergent composition of claim 1, except component (A) arrives (D), also comprise:

(E) 0.01% mass ratio is to the thickening material of 5% mass ratio.

3. according to the anti-soiling detergent composition of claim 1, except above component, also comprise:

(F) 0.1% mass ratio is to the water-soluble solvent of 20% mass ratio.

4. according to the anti-soiling detergent composition of claim 1, wherein, the polyetheramides modification organopolysiloxane of component (A) is the polyetheramides modification organopolysiloxane by an average group accepted way of doing sth (1) expression

R ¹ _aR ² _bQ ¹ _cQ ² _dSiO _{(4-a-b-c-d)/2} (1)

Wherein, a and d are zero or positive number; B, c is a positive number, makes 1.9≤a+b+c+d≤2.2; R ¹Be hydrogen atom, hydroxyl, or that replace or unsubstituted monovalence alkyl with 1 to 6 carbon atom; R ²It is monovalence alkyl with 1 to 6 carbon atom; Q ¹Be to contain by general formula (2) or (3) represented group

Wherein, R ³And R ⁵It is the bivalent hydrocarbon radical that has 2 to 18 carbon atoms; R ⁴And R ⁶Be hydrogen atom or the monovalence alkyl that has 1 to 6 carbon atom; X is by the represented group of general formula 4

-R ⁷ _eO _f-(C ₂H ₄O) _g-(R ⁸O) _h-Y (4)

Wherein, e and f respectively do for oneself 0 or 1; G and h be zero or 1 or than 1 bigger positive integer; R ⁷It is the bivalent hydrocarbon radical that has 2 to 18 carbon atoms; R ⁸It is the bivalent hydrocarbon radical that has 3 to 10 carbon atoms; Y is a hydrogen atom, has the monovalence alkyl of 1 to 18 carbon atom, acyl group, or isocyanate group; Q ²Be to contain by the represented group of general formula (5)

-R ⁹ _iO _j-(C ₂H ₄O) _k-(R ¹⁰O) _m-Z (5)

Wherein, i and j respectively do for oneself 0 or 1; K be 1 or than 1 bigger positive integer; M be zero or 1 or than 1 bigger positive integer; R ⁹It is the bivalent hydrocarbon radical that has 2 to 18 carbon atoms; R ¹⁰It is the bivalent hydrocarbon radical that has 3 to 10 carbon atoms; Z is selected from hydrogen atom, has the monovalence alkyl of 1 to 18 carbon atom, acyl group, or isocyanate group; Yet d and g can not be zero simultaneously.

5. according to the anti-soiling detergent composition of claim 1, wherein, the polyetheramides modification organopolysiloxane of component (A) is the polyetheramides modification organopolysiloxane by an average group accepted way of doing sth (6) expression

R ¹ _aR ² _bQ ¹ _cQ ² _dQ ³ _e1SiO _{(4-a-b-c-d-e1)/2} (6)

Wherein, a and d are zero or positive number; B, c and e1 are positive number, make 1.9≤a+b+c+d+e1≤2.2; R ¹Be hydrogen atom, hydroxyl, or that replace or unsubstituted monovalence alkyl with 1 to 6 carbon atom; R ²It is monovalence alkyl with 1 to 6 carbon atom; Q ¹Be to contain by general formula (2) or (3) represented group

Wherein, R ³And R ⁵It is the bivalent hydrocarbon radical that has 2 to 18 carbon atoms; R ⁴And R ⁶Be hydrogen atom or the monovalence alkyl that has 1 to 6 carbon atom; X is by the represented group of general formula 4

-R ⁷ _eO _f-(C ₂H ₄O) _g-(R ⁸O) _h-Y (4)

Wherein, e and f respectively do for oneself 0 or 1; G and h be zero or 1 or than 1 bigger positive integer; R ⁷It is the bivalent hydrocarbon radical that has 2 to 18 carbon atoms; R ⁸It is the bivalent hydrocarbon radical that has 3 to 10 carbon atoms; Y is a hydrogen atom, has the monovalence alkyl of 1 to 18 carbon atom, acyl group, or isocyanate group; Q ²Be to contain by the represented group of general formula (5)

-R ⁹ _iO _j-(C ₂H ₄O) _k-(R ¹⁰O) _m-Z (5)

Wherein, i and j respectively do for oneself 0 or 1; K be 1 or than 1 bigger positive integer; M be zero or 1 or than 1 bigger positive integer; R ⁹It is the bivalent hydrocarbon radical that has 2 to 18 carbon atoms; R ¹⁰It is the bivalent hydrocarbon radical that has 3 to 10 carbon atoms; Z is selected from hydrogen atom, has the monovalence alkyl of 1 to 18 carbon atom, acyl group, or isocyanate group; D and g can not be zero simultaneously; Q ³Be to contain by general formula (7) or (8) represented group

Wherein, R ³And R ⁵It is the bivalent hydrocarbon radical that has 2 to 18 carbon atoms; R ⁴And R ⁶Be hydrogen atom or the monovalence alkyl that has 1 to 6 carbon atom.

6. according to the anti-soiling detergent composition of claim 2, wherein, the thickening material of component (E) is at least a saccharan that is selected from multiviscosisty, carboxy vinyl polymer, cross linked polyacrylate, and the compound among their salt.

7. according to the anti-soiling detergent composition of claim 3, wherein, the water-soluble solvent of component (F) is to be selected from ethanol, at least a compound among glycol ether and the terpene base hydrocarbon solvent.

8. according to the anti-soiling detergent composition of claim 1, wherein, this anti-soiling detergent composition is applied to hard surface.

9. according to the anti-soiling detergent composition of claim 1, wherein, this anti-soiling detergent composition is applied to the toilet, toilet rack, perhaps bathroom.

10. according to the anti-soiling detergent composition of claim 2, except above component, also comprise:

(F) 0.1% mass ratio is to the water-soluble solvent of 20% mass ratio.

11. according to the anti-soiling detergent composition of claim 2, wherein, the polyetheramides modification organopolysiloxane of component (A) is to be polyetheramides modification organopolysiloxane by an average group accepted way of doing sth (1) expression

R ¹ _aR ² _bQ ¹ _cQ ² _dSiO _{(4-a-b-c-d)/2} (1)

Wherein, a and d are zero or positive number; B, c is a positive number, makes 1.9≤a+b+c+d≤2.2; R ¹Be hydrogen atom, hydroxyl, or that replace or unsubstituted monovalence alkyl with 1 to 6 carbon atom; R ²It is monovalence alkyl with 1 to 6 carbon atom; Q ¹Be to contain by general formula (2) or (3) represented group

Wherein, R ³And R ⁵It is the bivalent hydrocarbon radical that has 2 to 18 carbon atoms; R ⁴And R ⁶Be hydrogen atom or the monovalence alkyl that has 1 to 6 carbon atom; X is by the represented group of general formula 4

-R ⁷ _eO _f-(C ₂H ₄O) _g-(R ⁸O) _h-Y (4)

Wherein, e and f respectively do for oneself 0 or 1; G and h be zero or 1 or than 1 bigger positive integer; R ⁷It is the bivalent hydrocarbon radical that has 2 to 18 carbon atoms; R ⁸It is the bivalent hydrocarbon radical that has 3 to 10 carbon atoms; Y is a hydrogen atom, has the monovalence alkyl of 1 to 18 carbon atom, acyl group, or isocyanate group; Q ²Be to contain by the represented group of general formula (5)

-R ⁹ _iO _j-(C ₂H ₄O) _k-(R ¹⁰O) _m-Z (5)

Wherein, i and j respectively do for oneself 0 or 1; K be 1 or than 1 bigger positive integer; M be zero or 1 or than 1 bigger positive integer; R ⁹It is the bivalent hydrocarbon radical that has 2 to 18 carbon atoms; R ¹⁰It is the bivalent hydrocarbon radical that has 3 to 10 carbon atoms; Z is selected from hydrogen atom, has the monovalence alkyl of 1 to 18 carbon atom, acyl group, or isocyanate group; Yet d and g can not be zero simultaneously.

12. according to the anti-soiling detergent composition of claim 10, wherein, the polyetheramides modification organopolysiloxane of component (A) is the polyetheramides modification organopolysiloxane by an average group accepted way of doing sth (1) expression

R ¹ _aR ² _bQ ¹ _cQ ² _dSiO _{(4-a-b-c-d)/2} (1)

Wherein, a and d are zero or positive number; B, c is a positive number, makes 1.9≤a+b+c+d≤2.2; R ¹Be hydrogen atom, hydroxyl, or that replace or unsubstituted monovalence alkyl with 1 to 6 carbon atom; R ²It is monovalence alkyl with 1 to 6 carbon atom; Q ¹Be to contain by general formula (2) or (3) represented group

Wherein, R ³And R ⁵It is the bivalent hydrocarbon radical that has 2 to 18 carbon atoms; R ⁴And R ⁶Be hydrogen atom or the monovalence alkyl that has 1 to 6 carbon atom; X is by the represented group of general formula 4

-R ⁷ _eO _f-(C ₂H ₄O) _g-(R ⁸O) _h-Y (4)

Wherein, e and f respectively do for oneself 0 or 1; G and h be zero or 1 or than 1 bigger positive integer; R ⁷It is the bivalent hydrocarbon radical that has 2 to 18 carbon atoms; R ⁸It is the bivalent hydrocarbon radical that has 3 to 10 carbon atoms; Y is a hydrogen atom, has the monovalence alkyl of 1 to 18 carbon atom, acyl group, or isocyanate group; Q ²Be to contain by the represented group of general formula (5)

-R ⁹ _iO _j-(C ₂H ₄O) _k-(R ¹⁰O) _m-Z (5)

Wherein, i and j respectively do for oneself 0 or 1; K be 1 or than 1 bigger positive integer; M be zero or 1 or than 1 bigger positive integer; R ⁹It is the bivalent hydrocarbon radical that has 2 to 18 carbon atoms; R ¹⁰It is the bivalent hydrocarbon radical that has 3 to 10 carbon atoms; Z is selected from hydrogen atom, has the monovalence alkyl of 1 to 18 carbon atom, acyl group, or isocyanate group; Yet d and g can not be zero simultaneously.

13. according to the anti-soiling detergent composition of claim 2, wherein, the polyetheramides modification organopolysiloxane of component (A) is the polyetheramides modification organopolysiloxane by an average group accepted way of doing sth (6) expression

R ¹ _aR ² _bQ ¹ _cQ ² _dQ ³ _e1SiO _{(4-a-b-c-d-e1)/2} (6)

Wherein, a and d are zero or positive number; B, c and e1 are positive number, make 1.9≤a+b+c+d+e1≤2.2; R ¹Be hydrogen atom, hydroxyl, or that replace or unsubstituted monovalence alkyl with 1 to 6 carbon atom; R ²It is monovalence alkyl with 1 to 6 carbon atom; Q ¹Be to contain by general formula (2) or (3) represented group

Wherein, R ³And R ⁵It is the bivalent hydrocarbon radical that has 2 to 18 carbon atoms; R ⁴And R ⁶Be hydrogen atom or the monovalence alkyl that has 1 to 6 carbon atom; X is by the represented group of general formula 4

-R ⁷ _eO _f-(C ₂H ₄O) _g-(R ⁸O) _h-Y (4)

Wherein, e and f respectively do for oneself 0 or 1; G and h be zero or 1 or than 1 bigger positive integer; R ⁷It is the bivalent hydrocarbon radical that has 2 to 18 carbon atoms; R ⁸It is the bivalent hydrocarbon radical that has 3 to 10 carbon atoms; Y is a hydrogen atom, has the monovalence alkyl of 1 to 18 carbon atom, acyl group, or isocyanate group; Q ²Be to contain by the represented group of general formula (5)

-R ⁹ _iO _j-(C ₂H ₄O) _k-(R ¹⁰O) _m-Z (5)

Wherein, i and j respectively do for oneself 0 or 1; K be 1 or than 1 bigger positive integer; M be zero or 1 or than 1 bigger positive integer; R ⁹It is the bivalent hydrocarbon radical that has 2 to 18 carbon atoms; R ¹⁰It is the bivalent hydrocarbon radical that has 3 to 10 carbon atoms; Z is selected from hydrogen atom, has the monovalence alkyl of 1 to 18 carbon atom, acyl group, or isocyanate group; D and g can not be zero simultaneously; Q ³Be to contain by general formula (7) or (8) represented group

Wherein, R ³And R ⁵It is the bivalent hydrocarbon radical that has 2 to 18 carbon atoms; R ⁴And R ⁶Be hydrogen atom or the monovalence alkyl that has 1 to 6 carbon atom.

14. according to the anti-soiling detergent composition of claim 10, wherein, the polyetheramides modification organopolysiloxane of component (A) is the polyetheramides modification organopolysiloxane by an average group accepted way of doing sth (6) expression

R ¹ _aR ² _bQ ¹ _cQ ² _dQ ³ _e1SiO _{(4-a-b-c-d-e1)/2} (6)

Wherein, a and d are zero or positive number; B, c and e1 are positive number, make 1.9≤a+b+c+d+e1≤2.2; R ¹Be hydrogen atom, hydroxyl, or that replace or unsubstituted monovalence alkyl with 1 to 6 carbon atom; R ²It is monovalence alkyl with 1 to 6 carbon atom; Q ¹Be to contain by general formula (2) or (3) represented group

Wherein, R ³And R ⁵It is the bivalent hydrocarbon radical that has 2 to 18 carbon atoms; R ⁴And R ⁶Be hydrogen atom or the monovalence alkyl that has 1 to 6 carbon atom; X is by the represented group of general formula 4

-R ⁷ _eO _f-(C ₂H ₄O) _g-(R ⁸O) _h-Y (4)

Wherein, e and f respectively do for oneself 0 or 1; G and h be zero or 1 or than 1 bigger positive integer; R ⁷It is the bivalent hydrocarbon radical that has 2 to 18 carbon atoms; R ⁸It is the bivalent hydrocarbon radical that has 3 to 10 carbon atoms; Y is a hydrogen atom, has the monovalence alkyl of 1 to 18 carbon atom, acyl group, or isocyanate group; Q ²Be to contain by the represented group of general formula (5)

-R ⁹ _iO _j-(C ₂H ₄O) _k-(R ¹⁰O) _m-Z (5)

Wherein, i and j respectively do for oneself 0 or 1; K be 1 or than 1 bigger positive integer; M be zero or 1 or than 1 bigger positive integer; R ⁹It is the bivalent hydrocarbon radical that has 2 to 18 carbon atoms; R ¹⁰It is the bivalent hydrocarbon radical that has 3 to 10 carbon atoms; Z is selected from hydrogen atom, has the monovalence alkyl of 1 to 18 carbon atom, acyl group, or isocyanate group; D and g can not be zero simultaneously; Q ³Be to contain by general formula (7) or (8) represented group

Wherein, R ³And R ⁵It is the bivalent hydrocarbon radical that has 2 to 18 carbon atoms; R ⁴And R ⁶Be hydrogen atom or the monovalence alkyl that has 1 to 6 carbon atom.

15. according to the anti-soiling detergent composition of claim 12, wherein, the thickening material of component (E) is at least a saccharan that is selected from multiviscosisty, carboxy vinyl polymer, cross linked polyacrylate, and the compound of their salt.

16. according to the anti-soiling detergent composition of claim 14, wherein, the thickening material of component (E) is at least a saccharan that is selected from multiviscosisty, carboxy vinyl polymer, cross linked polyacrylate, and the compound of their salt.

17. according to the anti-soiling detergent composition of claim 15, wherein, the water-soluble solvent of component (F) is to be selected from ethanol, at least a compound among glycol ether and the terpene base hydrocarbon solvent.

18. according to the anti-soiling detergent composition of claim 16, wherein, the water-soluble solvent of component (F) is to be selected from ethanol, at least a compound among glycol ether and the terpene base hydrocarbon solvent.

19. according to the anti-soiling detergent composition of claim 17, wherein, this anti-soiling detergent composition is applied to hard surface.

20. according to the anti-soiling detergent composition of claim 18, wherein, this anti-soiling detergent composition is applied to hard surface.

21. according to the anti-soiling detergent composition of claim 17, wherein, this anti-soiling detergent composition is applied to the toilet, toilet rack, perhaps bathroom.

22. according to the anti-soiling detergent composition of claim 18, wherein, this anti-soiling detergent composition is applied to the toilet, toilet rack, perhaps bathroom.