CN101528908A - Bleaching agent composition - Google Patents

Abstract

The present invention discloses a bleaching agent composition which contains an alkali metal hypochlorite salt (a), an amphoteric polymer compound (b) having, as constitutional units, a monomer unit (b1) containing at least one of a quaternary ammonium group, a tertiary amine group and a secondary amine group and a monomer unit (b2) containing an anionic group, a quaternary ammonium surface active agent (c), and water (d) at specific ratios.

Description

Whitener composition

Technical field

The present invention relates to whitener composition.

Background technology

According to the difference of object cleaning face, the dirt of crust has varied in the room.Common situation has: easily adhere to modified oils and the dust dirt after compound at the kitchen range content; In lavatory and bathroom, inorganic substance and organic substance form insoluble salt and directly become dirt; Or with these dirts as matrix bacterium and mold propagates and become dirt.In the dirt of crust, remove fully as the sanitising agent of principal constituent with tensio-active agent and abrasive from very difficult use of the black dirt of these bacteriums and mould, can use the chlorine class bleach clean-up agent that has cooperated hypochlorite.

All the time, the agent of chlorine class bleach clean-up has shown effect of sufficient for ceramic tile and seam, other black dirts, but recently, except ceramic tile and seam, the mildew example of bacterium of the resin portion of sealing material of the interstitial material of used silicone resin class or soft polyvinyl chloride (PVC) RESINS class etc. increases in junctions such as wall and bathing pools, even and, also be difficult to bleaching, decompose and remove the mould that these are given birth in resin portion for the existing bleach clean-up agent of ceramic tile and seam performance effect of sufficient.

About cooperating the SYNTHETIC OPTICAL WHITNER of hypochlorite, disclose and used the bleach clean-up agent composition of hypochlorite and cation compound among JP-A2002-212593 and the JP-A2002-256289.In addition, disclose and used the bleaching cleansing composition of hypochlorite and amphiphilic polymers among the JP-A2002-161298.

And, as being the correlation technique of the treatment agent of purpose with the anti-fouling effect, a kind of crust sterilization stain control agent is disclosed among the JP-A2002-060786, the bactericidal properties compound that it contains polymkeric substance (this polymkeric substance has the monomeric unit that contains quaternary ammonium group) and contains quaternary ammonium group.In addition, disclose a kind of crust cleanser compositions among the JP-A2002-060784, it contains polymkeric substance (this polymkeric substance has the monomeric unit that contains quaternary ammonium group) and tensio-active agent.

Summary of the invention

The present invention relates to a kind of whitener composition, it contains: (a) hypochlorous acid an alkali metal salt (below, be called (a) composition) 0.5～5.0 quality %; (b) with monomeric unit (b1) and monomeric unit (b2) as constitute unitary amphoteric polymer compound (below, be called (b) composition) 0.005～1 quality %, monomeric unit (b1) have in quaternary ammonium group, tertiary amine groups and the secondary amine at least any one, monomeric unit (b2) has the anionic property group; (c) quaternary ammonium type tensio-active agent (below, be called (c) composition) 0.005～0.5 quality %; And, (d) water (below, be called (d) composition).

And, the present invention relates to remove the method for mould, it is characterized in that, the whitener composition of the invention described above is used to mildew the resin of bacterium to remove mould.

Embodiment

Disclose a kind of mould technology that can improve bleachability among JP-A2002-212593, JP-A2002-256289 and the JP-A2002-161298, but need have the SYNTHETIC OPTICAL WHITNER of stronger bleaching effect for growth on silicone resin interstitial material that in bathing pool, seam or the window etc. in bathroom, uses or the polyvinyl chloride sealing material etc. for waterproof.Do not mention SYNTHETIC OPTICAL WHITNER among JP-A2002-060786 and the JP-A2002-060784.

Problem of the present invention provides the whitener composition of bleaching power excellence, and the whitener composition that shows excellent bleaching power for the mould in the resin portion growth particularly is provided.

The whitener composition of bleaching power excellence can be provided according to the present invention, the whitener composition that shows excellent bleaching power for the mould in the resin portion growth particularly is provided.

(a) composition

As the hypochlorous acid an alkali metal salt of (a) composition, can enumerate clorox, potassium hypochlorite etc., preferred especially clorox.Hard surface of the present invention is 0.5～5.0 quality % with the content of (a) composition in the bleach clean-up agent composition, is preferably 1.0～4.0 quality %, more preferably the scope of 2.0～3.0 quality %.(a) content of composition is that 0.5 quality % can be bleached power when above fully, in addition, can obtain satisfactory stability when 0.5 quality % is following.

(b) composition

Among the present invention, use the macromolecular compound that contains monomeric unit (b1) and monomeric unit (b2) as (b) composition, monomeric unit (b1) has at least a (the constituting unit (b1) hereinafter referred to as monomer) in quaternary ammonium group, tertiary amine groups and the secondary amine, and monomeric unit (b2) has anionic property group (constituting unit (b2) hereinafter referred to as monomer).

Constitute unit (b1) as monomer, preferably derive from following monomeric monomeric unit, this monomer is to be selected from the monomer shown in the following general formula (1) and with the monomeric monomer shown in the following general formula (2).

(in the formula, R ¹, R ², R ³, R ⁷, R ⁸, R ⁹Represent independently that respectively hydrogen atom or carbonatoms are 1～3 alkyl.X, Y respectively independently expression be selected from carbonatoms be 1～12 alkylidene group ,-COOR ¹²-,-CONHR ¹²,-OCOR ¹²-,-R ¹³-OCO-R ¹²-group.Herein, R ¹², R ¹³Represent independently that respectively carbonatoms is 1～5 alkylidene group.R ⁴Be that carbonatoms is 1～3 alkyl, hydroxyalkyl or R ¹R ²C=C (R ³)-X-.R ⁵Be that carbonatoms is 1～3 alkyl or hydroxyalkyl, R ⁶Be that carbonatoms is 1～3 alkyl, hydroxyalkyl or benzyl, Z-represents negatively charged ion.R ¹⁰Be that hydrogen atom, carbonatoms are 1～3 alkyl or hydroxyalkyl or R ⁷R ⁸C=C (R ⁹)-Y-.R ¹¹Be that hydrogen atom, carbonatoms are 1～3 alkyl or hydroxyalkyl.)

Monomer constitutes in the unit (b1), and as the monomeric unit with quaternary ammonium group, the monomer of preferred following general formula (3) constitutes the unit.

(in the formula, R ^1bBe that carbonatoms is 1～3 alkyl or hydroxyalkyl, m and n are respectively 0 or 1 numbers, m+n=1.Z ^-It is anionic group.)

R in the general formula (3) ^1bBe preferably methyl, Z ^-Be preferably halide-ions, sulfate ion, phosphate anion, carbonatoms and be 1～12 fatty acid radical ion or be the Phenylsulfonic acid radical ion that 1～3 alkyl replaces, be preferably chlorion especially by 1～3 carbonatoms.N is preferably 0.

Constitute unit (b2) as monomer, the monomer of preferred following general formula (4) constitutes the unit.

(in the formula, R ^2bBe hydrogen atom, methyl or-COOM, R ^3bBe hydrogen atom, methyl or hydroxyl.A is-COOM or-ph-SO ₃M.Herein, M is hydrogen atom, basic metal or alkaline-earth metal, and ph represents phenyl ring.)

(b) of the present invention composition can carry out common polyreaction manufacturing with the pairing monomer in monomer formation unit that constitutes (b) composition and obtain.Perhaps can be, finally to obtain (b) composition by macromolecular compound is carried out aftertreatment.For example, under the situation of macromolecular compound with quaternary ammonium group, except carry out method that polyreaction obtains with the monomer that has quaternary ammonium group in the monomer originally, also can be for having that amino monomer carries out polyreaction and the product that obtain carries out the season processing and obtains (b) composition.Certainly too for the anionic property group.Certainly, be used to obtain to carry out the used monomer of macromolecular compound of aftertreatment, can be selected from the material of the structure of considering aftertreatment.

As by the monomer shown in the general formula (1), can enumerate acryloyl (or methacryloyl) aminoalkyl group (carbonatoms is 1～5)-N, N, N-trialkyl (carbonatoms is 1～3) quaternary ammonium salt, acryloyl (or methacryloyl) oxyalkyl (carbonatoms is 1～5)-N, N, N-trialkyl (carbonatoms is 1～3) quaternary ammonium salt, N-(ω-thiazolinyl (carbonatoms is 2～10))-N, N, N-trialkyl (carbonatoms is 1～3) quaternary ammonium salt, N, N-two (ω-thiazolinyl (carbonatoms is 2～10))-N, N-dialkyl group (carbonatoms is 1～3) quaternary ammonium salts etc. constitute the monomeric unit of general formula (3) by these.And, as by the monomer shown in the general formula (2), can enumerate acryloyl (or methacryloyl) aminoalkyl group (carbonatoms is 1～5)-N, N-dialkyl group (carbonatoms is 1～3) amine, acryloyl (or methacryloyl) oxyalkyl (carbonatoms is 1～5)-N, N-dialkyl group (carbonatoms is 1～3) amine, N-(ω-thiazolinyl (carbonatoms is 2～10))-N, N-dialkyl group (carbonatoms is 1～3) amine, N, N-two (ω-thiazolinyl (carbonatoms is 2～10))-N-alkyl (carbonatoms is 1～3) amine, allylamine, the diallyl methylamine, diallylamine etc.

The monomer that obtains for the monomer polymerization that makes general formula (2) constitutes the unit, by implementing alkylation and can make (b) composition with quaternizing agents such as methyl chloride, dimethyl sulfate, diethyl sulfuric acid, oxyethane, propylene oxide.In addition, under the situation of using oxyethane and/or propylene oxide, (Z is and above-mentioned negatively charged ion Z must to use ZH ^-Corresponding group) the acid neutralization amino shown in makes it reaction.

As the pairing monomer of general formula (4), can enumerate vinylformic acid or its salt, methacrylic acid or its salt, Ba Dousuan or its salt, Alpha-hydroxy vinylformic acid or its salt, toxilic acid or its salt, Maleic Acid, Anhydrous, styrene sulfonate.And, make the styrene sulfonate polymerization and the monomer that obtains constitutes the unit, also the compound sulfonation that can polymerizing styrene be obtained with sulphonating agents such as sulphur trioxide, chlorsulfonic acid, sulfuric acid obtains through neutralization again.

In the present invention, constitute the unit as monomer with quaternary ammonium group, special preferred polymeric N, N-diallyl-N, the monomer that N-dialkyl group (carbonatoms is 1～3) quaternary ammonium salt obtains constitutes the unit, perhaps will make N with quaternizing agents such as methyl chloride, dimethyl sulfate, diethyl sulfuric acid, oxyethane, propylene oxide, the monomer after N-diallyl-N-alkyl (carbonatoms is 1～3) the amine polymerization constitutes the monomer formation unit that the unit alkylation obtains.And constitute the unit as monomer with anionic property group, preferably will be selected from the monomer polymerization of vinylformic acid or its salt, methacrylic acid or its salt, toxilic acid or its salt, Maleic Acid, Anhydrous and the monomer that obtains constitutes the unit.

The mol ratio of preferred (total mole number of quaternary ammonium group, tertiary amine groups and secondary amine)/(total mole number of anionic property group) of (b) of the present invention composition is 30/70～95/5, more preferably 40/60～70/30, be preferably 50/50～70/30 especially.

The preferably such macromolecular compound of (b) of the present invention composition: constitute in the unit at the whole monomers that constitute (b) composition, monomer constitutes the total of unit (b1) and monomer formation unit (b2), the total of the monomeric unit (4) shown in monomeric unit (3) shown in the especially above-mentioned general formula (3) and the above-mentioned general formula (4), be 50～100 moles of %, be preferably 70～100 moles of %, more preferably 80～100 moles of % are preferably 90～100 moles of % especially.And, consider from the aspect of bleach clean-up effect and storage stability, in (b) of the present invention composition, the total that monomer with quaternary ammonium group, tertiary amine groups and/or secondary amine (being preferably quaternary ammonium group) constitutes unit (b1) accounts for 30～90 moles of % in whole monomers formations unit of formations (b) composition, more preferably 40～80 moles of % are preferably 50～70 moles of % especially.

In the present invention, monomer constitutes unit (b1) and monomer constitutes unit (b2) except containing, especially the monomeric unit (4) shown in monomeric unit (3) shown in the above-mentioned general formula (3) and the above-mentioned general formula (4) also can contain the monomer that can obtain with monomer (b3) copolymerization of its copolymerization and constitute the unit in addition in the scope that does not influence effect of the present invention.Particularly, can enumerate acrylamide, N, N-dimethylamino-propyl acryloyl (methacryloyl) amine, N, N-dimethyl allene acyl (methacryloyl) amine, N, N-dimethylaminoethyl acryloyl (methacryloyl) amine, N, N-dimethylaminoethyl acryloyl (methacryloyl) amine, N-vinyl-2-hexanolactam, N-vinyl-2-Pyrrolidone, vinylformic acid (methacrylic acid) alkyl (carbonatoms is 1～5) ester, vinylformic acid (methacrylic acid) 2-hydroxyl ethyl ester, vinylformic acid (methacrylic acid)-N, N-dimethylamino alkyl (carbonatoms is 1～5) ester, vinyl acetate, ethene, propylene, n-butene, iso-butylene, positive amylene, isoprene, 2-methyl-1-butene alkene, n-hexylene, the 2-Methyl-1-pentene, the 3-Methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butylene, vinylbenzene, Vinyl toluene (Vinyltoluene), alpha-methyl styrene, oxyethane, propylene oxide, the 2-vinyl pyridine, 4-vinylpridine, sulfurous gas.

Most preferably make sulfurous gas copolymer-1～15 mole % and compound of obtaining in (b) composition among the present invention.

(b) of the present invention composition can obtain by any polymerization, but preferred especially radical polymerization, and this polymerization can be at body, solution, or carry out in the emulsification system.Radical polymerization can be used known radical initiator as initiator by the heating beginning: 2, and 2 '-azo (2-amidine propane) dihydrochloride, 2, the azo-initiator of 2 '-azo (N, N-dimethylene isobutyl amidine) dihydrochloride etc.; Hydrogen peroxide and benzoyl peroxide, tertbutyl peroxide (t-butyl hydroperoxide), isopropyl benzene hydroperoxide, methylethyl ketone peroxide (methyl ethyl ketone peroxide), peroxybenzoic acid organo-peroxides such as (perbenzoic acid); Persulphates such as Sodium Persulfate, Potassium Persulphate, ammonium persulphate; Hydrogen peroxide-Fe ^{3 +}Deng redox initiator etc.Also can exist at photosensitizers/or not in the presence of, through rayed, radiation exposure and initiated polymerization.

The weight-average molecular weight of (b) of the present invention composition is preferably 1000～6000000, and more preferably 5000～3000000, more preferably 10000～2000000.As developping agent, obtain with gel permeation chromatography as reference material by polyoxyethylene glycol by the mixed solvent (phosphoric acid buffer) of acetonitrile and water for this weight-average molecular weight.

In composition, (b) content of composition is 0.005～1 quality %, is preferably 0.005～0.2 quality %, more preferably 0.008～0.18 quality %, more preferably 0.01～0.15 quality %.

(c) composition

(c) preferably to have a carbonatoms be 6～18 alkyl to the quaternary ammonium type tensio-active agent of composition, more preferably have a carbonatoms and be 6～12 alkyl, or preferred balance anion is a chlorion.Material shown in the more preferably following general formula (5).

(in the formula, R ^1cBe that carbonatoms is 6～18 alkyl, 6～12 alkyl more preferably, R ^2c, R ^3cBe to represent methyl or ethyl, R respectively independently ^4cBe that carbonatoms is 1～3 alkylidene group.M ^-Be that halide-ions or carbonatoms are 1～3 alkyl sulfate ion or to have carbonatoms be that 1～3 alkyl is as substituent Phenylsulfonic acid radical ion.)

(c) composition, wherein with the quaternary ammonium type tensio-active agent shown in the above-mentioned general formula (5), can improve the inadequate bleach clean-up effect of the pollution that existing chlorine class SYNTHETIC OPTICAL WHITNER causes resin for bacterium or mould, think that this is because the quaternary ammonium type tensio-active agent helps the contact of hypochlorite ion for hydrophobic material.

The invention provides for the effective whitener composition of resinous material, when the object resin is under the situation of vinyl chloride resin used in the sealing material etc. of window frame, the R in the above-mentioned general formula (5) ^1cEffect is best during for the compound of carbonatoms 8.

In whitener composition of the present invention, (c) composition contains 0.005～0.5 quality %, preferably contains 0.008～0.3 quality %, more preferably contains 0.01～0.2 quality %.In this scope, has good storage stability and to the scrubbing effect of resene.

Whitener composition of the present invention is considered from the effect aspect of bleach clean-up, (c) composition and (b) mass ratio of composition be preferably (c)/(b)=0.10～7.0, more preferably 0.28～5.0.

＜other compositions 〉

Whitener composition of the present invention can contain alkali metal chloride (below, be called (e) composition).Can enumerate sodium-chlor and Repone K as alkali metal chloride, they also can contain in the hypochlorous acid alkali metal salt soln.Consider that from the aspect of storage stability in whitener composition of the present invention, (e) content of composition is preferably 0.001～3.0 quality %, more preferably 0.01～1.0 quality %.For the concentration that makes the alkali metal chloride in the hypochlorous acid alkali metal salt soln is reduced to this scope, for example, can make the alkali metal chloride crystallization, and filter by cooling hypochlorous acid aqueous solution of alkali metal salt, reach above-mentioned concentration range thus.

In addition, whitener composition of the present invention also can contain alkali metal hydroxide (below, be called (f) composition).The alkali metal hydroxide of so-called (f) composition is meant the alkalimetal ion that exists in the whitener composition and the combination of hydroxide ion, i.e. free alkali is not considered when combined with other counterions.For example, under other organic acid situations of cooperation,, but, it is not regarded as alkali metal hydroxide owing to become the organic acid counterion even cooperate as alkali metal hydroxide.Alkali metal hydroxide can be enumerated sodium hydroxide, potassium hydroxide etc., wherein preferred sodium hydroxide.In common chlorine class SYNTHETIC OPTICAL WHITNER etc.,, has the tendency that cooperates a large amount of alkali metal hydroxides in order to obtain the stability of hypochlorite.But, in the present invention, for obtain for attached to resene particularly from the sufficient cleaning effect of the dirt of mould, the content of (f) composition in composition is preferably 0.2～3.0 quality %, more preferably 0.2～1.0 quality % is preferably 0.3～0.8 quality % especially.If (f) content of composition is more than 0.2 quality %, then because alkalescence is abundant, (a) stability of the hypochlorous acid an alkali metal salt of composition also improves.In addition, if (f) content of composition is below 3.0 quality %, then except the stability of the hypochlorous acid an alkali metal salt that can increase (a) composition,, also can obtain effect of sufficient for the mould dirt on the resin because bleaching speed is suitable.And in the present invention, the content of (f) composition in the composition is measured according to the method for ASTMD 2022-89 record.That is, this method is measured the amount of the free alkali in the SYNTHETIC OPTICAL WHITNER as sodium hydroxide (NaOH), also will adopt the amount of the amount of the free alkali in the composition that this method obtains as (f) composition in the composition among the present invention.

The present invention also can use the tensio-active agent beyond (c) composition, consider from the storage stability aspect, the use level of this tensio-active agent comprises that the total amount of (c) composition is below the 5.0 quality %, is preferably below the 3.0 quality %, more preferably below the 1.0 quality %.As the tensio-active agent that can use in the present invention, preferably has carbonatoms and is the tensio-active agent of 6～22 alkyl, particularly, can enumerate alkylsulfonate, chain alkyl sulfonate, alkyl sulfuric ester salt, alkylbenzene sulfonate, sulfonated alkyl naphathalene, alkyl sulfo succinate, alkyl diphenyl base ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, alkylphosphonic, polyxyethylated sulfuric acid, polyxyethylated aromatic yl acid ester salt, the anion surfactant (except the nitrogenous analog anion surfactants such as amino acid derivative) of polyoxyethylene alkyl phenyl ether sulfonate etc., alkyl amine oxide, carboxybetaine, in the amphotericses such as sultaine more than a kind.Wherein, the atomizer (Trigger Sprayer) that uses the triggering device formula is when spraying, from forming the viewpoint of good bubble, preferred amine oxide.But, in above-mentioned tensio-active agent, with regard to anion surfactant particularly with regard to alkylsulfonate, the alkyl sulfuric ester salt, think because it combines with the cats product electricity in cleaning liquor, hindered the effect that multiplies each other of hypochlorite ion among the present invention ((a) composition) and cats product ((c) composition), thereby found to have the tendency that bleaching effect reduces.Therefore, with regard to alkylsulfonate, alkyl sulfuric ester salt, the mol ratio of the cats product in the preferred composition (comprising (c) composition)/(alkylsulfonate and/or alkyl sulfuric ester salt) is more than 0.2, more preferably more than 0.5, more preferably more than 1.

In whitener composition of the present invention, replaced the hydrotropic agent of selecting in Phenylsulfonic acid that 1～3 carbonatoms is 1～3 alkyl and the salt thereof (Hydrotropes) and increased storage stability by cooperating.As other any compositions, can cooperate fragrance component.As the example of the fragrance component that can be engaged in the hypochlorite system, can be with reference to Japanese JP-A50-74581 and JP-A62-205200, can be monomer perfume and with the cooperation spices of their combinations.Usually contain spices 0.001～0.5 quality % in the composition,, when decision gradation composition and use level, must note owing to may influence stability.

The remainder of composition of the present invention is water ((d) composition), considers storage stability, preferably removes the ion exchanged water or the distilled water of metal ion that trace exists etc.From the viewpoint of storage stability, the content of water is preferably 80～98 quality % in composition, more preferably 90～98 quality %.And, consider from the viewpoint of storage stability and bleaching effect, preferably the pH of composition 20 ℃ the time is adjusted into 12.5～13.5.

In addition, from implemented the viewpoint of spraying by triggering device, the viscosity of composition of the present invention is preferably lower, and the viscosity in the time of 20 ℃ is preferably 1～20mPas, is preferably 1～10mPas especially.

Suitable the having of using method as whitener composition of the present invention: the method that the atomizer (Sprayer) of the atomizer of (1) use triggering device formula etc. is directly sprayed to object; (2) composition is infiltrated in the absorptive pliability material, with the method for its wiping object thing; And (3) are immersed in object the method in the solution of dissolved composition.From the viewpoint of the simplicity method of preferred (1) especially.Preferably can be as atomizer with cooperating (a)～(d) composition and further cooperating the whitener composition of any composition to make the atomizer of the triggering device formula that blister sprays, for every 1m ²Object is preferably sprayed with the ratio of 5～15g.By for example being applicable to the described method in above-mentioned (1)～(3), whitener composition of the present invention can remove the mould of taking place on the resin on the resin that mildews.Can enumerate the various resins that are used for bathroom, lavatory, kitchen etc. of silicone resin, vinyl chloride resin etc. as the object resin.Whitener composition of the present invention is suitable for hard surface.

Embodiment

The following examples are set forth enforcement of the present invention, and embodiment is an illustration of the present invention, but the present invention is not limited thereto.

(bleaching power)

The soft PVC resin-sealing material of using in the bathroom window frame of general family is mildewed, get test film and be cut into the 1cm degree as assess sample.(Japanese electric look Industrial Co., Ltd makes, and the ND-300A) lightness of evaluation of measuring sample (L value), the difference of employing L value are the assess sample below ± 2 to use colour examining colour-difference-metre.Get 2 pieces low dirt cleansing tissues (Kimwipes) and overlay (Kimberly-Clark company manufacturing on the test film, 3cm * 3cm), splash into the liquid bleaching agent composition 0.5ml shown in table 1, the table 2 places 10 minutes after washings, air-dry, measure lightness (L value) with above-mentioned colour examining colour-difference-metre.With the difference of the L value before and after estimating as bleaching power.The big more bleaching effect that shows of the difference of L value is good more.The result is shown in table 1, table 2.In the part comparative example, polymkeric substance b ' is shown as (c)/(b) mass ratio as (b) component list.

(storage stability)

The part composition of table 1, table 2 was preserved for 2 weeks the storage stability of the clorox after preserving by effective chlorine residue rate evaluation down at 50 ℃.In addition, effectively the chlorine residue rate is obtained according to following formula:

Effective chlorine residue rate (%)=(preserving effective chlorine density in the composition of back)/(preserving effective chlorine density in the preceding composition) * 100.

Table 3

Claims (6)

1. a whitener composition is characterized in that,

Contain:

(a) hypochlorous acid an alkali metal salt 0.5～5.0 quality %;

(b) with monomeric unit (b1) and monomeric unit (b2) as constituting unitary amphoteric polymer compound 0.005～1 quality %, described monomeric unit (b1) have in quaternary ammonium group, tertiary amine groups and the secondary amine at least any one, described monomeric unit (b2) has the anionic property group;

(c) quaternary ammonium type tensio-active agent 0.005～0.5 quality %; And

(d) water.

2. whitener composition as claimed in claim 1 is characterized in that,

Described (b) composition has as monomeric unit (b1) and derives from following monomeric monomeric unit, and above-mentioned monomer is to be selected from the monomer shown in the following general formula (1) and with the monomeric monomer shown in the following general formula (2),

In the formula, R ¹, R ², R ³, R ⁷, R ⁸, R ⁹Independent respectively, be that hydrogen atom or carbonatoms are 1～3 alkyl; X, Y are respectively independent, be selected from carbonatoms be 1～12 alkylidene group ,-COOR ¹²-,-CONHR ¹²,-OCOR ¹²-,-R ¹³-OCO-R ¹²-group; At this, R ¹², R ¹³Independent respectively, be that carbonatoms is 1～5 alkylidene group; R ⁴Be that carbonatoms is 1～3 alkyl, hydroxyalkyl or R ¹R ²C=C (R ³)-X-; R ⁵Be that carbonatoms is 1～3 alkyl or hydroxyalkyl, R ⁶Be that carbonatoms is 1～3 alkyl, hydroxyalkyl or benzyl; Z ^-The expression negatively charged ion; R ¹⁰Be that hydrogen atom, carbonatoms are 1～3 alkyl or hydroxyalkyl or R ⁷R ⁸C=C (R ⁹)-Y-; R ¹¹Be that hydrogen atom, carbonatoms are 1～3 alkyl or hydroxyalkyl.

3. whitener composition as claimed in claim 1 or 2 is characterized in that,

Described (b) composition is to contain with the monomeric unit (3) shown in the following general formula (3) and with the multipolymer of the monomeric unit (4) shown in the following general formula (4), and wherein monomeric unit (3) and monomeric unit (4) account for 50～100 moles of % in whole monomeric units,

In the formula, R ^1bBe that carbonatoms is 1～3 alkyl or hydroxyalkyl, m and n are respectively 0 or 1 numbers, m+n=1; Z ^-It is anionic group;

In the formula, R ^2bBe hydrogen atom, methyl or-COOM; R ^3bBe hydrogen atom, methyl or hydroxyl; A is-COOM or-ph-SO ₃M; Herein, M is hydrogen atom, basic metal or alkaline-earth metal, and ph represents phenyl ring.

4. as any described whitener composition in the claim 1～3, it is characterized in that,

Described (c) composition is with the quaternary ammonium type tensio-active agent shown in the following general formula (5),

In the formula, R ^1cBe that carbonatoms is 6～18 alkyl; R ^2c, R ^3cIndependent respectively, expression methyl or ethyl; R ^4cBe that carbonatoms is 1～3 alkylidene group; M ^-Be that halide-ions or carbonatoms are 1～3 alkyl sulfate ion or to have carbonatoms be that 1～3 alkyl is as substituent Phenylsulfonic acid radical ion.

5. as any described whitener composition in the claim 1～4, it is characterized in that,

(c) composition and (b) mass ratio of composition be (c)/(b)=0.10～7.0.

6. a method of removing mould is characterized in that,

Be used to the to mildew resin of bacterium of any described whitener composition in the claim 1～5.