JP5512932B2 - Hydrophilic treatment agent - Google Patents

Description

  The present invention relates to a hydrophilic treatment agent, a hydrophilic treatment method using the same, and a cleaning method, and more particularly, a hydrophilic treatment agent that makes a solid surface hydrophilic and easily wets water, and a hydrophilic treatment method using the same. And a cleaning method.

Conventionally, various techniques for imparting hydrophobicity by surface treatment of a solid surface such as glass, metal, and fiber, and conversely, imparting hydrophilicity are known. For example, as a hydrophobization treatment, clothes are treated with a soft finish after washing, a water repellent is sprayed on ski wear, etc. to give a waterproof effect, or the painted surface of a car is waxed Widely done.
On the other hand, as hydrophilization treatment, for example, Patent Document 1 shows that specific benzotropolones are effective in improving the hydrophilicity of the solid surface.

Japanese Patent Laid-Open No. 7-233397

If the surface of the solid surface is made hydrophilic for the purpose of reducing the contact angle with water and making the solid surface easy to get wet with water, dirt attached to the solid surface after the treatment can be easily removed during cleaning, In addition to anti-fouling effects, it is considered that anti-fogging effects such as glass and mirrors, improvement of clothing comfort, anti-static, and imparting anti-fouling properties to the surface of sealed water systems can be expected.
However, there are surprisingly few products that apply hydrophilization technology, and it cannot be said that they are widely spread. This is due to the fact that no hydrophilizing agent is known that has a sufficiently satisfactory effect.
In view of the above, an object of the present invention is to provide a strong hydrophilizing agent capable of hydrophilizing a solid surface, a hydrophilizing method using the same, and a cleaning method.

  As a result of studying the wettability of water on the solid surface of various compounds and their persistence, the present inventors have used a compound containing an alkyl ether carboxylic acid and an alkyl ether carboxylate in a specific composition ratio. It has been found that it has an excellent hydrophilizing effect on various solid surfaces, and the present invention has been completed.

That is, the present invention
[1] The following general formula (1)
_{^{[R 1 -O- (CH 2 CH}} 2 O) n 1 -CH 2 COOH] p [R 2 -O- (CH 2 CH 2 O) n 2 -CH 2 COO (1 / r) M] q (1 )
Wherein R ¹ and R ² are each independently a hydrocarbon group having 8 to 22 carbon atoms, n ₁ and n ₂ are each a number in the range of 1 to 30, and M is an alkali metal or an alkaline earth metal. And r represents the valence of M, and p and q each represents an independent natural number satisfying the value of p / q in the range of 0.35 to 2.5.)
A hydrophilizing agent containing a compound represented by:

[2] A method for hydrophilizing a solid surface, wherein the solid surface is brought into contact with a solution containing the hydrophilizing agent described in [1], and [3] a hydrophilizing treatment using the hydrophilizing agent described in [1] above. A cleaning method having a step of simultaneously performing a cleaning treatment with a surfactant,
Is to provide.

  According to the hydrophilic treatment agent of the present invention and the hydrophilic treatment method using the same, the hydrophilicity of the solid surface is improved by the hydrophilic treatment. As a result, various solid surfaces can be easily cleaned, and effects such as prevention of redeposition of soil can be obtained.

[Hydrophilic treatment agent]
The hydrophilic treatment agent of the present invention contains a compound represented by the following general formula (1).
_{^{[R 1 -O- (CH 2 CH}} 2 O) n 1 -CH 2 COOH] p [R 2 -O- (CH 2 CH 2 O) n 2 -CH 2 COO (1 / r) M] q (1 )
Wherein R ¹ and R ² are each independently a hydrocarbon group having 8 to 22 carbon atoms, n ₁ and n ₂ are each a number in the range of 1 to 30, and M is an alkali metal or an alkaline earth metal. And r represents the valence of M, and p and q each represents an independent natural number satisfying the value of p / q in the range of 0.35 to 2.5.)

In the general formula (1), the hydrocarbon group having 8 to 22 carbon atoms represented by each of R ¹ and R ² is a linear or branched alkyl group having 8 to 22 carbon atoms or a carbon group having 8 to 22 carbon atoms. Twenty-two linear or branched alkenyl groups are preferred.
Examples of the linear or branched alkyl group having 8 to 22 carbon atoms include various octyl groups, decyl groups, dodecyl groups, tetradecyl groups, hexadecyl groups, octadecyl groups, icosyl groups, docosyl groups, and the like. Examples of the linear or branched alkenyl group having 8 to 22 include various octenyl groups, decenyl groups, dodecenyl groups, tetradecenyl groups, hexadecenyl groups, octadecenyl groups, icocenyl groups, dococenyl groups, and the like.
In the present invention, the hydrocarbon group represented by each of R ¹ and R ² is preferably a hydrocarbon group having 10 to 18 carbon atoms, more preferably a hydrocarbon group having 12 to 18 carbon atoms, Preferably it is a 14-18 hydrocarbon group, Most preferably, it is a 15-18 hydrocarbon group. In the present invention, R ¹ and R ² may be the same or different from each other.

In the general formula (1), M represents an alkali metal or an alkaline earth metal, and specific examples include lithium, sodium, potassium, magnesium, calcium, etc. From the viewpoint of solubility, sodium and potassium are Preferably used.
In the general formula (1), n ₁ and n ₂ each represent an average addition mole number of ethylene oxide, a number ranging from 1 to 30. From the viewpoint of foamability and usability when used for washing, n ₁ and n ₂ are each more preferably from 1 to 20, and more preferably from 1 to 15.

  In the general formula (1), p and q each represent an independent natural number satisfying a value of p / q of 0.35 to 2.50. From the viewpoint of excellent hydrophilization performance, p / q The value of is preferably in the range of 0.40 to 2.5, and more preferably in the range of 0.42 to 2.3. Moreover, it is preferable that the value of p / q is 0.6-1.8 from a viewpoint of the sustainability of hydrophilization performance.

That is, the compound represented by the general formula (1) includes an alkyl ether carboxylic acid represented by R ¹ —O— (CH ₂ CH ₂ O) n ₁ —CH ₂ COOH, and R ² —O— (CH ₂ CH ₂ O) n ₂ —CH ₂ COO (1 / r) M and a compound having an alkyl ether carboxylate represented by p / q in a ratio of 0.35 to 2.5, preferably an alkyl ether A complex of a carboxylic acid and an alkyl ether carboxylate, and more preferably a complex of p = q. Here, the “composite” means an aggregate formed by combining the alkyl ether carboxylic acid and the alkyl ether carboxylate at a ratio indicated by p / q, and has one chemical characteristic as the aggregate. The thing which has.

  Preferred examples of the compound represented by the general formula (1) from the viewpoint of surface hydrophilization include polyoxyethylene [ethylene oxide (EO) average addition mole number: 4] lauryl ether carboxylic acid, polyoxyethylene (EO average). Addition mole number: 8) Octyl ether carboxylic acid, polyoxyethylene (EO average addition mole number: 8) Palmityl ether carboxylic acid, polyoxyethylene (EO average addition mole number: 2) Octyl ether carboxylic acid, polyoxyethylene ( EO average addition mole number: 2) Carboxylic acid such as lauryl ether carboxylic acid, polyoxyethylene (EO average addition mole number: 10) lauryl ether carboxylic acid, polyoxyethylene (EO average addition mole number: 4) myristyl ether carboxylic acid Etc. and their alkali metal salts or alkaline earth metals More preferably, polyoxyethylene (EO average addition mole number: 4) lauryl ether carboxylic acid, polyoxyethylene (EO average addition mole number: 8) octyl ether carboxylic acid, polyoxyethylene ( EO average addition mole number: 8) Palmityl ether carboxylic acid, polyoxyethylene (EO average addition mole number: 2) lauryl ether carboxylic acid, polyoxyethylene (EO average addition mole number: 10) lauryl ether carboxylic acid, and poly A complex of each of oxyethylene (EO average addition mole number: 4) myristyl ether carboxylic acid and its sodium salt is mentioned. In the present invention, the compound represented by the general formula (1) is more preferably an equivalent complex of the carboxylic acid and its sodium salt.

  The method for preparing the compound represented by the general formula (1) is not particularly limited. For example, an alkali metal compound or alkaline earth is added to a polyoxyethylene alkyl (or alkenyl) ether carboxylic acid solution obtained by a known method. The method of adding a metal compound is mentioned. Here, as the alkali metal compound or alkaline earth metal compound, an alkali metal or alkaline earth metal hydroxide represented by M in the general formula (1) can be used.

The alkali metal compound or alkaline earth metal compound is preferably added to a solution such as water in an amount such that the p / q of the carboxylic acid and the resulting salt is a desired value. Preferably it is 0.4-2.9 equivalent with respect to 1 equivalent of carboxylic acid, More preferably, it is 0.4-2.5 equivalent, Furthermore, 0.6-1.7 equivalent is added. These are mixed for a predetermined time at a temperature of 20 to 80 ° C., for example.
From the viewpoint of the object of the present invention, the hydrophilic treatment agent of the present invention preferably contains 0.01 to 100% by mass of the compound represented by the general formula (1), more preferably 10 to 100% by mass. %contains

  Furthermore, in the hydrophilization treatment agent of the present invention, in addition to the compound represented by the general formula (1), lower alcohols such as ethyl alcohol and isopropyl alcohol; solubilization of toluene sulfonate, xylene sulfonate, urea and the like Agents; viscosity modifiers such as clay minerals and water-soluble polymer compounds; water-insoluble abrasives such as calcite, silica, calcium phosphate, zeolite, calcium carbonate, polyethylene, nylon and polystyrene; humectants such as glycerin and sorbitol; cationic cellulose Feeling improvers such as citrates; chelating agents such as citrate, NTA and EDTA; alkali builders such as sodium carbonate and sodium silicate; enzymes, dyes, fragrances, antiseptic and antifungal agents and the like can be added.

[Hydrophilic treatment method]
The present invention also provides a method for hydrophilizing a solid surface, wherein the solid surface is brought into contact with a solution containing a hydrophilizing agent. The method for contacting the hydrophilizing agent-containing solution with the solid surface is not particularly limited. For example, the method can be performed by immersing the solid in the hydrophilizing agent-containing solution or spraying the solution onto the solid surface.
In the hydrophilization treatment method of the present invention, from the viewpoint of the surface hydrophilization effect, it is more preferable that the solid surface is previously brought into contact with the solution containing the hydrophilization treatment agent.

An aqueous solution is preferable as the solution containing the hydrophilic treatment agent.
Examples of the solid surface to which the hydrophilizing agent of the present invention is applied include, for example, hard surfaces such as glass, ceramics, porcelain, and enamel; metal surfaces such as aluminum, stainless steel, and brass; plastic surfaces such as polyethylene, polypropylene, and melamine resin; Examples include natural fiber surfaces such as cotton, silk, and wool; synthetic fiber surfaces such as polyester, nylon, and rayon; hair, nails, and teeth.

The content of the hydrophilization treatment agent in the solution containing the hydrophilization treatment agent depends on the treatment conditions, but from the viewpoint of the surface hydrophilization effect, for example, the amount of the compound represented by the general formula (1) is hydrophilic. It is preferable that it is 0.01-15 mass% in a chemical conversion agent containing solution, it is more preferable that it is 0.01-10 mass%, and it is still more preferable that it is 0.01-5 mass%.
The treatment conditions for the hydrophilization treatment are not particularly limited and can be appropriately selected depending on the purpose. For example, in the case of the immersion method, from the viewpoint of the surface hydrophilization effect, 0.5 to 60 minutes at about 5 to 50 ° C. It is preferable to carry out to the extent.

[Cleaning method]
The present invention also provides a cleaning method having a step of simultaneously performing a hydrophilic treatment with a hydrophilic treatment agent containing the compound represented by the general formula (1) and a cleaning treatment with a surfactant.
As the surfactant used herein, except for the compound represented by the general formula (1), ordinary anionic surfactants, nonionic surfactants, amphoteric surfactants, and cationic surfactants Any one or a combination of two or more of these may be mentioned, but from the viewpoint of detergency, an anionic surfactant and a nonionic surfactant are preferred.

Examples of the anionic surfactant include a sulfate ester salt (AS) of an alcohol having 10 to 18 carbon atoms, a sulfate ester salt (ES) of an alkoxylated product of an alcohol having 8 to 20 carbon atoms, an alkylbenzene sulfonate (LAS), Paraffin sulfonate, α-olefin sulfonate, α-sulfo fatty acid salt, α-sulfo fatty acid alkyl ester salt or fatty acid salt, and alkyl sulfate are preferable. In the present invention, alkyl sulfate (AS) and alkyl ether sulfate (ES) represented by the following general formula (2) are particularly preferable.
RO (AO) _m SO ₃ M ₁ (2)
(In the formula, R represents a hydrocarbon group having 9 to 24 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, M ₁ represents a hydrogen atom, an alkali metal or NH ₄ , and m represents an average value. It is a number from 0 to 4.)

  In the general formula (2), the hydrocarbon group having 9 to 24 carbon atoms represented by R is preferably a hydrocarbon group having 12 to 20 carbon atoms, and more preferably a linear or branched alkyl group. Group or alkenyl group. When the number of carbon atoms of the hydrocarbon group represented by R is within the above range, the balance between the surface activity and the solubility in water of the compound represented by the general formula (2) is good. Each of the alkyl group and the alkenyl group may be linear or branched, and specifically, a decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, icosyl group, docosyl group, And an oleyl group (each substituent includes its isomer).

In the general formula (2), the alkylene group having 2 to 4 carbon atoms represented by A may be linear or branched, for example, ethylene group, propylene group, 1-methyltrimethylene group, Although a trimethylene group, a tetramethylene group, etc. can be mentioned, Among these, an ethylene group or a propylene group is suitable, and an ethylene group is more preferable.
Examples of the alkali metal represented by M ₁ include sodium, potassium, and lithium. Among these, sodium or potassium is preferable, and sodium is more preferable.
Moreover, m is a number of 0-4 by an average value, Preferably it is 0.1-2, More preferably, it is a number of 0.5-1.5.

Nonionic surfactants include polyoxyalkylene alkyl (carbon number 8-20) ether, alkyl polyglycoside, polyoxyalkylene alkyl (carbon number 8-20) phenyl ether, polyoxyalkylene sorbitan fatty acid (carbon number 8-8). 22) Ester, polyoxyalkylene glycol fatty acid (carbon number 8 to 22) ester, and polyoxyethylene polyoxypropylene block polymer are preferable. In particular, the nonionic surfactant is preferably a polyoxyalkylene alkyl ether obtained by adding an average of 4 to 20 moles of an alkylene oxide such as ethylene oxide or propylene oxide to an alcohol having 10 to 18 carbon atoms. As the nonionic surfactant, those having an HLB value (calculated by the Griffin method) of 10.5 to 15.0, more preferably 11.0 to 14.5 are preferable.
Although the said surfactant can also be used independently, Preferably, it uses combining 2 or more types. In particular, it is more preferable to use a combination of the anionic surfactant and the nonionic surfactant. In addition, an anionic surfactant and / or a nonionic surfactant can be appropriately used in combination with an amphoteric surfactant or a cationic surfactant.

The surfactant may be contained in the hydrophilic treatment agent of the present invention, but from the viewpoint of simultaneously performing the hydrophilic treatment and the cleaning treatment, as a surfactant composition separately from the hydrophilic treatment agent of the present invention, It can be used in combination with the hydrophilic treatment agent of the present invention. For example, it is preferably contained in a solution containing the hydrophilic treatment agent.
The surfactant is preferably contained in an amount of 0.1 to 60% by mass, and 1 to 50% by mass in the solution containing the hydrophilizing agent of the invention from the viewpoint of the purpose of the present invention and detergency. More preferably.

The cleaning method of the present invention includes a step of simultaneously performing a hydrophilic treatment of the solid surface with the compound represented by the general formula (1) and a cleaning treatment with the surfactant. Here, “simultaneously” means that the hydrophilization treatment and the washing treatment are performed in the same step, and are not limited to the case where they proceed completely simultaneously.
For specific cleaning treatment conditions, any of ordinary methods in the cleaning field can be used.

Example 1
Polyoxyethylene (EO average added mole number: 4) 50 g of lauryl ether carboxylic acid, 3.33 g of sodium hydroxide and 946.7 g of water were placed in a 1 liter beaker, placed in a 50 ° C. water bath and stirred for 1 hour. The mixture was allowed to stand at room temperature for a day to obtain polyoxyethylene (EO average addition mole number: 4) sodium lauryl ether carboxylate having a p / q of 0.43 in the general formula (1).
The structure was analyzed by gas chromatography (GC), the amount of proton was measured by neutralization titration, and the amount of sodium was measured by atomic absorption spectrometry. The resulting compound had a p / q of 0.43. This was confirmed to be a composite of polyoxyethylene (EO addition mole number: 4) lauryl ether carboxylic acid and polyoxyethylene (EO addition mole number: 4) sodium lauryl ether carboxylate.

Examples 2 to 6 and Comparative Examples 1 and 2
In Example 1, general formula (Equivalent to EO average addition mole number: 4) lauryl ether carboxylic acid and the amount of each of this and sodium hydroxide used was changed as shown in Table 1. A compound represented by 1) and a comparative product thereof were prepared. As a result of measurement in the same manner as in Example 1, it was confirmed that the composite had p / q values shown in Table 1.

(Measurement of contact angle)
About the compound obtained in Examples 1-6 and Comparative Examples 1 and 2, and polyoxyethylene (1) sodium lauryl ether sulfate ester (Comparative Example 3) as a comparison, each 0.25 mass% aqueous solution, and these In each of the water containing no water (Comparative Example 4), the polyethylene substrate was immersed for 30 minutes at 25 ° C. and dried for 5 minutes or more, and then contact angle meter (CA-X150 type,
The contact angle of pure water was measured by Kyowa Interface Science Co., Ltd. The results are shown in Table 1.

  According to the hydrophilization treatment agent of the present invention, the hydrophilicity of the solid surface is improved by the hydrophilization treatment, so that dirt such as glass, metal, earthenware, and fibers can be easily removed, and dirt can be prevented from reattaching. Since the effect can be obtained, the hydrophilization treatment agent of the present invention is particularly suitably used as a hard surface cleaning agent such as household and commercial tableware detergents, residential detergents, and industrial metal surface cleaners. .

Claims (4)

The following general formula (1)
_{^{[R 1 -O- (CH 2 CH}} 2 O) n 1 -CH 2 COOH] p [R 2 -O- (CH 2 CH 2 O) n 2 -CH 2 COO (1 / r) M] q (1 )
Wherein R ¹ and R ² are each independently a hydrocarbon group having 8 to 22 carbon atoms, n ₁ and n ₂ are each a number in the range of 1 to 30, and M is an alkali metal or an alkaline earth metal. And r represents the valence of M, and p and q each represents an independent natural number satisfying the value of p / q in the range of 0.35 to 2.5.)
A plastic surface hydrophilizing agent containing a compound represented by the formula: A method for hydrophilizing a plastic surface , comprising bringing the plastic surface into contact with a solution containing the hydrophilizing agent according to claim 1.   The hydrophilization processing method of Claim 2 in which the solution containing a hydrophilization treatment agent contains 0.01-15 mass% of this hydrophilization treatment agent as a compound represented by General formula (1). A cleaning method comprising a step of simultaneously performing a hydrophilic treatment with a hydrophilic treatment agent according to claim 1 and a cleaning treatment with a surfactant on a plastic surface .