JP2000345106A - Coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating composition that comprises a water-based solution including a cyclodextrin, or the like, forms a high degree antifogging coating membrane to a solid surface and simultaneously forms the coating membrane having both of hydrophilic and hydrophobic properties on the solid surface. SOLUTION: This coating composition is a water-based solution including (A) a cyclodextrin, for example, a modified β-cyclodextrin, or the like, (B) an antistatic agent, (C) a surfactant, for example, an organoboron surfactant, or the like, and (D) a hydrophilic binder, for example, carboxymethylcellulose, or the like. In a preferred embodiment, (E) a hydrophobic polymer binder, for example, a silicone rubber, or the like, may be used instead of the component D, a ferric [Fe (II)] compound and a chelating agent are used as the component B. Further, a slightly volatile and hydrophilic organic solvent is preferably admixed, for example, and in a preferred embodiment, the component D is used in an amount of 5-80 pts.wt. and the component E is used in an amount of 5-50 pts.wt. per 100 pts.wt. of water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition and an antistatic agent which provide an antifogging film or a hydrophilic and water repellent film.

[0002]

2. Description of the Related Art Various methods are known for modifying a solid surface. For example, a method of forming a hydrophilic film on the solid surface to impart hydrophilicity to the solid surface, a method of forming a hydrophobic film on the solid surface to impart water repellency to the solid surface, and the like are known. The conventional method for modifying the solid surface is mainly a method using a polymer substance corresponding to the intended surface modification, but in such a conventional method, the modification effect is not yet achieved. It was not enough. In addition, in the conventional method for modifying a solid surface, there is no known method for simultaneously providing the solid surface with both hydrophilicity and water repellency at low cost.

[0003]

SUMMARY OF THE INVENTION The present invention provides a coating composition that provides a highly anti-fog coating on a solid surface, and a coating that provides a coating having both hydrophilic and water repellent properties on a solid surface. An object of the present invention is to provide a composition and an antistatic agent.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, (i) cyclodextrin, (ii) antistatic agent, (iii) surfactant and (i)
v) A coating composition is provided which provides an antifogging film characterized by comprising a water-soluble liquid containing a hydrophilic binder. According to the present invention, there is provided a hydrophilic liquid comprising an aqueous liquid containing (i) cyclodextrin, (ii) an antistatic agent, (iii) a surfactant, and (iv) a hydrophobic polymer binder. The present invention provides a coating composition which provides an amphoteric coating having water repellency. Further, according to the present invention, there is provided an antistatic agent comprising an iron (II) compound and a chelating agent.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The cyclodextrin used in the present invention is a conventionally known substance, which includes α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.
Cyclodextrins and modified products thereof are included. In the present invention, β-cyclodextrin and modified products thereof are preferably used. The modified cyclodextrin includes those in which a part of OH groups contained in cyclodextrin is substituted with the following substituents. In this case, the substitution rate of -OZ is 0.1 to 0.6, preferably 0.2 to 0.5. —OZ (1) In the above formula, Z represents an alkyl group having 1 to 12, preferably 1 to 6 carbon atoms, an acyl group or an acyloxy group having an alkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, It may be a monochlorotriazinyl group represented by the following general formula (2).

Embedded image In the above formula, R is Cl or NR ¹ R ² (R ¹ , R ² : carbon number 1)
To 6 alkyl groups). The compounding amount is 1 to 20 parts by weight, preferably 2 to 5 parts by weight based on 100 parts by weight of water. The cyclodextrin provides stability to the aqueous composition and provides a hydrophilic coating.

[0006] As the antistatic agent used in the present invention, conventionally known antistatic agents can be used. Examples of such a material include anionic surfactants, cationic surfactants, amphoteric surfactants, and the like, and conductive resins such as a polyvinylbenzyl-type cationized resin and a polyacrylic acid-type cationized resin. Used. The antistatic agent imparts antistatic properties to the resulting film and prevents dust and the like from adhering to the film. The compounding amount of the antistatic agent may be any amount that gives the desired antistatic ability to the obtained film, but is generally 0.1 to 1 as a solid.
0% by weight, preferably 0.5 to 5% by weight.

In the present invention, iron (I)
I) Combinations of compounds and chelating agents can be used. The combination of the iron (II) compound and the chelating agent has not been used as an antistatic agent, but according to the research of the present inventors, it has a water-soluble property, It has been found that it can be used advantageously as a good antistatic agent. Examples of iron (II) compounds include inorganic salts of iron (II) such as ferrous sulfate, ferrous chloride, ferrous bromide, and ferrous iodide, as well as ferrous gallate and malic acid. First
Organic salts of iron (II) such as iron and ferrous fumarate are exemplified. Any chelating agent can be used as long as it has a chelating ability for iron ions. Such materials include, for example, ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, 1,2-diaminocyclohexanetetraacetic acid, hydroxyethyl Polyaminocarboxylic acids such as ethylenediamine triacetic acid and dihydroxyethylglycine or water-soluble salts thereof; polyaminophosphoric acids such as ethylenediaminetetrakis (methylenephosphonic acid) and nitrilotris (methylenephosphonic acid) and water-soluble salts thereof; citric acid, gluconic acid and the like Or a water-soluble salt thereof, an alkyldiphosphonic acid or a water-soluble salt thereof, and the like. These chelating agents can be used alone or in the form of a mixture. In the present invention, in particular, polyaminocarboxylic acids such as EDTA and iminoniacetic acid and water-soluble salts thereof (sodium salts, potassium salts, etc.)
Is preferred. The ratio of the iron (II) compound to the chelating agent is at least 1 equivalent, preferably 1.2 to 5 equivalents, more preferably 1.2, per equivalent of the iron (II) compound.
~ 2 equivalents.

The surfactant used in the present invention includes nonionic, anionic, cationic and amphoteric surfactants. In the case of the present invention, use of an organic boron surfactant is particularly preferred. preferable. This boron-based surfactant is represented by the following general formula (3).

Embedded image (Wherein, R represents an alkyl group or alkenyl group having 7 to 21 carbon atoms, X represents H or COR, and p and q represent 1 to
20 represents a number, and p + q is 20 to 30, preferably 23
The organic boron-based surfactant is an anionic nonionic surfactant, has water solubility, and has a trade name such as Emalbon T-20 to T-160. It is sold from.

The anionic surfactants include sodium lauryl sulfate, sodium N-lauroyl sarcosinate, sodium dodecylbenzenesulfonate, α-
Sodium sulfo fatty acid alkyl ester, sodium myristyl sulfate, sodium N-myristril sarcosine, sodium hydrogenated coconut fatty acid monoglyceride monosulfate, sodium lauryl sulfoacetate, α-
N-acyl glutamates such as sodium olefin sulfonate, sodium N-lauroyl glutamate, sodium N-palmitoyl glutamate, N-methyl-N
N-acyl taurates such as sodium acyl taurine;

Examples of the nonionic surfactant include sucrose fatty acid esters, polyoxyethylene fatty acid esters such as polyoxyethylene hydrogenated castor oil, polyglycerin fatty acid esters, alkyl glycosides, sorbitan fatty acid esters, and polyoxyethylene sorbitan monostearate. Polyoxyethylene sorbitan fatty acid ester, alkyldimethylamine oxide, maltitol fatty acid ester, sugar alcohol fatty acid ester such as lactol fatty acid ester, alkylol amite, fatty acid ethanolamide such as lauric acid mono- or diethanolamide, polyoxyethylene higher Alcohol ether, polyoxyethylene polyoxypropylene copolymer, polyoxyethylene polyoxypropylene fatty acid ester or pluronic acid And the like.

The above zwitterionic surfactants include betaine acetate types such as betaine alkyldimethylaminoacetate and betaine fatty acid amidopropyldimethylaminoacetate;
There are imidazoline types such as N-fatty acid acyl-N-carboxymethyl-N-hydroxyethylethylenediamine salt, and in addition, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, N-
N-alkyldiaminoethylglycine such as lauryldiaminoethylglycine and N-myristyldiaminoethylglycine; and sodium N-alkyl-1-hydroxyethylimidazoline betaine.

As the above-mentioned surfactant, it is preferable to use one having high water solubility, and its HLB is 10 or more, preferably 15 or more. This surfactant enhances the decomposability of the components in water, and gives a homogeneous composition with good stability.

As the hydrophilic binder, various conventionally known hydrophilic polymer substances are used. As such, carboxymethylcellulose, sodium carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, sodium carboxymethylhydroxymethylcellulose, polyvinyl alcohol,
Examples include polyvinylpyrrolidone, polyethylene oxide, sodium polyacrylate, xanthan gum, karaya gum, gum arabic, tragacanth gum, carrageenan, sodium alginate and the like. Examples of the hydrophilic binder include inorganic binders such as gelling silica. Further, an aqueous emulsion containing acrylic resin fine particles and, if necessary, inorganic fine particles can be used. The hydrophilic binder has a function of forming a hydrophilic film on a solid surface. The amount of water is 10
5 to 80 parts by weight, preferably 20 to 100 parts by weight,
50 parts by weight.

As the hydrophobic binder used in the present invention, conventionally known various binders are used. Such substances include hydrophobic rubber-like substances such as silicone rubber, hydrocarbon rubber, and fluorine-containing hydrocarbon rubber. Specific examples thereof include silicone rubber, fluorine rubber, butadiene rubber, chloride rubber, chloroprene rubber, isoprene rubber, ethylene-propylene rubber, butyl rubber (such as polybutene rubber and polyisobutylene rubber), and acrylic rubber. Other hydrophobic binders include:
Polyvinyl butyl ether and the like.

[0015] These hydrophobic binders have a function of forming a hydrophobic (water-repellent) film on the solid surface. The mixing amount is 5 to 50 parts by weight with respect to 100 parts by weight of water,
Preferably it is 10 to 30 parts by weight.

In the coating composition of the present invention, the composition for providing an antifogging film (antifogging composition) includes (i) cyclodextrin, (ii) an antistatic agent, (iii) a surfactant and (iv) ) It can be obtained by uniformly stirring a hydrophilic binder in water. In this antifogging composition, the amount of cyclodextrin was 100
It is 1 to 20 parts by weight, preferably 2 to 5 parts by weight based on parts by weight. The compounding amount of the antistatic agent is 1 to 10 parts by weight, preferably 2 to 5 parts by weight based on 100 parts by weight of water.
The amount of the surfactant is 1 to 3 with respect to 100 parts by weight of water.
0 parts by weight, preferably 3 to 10 parts by weight. When the surfactant to be used has an antistatic property, the surfactant is also used as an antistatic agent, so that it is not necessary to particularly mix the antistatic agent.

The antifogging composition of the present invention comprises, in addition to the above components,
It may contain a non-volatile hydrophilic organic solvent. In this case, the non-volatile hydrophilic organic solvent has a boiling point of 160 ° C.
Above, preferably 180 ° C. or higher, specific examples thereof include monohydric alcohols such as isopropylene alcohol, butyl alcohol, and hexyl alcohol, and polyhydric alcohols such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, and glycerin. Is mentioned. The compounding amount is 5 to 50 parts by weight, preferably 10 to 20 parts by weight per 100 parts by weight of water. The hardly volatile hydrophilic organic solvent enhances the hydrophilicity of the obtained coating and gives the coating flexibility.

The anti-fogging composition of the present invention can contain a porous fine powder. The average particle size is 1 μm or less, preferably 0.5 μm or less, and the finer particles are more preferable. Specific examples thereof include silica, alumina, titania, zirconia, magnesia, calcium carbonate, zeolite, and cellulose powder. The compounding amount is an amount that does not impair the transparency of the coating, and is usually
It is 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of water. This porous fine powder provides stability to the composition.

To form a film on a solid surface using the antifogging composition of the present invention, the composition is applied to the solid surface and dried. The film formed at this time is extremely rich in hydrophilicity, has anti-fogging properties, and does not cause fogging even when water vapor is blown on its surface. In addition, since the coating in this case is antistatic, it is difficult for dust such as dust to adhere thereto.

The film formed with the antifogging composition of the present invention has antifogging properties mainly due to cyclodextrin, hydrophilic surfactant and hydrophilic binder contained in the composition. It is considered something. And it is thought that the reason why the composition of the present invention is stably maintained over a long period of time is due to the dispersing effect of cyclodextrin contained in the composition.

The antifogging composition according to the present invention is applied to a solid surface where antifogging property is required, for example, a glass such as a mirror or a window glass, or a surface of a transparent plastic.

In the coating composition of the present invention, a composition having both a hydrophilic property and a water-repellent property (amphoteric composition) is
(I) cyclodextrin, (ii) antistatic agent, (ii)
It can be obtained by uniformly stirring i) a surfactant and (iv) a hydrophilic binder in water. In this amphoteric composition, the amount of cyclodextrin is 5 to 10 parts by weight, preferably 6 to 8 parts by weight per 100 parts by weight of water.
Parts by weight. The compounding amount of the antistatic agent is 0.5 to 15 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of water. The amount of the surfactant is per 100 parts by weight of water,
It is 5 to 20 parts by weight, preferably 10 to 18 parts by weight.
The blending amount of the hydrophobic binder is 15 per 100 parts by weight of water.
To 30 parts by weight, preferably 20 to 25 parts by weight.

The amphoteric composition of the present invention may contain a hardly volatile hydrophilic organic solvent in addition to the above components. The compounding amount is 10 to 30 parts by weight, preferably 15 to 25 parts by weight, per 100 parts by weight of water. The hydrophilic organic solvent enhances the hydrophilicity of the obtained coating and gives the coating flexibility.

The amphoteric composition of the present invention can contain a porous fine powder. The average particle size is 1 μm or less, preferably 0.5 μm or less, and the finer particles are more preferable. The compounding amount is within a range that does not impair the transparency of the coating, and is usually 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of water. This porous fine powder provides stability to the composition.

In order to form a film on a solid surface using the amphoteric composition of the present invention, the composition is applied to the solid surface and dried. The film formed at this time is a film having hydrophilicity and hydrophobicity (water repellency). When water is applied to the surface of the film, the water spreads as if it was once wetted on the surface of the film. After that, water is repelled from the coating surface. In addition, since the coating in this case is antistatic, it is difficult for dust such as dust to adhere thereto.

It is considered that the reason why the film formed by the amphoteric composition of the present invention has hydrophilicity is mainly attributable to the hydrophilic cyclodextrin and the hydrophilic surfactant contained in the composition. . In addition, it is considered that the hydrophilicity is enhanced by the non-volatile hydrophilic organic solvent which is supplemented to the composition. On the other hand, it is considered that the reason why the coating formed by the composition of the present invention has water repellency is due to the hydrophobic binder contained in the composition. It is considered that the reason why the composition of the present invention is stably maintained for a long period of time is due to the dispersing effect of cyclodextrin contained in the composition.

The amphoteric composition according to the present invention can be used on a solid surface (including a metal surface, a ceramic surface, a plastic surface, and a woody surface), for example, surfaces of various vehicle bodies such as automobiles and trains; It is applied to floor surfaces and outer wall surfaces; pottery surfaces such as toilets; mirror surfaces; window glass surfaces, and the surface of textiles such as paper and cloth.

[0028]

Next, the present invention will be described in more detail with reference to examples. In addition, all the parts and% shown below are based on weight.

Example 1 The following components were uniformly stirred and mixed to prepare an antifogging aqueous composition. Warm water (about 60 ° C.) 100 parts Iron (II) compound / chelating agent-containing aqueous solution A 100 parts Cyclodextrin A 10 parts Surfactant A 20 parts Silica A 5 parts Propylene glycol 10 parts Cellosolve acetate 2 parts Antifoaming agent A 1 Part hydrophilic binder A 30 parts

Next, the aqueous coating solution A is applied to the lower half surface of the mirror surface and dried at normal temperature. In this case, the coating amount after drying was about 0.5 g / m ² . Coating liquid A in this case
The antifogging effect of the coating formed by the above was evaluated as follows. (Evaluation of anti-fog property) Warm water 2 of 90 ° C in a beaker (500 ml)
Add 00 ml, use the mirror as a lid of the beaker, close the opening of the beaker with the mirror surface facing down. After standing for about 30 seconds, the mirror surface is visually observed for fogging. As a result, there was no fogging on the mirror surface coated with the coating liquid A, and fine water droplets adhered to the untreated mirror surface, causing fogging. Next, when a water droplet was dropped on this mirror surface, the water droplet spread on the treated surface without forming a polka dot and being uniformly applied. On the other hand, on the surface that had not been treated, polka dots were formed and a uniform wet state was not formed.

The specific contents of the above components are as follows. (1) Iron (II) / chelating agent-containing aqueous solution A Water 100 parts ferrous sulfate _{(FeSO 4 · 7H 2 O)} 5 parts of a chelating agent (EDTA) (ethylene diamine tetrasodium acetate) formed by adding 1 part (2) Cyclodextrin A Monochlorotriazinyl modified β-cyclodextrin sold by Yokohama International Bio-Institute, Ltd. (trade name “MC
T-β-CD ”) (3) Surfactant A“ Emalbon T-80 ”(polyoxyethylene glycerol borate-oleate) sold by Toho Chemical Industry Co., Ltd.
HLB: 16.3 (4) Silica A “Nip Seal” sold by Nippon Silica Co., Ltd., average particle size 0.5 μm (5) Defoamer A “Adecanate” manufactured by Asahi Denka Co., Ltd. (6) Hydrophilic Aqueous Binder A "Aqua Binder" (acryl-ceramic) manufactured by Efnica Corporation, solid content concentration: 55 wt%

Example 2 The amphoteric aqueous composition was prepared by uniformly stirring and mixing the following components, and a coating liquid B was prepared. Warming water (about 60 ° C.) 100 parts Iron (II) compound / chelating agent aqueous solution A 100 parts Cyclodextrin A 20 parts Surfactant A 20 parts Silica A 10 parts Propylene glycol 10 parts Cellosolve acetate 10 parts Antifoaming agent A 10 parts Hydrophobic binder B 100 parts The hydrophobic binder B is a hydrophobic rubber-based clear binder (trade name "BS binder" manufactured by Efnica Corporation, solid content concentration: 50 wt%).

Next, the aqueous coating solution B is applied to a half of the hood of a car with a soft cloth and dried at normal temperature.
Using a hose, tap water is discharged from the windshield side onto the hood. As a result, it was confirmed that water uniformly flowed on the treated surface to which the coating liquid B was applied, while water scattered on the untreated surface. Next, when water discharge is stopped, residual water on the treated surface immediately falls off the bonnet surface without leaving any water droplets, while water droplets do not immediately fall on the untreated surface and remain on the bonnet surface. It was confirmed that it was still.

Example 3 An automobile was coated with the coating solution B of the present invention. That is, the coating solution B is contained in a sponge, coated on the entire surface, and then wiped off with a cloth. Then, tap water is discharged into this. Water spreads over the entire surface and flows along the side from the roof and bonnet, and a clean water film is formed especially on the horizontal roof and bonnet. As soon as the tap was stopped, the water film was cut off immediately from the place where the discharge was stopped, for example, from the high part of the bonnet, and it was confirmed that drainage was very good and almost no water droplets remained. The film formed by applying the film coating solution B was hard to be stained, and the light was retained for a long time.

Example 4 An outdoor vending machine (white) was coated with the coating solution B of the present invention. The coating method in this case was performed on one half of the side of the vending machine and observed over time. As a result, it was confirmed that the surface to which the coating liquid B of the present invention was applied did not show any particular stain even after 6 months, whereas the uncoated surface had much stain. Was.

Example 5 The antistatic method of the woven fabric which was surface-treated using each of the coating solutions A and B of Example 1 and Example 2 was evaluated according to the JIS L1094 method. The half-life of the charge is 120 seconds or more, and its triboelectric voltage is 40
In contrast, in the case of the treatment, the half-life of the charge was about 15 seconds, and the triboelectric voltage was about 2500 V.
Met. From the above results, it is understood that the film formed from the composition of the present invention has a good antistatic ability.

[0037]

The antifogging coating composition of the present invention comprises:
A highly hydrophilic coating is applied to various solid surfaces, and the solid surface is used as an antifogging surface. In addition, since this coating has an antistatic property, it is very difficult for stains to occur. On the other hand, the amphoteric coating composition of the present invention gives an amphoteric coating having hydrophilicity and water repellency to various solid surfaces. In addition, since this coating has antistatic properties, it is very difficult to stain. Further, when dirt is generated on the surface, the dirt can be removed by discharging water on the dirt surface. Then, after the water discharge is stopped, the remaining liquid on the surface is repelled from the surface and falls, and the surface is easily dried only by leaving it. In addition, since this coating has an antistatic property, it is very difficult for stains to occur.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/14 C08L 101/14 C09D 7/12 C09D 7/12 Z C09K 3/16 102 C09K 3/16 102G 103 103Z 103B 3/18 3/18 101 101 102 102 102 G02B 1/10 G02B 1/10 Z F term (reference) 2K009 CC02 CC21 CC24 CC47 DD02 EE02 EE03 4H020 AA03 AA04 AA06 AB02 AB05 AB06 BA02 BA12 4J002 AB021 AB051 AB051 AC091 AC121 BB151 BB181 BB241 BD121 BE021 BE061 BG011 BG041 BJ001 CH021 CH053 CP031 DD077 DD087 DG047 EF037 EG026 EG047 EG057 EH046 EN036 EN116 EN117 EP016 ES007 EU017 EU106 EV186 EV256 FD127 FA01 FD 090127 FD 173

Claims (5)

[Claims] 1. A coating for providing an antifogging coating, comprising: an aqueous liquid containing (i) cyclodextrin, (ii) an antistatic agent, (iii) a surfactant, and (iv) a hydrophilic binder. Composition. 2. Hydrophilicity and water repellency comprising an aqueous liquid containing (i) cyclodextrin, (ii) an antistatic agent, (iii) a surfactant, and (iv) a hydrophobic polymer binder. A coating composition that provides an amphoteric film of 3. The composition according to claim 1, wherein said antistatic agent comprises an iron (II) compound and a chelating agent. 4. The composition according to claim 1, which comprises a non-volatile hydrophilic organic solvent. 5. An antistatic agent comprising an iron (II) compound and a chelating agent.