JP3667432B2 - Water-repellent / antistatic coating composition and method for producing coated substrate - Google Patents

Description

【００６８】
実施例２
実施例１同様に、アルミニウムイソプロポキシド加水分解液(A-2) とエタノール(E-1) との混合液にステアリン酸(B-1) を加え、ステアリン酸アルミニウムジソープを生成させてステアリン酸アルミニウムジソープ及びアルミニウムイソプロポキシド加水分解液混合溶液を調製した。別途、カルシウムエトキシド加水分解液(A-3) 、オレイン酸（B-2 ）及びエタノール(E-1) の混合溶液を作成し、80℃で10分間加熱撹拌した。これを上記ステアリン酸アルミニウムジソープ及びアルミニウムイソプロポキシド加水分解液混合溶液と混合し、10分間撹拌し、SH6040(A-1) 、ケイフッ化水素酸水溶液（40％）(D) 、エタノール(E-1) 、ｎ−ブタノール(E-2) 、Ｎ，Ｎ−ジメチルベンジルアミン(C) を加え、10分間撹拌し、塗工液を調製した。表２に上記各成分の使用量を示す。その塗工液にポリカーボネート片をディッピングし、120 ℃〜150 ℃で５分間乾燥した。上記塗工ポリカーボネート片を実施例１と同様にして、評価を行った結果、接触角は106 °、電気抵抗値は10⁵ Ωであった。
【００６９】

【００７０】
比較例１
実施例１同様に未塗工のスライドガラス板を自動接触角測定システムを用い液滴法で測定した結果、接触角は26°であった。また、実施例１同様にカーボンブラックを吸引する距離及び吸引量を調べた結果、カーボンブラックは吸引付着された。
【００７１】
上記実施例と比較例の結果より、実施例の被膜組成物による被膜は、比較例のものに比べて、撥水性及び帯電防止性に優れている。
【００７２】
【発明の効果】
以上詳述したように、本発明の被膜組成物は、撥水性及び帯電防止性に優れた被膜を提供することができる。また、本発明の被膜組成物を被覆した被覆基材の製造方法は、撥水性及び帯電防止性に優れた被覆基材を提供することができる。この被覆基材は情報・電子産業の精密機器、光学機器などにおいて極めて有用である。[0001]
[Industrial application fields]
In the fields of precision equipment and optical equipment in the information and electronics industries, the present invention is a coating on plastics, glass and other various materials, which has antistatic properties and a high water repellency, insolubility and high surface hardness. The present invention relates to a water repellent / antistatic coating composition that can be formed and a method for producing a coated substrate.
[0002]
[Prior art and problems to be solved by the invention]
Originally, the antistatic property is that the charged surface is made to leak quickly by making the surface of the base material conductive, and the generated charge may be reduced as much as possible by surface contact. A particularly important method of charge leakage is
1. Method of applying antistatic agent to substrate surface (surface coating method)
2. Method of kneading an antistatic agent into polymer materials, etc., and transferring a part to the surface (internal kneading method)
However, both are thin layers of an antistatic agent and are made conductive by coating the surface. The antistatic agent is mostly a surfactant and a metal thin film is also used.
[0003]
Various attempts have been made as a surface coating method, but when a surfactant solution is used as an antistatic agent, the lipophilic part of the surfactant is adsorbed on the surface of the base material (for example, a polymer material). When the hydrophilic polar part is arranged facing outside (in the room air), a conductive layer is formed due to the adsorption of moisture in the air and the polarization effect of the surfactant and the polarization of the moisture, resulting in an antistatic effect.
[0004]
In this case, the surfactant or the like easily falls off from the surface, and further, the effect is diminished by moving away from the surface or moving into the film layer.
[0005]
Despite the ease of processing, the surface coating method of the substrate has its durability. Therefore, by using an internal kneading method, a polymer type surfactant is polymerized with a monomer containing a quaternary ammonium salt such as acrylic acid or methacrylic acid or a tertiary amine, or an ionic polymer is added to the vehicle, Those containing inorganic conductive fine particles are used as conductive paints.
[0006]
In addition, as a method using an inorganic polymer, a thin film having polysiloxane as the main chain is made and made conductive by interaction with moisture adsorbed as a hygroscopic surface, or charged by combining polysiloxane and a surfactant. I make a protective coating. Although these are both advantages and disadvantages, even if the water-absorbent coating film is essentially an antistatic coating film, the surfactant is washed away with water and the conductive layer disappears, and contaminants in the air are removed by moisture. It is very disturbing because it absorbs inside.
[0007]
Regarding water repellency, wax, oil, silicone resin, metal soap, etc. have been used as a base for water repellents, but there are problems with heat resistance and weather resistance when they are put to practical use. There is nothing satisfactory.
[0008]
For example, during exposure to the outside world, resistance to adhesion contamination such as dust and iron powder is low, and the durability of the water repellent effect is impaired by acid rain and sunlight.
[0009]
As a measurement standard for water repellency, the contact angle of water is often used. PTFE (Teflon) developed by DuPont, USA, has the chemical formula: -CF₂-CF₂It is a polymer comprising-, has a low surface energy, and water repellency is known as a water contact angle of 110 °.
[0010]
Furthermore, in recent research, graphite fluoride has been discovered and exhibits strong water repellency (contact angle l80 °) and excellent lubricity. -CH smaller than surface energy_ThreeIs 3. l × 10^-Four -CF for N / cm_ThreeIs 1.9 x 10^-Four N / c m is said to be the smallest among the substances, and water repellency is large when the polarizability is small.
[0011]
Since PTFE and graphite fluoride are organic polymer materials, the matrix is weak against heat and abrasion, and metal plating incorporating fluoride particles is considered to be combined with metal. However, this method is also far from practical use because a metal complex having a high fluorine concentration generates a so-called anodic effect in the electrolytic solution, and electrolysis stops or precipitation of fluoride occurs.
[0012]
Metal soap has a water repellency of 110 ° for calcium stearate, 120 ° for aluminum stearate and 135 ° for zinc stearate, which is the largest among general organic materials. However, metal soap is mostly fine powder, and in order to form a molecular film, after attaching these fine powder to the substrate surface, it is heated to the melting point or higher to form a water-repellent film. However, being weak against heat and wear is its weak point.
[0013]
In general, water repellency and antistatic properties are opposite to each other. Conventional antistatic agents are mostly hydrophilic, and water repellency or hydrophobic polymers have a problem in chargeability.
[0014]
Accordingly, an object of the present invention is to provide a coating composition excellent in both water repellency and antistatic properties.
[0015]
Another object of the present invention is to provide a method for producing a coated substrate excellent in both water repellency and antistatic properties.
[Means for Solving the Problems]
[0016]
As a result of diligent research in view of the above object, the present inventor has produced a metal soap by reacting an inorganic alkoxide with a fatty acid in an organic solvent, and converted the inorganic alkoxide into a three-dimensional skeleton of a polymer obtained by polycondensation after hydrolysis. By providing a coating composition in which the above metal soap is cross-linked, the surface of the metal soap has a water repellent characteristic (contact angle with water of 120 °), and an interface consisting of polar and nonpolar characteristics unique to the metal soap. By forming an antistatic molecule due to activity, a coating having insolubility and high surface hardness, water repellency and antistatic properties can be obtained, and heat treatment at a predetermined temperature after coating the coating composition Then, it discovered that the coating base material which has water repellency and antistatic property was obtained, and came up with this invention.
[0017]
That is, the water-repellent and antistatic coating composition of the present invention is
(A) (a) inorganic alkoxide and / or (b) a polymer obtained by hydrolyzing and polycondensing (a) inorganic alkoxide;
(B) fatty acids,
(C) a catalyst;
(D) silicohydrofluoric acid,
(E) It comprises a hydrous organic solvent.
[0018]
In addition, the method for producing a coated substrate having a water-repellent / antistatic coating comprises a step of applying a film formed of the above-described coating composition on at least one surface of the substrate and a heat treatment at 80 ° C. or higher for repelling. It includes the step of forming an aqueous / antistatic coating.
[0019]
The present invention will be described in detail below.
[1] Composition components
(A) (a) Inorganic alkoxide and / or (b) OH group-containing polymer
(a) Inorganic alkoxide
(1) General formula
The inorganic alkoxide used in the present invention has the following formula (I):
M (OR)_n(X)_an      (I)
(Wherein M is an inorganic atom selected from the group consisting of Si, Al, Ti, Zr, Ca, Fe, V, Sn, Li, Be, Y, B and P, and R is an alkyl group, X is a hydrocarbon group, a hydrocarbon group having a functional group or a halogen, a is a valence of M, and n is an integer from 0 to a). Is preferred.
[0020]
(2) When n = a
Of the compounds of the above formula (I), generally used is n = a, that is, a compound in which only an alkoxide group is bonded to M.
[0021]
(I) alkoxysilane
When M is Si, a is 4. Such alkoxides are Si (OR¹)_FourIt is represented by Where R¹Is preferably an alkyl group having 1 to 4 carbon atoms (hereinafter referred to as a lower alkyl group). Such alkoxysilanes include Si (OCH_Three)_Four, Si (OC₂H_Five)_FourEtc.
[0022]
(Ii) Aluminum alkoxide
When M is Al, the a is 3. Such alkoxides are Al (OR²)_ThreeIt is represented by Where R²Is preferably a lower alkyl group. As such an aluminum alkoxide, Al (OCH_Three)_Three, Al (OC₂H_Five)_ThreeAl (On-C_ThreeH₇)_ThreeAl (O-i-C_ThreeH₇)_Three, Al (OC_FourH₉)_ThreeEtc. The aluminum alkoxide is usually used as a mixture with the alkoxysilane. By using the aluminum alkoxide, the surface hardness and heat resistance of the resulting coating are improved.
[0023]
The amount of aluminum alkoxide to be used is preferably in the range of 40 parts by weight or less, more preferably about 30 parts by weight with respect to 100 parts by weight of the alkoxysilane. If it exceeds 40 parts by weight, the polymer formed tends to gel, and cracks may occur in the resulting coating.
[0024]
(Iii) Titanium alkoxide
When M is Ti, a is 4. Such alkoxides are Ti (OR^Three)_FourIt is represented by Where R^ThreeIs preferably a lower alkyl group. As such a titanium alkoxide, Ti (OCH_Three)_Four, Ti (OC₂H_Five)_Four, Ti (OC_ThreeH₇)_Four, Ti (OC_FourH₉)_Four, Ti (O-i-C_ThreeH₇)_FourEtc.
[0025]
(Iv) Zirconium alkoxide
When M is Zr, a is 4. Such alkoxides are Zr (OR^Four)_FourIt is represented by Where R^FourIs preferably a lower alkyl group. Such zirconium alkoxides include Zr (OCH_Three)_Four, Zr (OC₂H_Five)_Four, Zr (O-i-C_ThreeH₇)_Four, Zr (Ot-C_FourH₉)_Four, Zr (On-C_FourH₉)_FourEtc.
[0026]
(V) Other alkoxides
As an alkoxide other than the above, for example, Ca (OC₂H_Five)₂, Fe (OC₂H_Five)_Three, V (O-i-C_FourH₉)_Three, Sn (O-i-C_FourH₉)_Four, Li (OC₂H_Five), Be (OC₂H_Five)₂, B (OC₂H_Five)_Three, Y (OCH_Three)_Three, Y (OC₂H_Five)_Three, P (OCH_Three)_Three, P (OC₂H_Five)_ThreeEtc.
[0027]
(3) When n ≤ a-1
Of the inorganic alkoxides represented by formula (I), when n ≦ a−1, that is, a compound in which a group X other than an alkoxy group is bonded to M, for example, X is a halogen such as Cl or Br. There are compounds. As described later, a compound in which X is a halogen is hydrolyzed in the same manner as an alkoxy group to generate an OH group and undergo a polycondensation reaction. X may also be a hydrocarbon group or a hydrocarbon group having a functional group, and the hydrocarbon group usually has 1 to 15 carbon atoms. Such groups remain as organic moieties in the polymer produced by the polycondensation reaction after hydrolysis. As the functional group, a carboxyl group, a carbonyl group, an amino group, a vinyl group, an epoxy group, and the like are preferable. Such a group is suitable for increasing the insolubility of the film.
[0028]
Examples of the compound of formula (I) having X include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethinesilane, γ-glycidoxypropyltrimethoxysilane, and γ-aminopropylmethoxy. Silane etc. are mentioned.
[0029]
(b) OH group-containing polymer
Instead of or simultaneously with the inorganic alkoxide described above, a polymer having an OH group obtained by previously hydrolyzing and polycondensing the inorganic alkoxide can be used. As will be described later, this polymer is produced by hydrolysis and polycondensation of an inorganic alkoxide in the presence of an acid and a base catalyst. This polymer is a relatively low-molecular oligomer, and for example, the molecular weight is preferably 700 to 900. The hydrolysis and polycondensation reaction of inorganic alcoside is generally performed at a temperature of 25 ° C. for 2 hours.
[0030]
(B) Fatty acids
Fatty acids used in the present invention include fatty acids and salts thereof, and fatty acids include saturated fatty acids and unsaturated fatty acids.
[0031]
(1) Saturated fatty acids
Examples of the saturated fatty acid used in the present invention include capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid, and stearic acid is particularly preferable. As the salts of saturated fatty acids, metal soaps formed by combining with the inorganic alkoxide are preferable. This metal soap mainly contributes to the water repellency of the coating film of the coating composition of the present invention.
[0032]
The amount of saturated fatty acid used is preferably 8 to 13 parts by weight with respect to 100 parts by weight of the inorganic alkoxide. When the amount is less than 8 parts by weight, the water repellency of the film becomes poor, and when it exceeds 13 parts by weight, the surface hardness decreases.
[0033]
As a saturated fatty acid used in the present invention, for example, stearic acid is combined with aluminum in an organic solvent of aluminum isopropoxide to produce aluminum stearate disoap. Aluminum stearate disoap has a high water repellency and a contact angle with water of 120 °. The surface water repellency of the resulting coating is dramatically improved and the polar-nonpolar nature of metal soap Due to the surface activity, antistatic performance is exhibited. The amount of stearic acid used is preferably 20 to 70 parts by weight and more preferably 45 parts by weight with respect to 100 parts by weight of aluminum isopropoxide. When the amount is less than 20 parts by weight, the water repellency of the coating becomes poor, and when it exceeds 70 parts by weight, the surface hardness decreases.
[0034]
(2) Unsaturated fatty acids
Examples of the unsaturated fatty acid used in the present invention include oleic acid, linoleic acid, and linolenic acid, and oleic acid is particularly preferable. As the salt of unsaturated fatty acid, metal soap formed by combining with the inorganic alkoxide is preferable. Since this metal soap has excellent conductivity, it mainly contributes to the antistatic property of the coating film of the coating composition of the present invention.
[0035]
The amount of the unsaturated fatty acid used is preferably 4 to 10 parts by weight with respect to 100 parts by weight of the inorganic alkoxide. When the amount is less than 4 parts by weight, the conductivity is lost, and when it exceeds 10 parts by weight, the surface hardness is lowered.
[0036]
As an unsaturated fatty acid used in the present invention, for example, oleic acid reacts with calcium ethoxide in an organic solvent to produce calcium oleate. Calcium oleate is originally an ionic bond and exhibits an antistatic function by performing ionic conduction, but its water repellency is also the second best after aluminum stearate. Since the film obtained by this is ion-bonding, it has electrical conductivity, good antistatic properties, and electrical conductivity (surface resistance of 10^FourΩ), water repellency, water contact angle 180 °. The amount of oleic acid used is 30 to 60 parts by weight with respect to 100 parts by weight of calcium ethoxide. Preferably, it is 50 parts by weight. When the amount is less than 30 parts by weight, the conductivity is lost, and when the amount is 60 parts by weight or more, the surface hardness decreases.
[0037]
(C) Catalyst
Examples of the catalyst used in the present invention include an acid catalyst and a base catalyst.
[0038]
(1) Acid catalyst
The acid catalyst is used for the hydrolysis reaction of the inorganic alkoxide. Therefore, when using a polymer having an OH group in which inorganic alkoxide is previously hydrolyzed to some extent and polycondensed, an acid catalyst is not required.
[0039]
Examples of the acid catalyst include (1) mineral acids such as hydrochloric acid, sulfuric acid and nitric acid, (2) anhydrides of mineral acids such as hydrogen chloride gas, (3) tartaric acid, phthalic acid, maleic acid, dodecyl succinic acid, hexahydro Phthalic acid, methyl nadic acid, pyromellitic acid, benzophenone tetracarboxylic acid, dichlorosuccinic acid, chlorendic acid, phthalic anhydride, maleic anhydride, dodecyl succinic anhydride, hexahydrophthalic anhydride, methyl nadic anhydride, anhydrous Examples include organic acids such as pyromellitic acid, benzophenone tetracarboxylic anhydride, dichlorosuccinic anhydride, and chlorendic anhydride, and anhydrides thereof.
[0040]
The amount of the acid catalyst used is preferably 0.01 to 0.5 parts by weight, particularly preferably 0.015 to 0.3 parts by weight, based on 100 parts by weight of the inorganic alkoxide. If the amount is less than 0.01 part by weight, the hydrolysis may be insufficient. If the amount exceeds 0.5 part by weight, the polycondensation reaction proceeds and the viscosity may increase.
[0041]
(2) Base catalyst
The base catalyst is mainly used as a catalyst for polycondensation reaction of the hydrolyzate of the inorganic alkoxide, and as a catalyst for rapid crosslinking reaction and formation of a three-dimensional network structure. As a result, the metal portion of the metal soap generated from the inorganic alkoxide and the fatty acid is crosslinked to the three-dimensional network structure and is included in the three-dimensional network structure.
[0042]
The base catalyst is preferably a tertiary amine that is substantially insoluble in water and soluble in an organic solvent. Preferable base catalysts include N, N-dimethylbenzylamine, tripropylamine, tributylamine, and tripentylamine, and N, N-dimethylbenzylamine is particularly preferable.
[0043]
The amount of the base catalyst used is preferably 0.01 to 1 part by weight and particularly preferably 0.05 part by weight in 100 parts by weight of the coating composition of the present invention. If the amount is less than 0.01 parts by weight, the polycondensation reaction proceeds slowly. If the amount exceeds 1 part by weight, the polycondensation reaction proceeds rapidly. May decrease.
[0044]
(D) Hydrosilicofluoric acids
Examples of the silicohydrofluoric acid used in the present invention include silicohydrofluoric acid and salts thereof. The salt of hydrosilicofluoric acid is preferably a metal fluoride salt formed by combining with the inorganic alkoxide. The silicohydrofluoric acid is preferably a high-density SiO in the presence of the mineral acid as the acid catalyst, the saturated and unsaturated fatty acids.₂And this SiO₂The metal fluoride salt contributes to the water repellency and antistatic properties of the coating composition of the present invention.
[0045]
The amount of silicofluoric acid used is preferably 0.1 to 3 parts by weight in 100 parts by weight of the coating composition of the present invention.
[0046]
(E) Hydrous organic solvent
Examples of the organic solvent used in the present invention include water-compatible solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and butyl alcohol. This organic solvent is used with water. The amount of the organic solvent used is preferably 100 to 5000 parts by weight, particularly preferably about 3000 parts by weight, based on 100 parts by weight of the total of (A) to (D). The amount of water used is preferably 3 to 5 parts by weight with respect to 100 parts by weight of the organic solvent.
[0047]
(F) Other ingredients
The coating composition of the present invention may further contain at least one polyacrylic acid. Examples of the polyacrylic acids include polyacrylic acid, polymethacrylic acid, and salts thereof. The amount of the polyacrylic acid used is preferably 0.3 to 1 part by weight with respect to 100 parts by weight of the above (A) to (E).
[0048]
[2] coated substrate
[A] Base material
As the base material used in the present invention, glass, plastic, metal and the like are preferable.
[0049]
[B] Method for producing coating
(1) Application of coating composition
Each component of the water-repellent / antistatic coating composition is mixed to obtain a transparent coating solution. This coating solution is applied to at least one side of the substrate. The coating method is not particularly limited, and spray coating, registration coating, brush coating, roll coater coating, and the like can be used.
[0050]
(2) Heating / drying
The coated substrate is heated and dried at a temperature of 80 ° C. or higher, preferably in the range of 80 ° C. to 150 ° C., to obtain the water-repellent / antistatic coating of the present invention. If necessary, the heating / drying treatment may be performed after the coating liquid is applied several times.
[0051]
[C] Characteristics of coating
The film thickness of the obtained film is preferably from 0.05 to 1.0 μm, particularly preferably from 0.08 to 0.1 μm. The film thickness of the coating can be adjusted as appropriate by coating the coating solution thickly or by coating several times.
[0052]
The film thus obtained gives water repellency and antistatic properties to the surface of the substrate. The formed film is insoluble in water and organic solvents, and has high surface hardness, abrasion resistance, and weather resistance.
[0053]
[Action]
In the water-repellent / antistatic coating composition of the present invention, the inorganic alkoxide is hydrolyzed by the action of an acid catalyst in an organic solvent solution, and mainly the alkoxy group is changed to an OH group, and a polycondensation action is started. The deprotonation of the OH group occurs by the action of the base catalyst added thereto, and as a result, the hydrolyzate proceeds with polycondensation to form an inorganic alkoxide three-dimensional network structure. On the other hand, the fatty acid salt is preferably a metal soap as a reaction product of an inorganic alkoxide and a fatty acid, crosslinked to the inorganic alkoxide three-dimensional network structure, and excellent in water repellency and antistatic properties. Things are obtained.
[0054]
Specifically, by reacting aluminum isopropoxide as an inorganic alkoxide with a fatty acid such as stearic acid in an organic solvent solution, metal soap such as aluminum stearate trisoap is generated, and aluminum stearate trisoap is in the air. It is easily hydrolyzed by water and the like, and becomes aluminum stearate aluminum disoap and fatty acid. The same applies to the case where oleic acid and calcium ethoxide are reacted as necessary to form calcium oleate.
[0055]
An inorganic alkoxide in which X is a hydrocarbon group having an epoxy group in the formula (I) is added to an organic solvent solution containing the above-mentioned aluminum isopropoxide, aluminum stearate disoap and, if necessary, calcium oleate, and organic Hydrolysis with mineral acid in solvent solution. After that, a base catalyst is added to this solution, and in the presence of the base catalyst, ring opening and polycondensation reaction are started for the epoxy group, and polycondensation reaction is started for OH group generated from the alkoxide group by hydrolysis. Coating with good transparency and adhesion by cross-linking aluminum stearate disoap and calcium oleate to the inorganic alkoxide three-dimensional network structure by sol-gel method, and simultaneously mixing and stirring hydrofluoric acid Obtain a liquid. The surface hardness of the coating film by this coating solution is 4H to 5H, and a transparent film having good insolubility and adhesion can be formed.
[0056]
As the antistatic coating, a metal sorbate such as calcium oleate with a large ionic bond and aluminum stearate with a large dipole moment is partially cross-linked to a three-dimensional inorganic alkoxide network structure by a sol-gel method. Through the surface micropores in the porous part of the original network structure, it becomes a surface activity consisting of polar and nonpolar inherent to metal soap, forms an antistatic molecule, and with the drying shrinkage of the inorganic alkoxide three-dimensional network part, The antistatic molecule moves from the inside of the hole to the back surface, and the antistatic effect of the minimum monomolecular film appears.
[0057]
Originally, it has been clarified that metal soap is an ion-bonding property between a fatty acid and a metal and has considerable conductivity even in an organic solvent. In particular, calcium oleate undergoes charge transfer by ionic conduction. Aluminum stearate disoap has a large dipole moment, improved solubility in the presence of alcohol and amine, and its molecular structure is chain-like or network-like, coupled with the presence of calcium oleate, and the mechanism of charge transfer Configure. If necessary, an acetylacetonate solution of In and Sn may be prepared and mixed with the coating solution.
[0058]
This antistatic coating has a surface resistance of 10^Four~Ten⁷The antistatic effect is excellent. It can also be used for electronic parts.
[0059]
Further, as the water repellent film, aluminum stearate formed by aluminum isopropoxide and stearic acid in an aluminum alkoxide solution and an inorganic alkoxide solution in which X is a hydrocarbon group having an epoxy group in the chemical formula (I) Due to the presence of disoap, calcium oleate formed by optionally reacted calcium ethoxide and oleic acid, and aluminum fluoride formed by silicohydrofluoric acid and aluminum isopropoxide. It is highly water-based and almost close to a contact angle of 120 ° with water.
[0060]
Originally, metal soap is CH with low surface energy._ThreeAre regularly arranged, the surface cohesive energy is very small as a whole, and it has a good slip property. Its cohesive energy is CF_ThreeIs considered to be the second lowest.
[0061]
The water repellency / lubricant and antistatic properties work side by side to prevent contaminants in the air (cigarette smoke, various oxides, dust, etc.) from adsorbing to the substrate surface, rainwater, moisture, etc. Falls off without adhering to the surface of the substrate due to self-surface tension and gravity difference.
[0062]
【Example】
Hereinafter, the present invention will be described based on examples.
[0063]
Example 1
1. Preparation and coating of coating composition
Using each component shown in Table 1 (unit:% by weight), the coating composition of the present invention was prepared and coated by the following procedure.
[0064]
Aluminum isopropoxide hydrolyzed solution (hydrolyzed solution in which aluminum isopropoxide is sufficiently hydrolyzed with a mineral acid catalyst (HCl 35%) and reacted almost exclusively with the water of the mineral acid catalyst, and the water is converted to isopropanol. At Al₂O_ThreeStearic acid (B) was added to a mixed solution of (A-2) and ethanol (E-1), and the mixture was heated and stirred at 80 ° C. for 20 minutes.
[0065]
After aluminum stearate disoap was formed in the above solution, it was left at room temperature (25 ° C.) for 40 to 60 minutes. When γ-glycidoxypropylmethoxysilane (trade name “SH6040”, manufactured by Toray Dow Corning Co., Ltd.) (A-1) is added thereto, γ-glycidoxypropylmethoxysilane is produced by the action of the mineral acid in the solution. Of the methoxy group started to hydrolyze. Further, add an aqueous solution of hydrofluoric acid (40%) (D) and ethanol (E-1), n-butanol (E-2), N, N-dimethylbenzylamine (C) and stir for 10 minutes. Thus, a coating liquid as a coating composition of the present invention was prepared. In the coating solution, SiO₂And a metal fluoride salt were formed, and the epoxy group of SH6040 was ring-opening polymerized. This transparent coating solution was applied to one side of a glass plate, and heated and dried at 150 ° C. for 10 minutes.
[0066]
2. Evaluation
As a result of measuring the coated glass plate by a droplet method using an automatic contact angle measurement system (manufactured by Kyowa Interface Science Co., Ltd.), the contact angle was 110 °. Further, after rubbing with paper or cloth, the distance and amount of suction of carbon black using carbon black were examined. As a result, there was almost no suction or adhesion. Furthermore, the electrical resistance value of the coated glass plate is 10⁷It was below Ω.
[0067]

[0068]
Example 2
In the same manner as in Example 1, stearic acid (B-1) was added to a mixture of aluminum isopropoxide hydrolyzate (A-2) and ethanol (E-1) to form aluminum stearate disoap to produce stearin. A mixed solution of aluminum acid dissoap and aluminum isopropoxide hydrolyzate was prepared. Separately, a mixed solution of calcium ethoxide hydrolyzate (A-3), oleic acid (B-2) and ethanol (E-1) was prepared, and heated and stirred at 80 ° C. for 10 minutes. This was mixed with the above aluminum stearate disoap and aluminum isopropoxide hydrolyzed mixed solution, stirred for 10 minutes, SH6040 (A-1), hydrofluoric acid aqueous solution (40%) (D), ethanol (E -1), n-butanol (E-2) and N, N-dimethylbenzylamine (C) were added and stirred for 10 minutes to prepare a coating solution. Table 2 shows the amount of each component used. A polycarbonate piece was dipped into the coating solution and dried at 120 ° C. to 150 ° C. for 5 minutes. The coated polycarbonate piece was evaluated in the same manner as in Example 1. As a result, the contact angle was 106 ° and the electric resistance value was 10 °.^FiveΩ.
[0069]

[0070]
Comparative Example 1
As in Example 1, an uncoated slide glass plate was measured by a droplet method using an automatic contact angle measurement system. As a result, the contact angle was 26 °. Further, as a result of investigating the distance and amount of suction of carbon black as in Example 1, carbon black was sucked and adhered.
[0071]
From the results of the above examples and comparative examples, the coating films of the coating compositions of the examples are superior in water repellency and antistatic properties compared to those of the comparative examples.
[0072]
【The invention's effect】
As described above in detail, the coating composition of the present invention can provide a coating excellent in water repellency and antistatic properties. Moreover, the manufacturing method of the coating base material which coat | covered the coating composition of this invention can provide the coating base material excellent in water repellency and antistatic property. This coated substrate is extremely useful in precision equipment and optical equipment in the information and electronics industries.

Claims (9)

(A) (a) inorganic alkoxide and / or (b) a polymer obtained by hydrolyzing and polycondensing (a) inorganic alkoxide;
(B) fatty acids,
(C) a catalyst;
(D) hydrosilicofluoric acids,
(E) A water-repellent and antistatic coating composition comprising a water-containing organic solvent. The water-repellent / antistatic coating composition according to claim 1, wherein the (A) (a) inorganic alkoxide has the chemical formula (I):
M (OR) _n (X) _a−n (I)
(Where M is an inorganic atom selected from the group consisting of Si, Al, Ti, Zr, Ca, Fe, V, Sn, Li, Be, Y, B and P, R is an alkyl group, and X Is a hydrocarbon group, a hydrocarbon group having a functional group, or a halogen, a is a valence of M, and n is an integer from 0 to a). A water-repellent and antistatic coating composition characterized by The water repellent / antistatic coating composition according to claim 2, wherein X in the chemical formula (I) is a hydrocarbon group having a carbonyl group, a carboxyl group, an amino group, a vinyl group, or an epoxy group. Water repellent and antistatic coating composition characterized by The water-repellent / antistatic coating composition according to claim 1, wherein the (A) (a) inorganic alkoxide is Si (OC ₃ H ₇ ) ₄ , Al (Oi-C ₃ H ₇ ) ₃ , _{Ti (O-i-C 3} H 7) 4, Zr (O-i-C 3 H 7) 4, Zr (O-n-C 4 H 9) 4, Ca (OC 2 H 5) 2, Fe ( _{OC 2 H 5,) 3,} V (O-i-C 4 H 9) 4, Sn (OC 2 H 5) 4, Sn (O-i-C 4 H 9) 4, Li (OC 2 H 5) , Be (OC ₂ H ₅ ) ₂ , B (OC ₂ H ₅ ) ₃ , Y (OCH ₃ ) ₃ , Y (OC ₂ H ₅ ) ₃ , P (OCH ₃ ) ₃ and P (OC ₂ H ₅ ) ₃ A water repellent / antistatic coating composition, characterized in that it is at least one selected from the group consisting of: In repellent, antistatic coating composition according to claim 1, wherein the (B) fatty acids, comprising capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and salts thereof A water-repellent and antistatic coating composition, which is at least one selected from the group. The water repellent / antistatic coating composition according to any one of claims 1 to 4, wherein the (B) fatty acids are at least one selected from the group consisting of oleic acid and salts thereof. A water-repellent and antistatic coating composition. The water repellent / antistatic coating composition according to any one of claims 1 to 6, wherein the (D) hydrosilicofluoric acid is selected from the group consisting of silicohydrofluoric acid and salts thereof. A water-repellent and antistatic coating composition characterized by In repellent, antistatic coating composition according to claim 1, wherein the (C) catalyst, N, repellent, antistatic coating, which is a N- dimethylbenzylamine Composition. In the manufacturing method of the coating base material which has a water repellent and antistatic film, the film | membrane formed with the water repellent and antistatic film composition in any one of Claims 1-8 is applied to the at least single side | surface of a base material. A method for producing a coated substrate having a water-repellent / antistatic coating, characterized by comprising a step of processing and a step of forming a water-repellent / antistatic coating by heat treatment at 80 ° C. or higher.