JP5919027B2 - Process for producing plastic laminate for curing scale-like metal oxide fine particles - Google Patents

Description

  The present invention relates to a plastic laminate for curing scaly metal oxide fine particles. More specifically, the present invention relates to a plastic laminate in which a hard coat layer that has been subjected to a hydrophilic treatment is formed on a plastic substrate layer, which provides excellent abrasion resistance and antifouling properties when the scaly metal oxide fine particles are cured. is there.

Plastics are excellent in terms of lightness, moldability, and the like, and are used in various fields such as automobile parts, home appliance parts, housings, containers, films, and sheets. Especially for transparent plastics, it is used for various windows, optical lenses, mirrors, glasses, goggles, sound insulation walls, traffic light lenses, headlight lenses, curve mirrors, windshields, nameplates, etc., where glass has been used. . However, the plastic substrate has insufficient surface wear resistance, and is easily scratched during use, resulting in a problem that the mechanical properties deteriorate due to the scratch. In addition, since many plastics have a lipophilic surface, they have a problem of being easily soiled.
In order to compensate for this drawback, a plastic laminate in which a hard coat layer made of melamine resin, siloxane resin, (meth) acrylic resin or the like is formed on the surface of the plastic substrate layer has been proposed (for example, Patent Document 1). ). However, the wear resistance suitable for scenes with many physical irritation caused by dust and the like is not sufficient, and further improvement has been demanded. Moreover, it was still a problem about being easy to get dirty.

On the other hand, scale-like titanium oxide fine particles (titania nanosheets) are included on the surface of the base layer for the purpose of obtaining excellent antifouling properties and having hardness suitable for scenes where there is a lot of physical irritation caused by sand dust. A laminate in which a coating agent is fired has been proposed (for example, Patent Document 2). However, according to this patent document, the hardness of nanosheets varies greatly depending on the firing temperature, and sufficient hardness is not exhibited unless firing at 400 ° C. or higher. It was unclear whether soiling could be obtained.
On the other hand, in a hard coat film in which a hard coat layer and a function-imparting layer are laminated in this order on a transparent base film, a hard coat film in which a hydrophilic treatment is performed on the surface of the hard coat layer has been proposed. (For example, patent document 3). However, the purpose of applying a hydrophilic treatment on the surface of the hard coat layer is to eliminate the occurrence of repellency of the function-imparting layer and the adhesion problem between the resin layers, and it is excellent when a specific hard coat agent is used. It was unclear whether the hardness and antifouling property could be obtained.
Therefore, there is still a plastic laminate in which a hard coat layer formed with a hydrophilic treatment is formed on a plastic substrate layer, which provides excellent wear resistance and antifouling properties when the scaly metal oxide fine particles are cured. The current situation is not.

International Publication No. 2007-105741 Pamphlet JP 2005-290369 A JP 2003-326649 A

An object of the present invention is to provide a hard coat layer that has been subjected to a hydrophilic treatment on a plastic substrate layer, whereby excellent abrasion resistance and antifouling properties can be obtained by forming a layer on which scale-like metal oxide fine particles are cured. It is in providing the manufacturing method of the laminated body in which this was formed.

According to the present invention, the above problem is solved by the following configuration.
1 . (I) A hard coat layer is formed on the plastic substrate layer with a hard coat agent in which the colloidal silica and / or alkoxysilane hydrolysis condensate is 30% by weight or more based on the total weight of the hard coat excluding the solvent,
(Ii) The formed hard coat layer is subjected to a hydrophilic treatment by irradiation with vacuum ultraviolet rays.
Including each step,
A method for producing a plastic laminate for curing flaky metal oxide fine particles having a water contact angle of a hard coat layer of 30 ° or less.
2 . 2. The manufacturing method according to item 1 , wherein the plastic substrate layer is made of a transparent plastic.
3 . 3. The method according to item 1 or 2 , wherein the plastic substrate layer is made of a polycarbonate resin.
4 . The manufacturing method according to any one of the preceding items 1 to 3 , wherein the plastic laminate is a material for forming a window member.
5 . The manufacturing method according to any one of the preceding items 1 to 4 , wherein the plastic laminate is a material for forming a vehicle window member.
6 . Flaky metallic oxide particles, the minimum width 10nm or more, the thickness 10nm or less, the production method according to any one of items 1 to 5 is smallest width / thickness 10 or more.

Plastic laminate obtained by the production method of the present invention, flaky metal oxide excellent wear resistance and antifouling property and curing the particles is obtained thereon. Therefore, the industrial effect that it plays is exceptional.

  Hereinafter, the present invention will be described in detail.

<About hard coat layer>
The hard coat layer used in the present invention is formed on a plastic substrate. As the hard coat agent used in the hard coat layer, a hard coat agent in which colloidal silica and / or alkoxysilane hydrolysis condensate is 30% by weight or more based on the total weight of the hard coat agent excluding the solvent is used. The colloidal silica and / or alkoxysilane hydrolysis condensate is preferably 50% by weight or more, and more preferably 70% by weight. Above the lower limit, it is preferable because excellent antifouling properties and abrasion resistance can be obtained when the scaly metal oxide fine particles containing an element having metal catalytic properties as a constituent element are cured on the hard coat layer.

The scaly metal oxide fine particles themselves have a charge, and since they have a structure having a M—O—H group on the surface, they have a high affinity with Si—O—H. Therefore, it is presumed that the scale-like metal oxide fine particles are excellent in orientation and the antifouling property is improved.
The hard coat agent in which the colloidal silica and / or alkoxysilane hydrolysis condensate is 30% by weight or more can be obtained by mixing an organic solvent-dispersed colloidal silica with a silicone resin hard coat agent or an organic resin hard coat agent. .

The silicone resin hard coat agent forms a cured resin layer having a siloxane bond. For example, partial hydrolysis of a compound mainly composed of a compound corresponding to a trifunctional siloxane unit (trialkoxysilane compound, etc.). Condensates, preferably partially hydrolyzed condensates containing compounds corresponding to tetrafunctional siloxane units (tetraalkoxysilane compounds, etc.), and partially hydrolyzed condensates further filled with metal oxide fine particles such as colloidal silica Is mentioned. The silicone resin hard coat agent may further contain a bifunctional siloxane unit and a monofunctional siloxane unit. These include alcohols generated during the condensation reaction (in the case of a partially hydrolyzed condensate of alkoxysilane), etc., but if necessary, may be dissolved or dispersed in any organic solvent, water, or a mixture thereof. Good. Examples of the organic solvent for this purpose include lower fatty acid alcohols, polyhydric alcohols and ethers thereof, and esters. In addition, in order to obtain a smooth surface state, various surfactants such as siloxane-based and alkyl fluoride-based surfactants may be added to the hard coat layer.
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.

  Examples of the resin that forms such a primer layer (first layer) include urethane resins, acrylic resins, polyester resins, epoxy resins, melamine resins, amino resins, and polyester acrylates, urethane acrylates, and epoxy resins, which are composed of various blocked isocyanate components and polyol components Various polyfunctional acrylic resins such as acrylate, phosphazene acrylate, melamine acrylate, amino acrylate and the like can be mentioned, and these can be used alone or in combination of two or more. Among these, an acrylic resin and a polyfunctional acrylic resin preferably include 50% by weight, more preferably 60% by weight or more, and those composed of an acrylic resin and a urethane acrylate are particularly preferable. These can be applied either by applying a predetermined reaction after application of an unreacted material to obtain a cured resin, or by directly applying the reacted resin to form a cured resin layer. In the latter case, the resin is usually dissolved in a solvent to form a solution, which is then applied and then the solvent is removed. In the former case, a solvent is generally used.

Examples of the organic resin hard coat agent include melamine resin, urethane resin, alkyd resin, acrylic resin, or polyfunctional acrylic resin. Here, examples of the polyfunctional acrylic resin include resins such as polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate, and phosphazene acrylate.
In addition, the resin that forms the hard coat layer includes a light stabilizer, an ultraviolet absorber, a catalyst, a thermal / photopolymerization initiator, a polymerization inhibitor, an antifoaming agent, a leveling agent, a thickening agent, a suspending agent, a sag. Inhibitors, flame retardants, organic / inorganic pigments / dyes, various additives and additive aids can be included.

As a coating method, a method such as a bar coating method, a dip coating method, a flow coating method, a spray coating method, a spin coating method, or a roller coating method is appropriately selected according to the shape of a molded body that is a base material to be coated. be able to.
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.

<Hydrophilicity of hard coat layer>
Hydrophilizing the surface of the hard coat layer is performed by vacuum ultraviolet irradiation. By treating the surface of the hard coat layer in a way this, the water contact angle of the hard coat layer to 30 ° or less. The water contact angle is preferably 20 ° or less, and more preferably 10 ° or less. Below the upper limit, when the scaly metal oxide fine particles are cured, excellent wear resistance and antifouling properties are obtained.

<About scaly metal oxide fine particles>
In the present invention, scaly metal oxide fine particles (hereinafter sometimes referred to as nanosheets) are sheet-like metal oxide fine particles having a high aspect ratio of less than 10 nm in thickness. Although the formation method in particular of a topcoat layer is not restrict | limited, It passes through the application | coating process of a nanosheet dispersion liquid, a drying process, and an immobilization process.

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. Can be selected as appropriate. After the nanosheet is applied, the solvent is dried and removed at a temperature from room temperature to a temperature lower than the heat distortion temperature of the substrate, and then fixed. Fixing is preferably performed at 200 ° C. or lower because excellent wear resistance and appearance can be obtained even if the base material is plastic. Furthermore, it is preferable to perform curing 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 because of excellent wear resistance.
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.
The thickness of the nanosheet 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 nanosheet layer is not less than the lower limit, it is preferable because the wear resistance is excellent, and when the thickness is not more than the upper limit, the nanosheet layer can be sufficiently fixed.

In addition, the scale-like metal oxide fine particles have a photocatalytic element as a constituent element particularly when imparting antifouling properties. 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.

<About plastic substrate layer>
The plastic substrate layer used in the present invention is a molded product of a plastic substrate and preferably has a thickness of 0.05 to 20 mm, preferably 1 to 10 mm. The plastic substrate 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) and the like, polystyrene, polyarylate, polyethersulfone, polyetheretherketone, polyimide, phenolic 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.

  The polycarbonate resin is not only bisphenol A type polycarbonate but also high heat resistance or low water absorption polycarbonate resin polymerized using other dihydric phenols, and high heat resistance polymerized using aliphatic diol. Various polycarbonate resins may be used. The polycarbonate resin may be produced by any production method, and in the case of interfacial polycondensation, a terminal stopper of a monohydric phenol is usually used. The polycarbonate resin may also be a branched polycarbonate resin obtained by polymerizing trifunctional phenols, and further a copolymer obtained by copolymerizing an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, or a divalent aliphatic or alicyclic alcohol. Polycarbonate may be used. When the viscosity average molecular weight of the polycarbonate resin is in the range of 13,000 to 40,000, it can be applied to a wide range of fields. When the viscosity average molecular weight is less than 20,000, it is excellent in fluidity and suitable for a complicated shape or a large resin molded product (for example, a back door window) among vehicle resin windows, and the viscosity average molecular weight is 20,000 or more. If it exists, it will be excellent in strength and suitable for general resin windows for vehicles. In the resin window for vehicles, which is a preferred application of the present invention, it is necessary to select a molecular weight in accordance with the intended molded product. Since the resin plate of the present invention is thick, distortion at the time of molding is within an allowable limit even at a relatively high molecular weight. The upper limit of the viscosity average molecular weight is more preferably 35,000, still more preferably 30,000 from the viewpoint of versatility.

  In addition, the viscosity average molecular weight should just be satisfied as the whole polycarbonate resin, and what satisfy | fills this range by 2 or more types of mixtures from which molecular weight differs is included. In particular, mixing of a polycarbonate having a viscosity average molecular weight exceeding 50,000 (more preferably 80,000 or more, more preferably 100,000 or more) may be advantageous in terms of increasing entropy elasticity at the time of melting. For example, the present invention is effective in suppressing jetting. The effect of improving the entropy elasticity becomes more prominent as the molecular weight of the polycarbonate is higher, but the upper limit of the molecular weight is practically 2 million, preferably 300,000, more preferably 200,000. When such a polycarbonate resin is blended in an amount of 0.5 to 20% by weight, preferably 1 to 10% by weight, a predetermined effect can be obtained without particularly impairing moldability.

The viscosity average molecular weight (M) of the polycarbonate resin is obtained by inserting the specific viscosity (η _sp ) obtained at 20 ° C. from a solution of 0.7 g of the polycarbonate resin in 100 ml of methylene chloride into the following equation. Details of the polycarbonate resin are described in, for example, JP-A-2002-129003.
η _sp /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7
As specific examples of various polycarbonate resins polymerized using other dihydric phenols and having high heat resistance or low water absorption, the following can be suitably exemplified.

  (1) In 100 mol% of the dihydric phenol component constituting the polycarbonate, 4,4 '-(m-phenylenediisopropylidene) diphenol (hereinafter abbreviated as "BPM") component is 20 to 80 mol% (more preferable) 40 to 75 mol%, more preferably 45 to 65 mol%), and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter abbreviated as "BCF") component is 20 to 20 mol. Copolycarbonate which is 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).

  (2) In 100 mol% of the dihydric phenol component constituting the polycarbonate, the bisphenol A component is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%), And a BCF component in an amount of 5 to 90 mol% (more preferably 10 to 50 mol%, and still more preferably 15 to 40 mol%).

  (3) In 100 mol% of the dihydric phenol component constituting the polycarbonate, the BPM component is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%), and The 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane component is 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%). Copolycarbonate.

  (4) In 100 mol% of the dihydric phenol component constituting the polycarbonate, 2,2-bis (4-hydroxy-3-methylphenyl) propane (hereinafter abbreviated as "bisphenol C") component is 40 to 90 mol% ( More preferably, it is 50 to 80 mol%) and the bisphenol A component is 10 to 60 mol% (more preferably 20 to 50 mol%).

On the other hand, specific examples of various heat-resistant polycarbonate resins polymerized using an aliphatic diol include polycarbonates in which the aliphatic diol constituting the polycarbonate is isosorbide, isomannide, or isoidide. Of these, isosorbide (1,4; 3,6-dianhydro-D-sorbitol) is particularly preferable because of its ease of production and excellent heat resistance.
These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used.
The production methods and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.

  Said thermoplastic resin can contain conventionally well-known various additives in the range which does not impair said transparency. Examples of such additives include heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, colorants, mold release agents, sliding agents, infrared absorbers, light diffusing agents, fluorescent whitening agents, and antistatic agents. Examples include agents, flame retardants, flame retardant aids, plasticizers, reinforcing fillers, impact modifiers, photocatalytic antifouling agents, and photochromic agents. The heat stabilizer, the antioxidant, the ultraviolet absorber, the light stabilizer, the colorant, the release agent, and the like can be blended with known appropriate amounts in the above thermoplastic resins.

  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 of hard coat layer>
(1) Water contact angle measurement The water contact angle of the hard coat layer whose surface was hydrophilized was measured using a contact angle meter (Dropmaster M-301, manufactured by Kyowa Interface Science).

<Evaluation after scaly metal oxide fine particle curing>
(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.) 8 parts of Irgacure 184), 250 parts of 1-methoxy-2-propanol, 100 parts of 2-propanol, 360 parts of organic solvent-dispersed colloidal silica (Nissan Chemical Industry Co., Ltd. IPA-ST solid content concentration 30%) An ultraviolet curable acrylate hard coat agent (I-2) was obtained.

(Reference Example 4) Preparation of UV-curable acrylate hard coat agent (I-3) 100 parts of polyfunctional acrylate oligomer (Shin Nakamura Chemical Co., Ltd. U-15HA), phenyl-1-hydroxycyclohexyl ketone (BASF Corp.) 5 parts of Irgacure 184), 250 parts of 1-methoxy-2-propanol, 100 parts of 2-propanol, 150 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-3) was obtained.

(Reference Example 5) Preparation of UV-curable acrylate hard coat agent (I-4) 100 parts of polyfunctional acrylate oligomer (U-15HA manufactured by Shin-Nakamura Chemical Co., Ltd.), phenyl-1-hydroxycyclohexyl ketone (BASF Corporation) 5 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-4) was obtained.

(Reference Example 6) Preparation of melamine resin hard coat agent (I-5) 100 parts of hexamethoxymethylol melamine (Simel 350 manufactured by Mitsui Chemicals, Inc.), 25 parts of polyethylene glycol (molecular weight 200), 1,4-butanediol 45 Parts, 118 parts of isopropyl alcohol, 244 parts of isobutanol, 7 parts of maleic acid and 6 parts of 2,4-dihydroxybenzophenone were mixed to obtain a melamine resin hard coat agent (I-5).

<II. Preparation of sample used for scale-like metal oxide fine particle hardened layer (nanosheet layer)>
Reference Example 7 Preparation of Niobia Nano Sheet Coating Agent (II-1) 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-1) having a solid concentration of 1% 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 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 8) Preparation of titania nanosheet coating agent (II-2) Cesium carbonate and titanium oxide were mixed at a molar ratio of 1: 5.3, and calcination was performed 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-2) having a solid concentration of 0.3% 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 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.

Example 1
The acrylic primer coating agent (A-1) obtained in Reference Example 1 was added to a sheet made of polycarbonate resin (hereinafter abbreviated as PC resin) (PC-1111 sheet 150 × 150 × 5 mm manufactured by Teijin Chemicals Ltd.) Both surfaces were applied by a dip coating method so that the film thickness after thermosetting was 5.0 μm, left 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 hydrophilized by irradiating light (40 nW / cm ² ) from a xenon excimer lamp at a distance of 0.5 mm from the lamp for 1 minute (VUV irradiation).
Thereafter, the niobia nanosheet coating agent (II-1) obtained in Reference Example 7 was applied by dip coating so that the film thickness after curing was 15 nm, and allowed to stand at 25 ° C. for 5 minutes, and then capacitively coupled. Plasma is generated by an internal 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. And 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 was obtained in the same manner as in Example 1 except that the irradiation time of the irradiation light (40 nW / cm ² ) from the xenon excimer lamp was changed to 20 seconds. The evaluation results of the obtained laminate are shown in Table 1.

Example 3
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 1 except that both surfaces were coated by 1 and left to stand at 25 ° C. for 1 minute and at 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 4
Example except that the PC resin sheet (150 × 150 × 5 mm) in Example 1 was changed to a sheet (150 × 150 × 1 mm) made of polyethersulfone resin (PES, Sumika Excel manufactured by Sumitomo Chemical Co., Ltd.) 1 to obtain a plastic laminate. 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-3) obtained in Reference Example 4 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 1 except that both surfaces were coated by 1 and left to stand at 25 ° C. for 1 minute and at 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
The acrylic primer coating agent (A-1) obtained in Reference Example 1 was added to a sheet made of polycarbonate resin (hereinafter abbreviated as PC resin) (PC-1111 sheet 150 × 150 × 5 mm manufactured by Teijin Chemicals Ltd.) Both surfaces were applied by a dip coating method so that the film thickness after thermosetting was 5.0 μm, left 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-2) obtained in Reference Example 8 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.

Comparative Example 1
A dip coating method in which the UV curable acrylate hard coating agent (I-4) obtained in Reference Example 5 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 3 except that the coating was applied on both sides and allowed to stand at 25 ° C. for 1 minute and at 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.

Comparative Example 2
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-5) obtained in Reference Example 6 was applied to the sheet by a dip coating method 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 1 except that heat curing was performed at 120 ° C. for 1 hour. The evaluation results of the obtained laminate are shown in Table 1.

Comparative Example 3
A polycarbonate resin laminate in the same manner as in Comparative Example 1, except that the irradiation light (40 nW / cm ² ) from the xenon excimer lamp was irradiated for 1 minute at a distance of 0.5 mm from the lamp and the surface was not hydrophilized. Got. The evaluation results of the obtained laminate are shown in Table 1.

Comparative Example 4
A polycarbonate resin laminate in the same manner as in Comparative Example 2 except that the irradiation light (40 nW / cm ² ) from the xenon excimer lamp was irradiated for 1 minute at a distance of 0.5 mm from the lamp to make the surface hydrophilic. Got. The evaluation results of the obtained laminate are shown in Table 1.

Comparative Example 5
Without forming a hard coat layer on a PC resin sheet (150 × 150 × 5 mm), a nanosheet layer was formed under the same conditions as in Example 1 to obtain a polycarbonate resin laminate. The evaluation results of the obtained laminate are shown in Table 1.

Comparative Example 6
Instead of irradiating light (40 nW / cm ² ) from a xenon excimer lamp at a distance of 0.5 mm from the lamp for 1 minute, the surface was made hydrophilic by thoroughly polishing with a 2.5% cerium oxide aqueous dispersion. Obtained a polycarbonate resin laminate in the same manner as in Example 1. The evaluation results of the obtained laminate are shown in Table 1.

The plastic laminate obtained by the production method of the present invention has excellent wear resistance and antifouling properties when the scaly metal oxide fine particles are cured thereon. 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 (6)

(I) A hard coat layer is formed on the plastic substrate layer with a hard coat agent in which the colloidal silica and / or alkoxysilane hydrolysis condensate is 30% by weight or more based on the total weight of the hard coat excluding the solvent,
(Ii) The formed hard coat layer is subjected to a hydrophilic treatment by irradiation with vacuum ultraviolet rays.
Including each step,
A method for producing a plastic laminate for curing flaky metal oxide fine particles having a water contact angle of a hard coat layer of 30 ° or less. The manufacturing method according to claim 1 , wherein the plastic substrate layer is made of a transparent plastic. Plastic substrate layer, the manufacturing method according to claim 1 or 2 made of a polycarbonate resin. The manufacturing method according to any one of claims 1 to 3 , wherein the plastic laminate is a material for forming a window member. The manufacturing method according to any one of claims 1 to 4 , wherein the plastic laminate is a material for forming a vehicle window member. The production method according to any one of claims 1 to 5 , wherein the scaly metal oxide fine particles have a shortest width of 10 nm or more, a thickness of 10 nm or less, and a shortest width / thickness of 10 or more.