WO2005100524A1

WO2005100524A1 - Hydrophilizing agent

Info

Publication number: WO2005100524A1
Application number: PCT/JP2004/017191
Authority: WO
Inventors: Tsuyoshi Sakamoto
Original assignee: Kobayashi Pharmaceutical Co., Ltd.
Priority date: 2004-03-31
Filing date: 2004-11-18
Publication date: 2005-10-27
Also published as: JP2005281632A; JP3777465B2

Abstract

[PROBLEMS] To provide a hydrophilizing agent excellent in hydrophilization performance and antifouling properties. [MEANS FOR SOLVING PROBLEMS] The hydrophilizing agent is characterized by containing an aromatic sulfonic acid compound/formalin condensate, e.g., a water-soluble salt of a naphthalenesulfonic acid/formalin condensate. The hydrophilizing agent is preferably used in combination with an anionic surfactant of the sulfonic salt type or sulfuric ester salt type.

Description

Specification

Hydrophilic treatment agent

Technical field

[0001] The present invention relates to a hydrophilic treatment agent capable of imparting hydrophilicity to a surface to be treated, and more specifically, a hard surface such as ceramics and glass; a metal surface such as stainless steel; polyethylene, polyester, polyamide, The present invention relates to a hydrophilic treatment agent for making a plastic surface such as melamine, rayon or the like; a solid surface such as a surface of a natural material such as wool hydrophilic, so as to be easily wetted by water. Background art

[0002] Conventionally, as a coating agent for preventing dirt from adhering to a solid surface of a toilet or the like, a coating agent containing a fluorine-based amphiphile, as described in Patent Document 1, has been known. I have.

[0003] The above-mentioned coating agent is a hydrophobic treatment agent that imparts hydrophobicity to a solid surface, and the treated solid surface exhibits water repellency. It becomes possible to effectively suppress the adhesion of such hydrated soil.

Patent Document 1: JP-A-2000-144177

Disclosure of the invention

Problems to be solved by the invention

[0004] However, with the above-mentioned coating agent, once the dirt has adhered to the solid surface, it is more difficult to remove the dirt by washing with water than to the uncoated surface. There was a problem that there was.

[0005] The inventors of the present invention have conducted various studies on the cause, and the following reasons have been considered. That is, since the coating agent is used in an environment that comes into contact with water, the fluorine-based amphiphilic substance contained in the coating agent is required to have the property of dissolving or dispersing in water.

[0006] In other words, the fluorine-based amphiphilic substance has both hydrophobic and hydrophilic properties, and the solid surface treated with such a compound certainly exhibits water repellency, but has a fatty acid property. However, the oil is not hydrophobized to such an extent as to repel oil. [0007] On the other hand, looking specifically at the constituents of soil using stool as an example, about 80% of the solid content is composed of fatty acids. Therefore, once the stool adheres to the toilet, the fatty acid constituting the stool and the coated toilet have the same degree of hydrophobicity to each other, so that the stool exhibits good adhesion that is easy to fit into.

[0008] Further, when stool attached to the toilet is washed away with water, the adherence between the stool and the toilet is further increased because the hydrophobic substance has a property of attracting each other in the water, and as a result, both the stool and the toilet are in contact with each other. It was thought that water infiltrated between the interfaces, making it difficult to remove the stool attached to the toilet simply by washing with water.

[0009] From the above study results, it is inferred that it is effective to make the solid surface hydrophilic so that the solid surface can be easily wetted with water in order to easily remove dirt attached to the solid surface by washing with water. At present, there is no known hydrophilic treatment agent having sufficient hydrophilicity.

[0010] Therefore, an object of the present invention is to provide a hydrophilic treatment agent having excellent hydrophilicity.

Means for solving the problem

[0011] As a result of studies by the present inventors to solve the above-mentioned problems, the aromatic sulfonic acid-based formalin condensate has excellent hydrophilizing performance on a solid surface. The inventors of the present invention have found that the surface of a solid surface that has been subjected to a hydrophilic treatment has a reduced contact angle with water and is easily wetted with water, so that dirt attached to the solid surface can be easily removed by washing with water. It was completed.

That is, the present invention provides a hydrophilic treating agent containing an aromatic sulfonic acid-based formalin condensate. Here, examples of the aromatic sulfonic acid-based formalin condensate include naphthalene sulfonic acid-based formalin condensate, melamine sulfonic acid-based formalin condensate, and α-sulfonic sulfonic acid-based formalin condensate.

[0013] From the viewpoint of hydrophilicity, these are preferably used as water-soluble salts such as alkali metal salts, alkaline earth metal salts, ammonium salts, mono-, di- and triethanolamine salts, and particularly naphthalenesulfonic acid. Water-soluble salts of formalin condensates are more preferred.

[0014] The water-soluble salt of the aromatic sulfonic acid-based formalin condensate is, for example, sulfonated naphthalene, melamine, a-line or the like using a sulfonating agent, and then condensed by adding formalin thereto. It can be manufactured by neutralization. [0015] The hydrophilic treating agent according to the present invention is excellent in hydrophilizing performance. Therefore, even if dirt adheres to the solid surface, water easily penetrates into the interface between the solid surface and the dirt, and the dirt floats off the solid surface and is removed, that is, it exhibits an excellent antifouling property. Therefore, it can be suitably used as an antifouling detergent.

[0016] However, although the water-soluble salt of the aromatic sulfonic acid-based formalin condensate has excellent hydrophilicity, it does not have very high detergency. Therefore, when the hydrophilic treatment agent of the present invention is used as an antifouling cleaning agent, if a surfactant is added as a cleaning component in addition to the aromatic sulfonic acid-based formalin condensate, dirt on the solid surface is reduced. If so, water is more likely to penetrate into the interface between the solid surface and the soil due to the action of the surfactant, and a cleaner having more excellent antifouling properties can be obtained.

[0017] In this case, the surfactant may be an ionic surfactant, a non-ionic surfactant, or a cationic surfactant, but may be an aromatic sulfonic acid-based formalin condensation. From the viewpoint that the substance itself has a sulfone group and has an aionic property, it is preferable to use an a-on surfactant having similar properties.

[0018] Furthermore, when a sulfonate type a-on surfactant or a sulfate ester type a-on surfactant is used among the a-on surfactants, the antifouling property can be synergistically enhanced. Is more preferable in that the effect of improving the feeling of use and the like is exhibited.

Specifically, examples of the sulfonate type a-one surfactant include alkyl benzene sulfonate, dialkyl sulfosuccinate, α-leufine sulfonic acid salt, alkane sulfonate, and calcium sulfonic acid. Methyl taurate and the like can be mentioned. In addition, examples of the sulfate ester type aone surfactant include an alkyl sulfate, a polyoxyethylene alkyl ether sulfate, and the like.

[0020] In addition to the above-mentioned surfactants, the hydrophilic treating agent of the present invention includes a perfume, a deodorant component, a coloring agent, an emulsifying solubilizer of an oil component, a bactericide, a chelating agent, a bulking agent, and a solubility modifier. , A bleaching agent, a water repellent, a filler, a ΡΗ regulator, a thickener, a drug stability improver, a moldability improver, an inorganic builder, an organic builder, an enzyme, and the like can be appropriately compounded.

In order to hydrophilize a solid surface using the hydrophilic treatment agent of the present invention, the hydrophilic treatment agent is dissolved in water or a solvent in advance and the solid surface is immersed in the obtained hydrophilic treatment solution.ヽヽ It is also possible to spray the solution onto a solid surface. Alternatively, the hydrophilic treatment agent may be formed into a solid form, brought into contact with washing water and gradually dissolved in water, and the solid surface may be washed with the washing water in which the hydrophilic treatment agent has been dissolved.

[0022] The hydrophilic treating agent of the present invention can be used for various purposes by utilizing its excellent hydrophilicity in addition to the antifouling detergent. For example, it is used to increase the wettability of the sample surface prior to treatment in an aqueous solution such as plating or etching, used to prevent fogging of glass or mirrors, or as an antistatic agent. You can also. In this case, the compounding components may be appropriately selected according to each application.

[0023] Even when the hydrophilic treatment agent of the present invention is used for applications other than antifouling detergents, it is desirable to remove dirt attached to the solid surface as much as possible in order to enhance the hydrophilization effect of the solid surface. . Therefore, the hydrophilic treatment agent preferably contains a surfactant such as a sulfonate-type surfactant or an ester-sulfate-type surfactant as a preferred surfactant. More preferred to use.

The invention's effect

[0024] In the present invention, since the solid surface is treated with a hydrophilic treatment agent containing an aromatic sulfonic acid-based formalin condensate, it is possible to effectively hydrophilize the solid surface, and to obtain an excellent antifouling effect. Obtainable. In particular, the hydrophilic treatment agent of the present invention can be suitably used as an antifouling detergent, and by incorporating a surfactant, the antifouling effect can be further improved.

Example 1

[Preparation of Hydrophilic Treatment Agent Aqueous Solution]

The surface of the toilet was subjected to a hydrophilic treatment using the hydrophilic treating agent according to the present invention, and its hydrophilicity and antifouling properties were evaluated. Specifically, two types of aromatic sulfonic acid-based formalin condensate, naphthalene sulfonate formalin condensate and melamine sulfonate formalin condensate, are dissolved in water to obtain 2 ppm and lO ppm concentrations. An aqueous solution was prepared.

[0026] The hydrophilicity-imparting performance and antifouling property when an aromatic sulfonic acid-based formalin condensate was used in combination with an aeon surfactant were also evaluated. Specifically, naphthalene A mixture of the same amount of sulfonate formalin condensate and sodium α-olefin sulfonate was dissolved in water to prepare 2 ppm and 10 ppm aqueous solutions, and these were combined to test six types of the product of the present invention. A liquid was prepared.

[0027] As a comparative product, an aqueous solution having a concentration of 1 ppm was prepared using a fluorine compound, sodium α-leu- finsulfonate and a water-soluble cationized polymer. Produced. Table 1 shows the details of the eleven types of test solutions for the products of the present invention and comparative products.

[Table 1]

[Hydrophilic treatment of toilet bowl surface]

The toilet was hydrophilized using 11 kinds of test liquids shown in Table 1. Specifically, the process of applying each test solution to a test panel in which an INAX toilet was cut into a size of 2 x 3 cm and drying it at room temperature for 30 minutes was repeated three times to make the test panel surface coated.

[Evaluation test]

(1) Evaluation of hydrophilization performance

Using the test panel after the above-mentioned hydrophilization treatment, the contact angle of the water droplet when distilled water was dropped on the surface was measured with a contact angle meter (cax-150 manufactured by Kyowa Interface Chemical Co., Ltd.), and the panel surface was hydrophilized. Was evaluated. Table 2 shows the results. [0031] [Table 2]

(2) Evaluation of antifouling property using actual toilet

The test solution was evaluated for antifouling properties when used as a toilet antifouling detergent. Specifically, the process of storing the test solution in a toilet tank, flushing and drying at room temperature for 30 minutes is repeated three times to make the toilet surface coated.

[0033] A certain amount of stool model dirt is applied thereto. After that, flush the test liquid stored in the toilet tank and visually check the toilet bowl for remaining stains. As the model soil, a mixture of salad oil and carbon black at a weight ratio of 100: 2 was used. The evaluation was performed based on the following criteria. Table 3 shows the results.

◎: There is no stain.

〇: Slightly adhered.

Δ: Slightly adhered.

X: There is considerable dirt.

[0034] [Table 3]

[0035] [Evaluation results]

From Table 2, it was confirmed that all the test panels treated with the product of the present invention had a water contact angle of less than 30 °, and the test panel surface was favorably hydrophilized by the hydrophilization treatment. In fact, even in an antifouling property evaluation test using a toilet bowl, as shown in Table 3, the product of the present invention has good antifouling properties even when it slips off, and cleanly removes dirt adhering to the panel surface. The result is that it is possible to do. In particular, products 5 and 6 of the present invention, in which a formalin naphthalene sulfonate condensate and sodium α-lefin sulfonic acid are used in combination, have synergistically improved antifouling properties. [0036] That is, the concentrations of the naphthalene sulfonate formalin condensate and the α-sodium refin sulfonate contained in the product 6 of the present invention are 1Z2 of the product 1 of the present invention and the comparative product 3, which are each used alone. Nevertheless, the evaluation of the antifouling property is equivalent to that of the present invention 2 which is a naphthalene sulfonate formalin condensate lOppm concentration. It was confirmed that the antifouling property was significantly improved by using in combination.

[0037] On the other hand, the comparative products all have a contact angle of water of 30 ° or more, which indicates that dirt is likely to adhere. In particular, the water contact angle of Comparative Product 4 using the water-soluble cationic polymer was the highest at 70 °, followed by Comparative Products 1 and 2 using the fluorine compound, which was 60 °.

[0038] When an antifouling property evaluation test was actually performed using a toilet using the comparative product, the comparative product 3 having a water contact angle of 30 ° was evaluated as better than the comparative product 3 with a triangle. Comparative products 1, 2 and 4 with higher water contact angles were all rated X. From the above results, it was confirmed that the contact angle of water and the antifouling property were closely related.

Example 2

Next, as a hydrophilic treatment agent, a surfactant was added as a cleaning component to an aromatic sulfonic acid-based formalin condensate, and sodium sulfate, a dye, and a fragrance were further added to produce a press-formed product. Using this as an antifouling detergent for toilets, the antifouling properties of actual toilets were evaluated. Details are described below.

[Preparation of antifouling detergent for toilet]

Table 4 shows the formulation of each sample. In the table, as the aromatic sulfonic acid-based formalin condensate, two types of the naphthalene sulfonic acid formalin condensate used in Example 1 and the melamine sulfonic acid formalin condensate were used, and the detergency and the durability were used as cleaning components. In consideration of the above, anionic surfactant and nonionic surfactant were used in combination.

As the anionic surfactant, an amino acid salt, a fatty acid salt, a sulfonate type surfactant and a sulfate ester type surfactant were used, and these were used in various combinations. In addition, a block copolymer of polyoxyethylene. Polyoxypropylene / polyoxybutylene (） block copolymer) was used as the non-one surfactant. [0042] As a comparative product, a product prepared by adding only the other components without adding an aromatic sulfonic acid-based formalin condensate was prepared. In the comparative product, the amount of the extender, sodium sulfate, was increased by the amount of the aromatic sulfonic acid-based formalin condensate, and the amount of other components was kept constant.

[Table 4]

Amino acid salt: Lauryl sarcosine Na

Fatty acid salt: stearic acid Na stone

Sulfo fatty acid ester salt: Na lauryl sulfoacetic acid

α-olefin sulfonic acid salt: 0; Na-olefin sulfonic acid (C = 14-18)

Dialkyl sulfosuccinate: Dioctyl sulfosuccinate Na

Sulfonate type anionic surfactant Alkylbenzenesulfonate: Linear alkylbenzenesulfonate Na

Alkane sulfonate: Secondary alkane sulfonate Na

Alkyl sulfate: triethanol-lamine alkyl sulfate (C = 12, 13)

Sulfate ester type anionic surfactant Polyoxyethylene alkyl ether sulfate: Polyoxyethylene lauryl ether sulfate Na

Nonionic surfactant: EO / PO / BO block copolymer

The toilet antifouling detergent prepared in Table 4 was placed under the water tap of the toilet tank, and the water released from the tap was set so that it came into contact with the toilet antifouling detergent. Next, the water in the tank was flushed to dissolve the toilet antifouling detergent, so that an aqueous solution of the antifouling detergent (about 10-15 ppm) was stored in the tank.

[0045] After the preparation so far, the process of flushing the aqueous solution of the antifouling cleaning agent in the tank and drying it at room temperature for 30 minutes was repeated three times to make the toilet bowl surface coated. After applying a certain amount of the above-mentioned model soil to the toilet tank, the aqueous solution of the antifouling cleaning agent in the toilet tank was flushed only once, and the remaining amount of soil on the toilet was visually checked. The criteria were four steps as described above. Table 4 shows the results.

[Evaluation results]

From Table 4, it can be seen that the inventive product 7-16 containing the aromatic sulfonic acid-based formalin condensate has an antifouling property of at least 〇, whereas the aromatic sulfonic acid-based formalin condensate is Without blending, Comparative Product 6-14 had an antifouling property of X even if it slipped.

[0047] Among the products of the present invention, in particular, when a sulfonate-type surfactant other than a sulfo fatty acid ester salt is used as one type of anionic surfactant (Products 7-10 of the present invention), or On the other hand, when the sulfate ester type a-on surfactant was used (Products 11 and 12 of the present invention), the antifouling property was remarkably improved as compared with when other a-on surfactants were used.

From the above results, the antifouling property was improved by using the aromatic sulfonic acid-based formalin condensate in combination with the sulfonate-type surfactant or the sulfate ester-type surfactant. It was confirmed that they could be synergistically enhanced.

Claims

The scope of the claims

[1] A hydrophilic treatment agent comprising an aromatic sulfonic acid-based formalin condensate.

[2] The hydrophilic treatment agent according to claim 1, wherein the aromatic sulfonic acid-based formalin condensate is a water-soluble salt of a naphthalene sulfonic acid formalin condensate or a water-soluble salt of a melamine sulfonic acid formalin condensate.

3. The hydrophilic treatment agent according to claim 1, further comprising a surfactant.

4. The hydrophilic treatment agent according to claim 3, wherein the surfactant is a sulfonate-type ionic surfactant or a sulfate ester-type ionic surfactant.

[5] An antifouling detergent for toilets, comprising the hydrophilic treatment agent according to any one of [14] to [14].