WO2014062652A1

WO2014062652A1 - Vehicle member

Info

Publication number: WO2014062652A1
Application number: PCT/US2013/065003
Authority: WO
Inventors: Naota SUGIYAMA; Yorinobu Takamatsu; Saori Ueda; Haruyuki Mikami; Jiro Hattori; Hidemi NAKABAYASHI; Akira Nakamura
Original assignee: 3M Innovative Properties Company
Priority date: 2012-10-17
Filing date: 2013-10-15
Publication date: 2014-04-24
Also published as: JP2014079974A

Abstract

A vehicle member comprising: a substrate layer having a first surface and a second surface on an opposite side as the first surface, and a hard coat layer disposed on the first surface of the substrate layer; the hard coat layer containing a nanoparticle mixture and a binder; the nanoparticles constituting from 40 to 95 mass% of the entire mass of the hard coat layer; from 10 to 50 mass% of the nanoparticles having an average particle size in a range of 2 to 200 nm; from 50 to 90 mass% of the nanoparticles having an average particle size in a range of 60 to 400 nm; and a ratio of the average particle size of the nanoparticles having the average particle size in the range of 60 to 400 nm to the average particle size of the nanoparticles having the average particle size in the range of 2 to 200 nm being in a range of 2:1 to 200:1.

Description

VEHICLE MEMBER

Field of the Invention

The present disclosure relates to vehicles, and in particular to a vehicle member.

Background

Various members are used on the interiors and exteriors of vehicles such as two- wheeled vehicles or automobiles. Although the performance required for each member differs depending on the function or purpose thereof, resistance to scratching due to sand, wiping with a cloth or the like, or fingernails is commonly required for each member. Therefore, scratch resistance is typically imparted by performing hard coat treatment on the surface of a member.

Hard coat materials containing Si0₂ nanoparticles modified by a photocurable silane coupling agent are described in U.S. Patent Nos. 5104929 and 7074463.

There is also a strong demand to impart the surfaces of vehicle members used on the exterior, in particular, with anti-smudge properties. Hard coat materials having anti-smudge properties and having an easily washable surface obtained by curing a polymerizable composition containing a fluorine compound having a hexafluoropropylene oxide site are described in U.S. Patent No. 7718264 and U.S. Patent Application Publication No.

2008/0124555.

Summary of the Invention

An object of the present disclosure is to provide a vehicle member with excellent scratch resistance.

In one aspect of the present invention, a vehicle member is provided that includes: a substrate layer having a first surface and a second surface on an opposite side as the first surface, and a hard coat layer disposed on the first surface of the substrate layer; the hard coat layer containing a nanoparticle mixture and a binder; the nanoparticles constituting from 40 to 95 mass% of the entire mass of the hard coat layer; from 10 to 50 mass% of the nanoparticles having an average particle size in a range of 2 to 200 nm; from 50 to 90 mass% of the nanoparticles having an average particle size in a range of 60 to 400 nm; and a ratio of the average particle size of the nanoparticles having the average particle size in the range of 60 to 400 nm to the average particle size of the nanoparticles having the average particle size in the range of 2 to 200 nm being in a range of 2: 1 to 200: 1.

With the present invention, it is possible to provide a vehicle member with excellent scratch resistance. Further, with the vehicle member of the present invention, it is possible to provide a vehicle member with excellent impact resistance. In addition, with the vehicle member of the present invention, it is possible to provide a vehicle member with excellent anti- fogging properties. Note that the description above should not be considered as a complete disclosure of all embodiments of the present invention or of the advantages related to the present invention.

Detailed Description

The present invention will be described in further detail hereinafter with the purpose of illustrating representative embodiments of the present invention, but the present invention is not limited to these embodiments.

In the present disclosure, "(meth)acrylic" refers to "acrylic or methacrylic", and "(meth)acrylate" refers to "acrylate or methacrylate".

The vehicle member of the present disclosure has a substrate layer and a hard coat layer.

The substrate layer has a first surface and a second surface on the opposite side as the first surface, and the hard coat layer is disposed on the first surface.

A rigid material or a flexible material may be used as the substrate layer. A "rigid material" refers to a material that cannot undergo mechanical stress such as bending or stretching without significant irreversible change, and a "flexible material" refers to a material that can undergo mechanical stress such as bending or stretching without significant irreversible change.

Examples of rigid materials include plastics (polymer plates), sheet glass, metallic sheets, and the like. The rigid material may be transparent or opaque. As used herein,

"transparent" indicates that total transmittance is 90% or more and "opaque" indicates that total transmittance is not more than 90%.

Examples of the plastic (polymer plate) include those made of polycarbonate (PC), polymethyl methacrylate (PMMA), styrene-acrylonitrile copolymers, acrylonitrile butadiene styrene copolymer (ABS), a blend of PC and PMMA, or a laminate of PC and PMMA.

Examples of metallic sheets include steel sheets, aluminum sheets, nickel sheets, nickel-chromium sheets, stainless steel sheets, and the like. These sheets may be applied by coating or metal vapor deposition.

An example of a flexible material is a film. Films may be transparent or opaque.

Examples of representative films include those made of polycarbonate, poly(meth)acrylate (e.g., polymethyl methacrylate (PMMA), polyolefins (e.g., polypropylene (PP)), polyurethane, polyesters (e.g., polyethylene terephthalate (PET)), polyamides, polyimides, phenolic resins, cellulose diacetate, cellulose triacetate, polystyrene, styrene-acrylonitrile copolymers, acrylonitrile butadiene styrene copolymer (ABS), epoxies, polyethylene, polyacetate and vinyl chloride, or glass. These films may be subjected to metal vapor deposition with aluminum, tin, or the like.

In addition, a multi-layer optical film (also called an "MOF" hereafter) comprising layers of two different types of alternately laminated materials, a metal thin-film laminated film, or the like may be used as the substrate layer. Examples of multi-layer optical films that can be used include those described in U.S. Patent Nos. 3610724, 3711 176, 4446305, 4540623, 5448404, 5882774, 6045894, and 6531230, International Publication No. 99/39224, and U.S. Patent Application Publication No.

2001/0022982.

The multi-layer optical film may contain two different types of alternately laminated polymer layers. In several embodiments, at least one type of the alternately laminated polymer layers has birefringence. In several embodiments, one of the alternately laminated polymer layers has birefringence, and the other polymer layer has isotropy. In some embodiments, the multi-layer optical film can be formed by alternately laminating layers of a first polymer such as polyethylene terephthalate (PET) or a polyethylene terephthalate copolymer (coPET), for example, and a second polymer such as poly(methyl methacrylate) (PMMA) or a poly(methyl methacrylate) (PMMA) copolymer (coPMMA), for example. In other embodiments, the multilayer optical film can be formed by alternately laminating layers of a first polymer such as polyethylene terephthalate (PET), for example, and a second polymer such as a poly(methyl methacrylate-ethyl acrylate) copolymer, for example. In other embodiments, the multi-layer optical film can be formed by alternately laminating layers of a first polymer such as glycol- modified polyethylene terephthalate or a glycol-modified polyethylene terephthalate copolymer (coPETG), for example, and a second polymer such as polyethylene naphthalate (PEN) or a polyethylene naphthalate copolymer (coPEN), for example. In other embodiments, the multi- layer optical film can be formed by alternately laminating layers of a first polymer such as polyethylene naphthalate (PEN) or a polyethylene naphthalate copolymer (coPEN), for example, and a second polymer such as poly(methyl methacrylate) (PMMA) or a poly(methyl

methacrylate) copolymer (coPMMA), for example. Examples of useful combinations of polymer layers are described in U.S. Patent No. 6352761.

A film formed by laminating a metal thin-film layer on a film such as a polyolefin (for example, polyethylene (PE), polypropylene (PP), or the like), polyurethane, polyester (for example, polyethylene terephthalate (PET) or the like), poly(meth)acrylate (for example, polymethyl methacrylate (PMMA) or the like), or polyvinyl chloride may be used as the metal thin-film laminated film. The metal thin-film layer may contain materials such as aluminum, silver, copper, gold, nickel, or stainless steel and may be formed by laminating a foil produced by thinly rolling these materials on a film or depositing these materials on the surface of a film by vacuum deposition, ionization deposition, sputtering, ion plating, or the like. It is preferable to use a metal thin film containing aluminum, silver, or copper having high infrared reflectivity, and it is advantageous to use aluminum due to its low cost.

The thickness of the metal thin-film layer should be a thickness such that the layer reflects light of the target wavelength region from the visible light region to the infrared region (from 380 to 2500 nm or higher) of the sunlight spectrum and is typically in a range of approximately 10 to 300 nm (from approximately 20 to 200 nm in several embodiments). The substrate layer may further contain a decorative layer such as a printed layer having a desired pattern, a coloring layer, a metal thin-film layer, or a metal flake (metallic) layer, as necessary. The decorative layer can impart the vehicle member with a design.

The vehicle member may further contain a junction layer. Known rubber, acrylic, polyurethane, polyolefin, polyester, and silicone adhesives or pressure-sensitive adhesives can be used as junction layers. Of these, acrylic pressure-sensitive adhesives and silicone pressure- sensitive adhesives are preferable. The junction layer may be formed by directly applying an adhesive or a pressure-sensitive adhesive to the substrate layer, or the junction layer formed by coating an adhesive or a pressure-sensitive adhesive on a release liner or the like and laminating and transferring the junction layer onto the substrate layer.

The thickness of the junction layer is typically in a range of approximately 1 to 100 μηι. The junction layer may also contain known additives such as ultraviolet absorbers.

By using a layer of a silicone rubber having good wettability and very low adhesive strength as a junction layer, it is possible to obtain a vehicle member which can be easily attached and has excellent repositioning properties (properties enabling the member to be reapplied after being peeled). The layer described in Japanese Unexamined Patent Application Publication No. 201 1 - 183742 can be used as such a silicone rubber layer.

The silicone rubber layer can be formed, for example, by applying a mixture of a silicone main component containing a reactive polydimethylsiloxane or the like, a crosslinking agent, and a curing catalyst to the substrate layer and then curing the layer. Three types of combinations of the silicone main component, crosslinking agent, and curing catalyst can be suggested, for example: (i) a condensation type (humidity curing type) using a

polydimethylsiloxane containing a terminal hydroxyl group and/or a copolymer of a

polydimethylsiloxane and a polydiphenylsiloxane as the silicone main component, a

multifunctional alkoxysilane-type crosslinking agent as the crosslinking agent, and dibutyl tin dilaurate or the like as the curing catalyst; (ii) an additive type using a polydimethylsiloxane containing a vinyl group and/or a copolymer of a polydimethylsiloxane and a

polydiphenylsiloxane or the like as the silicone main component, a siloxane-type crosslinking agent containing Si-H or the like as the crosslinking agent, and a platinum catalyst or the like as the curing catalyst; and (iii) a silicone polyurea type using a polydimethylsiloxane containing a terminal amino group and/or a copolymer of a polydimethylsiloxane and a polydiphenylsiloxane or the like as the silicone main component, a crosslinking agent containing a polyisocyanate group or the like as the crosslinking agent, and dibutyl tin dilaurate or the like as the catalyst.

The weight average molecular weight of the silicone main component is typically in a range of approximately 50,000 to 2 million (from approximately 100,000 to 1 million or from approximately 300,000 to 500,000 in several embodiments). The compounding ratio of the silicone main component and the crosslinking agent can be determined so that the gel percentage of the silicone rubber layer after curing is at least approximately 90%, at least approximately 95%, or at least approximately 98%. The amount of the curing catalyst that is used is typically in a range of approximately 0.0001 to 3.0 mass% (from approximately 0.00015 to 2.0 mass% or from approximately 0.001 to 1.0 mass% in several embodiments) of the mass of the silicone main component in the case of a condensation type or silicone polyurea type layer, and within a range of approximately 1.0 to 100 ppm (from approximately 2.0 to 90 ppm or from

approximately 5.0 to 80 ppm in several embodiments) of the mass of the silicone main component in the case of an additive type layer.

The thickness of the silicone rubber layer should be such that the vehicle member does not peel away from the adherend due to its own weight and is in a range of approximately 2.0 to 30 μηι (from approximately 3.0 to 25 μηι or from approximately 5.0 to 20 μηι in several embodiments).

In several embodiments, the surface of the substrate layer is primed or a primer layer is disposed on the surface of the substrate layer in order to improve the adhesion of the hard coat layer and the substrate layer. In particular, when the substrate layer is a film with poor adhesiveness such as polypropylene, polyvinyl chloride, or the like, priming or a primer layer is particularly effective.

Priming is known in this technical field, and examples include plasma treatment, corona discharge treatment, flame treatment, electron beam irradiation, surface roughening, ozone treatment, chemical oxide treatment using chromic acid or sulfuric acid, and the like.

Examples of materials used for the primer layer include (meth)acrylic resins

(homopolymers of (meth)acrylates, copolymers of two or more types of (meth)acrylates, or copolymers of (meth)acrylates and other polymerizable monomers), urethane resins (for example, 2-solution curable urethane resins consisting of a polyol and an isocyanate curing agent), (meth)acryl-urethane copolymers (for example, acryl-urethane block copolymers), polyester resins, butyral resins, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl acetate copolymers, chlorinated polyolefins such as chlorinated polyethylenes or chlorinated polypropylenes, and copolymers and derivatives thereof (for example, chlorinated ethylene-propylene copolymers, chlorinated ethylene-vinyl acetate copolymers, acryl-modified chlorinated polypropylenes, maleic anhydride modified chlorinated polypropylenes, and urethane modified chlorinated polypropylenes), and the like. When the substrate layer is a polypropylene film, it is

advantageous for the primer layer to contain a chlorinated polypropylene or a modified chlorinated polypropylene.

The primer layer can be formed by applying a primer solution prepared by dissolving the aforementioned resins in a solvent using a known method in this technical field and then drying the solution. A thickness of the primer layer is typically within the range of

approximately 0.1 to 20 μηι (in several embodiments, from approximately 0.5 to 5 μηι).

Examples of representative binders contained in the hard coat layer include resins obtained by polymerizing a curable monomer and/or a curable oligomer and resins obtained by polymerizing sol-gel glass. More specific examples include acrylic resins, urethane resins, epoxy resins, phenol resins, and polyvinyl alcohol resins. Further, the curable monomer or curable oligomer can be selected from known curable monomers or curable oligomers in this technical field, and it is possible to use a mixture of two or more curable monomers, a mixture of two or more curable oligomers, or a mixture of one or two or more curable monomers and one or two or more curable oligomers. In several embodiments, examples of resins include dipentaerythritol pentaacrylate (available from the Sartomer Company (Exton, PA) under the product name "SR399", for example), pentaerythritol triacrylate isophorone diisocyanate (IPDI) (available from Nippon Kayaku Co., Ltd. (Tokyo Japan) under the product name "UX-5000", for example), urethane acrylate (available from Nippon Synthetic Chemical Industry Co., Ltd. (Osaka, Japan) under the product names "UV1700B" and "UB6300B", for example), trimethylhydroxyl diisocyanate/hydroxyethyl acrylate (TMHDI/HEA, available from the Daicel-Cytec Company, Ltd. (Tokyo Japan) under the product name "Ebecryl 4858", for example), polyethylene oxide (PEO) modified bis-A-diacrylate (available from the Nippon Kayaku Co., Ltd. (Tokyo Japan) under the product name "R551 ", for example), PEO modified bis-A-epoxy acrylate (available from Kyoeisha Chemical Co., Ltd. (Osaka, Japan) under the product name "3002M", for example), silane-based UV curable resins (available from the Nagase ChemteX Corporation (Osaka, Japan) under the product name "SK501M", for example), and 2-phenoxyethyl methacrylate (available from the Sartomer Company under the product name "SR340", for example), and compounds polymerized using these mixtures. For example, improvements in the adhesiveness to polycarbonates are observed when 2-phenoxyethyl methacrylate is used within the range of approximately 1.0 to 20 mass%. Simultaneous improvements in the hardness, impact resistance, and flexibility of the hard coat are observed when a difunctional resin (for example, PEO modified bis-A-diacrylate "R551 ") and trimethylhydroxyl

diisocyanate/hydroxyethyl acrylate (TMHDI/HEA) (available from the Daicel-Cytec Company, Ltd. under the product name "Ebecryl 4858", for example) are used.

The amount of the binder in the hard coat layer is typically from approximately 5 to 60 mass% and, in several embodiments, is from approximately 10 to 40 mass% or from

approximately 15 to 30 mass% of the total mass of the hard coat layer. With the present disclosure, it is possible to form a hard coat layer with a relatively small amount of a binder.

The hard coat layer may be further crosslinked with a crosslinking agent, as necessary. Examples of representative crosslinking agents include polyfunctional (meth)acrylic monomers and polyfunctional (meth)acrylic oligomers selected from a group comprising: (a) compounds having two (meth)acrylic groups such as 1,3-butylene glycol diacrylate, 1 ,4-butanediol diacrylate, 1 ,6-hexanediol diacrylate, 1 ,6-hexanediol monoacrylate monomethacrylate, ethylene glycol diacrylate, alkoxylated aliphatic diacrylate, alkoxylated cyclohexane dimethanol diacrylate, alkoxylated hexanediol diacrylate, alkoxylated neopentyl glycol diacrylate, caprolactone modified neopentyl glycol hydroxypivalate diacrylate, caprolactone modified neopentyl glycol hydroxypivalate diacrylate, cyclohexane dimethanol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, ethoxylated (10) bisphenol-A-diacrylate, ethoxylated (3) bisphenol-A-diacrylate, ethoxylated (30) bisphenol-A diacrylate, ethoxylated (4) bisphenol-A- diacrylate, hydroxypivalaldehyde modified trimethylol propane diacrylate, neopentyl glycol diacrylate, polyethylene glycol (200) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, propoxylated neopentyl glycol diacrylate, tetraethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, and the like; (b) compounds having three (meth)acrylic groups such as glycerol triacrylate, trimethylol propane triacrylate, ethoxylated triacrylate (for example, ethoxylated (3) trimethylol propane triacrylate, ethoxylated (6) trimethylol propane triacrylate, ethoxylated (9) trimethylol propane triacrylate, ethoxylated (20) trimethylol propane triacrylate, and the like), pentaerythritol triacrylate, propoxylated triacrylate (for example, propoxylated (3) glyceryl triacrylate, propoxylated (5.5) glyceryl triacrylate, propoxylated (3) trimethylol propane triacrylate, propoxylated (6) trimethylol propane triacrylate, and the like), trimethylol propane triacrylate, tris-(2-hydroxyethyl) isocyanurate triacrylate, and the like; (c) compounds having four (meth)acrylic groups such as ditrimethylol propane tetraacrylate, dipentaerythritol pentaacrylate, ethoxylated (4) pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexaacrylate, and the like; (d) oligomer (meth)acrylic compounds such as urethane acrylate, polyester acrylate, epoxy acrylate, and the like;

polyacrylamide analogs of the above; and combinations thereof. Such compounds are commercially available, and at least several of these compounds are available from the Sartomer Company, UCB Chemicals Corporation (Smyrna, GA), the Aldrich Chemical Company

(Milwaukee, WI), and the like. Examples of other useful (meth)acrylates include hydantoin portion-containing poly(meth)acrylates, such as are disclosed in U.S. Patent No. 4262072.

A preferred crosslinking agent comprises at least three (meth)acrylic groups.

Preferable commercially available crosslinking agents include those available from the Sartomer Company such as trimethylol propane triacrylate (TMPTA) (product name: "SR351 "), pentaerythritol tri/tetraacrylate (PETA) (product names: "SR444" and "SR295"), and dipentaerythritol pentaacrylate (product name: "SR399"). Further, mixtures of polyfunctional (meth)acrylates and monofunctional (meth)acrylates such as a mixture of PETA and 2- phenoxyethyl acrylate (PEA) can also be used. These preferable crosslinking agents can be used as curable monomers or curable oligomers.

The nanoparticle mixture contained in the hard coat layer constitutes from

approximately 40 to 95 mass% of the entire mass of the hard coat layer and, in several embodiments, constitutes from approximately 60 to 90 mass% or from approximately 70 to 85 mass% of the entire mass of the hard coat layer. The nanoparticle mixture contains from approximately 10 to 50 mass% of nanoparticles having an average particle size within the range of approximately 2 to 200 nm (hereafter called the small particle group or the first nanoparticle group) and from approximately 50 to 90 mass% of nanoparticles having an average particle size within the range of approximately 60 to 400 nm (hereafter called the large particle group or the second nanoparticle group). For example, the nanoparticle mixture may be obtained by mixing the first nanoparticle group with an average particle size of approximately 2 to 200 nm and the second nanoparticle group with an average particle size of approximately 60 to 400 nm at a mass ratio of approximately 10:90 to 50:50.

The average particle size of the nanoparticles can be measured with a transmission electron microscope (TEM) using technology commonly used in this technical field. In the measurement of the average particle size of the nanoparticles, a sol sample for a TEM image can be prepared by dripping a sol sample into a 400-mesh copper TEM grid having an ultra-thin carbon substrate on the upper surface of mesh lace-like carbon (available from Ted Pella Inc. (Redding, CA)). Some liquid droplets can be removed by bringing the droplets into contact with filter paper as well as the side or bottom portion of the grid. The remaining sol solvent can be removed by heating or allowing the solution to stand at room temperature. This allows the particles to rest on the ultra-thin carbon substrate and to be imaged with the least interference from the substrate. Next, the TEM image can be recorded at many positions spanning the entire grid. Sufficient images are recorded to enable the measurement of the particle sizes of 500 to 1000 particles. Next, the average particle size of the nanoparticles can be calculated based on the particle size measurements of each of the samples. TEM images can be obtained using a high- resolution transmission electron microscope (using an LaB₆ source) operating at 300 KV

(available from the Hitachi High-Technologies Corporation under the product name "Hitachi H- 9000"). The images can be recorded using a camera (available from Gatan, Inc. (Pleasanton, CA) under the product name "GATAN ULTRASCAN CCD", for example: model No. 895, 2k x 2k chip). The images can be taken at a magnification of 50,000 and 100,000 times. Images can be taken at a magnification of 300,000 times for several samples.

The nanoparticles are typically inorganic particles. Examples of inorganic particles include inorganic oxides such as alumina, tin oxide, antimony oxide, silica (SiO, Si0₂), zirconia, titania, ferrite, and the like, as well as mixtures thereof, or mixed oxides thereof; metal vanadate, metal tungstate, metal phosphate, metal nitrate, metal sulfate, metal carbide, and the like. An inorganic oxide sol can be used as inorganic oxide nanoparticles. In the case of silica nanoparticles, for example, a silica sol obtained using liquid glass (sodium silicate solution) as a starting material can be used. A silica sol obtained from liquid glass may have a very narrow particle size distribution depending on the manufacturing conditions; therefore, when such a silica sol is used, a hard coat layer having desired characteristics can be obtained by more accurately controlling the filling rate of nanoparticles in the hard coat layer.

The average particle size of the small particle group is within the range of

approximately 2 to 200 nm. The particle size is preferably from approximately 2 to 150 nm, from approximately 3 to 120 nm, or from approximately 5 to 100 nm. The average particle size of the large particle group is within the range of approximately 60 to 400 nm. The particle size is preferably from approximately 65 to 350 nm, from approximately 70 to 300 nm, or from approximately 75 to 200 nm.

The nanoparticle mixture contains a particle size distribution of at least two different types of nanoparticles. The particle size distribution of the nanoparticle mixture may exhibit bimodality or multimodality with peaks at the average particle size of the small particle group and the average particle size of the large particle group. In addition to the particle size distribution, the nanoparticles may be the same or different from one another (for example, surface-modified or not surface-modified compositionally). In several embodiments, a ratio of the average particle size of nanoparticles having an average particle size within the range of approximately 2 to 200 nm to the average particle size of nanoparticles having an average particle size within the range of approximately 60 to 400 nm is within the range of 2: 1 to 200: 1 and, in several embodiments, is within the range of 2.5: 1 to 100: 1 or 2.5: 1 to 25: 1. Examples of preferable combinations of average particle sizes include combinations of 5 nm/190 nm, 5 nm/75 nm, 20 nm/190 nm, 5 nm/20 nm, 20 nm/75 nm, 75 nm/190 nm, and 5 nm/20 nm/190 nm. By using a mixture of nanoparticles of different sizes, it is possible to fill the hard coat layer with a large amount of nanoparticles and thereby increase the hardness of the hard coat layer.

In addition, the transparency (haze or the like) and hardness can be varied by selecting the type, amount, size, and ratio of the nanoparticles, for example. In several embodiments, a hard coat layer having both a desired transparency and hardness can be obtained.

The mass ratio (%) of the small particle group and the large particle group can be selected in accordance with the particle size used or the combination of particle sizes used. A preferable mass ratio can be selected in accordance with the particle size used or the combination of particle sizes used by using software available under the product name "CALVOLD2" and can be selected based on a simulation between the mass ratio and filling rate of the small particle group and the large particle group for the combination of particle sizes (small particle group/large particle group), for example (see also "Verification of a Model for Estimating the Void Fraction in a Three-Component Randomly Packed Bed," M. Suzuki and T. Oshima:

Powder Technol., 43, 147-153 (1985)). The simulation results are illustrated in FIG. 2.

According to this simulation, the mass ratio (small particle group: large particle group) for a combination of 5 nm/190 nm is from approximately 45:55 to 13:87 or from approximately 40:60 to 15:85. The mass ratio for a combination of 5 nm/75 nm is preferably from approximately 45:55 to 10:90 or from approximately 35:65 to 15:85. The mass ratio for a combination of 20 nm/190 nm is preferably from approximately 45:55 to 10:90. The mass ratio for a combination of 5 nm/20 nm is preferably from approximately 50:50 to 20:80. The mass ratio for a combination of 20 nm/75 nm is preferably from approximately 50:50 to 22:78. The mass ratio for a combination of 75 nm/190 nm is preferably from approximately 50:50 to 27:73. In several embodiments, using a preferable combination of particle sizes and nanoparticles makes it possible to increase the amount of nanoparticles with which the hard coat layer is filled and to adjust the transparency and hardness of the resulting hard coat layer.

The thickness of the hard coat layer is typically within the range of approximately 80 nm to 30 μηι (in several embodiments, from approximately 200 nm to 20 μηι or from

approximately 1 to 10 μηι), however, the hard coat layer can sometimes be used effectively even when the thickness deviates from these ranges. Using a mixture of nanoparticles of different sizes sometimes makes it possible to obtain a hard coat layer with a greater thickness and higher hardness.

The surface of the nanoparticles may be modified using a surface treatment agent as necessary. A surface treatment agent typically has a first terminal bonding to the particle surface (via covalent bonds, ionic bonds, or strong physisorption) and a second terminal which gives the particles compatibility with resins and/or reacts with resins during curing. Examples of surface treatment agents include alcohols, amines, carboxylic acids, sulfonic acids, phosphonic acids, silanes, and titanates. The preferred type of surface treatment agent is determined, in part, by the chemical nature of the nanoparticle surface. When silica or another siliceous filler are used as nanoparticles, a silane is preferable. Silanes and carboxylic acids are preferred for metal oxides. Surface modification may be performed before, during, or after mixing with a curable monomer or a curable oligomer. When a silane is used, the reaction between the silane and the

nanoparticle surface is preferably performed before mixing with the curable monomer or the curable oligomer. The required amount of the surface treatment agent is determined by several factors such as the particle size and type of the nanoparticles and the molecular weight and type of the surface treatment agent. It is typically preferable for one layer of a surface treatment agent to be deposited onto the surface of the particles. The required deposition procedure or reaction conditions are also determined by the surface treatment agent that is used. When a silane is used, it is preferable to perform surface treatment for approximately 1 to 24 hours at a high

temperature under acidic or basic conditions. A high temperature or long period of time is typically unnecessary in the case of a surface treatment agent such as a carboxylic acid.

Representative examples of surface treatment agents include compounds such as isooctyltrimethoxysilane, polyalkyleneoxide alkoxysilane (available from Momentive Specialty Chemicals, Inc. (Columbus, OH) under the product name "SILQUEST A1230", for example), N- (3-triethoxysilyl propyl) methoxyethoxy ethoxyethyl carbamate, 3-(methacryloyloxy) propyl trimethoxysilane (available from Alfa Aesar (Ward Hill, MA) under the product name

"SILQUEST A174", for example), 3-(acryloyloxy) propyl trimethoxysilane, 3-(methacryloyloxy) propyl triethoxysilane, 3-(methacryloyloxy) propyl methyl dimethoxysilane, 3-(acryloyloxy) propyl methyl dimethoxysilane, 3-(methacryloyloxy) propyl dimethyl ethoxysilane, 3- (methacryloyloxy) propyl dimethyl ethoxysilane, vinyl dimethyl ethoxysilane, phenyl trimethoxysilane, n-octyl trimethoxysilane, dodecyl trimethoxysilane, octadecyl trimethoxysilane, propyl trimethoxysilane, hexyl trimethoxysilane, vinyl methyl diacetoxysilane, vinyl methyl diethoxysilane, vinyl triacetoxysilane, vinyl triethoxysilane, vinyl triisopropoxysilane, vinyl trimethoxysilane, vinyl triphenoxysilane, vinyl tri(t-butoxy) silane, vinyl tri(isobutoxy) silane, vinyl triisopropenoxysilane, vinyl tris-(2-methoxyethoxy) silane, styryl ethyl trimethoxysilane, mercapto propyl trimethoxysilane, 3-glycidoxy propyl trimethoxysilane, acrylic acid, methacrylic acid, oleic acid, stearic acid, dodecanoic acid, 2- [2-(2-methoxyethoxy)ethoxy] acetic acid (MEEAA), β-carboxyethyl acrylate, 2-(2-methoxyethoxy)acetic acid, and methoxy phenyl acetic acid and mixtures thereof.

The binder of the hard coat layer may further contain known additives such as an ultraviolet absorbent, an anti-smudge agent, an anti- fogging agent, a leveling agent, an ultraviolet reflecting agent, an anti-static agent, or the like, or another chemical which provides a function of facilitating cleaning as necessary.

In some embodiments, the anti-smudge agent is contained in the binder of the hard coat layer. Anti-smudge agents have been observed to improve the washability of the hard coat layer surface (for example, through prevention of adhesion of fingerprints, oil resistance, dust prevention, and/or anti-smudge functions). A fluorinated (meth)acrylic compound may be used as an anti-smudge agent. Examples of fluorinated (meth)acrylic compounds include the HFPO urethane acrylate or modified HFPO described in Japanese Unexamined Patent Application Publication No. 2008-538195. The fluorinated (meth)acrylic compound may be included in the binder of the hard coat layer as an unreacted fluorinated (meth)acrylic compound, as a reaction product resulting from a reaction with a curable monomer or a curable oligomer, or as a combination thereof. A silicone polyether acrylate (available from Evonic Goldschmidt GmbH (Essen, Germany) under the product name "TEGORAD2250", for example) can also be used as an anti-smudge agent.

In the present disclosure, HFPO refers to a perfluoroether site expressed by

F(CF(CF₃)CF₂0)_nCF(CF₃)- (n is from 2 to 15) and a compound containing such a perfluoroether site.

The anti-smudge agent is preferably a polyfunctional fluorinated (meth)acrylic compound. The polyfunctional fluorinated (meth)acrylic compound has a plurality of

(meth)acrylic groups and can therefore react with a curable monomer or a curable oligomer as a crosslinking agent or can interact non-covalently with functional groups contained in the binder in a plurality of sites. As a result, the durability of the anti-smudge properties can be increased. When a polyfunctional fluorinated (meth)acrylic compound is used as the anti-smudge agent, it may be possible to also increase scratch resistance by reducing the coefficient of friction of the hard coat layer surface. When a polyfunctional fluorinated (meth)acrylic compound having three or more (meth)acrylic groups is used, it is possible to further increase the durability of the anti- smudge properties. Since perfluoroether groups provide the hard coat layer with excellent anti-smudge properties, the polyfunctional fluorinated (meth)acrylic compound is preferably a perfluoroether compound having two or more (meth)acrylic groups.

The polyfunctional perfluoroether (meth)acrylates described in Japanese Unexamined Patent Application Publication No. 2008-538195 and Japanese Unexamined Patent Application

Publication No. 2008-527090, for example, can be used as perfluoroether compounds having two or more (meth)acrylic groups. Specific examples of such polyfunctional perfluoroether

(meth)acrylates include:

HFPO-C(0)N(H)CH(CH₂OC(0)CH=CH₂)₂;

HFPO-C(0)N(H)C(CH₂CH₃)(CH₂OC(0)CH=CH₂)₂;HFPO-C(0)NHC(CH₂OC(0)CH=CH₂)₃;

HFPO-C(0)N(CH₂CH₂OC(0)CH=CH₂)₂;

HFPO-C(0)NHCH₂CH₂N(C(0)CH=CH₂)CH₂OC(0)CH=CH₂;

HFPO-C(0)NHCH(CH₂OC(0)CH=CH₂)₂;

HFPO-C(0)NHC(CH₃)(CH₂OC(0)CH=CH₂)₂;

HFPO-C(0)NHC(CH₂CH₃)(CH₂OC(0)CH=CH₂)₂;

HFPO-C(0)NHCH₂CH(OC(0)CH=CH₂)CH₂OC(0)CH=CH₂;

HFPO-C(0)NHCH₂CH₂CH₂N(CH₂CH₂OC(0)CH=CH₂)₂;

HFPO-C(0)OCH₂C(CH₂OC(0)CH=CH₂)₃;

HFPO-C(0)NH(CH₂CH₂N(C(0)CH=CH₂))₄CH₂CH₂NC(0)-HFPO;

CH₂=CHC(0)OCH₂CH(OC(0)HFPO)CH₂OCH₂CH(OH)CH₂OCH₂CH(OC(0)HFPO)CH₂OCO CH=CH₂; and

HFPO-CH₂0-CH₂CH(OC(0)CH=CH₂)CH₂OC(0)CH=CH₂.

The polyfunctional perfluoropolyether (meth)acrylate described above can be synthesized, for example, via a first step of reacting a poly(hexafluoropropylene oxide) ester such as HFPO-C(0)OCH₃ or a poly(hexafluoropropylene oxide) acid halide: HFPO-C(0)F with a material containing at least three alcohols or primary or secondary amino groups to produce an HFPO-ester having an HFPO-amide polyol or polyamine, an HFPO-ester polyol or polyamine, an HFPO-amide, or a mixed amine and an alcohol group, and a second step of (meth)acrylating the alcohol group and/or amine group with a (meth)acryloyl halide, a (meth)acrylic acid anhydride, or a (meth)acrylic acid. Alternatively, the polyfunctional perfluoropolyether (meth)acrylate can be synthesized using a Michael-type addition reaction of a reactive perfluoroether such as an adduct of HFPO-C(0)N(H)CH₂CH₂CH₂N(H)CH₃ and trimethylol propane triacrylate (TMPTA) and a poly(meth)acrylate.

A preferable polyfunctional fluorinated (meth)acrylic compound is one in which the perfluoroether site is divalent and (meth)acrylic groups bond with both terminals directly or via other groups or bonds (ether bonds, ester bonds, amide bonds, urethane bonds, or the like). Although not bound by any particular theory, it is thought that such a compound forms a firm bond with the hard coat layer so as to improve the durability of the anti-smudge properties, and the perfluoroether site between (meth)acrylic groups migrates to the hard coat layer surface so as to be easily oriented in the in-plane direction. As a result, it may be possible to sufficiently express anti-smudge properties.

The polyfunctional fluorinated (meth)acrylic compound may contain siloxane units. When the nanoparticles are inorganic oxides, the polyfunctional fluorinated (meth)acrylic compound containing siloxane units is more firmly held onto the hard coat layer not only by the reaction between the (meth)acrylic groups and the curable monomer or the curable oligomer, but also by interactions between siloxane bonds and the nanoparticles, which is thought to further increase the durability of the anti-smudge properties. The nanoparticles are preferably silica nanoparticles which are chemically similar to and have high affinity with siloxane bonds.

The polyfunctional fluorinated (meth)acrylic compound containing siloxane units can be synthesized, for example, by adding (hydrosilylating) a perfluoropolyether compound having one or two or more unsaturated ethylene groups to a straight-chain or cyclic oligosiloxane or polysiloxane (hydrogen siloxane) containing three or more Si-H bonds in the presence of a platinum catalyst or the like at a volume of less than one equivalent with respect to the Si-H bonds, similarly adding (hydrosilylating) a hydroxyl group-containing unsaturated ethylene compound to the remaining Si-H bonds in the presence of a platinum catalyst or the like, and then reacting the hydroxyl groups with an epoxy (meth)acrylate, urethane (meth)acrylate, or the like. The partial molecular weight of the perfluoroether site calculated from the chemical formula may be from 500 to 30,000.

In order to sufficiently express the anti-smudge properties imparted by the fluorinated site, it is preferable for the siloxane units to be cyclic siloxane units derived from tetramethyl cyclotetrasiloxane, pentamethyl cyclopentasiloxane, or the like. The number of silicon atoms constituting the cyclic siloxane units is preferably from 3 to 7.

An example of a polyfunctional fluorinated (meth)acrylic compound containing siloxane units is a perfluoropolyether compound having two or more (meth)acrylic groups as described in Japanese Unexamined Patent Application Publication No. 2010-285501, for example. For example, the compounds of formulas (19) and (21) in this publication have structures in which cyclic siloxanes with four silicon atoms respectively bond to both terminals of a divalent perfluoropolyether group: -CF₂(OCF₂CF₂)p(OCF₂)_qOCF₂- (p/q=0.9, p+q«45), and three acryloyloxy groups bond with each of these cyclic siloxanes via urethane bonds, which is suited to the hard coat layer of the present disclosure.

The amount of the anti-smudge agent that is added may be, for example, within the range of approximately 0.01 to 20 parts by mass (in several embodiments, from approximately 0.1 to 10 parts by mass or from approximately 0.2 to 5 parts by mass) with respect to a total of 100 parts by mass of the nanoparticles, the curable monomer, and the curable oligomer.

In some embodiments, an anti- fogging agent is contained in the binder of the hard coat layer. In this case, the fogging of the vehicle member can be prevented. For example, when the binder of the hard coat layer of the vehicle mirror or the vehicle mirror film contains an anti- fogging agent, it is possible to prevent fogging or dew formation on the mirror. The anti- fogging agent can be mixed with the curable monomer or the curable oligomer. Anionic, cationic, nonionic or amphoteric surfactants can be used as the anti-fogging agent, examples of which include sorbitan surfactants such as sorbitan monostearate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monobehenate, and esters of sorbitan, alkylene glycol condensates, and fatty acids; glycerin surfactants such as glycerin monopalmitate, glycerin monostearate, glycerin monolaurate, diglycerin monopalmitate, glycerin dipalmitate, glycerin distearate, diglycerin monopalmitate/monostearate, triglycerin monostearate, triglycerin distearate, or alkylene oxide adducts thereof; polyethylene glycol surfactants such as polyethylene glycol monostearate, polyethylene glycol monopalmitate, and polyethylene glycol alkyl phenyl ether; trimethylol propane surfactants such as trimethylol propane monostearate; pentaerythritol surfactants such as pentaerythritol monopalmitate and pentaerythritol monostearate; alkylene oxide adducts of alkyl phenol; esters of sorbitan/glycerin condensates and fatty acids and esters of sorbitan/alkylene glycol condensates and fatty acids; diglycerin diolate sodium lauryl sulfate, sodium dodecyl benzene sulfonate, cetyl trimethyl ammonium chloride, dodecylamine hydrochloride, lauryl amide laurate ethyl phosphate, triethyl cetyl ammonium iodide, oleylamino diethylamine hydrochloride, dodecylpyridinium salts, and isomers thereof. The anti-fogging agent may also have functional groups which react with the curable monomer or the curable oligomer.

The amount of the anti-fogging agent that is added may be, for example, within the range of approximately 0.01 to 20 parts by mass (in several embodiments, from approximately 0.1 to 15 parts by mass or from approximately 0.2 to 10 parts by mass) with respect to a total of 100 parts by mass of the nanoparticles, the curable monomer, and the curable oligomer.

A hard coat precursor that can be used to form a hard coat layer contains the nanoparticle mixture described above, a curable monomer and/or a curable oligomer, a reaction initiator, and, if necessary, a solvent such as methyl ethyl ketone (MEK) or l-methoxy-2- propanol (MP-OH) and the additives described above such as an ultraviolet absorbent, an anti- smudge agent, an anti-fogging agent, a leveling agent, an ultraviolet reflecting agent, an antistatic agent, or the like. The hard coat precursors of some embodiments contain a nanoparticle mixture and a binder, wherein the nanoparticles constitute from 40 to 95 mass% of the total mass of the nanoparticles and the binder. From 10 to 50 mass% of the nanoparticles have an average particle size within the range of 2 to 200 nm, and from 50 to 90 mass% of the nanoparticles have an average particle size within the range of 60 to 400 nm. The ratio of the average particle size of nanoparticles having an average particle size within the range of 60 to 400 nm to the average particle size of nanoparticles having an average particle size within the range of 2 to 200 nm is within the range of 2: 1 to 200: 1.

As is generally known in this technical field, a hard coat precursor can be prepared by combining specific components of the hard coat precursor. For example, the hard coat precursor can be prepared by preparing a modified or non-modified nanoparticle sol of two or more different sizes with a desired solid content by mixing a curable monomer and/or a curable oligomer together with a reaction initiator in a solvent and adding a solvent. A photoinitiator or thermal polymerization initiator known in this technical field, for example, may be used as the reaction initiator. Depending on the curable monomer and/or the curable oligomer used, it may be unnecessary to use a solvent.

When surface-modified nanoparticles are used, the hard coat precursor can be prepared as follows, for example. An inhibitor and a surface-modifying agent are added to a solvent in a container (for example, in a glass vial), and the resulting mixture is added to an aqueous solution in which nanoparticles are dispersed and is then stirred. The container is sealed and placed in an oven for several hours (for example, 16 hours) at a high temperature (for example, 80°C). Next, a rotary evaporator, for example, is used at a high temperature (for example, 60°C) to remove the water from the solution. By pouring the solvent in the solution and then evaporating the solution, the remaining water is removed from the solution. It is sometimes preferable to repeat the latter half of the steps several times. The concentration of the nanoparticles can be adjusted to a desired concentration (mass%) by adjusting the volume of the solvent.

Technology for applying the hard coat precursor (solution) to the surface of a substrate layer is known in this technical field, and examples include bar coating, dip coating, spin coating, capillary coating, spray coating, gravure coating, screen printing, and the like. The coated hard coat precursor is dried as necessary and can be cured with a known polymerization method in this technical field such as photopolymerization using ultraviolet rays or electron beams, thermal polymerization, or the like. In this way, a hard coat layer can be formed on a substrate layer.

The vehicle members exemplified in the present disclosure will be described hereinafter. A vehicle window, for example, may comprise a hard coat layer and a substrate layer comprising a sheet glass or a transparent polymer plate. The vehicle window can be obtained by forming a hard coat layer on the first surface of the substrate layer with the method described above. A polycarbonate can be used as a preferable substrate of the polymer plate. The vehicle window has excellent scratch resistance, impact resistance, and, when the binder of the hard coat layer contains an anti-smudge agent, an anti-smudge effect.

A vehicle mirror may have a configuration in which, for example, a hard coat layer is formed on the first surface of a transparent polymer plate (rigid) and a multi-layer optical film or a metal thin-film laminated film is laminated on the second surface via an adhesive layer consisting of a known adhesive (pressure-sensitive adhesive). The vehicle mirror can be obtained by forming a hard coat layer on the first surface of the substrate layer with the method described above, laminating an adhesive layer on the second surface, and then laminating a multi-layer optical film or a metal thin-film layer with a known method. The vehicle mirror has excellent scratch resistance, impact resistance, and, when the binder of the hard coat layer contains an anti-fogging agent, an anti-fogging effect. By providing a junction layer on the surface of the opposite side of the adhesive layer of the multi-layer optical film or the metal thin- film laminated film, it is possible to install the vehicle mirror at a desired position inside or outside the vehicle. When a junction layer is not provided, the mirror may be installed by a physical fixing means. By using a repositionable layer such as a silicone rubber layer as the junction layer, it is possible to provide a removable vehicle mirror.

A vehicle mirror film may have a configuration in which, for example, a multi-layer optical film or a metal thin- film laminated film is used as a substrate, wherein a hard coat layer is laminated on the first surface and a junction layer is laminated on the second surface thereof. The vehicle mirror film can be obtained by forming a hard coat layer on the first surface of the substrate layer with the method described above and laminating a junction layer on the second surface. The vehicle mirror film has excellent scratch resistance, impact resistance, and, when the binder of the hard coat layer contains an anti-fogging agent, an anti-fogging effect. The vehicle mirror film can be installed at a desired position inside or outside the vehicle, and by using a repositionable layer such as a silicone rubber layer as the junction layer, it is possible to provide a removable vehicle mirror film.

A vehicle body part may have a configuration in which, for example, a metallic sheet such as a painted steel sheet is used as a substrate and a hard coat layer is provided on the first surface thereof (on the painted surface in the case of a painted sheet). The vehicle body part is obtained by forming a hard coat layer on the first surface of the substrate layer with the method described above. A body part refers to at least one part of the structure serving as the building frame of the vehicle body. Since the vehicle body part has excellent scratch resistance and impact resistance, it is possible to provide a vehicle body with excellent scratch resistance and impact resistance.

A vehicle surface-protecting member may have a configuration in which, for example, a hard coat layer is laminated on the first surface of a substrate consisting of a flexible film and a junction layer comprising a pressure-sensitive adhesive is laminated on the second surface. The vehicle surface-protecting member is obtained by forming a hard coat layer on the first surface of the substrate layer with the method described above and laminating a junction layer comprising an acrylic pressure-sensitive adhesive, for example, on the second surface. The vehicle surface- protecting member has excellent scratch resistance and impact resistance. In particular, this member can be used to protect the vehicle surface of a two-wheeled vehicle. The vehicle surface-protecting member also has an anti-smudge effect when the binder of the hard coat layer contains an anti-smudge agent. In particular, it is possible to prevent the body of a two-wheeled vehicle or the like from being contaminated when traveling in unpaved locations, as in the case of an off-road motorcycle.

A vehicle decorative film may have a configuration in which, for example, a decorative layer such as a printed layer, a coloring layer, a metal thin- film layer, or a metal flake (metallic) layer is provided on the first surface of a substrate layer consisting of a film, and a hard coat layer is further provided on the surface of the decorative layer, while a junction layer consisting of a pressure-sensitive adhesive is laminated on the second surface of the substrate layer. The vehicle decorative film is obtained by forming a hard coat layer on the first surface of the substrate layer with the method described above and laminating a junction layer consisting of an acrylic pressure-sensitive adhesive, for example, on the second surface. The vehicle decorative film may be a painting-alternative film for the exterior of the vehicle or a decorative film for imparting a design to the interior of the vehicle. Alternatively, the substrate layer itself may be colored, or the layer may contain metal flakes or the like. The vehicle decorative film has excellent scratch resistance, impact resistance, and, when the binder of the hard coat layer contains an anti-smudge agent, an anti-smudge effect.

The vehicle members are not limited to these forms and may be various other members used on the interiors and exteriors of vehicles (for example, a visor or a mudflap in which a hard coat layer is formed on a polymer plate).

EXAMPLES

In the following examples, specific embodiments of the present disclosure are illustrated, but the present invention is not limited to these embodiments. All parts and percentages are based on mass unless otherwise indicated.

The characteristics of the vehicle member of the present disclosure were evaluated in accordance with the following methods.

1. Pencil Hardness

The pencil hardness of the hard coat layer of the vehicle member was determined using a 750 g weight in accordance with JIS K5600-5-4 (1999).

2. Contact Angle

The water contact angle of the hard coat layer surface of a window film was measured by the Sessile Drop method using a contact angle meter (acquired from Kyowa Interface Science Co., Ltd. under the product name "DROPMASTER FACE"). The volume of liquid droplets was set to 4 μΕ for static measurements. The value of the water contact angle was calculated from the average of five measurements.

3. Optical Characteristics

Haze and total transmittance (TT) were measured using a haze meter NDH-5000W (acquired from Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7136 (2000) and JIS K 7361-1 (1997), respectively. The glossiness values at 60° and 20° were measured using a TASCO TMS-724 (made by TASCO Japan). The reflectivity values at observation angles of 5°, 15°, 25°, 35°, 45°, 55°, and 65° were measured at a wavelength of 550 nm using a

spectrophotometer (V-650/ARMV-734, made by the JASCO Corporation).

4. Steel Wool Abrasion Resistance Tests One aspect of scratch resistance was evaluated based on changes in haze, total transmittance (TT), glossiness, and reflectivity before and after steel wool abrasion resistance tests. In steel wool abrasion resistance tests, the hard coat layer surface of a window film was subjected to 200 cycles of abrasion using a 32 mm square piece of #0000 steel wool at a speed of 60 cycles/minute of 85 mm strokes under a load of 1 kg. Haze and total transmittance (TT) were measured in accordance with "3. Optical Characteristics" described above.

5. Sand-falling Abrasion Resistance Tests

One aspect of scratch resistance was evaluated based on changes in haze, total transmittance (TT), glossiness, and reflectivity before and after sand- falling abrasion resistance tests in accordance with JIS T 8147 (2003). Haze and total transmittance (TT) were measured in accordance with "3. Optical Characteristics" described above.

6. Adhesive Force Tests

A sample with a width of 25 mm was adhered to each substrate using a 2.0 kg roller, and the adhesive force was measured at 25°C at a peeling angle of 180° and a peeling rate of 300 mm/minute. In Example 79, a sample with a width of 100 mm was used.

7. Anti- fogging Tests

A thermometer was placed in one opening of a two-neck flask containing 750 ml of water. The other opening was covered with a lid, and the water temperature was maintained at 50°C. The lid was removed and the water was immediately replaced with a sample. The sample surface was observed visually, and the time that the sample began to fog was measured. An evaluation of "Good", "Fair", "Poor", or "Bad" was given when the time that fogging began was longer than 60 seconds, at least 30 seconds, shorter than 30 seconds, or shorter than 10 seconds, respectively.

The reagents, raw materials, and the like used in these examples are shown in Table 1. Preparation of Surface-Modified Silica Sol (Sol 1)>

A surface-modified silica sol ("sol 1 ") was prepared as follows. First, 5.95 g of SILQUEST A174 and 0.5 g of PROSTAB was added to a mixture of 400 g of NALCO 2329 and 450 g of 1 -methoxy-2-propanol in a glass vial and stirred at room temperature for 10 minutes. The glass vial was sealed and placed in an oven at 80°C for 16 hours. Water was removed from the resulting solution with a rotary evaporator until the solid content of the solution reached nearly 45 mass% at 60°C. 200 g of l-methoxy-2-propanol was added to the resulting solution, and the remaining water was removed at 60°C using a rotary evaporator. The latter half of the steps were repeated twice so as to further remove water from the solution. Finally, the concentration of all of the Si0₂ nanoparticles was adjusted to 45 mass% by adding 1 -methoxy-2- propanol, and an Si0₂ sol (hereafter called "sol 1 ") containing surface-modified Si0₂ nanoparticles having an average particle size of 75 nm was obtained.

Preparation of Surface-Modified Silica Sol (Sol 2)> A surface-modified silica sol ("sol 2") was prepared as follows. Modification was performed with the same method as for sol 1 with the exception of using 400 g of NALCO 2327, 25.25 g of SILQUEST A174, and 0.5 g of PROSTAB, and an Si0₂ sol (hereafter called "sol 2") containing 45 mass% of surface-modified Si0₂ nanoparticles having an average particle size of 20 nm was obtained.

First, 108.33 g of sol 1, 58.33 g of sol 2, and 25.0 g of Kayarad UX-5000 were mixed.

Next, 2.00 g of Irgacure 2959 was added to the mixture as a photopolymerization initiator, and 0.01 g of BYK-UV3500 was added to the mixture as a leveling agent. The mixture was then adjusted so that the solid content was 50.5 mass% by adding 1 -methoxy-2-propanol, and a hard coat precursor HC- 1 was thus prepared.

HC-2 through HC-35 were prepared in the same manner as HC-1 using the materials listed in Tables 1 to 8.

< Preparation of an acrylic pressure-sensitive adhesive (PSA) layer (AD-1) >

An ethyl acetate solution of an acrylic pressure-sensitive adhesive (PSA solution) was obtained by mixing 90.00 g of isoamyl acrylate (light acrylate IAA), 10.00 g of acrylic acid, 150.00 g of ethyl acetate as a solvent, and 0.20 g of V-65 as a polymerization initiator and reacting the mixture for 24 hours at 50°C. As a crosslinking agent, 0.80 g of an epoxy compound E-5XM was added to 100.00 g of the PSA solution described above. The resulting solution was applied to a peeling treatment polyester film (acquired from Dupont Teijin Films under the product name "Purex A71 ") with a thickness of 38 μηι and dried for 10 minutes at 100°C to obtain an acrylic PSA layer (AD-1) with a thickness of 25 μηι.

First, 100 g of ethyl acetate and 0.3 g of CAT-PT-50L as a silicone curing catalyst were mixed with 100 g of a KS-847T silicone rubber solution. The silicone rubber solution was applied to a desired surface and dried for 10 minutes at 100°C.

Examples 1 to 13 and Comparative Example 1

A polycarbonate substrate (150x70x2.0 mm, Takiron #1600 made by Takiron Co.,

Ltd.) was fixed to the top of a glass sheet with a leveling mechanism. The hard coat precursor HC-1 was applied to the polycarbonate substrate using a #16 Meyer rod and dried for 5 minutes at 60°C in air. Next, the coated surface was irradiated with ultraviolet rays (UV-A) using an H- valve (DRS model) from Fusion UV System Inc. so that the total amount of irradiation was 900 mJ/cm² or 700 mJ/cm² in a nitrogen gas atmosphere. The thickness of the hard coat layer was 9.5 μηι. In this manner, the hard coat layer of Example 1 was formed on the polycarbonate substrate. <Examples 2 to 13>

The hard coat layers of Examples 2 to 13 were formed on polycarbonate substrates in the same manner as in Example 1 with the hard coat precursors, Meyer rods, and curing conditions described in Table 9.

An untreated polycarbonate substrate (150x70x2 mm, Takiron 1600 made by Takiron Co., Ltd.) was used as Comparative Example 1.

Tests were performed on each sample, and the results are shown in Table 9.

Examples 14 to 20 and Comparative Example 2

A polypropylene substrate (150x53x2 mm, white polypropylene produced by Shin- Kobe Electric Co., Ltd.) was fixed to the top of a glass sheet with a leveling mechanism. The hard coat precursor HC-1 was applied to the polycarbonate substrate using a #16 Meyer rod and dried for 5 minutes at 60°C in air. Next, the coated surface was irradiated with ultraviolet rays (UV-A) using an H-valve (DRS model) from Fusion UV System Inc. so that the total amount of irradiation was 900 mJ/cm² or 700 mJ/cm² in a nitrogen gas atmosphere. The thickness of the hard coat layer was 9.5 μηι. Samples were prepared as described above.

The samples of Examples 15 to 20 were prepared in the same manner as in Example 14 with the hard coat precursors, Meyer rods, and curing conditions described in Table 10 after the substrate was plasma-treated in Examples 17 and 18 and after the substrate was primer-treated in Examples 19 and 20.

An untreated polypropylene substrate (150x53x2 mm, white polypropylene produced by Shin-Kobe Electric Co., Ltd.) was used as Comparative Example 2.

Tests were performed on each sample, and the results are shown in Table 10.

Examples 21 to 25 and Comparative Examples 3 and 4

Samples were prepared with the materials and conditions described in Table 1 1 in the same manner as in Example 14 with the exception of using a cycloolefin polymer substrate

ZEONOR1020R (100x 150x2 mm, made by the Zeon Corporation) for Examples 21 to 23 and a cycloolefin polymer substrate ZEONOR1600 (100x 150x2 mm, made by the Zeon Corporation) for Examples 24 and 25, as substrates. In Examples 22 to 25, a hard coat precursor was applied after the substrate surface was plasma-treated.

An untreated cycloolefin polymer substrate ZEONOR1020R (100x 150x2 mm, made by the Zeon Corporation) was used as Comparative Example 3, and an untreated cycloolefin polymer substrate ZEONOR1600 (100x 150x2 mm, made by the Zeon Corporation) was used as Comparative Example 4.

Tests were performed on each sample, and the results are shown in Table 1 1.

Examples 26 to 37 and Comparative Examples 5 to 10

A coating film with a thickness of 30 μηι after drying was obtained by applying an acrylic melamine black paint (made by Kansai Paint Co., Ltd.) to an electrocoated cold-rolled steel sheet and drying the sheet at room temperature. Next, an organic solvent-type clear coat paint KINO #1200TW (made by Kansai Paint Co., Ltd.) was applied and dried for 30 minutes at 140°C, and a clear coat with a thickness of 40 μηι after drying was formed to obtain a black painted steel sheet. This black painted steel sheet was used as Comparative Example 5. A hard coat precursor (HC-15) was applied to the black painted surface using a #12 Meyer rod and dried for 5 minutes at 60°C in air. Next, the coated surface was irradiated with ultraviolet rays (UV-A) using an H-valve (DRS model) from Fusion UV System Inc. so that the total amount of irradiation was 900 mJ/cm² in a nitrogen gas atmosphere. The thickness of the hard coat layer was 5 μηι. The sample of Example 26 was prepared as described above. The sample of Example 27 was prepared in the same manner as in Example 26 with the exception of using a hard coat precursor (HC-14) containing an anti-smudge agent.

A coating film with a thickness of 30 μηι after drying was obtained by applying an acrylic melamine white paint (made by Kansai Paint Co., Ltd.) to an electrocoated cold-rolled steel sheet and drying the sheet at room temperature. Next, an organic solvent-type clear coat paint KINO #1200TW (made by Kansai Paint Co., Ltd.) was applied and dried for 30 minutes at 140°C, and a clear coat with a thickness of 40 μηι after drying was formed to obtain a white painted steel sheet. This white painted steel sheet was used as Comparative Example 6. A hard coat precursor (HC-17) was applied to the black painted surface using a #12 Meyer rod and dried for 5 minutes at 60°C in air. Next, the coated surface was irradiated with ultraviolet rays (UV-A) using an H-valve (DRS model) from Fusion UV System Inc. so that the total amount of irradiation was 900 mJ/cm² in a nitrogen gas atmosphere. The thickness of the hard coat layer was 5 μηι. The sample of Example 28 was prepared as described above. The sample of Example 29 was prepared in the same manner as in Example 28 with the exception of using a hard coat precursor (HC- 18) containing an anti-smudge agent.

A coating film with a thickness of 30 μηι after drying was formed by applying an acrylic melamine silver paint (made by Kansai Paint Co., Ltd.) to an electrocoated cold-rolled steel sheet and drying the sheet at room temperature. Next, an organic solvent-type clear coat paint KINO #1200TW (made by Kansai Paint Co., Ltd.) was applied and dried for 30 minutes at 140°C, and a clear coat with a thickness of 40 μηι after drying was formed to obtain a silver painted steel sheet. This silver painted steel sheet was used as Comparative Example 7. A hard coat precursor (HC-13) was applied to the black painted surface using a #12 Meyer rod and dried for 5 minutes at 60°C in air. Next, the coated surface was irradiated with ultraviolet rays (UV-A) using an H-valve (DRS model) from Fusion UV System Inc. so that the total amount of irradiation was 900 mJ/cm² in a nitrogen gas atmosphere. The thickness of the hard coat layer was 5 μηι. The sample of Example 30 was prepared as described above. The sample of Example 31 was prepared in the same manner as in Example 30 with the exception of using a hard coat precursor (HC- 16) containing an anti-smudge agent.

A coating film with a thickness of 15 μηι after drying was formed by applying a water- based black paint (made by Kansai Paint Co., Ltd.) to a polypropylene substrate (made by Paltek Corporation) and drying the substrate for 5 minutes at 80°C. Next, a clear coating RK7171 (made by Kansai Paint Co., Ltd.) was applied and dried for 20 minutes at 120°C, and a clear coat with a thickness of 30 μηι after drying was formed to obtain a black polypropylene sheet. This black polypropylene sheet was used as Comparative Example 8. A hard coat precursor (HC-15) was applied to the black painted surface of the black polypropylene sheet using a #12 Meyer rod and dried for 5 minutes at 60°C in air. Next, the coated surface was irradiated with ultraviolet rays (UV-A) using an H-valve (DRS model) from Fusion UV System Inc. so that the total amount of irradiation was 900 mJ/cm² in a nitrogen gas atmosphere. The thickness of the hard coat layer was 5 μηι. The sample of Example 32 was prepared as described above. The sample of Example 33 was prepared in the same manner as in Example 32 with the exception of using a hard coat precursor (HC- 14) containing an anti-smudge agent.

A coating film with a thickness of 15 μηι after drying was formed by applying a water- based white paint (made by Kansai Paint Co., Ltd.) to a polypropylene substrate (made by Paltek Corporation) and drying the substrate for 5 minutes at 80°C. Next, a clear coating RK7171 (made by Kansai Paint Co., Ltd.) was applied and dried for 20 minutes at 120°C, and a clear coat with a thickness of 30 μηι after drying was formed to obtain a white polypropylene sheet. This white polypropylene sheet was used as Comparative Example 9. A hard coat precursor (HC- 17) was applied to the white painted surface of the white polypropylene sheet using a #12 Meyer rod and dried for 5 minutes at 60°C in air. Next, the coated surface was irradiated with ultraviolet rays (UV-A) using an H-valve (DRS model) from Fusion UV System Inc. so that the total amount of irradiation was 900 mJ/cm² in a nitrogen gas atmosphere. The thickness of the hard coat layer was 5 μηι. The sample of Example 34 was prepared as described above. The sample of Example 35 was prepared in the same manner as in Example 34 with the exception of using a hard coat precursor (HC- 18) containing an anti-smudge agent.

<Examples 36 and 37 and Comparative Example 10> A coating film with a thickness of 15 μηι after drying was formed by applying a water- based silver paint (made by Kansai Paint Co., Ltd.) to a polypropylene substrate (made by Paltek Corporation) and drying the substrate for 5 minutes at 80°C. Next, a clear coating RK7171 (made by Kansai Paint Co., Ltd.) was applied and dried for 20 minutes at 120°C, and a clear coat with a thickness of 30 μηι after drying was formed to obtain a silver polypropylene sheet. This silver polypropylene sheet was used as Comparative Example 10. A hard coat precursor (HC-13) was applied to the silver painted surface of the silver polypropylene sheet using a #12 Meyer rod and dried for 5 minutes at 60°C in air. Next, the coated surface was irradiated with ultraviolet rays (UV-A) using an H-valve (DRS model) from Fusion UV System Inc. so that the total amount of irradiation was 900 mJ/cm² in a nitrogen gas atmosphere. The thickness of the hard coat layer was 5 μηι. The sample of Example 36 was prepared as described above. The sample of Example 37 was prepared in the same manner as in Example 36 with the exception of using a hard coat precursor (HC- 16) containing an anti-smudge agent.

Tests were performed on each sample, and the results are shown in Table 12.

Examples 38 to 48 and Comparative Examples 1 1 to 15

A film with an adhesive layer (Scotchcal (TM) made by Sumitomo 3M Limited) was prepared by laminating the AD- 1 prepared above on a transparent polyvinyl chloride film with a thickness of 50 μηι. A hard coat precursor (HC-19) was applied to the surface on the opposite side as the adhesive layer of the film with an adhesive layer using a #8 Meyer rod and dried for 5 minutes at 60°C in air. Next, the coated surface was irradiated with ultraviolet rays (UV-A) using an H-valve (DRS model) from Fusion UV System Inc. so that the total amount of irradiation was 900 mJ/cm² in a nitrogen gas atmosphere. The thickness of the hard coat layer was 4 μηι. The sample of Example 38 was prepared as described above.

The samples of Examples 39 to 45 were prepared in the same manner as in Example 38 using the materials listed in Table 13.

A film with an adhesive layer (Scotchcal (TM) made by Sumitomo 3M Limited) prepared by laminating AD-1 on a transparent polyvinyl chloride film with a thickness of 50 μηι was used as Comparative Example 1 1. A film prepared by laminating AD-1 on a thermosetting polyurethane film (made by Sheedom Co., Ltd.) with a thickness of 150 μηι was used as Comparative Example 12. A film prepared by laminating AD-1 on a transparent polypropylene (PP) film (corona-treated AQUA (TM), made by Sheedom Co., Ltd.) with a thickness of 200 μηι was used as Comparative Example 13. A film prepared by laminating AD-1 on a transparent

PET film (Lumirror (TM), made by Toray Industries, Inc.) with a thickness of 75 μηι was used as Comparative Example 14.

<Examples 46 to 48 and Comparative Example 15> A hard coat precursor HC-19 was applied to a transparent PET film (Emblet (TM) S-50, made by Unitika Ltd.) with a thickness of 50 μηι using a #8 Meyer rod and dried for 5 minutes at 60°C. Next, the coated surface was irradiated with ultraviolet rays (UV-A) using an H-valve (DRS model) from Fusion UV System Inc. so that the total amount of irradiation was 900 mJ/cm². The thickness of the hard coat layer was 4 μηι. AD-2 was formed on the surface on the opposite side as the hard coat treated surface of the transparent PET film so that the thickness after drying was 7 μηι. In this way, the hard coat treated protective film sample of Example 46 having excellent repositioning properties was prepared. The hard coat treated protective film samples of Examples 47 and 48 having excellent repositioning properties were prepared in the same manner as in Example 46 by applying hard coat precursors HC-20 and HC-21 to a transparent PET film, curing the hard coat precursors by ultraviolet irradiation, and forming a silicone rubber layer with a thickness of 7 μηι on the surface of the opposite side as the hard coat treated surface of the transparent PET film. The sample of Comparative Example 15 was prepared by forming a silicone rubber layer with a thickness of 7 μηι on a transparent PET film with a thickness of 50 μηι (Emblet (TM) S-50, made by Unitika Ltd.).

Each sample was adhered to a float glass (53 mm* 100 mm><3.0 mm, acquired from Taiyu Kizai K.K.) using a 2.0 kg roller, and tests were performed. In Examples 38 to 40 and 45 to 48 and Comparative Examples 1 1, 14, and 15, the same tests were performed on samples adhered to polycarbonate (PC) sheets (53 mm* 100 mm* 1.0 mm, NF2000, acquired from Taiyu Kizai K.K.) using a 2.0 kg roller. The results are shown in Tables 13 and 14.

Examples 49 to 54 and Comparative Example 16: Hard coat treated polyvinyl chloride decorative films

A hard coat precursor HC-23 was applied to a black polyvinyl chloride film having embossing on the surface with a thickness of 100 μηι (JS 1500 (3655CF) ORG, made by

Sumitomo 3M Limited) using a #12 Meyer rod and dried for 5 minutes at 60°C. Next, the coated surface was irradiated with ultraviolet rays (UV-A) using an H-valve (DRS model) from Fusion UV System Inc. so that the total amount of irradiation was 900 mJ/cm². The thickness of the hard coat layer was 5 μηι. AD- 1 was laminated on the surface of the opposite side as the hard coat layer of the black polyvinyl chloride film to prepare the hard coat treated decorative film sample of Example 49. The hard coat treated decorative film samples of Examples 50 to 54 were prepared in the same manner as in Example 49 using the hard coat precursors HC-24 to HC-28. Comparative Example 16 was prepared by laminating AD- 1 on a black polyvinyl chloride film having embossing on the surface with a thickness of 100 μηι (JS 1500 (3655CF) ORG, made by Sumitomo 3M Limited).

The respective samples of Examples 49 to 54 and Comparative Example 16 were adhered to stainless steel sheets (53 mm* 100 mm* 1.0 mm, SUS304-BA made by Nippon Testpanel Co., Ltd.) using a 2.0 kg roller, and tests were performed. The results are shown in Table 15. Examples 55 to 60 and Comparative Example 17: Hard coat treated PP decorative films The hard coat treated decorative film samples of Examples 55 to 60 were prepared in the same manner as in Example 49 under the conditions described in Table 16 using a corona- treated black polypropylene film having embossing on the surface with a thickness of 80 μηι (MBF-28PH, made by Hayashikazuji Co., Ltd.). Comparative Example 17 was prepared by laminating AD-1 on a corona-treated black polypropylene film having embossing on the surface with a thickness of 80 μηι (MBF-28PH, made by Hayashikazuji Co., Ltd.).

The respective samples of Examples 55 to 60 and Comparative Example 17 were adhered to aluminum sheets (53 mm* 100 mm* 1.0 mm, A5250P made by Coating Tester Co., Ltd.) using a 2.0 kg roller, and tests were performed. The results are shown in Table 16.

Examples 61 to 66 and Comparative Example 18: Hard coat treated decorative films with excellent repositioning properties

A hard coat precursor HC-23 was applied to a white PET film with a thickness of 15 μηι (Teflex FW2, made by Dupont Teijin Films) using a #12 Meyer rod and dried for 5 minutes at 60°C. Next, the coated surface was irradiated with ultraviolet rays (UV-A) using an H-valve

(DRS model) from Fusion UV System Inc. so that the total amount of irradiation was 900 mJ/cm². The thickness of the hard coat layer was 5 μηι. AD-2 was laminated on the surface of the opposite side as the hard coat layer of the white PET film so that the thickness after drying was 7 μηι. In this way, the hard coat treated decorative film sample of Example 61 having excellent repositioning properties was prepared.

The hard coat treated decorative film samples of Examples 62 to 66 having excellent repositioning properties were prepared in the same manner as in Example 61 using hard coat precursors HC-24 to HC-28 on white PET films. The sample of Comparative Example 18 was prepared by forming AD-2 with a thickness of 7 μηι on a white PET film with a thickness of 15 μηι (Teflex FW2, made by Dupont Teijin Films).

The respective samples of Examples 61 to 66 and Comparative Example 18 were adhered to polycarbonate sheets (53 mm* 100 mm* 1.0 mm, NF2000 made by Taiyu Kizai K.K.) using a 2.0 kg roller, and tests were performed. The results are shown in Table 17.

Examples 67 to 72 and Comparative Example 19: Metallic hard coat treated decorative films

An ethyl acetate solution of an acrylic copolymer was obtained by mixing 97 g of acrylic ester M, 3 g of acrylic ester HISS, 150 g of ethyl acetate, and 0.6 g of V-601 as an initiator and reacting the mixture for 24 hours at 65°C. Next, 2.7 g of Duranate TPA-100 (low- viscosity HDI polyisocyanurate, made by Asahi Kasei Corporation) was added to the resulting ethyl acetate solution of the acrylic copolymer. This was applied to a polyester film with a thickness of 75 μηι (Lumirror T60, made by Toray Industries, Inc.) and dried for 10 minutes at 120°C to form an acrylic top layer with a thickness of 60 μηι. A primer solution (E-295T and C- 55 isocyanate compound, made by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) was applied to the resulting acrylic top layer so that the thickness after drying was 15 μηι and then dried for 5 minutes at 100°C. Next, this was laminated on a tin-deposited polyurethane film with a thickness of 30 μηι (made by Oike & Co. Ltd.). A hard coat precursor HC-23 was applied to the surface of the acrylic top layer from which the polyester film was peeled using a #8 Meyer rod and then dried for 5 minutes at 60°C. Next, the coated surface was irradiated with ultraviolet rays (UV-A) using an H-valve (DRS model) from Fusion UV System Inc. so that the total amount of irradiation was 900 mJ/cm². The thickness of the hard coat layer was 5 μηι. 15 g of Asaprene 1205 (styrene-butadiene rubber, made by Asahi Kasei Corporation), 35 g of Asaprene T-41 1 (styrene-butadiene/styrene elastomer, made by Asahi Kasei Corporation), 50 g of Picolite A- 135 (polyterpene resin, made by Pinova, Inc.), and 150 g of toluene were mixed. The resulting solution was applied to a polyester film with a thickness of 38 μηι (Purex A71, made by Dupont Teijin Films) and dried for 10 minutes at 100°C to form a rubber adhesive layer with a thickness of 30 μηι. The metallic hard coat treated decorative film of Example 67 was prepared by laminating the resulting adhesive layer on the surface of the opposite side as the hard coat layer of the tin-deposited polyurethane film.

The metallic hard coat treated decorative films of Examples 68 to 72 were prepared in the same manner as in Example 67 using the hard coat precursors and anti-smudge agents described in Table J.

Comparative Example 19 was prepared in the same manner as in Example 67 with the exception that a hard coat layer was not formed.

The respective samples of Examples 67 to 72 and Comparative Example 19 were adhered to polypropylene sheets (53 mm* 100 mm><2.0 mm, made by Paltek Corporation) using a 2.0 kg roller, and tests were performed. In steel wool abrasion resistance tests, the surface roughness (Ra) before and after abrasion was measured using a three-dimensional optical surface profiler (NewView6000, made by Zygo Corporation). The observation area was 0.72 mmx0.54 mm. The results are shown in Table 18.

Examples 73 to 83 and Comparative Examples 20 and 21

<Examples 73 to 75 and 78 and Comparative Example 20 >Mirror films

The AD- 1 prepared above was laminated on an ESR2 (multi-layer optical film, made by 3M), and this was used as Comparative Example 20. A hard coat precursor (HC-29) was applied to the surface of the opposite side as the adhesive layer of the film with an adhesive layer of the resulting laminated film using a #16 Meyer rod and dried for 5 minutes at 60°C in air. Next, the coated surface was irradiated with ultraviolet rays (UV-A) using an H-valve (DRS model) from Fusion UV System Inc. so that the total amount of irradiation was 900 mJ/cm² in a nitrogen gas atmosphere. The thickness of the hard coat layer was 9 μηι. The hard coat treated mirror film sample of Example 73 was prepared as described above. Examples 74, 75, and 78 were prepared in the same manner as in Example 73 using the hard coat precursors, additives, and the like described in Table 19 or 21.

<Examples 76, 77, and 79>Mirror films having excellent repositioning properties

Mirror film samples having excellent repositioning properties in Examples 76 and 77 were prepared using AD-2 with a thickness of 7 μιη instead of AD- 1 and using the hard coat precursors and anti-smudge agents described in Table 20 or 21.

<Examples 80 to 83 and Comparative Example 21>Mirror films having excellent repositioning properties using aluminum-deposited films

The hard coat precursors HC-29 to HC-32 were applied to polyester films covered by aluminum deposition with a thickness of 50 μιη (acquired from Oike & Co., Ltd. under the product name "Tetrite") using a #16 Meyer rod and dried for 5 minutes at 60°C. Next, the coated surface was irradiated with ultraviolet rays (UV-A) using an H-valve (DRS model) from Fusion UV System Inc. so that the total amount of irradiation was 900 mJ/cm². The thickness of the hard coat layer was 9 μιη. The samples of Examples 80 to 83 were prepared by forming AD-2 with a thickness of 7 μιη on the surface of the opposite side as the hard coat layer on the polyester film covered by aluminum deposition. A sample without a hard coat layer was also prepared and used as Comparative Example 21.

The respective samples were adhered to polycarbonate (PC) sheets (53 mmx lOO mmx2.0 mm, Takiron #1600 made by Takiron Co., Ltd.) using a 2.0 kg roller, and tests were performed. The results are shown in Tables 19 to 23. The reflectivity values before and after steel wool abrasion tests were measured.

Examples 84 to 89 and Comparative Examples 22 and 23

The AD- 1 prepared above was laminated on an ESR2 (multi-layer optical film, made by 3M), and samples prepared by laminating this on adherends were used as Comparative Examples 22 and 23. Polycarbonate (53x 100x2.0 mm, Takiron #1600 made by Takiron Co., Ltd.) was used as an adherend in Examples 84, 86, and 88 and Comparative Example 22, and polymethylmethacrylate (PMMA) (53x 100x2.0 mm, Acrylite L made by Mitsubishi Rayon Co., Ltd.) was used as an adherend in Examples 85, 87, and 89 and Comparative Example 23. The samples of Examples 84 to 89 were prepared by forming hard coat layers with a thickness of 9 μιη on the surface of the resulting sample substrate (ESR2) in the same manner as in Example 26 using the hard coat precursors, additives, and the like described in Tables 25 to 27.

Tests were performed on each of the samples. The results are shown in Tables 24 to 27. [Table 1]

[Table 2]

Hard Coat Precursor Composition (Compounding amounts are shown in grams)

[Table 3]

Hard Coat Precursor Composition (Compounding amounts are shown in grams)

[Table 4]

Hard Coat Precursor Composition (Compounding amounts are shown in grams)

[Table 5]

Hard Coat Precursor Composition (Compounding amounts are shown in grams)

[Table 6]

Hard Coat Precursor Composition (Compounding amounts are shown in grams)

[Table 7]

Hard Coat Precursor Composition (Compounding amounts are shown in grams)

[Table 8]

Hard Coat Precursor Composition (Compounding amounts are shown in grams)

[Table 9]

[Table 10]

[Table 11]

[Table 12]

[Table 13]

[Table 14]

[Table 15]

[Table 16]

[Table 17]

[Table 18]

[Table 19]

[Table 20]

[Table 21]

[Table 22]

[Table 23]

[Table 24]

Comparative example 22 Comparative example 23

Substrate PC PMMA

Hard coat - - precursor

Water 86.0 62.4

contact

angle (°)

Pencil 3B 2H

hardness

Angle of Initial After steel After sand- Initial After steel After sand- incidence wool falling tests wool falling tests abrasion abrasion

tests tests

5° 98.9 70.8 34.6 98.9 84.9 35.4

15° 99.1 69.9 33.2 99.1 84.5 34.6

25° 99.3 68.0 30.6 99.3 83.6 32.5

35° 99.3 63.7 27.0 99.3 82.1 29.3

45° 99.1 56.7 22.5 99.1 79.8 25.0

55° 98.4 49.5 17.9 98.4 76.2 20.4

65° 98.3 41.9 15.6 98.3 72.0 17.6

[Table 25]

Example 84 Example 85

Substrate PC PMMA

Hard coat HC-33 HC-33

precursor

Water 86.8 86.8

contact

angle (°)

Pencil H 8H

hardness

tests tests

5° 98.3 97.9 88.6 99.8 99.2 90.6

15° 98.5 97.9 88.3 99.9 99.4 90.4

25° 98.4 97.9 87.6 99.9 99.3 89.6

35° 98.5 97.7 86.3 99.8 99.2 88.3

45° 98.1 97.3 84.2 99.7 99.1 86.3

55° 97.3 96.6 81.4 99.1 98.5 83.5

65° 97.0 95.7 78.5 99.0 98.4 81.2 [Table 26]

[Table 27]

Claims

What is Claimed is:

1. A vehicle member comprising: a substrate layer having a first surface and a second surface on an opposite side as the first surface, and a hard coat layer disposed on the first surface of the substrate layer;

the hard coat layer containing a nanoparticle mixture and a binder; the nanoparticles constituting from 40 to 95 mass% of the entire mass of the hard coat layer; from 10 to 50 mass% of the nanoparticles having an average particle size in a range of 2 to 200 nm; from 50 to 90 mass% of the nanoparticles having an average particle size in a range of 60 to 400 nm; and a ratio of the average particle size of the nanoparticles having the average particle size in the range of 60 to 400 nm to the average particle size of the nanoparticles having the average particle size in the range of 2 to 200 nm being in a range of 2: 1 to 200: 1.

2. The vehicle member according to claim 1, wherein the substrate layer comprises a rigid material.

3. The vehicle member according to claim 2, wherein the rigid material is a polymer.

4. The vehicle member according to claim 3, wherein the vehicle member is a vehicle window.

5. The vehicle member according to claim 3, further comprising a mirror layer.

6. The vehicle member according to claim 5, wherein the vehicle member is a vehicle mirror.

7. The vehicle member according to claim 2, wherein the rigid material is a painted sheet.

8. The vehicle member according to claim 7, wherein the vehicle member is a vehicle body part.

9. The vehicle member according to claim 1, wherein the substrate layer comprises a flexible material.

10. The vehicle member according to claim 9, further having a junction layer on the second surface of the substrate layer.

1 1. The vehicle member according to claim 9 or 10, wherein the substrate layer comprises a transparent polymer.

12. The vehicle member according to claim 1 1, wherein the vehicle member is a surface- protecting member for a vehicle.

13. The vehicle member according to claim 9 or 10, wherein the substrate layer is a decorative layer.

14. The vehicle member according to claim 13, wherein the vehicle member is a decorative film for a vehicle.

15. The vehicle member according to claim 9 or 10, further comprising a mirror layer.

16. The vehicle member according to claim 15, wherein the vehicle member is a vehicle mirror film.