JP4979908B2 - Hard surface drainage imparting agent - Google Patents

Description

  TECHNICAL FIELD The present invention relates to an agent for imparting water drainage to hard surfaces such as plastic, glass, and metal, and a hard surface cleaning agent containing the same.

  In bathrooms, bathrooms, bathtubs, sinks, and other plastic products, glass products, metal products, etc. in the home, water drops adhere to the surface of equipment after use due to water splashing from faucets and showers during use. , Easy to remain. In the case of a bathroom, these water droplets remain damp and tend to cause mold, etc.In the case of a sink, the remaining water droplets are gradually dried while maintaining the shape at the time of attachment, and are in a small ring shape. It will be easier to keep track of. For such an inconvenient state, the general response of consumers is, for example, in the case of a sink, wipe the water again with a cloth, etc., and pay effort to keep the beauty, In the case of a bathtub, the effort is made to remove moisture from the bathroom by opening windows and doors, or by operating a ventilation fan, etc., but efforts are made to dry it. From the point of view, none of them was a satisfactory coping method.

  In addition, even when tableware with a hard surface such as plastic or glass is washed and rinsed, water spots derived from the hardness component of water and cloudiness remain on the hard surface, which impairs the beauty of tableware and the like. . In addition, since the surface is wetted with water after cleaning glass or the like, a great amount of labor is required for the wiping operation after cleaning.

As a technique for solving such a problem, Patent Document 1 discloses a cleaning composition for a hard surface containing a hydrophilic polymer and a surfactant. As a preferred hydrophilic polymer, a molecular weight of about 5000 to about 5000 is disclosed. Polymers having 200,000 amine oxide groups are described. Patent Document 2 discloses a hard surface cleaning composition containing a surfactant and a water-soluble oxazoline polymer, and Patent Document 3 discloses a hard surface containing a surfactant and a water-soluble polymer such as poly (dimethylacrylamide). Detergent compositions are disclosed. Patent Document 4 discloses a quick-drying imparting agent and a quick-drying detergent containing a cationic copolymer having a cationic constituent part and an amine oxide group-containing constituent part.
Special table 2003-528164 gazette Japanese Patent Application Laid-Open No. 8-25396 Japanese Patent Laid-Open No. 8-253797 JP 2003-183694 A

In the above prior art, the water drainage property, particularly the sustainability of the water drainage, has not been sufficiently satisfied.
Accordingly, an object of the present invention is to provide a hard surface drainage imparting agent capable of imparting good water drainage property, particularly water drainage sustainability, to a hard surface such as plastic, glass, metal, and the like. It is to provide a hard surface cleaner.

  The present invention includes a hard surface drainage imparting agent containing a cationized polysaccharide having a weight average molecular weight of 1,000,000 to 10,000,000 (hereinafter referred to as component (a)), the drainage imparting agent, and a surfactant. The present invention relates to a hard surface cleaning agent, and a method of applying the drainage imparting agent or the cleaning agent to a hard surface and imparting water drainage sustainability to the hard surface.

  The drainage imparting agent and hard surface cleaning agent of the present invention are applied to a hard surface and then rinsed to prevent water droplets from remaining to improve drainage, and even after repeated rinses, the persistence of drainage Is excellent.

[(A) Component and drainage imparting agent]
Specific examples of the cationized polysaccharide (a) used in the present invention include cationized starch, cationized cellulose, cationized guar gum, cationized locust bean gum, cationized fenugreek gum, cationized tara gum, and cationized curdlan. And cationized carrageenan. Among them, cationized starch, cationized cellulose, and cationized guar gum are preferable, and cationized cellulose is particularly preferable.

  In general, the cationized polysaccharide may be a commercially available product as it is, or a non-cationized modified polysaccharide such as a non-modified or hydroxyethyl-modified or hydroxypropyl-modified product that is also available. It can also be obtained by reacting with a cationizing agent. As a cationizing agent, halides containing quaternary or tertiary nitrogen such as glycidyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, 3-chloropropyltrimethylammonium chloride, glycidyldimethylammonium chloride, etc. , Halohydrins and epoxides.

The weight average molecular weight of the cationized polysaccharide used in the present invention is 1 million or more, preferably 1.3 million or more, more preferably 2 million or more, from the viewpoint of increasing the persistence on the hard surface and obtaining good water drainage. 2.5 million or more is particularly preferable. Further, from the viewpoint of obtaining an appropriate water drainage rate, it is 10 million or less, preferably 7.5 million or less, more preferably 5 million or less, and particularly preferably 4.5 million or less.
Here, the weight average molecular weight of the cationized polysaccharide is a value obtained by pullulan as a standard by gel permeation chromatography as shown in the following examples.

  The nitrogen content of the cationized polysaccharide used in the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and more preferably 1% by mass from the viewpoint of increasing the adsorptivity to a hard surface (particularly glass). The above is particularly preferable. Moreover, 10 mass% or less is preferable from a viewpoint which suppresses formation of precipitation by formation of a salt with surfactant, 5 mass% or less is further more preferable, and 2 mass% or less is especially preferable.

  The nitrogen content of the cationized polysaccharide can be determined by colloid titration using polyvinyl potassium sulfate. This method is based on the principle of a stoichiometric reaction between a nitrogen cation and potassium polyvinyl sulfate ("Colloidal titration method" written by Junichi Sente (1969)).

  The drainage imparting agent of the present invention contains the cationized polysaccharide (a) and preferably contains water. The drainage imparting agent of the present invention can adjust the concentration of the component (a) according to the treatment of the hard surface. In addition, a concentrated solution of component (a) can be prepared and diluted with water at the time of use.

[Cleaning agent for hard surface]
The hard surface cleaning agent of the present invention contains the drainage imparting agent of the present invention and a surfactant (hereinafter referred to as component (b)). Furthermore, it is preferable to contain water.

  As the surfactant of the component (b) used in the present invention, one or more selected from anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used.

  Anionic surfactants include higher fatty acid salts, higher alcohol sulfates, higher alcohol sulfonates, sulfated fatty acid salts, sulfonated fatty acid salts, phosphate ester salts, fatty acid ester sulfate esters, fatty acid ester sulfonic acids. Ester salts, sulfonic acid ester salts of higher alcohol ethers, higher alcohol ether-substituted acetates, condensation products of fatty acids and amino acids, alkylolated sulfates of fatty acid amides, alkylated sulfonates of fatty acid amides, sulfosuccinic acid ester salts Alkyl benzene sulfonate, alkyl phenol sulfonate, alkyl naphthalene sulfonate, alkyl benzimidazole sulfonate, amide ether carboxylic acid or salt thereof, ether carboxylic acid or salt thereof, N-acyl-N-methyl tauri Or a salt thereof, amide ether sulfuric acid or a salt thereof, N-acyl glutamic acid or a salt thereof, N-amidoethyl-N-hydroxyethyl acetic acid or a salt thereof, acyloxyethanesulfonic acid or a salt thereof, N-acyl-β-alanine or a salt thereof N-acyl-N-carboxyethyltaurine or a salt thereof, N-acyl-N-carboxyethylglycine or a salt thereof, and alkyl or alkenylaminocarbonylmethylsulfuric acid or a salt thereof.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylene ether, polyoxyethylene sorbitan fatty acid ester, alkyl polyglycoside, sucrose fatty acid ester, and alkyl polyglycerin ether.

  Examples of cationic surfactants include alkyl (carbon number 10 to 20) trimethylammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride; distearyldimethylammonium chloride and dialkyl (carbon numbers 12 to 18). Dialkyldimethylammonium salts such as dimethylammonium chloride; alkyldimethylbenzylammonium salts such as alkyl (C12-18) dimethylbenzylammonium chloride; substituted benzalkonium salts; monocationic compounds such as benzethonium salts, N-alkyl- Examples thereof include polycation compounds such as N, N, N ′, N ′, N′-pentamethyl-propyleneammonium salt.

  Examples of amphoteric surfactants include amine oxides such as alkyldimethylamine oxide, betaines such as alkyl N, N-dimethylacetic acid betaine, fatty acid amidopropyl-N, N-dimethylacetic acid betaine, and alkylcarboxymethylhydroxyethylimidazolium betaine. Can be mentioned.

  Among these surfactants, anionic surfactants, nonionic surfactants and amphoteric surfactants are preferable, and one or more of these can be used in combination.

  The content of the component (a) in the hard surface cleaning agent of the present invention is preferably 0.001 to 5% by mass, more preferably 0.01 to 5% by mass, from the viewpoint of obtaining good drainage. 0.01 to 3% by mass is particularly preferable. In addition, the content of the component (b) is preferably 0.001 to 20% by mass, more preferably 0.01 to 15% by mass, and 0.01 to 10% by mass from the viewpoint of obtaining good drainage and cleaning properties. % Is particularly preferred.

  Further, the mass ratio of the component (a) to the component (b) is (a) / (b) = 0.01 / 20 to 5 / 0.01, more preferably 0, from the viewpoint of obtaining good drainage and detergency. 1/15 to 5 / 0.1, particularly 0.1 / 10 to 3 / 0.1 is preferable.

  The hard surface cleaning agent of the present invention preferably contains a water-soluble solvent (hereinafter referred to as component (c)). Examples of the water-soluble solvent include monohydric alcohols having 1 to 5 carbon atoms such as ethanol and isopropyl alcohol, polyhydric alcohols having 2 to 8 carbon atoms such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin and isoprene glycol, (Poly) alkylene glycol monoalkyl ether such as diethylene glycol monoalkyl (carbon number 4 to 8) ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and the alkyl group has carbon number 3-8 monoalkyl glyceryl ether etc. are mentioned.

  0.001-20 mass% is preferable and, as for content of (c) component in the cleaning agent of this invention, 0.001-10 mass% is still more preferable.

  A chelating agent (hereinafter referred to as component (d)) can be blended in the hard surface cleaning agent of the present invention. Examples of chelating agents include tripolyphosphoric acid, pyrophosphoric acid, orthophosphoric acid, hexametaphosphoric acid and alkali metal salts thereof; ethylenediaminetetraacetic acid, hydroxyiminodiacetic acid, dihydroxyethylglycine, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylene Ethylenetetramine hexaacetic acid and alkali metal salts or alkaline earth metal salts thereof; aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, aminotrimethylene Phosphonic acid and alkali metal salts or alkaline earth metal salts thereof; a single polymer or copolymer of a monomer selected from acrylic acid and methacrylic acid; Rylic acid-maleic acid copolymer, poly α-hydroxyacrylic acid and alkali metal salts thereof; polyvalent carboxylic acid selected from citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid and the like Alkali glycine-N, N-diacetic acid, aspartic acid-N, N-diacetic acid, serine-N, N-diacetic acid, glutamic acid diacetic acid, ethylenediamine disuccinic acid, or a salt thereof .

  The content of the component (d) in the cleaning agent of the present invention is preferably 0.001 to 15% by mass, and more preferably 0.01 to 10% by mass.

  A hydrotrope agent (hereinafter referred to as component (e)) can be blended with the hard surface cleaning agent of the present invention. Examples of the hydrotrope agent include benzenesulfonic acid substituted with 1 to 3 alkyl groups having 1 to 3 carbon atoms or a salt thereof. More specifically, preferable examples include p-toluenesulfonic acid, m-xylenesulfonic acid, p-cumenesulfonic acid, ethylbenzenesulfonic acid and the like. When a salt is used, sodium salt, potassium salt and magnesium salt are preferred. It is good.

  The content of the component (e) in the cleaning agent of the present invention is preferably 0.001 to 15% by mass, and more preferably 0.01 to 10% by mass.

  In addition to the above components, for example, a fragrance, an antibacterial agent, a viscosity modifier, a pigment, a dye, a suspending agent and the like are added to the hard surface cleaning agent of the present invention within a range not impairing the effects of the present invention. be able to.

  The composition for the hard surface cleaning agent of the present invention is preferably adjusted in accordance with the treatment of the hard surface. Moreover, each concentrated solution can be prepared and can be diluted and used at the time of use.

  Further, the pH of the detergent for hard surface of the present invention at 20 ° C. is preferably 2 to 11, more preferably 3 to 10, particularly 4 to 8 from the viewpoint of safety during work and damage to the hard surface. Examples of pH adjusters include inorganic acids such as hydrochloric acid and sulfuric acid, acid agents such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, and maleic acid, and sodium hydroxide and potassium hydroxide. Ammonia and its derivatives, amine salts such as monoethanolamine, diethanolamine and triethanolamine, and alkali agents such as sodium carbonate and potassium carbonate may be used alone or in combination. In addition, these acid agents and alkali agents may be used in combination as a buffer system.

[Method of imparting water drainage durability to hard surface]
The application method of the drainage imparting agent or the cleaning agent of the present invention to the hard surface can be appropriately selected according to the width (area) of the hard surface. For example, it can be performed by spraying about 0.1 mL to 10 mL of an aqueous solution having a component (a) content of 0.5 mass% per 10 cm ^{2 and} spreading it thinly using a sponge or the like.

  The drainage imparting agent and the cleaning agent of the present invention can impart good drainage to a hard surface, and can also impart the sustainability of drainage.

Here, the water drainage is a phenomenon in which water droplets do not remain on the hard surface when the water drainage imparting agent or cleaning agent is applied to the hard surface and then rinsed with water (for example, the surface is once covered with a water film. After that, the phenomenon that the water drains slowly from the upper end. The sustainability of water drainage means that the water drainage phenomenon occurs even if the water is drained and then rinsed with water again, and this is repeated, and the number of times the water drainage phenomenon occurs is preferably 10 times or more.
The cleaning agent of the present invention also has a cleaning effect on oil stains, protein stains, sebum stains and the like.

  The hard surface to which the drainage imparting agent or cleaning agent of the present invention is applied is excellent in drainage and its sustainability, so that mildew does not easily occur, and the drainage imparting agent and cleaning agent of the present invention are also suitable for antifungal treatment. It is. Further, since the water drainage is good, dirt attached to the hard surface, particularly hydrophobic dirt, can be easily washed away with water, so that the water drainage imparting agent and the cleaning agent of the present invention are also suitable for antifouling treatment. is there.

  The drainage imparting agent and the cleaning agent of the present invention may be applied to a hard surface that constitutes a facility around water, for example, a hydrophobic hard surface made of a material such as plastic, glass, ceramics, or metal. Specifically, it is preferably applied to glass, vinyl chloride (PVC), polypropylene, polyethylene, ABS, nylon, stainless steel, fiber reinforced plastic (FRP), tile, glass, and the like, particularly for glass and PVC. It is preferable to apply to.

  In the following examples, the weight average molecular weight and nitrogen content of the cationized polysaccharide were measured by the following methods.

<Measurement method of weight average molecular weight>
The gel permeation chromatography (GPC) was performed under the following conditions, and pullulan was used as a standard sample.

Measurement conditions Column name: α-M + α-M (manufactured by Tosoh Corporation)
Solvent: 0.15 mol / L Na ₂ SO ₄ , 1% CH ₃ COOH / water Flow rate: 1.0 mL / min
Column temperature: 40 ° C.

<Method for measuring nitrogen content>
The colloid titration method was used. That is, 0.1 g of cationized polysaccharide was precisely weighed and dissolved in ion-exchanged water so as to be a 0.1% by mass aqueous solution. 10 g of this cationized polysaccharide aqueous solution was precisely weighed (Ag), diluted 5 times, added with 3 drops of toluidine blue, and titrated with an aqueous N / 400 potassium potassium sulfate (PVSK) solution. The end point is blue → (red) purple. When the PVSK amount required for the titration is B mL and the PVSK amount required for the blank (an aqueous solution in which the cationized polysaccharide is not dissolved) is C mL, the nitrogen content is obtained by the following formula. Note that f is a factor of N / 400 PVSK.

Example 1
A water drainage imparting agent having the composition shown in Table 1 was prepared using the following component (a) of the present invention and a comparative product. The pH of the water drainage imparting agent was adjusted to 7.5 (20 ° C.) with sodium hydroxide and hydrochloric acid. About the obtained drainability imparting agent, the drainability of the hard surface (glass and PVC) and the sustainability of drainage were evaluated by the following method. The results are shown in Table 1.

-(A) Component (a-1): Cationized cellulose Poise C-60H (manufactured by Kao Corporation, weight average molecular weight 2 million, nitrogen content 2.0 mass%):
(A-2): Cationized cellulose Poise C-80M (manufactured by Kao Corporation, weight average molecular weight 3.2 million, nitrogen content 1.5% by mass)
(A-3): Cationized cellulose Poise C-150L (manufactured by Kao Corporation, weight average molecular weight 4.4 million, nitrogen content 1.3% by mass)
(A-4): Cationized starch Neotac # 40T (manufactured by Nippon Shokuhin Kako Co., Ltd., weight average molecular weight 1.35 million, nitrogen content 0.04 mass%)
(A-5): Cationized guar gum JAGUAR C-13S (manufactured by Sanki Co., Ltd., weight average molecular weight of 7,300,000, nitrogen content of 1.4% by mass)
Comparative product (a′-1): Cationized cellulose Gelner QH-200 (manufactured by Daicel Chemical Industries, Ltd., weight average molecular weight 910,000, nitrogen content 1.7% by mass)
(A′-2): Carboxymethylcellulose Na salt (SUNROSE manufactured by Nippon Paper Industries Co., Ltd.)
(A′-3): 2-hydroxyethylcellulose (reagent, manufactured by Aldrich)
<Evaluation method for drainage>
Apply 2 mL of drainage imparting agent to the hard surface of a 20 mm × 70 mm × 2 mm evaluation substrate, rinse with water at 50 mL / second for 10 seconds, hold the surface of the substrate vertically, and form a water film on the hard surface. The time until disappearance was measured. In the case of running out of water, ◎ (20 seconds or less), ○ (20 seconds to 95 seconds or less), and Δ (95 seconds or more) were used according to the time until the water film disappeared completely. The case where 5 minutes or more were required until the water film disappeared, or the case where the water drainage phenomenon did not occur was marked as x.

<Evaluation method for sustainability of drainage>
As for the case where water breakage occurred, it was rinsed again with water, and this was repeated to measure the number of times the water breakage occurred, and this was regarded as the persistence of the water breakage.

Example 2
Using the components (a) ((a-2) to (a-5)) and the comparative products ((a′-1) to (a′-3)) shown in Example 1, the composition shown in Table 2 was drained. A property-imparting agent was prepared, and the drainage of the hard surface (FRP and stainless steel) and the durability of the drainage were evaluated in the same manner as in Example 1. The results are shown in Table 2.

Example 3
Using the blending components shown below, hard surface cleaners having the compositions shown in Table 3 were prepared. The pH of the cleaning agent was adjusted to 7.5 (20 ° C.) with sodium hydroxide and hydrochloric acid. About the obtained cleaning agent, the drainage property of the hard surface (glass, PVC, and stainless steel) and the sustainability of the drainage were evaluated by the following method. The results are shown in Table 3.

<Blending ingredients>
-(A) component and comparative product (a-1)-(a-5) and (a'-1)-(a'-3) similar to Example 1 were used.

(B) component (b-1): fatty acid (carbon number 12) amidopropyl-N, N-dimethyl-acetic acid betaine (c) component (c-1): diethylene glycol monobutyl ether (d) component (d- 1): Ethylenediaminetetraacetic acid Na
<Evaluation method of drainability and sustainability of drainage>
2 mL of the cleaning agent was applied to a hard surface for evaluation of 20 mm × 70 mm × 2 mm, and water drainage and water drainage persistence were evaluated in the same manner as in Example 1.

Example 4
(A) A hard surface cleaning agent having the composition shown in Table 4 was prepared using the same blending components as in Example 3 except that (a-2) to (a-5) were used as components. Similarly, the drainability of the hard surface (FRP) and the durability of the drainage were evaluated. The results are shown in Table 4.

Claims (3)

(A) a hard surface drainage imparting agent containing a cationized polysaccharide having a weight average molecular weight of 1,000,000 to 10,000,000 ,
(B) 0.01 to 10% by mass of a surfactant and
(C) 0.001-10 mass% of water-soluble solvents
A hard surface cleaning agent. The cleaning agent for hard surfaces according to claim 1, wherein the nitrogen content of the cationized polysaccharide contained in the hard surface drainage imparting agent is 0.01 to 10% by mass. 3. A method for applying a hard surface cleaning agent according to claim 1 or 2 to a hard surface and imparting water drainage to the hard surface.