JP5473740B2 - Liquid detergent composition for hard surfaces - Google Patents

Description

  The present invention relates to a hard surface liquid detergent composition capable of achieving both excellent cleaning power and sterilization power in the field of hard surface cleaning agents in toilets and bathrooms.

  Conventionally, there has been a demand for a composition that can achieve both excellent cleaning power and sterilization power for hard surfaces in toilets and bathrooms.

  As a conventional liquid detergent composition for hard surfaces, for example, Patent Document 1 discloses a combination of an anionic activator, zinc, and polyvalent carboxylic acid, and Patent Document 2 discloses silver fine particles and an anionic activator. A combination of these is disclosed. However, none of the anion activator counterions exchanged counterions with metal salts in the composition, so that the sterilization performance was not sufficiently satisfied.

  Patent Document 3 discloses a combination of a metal salt of an organic compound and a water-soluble polymer. However, the composition disclosed in the document 3 is used after being applied and dried, and does not exhibit detergency.

  Patent Document 4 discloses a combination of fine particles of a silver-based inorganic antibacterial agent and a dispersant. However, the composition disclosed in this document 4 contains no activator and cannot sufficiently remove the dirt adhered to the hard surface.

  Further, Patent Document 5 discloses a combination of a peroxide such as hydrogen peroxide, a metal / polydentate ligand complex, and a surfactant. However, the composition disclosed in Document 5 reacts with a peroxide and a metal compound to deactivate the effect, so that it has to be used immediately after compounding in order to exert detergency.

JP 2004-131626 A JP 2000-178595 A JP-A-11-107162 JP-A-6-247817 Japanese Patent Application Laid-Open No. 9-1332797

As described above, the conventional hard surface liquid detergent composition surprisingly has both excellent cleaning power and sterilization power for hard surfaces in the water, such as bathrooms, toilets, and kitchens. There was no liquid detergent composition that could be applied.
According to the study by the inventors, the hard surfaces of water-filled areas such as bathrooms, toilets, and kitchens are often wet with tap water, and sponge-made cleaning tools still contain tap water inside. It has been clarified that the actual condition of cleaning, which is often used, hinders the balance between excellent cleaning power and sterilization power.
That is, in the actual condition of the cleaning described above, there arises a problem that metal ions having sterilizing power contained in the detergent react with chlorine contained in tap water and deactivate. By the way, the reaction rate between silver ions and chloride ions is very fast. When tap water is used for dilution in the sterilization test (residual chlorine concentration is 0.4 mg / L), contact with silver sulfate by contact for 10 minutes The sterilizing power is almost inactivated. It is found that this phenomenon occurs when cleaning hard surfaces such as bathrooms, toilets, kitchens, etc., and that is why conventional liquid cleaning compositions for hard surfaces are insufficient in performance. It was done.

  The present invention has been made in view of the above-described conventional circumstances, and its problem is that it has excellent detergency against hard surface sebum and oil stains in bathrooms, toilets, kitchens, etc., and during cleaning. To provide a liquid detergent composition for hard surfaces that has high sterilizing power against gram-positive bacteria and gram-negative bacteria even when contacted with tap water, and has excellent storage stability (no precipitation occurs). It is in.

In order to solve the above-described problems, the present invention provides a hard surface liquid cleaning composition employing the following constitution.
[1] A hard surface liquid detergent composition comprising (A) a silver fine particle dispersion and (B) a surfactant, wherein the (A) silver fine particle dispersion comprises a glycidyl ether compound as a basic catalyst. In the molecule of polyglycerol diglycidyl ether (GDGE) obtained by addition polymerization in the presence of a functional group having at least one reducing ability selected from an alkoxide group, a sulfide group, and an amino group. By mixing the hyperbranched polymer (HBPf) and a solution containing silver ions (S-Ag), the silver ions induced in the hyperbranched polymer (HBPf) are reduced by the functional groups, and the hyperbranched polymer Silver fine particle-encapsulated hyperbranched polymer (HBPf-) in which a number of silver fine particles are formed in a polymer (HBPf) A liquid detergent composition for hard surfaces, which is Ag) .
[2] The average particle size based on the transmission electron microscopic observation of silver particles to produce the hyperbranched the polymer (HBPF), characterized in that it is less than a diameter of 1 nm 100 nm, the hardness according to the above [1] Liquid detergent composition for surfaces.
[ 3 ] The content of the (A) silver fine particle dispersion is 10 to 1000 ppm as a mass percentage with respect to the total amount of the cleaning composition, and the content of the (B) surfactant is the cleaning composition. Hard surface liquid detergent composition as described in said [1] or [ 2] characterized by being 0.5-15.0 mass% with respect to the whole quantity.

(A) The silver fine particle dispersion constituting the liquid detergent composition for hard surface according to the present invention is a silver derived inside a dendritic polymer (hyperbranched polymer (HBP _f )) containing a functional group having a reducing ability. transparent aqueous solution of ions inside space by the by a functional group is reduced becomes fine silver hyperbranched polymer (HBP _f) dispersed within the polymer, formed by holding silver particles containing hyperbranched polymer (HBP f _-Ag) It is.
The (A) silver fine particle dispersion (HBP _f -Ag) used in the present invention is obtained as a transparent aqueous solution and does not cause aggregation / precipitation and has excellent stability. Since the silver fine particles produced in the silver fine particle-encapsulated hyperbranched polymer are in the hyperbranched polymer (HBP _f ), direct contact with tap water is suppressed, and the sterilization power of the silver fine particles is effectively deactivated. Is prevented. And it is presumed that silver ions are gradually released from the silver particles in the hyperbranched polymer (HBP _f ) to sterilize the bacteria on the hard surface to be cleaned. However, the detailed mechanism of how (A) the silver fine particle dispersion comes into contact with the bacteria to kill the bacteria is not known in detail.
The composition of the hard surface liquid detergent composition according to the present invention has the specific silver fine particle dispersion and a surfactant as essential components, and by combining these, excellent detergency and sterilization are achieved. It is possible to obtain a composition that exhibits strength and is excellent in stability over time.

As described above, in the combination of the silver fine particles and the anion activator disclosed in Patent Document 2, the counterion of the anion activator counter-exchanges with the silver ion in the composition, so that the sterilization power is lost. There was a malfunction that could be used.
On the other hand, according to the liquid detergent composition for hard surfaces according to the present invention, even when an anionic surfactant is included as the surfactant as the component (B), the bactericidal power of the silver fine particles is not deactivated, It is possible to effectively exhibit the original cleaning performance of the anionic active agent.
As described above, in the conventional technique in which a naked silver ion is contained in a cleaning composition, the naked silver ion reacts with chlorine in tap water to form a salt insoluble in water, thereby removing the cleaning agent. Although there was a problem that the microbial power was reduced, according to the liquid detergent composition for hard surface of the present invention, when used after diluting in tap water, or when the hard surface to be treated is wet with tap water or Even when diluted with tap water during use, it can be used without sacrificing sterilizing power.

  The liquid detergent composition for hard surfaces according to the present invention comprises (A) a silver fine particle dispersion and (B) a surfactant. Hereinafter, these two components will be described in detail with respect to other components that can be optionally added.

((A) Silver fine particle dispersion)
The silver fine particle dispersion (A) used in the present invention comprises a hyperbranched polymer (HBP _f ) having at least one functional group having a reducing ability selected from an alkoxide group, sulfide group, and amino group in the molecule and silver ions. By mixing with the solution (S-Ag) containing, the silver ions induced in the hyperbranched polymer (HBP _f ) are reduced by the functional group, and a large number of them in the hyperbranched polymer (HBP _f ). It is a silver fine particle inclusion type hyperbranched polymer (HBP _f -Ag) in which silver fine particles are formed.
The hyperbranched polymer (HBP _f ) which is the “hyperbranched polymer (HBP)” having at least one functional group having a reducing ability in the molecule is at least 1 in so-called hyperbranched polymer (HBP) as described later. A functional group having a reducing ability of the species is added.
Accordingly, first, the hyperbranched polymer (HBP) used in the present invention will be described, and then the hyperbranched polymer (HBP _f ) having at least one functional group having a reducing ability in the molecule will be described. .

(Hyperbranched polymer (HBP))
The hyperbranched polymer (HBP), which is a matrix of the silver fine particle dispersion that is the component (A) used in the present invention, is a general term for polymers having a number of branch points in the molecule, and dendritic (dendritic) together with dendrimers. Classified as a polymer. There are many differences in physical properties from conventional linear polymers. For example, there are differences such as surface polyfunctionality, low viscosity, and amorphousness. In particular, due to the surface polyfunctionality, further compounds can be condensed to the polymer surface functional groups.

The weight average molecular weight (Mw) of the hyperbranched polymer (HBP) used in the present invention is preferably 500 to 100,000, and more preferably 6,000 to 28,000.
Here, the weight average molecular weight (Mw) of the hyperbranched polymer (HBP) can be determined by preparing a 0.5 mass% aqueous solution and performing gel permeation chromatography (GPC) measurement at a temperature of 40 ° C. For example, it can be determined by using “RI-71 (trade name)” manufactured by Shodex as a measuring device, using water as a mobile solvent, and using polyethylene glycol as a standard substance. In the examples described later, measurement is performed under these conditions.

  The polydispersity (Mw / Mn) of the hyperbranched polymer (HBP) is preferably 1 to 10, and more preferably 1 to 5. In addition, Mn of the denominator of the polydispersity (Mw / Mn) is a number average molecular weight.

Furthermore, the absolute molecular weight of the hyperbranched polymer (HBP) is preferably 1,000 to 1,000,000, and more preferably 28,000 to 154,000.
Here, the absolute molecular weight of the hyperbranched polymer (HBP) can be measured by a multi-angle laser light scattering (MALLS).
The measurement conditions of the absolute molecular weight may be performed, for example, by connecting a Wyatt multi-angle light scattering detector (trade name “DAWN DSP-F”) to the aforementioned gel permeation chromatography (GPC) measurement line. it can.

  The hyperbranched polymer (HBP) used as the matrix in the silver fine particle dispersion (A) of the present invention is not particularly limited as long as it has the above-described properties, but is preferably a hyperbranched polymer ( HBP) is represented by the following general formula (I) containing a glycidyl ether group and a hydroxyl group:

（式（Ｉ）中、Ｘは分子中にヘテロ原子を有していてもよい置換アルカンを示し、グリシジルエーテル基および水酸基は置換アルカンＸを構成する炭素のうち共通の炭素に結合していてもよいし、それぞれ異なる炭素に結合されていてもよく、ｍは２以上の整数を示し、ｎは１以上の整数を示し、ｍ＞ｎ＞０である。）で表される化合物
を含むグリシジルエーテル化合物（イ）を塩基性触媒（ロ）の存在下で付加重合させることにより得られる。

(In the formula (I), X represents a substituted alkane which may have a hetero atom in the molecule, and the glycidyl ether group and the hydroxyl group may be bonded to a common carbon among the carbons constituting the substituted alkane X. Each of which may be bonded to different carbons, m represents an integer of 2 or more, n represents an integer of 1 or more, and m>n> 0). It can be obtained by subjecting compound (a) to addition polymerization in the presence of a basic catalyst (b).

  The general structure of the hyperbranched polymer obtained by addition polymerization of the glycidyl ether compound (a) in the presence of the basic catalyst (b) is shown in the following formula (1).

上記概略構造式（１）に示したポリマーは、ポリグリセロールグリシジルエーテル（ＧＤＧＥ）であり、いわゆるハイパーブランチポリマー（ＨＢＰ）である。

The polymer shown in the general structural formula (1) is polyglycerol glycidyl ether (GDGE), which is a so-called hyperbranched polymer (HBP).

Below, the manufacturing method of a hyperbranched polymer (HBP) is demonstrated.
(Starting material (I))
As a starting material for obtaining a hyperbranched polymer (HBP), a glycidyl ether compound (I) containing “a compound having a hydroxyl group and a larger number of glycidyl ether groups than the hydroxyl group” is used. As the “compound having a hydroxyl group and a larger number of glycidyl ether groups than the hydroxyl group” contained in the starting material (a), the compound (a) represented by the above general formula (I) is used. The compound (a) represented by the general formula (I) is a compound containing one or more hydroxyl groups and a larger number of glycidyl ether groups than the hydroxyl groups, and two or more reactive equivalent glycidyl ether groups are converted to glycerol. In other words, it is a compound possessed in the skeleton.

  X in the general formula (I) represents a substituted alkane. In the present invention, the “substituted alkane” means one in which at least a part or all of the hydrogen atoms constituting the alkane are replaced with a substituent. The substituted alkane X of the general formula (I) is an alkane in which at least a part or all of the hydrogen atoms constituting the alkane are substituted with a chemical bond with a glycidyl ether group or a hydroxyl group.

  The number of carbon atoms constituting the substituted alkane is preferably 1-20, more preferably 1-10, and particularly preferably 1-5. If it exceeds 20, the desired degree of branching may not be ensured.

  The structure of the substituted alkane may be linear, branched or cyclic, and may include two or more thereof. Of the hydrogen atoms constituting the substituted alkane, a hydrogen atom that is not substituted with a glycidyl ether group or a hydroxyl group may be substituted with a halogen atom. Furthermore, a part of the substituted alkane may contain a hetero atom such as an oxygen atom or a nitrogen atom. That is, some of the substituted alkanes have bonds such as —C (═O) O— (ester bond), —C (═O) NH— (amide bond), —O— (ether bond). May be. Further, a part of the substituted alkane may be dehydrogenated and may have a double bond or a triple bond.

  Specifically, examples of the alkane constituting the substituted alkane include methane, ethane, propane, isopropane, butane, isobutane, pentane, isopentane, and cyclohexane.

  In the general formula (I), the bonding site of the glycidyl ether group and the hydroxyl group to the substituted alkane X is not particularly limited. That is, each glycidyl ether group and hydroxyl group may be bonded to a common carbon among the carbons constituting the substituted alkane X, or may be bonded to different carbons. For example, glycidyl ether groups and hydroxyl groups may be bonded alternately, or each may be unevenly distributed.

  M and n in the general formula (I) represent the number of bonds between the glycidyl ether group and the hydroxyl group in the compound (a) represented by the general formula (I), respectively. m is an integer of 2 or more. When m is large, the number of remaining epoxy groups that can be converted into various functional groups increases, which is preferable. However, when the number of epoxy groups is excessively large compared to the number of hydroxyl groups, the reaction may not proceed, so the upper limit of m is preferably 10, more preferably 5, and even more preferably 3. n represents an integer of 1 or more and is in a relationship of m> n> 0 with m. That is, n is an integer smaller than m.

  The compound (a) represented by the general formula (I) is preferably a compound having a glycerol skeleton. The glycerol skeleton means a skeleton in which hydrogen of three hydroxyl groups of glycerin (glycerol) is removed. Note that the glycerin includes a derivative having a substituent such as an alkyl group. Since the oxygen atom is bonded to three different carbon atoms, the glycerol skeleton is the smallest molecule having the advantage that the reactivity of the glycidyl ether group is equivalent, and a hyperbranched polymer (HBP) having a high degree of branching is obtained. In addition, since glycerin is required to be developed as a surplus substance in the oil and fat industry, the compound (a) represented by the general formula (I) can be said to be a preferable compound to be used.

  There are no particular limitations on the production conditions of the compound (a) represented by the general formula (I), and examples thereof include 2 such as glycerol, diglycerol, triglycerol, trimethylolpropane, penquelithritol, sorbitol, sucrose, and degraded starch. And compounds derived from a compound having one or more hydroxyl groups and epichlorohydrin.

  Specific preferred compound names for the derivative compound include glycerol diglycidyl ether, glycerol-1-glycidyl-3- (propyl-3-chloro-2-glycidyl ether) ether, diglycerol polyglycidyl ether, trimethylol. Propane diglycidyl ether, pentaerythritol polyglycidyl ether, and the like.

  The diglycerol polyglycidyl ether is preferably diglycerol diglycidyl ether or diglycerol triglycidyl ether. Examples of the pentaerythritol polyglycidyl ether include pentaerythritol diglycidyl ether.

  Among the above specific examples, glycerol diglycidyl ether is preferable. Glycerol diglycidyl ether includes glycerol-1,3-diglycidyl ether (formula (II)), trimethylolpropane diglycidyl ether (formula (III)) represented by the following structural formulas (II) to (IV), and 1- (2-oxiranylmethoxy) -3- [2-chloro-3- (2-oxiranylmethoxy) propoxy] propan-2-ol (formula (IV)) can be mentioned, among these In particular, glycerol-1,3-diglycidyl ether represented by the structural formula (II) is preferable. These specific glycerol diglycidyl ethers can be obtained from, for example, Denacol series manufactured by Nagase ChemteX Corporation. The product manufactured by Nagase ChemteX Corporation contains the diglycidyl ether compound represented by the structural formulas (II) to (IV), that is, the diglycidyl ether compound (a) represented by the general formula (I). It is a diglycidyl ether compound, not a compound consisting only of the diglycidyl ether compound (a) represented by the general formula (I). That is, the said commercial item is a mixture of the diglycidyl ether compound (a) represented by general formula (I) and another glycidyl ether compound.

  In addition, the starting material (A) for the ring-opening addition polymerization (A) used to obtain the hyperbranched polymer (HBP) used as the main carrier (matrix) for the silver fine particle dispersion (A) used in the present invention includes the above general formula (I). In addition to the compound (a) represented by formula (I), a glycidyl ether compound other than the compound (a) represented by the general formula (I) may be included.

(Glycidyl ether compounds other than the compound (a) represented by the general formula (I))
Examples of the glycidyl ether compound other than the compound (a) represented by the general formula (I) include the following general formula (I-2):

（式（Ｉ−２）中、Ｙは水酸基を含有しない置換基を示し、ｋは１以上の整数を示す。）で表される化合物（ａ２）、及び下記一般式（Ｉ−３）：

(In formula (I-2), Y represents a substituent not containing a hydroxyl group, and k represents an integer of 1 or more) and the following general formula (I-3):

（式（Ｉ−３）中、Ｚはエポキシ基を含有しない置換基を示し、ｌは１以上の整数を示す。）で表される化合物（ａ３）からなる群から選ばれる少なくとも１種を挙げることができる。

(In the formula (I-3), Z represents a substituent not containing an epoxy group, and l represents an integer of 1 or more.) At least one selected from the group consisting of the compound (a3) represented by be able to.

  The compound (a2) represented by the general formula (I-2) is not particularly limited, and examples thereof include 1,2-epoxypropane, 1,2-epoxybutane, 1,2-epoxypentane, 1,2 -Epoxyhexane, 1,2-epoxyoctane, oxiranylcyclohexane, glycidyl methyl ether, glycidyl ethyl ether, glycidyl propyl ether, glycidyl butyl ether, glycidyl pentyl ether, glycidyl hexyl ether, glycidyl cyclohexyl ether, glycidyl phenyl ether, glycidyl acrylate, Examples thereof include glycidyl methacrylate, 1,2: 5,6-diepoxyhexane, and 1,2: 7,8-diepoxyoctane.

  Examples of other glycidyl ether compounds include those in which hydroxyl groups such as glycerol, diglycerol, triglycerol, trimethylolpropane, pentaerythritol, sorbitol, sucrose, and decomposed starch other than the above are substituted with glycidyl ether groups; aliphatic, Examples thereof include aromatic and alicyclic glycidyl ethers, glycidyl esters, and EOPO (ethylene oxide and propylene oxide) adducts thereof.

  Further, the compound (a3) represented by the general formula (I-3) is not particularly limited. For example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, Lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, linolyl alcohol, benzyl alcohol, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol , Isopropylmethylphenol, dibutylhydroxytoluene, o-hydroxyanisole, m-hydroxyanisole, p-hydroxyanisole, butylhydroxyanisole, hydroxy Tyl acrylate, hydroxyethyl methacrylate, ethylene glycol, 1,3-propanediol, propylene glycol, diethylene glycol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, hydroquinone, 1,1-bis (4-hydroxyphenyl) Cyclohexane, glycerin, trimethylolpropane, erythritol, glyceraldehyde, erythrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose.

  The ring-opening polymerization for obtaining the hyperbranched polymer (HBP) used in the present invention is carried out using a mixture of the compound (a) represented by the general formula (I) and other compounds having a glycidyl ether group. In order to maintain a high degree of branching, it is desirable that the compound (a) represented by the general formula (I) is 30% by mass or more, more preferably 50% by mass or more of the whole mixture.

  As the starting material (a) for obtaining the hyperbranched polymer (HBP) used in the present invention, a mixture of the compound (a) represented by the general formula (I) and other compounds having a glycidyl ether group is used. When the hyperbranched polymer (copolymer) is obtained, the degree of branching of the obtained hyperbranched polymer can be controlled by adjusting the mixing ratio.

(Basic catalyst (b))
In order to synthesize the hyperbranched polymer (HBP), a glycidyl ether compound (I-1) consisting only of the compound (a) represented by the general formula (I) or a compound represented by the general formula (I) Using the glycidyl ether compound (a-2) containing (a) as the starting material (a), ring-opening addition polymerization using the basic catalyst (b) is performed on the starting material (a). The basic catalyst (b) acts on the hydroxyl group to react with the epoxy group, and does not act directly on the epoxy group. Therefore, a hyperbranched polymer (HBP) having an epoxy group can be finally obtained.

  Examples of the basic catalyst (b) include alkali metals, alkaline earth metals, hydrides thereof, alkoxides, hydroxides, alkylates, carbonates, and the like. Among these, for example, potassium carbonate, potassium hydroxide, potassium methoxide, sodium carbonate and the like are preferable.

  In the synthesis of the hyperbranched polymer, the glycidyl ether compound (I-1) consisting only of the compound (a) represented by the general formula (I) or the compound (a) represented by the general formula (I) is included. Using the glycidyl ether compound (I-2) as a starting material (I), this starting material (I) is subjected to addition polymerization (also referred to as ring-opening polymerization or ring-opening addition polymerization) in the presence of a basic catalyst (B). There is no particular limitation on the conditions for the polymerization.

  The blending amount of the basic catalyst (b) used is desirably 0.1 to 30% by mass, and preferably 1 to 20% by mass with respect to the starting material (a).

  As a method for introducing the basic catalyst (b), there are a method in which the basic catalyst is added in advance to the reaction vessel, a method in which the basic catalyst is dropped into the reaction vessel continuously, a method in which the basic catalyst (b) is dropped into the reaction vessel divided every predetermined time, and the like. Can be mentioned.

  The ring-opening addition polymerization proceeds without the presence of a solvent, but can also be carried out in various solvents. The type of solvent is not particularly limited, but hydrocarbon solvents such as benzene and toluene, ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, methylene chloride, chloroform , Halogenated hydrocarbon solvents such as chlorobenzene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, acetonitrile, propionitrile, benzonitrile, etc. Nitrile solvents, ester solvents such as ethyl acetate and butyl acetate, carbonate solvents such as ethylene carbonate and propylene carbonate, N, - dimethylformamide, N, include amide solvents such as N- dimethylacetamide. These may be used alone or in combination of two or more.

  Further, the reaction concentration [the concentration of the compound (a) represented by the general formula (I) with respect to the solvent (in the case of the starting material (a)), or another compound having a glycidyl ether group as the starting material (a) is used at the same time. In this case, the total concentration of the compound and the compound (a) represented by the general formula (I) with respect to the solvent] is 1% by mass to 100% by mass (no solvent), preferably 10% by mass to 100% by mass. %, More preferably 30% by mass to 100% by mass.

In the ring-opening addition polymerization, the monomer solution and the catalyst are preferably mixed under an inert gas (Ar, N _2, etc.). At this time, the monomer solution may be mixed at a time or dropped into the reaction system. The reaction temperature is preferably 30 ° C to 180 ° C, more preferably 60 ° C to 160 ° C. The reaction time is 0.5 to 10 hours, more preferably 1 to 7 hours to complete the polymerization.

  The selection of the reaction temperature and reaction time in the addition polymerization affects the degree of branching and the molecular weight. In the epoxy ring-opening polymerization in the present invention, first, a secondary alkoxide is selectively prepared by ring opening of an epoxy group, and then converted to a primary alkoxide by proton exchange equilibrium. Since active proton exchange improves the degree of branching, in order to promote rapid proton exchange and obtain a highly branched polymer, a reaction at a high temperature (for example, 50 ° C. or more, preferably 80 to 150 ° C.) desirable. If the reaction temperature is still high after the monomer consumption is complete, the terminal epoxy group may be ring-opened due to moisture in the system. It is desirable to quickly reduce to room temperature.

  After completion of the polymerization, the catalyst can be removed from the polymer by filtration, ion exchange, neutralization or the like. At this time, if necessary, the polymer is dissolved in a suitable solvent, for example, methanol. Further, the polymer may be purified by reprecipitation.

  Among the hyperbranched polymers obtained by ring-opening polymerization, for example, the hyperbranched polymer having a glycerol skeleton was measured by 13C-NMR of the preparation. References (Macromolecules 1999, 32, 4240-4246, Macromolecules 2000, 33, 8158-8166), which shows a strong resonance of 79 to 81 ppm specific to the trisubstituted carbon atom of the branching unit, confirming that it is a multibranched body.

  In the present invention, the hyperbranched polymer (HBP) suitable for use as the matrix of the silver fine particle dispersion (A) is a multi-branched body as described above, and therefore its structure is usually spherical. Confirmation of the spherical structure can be made by checking whether the weight average molecular weight measured by GPC and the absolute molecular weight measured by MALLS differ greatly (Frechet, M. et al. Am. Chem. Soc. 1999, 121, 2313 .; Sawamoto, et al. Macromolecules, 2001, 34, 7629.).

  That is, the value of GPC (manufactured by Shodex, trade name “RI-71”) and the value of the absolute molecular weight obtained by a multi-angle light scattering detector: MALLS (manufactured by Wyatt, trade name “DAWN DSP-F”) It can be determined according to the difference between the GPC measurement value and the MALLS value.

  When the GPC measurement value and the MALLS value are greatly different, it can be determined that the polymer is a spherical polymer. Usually, if the absolute molecular weight measured by MALLS is 2 times or more, preferably 3 times or more the weight average molecular weight measured by GPC, it can be determined as a spherical structure. Moreover, although an upper limit is not prescribed | regulated in particular, Usually, it is 10 times or less.

  The weight average molecular weight (Mw) and absolute molecular weight can be measured under the following measurement conditions. Measurement values in Examples described later are also obtained under the following measurement conditions.

(Weight average molecular weight (Mw), measurement conditions for absolute molecular weight)
The weight average molecular weight and absolute molecular weight are measured simultaneously by connecting a gel permeation chromatography and a multi-angle light scattering detector.

(measuring device)
Autosampler: Auto Sampler 23 (SIC System Instruments)
Pump: DS-4 (manufactured by Shodex)
Degasser: SD-8012 (manufactured by Lab-Quatec)
Oven: CO-8020 (manufactured by Tosoh)
Light scattering detector (MALLS): MALLS: DAWN DSP-F (manufactured by Wyatt)
RI detector: RI-71 (manufactured by Shodex)

(Elution conditions)
Column: TSK-GEL GMPWXL + TSK-GEL G2500PWXL (manufactured by Tosoh Corporation)
Mobile phase: water / acetonitrile = 80/20 v / v (NaNO3: 10 mM)
Column temperature: 40 ° C
Flow rate: 0.5 mL / min.

(Test substance)
Concentration: 0.5% aqueous solution (as a pretreatment for molecular weight measurement, GL Chromatodisc 13N (water system 0.45 μm (sold by: GL Sciences Inc.) is passed.)
Injection volume: 100 μL

(Calibration curve)
Standard sample: PEG (molecular weight 20,000, 13,000, 6,000, 4,000, 2,000, 1,500, 1,000, 600, 400)

  In the present invention, (A) a hyperbranched polymer (HBP) suitable for use as a matrix of the silver fine particle dispersion has an epoxy group at the terminal and a hydroxyl group in the molecule. The term “end” means the end of a branched chain constituting the polymer. The branched chain is formed from an alkane containing -C (= O) O- (ester bond), -C (= O) NH- (amide bond), ether bond (-O-), etc. in the middle. It has abundant substituents containing oxygen.

(Hyperbranched polymer (HBP _f ) having a functional group having at least one reducing ability in the molecule)
In the present invention, (A) the hyperbranched polymer (HBP) used as the matrix of the silver fine particle dispersion is used in a state where at least one functional group having a reducing ability is added. The hyperbranched polymer (HBP _f ) provided with a functional group having at least one reducing ability will be described below.

(Reducing ability)
The “reducing ability” referred to in the present invention refers to the ability to give electrons and reduce metal ions. When metal ions are reduced, single metal particles are generated.

(Functional group with reducing ability)
The “functional group having a reducing ability” as used in the present invention refers to a functional group having the ability to reduce silver ions. The “functional group having a reducing ability” is reduced by imparting electrons to silver ions and is itself oxidized.

(Hyperbranched polymer (HBP _f ) having a functional group with reducing ability)
The hyperbranched polymer (HBP _f ) having a functional group having a reducing ability can be prepared by the following three methods (i) to (iii).

  (I) When the hyperbranched polymer is synthesized, the hyperbranched polymer having a “site having reducing ability” is used as it is. Examples of such hyperbranched polymers that themselves have reducing ability include those in which the “functional group having reducing ability” is a hydroxyl group, and commercially available polyethyleneimine (manufactured by Kanto Chemical Co., Inc.) And polyamide amine dendrimer (manufactured by Sigma-Aldrich).

(Ii) A hyperbranched polymer having no reducing ability is used as a raw material, and a functional group having a reducing ability is acquired by adding a pH adjuster (such as NaOH) separately to the hyperbranched polymer.
Examples of the method for imparting the functional group having the reducing ability include a method of adding a pH adjuster to the hyperbranched polymer solution and adjusting the pH to 10 to 14. As a result of the pH adjustment, the terminal hydroxyl group of the hyperbranched polymer is converted to an alkoxide group, so that a “functional group having a reducing ability” is formed in the hyperbranched polymer, and the hyperbranched polymer itself has a reducing ability. . As the pH adjuster in this case, sodium hydroxide, potassium hydroxide, an aqueous ammonia solution or the like is used.

  The hyperbranched polymer to which the “functional group having a reducing ability” is added in this way can also be used in the (A) silver fine particle dispersion used in the present invention. As such hyperbranched polymers, “Polyglycerin-10 (trade name)” and “Polyglycerin-X (trade name)” manufactured by Daicel Chemical Industries, Ltd., “PG-2 (Product) manufactured by Hyperpolymers, Inc. are commercially available. Name) ”,“ Top Brain (trade name) ”manufactured by Toei Sangyo Co., Ltd.,“ Hyperbranched 2,2-bis (hydroxymethyl) propanoic acid polyester (trade name) ”produced by Sigma Aldrich,“ Bolton H2003 (product name), “Bolton H2004 (product name)”, “Bolton H30 (product name)”, “Bolton H40 (product name)”, and the like.

  (Iii) A hyperbranched polymer that does not have a reducing ability is used as a raw material, and a functional group having a reducing ability is acquired later by condensing a compound separately to the hyperbranched polymer.

The functional group having the reducing ability can be imparted, for example, as follows.
A compound that introduces an amino group, sulfide group, or the like has a functional group that originally has a reducing ability by subjecting it to a condensation reaction with a reaction site of a hyperbranched polymer (which can be exemplified by a hydroxy group, an epoxy group, or an isocyanate group). The functional group (NH-R, SR, etc.) which has a reducing ability can be introduce | transduced into the hyperbranched polymer which does not. An example of the reaction formula of this reaction is as follows.
HBP-RG + R-NH ₂ → HBP-NH-R
HBP-RG + R-SH → HBP-SR
(In the formula, HBP is a hyperbranched polymer that originally has no functional group having a reducing ability, RG represents a reaction site of the hyperbranched polymer, and R represents an organic group.)

More specifically, a hyperbranched polymer (HBP _f ) having a functional group (amino group, sulfide group) having a reducing ability can be synthesized by condensing the following compounds.

(Amino group)
The compound for introducing an amino group is not particularly limited, and tertiary amines, secondary amines, primary amines, and other aromatic amines can be used.

  Examples of the tertiary amine include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tricyclohexylamine, N-methylpyrrolidine, N-methylpiperidine, N-ethylpyrrolidine, N-ethylpiperidine and the like. it can.

  Examples of the secondary amine include N-methyl-D-glucamine, N-methylaminopropanediol, dimethylamine, diethylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i. Examples include -butylamine, di-sec-butylamine, di-t-butylamine, dicyclohexylamine, pyrrolidine, piperidine and the like.

  Examples of the primary amine include D-glucamine, methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, cyclohexylamine and the like.

  Examples of the other aromatic amines include aniline, o, m, p-toluidine, o, m, p-ethylaniline, xylidine, mesidine, o, m, p-chloroaniline, chlorotoluidine, dichloroaniline, and trichloroaniline. O, m, p-fluoroaniline, o, m, p-bromoaniline, fluorochloroaniline, o, m, p-aminophenol, o, m, p-aminothiophenol, anisidine, phenetidine, o, m, p-aminobenzoic acid, aminochlorophenol, aminobenzonitrile, cresidine, toluidinesulfonic acid, sulfanilic acid, chlorotoluidinesulfonic acid, aminonaphthalenesulfonic acid, aminobenzotrifluoride, aminobenzenesulfonic acid, p-aminoacetanilide, naphthylamine, Naphthylami Sulfonic acid or aminonaphthol sulfonic acid, N-methylaniline, N-ethylaniline, N-ethyltoluidine, diphenylamine, hydroxyphenylglycine or N-methylaminophenol sulfate, N, N-dimethylaniline, N-ethyl-N-hydroxy Ethyltoluidine, N, N-diethyltoluidine, N-benzyl-N-ethylaniline or N, N-diglycidylaniline, o, m, p-phenylenediamine, chloro-p-phenylenediamine, chloro-m-phenylenediamine, Phenylenediamines such as fluorophenylenediamine, dichlorophenylenediamine, methylphenylenediamine, dimethylphenylenediamine, chloromethylphenylenediamine, xylylenediamine, toluylenediamine, benzine Benzidines such as benzene, o-tolidine, dianicidin, dichlorobenzidine, diphenylmethanes such as diaminodiphenylmethane, diaminodichlorodiphenylmethane, diaminodimethyldiphenylmethane, diaminodiethyldiphenylmethane, naphthalenediamine, diaminobenzanilide, diaminodiphenyl ether, diaminostilbenzenedisulfonic acid, diamino Examples include phenol dihydrochloride, leucodiaminoanthraquinone, amino-N, N-diethylaminotoluidine hydrochloride or amino-N-ethyl-N- (β-methanesulfonamidoethyl) -toluidine sulfate hydrate. Of these, any compound having at least one amino group in the molecule may be used.

(Sulfide group)
The compound for introducing a sulfide group is not particularly limited, and alkylthiols (eg, α-thioglycerol, methyl mercaptan, ethyl mercaptan, etc.) that are thiol group-containing compounds, aryl thiols (eg, thiophenol). Thionaphthol, benzyl mercaptan, etc.), amino acids or derivatives thereof (eg, cysteine, glutathione, etc.), peptide compounds (eg, dipeptide compounds containing cysteine residues, tripeptide compounds, tetrapeptide compounds, 5 or more amino acid residues Including oligopeptide compounds), or proteins (for example, globular proteins having metallothionein or cysteine residues arranged on the surface). Of these, any compound having at least one sulfide group in the molecule may be used.

  As described above, a hyperbranched polymer that is acquired with a “functional group having a reducing ability” can also be used in the metal particle dispersion according to the present invention. Examples of such hyperbranched polymers include the products listed in (ii) above as commercially available products, and poly (glycerol-1,3-diglycidyl ether) derivatives can also be used.

(Silver ion)
Examples of the silver ion source that can be used in the silver fine particle dispersion (A) used in the present invention include silver sulfate, nitrate, acetate, acetylacetonate, perchlorate, and organic acid salt. It is done.

(Solvent of solution (S-Ag) containing silver ions)
Although the silver ions are present in the solution, polar solvents such as water and alcohols are mainly used as the solvent of this solution, but nonpolar solvents can also be used as long as the solvent dissolves silver. . Examples of the alcohols include methanol, ethanol, propanol, and butanol. Examples of other polar solvents include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, acetone, dimethyl sulfoxide (DMSO), Examples thereof include dimethylformamide (DMF).

(Protecting group)
The protecting group refers to an atomic group that improves the dispersion stability of silver fine particles generated by reduction of silver ions. The protecting group can be introduced by condensing a protecting group-introducing compound to the terminal functional group of the hyperbranched polymer.

(Protecting group-introducing compound)
Examples of the compound that condenses to the terminal functional group of the hyperbranched polymer as a protecting group include, for example, a hydroxy group, a ketone group, an acetyl group, an aldehyde group, a carboxyl group, an ester group, a thioester group, a nitrate ester group, a phosphate ester group, and an amide. Groups, thioamide groups, imide groups, amidine groups, amino groups, cyano groups, oxime groups, thiol groups, sulfide groups, disulfide groups, sulfonic acid groups, urea groups, urethane groups, nitro groups, ether groups, and the like. .

  More specifically, examples of the hydroxy group include glycidol and glycerin. Examples of the ether group include glycidol, glycerin, polyethylene glycol, and polypropylene glycol. Examples of the carboxyl group include citric acid. Carboxylic acids and carboxylic anhydrides can be mentioned.

  In the case where a functional group having a function as a protective group such as an amino group or a sulfide group has already been provided as a functional group having a reducing ability, it is not necessary to introduce a protective group.

((A) Content of silver fine particle dispersion)
The content of the (A) silver fine particle dispersion is preferably 10.0 to 1000 ppm, more preferably 50.0 to the total amount of the detergent composition from the viewpoint of sterilization power and storage stability. 300 ppm is desirable. If the content is less than 10.0 ppm, sufficient sterilizing power cannot be obtained, and if it exceeds 1000 ppm, there is a problem in stability such as precipitation.

((A) Particle size of silver fine particles in silver fine particle dispersion)
(A) The particle size of the silver fine particles in the silver fine particle dispersion can be measured as follows, but the silver ions introduced into the hyperbranched polymer (HBP _f ) having a functional group having a reducing ability. the amount, the structure of the hyperbranched polymer (HBP _f) inside the fine space, modifications density type and the functional group of the functional groups in the hyperbranched polymer (HBP _f), the temperature causes a reduction reaction, by factors such as time Because it is very different, it cannot be described uniquely.

((A) Conditions for measuring particle diameter of silver fine particles in silver fine particle dispersion)
A silver fine particle-containing hyperbranched polymer (HBP _f -Ag) aqueous solution (sample) is dropped on a TEM observation microgrid, vacuum-dried for 3 days, and then TEM observation of silver fine particles generated in the polymer is performed. From the obtained TEM image, the particle size of the silver fine particles is measured using image analysis software. The particle size is measured at N = 200. Also, the standard deviation σ is calculated from the result. From the average particle diameter R and standard deviation σ, the following general formula:
Dispersity K = (standard deviation σ) / (average particle size R)
Is used to define the degree of dispersion K, and the degree of dispersion K is calculated for each sample.

(Measurement device used for TEM observation)
TEM: Hitachi H-7600 (manufactured by Hitachi High-Technology Corporation)
Micro grid for TEM observation: STEM-150 Cu grid, Type B (spread product), Carbon reinforced (manufactured by Oken Shoji Co., Ltd.)
Image analysis software: Scion Image (made by Scion Corporation, USA)

((B) Surfactant)
As the surfactant (B) that can be used in the present invention, any of an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a semipolar surfactant, and a cationic surfactant can be used. Can be used. These may be used singly or in combination of two or more.

  Specific examples of the anionic surfactant include, for example, alkylbenzene sulfonate, alkane sulfonate, alkyl sulfate, alkyl polyoxyethylene sulfate, α-olefin sulfonate, alkylphenoxyphenyl disulfonate, fatty acid, and the like. Salt, α-sulfo fatty acid salt, ether carboxylate, alkyl phosphate salt, alkyl phosphate polyoxyethylene salt, dialkyl sulfosuccinate ester salt, alkyl sulfosuccinate salt, alkenyl succinate, N-acyl amino acid salt, N- Examples include acylmethyl taurine salt. These may be used singly or in combination of two or more.

  The anionic surfactant is preferably alkyl (C10-14) benzene sulfonate, secondary alkane (C14-17) sulfonate, alkyl (C12-14) polyoxyethylene sulfate (EO average addition) Mole number 1-5), α-olefin sulfonate (C12-14), alkyl (C10-12) phenoxyphenyl disulfonate. The counter ions (cations) of these anionic surfactants are alkali metal ions, alkaline earth metal ions, alkanolamine ions, ammonium ions, etc., preferably sodium ions.

  Nonionic surfactants include polyoxyalkylene (C2 to C4) alkyl ethers (EO average addition moles = 3 to 20), polyoxyethylene alkylphenyl ethers (EO average addition moles = 3 to 20), alkylpolyalkylenes. Examples include glucoside, fatty acid polyglycerin ester, fatty acid sucrose ester, and fatty acid alkanolamide. These may be used singly or in combination of two or more.

  The nonionic surfactant is preferably a polyoxyethylene adduct of a linear alcohol having 12 carbon atoms (EO average addition mole number of 3 to 20) or 2-ethylhexyl polyglycoxide.

  Specific examples of the amphoteric surfactant include alkylaminopropionic acid, fatty acid amidopropyl betaine, fatty acid dimethylaminoacetic acid betaine, alkylbetaine, alkylhydroxysulfobetaine, alkylamidobetaine, imidazolinium betaine, N-alkylamino acid and the like. It is done. Preferred are lauryldimethylaminoacetic acid betaine and lauric acid amidopropyl betaine. These may be single or a mixture of two or more.

  Specific examples of the semipolar surfactant include alkylamine oxide and alkylamidopropylamine oxide. N-dodecyldimethylamine oxide is preferred.

  Specific examples of the cationic surfactant include alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl ammonium salt, benzalkonium salt, benzethonium salt, pyridinium salt, imidazolinium salt and the like. Counter ions (anions) of these cationic surfactants are halogen ions and the like. These surfactants can be used alone or in admixture of two or more.

  (B) Surfactant used in the present invention has good detergency against sebum dirt and oil dirt, so alkyl (C10-14) benzene sulfonate, secondary alkane (C14-17) sulfonic acid Salt, alkyl (C12-14) polyoxyethylene sulfate (EO average addition mole number 1-5), α-olefin sulfonate (C12-14), alkyl (C10-12) phenoxyphenyl disulfonate, polyoxy Alkylene (C2 to C4) alkyl ether (EO average addition mole number = 3 to 20), alkyl polyglycoside, alkylamine oxide, fatty acid amidopropyl betaine, fatty acid dimethylaminoacetic acid betaine are more preferred, and alkyl (C10-14) benzenesulfone Acid salt, secondary alkane (C14-17) sulfonate, polio Shiarukiren (C2-C4) alkyl ether (EO average addition molar number = 3-20) are more preferable.

  (B) Specific examples of the surfactant include sodium alkyl (C12-14) benzenesulfonate (“Lypon LH-200” manufactured by Lion Corporation), secondary alkane (C14-17) sodium sulfonate ( "HOSTAPUR SAS 30A" manufactured by Clariant Japan Co., Ltd.), sodium α-olefin sulfonate (C10) (manufactured by Lion Corporation, trade name "Lipolane LB-440"), polyoxyethylene alkyl (C12-14) sodium ether sulfate (EO average added mole number = 3): (“Sanol LMT-1430” manufactured by Lion Corporation), alkyl (C10-12) sodium phenoxyphenyldisulfonate: (“DOWFAX 2A1” manufactured by DOWFAX), polyoxyethylene alkyl (C12 ) Ether (EO average addition mole) = 15): ("LAO-90" manufactured by Lion Chemical Co., Ltd.), 2-ethylhexyl polyglycoside ("AG6202" manufactured by Lion Akzo Co., Ltd.), n-dodecyldimethylamine oxide ("AX manufactured by Lion Akzo Co., Ltd.)" Agent "), lauryl dimethylaminoacetic acid betaine:" Levon LD-36 "manufactured by Sanyo Kasei Kogyo Co., Ltd., lauric acid amidopropyl betaine:" Enagicol L-30B "manufactured by Otsuka Kogyo Co., Ltd.

((B) Surfactant content)
The content of the (B) surfactant used in the present invention is 0.5 to 15.0% by mass (hereinafter simply referred to as “%”) with respect to the total amount of the detergent composition from the viewpoint of detergency and storage stability. More preferably, it is desirable to set the content to 1.0 to 8.0%. If the surfactant content is less than 0.5%, sufficient detergency cannot be obtained, and if it exceeds 15.0%, there is a concern that stability may occur, such as precipitation, and washing. It is uneconomical with no improvement in power.

(Other ingredients)
In addition to the above (A) silver fine particle dispersion and (B) surfactant, the hard surface cleaning composition of the present invention may optionally use additives that are usually added, if necessary. . Examples of such other components include solvents and fragrances exemplified below, other known water-soluble polymers, stabilizers, natural extracts, and pigments.

(solvent)
In the present invention, a solvent can be appropriately blended for the purpose of dissolving the components. Specific examples of the solvent include water, methanol, ethanol, n-propanol, isopropanol, n-butanol, s-butanol, t-butanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tri Examples include propylene glycol, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, glycerin, alkyl glyceryl ether, and phenoxyethanol. Among these, diethylene glycol monobutyl ether (DEMB) is preferably selected from the viewpoint of the effect of dissolving the components. The content is preferably 1 to 15% based on the total amount of the composition. If it is less than 1%, the storage stability is not preferable, and if it is 15% or more, the base odor is strong and not preferable. The solvent may be used alone or in combination of two or more.

(Fragrance)
In the present invention, a perfume can be appropriately blended for the purpose of perfume and the like.
The fragrance component is not particularly limited, but specific examples include aliphatic hydrocarbons, terpene hydrocarbons, aromatic hydrocarbons and other hydrocarbons, aliphatic alcohols, terpene alcohols, aromatic alcohols and other alcohols. , Ethers such as aliphatic ethers and aromatic ethers, oxides such as aliphatic oxides and terpene oxides, aldehydes such as aliphatic aldehydes, terpene aldehydes, hydrogenated aromatic aldehydes, thioaldehydes and aromatic aldehydes , Aliphatic ketones, terpene ketones, hydrogenated aromatic ketones, aliphatic cyclic ketones, ketones such as non-benzene aromatic ketones, aromatic ketones, acetals, ketals, phenols, phenol ethers, fatty acids, terpenes Carboxylic acids, hydrogenated aromatic carboxylic acids, aromatic carboxylic acids, etc. , Acid amides, aliphatic lactones, macrocyclic lactones, terpene lactones, hydrogenated aromatic lactones, aromatic lactones and other lactones, aliphatic esters, furan carboxylic acid esters, aliphatic cyclic carboxylic acid esters, cyclohexyl Synthetic fragrances such as carboxylic acid ester, terpene carboxylic acid ester, aromatic carboxylic acid ester, etc., nitromusks, nitriles, amines, pyridines, quinolines, pyrrole, indole, etc. Natural fragrances can be mentioned. A fragrance | flavor component may use individually or 2 types or more, and multiple are normally used.

  Examples of the hard surface liquid cleaning composition according to the present invention will be described below. In addition, this invention is not limited by the Example shown below.

  First, the preparation method of each component used in the following Examples and Comparative Examples is shown below. The compounding amount (mass%) of each component is a pure conversion value. In addition, the weight average molecular weight and absolute molecular weight of the components were determined according to the previously described (weight average molecular weight (Mw), measurement conditions for absolute molecular weight). Further, the particle size of the silver fine particles was determined by the above-described ((A) measurement conditions for the particle size of silver fine particles in the silver fine particle dispersion) and (measuring device used for TEM observation).

((A) Silver fine particle dispersion)
(Synthesis of polyglycerol diglycidyl ether (GDGE))
A 300 mL four-necked separable flask equipped with a stirrer, a reflux condenser and a nitrogen inlet tube is charged with 100 g of glycerol diglycidyl ether and 15 g of potassium carbonate, and the four-necked separable flask through the nitrogen inlet tube while stirring. Nitrogen gas was introduced into the inside. Subsequently, the four-neck separable flask into which nitrogen gas was introduced was heated in an oil bath at 140 ° C. for 300 minutes. After warming, the reaction mixture was dissolved in methanol, solids were removed by filtration, and the solvent was distilled off to obtain a viscous liquid polyglycerol diglycidyl ether (GDGE).

  The obtained polyglycerol diglycidyl ether (GDGE) has a converted molecular weight (weight average molecular weight) by GPC of 6000, an absolute molecular weight by MALLS of 28000, and an absolute molecular weight value by MALLS of 4. It was 7 times. This GDGE is a hyperbranched polymer (HBP) represented by the general structural formula (1) described above.

(Synthesis of hyperbranched polymer (HBP _f- 1a) to which an alkoxide group is added as a functional group having a reducing ability)
Here, the hyperbranched polymer (HBP _f- 1a) having a functional group having a reducing ability to synthesize the hyperbranched polymer (HBP-1a) represented by the following formula (1a) as described above. An intramolecular hydroxyl group is converted to an alkoxide group by adding an agent (such as NaOH). In the formula (1a), GDGE is a polyglycerol diglycidyl ether represented by the general structural formula (1) shown above.

先に示した概略構造式（１）で表されるポリグリセロールジグリシジルエーテル（ＧＤＧＥ）１００ｇに超純水１００ｇを加え溶解した。ここへ１％硫酸２０ｇを氷浴中でゆっくり滴下し、滴下終了後、１時間室温で攪拌した。この過程で、エポキシド基は開環し、水酸基に変換される。攪拌終了後、１Ｎ水酸化ナトリウム水溶液を用いて中和し、ｐＨを７付近に調整した。

100 g of ultrapure water was dissolved in 100 g of polyglycerol diglycidyl ether (GDGE) represented by the general structural formula (1) shown above. To this, 20 g of 1% sulfuric acid was slowly added dropwise in an ice bath, and after completion of the addition, the mixture was stirred for 1 hour at room temperature. In this process, the epoxide group is opened and converted to a hydroxyl group. After completion of stirring, the mixture was neutralized with 1N aqueous sodium hydroxide solution and the pH was adjusted to around 7.

The obtained reaction solution was transferred to a dialysis membrane and dialyzed against ion exchange water for 3 days. After dialysis, ion-exchanged water was distilled off with an evaporator to obtain a hyperbranched polymer (HBP-1a) represented by the formula (1a). Next, in order to give an alkoxide group having a reducing ability to the molecule of the hyperbranched polymer (HBP-1a), (HBP-1a) is again made into an aqueous solution, and caustic soda is further added thereto to make it alkaline. A hyperbranched polymer (HBP _f- 1a) having an alkoxide group having a reducing ability was obtained.

The functional group having the reducing ability of the obtained hyperbranched polymer (HBP _f- 1a) is an alkoxide group, and the converted molecular weight (weight average molecular weight) by GPC is 7500, the absolute molecular weight by MALLS is 31000, and by MALLS The absolute molecular weight value was 4.1 times the GPC weight average molecular weight value.

(Synthesis of hyperbranched polymer (HBP _f- 1b) having an amino group as a functional group having a reducing ability)
Here, the hyperbranched polymer (HBP _f- 1b) having a functional group having a reducing ability to be synthesized is a polymer represented by the following formula (1b). In the formula (1b), GDGE is a polyglycerol diglycidyl ether represented by the general structural formula (1) shown above.

先に示した概略構造式（１）で表されるポリグリセロールジグリシジルエーテル（ＧＤＧＥ）２０ｇをメタノール１０ｇに溶解し、ジエチルアミン（還元能を有する官能基導入成分）３．６ｇを加え、６５℃還流条件下１８時間加熱攪拌をした。得られた反応物からエバポレーターにより溶媒留去し、透析膜へ移しイオン交換水にて３日間透析を行った。透析後、イオン交換水をエバポレーターで留去し、ジエチルアミノ−ハイパーブランチポリグリセリン（ハイパーブランチポリマー（ＨＢＰ_ｆ−１ｂ）を得た。

Dissolve 20 g of polyglycerol diglycidyl ether (GDGE) represented by the general structural formula (1) shown above in 10 g of methanol, add 3.6 g of diethylamine (functional group-introducing component having a reducing ability), and reflux at 65 ° C. The mixture was stirred under heating for 18 hours under the conditions. The solvent was distilled off from the obtained reaction product with an evaporator, transferred to a dialysis membrane, and dialyzed against ion-exchanged water for 3 days. After dialysis, ion-exchanged water was distilled off with an evaporator to obtain diethylamino-hyperbranched polyglycerin (hyperbranched polymer (HBP _f- 1b).

The functional group having the reducing ability of the obtained hyperbranched polymer (HBP _f- 1b) is an amino group, the converted molecular weight (weight average molecular weight) by GPC is 13000, the absolute molecular weight by MALLS is 49000, and by MALLS. The absolute molecular weight value was 3.8 times the weight average molecular weight value by GPC.

(Synthesis of hyperbranched polymer (HBP _f- 1c) having a sulfide group as a functional group having a reducing ability)
Here, the hyperbranched polymer (HBP _f -1c) having a functional group having a reducing ability to be synthesized is a hyperbranched polymer represented by the following formula (1c). In the formula (1c), GDGE is a polyglycerol diglycidyl ether represented by the general structural formula (1) shown above.

先に示した概略構造式（１）で表されるポリグリセロールジグリシジルエーテル（ＧＤＧＥ）２０ｇをメタノール７．２ｇに溶解し、Ａ液とした。また、αチオグリセロール（還元能を持つ部位導入成分＋保護基形成成分）５．２ｇをカリウムメトキシド（２８％メタノール溶液）１．２ｇに溶解し、アルゴン雰囲気にて常温常圧下、１時間攪拌し、これをＢ液とした。

20 g of polyglycerol diglycidyl ether (GDGE) represented by the general structural formula (1) shown above was dissolved in 7.2 g of methanol to obtain a solution A. In addition, 5.2 g of α-thioglycerol (site introduction component having reducing ability + protecting group forming component) is dissolved in 1.2 g of potassium methoxide (28% methanol solution) and stirred for 1 hour at normal temperature and normal pressure in an argon atmosphere. This was designated as solution B.

The solution B was slowly added dropwise to the solution A, and the mixture was stirred under heating at 65 ° C. for 18 hours. The solvent was distilled off from the obtained reaction product with an evaporator, transferred to a dialysis membrane, and dialyzed against ion-exchanged water for 3 days. After dialysis, ion-exchanged water was distilled off with an evaporator to obtain thioglycerol-hyperbranched polyglycerin (hyperbranched polymer (HBP _f- 1c)).

The functional group having the reducing ability of the obtained hyperbranched polymer (HBP _f -1c) is a sulfide group, the converted molecular weight (weight average molecular weight) by GPC is 12000, the absolute molecular weight by MALLS is 65000, and by MALLS The absolute molecular weight value was 5.4 times the weight average molecular weight value by GPC.

(Synthesis of hyperbranched polymer (HBP _f- 1d) having an amino group as a functional group having a reducing ability)
Here, the hyperbranched polymer (HBP _f- 1d) having a functional group having a reducing ability to be synthesized is a hyperbranched polymer represented by the following formula (1d). In the formula (1d), GDGE is a polyglycerol diglycidyl ether represented by the general structural formula (1) shown above.

先に示した概略構造式（１）で表されるポリグリセロールジグリシジルエーテル（ＧＤＧＥ）１０ｇをメタノール１０ｇに溶解し、Ｎ−メチル−Ｄ−グルカミン（還元能を持つ部位導入成分＋保護基形成成分）４．８ｇ、テトラブチルアンモニウムブロミド（縮合触媒）０．１６ｇを加え、６５℃還流条件下１８時間加熱攪拌をした。得られた反応物からエバポレーターにより溶媒留去し、透析膜へ移しイオン交換水にて３日間透析を行った。透析後、イオン交換水をエバポレーターで留去し、メチルグルカミン−ハイパーブランチポリグリセリン（ハイパーブランチポリマー（ＨＢＰ_ｆ−１ｄ））を得た。

10 g of polyglycerol diglycidyl ether (GDGE) represented by the general structural formula (1) shown above is dissolved in 10 g of methanol, and N-methyl-D-glucamine (site introduction component having reducing ability + protecting group forming component) 4.8 g and tetrabutylammonium bromide (condensation catalyst) 0.16 g were added, and the mixture was stirred with heating at 65 ° C. under reflux for 18 hours. The solvent was distilled off from the obtained reaction product with an evaporator, transferred to a dialysis membrane, and dialyzed against ion-exchanged water for 3 days. After dialysis, ion-exchanged water was distilled off with an evaporator to obtain methylglucamine-hyperbranched polyglycerin (hyperbranched polymer (HBP _f- 1d)).

The functional group having the reducing ability of the obtained hyperbranched polymer (HBP _f- 1d) is an amino group, the converted molecular weight (weight average molecular weight) by GPC is 13000, the absolute molecular weight by MALLS is 69000, and by MALLS. The absolute molecular weight value was 5.3 times the GPC weight average molecular weight value.

(Synthesis of hyperbranched polymer (HBP _f- 1e) having an amino group as a functional group having a reducing ability)
Here, the hyperbranched polymer (HBP _f- 1e) having a functional group having a reducing ability to be synthesized is a polymer represented by the following formula (1e). In the formula (1e), GDGE is a polyglycerol diglycidyl ether represented by the structural formula (1) shown above.

先に示した概略構造式（１）で表されるポリグリセロールジグリシジルエーテル（ＧＤＧＥ）３０ｇをメタノール３２ｍＬに溶解し、３−メチルアミノ−１，２−プロパンジオール（還元能を持つ部位導入成分＋保護基形成成分）７．７ｇ、テトラブチルアンモニウムブロミド（縮合触媒）０．４７ｇを加え、６５℃還流条件下１８時間加熱攪拌をした。得られた反応物からエバポレーターにより溶媒留去し、透析膜へ移しイオン交換水にて３日間透析を行った。透析後、イオン交換水をエバポレーターで留去し、メチルアミノプロパンジオール−ハイパーブランチポリグリセリン（ハイパーブランチポリマー（ＨＢＰ_ｆ−１ｅ））を得た。

30 g of polyglycerol diglycidyl ether (GDGE) represented by the general structural formula (1) shown above was dissolved in 32 mL of methanol, and 3-methylamino-1,2-propanediol (site introduction component having reducing ability + (Protecting group forming component) 7.7 g and tetrabutylammonium bromide (condensation catalyst) 0.47 g were added, and the mixture was heated and stirred for 18 hours under reflux condition at 65 ° C. The solvent was distilled off from the obtained reaction product with an evaporator, transferred to a dialysis membrane, and dialyzed against ion-exchanged water for 3 days. After dialysis, ion-exchanged water was distilled off with an evaporator to obtain methylaminopropanediol-hyperbranched polyglycerin (hyperbranched polymer (HBP _f- 1e)).

The functional group having the reducing ability of the obtained hyperbranched polymer (HBP _f- 1e) is an amino group, and the converted molecular weight (weight average molecular weight) by GPC is 22000, the absolute molecular weight by MALLS is 154000, and by MALLS. The absolute molecular weight value was 7.0 times the GPC weight average molecular weight value.

(Synthesis of silver fine particle dispersions (A-1a) to (A-1e))
1 mL aqueous solution of hyperbranched polymers (HBP _f- 1a) to (HBP _f- 1e) having functional groups (alkoxide group, amino group, sulfide group) having the reducing ability (1a only alkaline) in sulfuric acid 5 mL of silver aqueous solution (0.1 mass% as a silver ion concentration) was added, and it stirred at room temperature for 3 hours, and obtained each aqueous solution of silver fine particle dispersion | distribution (A-1a)-(A-1e).

When the final concentration in the silver fine particle dispersion solution thus obtained is, for example, the case of the silver particle dispersion (A-1b), the concentration of the hyperbranched polymer (HBP _f ) is 0.5% by mass, the silver fine particles The content concentration of is 0.05% by mass. That is, the concentration of solid content (HBP _f + silver fine particles) in the silver fine particle dispersion solution is 0.55% by mass, that is, 5500 ppm.
In this case, that is, taking the hyperbranched polymer (HBP _f- 1b) as an example, the concentration of the functional group having the reducing ability of the hyperbranched polymer (HBP _f- 1b) is calculated to be 5 mM, and the silver ion is 4.6 mM. Yes, the reaction mechanism is an oxidation-reduction reaction of (1 mol of amino group) to (1 mol of silver ion), so that all silver ions are considered to be reduced. Similarly, silver particle dispersions (A-1a) and (A-1c) to (A-1e) using other hyperbranched polymers (HBP _f- 1a) and (HBP _f- 1c) to (HBP _f -1e). ), All the silver ions are considered to be reduced.

  About the production | generation of silver microparticles, ie, based on the surface plasmon absorption resulting from the production | generation of silver microparticles | fine-particles, the production | generation of silver microparticles | fine-particles was confirmed by changing a solution into yellow.

(Average particle diameter and degree of dispersion of silver fine particles produced in silver particle dispersions (A-1a) to (A-1e))
Using the measuring apparatus and measuring method described above, the average particle diameter and the degree of dispersion of the silver fine particles produced in the silver particle dispersions (A-1a) to (A-1e) were determined. The results are shown below.
Silver fine particles in the silver particle dispersion (A-1a): average particle size 12 nm, particle dispersity (K) 0.29
Silver fine particles in the silver particle dispersion (A-1b): average particle size 16 nm, particle dispersity (K) 0.36
Silver fine particles in the silver particle dispersion (A-1c): average particle size 2 nm, particle dispersity (K) 0.29
Silver fine particles in the silver particle dispersion (A-1d): average particle size 4 nm, particle dispersity (K) 0.23
Silver fine particles in the silver particle dispersion (A-1e): average particle size 8 nm, particle dispersity (K) 0.28

((B) Surfactant)
(B) The following ten surfactants (B1) to (B10) were prepared as surfactants.
(B1): Alkyl (C12-C14) sodium benzenesulfonate (“Lypon LH-200” manufactured by Lion Corporation)
(B2): Secondary alkane (C14 to C17) sodium sulfonate (“HOSTAPUR SAS 30A” manufactured by Clariant Japan Co., Ltd.)
(B3): Sodium α-olefin sulfonate (C10) (manufactured by Lion Corporation, trade name “Lipolane LB-440”)
(B4): Polyoxyethylene alkyl (C12-C14) sodium ether sulfate (EO average addition mole number = 3): (“Sanol LMT-1430” manufactured by Lion Corporation)
(B5): alkyl (C10-12) sodium phenoxyphenyl disulfonate: “DOWFAX2A1” manufactured by DOWFAX
(B6): Polyoxyethylene alkyl (C12) ether (EO average addition mole number = 15): (“LAO-90” manufactured by Lion Chemical Co., Ltd.)
(B7): 2-ethylhexyl polyglycoside (“AG6202” manufactured by Lion Akzo Co., Ltd.)
(B8): Lauryldimethylaminoacetic acid betaine: “Levon LD-36” manufactured by Sanyo Chemical Industries, Ltd.
(B9): Amidopropyl betaine laurate: “Enagicol L-30B” manufactured by Otsuka Oil Industry Co., Ltd.
(B10): n-dodecyldimethylamine oxide (“AX agent” manufactured by Lion Akzo Co., Ltd.)

(Common ingredients)
As a common component, diethylene glycol monobutyl ether (“Butyl Dioxitol (BDG) 95%” manufactured by Shell Chemicals Japan Co., Ltd.) was prepared.

(PH adjuster)
The pH of the liquid detergent compositions prepared in the following examples and comparative examples was unified to 7.5, and sulfuric acid (reagent) and sodium hydroxide (reagent) were used as pH adjusters for the adjustment. The amount used is very small.

(Examples 1 to 24)
The above-mentioned silver fine particle dispersions (A-1a) to (A-1e), surfactants (B1) to (B10), and common components (in all examples, the blending amount was unified to 10% by mass). ) Was used as a solvent, and 24 types of hard surface liquid detergent compositions (Examples 1 to 24) were prepared according to the composition ratios shown in the following (Table 1) to (Table 6). In addition, the compounding quantity (ppm) of silver fine particle dispersion (A-1a)-(A-1e) in each table _{| surface is} the liquid of solid content (HBPf + silver fine particle) in each compounded silver fine particle dispersion solution. Content relative to the total amount of cleaning agent.

(Comparative Examples 1-4)
Silver fine particle dispersion (B1), silver sulfate (comparison product of component (B) of the present invention), and common component (in all examples, the blending amount was unified to 10% by mass), using water as a solvent According to the composition ratio shown below (Table 7), four types of liquid detergent compositions for hard surfaces (Comparative Examples 1 to 4) were prepared.

  The performance (detergency, bactericidal power, and stability) of each hard surface liquid detergent composition obtained in Examples 1 to 24 and Comparative Examples 1 to 4 was evaluated using the following evaluation methods. did. The evaluation results are shown in the following (Table 1) to (Table 7).

(Detergency)
1 g of beef tallow: soybean oil = 1: 1 was attached to a slide glass, and the detergency when impregnating 50 mL of the liquid detergent composition solution of each example was visually evaluated according to the following evaluation criteria.
Judging from the actually required detergency in the hard surface liquid detergent composition, 5 or more of the following evaluation criteria are acceptable.
(Evaluation criteria)
Removal rate 100%: 10 points Removal rate 90% or more and less than 100%: 9 points Removal rate 80% or more and less than 90%: 8 points Removal rate 70% or more and less than 80%: 7 points Removal rate 60% or more and less than 70%: 6 Points Removal rate 50% or more and less than 60%: 5 points Removal rate 40% or more and less than 50%: 4 points Removal rate 30% or more and less than 40%: 3 points Removal rate 20% or more and less than 30%: 2 points Removal rate less than 20% : 1 point

(Sterilizing power)
It measured according to the following method.
(1) Preparation of control sample A 0.05% polysorbate (Tween 80) sterilized under high pressure steam was used.
(2) Preparation of test bacterial solution S. aureus and Escherichia coli are inoculated into TSA (Triptic Soy Agar) medium and cultured in advance at 37 ° C. for 18 to 20 hours. Next, this bacterium was inoculated into a TSA medium, pre-cultured at 37 ° C. for 18 to 20 hours, and then prepared to be 10 ⁶ CFU / mL using a sterilized 1 / 2NB (Nutrient Broth) medium.
(3) Preparation of model soil An aqueous bovine serum albumin solution having a concentration of 30 g / L is prepared using bovine serum albumin (Coh Fraction V). This aqueous solution is sterilized by filtration and used for testing. The bovine serum albumin aqueous solution was prepared immediately before the test and used only on the day of the test.
(4) Preparation of deactivator 30 g of a mixture of polypeptone, lecithin and polysorbate (“LP diluent Daigo (trade name), manufactured by Nippon Pharmaceutical Co., Ltd.) was dissolved in 1 L of purified water by heating and autoclaved under high pressure steam. Things were used.
(5) Sterilization of test tube Dry heat sterilization was performed at 180 ° C. for 1 hour.
(6) Test method (6-1) 0.1 mL of the test bacterial solution and 0.1 mL of the model soil were added to a sterilized test tube.
(6-2) To the test tube of (6-1) above, 0.8 mL of the evaluation sample or the control sample was added, and 9 mL of tap water was further added, and the mixture was allowed to stand after stirring.
(6-3) After standing for 10 minutes, 1 mL was collected by stirring and added to a sterile test tube containing 9 mL of an inactivating agent and stirred.
(6-4) The test tube of (6-3) above was applied to a TSA medium by the pour culture method, and the number of bacteria was determined after culturing at 37 ° C. for 36 to 48 hours.
(6-5) The log bacteria value of the evaluation sample was subtracted from the log bacteria value of the control sample to obtain the sterilization activity value.
The residual chlorine concentration of tap water used in this experiment was 0.4 mg / L, and was measured by the DPD method (residual chlorine measuring device (manufactured by SIBATA)).
Based on the obtained measured value, it evaluated by the following evaluation criteria. Practically, “Yes” or higher of the following evaluation criteria is acceptable.
(Evaluation criteria)
Bactericidal activity value 6 or more: Excellent Bactericidal activity value 4 or more and less than 6: Good Bactericidal activity value 2 or more and less than 4: Yes Bactericidal activity value 2 or less: Impossible

(Stability)
After leaving still for one month in a 50 degreeC thermostat, it evaluated visually based on the following evaluation criteria. Practically, “Yes” or higher of the following evaluation criteria is acceptable.
(Evaluation criteria)
No precipitation, no discoloration: Excellent No precipitation, slight discoloration: Good Slightly turbid, slightly discoloration: Yes Precipitation precipitation: No

上記（表１）に表示の実施例１〜５では、（Ａ）成分として銀微粒子分散体Ａ−１ａを用い、その配合量を変化させている。この（表１）から分かるように、（Ａ）成分の含有量（固形分濃度）が、洗浄剤組成物全量に対して１０〜１０００ｐｐｍの範囲内にあれば、洗浄力、除菌力、および保存安定性において、合格（可以上）範囲内の品質が得られることが分かる。

In Examples 1-5 shown in the above (Table 1), the silver fine particle dispersion A-1a is used as the component (A), and the blending amount thereof is changed. As can be seen from this (Table 1), if the content (solid content concentration) of the component (A) is within the range of 10 to 1000 ppm with respect to the total amount of the detergent composition, It can be seen that in the storage stability, a quality within a pass (or better) range is obtained.

上記（表２）に表示の実施例６〜９では、（Ａ）成分である銀微粒子分散体の種類を変化させている。この（表２）から分かるように、本発明に用いるハイパーブランチポリマー（ＨＢＰ_ｆ）の範囲内のものであれば、ハイパーブランチポリマー（ＨＢＰ_ｆ）の種類に関係なく、良好な特性の硬表面用液体洗浄剤組成物が得られることが分かる。

In Examples 6 to 9 shown in the above (Table 2), the type of the silver fine particle dispersion as the component (A) is changed. As can be seen from this (Table 2), as long as it is within the range of the hyperbranched polymer (HBP _f ) used in the present invention, regardless of the type of the hyperbranched polymer (HBP _f ), it is suitable for hard surfaces. It can be seen that a liquid detergent composition is obtained.

上記（表３）〜（表５）に表示の実施例１０〜２１では、（Ｂ）成分の種類と配合量を変化させている。これらの（表３）〜（表５）から分かるように、本発明に特有の（Ａ）成分を用いることにより、組み合わせる界面活性剤の種類にかかわらず、良好な特性が得られることが分かる。また、これらの表から、（Ｂ）界面活性剤の内、より好ましい組み合わせとしては、アルキルベンゼンスルホン酸塩、アルカンスルホン酸塩、ポリオキシエチレンアルキルエーテルが選択され得ることが分かる。

In Examples 10 to 21 shown in the above (Table 3) to (Table 5), the type and blending amount of the component (B) are changed. As can be seen from these (Table 3) to (Table 5), by using the component (A) specific to the present invention, it is understood that good characteristics can be obtained regardless of the type of surfactant to be combined. In addition, it can be seen from these tables that alkylbenzene sulfonate, alkane sulfonate, and polyoxyethylene alkyl ether can be selected as a more preferable combination of the surfactant (B).

上記（表６）に表示の実施例２２〜２５では、（Ｂ）成分として界面活性剤Ｂ１を用い、その配合量を変化させている。この（表６）から分かるように、（Ｂ）成分の含有量（純分濃度）が、洗浄剤組成物全量に対して０．５〜１５．０質量％の範囲内にあれば、洗浄力、除菌力、および保存安定性において、合格（可以上）範囲内の品質が得られることが分かる。

In Examples 22 to 25 shown in the above (Table 6), the surfactant B1 is used as the component (B), and the blending amount thereof is changed. As can be seen from this (Table 6), if the content (pure concentration) of the component (B) is in the range of 0.5 to 15.0% by mass with respect to the total amount of the cleaning composition, the detergency It can be seen that in the sterilization power and the storage stability, the quality within the pass (or better) range can be obtained.

（表７）に示すように、比較例１は、実施例１の組成から（Ｂ）界面活性剤を除去した組成である。（Ａ）銀微粒子分散体Ａ−１ａを有しているが、黄色ブドウ球菌および大腸菌に対する除菌力は界面活性剤による硬表面の洗浄作用と合わさって働かない、即ち、相乗的に効果を発揮できないため、除菌力が幾分低下している。比較例２および４は、（Ａ）成分の比較品と（Ｂ）界面活性剤を有する構成であるが、本発明の必須成分である（Ａ）銀微粒子分散体を用いていないため、除菌力において大きく劣る結果となっている。比較例３は、有効成分が（Ｂ）界面活性剤のみであるので、洗浄力はあるものの、除菌力がない結果となっている。

As shown in Table 7, Comparative Example 1 is a composition obtained by removing (B) surfactant from the composition of Example 1. (A) Although having silver fine particle dispersion A-1a, the sterilizing power against Staphylococcus aureus and Escherichia coli does not work in combination with the hard surface cleaning action by the surfactant, that is, synergistically exhibits the effect. Since it is not possible, the sterilization power is somewhat reduced. Comparative Examples 2 and 4 have a constitution having a comparative product of component (A) and (B) a surfactant, but (A) a silver fine particle dispersion which is an essential component of the present invention is not used. The result is greatly inferior in power. In Comparative Example 3, since the active ingredient is only the surfactant (B), although there is a detergency, there is no sterilizing power.

  As described above, the liquid detergent composition for hard surfaces according to the present invention has excellent detergency against sebum and oil stains on hard surfaces such as bathrooms, toilets, kitchens, etc. Even when contacted, it has a high sterilizing power against Gram-positive bacteria and Gram-negative bacteria and is excellent in storage stability.

Claims (3)

A liquid detergent composition for hard surface containing (A) a silver fine particle dispersion and (B) a surfactant, wherein the (A) silver fine particle dispersion contains a glycidyl ether compound in the presence of a basic catalyst. A hyperbranched polymer having a functional group having at least one reducing ability selected from an alkoxide group, a sulfide group, and an amino group in the molecule of polyglycerol diglycidyl ether (GDGE) obtained by addition polymerization with (HBPf) and a solution (S-Ag) containing silver ions are mixed, whereby the silver ions induced in the hyperbranched polymer (HBPf) are reduced by the functional groups, and the hyperbranched polymer (HBPf) ) Silver fine particle-containing hyperbranched polymer (HBPf-Ag) For hard surface liquid detergent composition which is a clear aqueous solution. Before SL average particle size based on the transmission electron microscopic observation of silver particles to produce a hyperbranched the polymer (HBPF) is, for hard surface liquid cleaning according to claim 1, characterized in that less than or more in diameter 1 nm 100 nm Agent composition. The content of the (A) silver fine particle dispersion is 10 to 1000 ppm in terms of parts by mass with respect to the total amount of the cleaning composition, and the content of the (B) surfactant is the cleaning composition. It is 0.5-15.0 mass% with respect to whole quantity, The liquid detergent composition for hard surfaces of Claim 1 or 2 characterized by the above-mentioned.