JPH0823071B2 - Rough surface coating forming composition and rough surface coating forming method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a film-forming composition, and more particularly, to a composition for forming a metal compound film having a rough surface and a rough surface film formation. Regarding the method.

The rough surface coating formed on the surface of a base material such as metal, glass, ceramics or plastic has a matte effect and a light reflection preventing effect because it scatters light, and therefore the present invention can be used in many surface treatment fields. .

[Conventional technology]

Conventionally, as a method for imparting light-scattering properties to a substrate surface, a method of roughening the substrate surface by a mechanical surface treatment such as sandblasting or a chemical surface treatment such as chemical etching, a resin in which a pigment is dispersed Is applied to the surface of the base material, and is adopted as a completed technology according to the demands of each field. As a method for forming a matte film or an antireflection film by a translucent metal compound on the surface of a substrate, a low-refractive-index single-layer thin film made of a metal compound such as SiO ₂ or MgF ₂ or a low-refractive index thereof A method for forming an optical interference film in which a film and a high refractive index film made of a metal compound such as TiO ₂ , ZrO ₂ , and HfO ₂ are alternately laminated on the substrate surface by a vacuum deposition method, a sputtering method, a CVD method, or the like. , And these are also adopted as completed technologies.

[Problems to be solved by the invention]

In the method of roughening the surface of the substrate, the matte effect of scattering the incident light to the rough surface side is excellent, but in the case of glass, plastic, etc. used for lighting fixtures, windows, etc. that also require transmission of light, The roughened surface makes it semi-transparent and reduces the light transmittance. The same applies to the method of forming the pigment-containing resin film. On the other hand, in the method of forming a transparent metal compound film, since only a smooth surface can be obtained, there is a limit in reducing the surface reflectance, and if necessary, the roughening method may be used in combination. It is necessary to roughen the coating surface.

An object of the present invention is to provide a method for forming a rough surface coating on a substrate surface by a coating and firing method which is one of the methods for forming a metal compound coating, and a coating forming composition used in the method. .

[Means for solving problems]

The present invention is Si, Ti, Ta, Al, Zr, In, Hf, La, Nb, Pb, Sb, Sn, Y,
W or Fe alkoxides, alkoxide polymers,
A hydrophobic plasticizer, which is liquid at room temperature, is added to an organometallic compound solution consisting of a solvent and one or more organometallic compounds selected from the group consisting of chelating compounds and acylating compounds. And a composition for forming a rough surface coating, which is applied to the surface of a base material and dried to thermally decompose the formed coating film.

The organometallic compounds used in the present invention are those which are soluble in organic solvents and which are thermally decomposable with the oxygen directly bonded or coordinated to the metal atom. Organic Si
Specific examples of the compounds include dimethyldimethoxysilane, diethyldiethoxysilane, dimethyldiisopropoxysilane, diethyldibutoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyl. Silane alkoxides having the same or different substituents, such as tributoxysilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane, diethoxydiisopropoxysilane, the same or different. When silane alkoxides are used in organic storage, acidic catalysts such as hydrochloric acid, nitric acid, phosphoric acid, acetic acid, etc. or sodium hydroxide,
Hydrolyzes in the presence of a basic catalyst such as potassium hydroxide,
Polycondensation silane alkoxide polymers having a degree of polymerization of 2 to 20, silane alkoxides or their polymers, and acetic acid,
Acylated products obtained by reacting carboxylic acids such as propionic acid and butyric acid, silane alkoxides or polymers thereof, and β-diketones such as acetylacetone and benzoylacetone, ketoacetoacetate and propionyl butyric acid, etc. For example, chelating compounds obtained by reacting acids, lower alkyl esters of keto acids, oxy acids such as glycolic acid and lactic acid, lower alkyl esters of oxy acids, diols, amino alcohols, etc. Can be mentioned. These compounds may be used alone or in combination of 2
It can be used as a mixture of two or more species.

As the metal compound other than the Si compound, a compound having the same substituent as the Si compound can be used.

The organic solvent is not particularly limited as long as it can dissolve the organometallic compound, and methanol, ethanol,
Lower alcohols such as isopropanol and butanol,
Esters such as methyl acetate and ethyl acetate, the aforementioned β-
A single solvent such as diketones, keto acids, ketoesters or a mixed solvent of two or more kinds is preferably used. More preferably, a solvent containing a lower alcohol as a main component, which is excellent in the solubility of the organometallic compound, the coating property of the solution on the substrate, and the thermal decomposability, is used.

The organometallic compound solution is one obtained by dissolving one kind or a substituent of the organometallic compound and / or two or more kinds having different metal species in the organic solvent, and if desired, a phosphorus compound such as phosphoric acid or boric acid. And those containing additives such as glass forming agents such as boron compounds. The concentration of the organometallic compound in the solution varies depending on the types of the organometallic compound and the solvent, the coating method of the solution on the surface of the base material, and the like, but is usually a metal oxide produced by thermal decomposition of the organometallic compound. It is 1 to 20% by weight in terms of the product. As the organic metal compound solution, a metal oxide forming composition which is commercially available for many metal species such as Si, Ti, Ta and Nb can also be used.

On the other hand, the hydrophobic plasticizer as an additive component is a plasticizer having a solubility in water at room temperature of 10 g / 100 g H ₂ O or less. For example, phthalic acid esters such as methyl phthalate, ethyl phthalate, butyl phthalate and octyl phthalate, aliphatic dibasic acid esters such as butyl adipate, octyl adipate and octyl sebacate, and methyl acetylricinoleate. , Oxyacid esters such as acetyl citrate tree (2 ethylhexyl), glycol esters such as diethylene glycol dibenzoate, fatty acid esters such as butyl oleate and tetrahydrofurfuryl oleate, tributyl phosphate, triphenyl phosphate, phosphate Phosphoric acid esters such as tri-2 ethylhexyl, chlorinated paraffins, polyesters, polyether polyols and the like can be used.

The composition for forming a rough surface coating of the present invention contains 100 ppm to 10 wt% of the hydrophobic plasticizer in the organometallic compound solution.
It is a solution containing addition.

In the present invention, the surface of the substrate is coated with the composition for forming a rough surface coating, dried in the atmosphere to form a coating film, and then the organic matter in the coating film is thermally decomposed to form a film on the substrate. A rough film is formed. There is no particular limitation on the method for applying the rough surface film-forming composition to the surface of the base material, and a coating method such as a dipping method, a spray method, a spinner method, a brush coating method or a printing method The material is appropriately selected in consideration of the shape and the like. Drying the substrate coated with the composition,
In the air, if necessary, in the presence of water vapor at room temperature to 150
By performing the heating at a temperature of ℃, a coating film mainly composed of an organometallic compound is formed on the surface of the base material. Then, the coating film is heated to thermally decompose organic substances in the coating film, thereby forming a rough surface coating mainly composed of a metal oxide on the surface of the substrate. By appropriately selecting the thermal decomposition temperature, a cured rough surface coating of a metal compound in which some organic substances remain, a metal oxide in which some hydroxyl groups remain, an amorphous metal oxide and a crystalline metal oxide It can be formed on the material surface. Depending on the type of organometallic compound, hydrophobic plasticizer, and organic solvent, a cured film of a metal compound with a partial organic residue at a thermal decomposition temperature of 80 to 250 ° C and a metal with a hydroxyl group remaining at 150 to 300 ° C It is possible to form an oxide film, an amorphous metal oxide film at 250 to 600 ° C, and a crystalline metal oxide film at 350 ° C or higher.

The rough surface coating formed by the method of the present invention is exemplified by an example of a metal oxide, SiO ₂ , TiO ₂ , Ta ₂ O ₅ , Al ₂ O ₃ , ZrO ₂ , In ₂ O ₃ and HfO.
Containing _{2, La 2 O 3, Nb} 2 O 3, PbO, Sb 2 O 4, SnO 2, Y 2 O 3, WO 3, Fe 2 O 3 mixture or two or more single or two or more of such A complex oxide may be used.

[Work]

In the present invention, as shown in FIGS. 1 (a) to 1 (e) attached, a rough surface coating having irregularities is formed on the surface of the substrate. The roughening effect begins to appear when the content of the hydrophobic plasticizer in the composition for forming a rough surface coating is about 100 ppm, and a translucent rough surface coating is formed when the content is 5 to 10 wt%.

Further, in the present invention, as shown in FIG. 2 attached, it is possible to form a rough surface coating capable of reducing the light reflectance without lowering the light transmittance.

That is, in the present invention, by adjusting the addition content of the plastic water-based plasticizer in the composition for forming a rough surface coating, it is possible to arbitrarily adjust the roughness, light reflectance and transmittance of the coating formed. it can.

In the present invention, the rough surface coating, when the composition for forming a rough surface coating applied to the surface of the substrate is dried to form a coating film, the coating film absorbs water vapor in the air or supplied as necessary, It is presumed that the hydrophobic plasticizer present in the film forms the core of the micelle structure, and a step is created between the micelle part and the non-micelle part due to thermal decomposition, and a rough surface film is formed. Presumed to be done.

〔Example〕

 The present invention will be described in more detail by way of examples.

However, the scope of the present invention is not limited to the following examples.

Example 1 and Comparative Example 1 Preparation of composition for forming rough surface coating: tetraethoxysilane; 186 g, ethanol; 634 g, acetic acid; 2
06 g and concentrated hydrochloric acid; 0.3 g were mixed, heated and held under reflux for 45 hours to cause a reaction, to obtain an acylated solution of a silane alkoxide polymer having a concentration converted to SiO ₂ of 5.0 wt%.

The obtained silane alkoxide polymer solution was added with octyl phthalate (DOP) as a hydrophobic plasticizer, polypropylene glycol (PPG-300) having a molecular weight of about 300 or about 1,
000 polypropylene glycols (PPG-1,000) were added and mixed to prepare a rough surface film-forming composition.

The use of the prepared rough surface film-forming composition is shown in Table 1.

Formation of rough surface coating: A soda glass plate is dipped in the prepared composition for forming a rough surface coating, pulled at a constant pulling rate, dried in air, and then held at a temperature of 500 ° C for 30 minutes to be baked. Then, a SiO ₂ rough surface coating was formed on both surfaces of the soda glass plate.

For comparison, a SiO ₂ coating was formed on both sides of a soda glass plate using the above-prepared silane alkoxide polymer solution without addition of a hydrophobic plasticizer.

 The film forming conditions are shown in Table 1.

Roughness measurement: The roughness of the formed SiO ₂ rough surface coating was measured using a thin film step measuring device (manufactured by Kosaka Laboratory). Sample number 1-
The roughness measurement curves of 1,1-2, 1-3, 1-6 and 1-7 are shown in FIGS. 1 (a) to 1 (e).

Optical property measurement: The visible light transmittance: T (%) and reflectance: R (%) of the soda glass plate on which the SiO ₂ rough surface coating was formed were measured.

The optical characteristic curves of the sample numbers 1-3, 1-4, 1-5 and 1-7 and the soda glass plate for comparison are shown in FIG.

Example 2 In a mixed solution of ethanol; 650 g, butyl acetate; 250 g, and acetylacetone; 150 g, the following composition formula was added. The titanium alkoxide polymer represented by the following formula was dissolved to obtain a solution of concentrated 5.0 wt% in terms of TiO ₂ . The resulting solution, PPG-1000; 5
00 ppm or DOP; 500 ppm was added and mixed to prepare a rough surface film forming composition.

Dip a soda glass plate in the prepared composition for forming a rough surface coating, pulling it at a constant pulling speed of 20 cm / min, and after drying in the air, hold it at a temperature of 500 ° C. for 30 minutes and burn it, soda glass A TiO ₂ rough surface coating was formed on both sides of the plate.

The roughness of the obtained rough surface coating was measured using the same apparatus as in Example 1, and as a result, a curve similar to the curve shown in FIG. 1 (b) was obtained.

Example 3 Methylethoxysilane; 200 g, tetraethoxysilane; 2
Mix 50g, ethanol; 880g and 20% hydrochloric acid; 1.5g, 70
The mixture was heated to 0 ° C., 150 g of water was added dropwise, and the temperature was maintained at 70 ° C. for 5 hours to complete the reaction to obtain a silane alcoside polymer solution having a SiO ₂ conversion concentration of 10 wt%.

PPG-1,000 was added to the obtained silane alkoxide polymer solution.
Was added in an amount of 5 wt% to prepare a composition for forming a rough surface film.

A spinner of the prepared composition for forming a rough surface coating was applied to a stainless steel plate (SUS304) so as to have a film thickness of 1 μm, then dried in the air, and then heated to 350 ° C. for 3 days.
It was held and baked for 0 minutes to form a SiO ₂ rough surface coating on the SUS plate.

The formed SiO ₂ rough surface coating was a matte film with good adhesion and no peeling observed in the cellotape peeling test.

Example 4 The silane alkoxide polymer solution obtained in Example 3 was treated with DO.
P; 500 ppm was added to prepare a rough film-forming composition.

A polycarbonate plate was dipped in the prepared composition, pulled up at a constant rate of a pulling rate of 30 cm / min, and air-dried. Then, it was kept at 100 ° C. for 2 hours and heat-treated to form a cured film of the silane alkoxide polymer on both surfaces.

The obtained cured film was a matte film having a pencil hardness of 3H and good adhesion.

〔The invention's effect〕

In the present invention, as shown in the above-mentioned Examples, the composition for forming a rough surface film of the present invention is used to perform various operations such as coating, drying and heat curing treatment on various substrate surfaces, as shown in FIG. A rough surface coating of a metal compound can be formed. Further, the roughness of the rough surface coating formed by selecting the type and addition amount of the hydrophobic plasticizer to be added to the composition for forming a rough surface coating can be arbitrarily adjusted,
As a result, it is possible to adjust the optical properties, that is, the light reflectance and the light transmittance, of the substrate on which the rough surface coating is formed.

In the present invention, not only the antireflection film and the matte film which have been conventionally used can be formed on the surface of the base material, but also the reflectance is lowered and the transmittance is improved as shown in FIG. A rough surface coating can be formed. This rough surface coating is extremely useful as a solar heat absorbing film.

The present invention provides a composition for forming a rough surface coating and a method for forming a rough surface coating, which are suitable for forming a rough surface coating of an organometallic compound on a substrate, and are of great industrial significance.

[Brief description of drawings]

1 is a curve showing the roughness of the rough surface coating obtained in Example 1 (a) The roughness surface curve of the rough surface coating obtained in Example No. 1-1 (b) Example No. 1 Roughness curve of the rough surface coating obtained in No.-2 (c) Roughness curve of the rough surface coating obtained in Example No. 1-3 (d) Roughness surface obtained in Example No. 1-6 Roughness Curve of Coating (e) Roughness Curve of Roughness Coating Obtained in Example No. 1-7 FIG. 2 is an optical characteristic of the glass plate formed with the roughening coating obtained in Example 1. Curve (T-a) (R-a) Light transmittance and light reflectance of glass plate of Example No. 1-3 (T-b) (R-b) Light transmission of glass plate of Example No. 1-4 And Light Reflectance (T-c) (R-c) Light Transmittance and Light Reflectance (T-d) (R-d) of Example No. 1-5 Glass Plate of Example No. 1-7 Light transmittance and light reflection of plate (T-e) (R-e) Light transmittance and light reflectance of uncoated glass plate for comparison

Claims (6)

[Claims] 1. Si, Ti, Ta, Al, Zr, In, Hf, La, Nb, Pb, Sb, Sn, Y,
W or Fe alkoxides, alkoxide polymers,
A hydrophobic plasticizer, which is liquid at room temperature, is added to an organometallic compound solution consisting of a solvent and one or more organometallic compounds selected from the group consisting of chelating compounds and acylating compounds. For forming a rough surface film. 2. The hydrophobic plasticizer is a phthalic acid ester, an aliphatic tribasic acid ester, an oxyacid ester, a glycol ester, a fatty acid ester, a phosphoric acid ester, a chlorinated paraffin, or a polyester. The composition according to claim (1), which is one kind or two or more kinds selected from the group consisting of and polyether polyols. 3. The composition according to claim 1, wherein the added amount of the hydrophobic plasticizer is 100 ppm to 10 wt% with respect to the organometallic compound solution. 4. Si, Ti, Ta, Al, Zr, In, Hf, La, Nb, Pb, Sb, Sn, Y,
W or Fe alkoxides, alkoxide polymers,
A hydrophobic plasticizer, which is liquid at room temperature, is added to an organometallic compound solution consisting of a solvent and one or more organometallic compounds selected from the group consisting of chelating compounds and acylating compounds. A method for forming a rough surface coating, which comprises applying the composition for forming a rough surface coating to a substrate surface and drying the composition, and thermally decomposing the formed coating film. 5. The method according to claim 4, wherein the composition coated on the surface of the substrate is dried in the atmosphere or in the presence of water vapor at a temperature from room temperature to 150 ° C. 6. The method according to claim 4, wherein the thermal decomposition of the coating film formed on the surface of the base material is carried out at a temperature of 80 ° C. or higher.