JP2013169710A - Method for forming cured layer containing scaly metal oxide fine particles - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a cured layer on a substrate suitable even in an environment receiving much physical stimulation from dust or the like and excellent in abrasion resistance without baking the same at a high temperature.SOLUTION: A method for forming a cured layer containing scaly metal oxide fine particles on a substrate. The method includes a (step-i) for preparing the substrate, a (step-ii) for coating the substrate with a scaly metal oxide fine particle dispersion to form a coating layer, a (step-iii) for drying the coating layer to form a dry layer, and a (step-iv) for curing the scaly metal oxide fine particle in the dry layer by at least one method selected from a group consisting of ionizing substance irradiation, ionizing irradiation, infrared irradiation, microwave irradiation, and hot water-vapour exposure to form the cured layer.

Description

  The present invention relates to a method for providing a method for forming a hardened layer having excellent wear resistance on a substrate.

For the purpose of having hardness suitable for scenes where there is a lot of physical irritation due to dust, etc., a laminate was proposed in which a coating agent containing scaly titanium oxide fine particles (titania nanosheets) was fired on the surface of the base layer. (For example, Patent Document 1). According to Patent Document 1, the hardness of the nanosheet varies greatly depending on the firing temperature, and sufficient hardness is not exhibited unless firing at 400 ° C. or higher.
However, firing at such a high temperature has undesirable effects such as deterioration of the substrate. For this reason, there has been a demand for a method with less heat load that does not depend on firing at a high temperature.

JP 2005-290369 A

  An object of the present invention is to provide a method for forming a hardened layer having excellent wear resistance, which is suitable for a scene where there is a lot of physical irritation due to dust and the like, on a substrate without firing at a high temperature.

According to the present invention, the above problem is solved by the following configuration.
1. A method of forming a cured layer containing scaly metal oxide fine particles on a substrate,
(Step-i) a step of preparing a substrate,
(Step-ii) A step of applying a scaly metal oxide fine particle dispersion on a substrate to form a coating layer,
(Step-iii) Step of drying the coating layer to form a dry layer, and (Step-iv) Scale-like metal oxide fine particles in the dry layer are irradiated with ionizing substance beam, ionizing radiation, infrared irradiation, micro A step of curing by at least one method selected from the group consisting of wave irradiation and high-temperature water vapor exposure to form a cured layer;
Including said method.
2. Process-iv is the method of the preceding clause 1 performed by ionizing substance beam irradiation.
3. Process-iv is the method of the preceding clause 1 or 2 performed by plasma irradiation.
4). 4. The method according to any one of items 1 to 3, wherein the substrate is a kind selected from the group consisting of glass, metal, ceramic, and plastic.
5. 5. The method according to any one of items 1 to 4, wherein the substrate is a transparent substrate.
6). The member manufactured by the method of any one of the preceding clauses 1-5.
7). 7. The member according to 6 above, wherein the member is used for windows.
8). 7. The member according to 6 above, wherein the member is used for a vehicle window.

  According to the method of the present invention, it is possible to form a hardened layer having excellent wear resistance, which is suitable for scenes where there is a lot of physical irritation due to dust and the like, on a substrate without firing at a high temperature. The method of the present invention has an advantage that the substrate is prevented from being deteriorated by being exposed to a high temperature. The cured layer obtained by the method of the present invention has antifouling property due to the photocatalytic function in addition to excellent wear resistance.

  Hereinafter, the present invention will be described in detail.

  The present invention includes (step-i) to (step-iv).

<(Step-i) Step of Preparing Substrate>
Step-i is a step of preparing a substrate. The substrate is preferably one selected from the group consisting of glass, metal, ceramic and plastic.
The plastic is not particularly limited, and polyolefin resin such as polyethylene and polypropylene, amorphous polyolefin resin such as polydicyclopentadiene, acrylic resin such as polycarbonate resin and polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, poly (ethylene-2, 6-naphthalate), polystyrene resin, polyarylate, polyethersulfone, polyetheretherketone, polyimide, phenol resin, urea resin, and the like. Among them, polycarbonate resins having excellent transparency, acrylic resins such as polymethyl methacrylate, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, poly (ethylene-2,6-naphthalate), polystyrene, polypropylene, polyarylate, polyethersulfone Is preferred. Furthermore, a polycarbonate resin having a high impact strength is more preferable.
Although there is no restriction | limiting in particular in the thickness of a base | substrate, 0.05-20 mm is preferable and 1-10 mm is more preferable.

  In addition, when the substrate is a plastic, it is preferable that a hard coat layer is formed on the substrate because better wear resistance can be obtained. The hard coat agent used for the hard coat layer is not particularly limited, and examples thereof include a silicone resin hard coat agent and an organic resin hard coat agent. Among these, when a hard coat layer is formed using a hard coat agent containing colloidal silica or an alkoxysilane hydrolyzed condensate, a top coat layer using scaly metal oxide fine particles is formed on the surface of the hard coat layer. In that case, since particularly excellent wear resistance is obtained. The silicone resin hard coat agent can be selected from a so-called two-coat type composed of a primer layer and a top layer and a so-called one-coat type formed from only one layer. The thickness of the hard coat layer is preferably 2 to 30 μm, more preferably 3 to 20 μm, still more preferably 4 to 10 μm. Above the lower limit, the wear resistance of the substrate is obtained, and below the upper limit, curing unevenness hardly occurs and the adhesion to the substrate is good.

  The surface of the hard coat layer is usually water-repellent and often repels the nanosheet dispersion liquid as it is. For this reason, it is preferable to apply the nanosheet dispersion liquid after hydrophilizing the hard coat layer surface. Examples of the method for hydrophilizing the hard coat layer surface include cerium oxide polishing, corona discharge treatment, burner treatment, atmospheric pressure plasma treatment, and vacuum ultraviolet irradiation treatment. By treating the surface of the hard coat layer by such a method, the top coat layer can be coated to a uniform thickness. Further, it is preferable to control the deposition direction of the topcoat layer by controlling the hydrophilicity.

<(Process-ii) Application process>
Step-ii is a step of forming a coating layer by applying a scale-like metal oxide fine particle dispersion on a substrate.
Scale-like metal oxide fine particles (hereinafter sometimes referred to as nanosheets) are sheet-like metal oxide fine particles having a high aspect ratio that is only 10 nm in thickness.

The nanosheet dispersion is a dispersion in which a sheet-like substance having a minimum width of 10 nm or more, a thickness of 10 nm or less, and a minimum width / thickness of 10 or more is dispersed in a solvent, and a mineral crystal is treated with a delamination substance and a dispersant. It is prepared with. The solvent to be used is not particularly limited, but water and alcohols such as methanol, ethanol, 2-propanol and 2-methyl-1-propanol, and ketones such as acetone, 2-butanone and 4-methyl-2-pentanone. , Ethers such as diethyl ether, tetrahydrofuran and dioxolane, ether alcohols such as 2-ethoxyethanol and 1-methoxy-2-propanol, dimethylformamide, dimethyl sulfoxide and the like are preferable, and water is particularly preferably used. These solvents may be used alone or in combination of two or more.
The concentration of the nanosheet in the nanosheet dispersion is preferably 0.01 to 10%, more preferably 0.1 to 2%. Nanosheets can be coated without gaps by using a dispersion with a concentration above the lower limit (depending on the surface condition of the substrate and the coating method), and it is appropriate to use a dispersion with a concentration below the upper limit. A nanosheet layer having a thickness can be obtained.

The nanosheet dispersion can be obtained by adding delamination and dispersion stabilizers such as amines to a mineral that takes layered crystals such as mica, and crushing and stirring. At this time, the delamination and dispersion stabilizer are coordinated on both surfaces of the nanosheet to prevent the nanosheets from being bonded again.
The nanosheet layer prepared by applying and drying such a dispersion is in a state where the amine used for separation and dispersion stability remains between the nanosheets. By applying energy to such a nanosheet, the substances between the nanosheets are removed to ensure close contact between the nanosheets and between the nanosheet and the substrate, and to perform a phase transition of the nanosheet crystal phase to ensure a necessary function.
There are no particular restrictions on the coating method of the nanosheet dispersion, and methods such as bar coating, dip coating, flow coating, spray coating, spin coating, and roller coating can be used depending on the shape of the substrate to be coated. It can be selected appropriately.

It is excellent that the scaly metal oxide fine particles have at least one element selected from the group consisting of Ti, Nb, Al, Si, W, Fe, Mn, Cr, Ca, and Mg as a constituent element. It is preferable from the point that abrasion resistance is obtained. Furthermore, when imparting antifouling property, an element having photocatalytic properties is used as a constituent element. By using scale-like metal oxide fine particles composed of such constituent elements, energy in the valence band is excited to the conduction band by absorption of energy (such as ultraviolet light) corresponding to the band gap. Holes (holes: h ⁺ ), which are shells of slag, generate electrons (e ⁻ ) in the conduction band. These electrons and holes react with water and oxygen on the surface of titanium oxide to generate radicals having extremely strong oxidizing power, and the radicals decompose almost all organic substances constituting dirt and bacteria. In addition, structural changes occur due to absorption of ultraviolet light, and the surface becomes highly hydrophilic so that dirt can be easily washed away with water. By such an action, a surface from which dirt can be easily removed is formed by irradiation with ultraviolet light. Among the constituent elements, Ti and Nb are preferable because they are excellent in photocatalytic property, have a superhydrophilic surface, and are excellent in antifouling property.

When the constituent element is Ti, for example, scaly metal oxide fine particles obtained by ion exchange and delamination of layered titanates such as potassium titanate, potassium magnesium titanate, and cesium titanate can be suitably used. . Furthermore, nanosheets synthesized from cesium titanate having a lipidocrocite structure (Cs _0.7 Ti _1.825 □ _0.175 O ₄ , □ are vacancies) have a plate-like structure with a large aspect ratio. In addition, since it is excellent in dispersibility, it is particularly preferable for forming a good-quality coat film. When the constituent element is Nb, scaly metal oxide fine particles obtained by ion exchange and delamination of layered potassium niobate represented by the composition formula KNb ₃ O ₈ or K ₄ Nb ₆ O ₁₇ are preferably used. be able to. In particular, the nanosheet represented by the composition [Nb ₃ O ₈ ] ⁻ has a highly symmetric structure, does not roll up into a roll shape, and maintains a stable sheet structure. Is particularly good at getting.

<(Process-iii) Drying process>
Step-iii is a step of drying the coating layer to form a dry layer. The drying is not particularly limited, but is performed by heating and removing at a temperature from room temperature to a temperature lower than the heat distortion temperature of the substrate.

<(Process-iv) Curing process>
Step-iv is a step of curing the scaly metal oxide fine particles in the dry layer to form a hardened layer. Curing is performed by at least one method selected from the group consisting of ionizing substance beam irradiation, ionizing radiation irradiation, infrared irradiation, microwave irradiation, and high-temperature water vapor exposure.

(Curing by ionizing radiation)
The ionizing material beam is a general term for the radiation of ionizing substances such as plasma, ions, and electrons. Since ionizing substances have a charge, their state can be controlled by an electric field, and high energy is locally applied. It is preferable because it can be added automatically. The plasma (state) refers to a state in which a substance is separated and freely moved into ions and electrons, and free electrons and ions in that state. The plasma state is generally formed at a high temperature or in a discharge environment, and is formed by performing glow discharge under vacuum, Townsend discharge, discharge by a high-frequency power source under atmospheric pressure, arc discharge at high temperature, or the like. Among them, low-temperature plasma generated by glow discharge or Townsend discharge under vacuum is characterized by extremely large differences in the temperature of carrier gas ions and the temperature of electrons, and it applies high energy to the surface while suppressing the temperature rise of the substrate. Is particularly preferable.

The type of plasma forming gas is not particularly limited, and examples include noble gases such as helium, neon, argon, and xenon, hydrogen, nitrogen, oxygen, carbon dioxide, etc., and noble gases such as helium, neon, argon, and xenon, and oxygen. It is preferable for maintaining the performance of the nanosheet.
The plasma formation is usually preferably performed under a pressure of 0.001 to 1000 Pa, more preferably 0.01 to 20 Pa, still more preferably 0.01 to 10 Pa, and particularly preferably 0.1 to 5 Pa. Above the lower limit, it is preferable because a plasma discharge state can be stably formed, and below the upper limit, it is preferable because the proportion of plasma particles having energy necessary for curing the nanosheet is increased. Although it depends on the size of the device and the capacity of the vacuum pump to be used, it cannot be generally stated, but in order to realize such a pressure, plasma forming gas is usually about 0.01 to 3 sccm per 1 cm ² of electrode as the gas flow rate. be introduced.
The glow discharge that is generally performed to form a plasma state is preferable because it can normally stably discharge at a state of 0.4 to 10 Pa, and the discharge state is stable at 0.001 to 1000 Pa by devising the apparatus. Maintained. The gas pressure and input power related to the plasma state both affect the amount of free electrons and the kinetic energy of each free electron, the gas pressure greatly affects the number of free electrons, and the input power greatly affects the total amount of free electrons. To do. For the same input power, the lower the gas pressure, the smaller the number of free electrons, and the greater the energy of individual free electrons.

When the nanosheet is irradiated with plasma, free electrons collide with the nanosheet to cause hardening of the nanosheet and transmit the energy to the substrate to cause an increase in temperature of the substrate. The greater the energy of individual free electrons, the more advantageous for curing the nanosheet, and the smaller the total energy of free electrons, the more advantageous for suppressing the rise in substrate temperature.
When the gas pressure is 5 Pa or less and the input power is 0.4 W / cm ² or more, the kinetic energy of each free electron becomes a preferable kinetic energy for curing the nanosheet, and the temperature rise of the substrate is suppressed by the input power of 5 W / cm ² or less. Is preferable. Further, by setting the gas pressure to 0.4 to 5 Pa, glow discharge can be performed in the range of input power of 0.1 to 5 W / cm ² . The range of the gas pressure and input power is preferable because the nanosheet can be efficiently cured while suppressing the temperature rise of the substrate.
The longer the plasma irradiation time is, the more the nanosheet is cured and is preferable. However, since the temperature of the substrate continues to rise during the plasma irradiation, it is necessary to set the plasma irradiation time within a range that the heat resistance of the substrate allows. The time during which plasma irradiation is possible depends on the gas pressure and the input power. For example, in the case of a gas pressure of 0.5 Pa and an input power of 1 W / cm ² , if the time is from 5 minutes to 10 minutes, It is preferable because the curing can proceed efficiently.

(Curing by ionizing radiation)
Ionizing radiation refers to radiation that has the effect of generating electrons and secondary electrons by colliding with a substance to blow off electrons from the substance. Specifically, ultraviolet rays, X rays, γ rays, neutron rays, electrons Wire, ion beam and the like. It has a very large energy, as can be seen from flipping electrons from the material, and this energy can remove the intercalation ligands and phase transition of the nanosheets by a different action from thermal vibration. It is preferable that the nanosheet can be cured while being suppressed.

(Curing by infrared irradiation)
Curing by infrared irradiation is preferable because the nanosheet is locally heated for a short time by applying vibration energy in the form of electromagnetic waves, so that the nanosheet can be cured while suppressing the temperature rise of the substrate. If laser light is used, it is possible to narrow the beam diameter from that of a normal infrared lamp.

(Curing by microwave irradiation)
In the microwave irradiation method, the nanosheet itself can be vibrated by resonance with the microwave, so that the nanosheet can be heated without transferring heat to the substrate, so that the nanosheet can be cured while suppressing the temperature rise of the substrate. This is preferable.

(Curing by exposure to high temperature steam)
Curing by exposure to high-temperature steam is preferable because high-temperature water molecules are sprayed so that heating occurs only at the portions where the water molecules collide and the temperature rise of the entire substrate is suppressed. Further, it is preferable because water molecules have an effect of removing amine-based ligands and becoming a catalyst for phase rearrangement.
Among these curing methods, ionizing substance beam irradiation is preferable from the viewpoint of suppressing the temperature rise of the substrate, and plasma irradiation is particularly preferable.
On the other hand, the thickness of the topcoat layer is preferably 3 to 100 nm after curing, more preferably 4 to 30 nm, and particularly preferably 5 to 20 nm. When the thickness of the topcoat layer is not less than the lower limit, it is preferable because the abrasion resistance is excellent, and when the thickness is not more than the upper limit, the topcoat layer can be sufficiently fixed.

  Hereinafter, although an example is given and explained in detail, the present invention is not limited to this unless it exceeds the purpose. In addition, evaluation in an Example and a comparative example followed the following method.

<Evaluation>
(1) Appearance The coat layer appearance (existence of foreign matter) of the test piece, the presence or absence of cracks (cracks), and the state of the base layer were visually confirmed. A case where the appearance was good was marked as ◯, and a case where the appearance was bad was marked as x.
(2) Adhesion 100 grids with a 1 mm interval are made on the coating layer with a knife, and a Nichiban adhesive tape (trade name “Serotape” (registered trademark)) is pressure-bonded, peeled off vertically and left on the substrate. It was evaluated by the number of round grids (conforming to JIS K5600-5-6).
(3) Pencil hardness A pencil was set at an angle of 45 ° with respect to the test piece, and the appearance was checked to see if the scratched test piece was scratched while pressing the pencil with a load of 750 g. The hardness of the hardest pencil that was not scratched was defined as the pencil hardness of the test piece (in accordance with JIS K5600-5-4).
(4) Steel wool hardness (SW)
A steel wool having a roughness of # 0000 was attached to a circular jig having a diameter of 1 mm, and it was reciprocated 20 times at a width of 5 cm in the front and back with a 1 kg load, and the degree of scratching was visually evaluated in the following five stages.
5: No scratch at all.
4: 1 to 5 scratches within 3 mm in length 3: 6 to 20 scratches within 3 mm in length 2: 20 to 50 scratches 1: 50 or more scratches (5) Abrasion resistance Using a wear wheel of CS-10F manufactured by Calibrase, a 1000-rotor Taber abrasion test was performed at a load of 500 g, and a difference ΔHt between the haze after the Taber abrasion test and the haze before the Taber abrasion test was measured and evaluated (ASTM D1044).
(Haze = Td / Tt × 100, Td: scattered light transmittance, Tt: total light transmittance)
(6) Water contact angle measurement after light irradiation After irradiating the test piece with 1 mW / cm ² ultraviolet light for 1 hour, the contact angle of the water droplet was measured using a contact angle meter (Dropmaster M-301, manufactured by Kyowa Interface Science). It was measured.

<I. Sample preparation for hard coat layer>
Reference Example 1 Preparation of Acrylic Primer Coating Agent (A-1) Equipped with a reflux condenser and a stirrer, 79.9 parts of ethyl methacrylate (hereinafter abbreviated as EMA) and cyclohexyl methacrylate (hereinafter referred to as CHMA) in a flask purged with nitrogen. 33.6 parts, 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA) 13.0 parts, methyl isobutyl ketone 126.6 parts (hereinafter abbreviated as MIBK) and 2-butanol (hereinafter referred to as 2-BuOH) (Omitted) 63.3 parts were added and mixed. The mixture was deoxygenated by bubbling nitrogen gas for 15 minutes, then heated to 70 ° C. under a nitrogen gas stream, 0.33 parts of azobisisobutyronitrile (hereinafter abbreviated as AIBN) was added, and nitrogen gas was added. The reaction was carried out in an air stream at 70 ° C. with stirring for 5 hours. Further, 0.08 part of AIBN was added, the temperature was raised to 80 ° C., and the mixture was reacted for 3 hours to obtain an acrylic copolymer solution (A) having a nonvolatile content concentration of 39.6%. The weight average molecular weight of the acrylic copolymer was 125,000 in terms of polystyrene from the measurement of GPC (column; Shodex GPCA-804, eluent: THF).
To 100 parts of the resulting acrylic copolymer solution (A), 43.2 parts of methyl isobutyl ketone, 21.6 parts of 2-butanol, and 83.5 parts of 1-methoxy-2-propanol were added and mixed, and tinuvin 400 (BASF Co., Ltd. triazine ultraviolet absorber) 5.3 parts, VESTANAT B1358 so that the isocyanate group becomes 1.0 equivalent with respect to 1 equivalent of the hydroxy group of the acrylic copolymer in the acrylic resin solution (A). / 100 (Degussa Japan Co., Ltd. Polyisocyanate Compound Precursor) 10.6 parts, 0.015 parts dimethyldineodecanoate tin is added and stirred at 25 ° C. for 1 hour, acrylic primer coat Agent (A-1) was obtained.

(Reference Example 2) Preparation of silicone resin hard coat agent (I-1) Water-dispersed colloidal silica dispersion (catalyst SN-35, produced by Catalytic Chemical Industry Co., Ltd., solid content concentration: 30% by weight) 1.3 parts of hydrochloric acid was added and stirred well. The dispersion was cooled to 10 ° C., and 162 parts of methyltrimethoxysilane was added dropwise with cooling in an ice-water bath. Immediately after the addition of methyltrimethoxysilane, the temperature of the mixture started to increase due to the reaction heat, and after 5 minutes from the start of the addition, the temperature rose to 60 ° C., and then the temperature of the mixture gradually decreased due to the cooling effect. The mixture was stirred at 30 ° C. for 10 hours so that the temperature of the mixed solution reached 30 ° C., and 0.8 parts of a methanol solution having a choline concentration of 45% by weight as a curing catalyst was added thereto. As a mixture, 5 parts of acetic acid and 200 parts of 2-propanol as a diluting solvent were mixed to obtain a silicone resin hard coat agent (I-1).

(Reference Example 3) Preparation of UV-curable acrylate hard coat agent (I-2) 100 parts of polyfunctional acrylate oligomer (Shin Nakamura Chemical Co., Ltd. U-15HA), phenyl-1-hydroxycyclohexyl ketone (BASF Corp.) 7 parts of Irgacure 184), 250 parts of 1-methoxy-2-propanol, 100 parts of 2-propanol, 50 parts of organic solvent-dispersed colloidal silica (IPA-ST solid content concentration 30%, manufactured by Nissan Chemical Industries, Ltd.) An ultraviolet curable acrylate hard coat agent (I-2) was obtained.

(Reference Example 4) Preparation of Melamine Resin Hard Coating Agent (I-3) 100 parts of hexamethoxymethylol melamine (Simel 350 manufactured by Mitsui Chemicals, Inc.), 25 parts of polyethylene glycol (molecular weight 200), 45 of 1,4-butanediol 45 Parts, isopropyl alcohol 118 parts, isobutanol 244 parts, maleic acid 7 parts, 2,4-dihydroxybenzophenone 6 parts were mixed to obtain a melamine resin hard coat agent (I-3).

<II. Sample preparation for topcoat layer>
Reference Example 5 Preparation of titania nanosheet coating agent (II-1) Cesium carbonate and titanium oxide were mixed at a molar ratio of 1: 5.3, and baked twice at 800 ° C. for 20 hours. A series of treatments of stirring, filtering and drying the produced cesium titanate in dilute hydrochloric acid was repeated four times to obtain layered titanic acid in which cesium ions were replaced with hydrogen ions. To this was added an aqueous tetrabutylammonium hydroxide solution as a delamination agent, stirred for 14 days, and then diluted with pure water to prepare a titania nanosheet aqueous dispersion having a solid content concentration of 3% by weight. The obtained titania nanosheet aqueous dispersion was diluted with ethanol to obtain a titania nanosheet coating agent (II-1) having a solid content concentration of 0.3% by weight.
The coating agent (II-1) was further diluted with ethanol to 0.01% by weight and applied onto a quartz glass plate by a dip coating method at a pulling rate of 3 cm per second.
When the surface of the obtained test piece was observed with an atomic force microscope and the size and thickness were measured, the obtained nanosheet had a dimension in the plane direction of 10 to 50 μm and a thickness of 2 to 5 nm.

Reference Example 6 Preparation of Niobium Nano Sheet Coating Agent (II-2) Potassium nitrate and niobium oxide were mixed at a molar ratio of 1: 3 (K: Nb) and calcined at 600 ° C. for 2 hours. The powder was pulverized and mixed, fired again at 900 ° C. for 20 hours, and gradually cooled to obtain potassium niobate (KNb ₃ O ₈ ). The produced potassium niobate was suspended and stirred in 1 M nitric acid, and ion exchange was performed for 24 hours. The supernatant was removed by centrifugation, and then washed with pure water. This series of ion exchange treatment was repeated four times to obtain layered niobic acid in which potassium ions were replaced with hydrogen ions. To this was added a 3-methoxypropylamine aqueous solution as a delaminating agent, stirred for 14 days, and then diluted with pure water to prepare a niobium nanosheet aqueous dispersion having a solid content concentration of 3% by weight. The obtained niobium nanosheet aqueous dispersion was diluted with ethanol to obtain a niobium nanosheet coating agent (II-2) having a solid concentration of 1% by weight.
The coating agent (II-2) was further diluted with ethanol to 0.01% by weight and applied onto a quartz glass plate by a dip coating method at a pulling rate of 3 cm per second.
When the surface of the obtained specimen was observed with an atomic force microscope and the size and thickness were measured, the obtained nanosheet had a dimension in the plane direction of 20 to 50 μm and a thickness of 3 to 8 nm.

Reference Example 7 Preparation of Mica Nano Sheet Coating Agent (II-3) Potassium carbonate, silicon oxide, aluminum oxide and magnesium oxide were mixed at a molar ratio of 1: 4: 3: 3 and baked at 800 ° C. for 20 hours. Went. A series of treatments of stirring, filtering and drying the produced various mica in dilute hydrochloric acid was repeated 4 times to wash out excess potassium oxide, and a mica mixture in which potassium ions were replaced with hydrogen ions was obtained. To this was added an aqueous tetrabutylammonium hydrochloride solution as an interlayer release agent, and the mixture was stirred for 14 days, and then diluted with pure water to prepare a mica nanosheet aqueous dispersion having a solid content concentration of 6% by weight. The obtained mica nanosheet aqueous dispersion was diluted with 2-propanol to obtain a mica nanosheet coating agent (II-3) having a solid concentration of 0.5% by weight.
The coating agent (II-3) was further diluted with ethanol to 0.01% by weight and applied onto a quartz glass plate by a dip coating method at a pulling rate of 3 cm per second.
When the surface of the obtained specimen was observed with an atomic force microscope and the size and thickness were measured, the obtained nanosheet had a dimension in the plane direction of 20 to 80 μm and a thickness of 1 to 4 nm.

Example 1
The acrylic primer coating agent (A-1) obtained in Reference Example 1 was applied to a sheet made of polycarbonate resin (hereinafter abbreviated as PC resin) (PC-1111 sheet manufactured by Teijin Chemicals Ltd., 150 × 150 × 5 mm). The film was coated on both sides by a dip coating method so that the film thickness after thermosetting was 5.0 μm, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 130 ° C. for 1 hour.
Next, the silicone resin hard coat agent (I-1) obtained in Reference Example 2 was applied on the surface of the molded plate by a dip coating method so that the film thickness after thermosetting was 4.0 μm, After standing at 25 ° C. for 20 minutes, it was thermoset at 120 ° C. for 1 hour. The coated sheet surface was made hydrophilic by irradiating light (40 nW / cm ² ) from a xenon excimer lamp for 1 minute at a distance of 0.5 mm from the lamp.
Thereafter, the titania nanosheet coating agent (II-1) obtained in Reference Example 5 was applied by dip coating so that the film thickness after curing was 20 nm, and allowed to stand at 25 ° C. for 5 minutes. Plasma is generated with an electrode type plasma generator under the conditions of plasma carrier gas: argon gas, process vacuum 0.5 Pa, RF power source 13.56 MHz 3600 W, electrode area 3600 cm ² and irradiated on the surface of the coated molding plate for 7 minutes. Cured to obtain a polycarbonate resin laminate. When the temperature of the substrate at the end of curing was measured by a thermocouple attached to the substrate surface, it was 130 ° C. The evaluation results of the obtained laminate are shown in Table 1.

Example 2
A polycarbonate resin laminate is obtained in the same manner as in Example 1 except that the niobia nanosheet coating agent (II-2) obtained in Reference Example 6 is applied by dip coating so that the film thickness after curing is 15 nm. It was. The evaluation results of the obtained laminate are shown in Table 1.

Example 3
A polycarbonate resin laminate was obtained in the same manner as in Example 2 except that plasma was applied for 9 minutes. The evaluation results of the obtained laminate are shown in Table 1.

Example 4
The nanosheet coating agent is applied so that the film thickness after curing is 5 nm, and plasma is generated under the conditions of plasma carrier gas: argon gas, process vacuum degree 1.1 Pa, RF power source 13.56 MHz 3600 W, electrode area 3600 cm ^2. Then, a polycarbonate resin laminate was obtained in the same manner as in Example 2 except that the surface of the coated molded plate was cured by irradiation for 7 minutes. The evaluation results of the obtained laminate are shown in Table 1.

Example 5
A dip coating method in which the UV curable acrylate hard coating agent (I-2) obtained in Reference Example 3 is applied to a PC resin sheet (150 × 150 × 5 mm) so that the film thickness after curing is 5.0 μm. The same as in Example 2 except that the coating was applied on both sides and allowed to stand at 25 ° C. for 1 minute and 80 ° C. for 1 minute, and then cured by irradiating with a high-pressure mercury lamp so that the integrated illuminance was 600 mJ / cm ^2. Thus, a PC resin laminate was obtained. The evaluation results of the obtained laminate are shown in Table 1.

Example 6
A PC resin sheet (150 × 150 × 5 mm) was dried by pouring a methanol solution of 0.2% 2-aminoethanol to remove dirt on the surface and to expose functional groups on the surface. The melamine resin hard coat agent (I-3) obtained in Reference Example 4 was applied to the sheet by dip coating so that the film thickness after curing was 5.0 μm, and left at 25 ° C. for 20 minutes. Thereafter, a PC resin laminate was obtained in the same manner as in Example 2 except that it was thermally cured at 120 ° C. for 1 hour. The evaluation results of the obtained laminate are shown in Table 1.

Example 7
A polycarbonate resin laminate was obtained in the same manner as in Example 1 except that the mica nanosheet coating agent (II-3) obtained in Reference Example 7 was applied by dip coating so that the film thickness after curing was 10 nm. . The evaluation results of the obtained laminate are shown in Table 1.

Example 8
A silicone resin hard coat coated PC sheet was prepared in the same manner as in Example 1, and the surface of the coated sheet was made hydrophilic by irradiating it with a butane gas burner for 2 seconds.
Thereafter, the niobia nanosheet coating agent (II-2) obtained in Reference Example 6 was applied by a dip coating method so that the film thickness after immobilization was 15 nm, and allowed to stand at 25 ° C. for 5 minutes. The nanosheet was cured by passing through a condensing lamp house equipped with two halogen infrared lamps at a speed of 5 m / min to obtain a PC resin laminate.
The evaluation results of the obtained laminate are shown in Table 1. In the condensing type lamp house, it was possible to condense up to a width of 5 cm by visual evaluation of the boundary between the bright part and the dark part. By allowing the sample to pass through the lamp at a speed of 5 m / min, the sample passes through the high temperature portion where the infrared rays are condensed for 0.6 seconds. At the infrared condensing point (line), the temperature of the stationary sample finally increased to 1000 ° C.

Example 9
A PC resin laminate was obtained in the same manner as in Example 9 except that the titania nanosheet coating agent (II-1) was applied by dip coating so that the film thickness after immobilization was 20 nm. The evaluation results of the obtained laminate are shown in Table 1.

Example 10
A silicone resin hard coat coated PC sheet was prepared in the same manner as in Example 1, and the surface of the coated sheet was irradiated with irradiation light (40 nW / cm ² ) from a xenon excimer lamp at a distance of 0.5 mm from the lamp for 30 seconds. Hydrophilized.
Thereafter, the titania nanosheet coating agent (II-1) was applied by dip coating so that the film thickness after immobilization was 20 nm, allowed to stand at 25 ° C. for 5 minutes, and then 10 mW / cm ² using an ArF excimer lamp. The PC resin laminate was obtained by irradiating with vacuum ultraviolet rays for 10 minutes under the conditions described above and fixing. The evaluation results of the obtained laminate are shown in Table 1.

Example 11
Except that the PC resin sheet (150 × 150 × 5 mm) of Example 6 was changed to a sheet (150 × 150 × 2 mm) made of polymethylmethacrylate resin (PMMA, Mitsubishi Rayon Co., Ltd. Dialite L) A plastic laminate was obtained in the same manner as in Example 6. The evaluation results of the obtained laminate are shown in Table 1.

Example 12
A plastic laminate was obtained in the same manner as in Example 6 except that the PC resin sheet (150 × 150 × 5 mm) in Example 6 was changed to a sheet (150 × 150 × 1 mm) made of polyethylene resin (PE). . The evaluation results of the obtained laminate are shown in Table 1. Since the polyethylene resin is opaque, a Taber abrasion test was not performed, but it was confirmed by steel wool hardness evaluation that excellent abrasion resistance was obtained.

Example 13
Example except that the PC resin sheet (150 × 150 × 5 mm) of Example 3 was changed to a sheet (150 × 150 × 1 mm) made of polyethersulfone resin (PES, Sumika Excel manufactured by Sumitomo Chemical Co., Ltd.) 3 to obtain a plastic laminate. The evaluation results of the obtained laminate are shown in Table 1.

Example 14
The niobium nanosheet coating agent (II-2) obtained in Reference Example 6 was applied to a glass plate (150 × 150 × 3 mm) by dip coating so that the film thickness after curing was 15 nm. A glass laminate was obtained under similar plasma irradiation conditions. The evaluation results of the obtained laminate are shown in Table 1. The evaluation results are shown in Table 1. The adhesion test was not performed because it was not possible to scratch the grid with a cutter knife on the glass plate.

Example 15
After washing the copper plate (150 × 150 × 3 mm) with 0.1M oxalic acid and then with pure water, the thickness of the niobium nanosheet coating agent (II-2) obtained in Reference Example 6 is 15 nm after curing. Was applied by dip coating, and a copper laminate was obtained under the same plasma irradiation conditions as in Example 1. Table 1 shows the results of measuring the steel wool hardness (SW) of the obtained copper laminate. Moreover, after leaving the obtained copper laminated body in a 60 degreeC95% RH environment for 2 weeks, it took out and observed the external appearance. The original metallic luster was maintained and no change in appearance was observed.

Example 16
After washing the copper plate (150 × 150 × 3 mm) with 0.1M oxalic acid and then with pure water, the niobium nanosheet coating agent (II-2) obtained in Reference Example 6 was cured to have a film thickness of 20 nm. A plasma is generated under the conditions of plasma carrier gas: argon gas, process vacuum 0.5 Pa, RF power source 13.56 MHz 1800 W, electrode area 3600 cm ² and irradiated on the surface of the coated stainless steel plate for 20 minutes. And cured to obtain a copper laminate. Table 1 shows the results of measuring the steel wool hardness of the obtained copper laminate. Moreover, after leaving the obtained copper laminated body in a 60 degreeC95% RH environment for 2 weeks, it took out and observed the external appearance. The original metallic luster was maintained and no change in appearance was observed.

Examples 17-24
A PC resin laminate was obtained in the same manner as in Example 1 except that plasma irradiation was performed under the conditions shown in Table 1. The evaluation results of the obtained laminate are shown in Table 1.

Comparative Example 1
Each evaluation result of the PC resin sheet (150 × 150 × 5 mm) is shown in Table 1.

Comparative Example 2
Acrylic primer coating agent (A-1) is coated on both sides of a PC resin sheet (150 × 150 × 5 mm) by a dip coating method so that the film thickness after thermosetting is 5.0 μm, and 20 minutes at 25 ° C. After standing, it was thermoset at 130 ° C. for 1 hour. Next, the silicone resin hard coat agent (I-1) obtained in Reference Example 2 was applied on the surface of the molded plate by a dip coating method so that the film thickness after thermosetting was 4.0 μm, After standing at 25 ° C. for 20 minutes, thermosetting was performed at 120 ° C. for 1 hour to obtain a PC resin laminate. The evaluation results of the obtained laminate are shown in Table 1.

Comparative Example 3
The copper plate (150 × 150 × 3 mm) was washed with 0.1 M oxalic acid and then with pure water to remove surface impurities. The results of measuring steel wool hardness are shown in Table 1. The copper plate was left in an environment of 60 ° C. and 95% RH for 2 weeks, and then taken out and observed for appearance. As a result, corrosion progressed, the metallic luster was lost, and the color turned greenish blue.

Comparative Example 4
Acrylic primer coating agent (A-1) is coated on both sides of a PC resin sheet (150 × 150 × 5 mm) by a dip coating method so that the film thickness after thermosetting is 5.0 μm, and 20 minutes at 25 ° C. After standing, it was thermoset at 130 ° C. for 1 hour. Next, the silicone resin hard coat agent (I-1) obtained in Reference Example 2 was applied on the surface of the molded plate by a dip coating method so that the film thickness after thermosetting was 4.0 μm, The mixture was allowed to stand at 25 ° C. for 20 minutes and then dried at 120 ° C. for 1 hour. The surface of the coated sheet was made hydrophilic by irradiating light (40 nW / cm ² ) from a xenon excimer lamp at a distance of 0.5 mm from the lamp for 30 seconds.
Thereafter, the niobia nanosheet coating agent (II-2) was applied by a dip coating method so that the film thickness after immobilization was 15 nm, and allowed to stand at 25 ° C. for 5 minutes to obtain a PC resin laminate. The niobia nanosheet was not immobilized on the hard coat layer and could be easily removed by wiping with a cloth. In the evaluation of wear resistance, the nanosheet layer was easily peeled off and removed, so that the performance of the underlying hard coat layer was reflected as it was. The evaluation results of the obtained laminate are shown in Table 1.

Comparative Example 5
Acrylic primer coating agent (A-1) is coated on both sides of a PC resin sheet (150 × 150 × 5 mm) by a dip coating method so that the film thickness after thermosetting is 5.0 μm, and 20 minutes at 25 ° C. After standing, it was thermoset at 130 ° C. for 1 hour. Next, the silicone resin hard coat agent (I-1) obtained in Reference Example 2 was applied on the surface of the molded plate by a dip coating method so that the film thickness after thermosetting was 4.0 μm, After standing at 25 ° C. for 20 minutes, it was thermoset at 120 ° C. for 1 hour. The surface of the coated sheet was made hydrophilic by irradiating light (40 nW / cm ² ) from a xenon excimer lamp at a distance of 0.5 mm from the lamp for 30 seconds.
Thereafter, the niobium nanosheet coating agent (II-2) was applied by dip coating so that the film thickness after immobilization was 15 nm, allowed to stand at 25 ° C. for 5 minutes, and then in an electric furnace at 400 ° C. for 2 minutes. Heated. During heating, the water in the PC resin was rapidly vaporized and foamed.

The method of curing a layer comprising scaly metal oxide fine particles on the substrate of the present invention can impart extremely high wear resistance and excellent antifouling property to the hard coat-coated plastic. Therefore, aircraft, vehicle, automobile window, construction machine window, building, house, garage, greenhouse, arcade window, headlight lens, optical lens, mirror, glasses, goggles, sound insulation wall, traffic light lens, It can be suitably used for curved mirrors, windshields, nameplates, other various sheets, films and the like.

Claims (8)

A method of forming a cured layer containing scaly metal oxide fine particles on a substrate,
(Step-i) a step of preparing a substrate,
(Step-ii) A step of applying a scaly metal oxide fine particle dispersion on a substrate to form a coating layer,
(Step-iii) Step of drying the coating layer to form a dry layer, and (Step-iv) Scale-like metal oxide fine particles in the dry layer are irradiated with ionizing substance beam, ionizing radiation, infrared irradiation, micro A step of curing by at least one method selected from the group consisting of wave irradiation and high-temperature water vapor exposure to form a cured layer;
Including said method.   The method according to claim 1, wherein step-iv is performed by ionizing substance beam irradiation.   The method according to claim 1, wherein step-iv is performed by plasma irradiation.   The method according to any one of claims 1 to 3, wherein the substrate is one kind selected from the group consisting of glass, metal, ceramic, and plastic.   The method according to any one of claims 1 to 4, wherein the substrate is a transparent substrate.   The member manufactured by the method as described in any one of Claims 1-5.   The member according to claim 6, wherein the member is used for a window.   The member according to claim 6, wherein the member is used for a vehicle window.