JP2005179526A - Stain-proof agent, and stain-proof treating method by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stain-proof agent having excellent stain-proof effects and effects for preventing corrosion of a metallic material; and to provide a stain-proof treating method by using the agent. <P>SOLUTION: The stain-proof agent comprises a copolymer composed of (A) a vinyl monomer having a fluoroalkyl group, (B) a vinyl monomer having a tertiary amino group and (C) a vinyl monomer having one or more kinds of hydrocarbon groups selected from a 1-12C linear or branched alkyl group, a cyclohexyl group and a benzyl group, and obtained by radically polymerizing the monomers in the presence of 0.01-20 mol% hypophosphorous acid (salt) or phosphorous acid (salt) based on the moles of the whole monomers. The stain-proof treating method involves spraying or coating the stain-proof treating liquid containing the stain-proof agent on a material to be treated, or dipping the material to be treated in the stain-proof treating liquid to impart the stain-proof properties to the material to be treated. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an antifouling agent and an antifouling treatment method using the same, and more specifically, a hard surface such as metal, glass and tile, and a soft surface composed of fibers, hair, etc., in particular, a hard metal. The present invention relates to an antifouling agent that imparts suitable antifouling properties and rust resistance to a surface and an antifouling treatment method using the same.

Conventionally, surface treatment agents comprising an amphiphilic copolymer comprising a specific ratio of a vinyl monomer having a fluoroalkyl group, a tertiary amine, or a quaternary ammonium group-containing vinyl monomer and an anionic vinyl monomer, such as stainless steel and plastic It shows that the antifouling property is high with respect to hard surfaces, soft surfaces such as hair and fibers, and proposes this (for example, see Patent Document 1). However, although the antifouling effect is high, the anticorrosion effect on metals is not sufficient, and improvement is still desired. In addition, a shoe coating solution containing a self-crosslinking acrylic emulsion and a copolymer of an acrylate ester having a perfluoroalkyl group is proposed, and the shoe coating solution has a leather retaining effect and a polishing effect, And it is supposed to give the antifouling property with high sustainability (for example, refer patent document 2).
JP 2002-105433 A Japanese Patent Laid-Open No. 10-10989

  Therefore, in view of the above circumstances, an object of the present invention is to provide an antifouling agent having an excellent antifouling effect and an excellent anticorrosion effect for metal materials, and an antifouling treatment method using the same.

The inventors have (A) a vinyl monomer having a fluoroalkyl group, (B) a vinyl monomer having a tertiary amino group, and (C) a hydrocarbon group having 1 to 12 carbon atoms. A copolymer obtained from radical polymerization in the presence of hypophosphorous acid (salt) or phosphorous acid (salt) is a soft surface such as fiber or hair. In addition to demonstrating extremely excellent antifouling properties to hard surfaces such as metals, glass and tiles, it has also been found to impart rust prevention properties to metal materials, leading to the present invention. is there.
That is, the antifouling agent of the present invention and the antifouling treatment method using the antifouling agent are characterized by having the following configurations or structures (1) to (4).

  (1). (A) a vinyl monomer having a fluoroalkyl group, (B) a vinyl monomer having a tertiary amino group, and (C) a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, and benzyl A copolymer comprising a vinyl monomer having at least one hydrocarbon group selected from vinyl monomers having a group, wherein hypophosphorous acid (salt) or An antifouling agent comprising a copolymer obtained by radical polymerization in the presence of 0.01 to 20 mol% of phosphorous acid (salt).

  (2). The copolymer is based on the total number of moles of monomer (A) the monomer is in the range of 5 to 70 mol%, (B) the monomer is in the range of 5 to 70 mol%, and (C) the monomer The antifouling agent according to the above (1), wherein the body is a copolymer in the range of 5 to 50 mol%.

(3). An antifouling treatment method for imparting antifouling properties to a material to be treated by spraying, applying, or immersing the antifouling treatment liquid containing the antifouling agent described in (1) above in the liquid.
(4). The antifouling treatment method according to (3), wherein the material to be treated is a metal.

  The antifouling agent of the present invention is excellent in the antifouling effect for preventing the adhesion of organic and inorganic dirt to hard and soft surfaces. Further, when a hard surface is treated by the antifouling treatment method of the present invention using such an antifouling agent, even if dirt is attached, the dirt can be easily wiped off by washing or wiping floss. Also exhibits removability. In particular, when applied to a hard metal surface, it also has corrosion resistance or rust resistance. Moreover, when applied to glasses such as glasses, it is effective against a small amount of fingerprint contamination.

Hereinafter, embodiments of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments and examples.
The antifouling agent of the present invention comprises (A) a vinyl monomer having a fluoroalkyl group, (B) a vinyl monomer having a tertiary amino group, and (C) a linear or branched chain having 1 to 12 carbon atoms. It consists of a copolymer comprising a vinyl monomer having one or more hydrocarbon groups selected from vinyl monomers having an alkyl group, a cyclohexyl group, and a benzyl group.

  As said (A) vinyl monomer which has a fluoroalkyl group, it is preferable to contain the fluorine atom in the range of 2-31, especially the range of 2-25 in the monomer. If the fluorine atom is included in such a range, the copolymer can exhibit antifouling properties and rust prevention properties. On the other hand, when the number of fluorine atoms exceeds 31, precipitation occurs in production and the reaction becomes worse.

Examples of such a monomer (A) include acrylic acid (or methacrylic acid) 1H, 1H, 2H, 2H-heptadecafluorodecyl ester, acrylic acid (or methacrylic acid) 1H, 1H, 5H-octafluoro. Pentyl esters, acrylic acid (or methacrylic acid) 2,2,3,3-tetrafluoropropyl ester, acrylic acid (or methacrylic acid) 2,2,2-trifluoroethyl ester, etc. Acrylic acid (or methacrylic acid) 1H, 1H, 2H, 2H-heptadecafluorodecyl ester and acrylic acid (or methacrylic acid) 1H, 1H, 5H-octafluoropentyl ester are preferred.
The monomer (A) is preferably contained in a proportion of 5 to 70 mol%, more preferably in a proportion of 20 to 60 mol%, based on the total number of moles of monomers. If it is less than 5 mol%, the antifouling effect is not sufficiently exhibited, and even if it exceeds 70 mol%, the effect does not change and it is uneconomical.

Examples of the vinyl monomer having a tertiary amino group (B) include acrylic acid (or methacrylic acid) -N, N-dialkyl (1 to 3 carbon atoms) aminoalkyl (1 to 5 carbon atoms) ester. , Acrylamide (or methacrylamide) -N, N-dialkyl (1 to 3 carbon atoms) aminoalkyl (1 to 5 carbon atoms) ester is preferred, especially acrylic acid (or methacrylic acid) -N, N-dimethyl. Aminoethyl, acrylamide (or methacrylamide) -N, N-dimethylaminopropyl are preferred. The monomer (B) can also be used after neutralizing the amine with an acid such as HCl.
The above (B) monomer is preferably contained in a proportion of 5 to 70 mol%, more preferably in a proportion of 20 to 60 mol%, based on the total number of moles of monomers. If it is less than 5 mol%, the durability is inferior, and if it exceeds 60 mol%, the antifouling property is lowered.

(C) The vinyl monomer having a hydrocarbon group is selected from vinyl monomers having a linear or branched alkyl group, a cyclohexyl group, or a benzyl group having 1 to 12 carbon atoms. These monomers may be used alone or as a mixture of two or more monomers. Examples of the vinyl monomer having a hydrocarbon group (C) include, for example, acrylic acid (or methacrylic acid) (linear or branched having 1 to 12 carbon atoms) alkyl ester, acrylic acid (or methacrylic acid) cyclohexyl. Esters and acrylic acid (or methacrylic acid) benzyl esters are preferred, and acrylic acid (or methacrylic acid) (C1-C12 linear or branched) alkyl esters are particularly preferred.
The vinyl monomer having a hydrocarbon group (C) is preferably contained in a proportion of 5 to 50 mol%, more preferably 10 to 40 mol%, based on the total number of moles of monomers. included. When the amount is less than 10 mol%, the film property of the treated surface is lowered, and when it exceeds 50 mol%, the antifouling property is lowered.

The antifouling agent of the present invention is obtained by radical polymerization in the presence of 0.01 to 20 mol% of hypophosphorous acid (salt) or phosphorous acid (salt) with respect to the total number of moles of the monomers. It consists of a copolymer. In particular, it is preferable that hypophosphorous acid (salt) or phosphorous acid (salt) is present in an amount of 0.1 to 10 mol%. When the amount of hypophosphorous acid (salt) or phosphorous acid (salt) is less than 0.01 mol%, corrosion resistance is not recognized, and when it exceeds 20 mol%, the amount of unreacted monomer increases. In addition, mol% with respect to the total number of moles of monomer means that when the total number of moles of monomers is 1 mole and hypophosphorous acid is used at 0.01 mole, 1 mole of hypophosphorous acid is added to the reaction system. % Means it was present. Moreover, hypophosphorous acid (salt) means hypophosphorous acid or hypophosphite. The same applies to phosphorous acid (salt).
Examples of the above hypophosphorous acid (salt) or phosphorous acid (salt) include, for example, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite, phosphorous acid, phosphorous acid Sodium acid, potassium phosphite and ammonium phosphite are preferred, and hypophosphorous acid and sodium hypophosphite are particularly preferred.

  The above copolymer is produced by a radical polymerization method. In this case, various conventionally known polymerization initiators can be used and are not particularly limited as long as they have the ability to initiate radical polymerization. For example, 2,2-azobisisobutyro Azo compounds such as nitrile, 2,2-azobis (2,4-divaleronitrile), 2,2-azobis (N, N-dimethyleneisobutylamidine), benzoyl peroxide, ammonium persulfate, potassium persulfate, peroxide Hydrogen and the like are preferable, and an azo compound is particularly preferable. Examples of the polymerization method include a solution polymerization method and a precipitation polymerization method. Specifically, water, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone and the like are preferable as the polymerization solvent. The polymerization temperature varies depending on the combination of the solvent and the initiator, and is preferably 20 to 200 ° C, more preferably 30 to 100 ° C. The reaction time is 1 to 24 hours.

  The monomers (A), (B), and (C) and the polymerization initiator may be charged in the reactor in advance, or may be mixed or added separately. Further, it may be added by dissolving in a polymerization solvent. As an addition method, it may be added all at once, may be added in several times, or may be added continuously, but the method of adding continuously is preferred from the point of sudden reaction and operability. Hypophosphorous acid (salt) or phosphorous acid (salt) may be charged into the reactor in advance, mixed with a monomer or a polymerization initiator, or added separately.

  The copolymer preferably has a weight average molecular weight of 1,000 to 500,000, more preferably 1,000 to 200,000, and still more preferably 1,000 to 100,000. This weight average molecular weight is obtained by GPC (gel permeation chromatography) using a tetrahydrofuran solvent mixed with triethylamine as a developing solvent and polystyrene as a standard substance. In addition, such a random copolymer is obtained by randomly polymerizing monomers A), (B), and (C), and a phosphate group is added to one end of the polymer. It seems that the addition of phosphoric acid groups demonstrates corrosion resistance to metals.

  The antifouling agent of the present invention preferably takes a form in which the above copolymer is dissolved in a solvent or dispersed in a dispersion medium, and the concentration of the copolymer in the solvent or the dispersion medium is preferably 0.01 to It is 35 mass%, More preferably, it is the range of 0.02-25 mass%. As long as the above-mentioned copolymer is stably dissolved or dispersed in a solvent or dispersion medium, it may be dissolved or dispersed in an emulsion, gel, liquid (compatible), or foam form. Common solvents or dispersion media such as water and organic solvents can be used.

The antifouling treatment method of the present invention is to impart antifouling properties to the material to be treated by spraying, applying, or immersing in the antifouling treatment liquid containing the antifouling agent.
Examples of the material to be treated include those having a hard surface such as glass, tile, earthenware, molded plastic, and metal, and those made of a soft surface such as fiber, hair, and skin. In particular, in the antifouling treatment method of the present invention, it is preferable to use a ceramic body made of glass, tile, or earthenware, or a metal as a material to be treated.

As described above, the antifouling treatment liquid is preferably prepared by dissolving the antifouling agent of the present invention in a solvent within the above concentration range or dispersing it in a dispersion medium. The antifouling treatment liquid, that is, the antifouling agent, imparts antifouling property to a target material having a hard or soft surface by a method of spraying with a spray device such as a trigger or aerosol, or a method of coating. Is preferred. Further, the material to be treated may be immersed in the antifouling treatment liquid.
It exhibits an excellent antifouling effect on a material to be treated such as a hard surface such as metal, glass, concrete, or wood, or a soft surface such as fiber or hair. In particular, it is suitable for hard surfaces such as metal and glass, and when applied to metal, in addition to the antifouling effect, rust prevention or corrosion resistance can also be imparted. When applied to glasses, window glass, optical glass as industrial precision parts, etc., the glass is excellent in antifouling properties against a small amount of sebum dirt such as fingerprints.

Hereinafter, the present invention will be described with reference to examples. However, the present invention is not limited to the following examples.
<Synthesis of copolymer>

Synthesis example 1
In a separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirring device,
37 g of ethanol was charged, and the temperature was raised to 78 ° C. while blowing nitrogen. 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate 17.5 g, dimethylaminoethyl methacrylate 15.4 g, methyl methacrylate 2.1 g mixed solution (1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate: Dimethylaminoethyl methacrylate: methyl methacrylate = 22: 64: 14 mol%), 0.32 g of sodium hypophosphite (1 mol% to the total number of monomers) was added to 18.6 g of ethanol, A solution prepared by dissolving 0.15 g of 2-azobis (2,4-divaleronitrile) in 9.3 g of ethanol was added over 3 hours, and the reaction was further performed for 5 hours. The weight average molecular weight of the obtained copolymer 1 was 30,000.

Synthesis Examples 2 and 3
The following copolymers 2 and 3 were synthesized by the same operation.
Copolymer 2: 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate: dimethylaminoethyl methacrylate: butyl methacrylate = 30: 60: 10 mol%, and the weight average molecular weight was 40,000.
Copolymer 3: 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate: dimethylaminoethyl acrylate: methyl methacrylate = 25: 50: 25 mol%, and weight average molecular weight was 20,000.
Synthesis example 4
Copolymer 4: Synthesized in the same manner as in Synthesis Example 1 except that sodium hypophosphite was not used. The weight average molecular weight was 100,000.

  Example 1 using 1% by mass ethanol solution of copolymer 1 above, Example 2 using 1% by mass ethanol solution of copolymer 2 and 1% by mass ethanol solution of copolymer 3 The following evaluation was made using Example 1 as a control, Example 1 using ethanol without a copolymer as a control, Comparative Example 1 and Comparative Example 2 using a 1% by weight ethanol solution of Copolymer 4 Went. The results are shown in Table 1 below.

<Evaluation of dirt adhesion prevention>
SUS304 mirror finish was used to evaluate the resistance to soiling (antifouling property). That is, after applying a 1% by weight ethanol solution of each copolymer and drying at room temperature, the degree of fingerprinting when a finger was pressed with a load of about 200 g was determined with the naked eye based on the following criteria, and the result was Table 1 shows.
(Evaluation criteria)
◎: Dirt is not present ○: Dirt is slightly present △: Dirt is slightly present x: Dirt is considerably adhered

<Rust prevention evaluation>
An Ni-coated steel sheet was used to evaluate the degree of surface discoloration. That is, after applying a 1% ethanol solution of each copolymer and drying at room temperature, the change in appearance when immersed in an electrolyte aqueous solution (5 g of NaCl per liter of water) for a whole day and night is judged with the naked eye based on the following criteria. The results are shown in Table 1.
(Evaluation criteria)
○: Almost no change Δ: Slightly dark ×: Very dark

  From the above results, it was found that Examples 1 to 3 showed not only an excellent antifouling effect but also an antirust effect. In Comparative Example 2, it was found that although some antifouling effect was seen, no rust prevention effect was seen.

  The antifouling agent of the present invention comprises (A) a vinyl monomer having a fluoroalkyl group, (B) a vinyl monomer having a tertiary amino group, and (C) carbonization having 1 to 12 carbon atoms. A copolymer comprising a vinyl monomer having a hydrogen group, comprising a copolymer obtained by radical polymerization in the presence of hypophosphorous acid (salt) or phosphorous acid (salt), such as fiber, hair, etc. Highly industrial applicability that not only provides excellent antifouling properties to hard surfaces such as metal, glass and tiles, but also provides rust prevention properties to metal materials. Is.

Claims (4)

  (A) a vinyl monomer having a fluoroalkyl group, (B) a vinyl monomer having a tertiary amino group, and (C) a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, and benzyl A copolymer comprising a vinyl monomer having at least one hydrocarbon group selected from vinyl monomers having a group, wherein hypophosphorous acid (salt) or An antifouling agent comprising a copolymer obtained by radical polymerization in the presence of 0.01 to 20 mol% of phosphorous acid (salt).   The copolymer is based on the total number of moles of monomer (A) the monomer is in the range of 5 to 70 mol%, (B) the monomer is in the range of 5 to 70 mol%, and (C) the monomer The antifouling agent according to claim 1, wherein the body is a copolymer in the range of 5 to 50 mol%.   An antifouling treatment method for imparting antifouling properties to a material to be treated by spraying, applying, or immersing the antifouling treatment liquid containing the antifouling agent according to claim 1 in the liquid.   The antifouling treatment method according to claim 3, wherein the material to be treated is a metal material.