JPH11172153A - Destaticizing coating material composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a destaticizing coating material composition capable of forming coated film having low dependence on humidity, temperature or the like, having stable destaticizing properties for a long period of time, excellent in optical physical properties such as transparency, colorlessness, durability, adhesivity and flexibility, or the like, and its use. SOLUTION: In this destaticizing coating material composition comprising a binder component having film-forming performances, a trivalent and/or a tetravalent metal element (Md) and Zn as metal components and zinc oxide- based particles showing zinc oxide crystallinity in terms of X-ray diffraction, the zinc oxide-based particles have the ratio of the total content of impurities H composed of a halogen metal ion and/or atom except F, sulfate SO4 <2-> and nitrate NO3 <-> to the number of zinc atoms (with the proviso that the number is calculated as the number of S atoms in the case of sulfate group and as the number of N atoms in the case of nitrate group) of <=0.5%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an antistatic coating composition and its use.

[0002]

2. Description of the Related Art Conventionally, as an antistatic coating composition, fine particles of conductive metal oxides such as zinc oxide and tin oxide have been used;
Paints are known which contain metal fine particles such as nickel; anionic, cationic, amphoteric surfactants and the like as antistatic agents. Of these, metal oxides, compositions containing fine particles of metal, etc., have a large particle size or, due to insufficient dispersibility in paints and coatings, have excellent transparency and coloring. No antistatic film was obtained. In addition, in order to impart antistatic properties, it is necessary to include a large amount of fine particles in the paint, the flexibility and adhesion of the resulting coating film is not sufficient, such as weather resistance, the coating film as an antistatic film It was not satisfactory even when used.

On the other hand, a paint containing a surfactant as an antistatic agent can provide a coating film having excellent transparency, but does not have an antistatic property at low humidity based on a conduction mechanism peculiar to the surfactant. Environmental dependency such as sufficient was high. In addition, because the weather resistance of the surfactant which is an antistatic agent is low,
The durability of the coating film is not sufficient, and if used for a long period of time, the coating film will deteriorate, coloring will occur, the surfactant will bleed, the antistatic performance will decrease, and blocking will occur in practical use. There were various problems.

[0004]

The problems to be solved by the present invention are low dependence on humidity, temperature, etc., stable antistatic properties for a long time, optical properties such as transparency and colorlessness, and durability. An object of the present invention is to provide an antistatic coating composition capable of forming a coating film having excellent properties, adhesion and flexibility, and its use.

[0005]

According to the present invention, there is provided an antistatic coating composition comprising a binder component having a film-forming ability, a trivalent and / or tetravalent metal element (Md) and Zn as a metal component. A zinc oxide-based particle exhibiting zinc oxide crystallinity in X-ray diffraction, wherein the zinc oxide-based particle contains ions and / or atoms of a halogen element other than F, sulfate sulfate SO ₄ ^{2 -} and nitrate NO ₃ ^- the total content of impurity H consisting of the atomic to zinc (provided that the number of atoms of S in the case of the sulfate in the case of nitrate anions calculated as the number of atoms of N) 0 in ratio 0.5% or less.

In the zinc oxide-based particles, a diffraction peak peculiar to crystalline zinc oxide appears, and the two lattice planes (100) and (002) are vertically oriented using the Scherrer method (approximation of Cauchy function). Crystallite size Ds (hk
When l) is obtained, Ds (002) / Ds (100) <2 is satisfied. When the crystallite size obtained by the Wilson method is Dw, 1 ≦ Dw ≦ 100 (nm) It is preferable that the zinc oxide-based particles are satisfied.

The antistatic coating composition preferably further contains a conductive auxiliary. The coated product according to the present invention is a coated product obtained by forming a coating film obtained from the above antistatic coating composition on the surface of a substrate.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the following, first, zinc oxide-based particles will be described, then the binder component will be described, and finally, the antistatic coating composition and the coated article of the present invention will be described. (Zinc oxide-based particles) Zinc oxide-based particles used in the present invention, in addition to the inherent ultraviolet shielding properties of zinc oxide-based particles, visible light transmittance, while showing infrared non-transparency, conductivity, etc.
It has low dependence on humidity, temperature, etc. and exhibits stable antistatic properties for a long period of time.

The zinc oxide particles are trivalent and / or tetravalent.
The valence metal element (Md) and Zn are metal components.
The content of Md is Md based on the total number of atoms of the metal component.
Is preferably 0.1 to 20%, more preferably 1 to 10%, and still more preferably 3 to 10%, expressed as a ratio of the number of atoms.
~ 8%. Exceeding the above range makes it difficult to produce fine particles having a high degree of uniformity in composition, crystal size, and the like, and below the above range results in insufficient infrared ray shielding properties such as heat rays, thereby deteriorating antistatic properties.

As the additive element Md, B, Al,
II of Ga, In, Tl, C, Si, Ge, Sn, Pb, etc.
Sc, Y, Ti, Z in addition to Group IB and IVB elements
r, Hf, V, Nb, Ta, Cr, Mo, W, Mn, T
c, Re, Fe, Rv, Os, Rh, Ir, La, C
e, Sb and the like. The zinc oxide-based particles used in the present invention need to exhibit zinc oxide crystallinity in X-ray diffraction.

The primary particle size of the zinc oxide-based particles is such that the crystallite diameter Dw determined by the Wilson method (Wilson method) is excellent in terms of excellent transmittance to light in a visible light wavelength region and excellent infrared shielding property. 1 to 50 nm (0.001 to 0.
It is preferable that these primary particles are dispersed without secondary aggregation. The dispersion particle diameter Dd of the zinc oxide-based particles is high in transparency and does not substantially affect the hue of the composition obtained when added to the composition, that is, the transparency is increased, and optical properties such as colorlessness are improved. Is preferably 1 μm or less from the viewpoint of giving The thickness is more preferably 0.5 μm or less, and further preferably 0.1 μm or less. Particularly, the thickness is preferably 0.05 μm or less. transparency,
It is preferable that the monodispersity is high from the viewpoints of adhesion and weather resistance. The monodispersity is determined by the ratio R (D
d / Dw), and R is preferably 10 or less, more preferably 3 or less, and particularly preferably 1.5 or less.

The dispersed particle size is a weight-based average particle size which can be measured by a dynamic light scattering method, a centrifugal sedimentation method or the like. If less than 0.1 μm, the former measurement method
When it is 0.1 μm or more, it is measured by the latter measurement method. The zinc oxide-based particles used in the present invention include those in which a polymer constitutes a matrix and the particles are dispersed in the matrix (polymer composite particles). It will have excellent properties. The content of the zinc oxide-based particles in the particles is not particularly limited, but is preferably in the range of 50 to 95% by weight based on the total amount of the composite particles in terms of zinc oxide.

[0013] Polymers used for the composite include acrylic resin polymers, alkyd resin polymers, amino resin polymers, vinyl resin polymers, epoxy resin polymers, polyamide resin polymers, polyimide resin polymers, and polyurethane resin polymers. In addition to polymers, polyester resin polymers, phenol resin polymers, organopolysiloxane polymers, acrylic silicone resin polymers, polyalkylene glycols, etc., polyolefin polymers such as polyethylene, polypropylene, etc. Plastic or thermosetting resin; synthetic rubber or natural rubber such as ethylene-propylene copolymer rubber, polybutadiene rubber, acrylonitrile-butadiene rubber; polysiloxane group-containing polymer, etc. It can be mentioned.

The shape of the composite particles is not particularly limited, but the surface of the composite particles is preferably rich in unevenness. This is because if the surface has irregularities, the affinity for a binder component or the like in a coating film or the like containing the composite particles increases. The average particle size of the composite particles is not particularly limited, but is usually in the range of 0.001 to 10 μm. Zinc oxide-based particles are compatible with a binder component having a film forming ability described below, dispersibility in an antistatic coating composition, dispersion stability, for the purpose of imparting weather resistance by reducing photocatalytic activity with zinc oxide. And those treated with a surface modifier.

As the preferred surface modifier, the above-mentioned polymers can be used.
Compounds containing an X group are mentioned. Wherein X is at least one selected from a hydrogen atom, a halogen atom and OR ¹ , and R ¹ is a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an acyl group. At least one selected from the group consisting of: M is a metal element, especially Si, Ti, Zr,
At least one selected from the group consisting of Al is preferred. Dispersibility (dispersibility in paints and solvents, paint stability, etc.)
From the viewpoint of imparting a polymer, a polymer having an organic polymer chain is exemplified. Preferred in terms of both weather resistance and dispersibility are polymers containing an MX group and having an organic polymer chain, such as a polysiloxane group-containing polymer and acrylic silicone.

The zinc oxide-based particles contain a monovalent or divalent metal element Ma in an atomic ratio of Ma to Md of 0.0000.
It is preferable that the content is included in the range of 1 ≦ Ma / Md <1. 0.
More preferably, 0001 ≦ Ma / Md ≦ 0.4. In addition, the atomic ratio to zinc is 0.0001 to
Preferably it is in the range of 2%. The existence effect of Ma
The point is that Md is uniformly contained (in a more monomeric state) in the ZnO crystal, the crystal surface is stabilized, and secondary aggregation and crystal growth are suppressed. Therefore, a fine crystal having high monodispersity is obtained. Therefore, it is possible to improve the antistatic property and the infrared shielding property while improving the transparency by increasing the amount of Md. Japanese Patent Application Laid-Open No. 8-253317 discloses that the presence of an alkali metal and an alkaline earth metal is not preferred.
47 lines), the above-mentioned effects are exhibited by positively including the above-mentioned range. If the amount of Ma is too small, no effect is exhibited, and if the amount of Ma is too large, the weather resistance of the coating film containing the particles may be reduced. The monovalent or divalent metal element Ma is an alkali metal element and / or an alkaline earth metal element, and includes lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like.

The zinc oxide particles used in the present invention are F
Except for halogen elements (that is, chlorine Cl, bromine Br,
Ions and / or atoms of iodine I), sulfate SO ₄
² and nitrate NO ₃ ^- the total content of (impurities H) is the number of atoms to zinc (provided that the number of atoms of S in the case of the sulfate in the case of nitrate anions calculated as the number of atoms of N) ratio It is important that it is 0.5% or less. It is more preferably at most 0.1%, further preferably at most 0.01%, particularly preferably at most 0.001%. This includes the case where no impurity H is contained. Only when the impurity H is not contained or does not exceed this range even if the impurity H is contained, it becomes a particle excellent in monodispersity, and it is possible to form a coating film excellent in adhesiveness and weather resistance as well as transparency. it can.

The zinc oxide particles used in the present invention have a lattice plane (10%) which is a diffraction peak specific to crystalline zinc oxide.
It is preferable that diffraction peaks are shown at (0), (002) and (101) and satisfy the following crystallite parameters. Using the Scherrer method, that is, Cauchy function approximation (Couchy function approximation), the crystallite size D perpendicular to each diffraction plane (hkl) is used.
When s (hkl) is obtained, Ds (002) / Ds (1
00) <2 is satisfied. More preferably, Ds (002)
/Ds(100)<1.2, more preferably 0.5 <
Ds (002) / Ds (100) <1.0. This is because when it is in this range, it is excellent in non-infrared transmittance and antistatic property.

When the size of the crystallite obtained by the Wilson method is Dw, 1 ≦ Dw ≦ 100 (n
m), more preferably 5 ≦ D
w ≦ 30 (nm). If Dw is too small, ultraviolet absorption, infrared transmission and antistatic properties decrease,
If it is too large, the transparency to visible light decreases. Dw preferably has a large crystallite from the viewpoint of non-infrared transmittance and antistatic properties, and preferably has a small Dw from the viewpoint of visible light transmittance. It is preferable that Dw is in the range of 5 to 30 nm in that both performances can be balanced. When Dw is in the above range, transparency, infrared blocking properties, ultraviolet absorbing properties and antistatic properties are excellent. Further, when the lattice distortion obtained by using the Wilson method is Aw, Aw is 0 ≦
It is preferable that Aw ≦ 1 (%) is satisfied. More preferably, it is in the range of 0 ≦ Aw ≦ 0.5 (%). When Aw is in the above range, it is considered that Md is contained more monomerically, but the infrared ray blocking property and the antistatic property are the highest.

The morphology of the zinc oxide particles used in the present invention, such as the shape and particle diameter, is not particularly limited. Specific examples of the shape include a flaky shape such as a spherical shape, an elliptical spherical shape, a cubic shape, a rectangular shape, a pyramid shape, a needle shape, a column shape, a rod shape, a tubular shape, a scale shape, a (hexagonal) plate shape, and the like. Preferably, the crystallite morphology is in the above range.

The zinc oxide-based particles used in the present invention are obtained by converting a carboxyl residue (carboxylic acid group) of a carboxylic acid to Zn
It is preferably contained in a weight ratio to O of 0.01 to 10%, more preferably 0.1 to 5%. When the carboxylic acid group is present on the particle surface, secondary aggregation is suppressed, and the transparency of the coating material is increased. On the other hand, if the number of carboxylic acid groups is too large, the formed film will have reduced infrared blocking properties and antistatic properties. When the amount of the carboxylic acid group is in the above range, both the monodispersity, the antistatic property and the infrared blocking performance are excellent. The zinc oxide-based particles have a carbonic acid group content of 10% or less, preferably 3% by weight, based on ZnO.
% Or less.

The zinc oxide-based particles used in the present invention can be handled as a dispersion dispersed in a solvent. This dispersion contains zinc oxide-based particles and a solvent as essential components. The zinc oxide-based particles are preferably contained at a ratio of 2 to 80% by weight in terms of metal oxide based on the total amount of the dispersion. Particularly, 20 to 60% by weight is preferable.

Examples of the solvent include water, alcohols, ketones, aliphatic and aromatic carboxylic esters, ethers, ether esters, aliphatic and aromatic hydrocarbons, halogenated hydrocarbons and the like. , Mineral oil, vegetable oil, wax oil, silicone oil and the like,
One or more of these solvents are used. Preferred solvents from the viewpoint of versatility, the boiling point at normal pressure is 40 ℃ ~
Selected from alcohols, aliphatic and aromatic hydrocarbons, halogenated hydrocarbons, aromatic and aliphatic carboxylic esters, ketones, (cyclic) ethers, ether esters, and water at 250 ° C. One or two
It is a mixed solvent of more than one kind. Further, methanol, ethanol, n-propanol, isopropyl alcohol, n
-Butanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether,
Ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether Acetate, 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, toluene, xylene, benzene, cyclohexane, n-hexane, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, isobutyl acetate, methyl ethyl ketone, methyl isobutyl ketone , Cyclohexanone, tetrahydrofuran, water Contains at least one or a mixture of two or more solvents selected from the group consisting of dispersion,
It is particularly preferable because it is easy to obtain a coating composition having higher dispersibility.

Next, a method for producing the zinc oxide particles used in the present invention will be described. As a method for producing zinc oxide-based particles used in the present invention, for example, a zinc compound is deposited by heating a solution (S) containing a Zn compound, a compound of Md and, if necessary, a compound of Ma. Method. Examples of the Zn compound used in the method for producing zinc oxide-based particles include zinc metal (zinc powder), zinc oxide (zinc white), zinc hydroxide, basic zinc carbonate, and mono- or di-substitutes which may have a substituent. -Carboxylates (e.g., zinc acetate, zinc octylate, zinc stearate, zinc oxalate, zinc lactate, zinc tartrate and zinc naphthenate), zinc (alkyl) alkoxides, β-
At least one selected from the group consisting of organic zinc compounds such as chelate compounds of zinc such as diketones, hydroxycarboxylic acids, keto esters, keto alcohols, amino alcohols, glycols, and quinolines is preferable. When these Zn compounds are used, the desalting step becomes unnecessary,
The number of steps is smaller than when using zinc chloride, zinc nitrate or zinc sulfate which requires a desalination step. These Zn
When a compound is used, particles having low or no content of the impurity H and excellent in monodispersity can be obtained. Among them, metallic zinc (zinc powder), zinc oxide (zinc white), zinc hydroxide, basic zinc carbonate and zinc acetate are preferred in that they are inexpensive and easy to handle. Zinc oxide, zinc hydroxide and zinc acetate
This is more preferable because it does not substantially contain impurities that hinder the reaction of forming zinc oxide crystals in the heating process, and it is easy to control the size and shape of the crystals and particles.
Particularly, zinc oxide produced by a gas phase method (French method, American method) is preferable. Zinc oxide of the gas phase method is not only available inexpensively, but in addition to being able to arbitrarily select the type of monocarboxylic acid, it is particularly easy to obtain fine particles having a controlled shape or particle diameter by using these materials, It is particularly preferable because even if it contains the impurity H, it is extremely small.

The metal (Md) compound used in the method for producing zinc oxide-based particles includes, for example, metals such as simple metals and alloys of metal Md; oxides; hydroxides;
Inorganic salts such as halides such as nitrates, sulfates, chlorides and fluorides; carboxylate salts such as acetate, propionate, butyrate and laurate; metal alkoxides; β-diketone, hydroxycarboxylic acid; All compounds containing a metal (Md), such as metal chelate compounds with ketoesters, ketoalcohols, aminoalcohols, glycols, quinolines, etc., can be mentioned. In the case where the metal Md is a metal element that can have a plurality of valences, such as In and Tl, a group consisting of a compound containing a low valent metal that can be finally changed to trivalent or tetravalent during the particle formation process. And at least one compound selected from the group consisting of a metal and an alloy. Among them, organic metals which do not contain impurities H such as metals, oxides, hydroxides, carbonates (including acidic and basic carbonates), acetates, alkoxide compounds and β-diketone compounds of the metal Md Complexes are preferred because they have little or no impurity H.

The metal (Ma) compound used in the method for producing zinc oxide-based particles includes, for example, metals of metal Ma, such as simple metals and alloys; oxides; hydroxides;
Inorganic salts such as halides such as nitrates, sulfates, chlorides and fluorides; carboxylate salts such as acetate, propionate, butyrate and laurate; metal alkoxides; β-diketone, hydroxycarboxylic acid; All compounds containing a metal (Ma), such as metal chelate compounds with keto esters, keto alcohols, amino alcohols, glycols, quinolines, and the like, can be mentioned. Among these, metal Ma
Organic metal complexes that do not contain impurities H, such as metals, oxides, hydroxides, carbonates (including acidic and basic carbonates), acetates, alkoxide compounds, and β-diketone compounds, are low in impurities H; Or it is preferable in that it does not exist.

The solution (S) preferably contains a monocarboxylic acid compound and an alcohol. A monocarboxylic acid compound is a compound having only one carboxyl group in the molecule. Specific examples of the compound include formic acid, acetic acid,
Saturated fatty acids (saturated monocarboxylic acids) such as propionic acid, isobutyric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, and stearic acid; acrylic acid,
Unsaturated fatty acids (unsaturated monocarboxylic acids) such as methacrylic acid, crotonic acid, oleic acid and linolenic acid; cyclic saturated monocarboxylic acids such as cyclohexanecarboxylic acid; aromatic monocarboxylic acids such as benzoic acid, phenylacetic acid and toluic acid Acids; anhydrides of the above-mentioned monocarboxylic acids such as acetic anhydride; halogen-containing monocarboxylic acids such as trifluoroacetic acid, monochloroacetic acid and o-chlorobenzoic acid; lactic acid. These monocarboxylic acid compounds may be used alone or 2
These may be used in combination.

Preferred monocarboxylic acid compounds are saturated fatty acids having a boiling point of less than 200 ° C. at 1 atmosphere. Specifically, formic acid, acetic acid, propionic acid, butyric acid, and isobutyric acid are preferred because particles having excellent monodispersity can be easily obtained. The saturated fatty acid is based on the total amount of the monocarboxylic acid compound.
Preferably used in the range of 60 to 100 mol%,
More preferably, it is used in the range of 80 to 100 mol%. If the ratio is less than the above range, the crystallinity of zinc oxide in the obtained particles may be reduced.

The monocarboxylic acid compound is an Md compound
The molar ratio of d is preferably 50 to 200 times. Also,
The molar ratio to Zn is preferably from 1.90 to 8 times. This is because particles having excellent monodispersibility and excellent in imparting antistatic properties and IR cut performance when a film is formed are easily obtained. Examples of the alcohol used in the method for producing zinc oxide-based particles include aliphatic monohydric alcohol (methanol, ethanol, isopropyl alcohol, n-butanol, t-butyl alcohol, stearyl alcohol, etc.) and aliphatic unsaturated monohydric alcohol (allyl). Alcohol, crotyl alcohol, propargyl alcohol, etc.),
Alicyclic monohydric alcohols (cyclopentanol, cyclohexanol, etc.), aromatic monohydric alcohols (benzyl alcohol, cinnamyl alcohol, methylphenylcarbinol, etc.), heterocyclic monohydric alcohols (furfuryl alcohol, etc.) Monohydric alcohols; alkylene glycols (ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5
-Pentanediol, 1,6-hexanediol, 1,
8-octanediol, 1,10-decanediol, pinacol, diethylene glycol, triethylene glycol, etc.), aliphatic glycols having an aromatic ring (hydrobenzoin, benzpinacol, phthalyl alcohol, etc.), alicyclic glycols (cyclo, etc.) Pentane-1,2-
Glycols such as diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, and polyoxyalkylene glycol (such as polyethylene glycol and polypropylene glycol); propylene glycol monoethyl ether, propylene glycol monoethyl ether, Propylene glycol monomethyl ether, tripropylene glycol monomethyl ether,
Derivatives of the above glycols such as 3-methyl-3-methoxybutanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, triethylene glycol monomethyl ether, ethylene glycol monoacetate, etc .;
Aromatic diols such as hydroquinone, resorcinol, 2,2-bis (4-hydroxyphenyl) propane and their monoethers and monoesters; trihydric alcohols such as glycerin and their monoethers, monoesters, diethers and diesters; is there. One or more of these alcohols are used.

The amount of the alcohol is preferably 1 to 30 times, more preferably 15 to 25 times the weight of the charged Zn compound in terms of zinc oxide. Also,
The molar ratio of alcohol to monocarboxylic acid compound is 1
It is preferable to set it to 10 to 10 times. In the solution (S), Ma
Is contained in a range of less than 1 in the atomic ratio (Ma / Md) of Ma of Ma compound to Md of Md compound contained in the solution (S), whereby the zinc oxide-based particles containing Ma as described above are contained. Can be easily obtained. By coexisting Ma, the amount of metal Md (addition ratio to zinc)
Regardless of the above, there is an effect that fine particles having excellent monodispersity can be obtained. Furthermore, the amount of the solvent necessary for obtaining the solution (S) containing the Md compound and the Zn compound can be reduced in the production method, and therefore, the desired zinc oxide-based particles can be obtained under economically excellent conditions. Is obtained.

From the viewpoint of the monodispersity of the obtained particles, the coexistence of Ma differs depending on the type of metal Md when the amount of metal Md relative to Zn is high. When the atomic ratio is 3% or more and Md is other than the above, it is effective when Md / Zn (atomic ratio) is 1% or more. As a preferred method for preparing the solution (S), the Md compound is uniformly dissolved in a solvent in advance, and the resulting solution (Sa) and a zinc compound or a liquid containing the zinc compound (either a solution or a suspension) are used. Method of mixing to obtain a solution (S) containing Md and zinc In advance, a part of the Md compound and the zinc compound are homogeneously dissolved in a solvent, and the obtained solution (Sb) is mixed with the remaining zinc compound or zinc. A method of mixing a liquid containing a compound (which may be a solution or a suspension) to obtain a solution (S) containing Md and zinc is used. For the above reasons, the Ma compound may be added as needed when preparing Sa, or in other cases, when preparing Sb.
In order to obtain the above-mentioned solutions (Sa, Sb), heating can be usually performed at 50 ° C. or higher, and it is preferable to perform heating at a refluxing temperature. Suitable solvents used for Sa and Sb include one or a mixture of two or more of the above-described monocarboxylic acids, anhydrides of the monocarboxylic acids, water, and the above-mentioned alcohols.

Further, the solution (S) is added, preferably 150
By heating to 200 ° C. to precipitate zinc oxide-based particles, a dispersion of particles having uniform crystallite size and no aggregation is easily obtained. The obtained dispersion is further heated in a closed container at a temperature of 200 ° C. or more and less than 400 ° C. for 1 minute to 24 hours in a non-oxidizing atmosphere where the atmosphere of the gas portion is 0.1% or less in oxygen concentration. By performing the treatment, particles having higher crystallinity and being excellent in imparting infrared blocking properties and antistatic properties when a film is formed can be obtained.
By setting the temperature of the heat treatment in the range of 220 to 300 ° C., particles having particularly excellent monodispersity can be obtained.
Further, it is not preferable to use an oxidizing atmosphere because the infrared ray blocking performance and the antistatic property may decrease.

The total content of impurities H in the solution (S)
The ratio of the number of atoms to zinc (calculated as the number of S atoms for sulfate groups and the number of N atoms for nitrates) is 0.5% or less, more preferably 0.1% or less, and even more preferably 0% or less. By setting the content to 0.01% or less, particularly 0.001% or less, it is possible to easily obtain the zinc oxide-based particles having little impurity H as described above. Of course, this also includes the case where the solution (S) does not contain the impurity H at all.

Since the solution (S) contains carbonate in a molar ratio of CO _{3 to} Zn of the Zn compound contained in the solution (S) in the range of 0.001 to 5%, the photocatalytic activity is suppressed. Particles can also be obtained. By the above manufacturing method, 0.5 <Ds (002) / Ds (100) <1.
0, 5 ≦ Dw ≦ 30 (nm), 0 ≦ Aw ≦ 0.5 (%)
And particles having an impurity H content of 0.5% or less, preferably 0.1% or less, with respect to zinc. (Binder component) The binder component used in the present invention has film-forming performance, binds zinc oxide-based particles, has excellent antistatic properties, transparency, optical properties such as colorlessness, durability, adhesion and It is a component that forms a coating film having excellent flexibility. This binder component contains a binder resin as an essential component, and may contain a crosslinking agent as needed.

Examples of the binder resin include thermoplastic or curable (thermo-curable, ultraviolet-curable, electron beam-curable, moisture-curable, combination thereof, etc.) synthetic resins and natural resins. As a synthetic resin, for example,
Alkyd resin, amino resin, vinyl resin, acrylic resin, epoxy resin, polyamide resin, polyurethane resin, thermosetting unsaturated polyester resin, phenol resin, chlorinated polyolefin resin, silicone resin, acrylic silicone resin, fluororesin, xylene resin, Examples thereof include petroleum resins, ketone resins, rosin-modified maleic resins, liquid polybutadienes, and coumarone resins, and one or more of these are used. Examples of the natural resin include shellac, rosin (pine resin), ester gum, cured rosin, bleached shellac, white shellac, and the like, and one or more of these are used.

Examples of the alkyd resin include ultra-short oil alkyd resin, short oil alkyd resin, medium oil alkyd resin,
Pure alkyd resin such as long oil alkyd resin and ultra-long oil alkyd resin; the above pure alkyd resin is modified with rosin, phenol, epoxy, styrene, urethane, silicon, amino resin, natural resin, synthetic resin, polymerizable monomer, etc. Modified alkyd resins; oil-free alkyd resins, oil-free alkyd resins including high molecular weight oil-free alkyd resins, and the like, and one or more of these are used.

Examples of the amino resin include melamine resins and melamine formaldehyde resins such as butylated melamine resin, methylated melamine resin and benzoguanamine resin; urea resins and urea resins such as butylated urea resin and butylated urea melamine resin; Examples thereof include amino alkyd co-condensation resins obtained by co-condensing a resin or a urea resin with an alkyd resin, and one or more of these are used.

Examples of the vinyl resin include vinyl chloride resins such as polyvinyl chloride, and copolymers of vinyl chloride with other polymerizable monomers (lower fatty acid vinyl esters such as vinyl acetate and vinyl propionate, and vinylidene chloride). A vinyl acetate resin such as polyvinyl acetate, a copolymer of vinyl acetate and other polymerizable monomers (ethylene, propylene, styrene, acrylate, vinyl propionate, vinylidene chloride, etc.); polyvinyl alcohol of various saponification degrees , Various modified (silicone-modified, carboxyl-modified, amino-modified, epoxy-modified, mercapto-modified, etc.) polyvinyl alcohol resins such as polyvinyl alcohol; polyvinyl butyral, vinyl butyral and other polymerizable monomers Butyral resin such as polymer It can be exemplified, and these are used singly or in combination.

As the acrylic resin, for example,
Copolymers containing (meth) acrylic acid and its ester as the main component of main chain; copolymers of (meth) acrylic acid ester, (meth) acrylic acid ester and vinyl monomer (styrene, vinyl ester, etc.) Thermoplastic acrylic resin such as a copolymer with a polymerizable monomer; (meth) acrylic acid,
Hydroxyalkyl esters of (meth) acrylic acid,
Thermosetting acrylic resin such as glycidyl ester of (meth) acrylic acid or heat-curable component added; modified with monomers other than (meth) acrylic monomer such as styrene, vinyltoluene and vinyl acetate A silyl-modified resin which is moisture-curable using a copolymer, an acrylic monomer having a hydrolyzable silyl group (alkoxysilyl group) as a copolymer component, and has a silicon concentration of 1% by weight or less in the resin; Epoxy curable acrylic resin using an acrylic compound having a basic nitrogen as a copolymer component and using an epoxy compound as a cross-linking agent component; acrylic resins having an oxidative polymerization function; and these may be used alone or in combination of two or more. Is done.

Examples of the epoxy resin include glycidyl ether types such as bisphenol A type, bisphenol F type, 2,6-xylenol type, brominated bisphenol A type, phenol novolak type and orthocresol novolac type; and synthesis of dimer acid and the like. Glycidyl ester type of fatty acid; aromatic amine type (glycidylamine type) and the like can be mentioned, and one or more of these are used.

When an epoxy resin is used as the binder resin, a curing agent may be used in combination. As the curing agent, for example, polymercaptan, aliphatic polyamine,
Aromatic polyamine, polyamide, tertiary amine, diethylaminopropylamine, imidazole, tertiary amine salt,
Examples thereof include alicyclic amines, acid anhydrides, boron fluoride / amine salts, dicyandiamide, and polyphenols, and one or more of these are used.

Examples of the polyurethane resin include one-component polyurethane resins such as oil-modified, moisture-curable, heat-curable, and lacquer types; and polyol-curable types (including various polyols such as acrylic polyol, polyester polyol, and polyether polyol). And a two-pack type polyurethane resin such as a catalyst-curable type, and one or more of these are used.

Examples of the phenol resin include a resol type phenol resin, a novolak type phenol resin, and a modification of these phenol resins with epoxy resin, alkyd resin, polyvinyl butyral resin, polyamide, acrylic resin, drying oil, rosin, petroleum resin and the like. One or more of these may be used.

Examples of the chlorinated polyolefin include chlorinated polyethylene resins, chlorinated polypropylene resins, and chlorinated rubbers, and one or more of these are used. Examples of the silicone resin (organopolysiloxane) include straight silicone resins such as dimethyl silicone and methyl phenyl silicone; alkyd-modified, epoxy-modified, polyester-modified, acrylic-modified, and urethane-modified silicone resins. One or more of these are used.

The acrylic silicone resin has a silicon concentration of 1% by weight or more contained in the resin, and examples thereof include an alkoxysilyl group-containing acrylic copolymer having a silicon concentration of 1% by weight or more. These are used alone or in combination of two or more. As fluororesin,
For example, polyvinyl fluoride, polyvinylidene fluoride, chlorotrifluoroethylene copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, ethylene / chlorotrifluoroethylene copolymer, tetrafluoroethylene / perfluoroalkylvinyl ether copolymer A thermoplastic fluororesin such as a coalesced resin; a solvent-soluble fluororesin such as an alternating copolymer (FEVE resin) of a fluoroolefin such as tetrafluoroethylene and a vinyl ether such as an alkyl vinyl ether, a hydroxyalkyl vinyl ether or a carboxyalkyl vinyl ether; Ride / hexafluoropropylene copolymer, tetrafluoroethylene / propylene copolymer, fluorine-containing silicone fluorine rubber, fluorine-containing vinyl ether fluorine Fluororubber such as rubber, fluorinated phosphazene-based fluororubber, and fluorinated thermoplastic elastomer; fluorinated epoxy resin, fluorinated polyimide, fluorinated silicone, and other fluorinated rubbers; Used above.

Some thermoplastic fluororesins do not dissolve in a solvent, but may be dispersed in water and / or an organic solvent or used in the form of a powder. The solvent-soluble fluororesin into which a crosslinking component such as a hydroxyl group is introduced can be cured with an isocyanate or melamine resin. Examples of the xylene resin include an unmodified xylene resin; a modified xylene resin such as phenol-modified and rosin-modified, and one or more of these are used.

Examples of the petroleum resin include a petroleum resin having 9 carbon atoms; a petroleum resin having 5 carbon atoms, and one or more of these are used. As the synthetic resin, natural or synthetic rubber such as ethylene-propylene copolymer rubber, polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene copolymer rubber, or the like may be used. Examples of components used in combination with the synthetic resin include cellulose nitrate, cellulose acetate butyrate, cellulose acetate, ethyl cellulose, hydroxypropylmethyl cellulose, and hydroxyethyl cellulose.

The form of the binder resin used in the antistatic coating composition is not particularly limited, and may be a solvent-soluble type, a water-soluble type, an emulsion type, a dispersion type (any solvent such as water / organic solvent) and the like. Can be mentioned. Examples of the water-soluble binder resin include a water-soluble alkyd resin, a water-soluble acryl-modified alkyd resin, a water-soluble oil-free alkyd resin (water-soluble polyester resin), a water-soluble acrylic resin, a water-soluble epoxy ester resin, and a water-soluble melamine. Resins and the like can be mentioned.

Examples of the emulsion type binder resin include alkyl (meth) acrylate copolymer dispersions; vinyl acetate resin emulsions, vinyl acetate copolymer resin emulsions, ethylene-vinyl acetate copolymer resin emulsions, acrylic acid esters (copolymers). ) Polymerized resin emulsion, styrene-acrylate (co)
Examples thereof include a polymerized resin emulsion, an epoxy resin emulsion, a urethane resin emulsion, an acryl-silicone emulsion, and a fluororesin emulsion.

When the antistatic coating composition of the present invention is used for the production of an antistatic film described below, the binder is preferably used in view of film forming conditions such as film forming temperature and flexibility and weather resistance of the obtained film. As the resin, a polyurethane resin, an acrylic resin, a fluororesin, or the like is preferable. Examples of the cross-linking agent used as a binder component include a cross-linking agent used in a drying oil system such as air (oxygen); a polyester resin such as a monofunctional or polyfunctional unsaturated monomer, a polyacryl resin, and an epoxy resin. Crosslinking agent; primary, secondary
Polyamines containing secondary amino groups, polyamides, amino resins having methylol groups, crosslinking agents used for binder resins having epoxy groups such as polybasic acids having carboxyl groups and high acid value polyesters; polyisocyanates having isocyanate groups, A crosslinking agent used for a hydroxyl-containing binder resin such as a polyisocyanate having a urethane group, a methylol group, a primary and / or secondary amino group, and an amino resin having an alkoxymethylene group;
A crosslinking agent used for a binder resin having a carboxyl group such as a metal chelating agent; a crosslinking agent used for a binder resin having a silicone group such as moisture, a polyfunctional epoxy compound, and a hydroxyl group-containing compound; Seeds or two or more are used.

Examples of the polyisocyanate in the above crosslinking agent include tolylene diisocyanate, 4,4
Diisocyanates such as 4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, naphthylene-1,5-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate; adducts of tolylene diisocyanate and trimethylolpropane; Adducts of methylolpropane, trimethylolpropane adducts of the above diisocyanates such as adducts of isophorone diisocyanate and trimethylolpropane; of the above diisocyanates such as isocyanurate-modified tolylene diisocyanate, isocyanurate-modified hexamethylene diisocyanate, and isocyanurate-modified isophorone diisocyanate Isocyanurate-modified product; biuret-modified hexamethylene Biuret modified products of the above diisocyanates such as isocyanate; the diisocyanates,
Trimethylolpropane adduct, isocyanurate modified product, biuret modified product, etc., prepolymerized and polymerized; modified diisocyanate, trimethylolpropane adduct, isocyanurate modified product, biuret modified product, prepolymerized product Alcohols, phenols, oximes,
Block-type polyisocyanates protected with an active methylene compound and the like can be mentioned.
Used over seeds. [Antistatic coating composition and coated article] The antistatic coating composition according to the present invention is a composition containing the above zinc oxide-based particles and a binder component as essential components.

The ratio of the zinc oxide-based particles to the total solid content of the binder component and the total amount of the zinc oxide-based particles is not particularly limited, but is preferably 50 to 95% by weight.
More preferably, it is 60 to 80% by weight. At this time,
The binder component also includes a curing agent such as a crosslinking agent. If the proportion of the zinc oxide-based particles is less than 50% by weight based on the total amount of the total solids, transparency and antistatic properties may be reduced. On the other hand, if the proportion of the zinc oxide-based particles exceeds 95% by weight, optical properties such as transparency and colorlessness, durability, weather resistance, adhesion and flexibility may be reduced. In particular, the weather resistance may rapidly decrease when the proportion of the zinc oxide-based particles exceeds 80% by weight. In order to solve this problem, it is preferable that the zinc oxide-based particles are previously subjected to surface modification such as treatment with a silane coupling agent or the above-mentioned MX group-containing polymer, but the zinc oxide-based particles are preferably May increase the production cost, and it may be necessary to improve the binder component.

When the antistatic coating composition of the present invention further contains a conductive auxiliary, the content of zinc oxide-based particles can be reduced without lowering the antistatic property, and the antistatic coating composition It is possible to improve the weather resistance, adhesion, flexibility, durability, and the like of the coating film obtained from the product. If the content of the zinc oxide-based particles is reduced when the conductive auxiliary is included, the antistatic property does not decrease because the conductive auxiliary acts as a bridge that connects the zinc oxide-based particles to each other. It is considered that the prevention efficiency is increased.

As the conductive auxiliary used in the present invention, it is preferable that at least a part of the surface is made of a conductive substance such as a metal, a conductive metal oxide, and a conductive organic substance. The conductive auxiliary may be a conductive auxiliary in which at least a part of a core material described later is coated with a conductive substance as long as at least the surface is made of a conductive substance. Examples of the metal used for the conductive auxiliary include iron,
Single metals such as nickel, copper, tin, aluminum, lead, zinc, silver; alloys such as stainless steel, copper / zinc alloys, copper / tin alloys, etc., and one or more of these are used .

Examples of the conductive metal oxide used for the conductive auxiliary include zinc oxide, Sb-doped tin oxide, Al-doped zinc oxide, Sn-doped indium oxide,
Cadmium stannate, rhenium oxide and the like can be mentioned, and one or more of these are used. Examples of the conductive organic substance used for the conductive auxiliary include polyacetylene (including one doped with a dopant such as iodine); polypyrrole (including one doped with a dopant such as periodate ion); polythiophene (periodine) including those doped with a dopant such as an acid ion); including those doped polyaniline (emeraldine base such dopants); polyparaphenylene (AsF ₅ and the like of the dopant including those doped); polyphenylene vinylene; polyalkyl Heterocycle-containing polymers such as polythiophene such as thiophene and polypyrrole; and conductive polymers such as derivatives obtained by introducing ester groups and alkyl groups into aromatic ring-containing polymers such as polyparaphenylene. , These are 1 Or they used two or more.

Examples of the core material constituting the conductive coating auxiliary agent include natural or synthetic mica such as muscovite, phlogopite, scale mica, sericite and fluorophlogopite, sepiolite (clay mineral), kaolinite , Talc, bentonite,
Natural or synthetic clay minerals such as montmorillonite, smectite, and pyrophyllite; organic fibers such as nylon and polyester; potassium titanate, aluminum borate, titanium oxide, silicon carbide, ferric oxide, zinc ferrite, magnesium ferrite, Glass, silica and the like can be mentioned, and one or more of these can be used.

The conductive material used to coat at least a part of the core material includes Sn, In, Zn, Sb,
Examples of the conductive metal oxide include Cd as a metal main component, and are colorless or less colored. The shape of the conductive auxiliary agent and the core material is not particularly limited, but may be spherical,
Oval sphere, cube, cuboid, pyramid, plate,
A rod shape or the like can be given. Of these, the anisotropic shape having a relatively large aspect ratio, such as a plate or a rod, and a large surface area increases the probability of contact with the zinc oxide-based particles, and connects the zinc oxide-based particles to each other to prevent static electricity. This is preferable because the efficiency is increased.

As the conductive auxiliary, those which are easily available and easily dispersed in the coating composition of the present invention include, for example, iron, nickel, copper, aluminum, lead, zinc, and the like.
Metal or alloy fiber such as stainless steel, or metal conductive auxiliary such as flaky silver or grape nickel; conductive metal oxide based such as acicular Sb-doped tin oxide particles or tetrapotted zinc oxide particles Conductive auxiliary: conductive coating such as Sb-doped tin oxide-coated potassium titanate whisker, Sb-doped tin oxide-coated aluminum borate whisker, Sb-doped tin oxide-coated titanium oxide whisker, Sb-doped tin oxide-coated mica, and polypyrrole-coated polyester fiber Auxiliaries and the like can be mentioned.

When the conductive auxiliary used in the present invention is plate-like particles, the thickness t is not particularly limited, but is preferably 0.005 to 1 μm, more preferably 0.008 to 0.5 μm. More preferably 0.008
~ 0.1 µm, most preferably 0.008-0.05 µm
m. When the thickness t is less than 0.005 μm, the mechanical strength of the plate-like particles decreases, and the durability may decrease. On the other hand, if the thickness t exceeds 1 μm, the transparency may be reduced. The length L of the plate-like particles is not particularly limited, but is preferably 0.02 to 50 μm, more preferably 0.05 to 20 μm, and most preferably 0.1 to 50 μm.
5 μm. If the length L is less than 0.02 μm, the antistatic property may be reduced. On the other hand, if the length L is 50
If it exceeds μm, durability, adhesion and flexibility may be reduced. The aspect ratio (L / t) of the plate-like particles is preferably 2 to 500, more preferably 4 to 500.
-100, most preferably 6-50.

The plate shape in the present invention may be any shape of a plate (projected from above), for example, circular, oval, spindle-shaped,
The shape includes a triangle, a square, a rhombus, a hexagon, an octagon, an irregular shape, and the like, and may be a flake, a flake, a scale, a hexagonal plate, or the like. When the conductive auxiliary agent used in the present invention is rod-shaped particles, the thickness d (the maximum thickness passing through the center of the rod-shaped particles) is not particularly limited, but is preferably 0.0
05 to 1 μm, more preferably 0.008 to 0.5 μm
m, more preferably 0.008 to 0.1 μm, and most preferably 0.008 to 0.05 μm. When the thickness d is less than 0.005 μm, the mechanical strength of the rod-shaped particles is reduced, and the durability may be reduced. On the other hand, the thickness d
Exceeds 1 μm, the transparency may be reduced.
The length L of the rod-shaped particles is not particularly limited, but is preferably 0.02 to 50 μm, and more preferably 0.05 to 50 μm.
It is 20 μm, most preferably 0.1-5 μm. If the length L is less than 0.02 μm, the antistatic property may be reduced. On the other hand, when the length L exceeds 50 μm, durability, adhesion, and flexibility may be reduced. The aspect ratio (L / t) of the rod-shaped particles is preferably 2 to 500, more preferably 4 to 100, and most preferably 6 to 50.

The rod shape in the present invention is a shape including a needle shape, a thread shape, a fiber shape, a whisker shape, a strip shape, a star shape, a tubular shape, a linear shape, a dendritic shape obtained by collecting a plurality of these shapes, a grape shape and the like.
The conductive auxiliary agent may be particles of other shapes other than plate-like particles and rod-like particles. Other shaped particles include, for example, polyhedral particles such as spherical, spheroidal, spindle, tetrahedral, hexahedral, octahedral, and dodecahedral. Triaxial average diameter [(L +
b + t) / 3] is preferably 0.005 to 10 μm,
More preferably, it is 0.05 to 2 μm.

When the antistatic coating composition of the present invention contains a conductive auxiliary together with the zinc oxide-based particles and the binder component, the ratio of the conductive auxiliary to the zinc oxide-based particles (100 × conductive auxiliary / zinc oxide) The (system particles) are not particularly limited, but are preferably 0.1 to 20% by weight, more preferably 0.3 to 5% by weight, and most preferably 0.5 to 3% by weight. If the ratio of the conductive auxiliary to the zinc oxide-based particles is less than 0.1% by weight, the antistatic property may be reduced. On the other hand, when the proportion of the conductive auxiliary exceeds 20% by weight, durability, adhesion and flexibility may be reduced.

When the antistatic coating composition of the present invention contains a conductive auxiliary, the ratio of the conductive auxiliary to the solid content of the binder component and the total amount of zinc oxide-based particles is not particularly limited, but is preferably used. Is 0.05 to 9.5% by weight, more preferably 0.25 to 5% by weight, and most preferably 0.25 to 1.5% by weight. If the ratio of the conductive auxiliary to the total amount is less than 0.05% by weight, the antistatic property may be reduced. On the other hand, when the ratio of the conductive auxiliary to the total amount exceeds 9.5% by weight, transparency, durability, adhesion, and flexibility may be reduced.

The antistatic coating composition of the present invention may contain a solvent, and is appropriately selected depending on the kind of the binder component and the like. Examples of the solvent include alcohols,
Aliphatic and aromatic carboxylic esters, ketones,
Organic solvents such as ethers, ether esters, aliphatic and aromatic hydrocarbons, and halogenated hydrocarbons;
Water; mineral oil; vegetable oil, wax oil, silicone oil, etc., and one or more of these are used.

The antistatic coating composition of the present invention may further comprise a curing agent such as a crosslinking agent, a curing catalyst such as a curing assistant, a plasticizer, and the like, in addition to zinc oxide-based particles, a binder component, and a conductive auxiliary, according to required performance. Antifoaming agents / Leveling agents; Thixotropic agents; Matting agents; Surfactants; Flame retardants; Pigment wetting agents / dispersants; Lubricants; Ultraviolet absorbers; Light stabilizers; Preservatives; fungicides; anti-algal agents;
It may contain additives such as a rust inhibitor, a dye, and a pigment.

Examples of the curing agent include a curing agent used in a drying oil system such as air (oxygen); a curing agent used in polyester resins such as monofunctional or polyfunctional unsaturated monomers, polyacrylic resins, and epoxy resins. Agent; first grade, 2
Polyamine containing a secondary amino group, polyamide, an amino resin having a methylol group, a curing agent used for a resin component having an epoxy group such as a polybasic acid having a carboxyl group or a high acid value polyester; a polyisocyanate having an isocyanate group; A curing agent used for a resin component having a hydroxyl group such as a polyisocyanate having a urethane group, a methylol group, a primary and / or secondary amino group, and an amino resin having an alkoxymethylene group; having a carboxyl group such as a metal chelating agent Curing agent used for resin component; curing agent used for resin component having a silicone group such as water, a polyfunctional epoxy compound, and a hydroxyl group-containing compound; and the like, and one or more of these can be used.

The polyisocyanate of the curing agent includes, for example, tolylene diisocyanate, 4,4'-
Diisocyanates such as diphenylmethane diisocyanate, hexamethylene diisocyanate, naphthylene-1,5-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate; adducts of tolylene diisocyanate and trimethylolpropane, and hexamethylene diisocyanate and trimethylolpropane Adducts, trimethylolpropane adducts of the above diisocyanates such as adducts of isophorone diisocyanate and trimethylolpropane; isocyanurate-modified diisocyanates such as isocyanurate-modified tolylene diisocyanate, isocyanurate-modified hexamethylene diisocyanate, and isocyanurate-modified isophorone diisocyanate Substance: biuret-modified hexamethylenediiso Biuret modified product of the above diisocyanate such as cyanate; diisocyanate, trimethylolpropane adduct, isocyanurate modified product, biuret modified product, etc., prepolymerized and polymerized; diisocyanate, trimethylolpropane adduct, isocyanate Nurate-modified, biuret-modified, prepolymerized, isocyanate groups in the polymerized modified product, alcohols, phenols, oximes, block-type polyisocyanates protected with an active methylene compound, etc. One or more of these are used.

Examples of the curing catalyst include curing catalysts used for drying oils such as metal dryers such as zinc naphthenate, calcium naphthenate and zirconium octylate, and organic dryers; redox initiators, sensitizers (ultraviolet rays, Curing catalysts used for polyester resins, polyacrylic resins, and epoxy resins such as electron beams, etc .; amines, metal compounds (need heat), organic acids (need heat),
A curing agent used for a binder resin having a hydroxyl group such as an inorganic acid (sometimes requiring heat); a curing catalyst used for a binder resin having a silicone group such as a metal compound or an amine (needs moisture or heat); Can be mentioned,
One or more of these are used.

Examples of the plasticizer include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, butylbenzyl phthalate, diisodecyl phthalate, tricresyl phosphate, diphenyl crezyl phosphate, and triphenyl sebacine phosphate Dibutyl acid and the like, and these can be used alone or in combination of two or more.

Examples of the antifoaming agent / leveling agent include acrylic antifoaming agent, acrylic leveling agent, vinyl antifoaming agent, vinyl leveling agent, silicone antifoaming agent, silicone leveling agent, and mineral type antifoaming agent. Foaming agents, thixotropic agents (thickening agents, anti-settling agents, anti-sagging agents) and the like can be mentioned, and one or more of these are used.

The form of the thixotropic agent is not particularly limited, and examples thereof include a solvent-based thixotropic agent and an aqueous-based thixotropic agent. Examples of the solvent-based thixotropic agent include, for example, organic bentonite-based, ultra-fine silica-based, surface-treated calcium carbonate-based inorganic fine particle-based solvent-based thixotropic agents; amide wax-based, hydrogenated castor oil wax-based, benzylidene sorbitol-based , Metal soaps (zinc stearate, aluminum stearate, etc.), polyethylene oxide type, polymerized vegetable oil type, sulfate ester type anionic surfactant type, polyether / ester type surfactant type, polycarboxylic acid amine salt type organic etc. And a thixotropic agent for a solvent system, and one or more of these are used.

Examples of the water-based thixotropic agent include, for example, inorganic fine particle-based water-based thixotropic agents such as ultrafine silica or magnesium aluminum silicate; xanthan gum, guar gum, sodium polyacrylate,
Acrylic acid / acrylic acid ester copolymers, polyvinyl alcohols, polyethylene oxides, urethane-modified polyethers, and other organic water thixotropic agents can be used, and one or more of these are used. .

Examples of the matting agent include hydrated silicon dioxide such as white carbon, and one or more of these are used. Examples of the surfactant include nonionic (polyethylene glycol type, polyhydric alcohol type, etc.), anionic type (sulfate ester type, sulfonic acid type, carboxylic acid type, phosphate ester type, etc.), and cationic type (amine salt type). , Quaternary ammonium salts, etc.) and amphoteric (amine acid type, betaine type, etc.) surfactants, etc., and one or more of these are used.

Examples of the flame retardant include antimony trioxide, aluminum hydroxide, chlorinated paraffin and the like, and one or more of these are used. Examples of the pigment wetting agent / dispersing agent include a solvent-based pigment wetting agent / dispersing agent and an aqueous-based pigment wetting agent / dispersing agent, and one or more of these are used.

Examples of the pigment wetting agent / dispersing agent for a solvent system include high molecular weight unsaturated polycarboxylic acid, polyether / polyester carboxylate, high molecular weight polyester acid polyamine salt, polycarboxylic acid salt, and high molecular weight polyester acid. Various high molecular weight compounds such as amide amine salt, long chain polyaminoamide phosphoric acid, aliphatic polyamide, salt of long chain polyaminoamide and high molecular polyester acid, high molecular polyether compound, etc .; phosphate ester, phosphate ester salt, fat Anionic compounds such as aliphatic alcohol sulfates, sulfonated oils and alkyl sulfonates;
Examples thereof include salts of aliphatic amines and cationic compounds such as quaternary ammonium salts, and one or more of these are used.

Examples of the water-based pigment wetting agent / dispersing agent include salts of high molecular weight polycarboxylic acid, salts of styrene / maleic acid copolymer, formalin condensate of naphthalene / sulfonic acid, and long-chain alkyl organic sulfonic acid. Salts, salts of ligninsulfonic acid, polyphosphoric acid, salts of polysilicic acid, long-chain alkylamine salts, polyethylene glycol derivatives, sorbitan fatty acid esters, and the like.
Seeds or two or more are used.

Examples of the lubricant include an aliphatic hydrocarbon lubricant, a higher aliphatic alcohol / higher fatty acid lubricant,
Fatty acid amide lubricants, metal soap lubricants, fatty acid ester lubricants, composite lubricants, etc.
Seeds or two or more are used. As an ultraviolet absorber,
For example, benzophenone, benzotriazole,
Examples thereof include anilide oxalate, cyanoacrylate, and triazine ultraviolet absorbers, and one or more of these are used.

Examples of the light stabilizer include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate. , Screws (2, 2, 6,
Hindered amine-based light stabilizers such as 6-tetramethyl-1-octyloxy-4-piperidyl) decandioate and the like can be mentioned, and one or more of these can be used.

Examples of the antioxidant include phenol-based (monophenol-based, bisphenol-based, polymer-based, etc.), sulfur compound-based (such as dilaurylthiodipropionate and dimyristylthiodipropionate), and phosphorus compounds. Systems (triphenyl phosphine, diphenyl isodecyl phosphate, etc.) and the like, and one or more of these are used.

Other (heat) stabilizers include, for example,
Examples thereof include a tin stabilizer, a lead stabilizer, and a stearic acid stabilizer, and one or more of these may be used. Examples of the tin-based stabilizer include di-n-octyltin bis (isooctylthioglycolate) salt, di-n-octyltin maleate polymer,
Di-n-octyltin-based stabilizers such as di-n-octyltin dilaurate and di-n-octyltin maleate; di-n-butyltin bismaleate; di-n-butyltin maleate Malate compounds such as ester salts, di-n-butyltin bisoctylthioglycol ester salts, mercapto compounds such as di-n-butyltin β-mercaptopropionate polymers, laurate compounds such as di-n-butyltin dilaurate, etc. Di-n-butyltin-based stabilizers; dimethyltin-based stabilizers such as dimethyltin bis (isooctylmercaptoacetate) salt and the like, and one or more of these can be used.

Examples of the lead stabilizer include tribasic lead sulfate, dibasic lead stearate, dibasic lead phosphite, lead stearate and the like.
Seeds or two or more are used. Examples of the stearic acid stabilizer include barium stearate, calcium stearate, magnesium stearate, aluminum stearate, lithium stearate, lithium 12-hydroxystearate, and the like. One or more of these can be used. used.

As other (thermal) stabilizers, stabilizers other than the above-mentioned tin-based stabilizers, lead-based stabilizers, and stearic acid-based stabilizers may be used.
Lithium behenate, lithium myristate, triphenyl phosphite, diphenyl isodecyl phosphite, trisnonyl phenyl phosphite, barium-zinc liquid composite stabilizer, calcium-zinc liquid composite stabilizer,
Cadmium-barium-zinc liquid composite stabilizers may be used, and one or more of these may be used.

The preservatives, fungicides and algicides include
For example, 1,2-benzisothiazolin-3-one,
Examples thereof include 5-chloro-2-methyl-4-isothiazolin-3-one, p-chloro-m-xylenol, and 2-hydroxymethylaminoethanol, and one or more of these are used. Examples of the anticorrosion / rust inhibitor include ethylamines and propylamines, and one or more of these are used.

When the antistatic coating composition of the present invention further contains a light stabilizer, the weather resistance is improved. As for the method of curing the antistatic coating composition, a heat curing method is economically preferable. The method for producing the antistatic coating composition of the present invention is not particularly limited. For example, a binder containing a zinc oxide-based particle, a binder component, and
A method of further mixing a conductive auxiliary agent can be used.

The coated article according to the present invention is obtained by forming a coating film obtained from the above antistatic coating composition on the surface of a substrate. Since this coated article has a coating film obtained from the antistatic coating composition on its surface, it has excellent antistatic properties, and the coating film has high weather resistance, adhesion and flexibility. Examples of the substrate include, for example, inorganic materials such as glass and ceramics, and substrates such as organic materials such as resins. Has high weather resistance and excellent flexibility. The shape of the inorganic or organic substance is not particularly limited, and examples thereof include a film, a sheet, a plate, and a fiber. Among these, they are useful for films, fibers, and the like described below.

The material of the resin used as the base material is not particularly limited. For example, LDPE, HDPE,
Polypropylene such as amorphous polyethylene, OPP (stretched polypropylene), CPP (crystallized polypropylene), and polyolefins such as polyisobutylene; EV
A (ethylene / vinyl acetate copolymer) type; polystyrene type; soft or hard polyvinyl chloride; EVOH (ethylene / vinyl alcohol copolymer) type; PVA type (vinylon type); PVDC type (polyvinylidene chloride); polyethylene Polyesters such as terephthalate, polyethylene naphthalate and polybutylene naphthalate; polycarbonates; polyurethanes; polyamides; polyimides; polyacrylonitriles; polysulfones; polyethersulfones; Imide type; aramid type; (meth) acrylic type; polyether ether ketone type; tetrafluoroethylene / ethylene copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, polytetrafluur Roechiren, polytrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride,
Examples thereof include tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene / hexafluoropropylene / perfluoroalkyl vinyl ether copolymer, and fluorine-based resins such as polychlorotrifluoroethylene.

When used in applications requiring extremely high visible light transmittance and transparency, such as optical lenses, PMM
A, MMA-styrene random copolymer, polycarbonate, transparent polypropylene, MMA and a copolymer such as α-methylstyrene or cyclohexyl methacrylate,
MMA modified type of ABS resin, polystyrene, polyarylate, polysulfone, polyethersulfone,
Various resins such as transparent epoxy resin, poly-4-methylpentene-1, fluorinated polyimide, amorphous fluorine resin, transparent phenoxy resin, amorphous nylon resin, and fluorene-based resin can be used as the base material.

Further, due to the problem of disposal, it is increasingly important to use a biodegradable resin as a base material in order to meet the demand for biodegradability. In such a case, for example, poly-3-hydroxybutyrate,
Chitin / chitosan, polyamino acid, cellulose,
It is preferable to use biodegradable plastics such as polycaprolactone, alginic acid, polyvinyl alcohol, aliphatic polyester, saccharide, polyurethane, and polyether as base materials.

As the base material, a primer layer or the like is previously provided for the purpose of improving the adhesion between the base material and the base material provided with a UV absorbing film in advance or the coating film obtained from the antistatic coating composition and the base material. What is arranged may be sufficient. Among these resins used as the base material, among plastic films and sheets, fluorine-based resins, polyester-based resins, (meth) acrylic-based resins, and polycarbonate-based resins are preferable because of their high weather resistance.

The coated article of the present invention can be produced, for example, by applying an antistatic coating composition to the surface of the substrate and curing the composition. The method for applying the antistatic coating composition to the substrate surface is not particularly limited, and includes a dipping method, a roll coater method, a flow coat method, a screen printing method, a bar coater method, a spin coater method, a brush coating method, and a spray method. And the like.

After applying the antistatic coating composition, heat curing (including room temperature curing) to improve physical properties such as chemical resistance such as water resistance, solvent resistance, acid resistance and alkali resistance, and scratch resistance. It is preferable to cure by a method such as moisture curing, ultraviolet curing, and electron beam curing. The dry film thickness of the coating film obtained from the antistatic coating composition is not particularly limited, and is preferably 0.5 to 50 μm, more preferably 0.2 to 5 μm.
μm, most preferably 0.5 to 2 μm.

The surface resistance ρ of the coating film obtained from the antistatic coating composition is not particularly limited, but is preferably 1
0 ¹⁰ Ω / □ or less, more preferably 10 ⁹ Ω / □ or less,
Most preferably, it is 10 ⁶ to 10 ⁹ Ω / □. The haze of the coating film obtained from the antistatic coating composition is not particularly limited, but is preferably 5% or less, more preferably 2% or less.
%, Most preferably 1% or less. Haze is a value obtained by measuring with a turbidimeter.

[0093]

EXAMPLES Examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. In the following examples, "part" and "part by weight" are indicated. Evaluation and the like in this example were performed by the following method. 1. Evaluation of zinc oxide-based particles <Particle composition> The content of added metal, the content of other metal, and the content of impurity H in the powder sample were determined by X-ray fluorescence analysis, atomic absorption analysis,
It was determined by plasma emission analysis, gravimetric analysis, elemental analysis and the like. <Crystallinity> Evaluated by powder X-ray diffraction. The evaluation criteria for crystallinity are as follows.

○: Diffraction peak of ZnO crystal. X: There is no diffraction peak of ZnO crystal. <Crystallite diameter Ds (hkl), Dw, Lattice strain Aw> Powder X-ray diffraction measurement of a powder sample was performed. Ds (hkl): Each diffraction surface (hkl) obtained by Scherrer method (by approximation of Cauchy function)
Dw, Aw: crystallite size and lattice strain determined by Wilson method <Carboxylic acid group content> 1 g of powder sample is mixed with 0.01 N aqueous sodium hydroxide solution After stirring for 3 days, the supernatant obtained by the centrifugation operation was measured by ion chromatography analysis. <Particle Concentration of Dispersion> A part of the dispersion was vacuum-dried at 100 ° C. until volatile components such as a solvent could be completely removed, and a dry powder was obtained.
The residue after heating for a period of time was regarded as a metal oxide, and the weight fraction of the metal oxide relative to the dispersion was determined. This value was defined as the particle concentration (concentration in terms of metal oxide) in the dispersion. 2. Evaluation of coating film obtained from antistatic coating composition <Surface resistance> A gold comb-shaped electrode was deposited on the coating film surface (thickness: 3).
0 nm ± 5 nm), and left standing for 12 hours under the conditions of temperature and humidity shown in the table under light-shielding conditions. Then, the surface resistance was measured under the same conditions using an electrometer 617 manufactured by Kesley Co. (applied voltage: 0.1 V). )did. The measurement of the surface resistance was performed under the measurement conditions (1) and (2) shown in the table.

The surface resistance of the coating film after the accelerated weathering test was J
An accelerated weather resistance test was performed for 200 hours using a sunshine carbon arc lamp type light resistance and weather resistance tester described in IS B 7753-93, and the surface resistance was measured thereafter. The surface resistance after the water resistance test was immersed in boiling water of pure water for 10 hours, and then the surface resistance was measured. <Visible Light Transparency and Transparency> The total light transmittance T and the haze H were measured by a turbidimeter (NDH-1001 DP manufactured by Nippon Denshoku Industries Co., Ltd.). <Transparency Durability> The transparency after the accelerated weathering test is based on JIS.
The accelerated weather resistance test was performed for 200 hours using a sunshine carbon arc lamp type light resistance and weather resistance tester described in B 7753-93, and thereafter, the measurement was performed. For the measurement of transparency, a turbidity meter (NDH-10, manufactured by Nippon Denshoku Industries Co., Ltd.)
01 DP), a difference ΔH (%) = H−H ₀ between the initial haze value H ₀ and the haze value H after the test was determined, and the evaluation was made according to the following evaluation criteria. The evaluation criteria for transparency are as follows.

AA: ΔH <1% A: 1% ≦ ΔH <5% B: 5% ≦ ΔH <10% C: 10% ≦ ΔH Evaluation of antistatic paint composition <Dispersibility> The dispersibility of zinc oxide-based particles in an antistatic paint composition and the like is measured by a particle analyzer using a dynamic light scattering method (NICOMP Model 370, Nozaki Sangyo Co., Ltd.).
Was used to determine a weight-based average particle diameter, which was defined as an average dispersed particle diameter Dd. The evaluation criteria for dispersibility are as follows.
However, in a system to which a crosslinking agent and a curing catalyst were added, the dispersibility was measured before adding these.

A: Dd ≦ 30 nm B: 30 nm <Dd ≦ 50 nm C: 50 nm <Dd ≦ 100 nm D: 100 nm <Dd <Dispersion stability> With the antistatic coating composition immersed in a bath at a bath temperature of 50 ° C., The appearance of the dispersion after standing for 30 days was evaluated. The evaluation criteria for dispersion stability are as follows.

A: A state without layer separation and no sediment. B: There is a sediment, but it is redispersed by shaking. C: It sediments, does not redisperse even if shaken, and gels. <Pot life> In producing the antistatic coating composition, after adding a crosslinking agent, the mixture was stirred at 20 ° C. to form a film every hour. The transparency and curability of each of the obtained coating films were examined, and the upper limit T of the stirring time at which these physical properties did not deteriorate was measured. The evaluation criteria for pot life are as follows.

A: T> 6 hours B: 6 hours ≧ T> 3 hours C: T ≦ 3 hours <Curability> A cotton impregnated with methyl ethyl ketone was rubbed 100 times on the coating film, and a rubbing test was performed. The surface condition of the coating film after the test was observed. The evaluation criteria for curability are as follows.

○: No change. Δ: The surface is scratched. X: The coating film dissolves. <Adhesion> The coating film was subjected to a cross-cut peeling test using a cellophane tape to examine the adhesion. The evaluation criteria for adhesion are as follows.

A: 100/100 (no peeling at all) B: 80/100 or more and less than 100/100 C: 50/100 or more and less than 80/100 D: less than 50/100 <Flexibility> Then, the presence or absence of cracks or peeling occurring on the surface was observed with a microscope. The evaluation criteria for flexibility are as follows.

○: No change. Δ: No peeling, but cracks are generated. ×: Peeled. -Example 1 (1)-Dispersion D1 (particle concentration 50% by weight) was prepared by dispersing zinc oxide particles P1 having the physical properties shown in Table 1 in toluene without surface modification. To this dispersion D1, a binder B1 shown in Table 3 and the like were mixed in the following formulation, and the mixture was mixed at 25 ° C.
For 3 hours to obtain an antistatic coating composition C1. Table 5 shows the physical properties of the antistatic coating composition C1.

Dispersion D1 (particle concentration 50% by weight) 40 parts by weight Binder B1 (nonvolatile content concentration 35%) 14.3 parts by weight Leveling agent (polysiloxane) 0.05 part by weight Toluene 35 parts by weight Obtained above The antistatic coating composition C1 was applied to the surface of a PET film by a bar gorgeer, dried with hot air at 80 ° C. for 2 minutes, and then cured at 50 ° C. for 3 days to obtain a dry film thickness of 0.1%.
A coating film (1) of 5 μm was obtained. Various physical properties of the coating film (1) were evaluated, and the results are shown in Table 7.

-Examples 1 (2) to 1 (7)-Zinc oxide-based particles P2 to P5 having physical properties shown in Table 1 were subjected to surface modification shown in Table 2, and dispersed in a solvent shown in Table 2. Dispersions D2 to D5 were prepared. These dispersions D2 to D5
In addition, binders B2 to B7 shown in Table 3 and the like were mixed and added in the composition shown in Table 4, respectively, and antistatic paint compositions C2 to C7 were obtained in the same manner as in Example 1 (1). Table 5 shows the physical properties of the antistatic coating compositions C2 to C7.

[0105]

[Table 1]

[0106]

[Table 2]

[0107]

[Table 3]

[0108]

[Table 4]

[0109]

[Table 5]

Each of the antistatic coating compositions C2 to C7 was formed into a film under the conditions shown in Table 6, and the coating films (2) to (7) were formed.
I got Table 6 also shows film forming conditions for obtaining the coating film (1) from the antistatic coating composition C1. The physical properties of the obtained coating films (2) to (7) were evaluated, and the results are shown in Table 7.

[0111]

[Table 6]

[0112]

[Table 7]

-Example 2 (1)-Dispersion D1 (particle concentration 50% by weight) and binder B1 used in Example 1 (1) were added to whisker-like particle powder (a titania whisker surface) as a conductive auxiliary. With antimony-containing tin oxide coating on it, length: 2μ
m, diameter: 0.1 μm, aspect ratio: 20) to prepare an antistatic coating composition C8 having the composition shown in Table 8. The antistatic coating composition C8 was formed under the film-forming conditions shown in Table 9,
Coating (8) was obtained. The physical properties of the obtained coating film (8) were evaluated, and the results are shown in Table 10.

-Example 2 (2)-Dispersion D2 and binder B used in Example 1 (2)
2 and the like, whisker-like particle powder (aluminum borate whisker having an antimony-containing tin oxide film formed on its surface, length: 18 μm, diameter:
0.8 μm, aspect ratio: 20) was added to prepare Antistatic Coating Composition C9 having the composition shown in Table 8. The coating film (9) was obtained from the antistatic coating composition C9 under the film forming conditions shown in Table 9. The physical properties of the obtained coating film (9) were evaluated, and the results are shown in Table 10.

-Example 2 (3)-Dispersion D2 and binder B used in Example 1 (2)
3 and the like, whisker-like particle powder (antimony-doped tin oxide whisker, length: 2.0
μm, diameter: 0.01 μm, aspect ratio: 200) to prepare an antistatic coating composition C10 having the composition shown in Table 8. The coating film (10) was obtained from the antistatic coating composition C10 under the film forming conditions shown in Table 9. The physical properties of the obtained coating film (10) were evaluated, and the results are shown in Table 10.

Comparative Example 1 In the same manner as in Example 1 (1) except that the particles P6 having the physical properties shown in Table 1 were used instead of the zinc oxide-based particles P1 used in Example 1 (1). The antistatic paint composition C11 was prepared. Table 5 shows the physical properties of the antistatic coating composition C11. The antistatic coating composition C11 was formed on a PET film in the same manner as in Example 1 (1) to obtain a coating film (11). The physical properties of the obtained coating film (11) were evaluated, and the results are shown in Table 10.

[0117]

[Table 8]

[0118]

[Table 9]

[0119]

[Table 10]

[0120]

The antistatic coating composition according to the present invention comprises:
Low dependence on humidity, temperature, etc., has long-term stable antistatic properties, optical properties such as transparency and colorlessness, durability,
A coating film excellent in adhesion and flexibility can be formed. The coated article according to the present invention has a long-term stable antistatic property,
The coating film formed on the surface has high optical properties such as transparency and colorlessness, durability, adhesion and flexibility.

Claims (6)

[Claims] 1. A binder component having a film forming performance,
Trivalent and / or tetravalent metal element (Md) and Zn
And a zinc oxide-based particle which exhibits zinc oxide crystallinity in X-ray diffraction using the metal component as a metal component, wherein the zinc oxide-based particle is an ion and / or atom of a halogen element other than F, Sulfate SO ₄ ^2- and nitrate NO ₃
^- the total content of impurity H consisting of atoms with respect to zinc (however, calculations as the number of N atoms in the case of atoms, nitrate of S in the case of sulfate radical) is 0.5% or less in ratio And an antistatic coating composition. 2. The zinc oxide-based particles exhibit a diffraction peak unique to crystalline zinc oxide, and are subjected to the Scherrer method (approximate Cauchy function) for two lattice planes (100) and (002). The crystallite size Ds (hk
1) When Ds (002) / Ds (100) <2 is satisfied, and when the crystallite size obtained by the Wilson method is Dw, 1 ≦ Dw ≦ 100 (nm) The antistatic coating composition according to claim 1, which is a zinc oxide-based particle that satisfies. 3. The antistatic coating composition according to claim 1, wherein Md is a metal element excluding Group IIIB and Group IVB. 4. The charge according to claim 1, wherein the ratio of the zinc oxide-based particles to the total amount of the solid content of the binder component and the zinc oxide-based particles is 50 to 95% by weight. Preventive paint composition. 5. The antistatic coating composition according to claim 1, further comprising a conductive auxiliary. 6. A coated article obtained by forming a coating film obtained from the antistatic coating composition according to claim 1 on the surface of a substrate.