JP2014030908A - Protection tool having hard coat - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a protection tool excellent in scratch resistance.SOLUTION: This protection tool comprises: a base material having a first surface; and a hard coat layer arranged on the first surface of the base material. The hard coat layer includes a mixture of nanoparticles and a binder, and the nanoparticles constitute 40-95 mass% of the whole mass of the hard coat layer. A portion of 10-50 mass% of the nanoparticles has an average particle size in the range of 2-200 nm, and a portion of 50-90 mass% of the nanoparticles has an average particle size in the range of 60-400 nm, and the ratio between an average particle size of the nanoparticles having the average particle size in the range of 60-400 nm and an average particle size of the nanoparticles having the average particle size in the range of 2-200 nm is in the range of 2:1 to 200:1.

Description

  The present disclosure relates to a protective device having a hard coat with improved scratch resistance.

  Protective glasses, eye protection such as goggles, respirators such as face shields, dust masks, gas masks, and sound protection such as earmuffs protect the worker from danger and improve workability. It is desirable to be good and comfortable to wear. Properties required for such protective equipment include scratch resistance, anti-fogging properties, fit properties, cost performance, and the like. In particular, a protective device used in a harsh environment such as a construction site is easily damaged during work, the workability and safety of the protective device are lowered, and the appearance is easily deteriorated. Therefore, a hard coat process is performed on the surface of the protective equipment for the purpose of improving scratch resistance.

U.S. Patent No. 5104929 and US Patent No. 7074463, a hard coat material comprising SiO ₂ nanoparticles modified with photocurable silane coupling agent.

  There is also a strong desire to impart antifouling properties to the hard coat surface. U.S. Pat. No. 7,718,264 and U.S. Patent Application Publication No. 2008/0124555 disclose antifouling property and easy cleaning that are obtained by curing a polymerizable composition to which a fluorine compound having a hexafluoropropylene oxide moiety is added. A hard coat material having a smooth surface is described.

US Pat. No. 5,104,929 US Pat. No. 7,074,463 U.S. Pat. No. 7,718,264 US Patent Application Publication No. 2008/0124555

  There is still a desire to increase the durability of the protective equipment. Accordingly, an object of the present disclosure is to provide a protective device having excellent scratch resistance.

  According to one embodiment of the present disclosure, a protective device including a base material having a first surface and a hard coat layer disposed on the first surface of the base material, wherein the hard coat layer is Comprising a mixture of nanoparticles and a binder, wherein the nanoparticles constitute 40% to 95% by weight of the total weight of the hard coat layer, and 10% to 50% by weight of the nanoparticles range from 2 nm to 200 nm. Having an average particle size, wherein 50% to 90% by weight of the nanoparticles have an average particle size in the range of 60 nm to 400 nm, and an average particle size of nanoparticles having an average particle size in the range of 60 nm to 400 nm; A protective device is provided wherein the ratio of the average particle size of the nanoparticles having an average particle size in the range of 2 nm to 200 nm is in the range of 2: 1 to 200: 1.

  The protective device of the present disclosure having a hard coat highly filled with nanoparticles on the surface of various substrates such as polycarbonate (PC), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polypropylene (PP), etc. Since it exhibits both excellent scratch resistance and impact resistance while maintaining its mechanical transparency, it can be used for a long time without deteriorating the performance of the protective equipment.

  The above description should not be regarded as disclosing all the embodiments of the present invention and all the advantages related to the present invention.

6 is a graph showing simulation results between mass ratios and packing ratios of small particle groups and large particle groups for several particle size combinations (small particle groups / large particle groups). It is a face shield which protects the face and head which are one embodiment of this indication. It is a gas mask which is one embodiment of this indication. It is an earmuff which is one embodiment of this indication. It is a schematic diagram of the steel wool abrasion resistance test apparatus used in the Example. It is a schematic diagram of the sand dropping abrasion resistance test apparatus used in the Example.

  Hereinafter, the present invention will be described in more detail for 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) acryl” means “acryl or methacryl”, and “(meth) acrylate” means “acrylate or methacrylate”.

  A protector according to an embodiment of the present disclosure includes a substrate having a first surface, a hard coat layer including a mixture of nanoparticles and a binder disposed on the first surface of the substrate.

  Typical binders contained in the hard coat layer include resins obtained by polymerizing curable monomers and / or curable oligomers, resins obtained by polymerizing sol-gel glass, and the like. More specific examples of the resin include acrylic resin, urethane resin, epoxy resin, phenol resin, and polyvinyl alcohol. Furthermore, the curable monomer or curable oligomer can be selected from curable monomers or curable oligomers known in the art, and a mixture of two or more curable monomers, a mixture of two or more curable oligomers. Alternatively, a mixture of one or more curable monomers and one or more curable oligomers may be used. In some embodiments, the resin includes dipentaerythritol pentaacrylate (eg, available from Sartomer Company, Exton, Pa. Under the trade designation “SR399”), pentaerythritol triacrylate isophorone diisocyanate (IPDI) (eg, , Available from Nippon Kayaku Co., Ltd. (Tokyo, Japan) as trade name “UX-5000”), urethane acrylate (for example, trade name “UV1700B” and trade name “from Nippon Synthetic Chemical Industry Co., Ltd., Osaka, Japan)” UB6300B "), trimethylhydroxyl diisocyanate / hydroxyethyl acrylate (TMHDI / HEA, for example, trade name" Ebecryl 4 "from Daicel Cytec Co., Ltd., Tokyo, Japan) 858 ", polyethylene oxide (PEO) modified bis-A diacrylate (available from Nippon Kayaku Co., Ltd. (Tokyo, Japan) as trade name" R551 "), PEO modified bis-A epoxy Acrylate (for example, available as trade name “3002M” from Kyoeisha Chemical Co., Ltd. (Osaka, Japan)), silane-based UV curable resin (eg, trade name “SK501M” from Nagase ChemteX Corporation (Osaka, Japan)) Available), and 2-phenoxyethyl methacrylate (for example, available from Sartomer under the trade designation “SR340”); and those polymerized using mixtures thereof. For example, using 2-phenoxyethyl methacrylate in the range of about 1.0% to about 20% by weight has been observed to improve adhesion to polycarbonate. Bifunctional resins (eg PEO-modified bis-A diacrylate “R551”) and trimethylhydroxyl diisocyanate / hydroxyethyl acrylate (TMHDI / HEA) (eg available from Daicel Cytec Co., Ltd. under the trade name “Ebecryl 4858”) ) Has been observed to simultaneously improve the hardness, impact resistance and flexibility of the hard coat.

  The amount of binder in the hardcoat layer is typically from about 5% to about 60% by weight of the total weight of the hardcoat layer, in some embodiments from about 10% to about 40%, or about 15 mass% to about 30 mass%. According to the present disclosure, the hard coat layer can be formed even if the amount of the binder is relatively small.

  If necessary, the hard coat layer may be further cured with another curable monomer or curable oligomer. Typical curable monomers or curable oligomers include (a) 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, and 1,6-hexanediol. Monoacrylate monomethacrylate, ethylene glycol diacrylate, alkoxylated aliphatic diacrylate, alkoxylated cyclohexanedimethanol diacrylate, alkoxylated hexanediol diacrylate, alkoxylated neopentyl glycol diacrylate, caprolactone modified neopentyl glycol hydroxypivalate di Acrylate, caprolactone modified neopentyl glycol hydroxypivalate diacrylate, cyclohexanedimethanol diacrylate, diethyleneglycol Diacrylate, dipropylene glycol diacrylate, ethoxylated (10) bisphenol A diacrylate, ethoxylated (3) bisphenol A diacrylate, ethoxylated (30) bisphenol A diacrylate, ethoxylated (4) bisphenol A diacrylate, hydroxy Pivalaldehyde-modified trimethylolpropane diacrylate, neopentyl glycol diacrylate, polyethylene glycol (200) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, propoxylated neopentyl glycol diacrylate, tetra Ethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, triethylene glycol diacrylate (B) glycerol triacrylate, trimethylolpropane triacrylate, ethoxylated triacrylate (eg ethoxylated (3) trimethylolpropane triacrylate) Ethoxylated (6) trimethylolpropane triacrylate, ethoxylated (9) trimethylolpropane triacrylate, ethoxylated (20) trimethylolpropane triacrylate, etc.), pentaerythritol triacrylate, propoxylated triacrylate (eg propoxylated) (3) Glyceryl triacrylate, propoxylated (5.5) Glyceryl triacrylate, propoxylated (3) Trimethylolpropane triacrylate, propylene Compounds having three (meth) acrylic groups such as ropoxylated (6) trimethylolpropane triacrylate), trimethylolpropane triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate; (c) ditrimethylolpropanetetra Acrylate, dipentaerythritol pentaacrylate, ethoxylated (4) compound having four or more (meth) acrylic groups such as pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexaacrylate; (d) Oligomeric (meth) acrylic compounds such as urethane acrylate, polyester acrylate, epoxy acrylate; the above polyacrylamide analogues; and this Include polyfunctional (meth) acrylic monomers and polyfunctional (meth) acrylate oligomer selected from the group consisting of. Such compounds are commercially available, and at least some are available from, for example, Sartomer, UCB Chemicals Corporation (Smyrna, GA), Aldrich Chemical Company, Milwaukee, Wis. Other useful (meth) acrylates include hydantoin moiety-containing poly (meth) acrylates as reported, for example, in US Pat. No. 4,262,072.

  Preferred curable monomers or curable oligomers contain at least three (meth) acrylic groups. Preferred commercially available curable monomers or curable oligomers are trimethylolpropane triacrylate (TMPTA) (trade name “SR351”), pentaerythritol tri / tetraacrylate (PETA) (trade names “SR444” and “SR295”), and Examples thereof include dipentaerythritol pentaacrylate (trade name “SR399”) available from Sartomer. Furthermore, a mixture of polyfunctional (meth) acrylate and monofunctional (meth) acrylate, such as a mixture of PETA and 2-phenoxyethyl acrylate (PEA), can also be used.

  The mixture of nanoparticles included in the hardcoat layer comprises about 40% to about 95% by weight of the total weight of the hardcoat layer, and in some embodiments, about 60% by weight of the total weight of the hardcoat layer. To about 90% by weight, or even about 70% to about 85% by weight. The mixture of nanoparticles comprises about 10% to about 50% by weight of nanoparticles having an average particle size in the range of about 2 nm to about 200 nm (hereinafter also referred to as a group of small particles or a first group of nanoparticles), and About 50% by mass to about 90% by mass of nanoparticles having an average particle size in the range of about 60 nm to about 400 nm (hereinafter also referred to as a group of large particles or a second group of nanoparticles). For example, the mixture of nanoparticles may comprise a first group of nanoparticles having an average particle size of about 2 nm to about 200 nm and a second group of nanoparticles having an average particle size of about 60 nm to about 400 nm of about 10:90 to about 50:50. It can be obtained by mixing at a mass ratio.

The average particle size of the nanoparticles can be measured with a transmission electron microscope (TEM) using techniques commonly used in the art. In measuring the average particle size of the nanoparticles, the sol sample was placed on a 400 mesh copper TEM grid with an ultra-thin carbon substrate on top of mesh lacey carbon (available from Ted Pella Inc. (Redding, Calif.)). By dripping, a sol sample for a TEM image can be prepared. Some of the droplets can be removed by contacting the side or bottom of the grid with the filter paper. The remainder of the sol solvent can be removed by heating or standing at room temperature. Thereby, particles can be left on the ultrathin carbon substrate, and imaging can be performed with the minimum interference from the substrate. The TEM image can then be recorded at a number of locations across the grating. Enough images are recorded to allow particle size measurements of 500-1000 particles. The average particle size of the nanoparticles can then be calculated based on the measured particle size in each sample. The TEM image can be obtained using a high-resolution transmission electron microscope (available under the trade name “Hitachi H-9000” from Hitachi High-Technologies Corporation) operating at 300 KV (using a LaB ₆ source). The images can be recorded using a camera (eg, available from Gatan, Inc. (Pleasanton, Calif.) Under the trade name “GATAN ULTRASCAN CCD”: model number 895, 2k × 2k chip). Images can be taken at 50,000x and 100,000x magnifications. In some samples, images can be taken at a magnification of 300,000 times.

Typically, the nanoparticles are inorganic particles. Examples of the inorganic particles include alumina, tin oxide, antimony oxide, silica (SiO, SiO ₂ ), zirconia, titania, ferrite and other inorganic oxides, a mixture thereof, or a mixed oxide thereof; metal vanadate, Examples thereof include metal tungstate, metal phosphate, metal nitrate, metal sulfate, and metal carbide. An inorganic oxide sol can be used as the inorganic oxide nanoparticles. For example, in the case of silica nanoparticles, silica sol obtained using water glass (sodium silicate solution) as a starting material can be used. Since silica sol obtained from water glass has a very narrow particle size distribution depending on the production conditions, the use of such silica sol can control the filling rate of nanoparticles in the hard coat layer more accurately, and can achieve desired characteristics. Can be obtained.

  The average particle size of the group of small particles ranges from about 2 nm to about 200 nm. Preferably, it is about 2 nm to about 150 nm, about 3 nm to about 120 nm, or about 5 nm to about 100 nm. The average particle size of the large group of particles ranges from about 60 nm to about 400 nm. Preferably, it is about 65 nm to about 350 nm, about 70 nm to about 300 nm, or about 75 nm to about 200 nm.

  The mixture of nanoparticles comprises a particle size distribution of at least two different nanoparticles. The particle size distribution of the mixture of nanoparticles may exhibit bimodality or multimodality that peaks at the average particle size of the group of small particles and the average particle size of the group of large particles. In addition to the particle size distribution, the nanoparticles may be the same or different (eg, compositionally surface modified or not surface modified). In some embodiments, the ratio of the average particle size of nanoparticles having an average particle size in the range of about 2 nm to about 200 nm and the average particle size of nanoparticles having an average particle size in the range of about 60 nm to about 400 nm is 2: 1 to 200: 1, and in some embodiments 2.5: 1 to 100: 1, or 2.5: 1 to 25: 1. Examples of preferable combinations of average particle diameters include 5 nm / 190 nm, 5 nm / 75 nm, 20 nm / 190 nm, 5 nm / 20 nm, 20 nm / 75 nm, 75 nm / 190 nm, or 5 nm / 20 nm / 190 nm. By using a mixture of nanoparticles having different sizes, it is possible to fill the hard coat layer with a large amount of nanoparticles and increase the hardness of the hard coat layer.

  Further, for example, by selecting the type, amount, size, and ratio of the nanoparticles, the transparency (such as haze) and hardness can be changed. In some embodiments, a hardcoat layer that combines the desired transparency and hardness can be obtained.

  The mass ratio (%) between the group of small particles and the group of large particles can be selected depending on the particle size used or a combination of particle sizes used. The preferred mass ratio can be selected according to the particle size used or a combination of particle sizes used, using software available under the trade name “CALVOLD2”, for example, a combination of particle sizes ( Selection of the model for Estimating the Void Fraction in can be selected based on simulations between the mass ratio of small particle groups and large particle groups and the packing factor for small particle groups / large particle groups) a Three-Component Randomly Packed Bed, "See also M. Suzuki and T. Shima: Powder Technol., 43, 147-153 (1985)). The simulation result is shown in FIG. According to this simulation, the mass ratio (small particle group: large particle group) is about 45:55 to about 13:87 or about 40:60 to about 15:85 at a combination of 5 nm / 190 nm; The mass ratio is about 45:55 to about 10:90 or 35:65 to about 15:85 in the 75 nm combination; the mass ratio is about 45:55 to about 10:90 in the 20 nm / 190 nm combination; 5 nm The mass ratio is about 50:50 to about 20:80 for the combination of 20 nm / 20 nm; the mass ratio is about 50:50 to about 22:78 for the combination of 20 nm / 75 nm; Preferably from about 50:50 to about 27:73.

  In some embodiments, the preferred combination of particle size and nanoparticles can be used to increase the amount of nanoparticles that fill the hardcoat layer and adjust the transparency and hardness of the resulting hardcoat layer can do.

  The thickness of the hard coat layer is generally in the range of about 80 nm to about 30 μm (in some embodiments, about 200 nm to about 20 μm, or about 1 μm to about 10 μm), but thicknesses outside these ranges Even in some cases, it can be usefully used. By using a mixture of nanoparticles of different sizes, it may be possible to obtain a hard coat layer that is thicker and harder.

  If necessary, the surface of the nanoparticles may be modified using a surface treatment agent. Generally, the surface treatment agent is a first end that binds to the particle surface (via covalent bonds, ionic bonds, or strong physisorption), renders the particles compatible with the resin, and / or is resin during curing. And a second end that reacts with. Examples of surface treating agents include alcohols, amines, carboxylic acids, sulfonic acids, phosphonic acids, silanes, and titanates. The preferred type of surface treatment is determined in part by the chemistry of the nanoparticle surface. Silane is preferred when silica and other siliceous fillers are used as the nanoparticles. In the metal oxide, silane and carboxylic acid are preferable. The surface modification can be performed either before, during, or after mixing with the curable monomer or curable oligomer. When silane is used, the reaction between the silane and the nanoparticle surface is preferably performed before mixing with the curable monomer or curable oligomer. The required amount of surface treatment agent depends on several factors such as the particle size and type of the nanoparticles, the molecular weight and type of the surface treatment agent. In general, it is preferred that approximately one surface treatment agent layer adhere to the surface of the particles. The required deposition procedure or reaction conditions also depend on the surface treatment used. When silane is used, the surface treatment is preferably carried out at high temperature for about 1 hour to about 24 hours under acidic or basic conditions. Surface treatment agents such as carboxylic acids usually do not require high temperatures and long time.

  Representative examples of the surface treatment agent include, for example, isooctyltrimethoxysilane, polyalkylene oxide alkoxysilane (for example, available from Momentive Specialty Chemicals, Inc. (Columbus, OH) under the trade name “SILQUEST A1230”), N— (3-triethoxysilylpropyl) methoxyethoxyethoxyethyl carbamate, 3- (methacryloyloxy) propyltrimethoxysilane (available from Alfa Aesar (Ward Hill, Mass.) Under the trade designation “SILQUEST A174”), 3- ( Acryloyloxy) propyltrimethoxysilane, 3- (methacryloyloxy) propyltriethoxysilane, 3- (methacryloyloxy) propylme Rudimethoxysilane, 3- (acryloyloxy) propylmethyldimethoxysilane, 3- (methacryloyloxy) propyldimethylethoxysilane, 3- (methacryloyloxy) propyldimethylethoxysilane, vinyldimethylethoxysilane, phenyltrimethoxysilane, n-octyl Trimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, vinylmethyldiacetoxysilane, vinylmethyldiethoxysilane, vinyltriacetoxysilane, vinyltriethoxysilane, vinyltriisopropoxy Silane, vinyltrimethoxysilane, vinyltriphenoxysilane, vinyltri (t-butoxy) silane, vinyltri (isobutoxy) Silane, vinyltriisopropenoxysilane, vinyltris (2-methoxyethoxy) silane, styrylethyltrimethoxysilane, mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, acrylic acid, methacrylic acid, oleic acid, stearin Compounds such as acid, dodecanoic acid, 2- [2- (2-methoxyethoxy) ethoxy] acetic acid (MEEAA), β-carboxyethyl acrylate, 2- (2-methoxyethoxy) acetic acid, methoxyphenylacetic acid, and mixtures thereof. Can be mentioned.

  If necessary, the binder of the hard coat layer is a known UV absorber, antifouling agent, antifogging agent, leveling agent, UV reflecting agent, antistatic agent, or other agents that add a cleaning facilitating function. These additives may be further included.

  In some embodiments, an ultraviolet absorber is included in the hard coat layer binder. A hard coat layer using an ultraviolet absorber can be suitably applied to a transparent substrate, and can provide, for example, an eye protector that protects a wearer's eyes from ultraviolet rays. The ultraviolet absorber can be mixed with a curable monomer or a curable oligomer. Known ultraviolet absorbers can be used, for example, benzophenone (for example, available under the trade name “Uvinul 3050” from BASF AG), benzotriazole (eg, available under the trade name “Tinvin 928” from BASF AG) ), Triazine-based (for example, available from BASF AG under the trade name “Tinuvin 1577”), salicylate-based, diphenylacrylate-based, cyanoacrylate-based UV absorbers, and hindered amine light stabilizers (HALS) (for example, BASF) (Available from AG under the trade name “Tinvin 292”). By using a combination of a known ultraviolet absorber and a hindered amine light stabilizer, the ultraviolet absorptivity of the hard coat layer can be further increased as compared with the case where each is used alone.

  The amount of the ultraviolet absorber added is, for example, from about 0.01 parts by weight to about 20 parts by weight (in some embodiments, about 0.1 parts by weight with respect to 100 parts by weight in total of the nanoparticles, the curable monomer, and the curable oligomer). 1 part by mass to about 15 parts by mass, or about 0.2 part by mass to about 10 parts by mass). In some embodiments, a protector that includes a UV absorber in the hard coat layer can achieve UV transmission of less than 3%.

  In some embodiments, an antifouling agent is included in the binder of the hard coat layer. It has been observed that the antifouling agent improves the ease of cleaning the hard coat layer surface (for example, prevention of fingerprint adhesion, oil prevention, dust prevention and / or antifouling function). A fluorinated (meth) acrylic compound can be used as an antifouling agent. Examples of the fluorinated (meth) acrylic compound include HFPO urethane acrylate or modified HFPO as described in JP-A-2008-538195. The fluorinated (meth) acrylic compound is included in the binder of the hard coat layer as an unreacted fluorinated (meth) acrylic compound, as a reaction product reacted with a curable monomer or curable oligomer, or as a combination thereof. . As an antifouling agent, a silicone polyether acrylate (for example, available from Evonik Goldschmidt GmbH (Essen, Germany) under the trade name “TEGORAD2250”) can also be used.

In the present disclosure, the _{HFPO, F (CF (CF 3} ) CF 2 O) n CF (CF 3) - (n is 2 to 15) includes perfluoroether moiety represented by, and such a perfluoroether site Means a compound.

  The antifouling agent is preferably a polyfunctional fluorinated (meth) acrylic compound. Since the polyfunctional fluorinated (meth) acrylic compound has a plurality of (meth) acrylic groups, it can react with a curable monomer or curable oligomer as a crosslinking agent, or a functional group contained in a binder at a plurality of sites. Can interact non-covalently with the group. As a result, antifouling durability can be enhanced. When a polyfunctional fluorinated (meth) acrylic compound is used as an antifouling agent, the coefficient of friction on the surface of the hard coat layer may be lowered to improve scratch resistance in some cases. When a polyfunctional fluorinated (meth) acrylic compound having 3 or more (meth) acrylic groups is used, the antifouling durability can be further improved.

  The polyfunctional fluorinated (meth) acrylic compound is preferably a perfluoroether compound having two or more (meth) acrylic groups because the perfluoroether group imparts excellent antifouling properties to the hard coat layer.

As the perfluoroether compound having two or more (meth) acryl groups, for example, a polyfunctional perfluoroether (meth) acrylate described in JP2008-538195A, JP2008-527090A, or the like is used. it can. As such a polyfunctional perfluoroether (meth) acrylate, specifically,
_{HFPO-C (O) N (} H) CH (CH 2 OC (O) CH = CH 2) 2;
_{HFPO-C (O) N (} H) C (CH 2 CH 3) (CH 2 OC (O) CH = CH 2) 2;
_{HFPO-C (O) NHC (} CH 2 OC (O) CH = CH 2) 3;
_{HFPO-C (O) N (} CH 2 CH 2 OC (O) CH = CH 2) 2;
_{HFPO-C (O) NHCH 2} CH 2 N (C (O) CH = CH 2) CH 2 OC (O) CH = CH 2;
_{HFPO-C (O) NHCH (} CH 2 OC (O) CH = CH 2) 2;
_{HFPO-C (O) NHC (} CH 3) (CH 2 OC (O) CH = CH 2) 2;
_{HFPO-C (O) NHC (} CH 2 CH 3) (CH 2 OC (O) CH = CH 2) 2;
_{HFPO-C (O) NHCH 2} CH (OC (O) CH = CH 2) CH 2 OC (O) CH = CH 2;
_{HFPO-C (O) NHCH 2} CH 2 CH 2 N (CH 2 CH 2 OC (O) CH = CH 2) 2;
_{HFPO-C (O) OCH 2} C (CH 2 OC (O) CH = CH 2) 3;
_{HFPO-C (O) NH (} CH 2 CH 2 N (C (O) CH = CH 2)) 4 CH 2 CH 2 NC (O) -HFPO;
_{CH 2 = CHC (O) OCH} 2 CH (OC (O) HFPO) CH 2 OCH 2 CH (OH) CH 2 OCH 2 CH (OC (O) HFPO) CH 2 OCOCH = CH 2;
_{HFPO-CH 2 O-CH 2} CH (OC (O) CH = CH 2) CH 2 OC (O) CH = CH 2
Etc.

The polyfunctional perfluoropolyether (meth) acrylate is, for example, a poly (hexafluoropropylene oxide) ester such as HFPO-C (O) OCH ₃ or a poly (hexafluoropropylene oxide) acid halide: HFPO-C (O). HFPO with HFPO-amide polyol or polyamine, HFPO-ester polyol or polyamine, HFPO-amide, or mixed amine and alcohol groups by reacting F with a material containing at least three alcohols or primary or secondary amino groups Synthesis through the first step of producing an ester, the second step of (meth) acrylating the alcohol group and / or amine group with (meth) acryloyl halide, (meth) acrylic anhydride, or (meth) acrylic acid To do You can. _{Alternatively, HFPO-C (O) N} (H) CH 2 CH 2 CH 2 N (H) CH 3 and the like adducts of trimethylol propane triacrylate (TMPTA), reactive perfluoroalkyl ether and poly (meth) acrylate It can also be synthesized using a Michael type addition reaction.

  As a polyfunctional fluorinated (meth) acrylic compound, the perfluoroether moiety is divalent, and both ends thereof are directly or via other groups or bonds (ether bond, ester bond, amide bond, urethane bond, etc.) ( Those having a (meth) acryl group bonded thereto are preferred. While not being bound by any theory, such a compound is more firmly bonded to the hard coat layer to enhance the antifouling durability, and the perfluoroether portion between the (meth) acryl groups is the hard coat layer. It is considered that it is easy to move to the surface and orient in the in-plane direction, and as a result, the antifouling property can be sufficiently developed.

  The polyfunctional fluorinated (meth) acrylic compound may contain siloxane units. When the nanoparticles are inorganic oxides, multifunctional fluorinated (meth) acrylic compounds containing siloxane units are not only the reaction of (meth) acrylic groups with curable monomers or curable oligomers, It is considered that the interaction with the particles allows the hard coat layer to be held more firmly, and the antifouling durability can be further enhanced. The nanoparticles are preferably silica nanoparticles that are chemically similar to siloxane bonds and have high affinity.

  The polyfunctional fluorinated (meth) acrylic compound containing a siloxane unit has, for example, one ethylenically unsaturated group added to a linear or cyclic oligosiloxane or polysiloxane (hydrogensiloxane) containing 3 or more Si—H bonds. Alternatively, a perfluoropolyether compound having two or more is added (hydrosilylation) in the presence of a platinum catalyst or the like in an amount of less than 1 equivalent with respect to the Si—H bond, and the hydroxyl group-containing ethylenic group is added to the remaining Si—H bond. Similarly, a saturated compound can be synthesized by addition (hydrosilylation) in the presence of a platinum catalyst and the like, and then reacting a hydroxyl group with epoxy (meth) acrylate, urethane (meth) acrylate, or the like. The partial molecular weight of the perfluoroether moiety calculated from the chemical formula can be 500-30000.

  The siloxane unit is preferably a cyclic siloxane unit derived from tetramethylcyclotetrasiloxane, pentamethylcyclopentasiloxane or the like in order to sufficiently exhibit the antifouling property due to the fluorinated site. The number of silicon atoms constituting the cyclic siloxane unit is preferably 3-7.

Examples of the polyfunctional fluorinated (meth) acrylic compound containing a siloxane unit include perfluoropolyether compounds having two or more (meth) acrylic groups described in JP 2010-285501 A. For example, the compounds of the formulas (19) and (21) in the same publication are divalent perfluoropolyether groups: —CF ₂ (OCF ₂ CF ₂ ) _p (OCF ₂ ) _q OCF ₂ — (p / q = 0. 9, p + q≈45), each having a structure in which cyclic siloxanes having 4 silicon atoms are bonded to both ends, and three acryloyloxy groups are bonded to these cyclic siloxanes via urethane bonds. The hard coat layer can be suitably used.

  The amount of the antifouling agent added is, for example, from about 0.01 parts by weight to about 20 parts by weight (in some embodiments, about 0.1 parts by weight with respect to 100 parts by weight in total of the nanoparticles, the curable monomer, and the curable oligomer). 1 part by mass to about 10 parts by mass, or about 0.2 part by mass to about 5 parts by mass).

  In some embodiments, an antifogging agent is included in the binder of the hard coat layer. In this embodiment, the hard coat layer is applied to the inside of the base material such as protective glasses and goggles, that is, the side facing the wearer, thereby preventing condensation of the lens and the like and ensuring the wearer's visual field. The antifogging agent can be mixed with a curable monomer or a curable oligomer. As an antifogging agent, anionic, cationic, nonionic or amphoteric surfactants can be used, for example, sorbitan monostearate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan and alkylene Sorbitan surfactants such as glycol condensate and fatty acid ester; glycerol monopalmitate, glycerol monostearate, glycerol monolaurate, diglycerol monopalmitate, glycerol dipalmitate, glycerol distearate, diglycerol Glycerin-based surfactants such as monopalmitate / monostearate, triglycerin monostearate, triglyceryl distearate, or alkylene oxide adducts thereof; polyethylene glycol monostearate Polyethylene glycol surfactants such as polyethylene glycol monopalmitate and polyethylene glycol alkylphenyl ether; trimethylolpropane surfactants such as trimethylolpropane monostearate; pentaerythritol monopalmitate, pentaerythritol monostearate Pentaerythritol surfactants such as alkylene oxide adducts of alkylphenols; esters of sorbitan / glycerin condensates with fatty acids, esters of sorbitan / alkylene glycol condensates with fatty acids; diglycerin dioleate sodium lauryl sulfate, Sodium dodecylbenzenesulfonate, cetyltrimethylammonium chloride, dodecylamine hydrochloride, lauric acid laurylamide Phosphate, triethyl cetyl ammonium iodide, oleyl amino diethylamine hydrochloride, dodecyl pyridinium salts, and isomers thereof. The antifogging agent may have a functional group that reacts with the curable monomer or curable oligomer.

  The amount of the antifogging agent added is, for example, about 0.01 parts by mass to about 20 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, about 0.1 parts by mass). 1 part by mass to about 15 parts by mass, or about 0.2 part by mass to about 10 parts by mass).

  The hard coat precursor that can be used to form the hard coat layer is a mixture of the above nanoparticles, curable monomers and / or curable oligomers, initiators, and optionally methyl ethyl ketone (MEK) or 1-methoxy. It includes the above-mentioned additives such as a solvent such as 2-propanol (MP-OH), an ultraviolet absorber, an antifouling agent, an antifogging agent, a leveling agent, an ultraviolet reflector, and an antistatic agent. The hard coat precursor of an embodiment includes a mixture of nanoparticles and a binder, the nanoparticles comprising 40% to 95% by weight of the total weight of the nanoparticles and binder, and 10% to 50% by weight of the nanoparticles. % Has an average particle size in the range of 2 nm to 200 nm, 50% to 90% by weight of the nanoparticles have an average particle size in the range of 60 nm to 400 nm, and an average particle size in the range of 60 nm to 400 nm. The ratio of the average particle size of the nanoparticles to the average particle size of the nanoparticles having an average particle size in the range of 2 nm to 200 nm is in the range of 2: 1 to 200: 1.

  As is generally known in the art, specific components of the hardcoat precursor can be combined to prepare the hardcoat precursor. For example, two or more different size modified or unmodified nanoparticle sols are mixed with a curable monomer and / or curable oligomer together with an initiator in a solvent and the solvent added to form the desired solid The hard coat precursor can be prepared by adjusting the content. As the reaction initiator, for example, a photoinitiator or a thermal polymerization initiator known in this technical field can be used. Depending on the curable monomer and / or curable oligomer used, the solvent may not be used.

  When using surface-modified nanoparticles, the hard coat precursor can be prepared as follows, for example. Inhibitors and surface modifiers are added to the solvent in a container (eg, in a glass bottle), and the resulting mixture is added to the aqueous solution in which the nanoparticles are dispersed, followed by stirring. The container is sealed and placed in an oven, for example at high temperature (eg 80 ° C.) for several hours (eg 16 hours). The water is then removed from the solution, for example using a rotary evaporator at high temperature (eg 60 ° C.). Solvent is added to the solution and then evaporated to remove residual water from the solution. It may be preferable to repeat the latter half of the steps several times. By adjusting the amount of solvent, the concentration of nanoparticles can be adjusted to a desired concentration (mass%).

  Techniques for applying a hard coat precursor (solution) to the surface of a substrate are known in the art, such as bar coating, dip coating, spin coating, capillary coating, spray coating, gravure coating, and screen printing. Can be mentioned. The coated hard coat precursor can be dried, if necessary, and cured by a polymerization method known in the art such as a photopolymerization method using ultraviolet rays or an electron beam or a thermal polymerization method. In this way, a hard coat layer can be formed on the substrate.

  As a base material of the protective device of the present disclosure, polyolefin (for example, polyethylene (PE), polypropylene (PP), etc.), polyurethane, polyester (for example, polyethylene terephthalate (PET), etc.), poly (meth) acrylate (for example, polymethyl) Methacrylate (PMMA)), polyvinyl chloride, polycarbonate (PC), polyamide, polyimide, phenolic resin, cellulose diacetate, cellulose triacetate, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile butadiene styrene copolymer (ABS), epoxy, polyacetate, Polymer materials such as PC and PMMA blends, PC and PMMA laminates, inorganic materials such as glass and ceramics, aluminum, nickel, nickel Chromium, such as a metallic material such as stainless steel can be used. Since it is comparatively light and strong when used as a protective device, it is preferable that the base material contains a material selected from the group consisting of polycarbonate, polymethyl methacrylate, polyethylene terephthalate and polypropylene.

  The base material may take a planar shape or a three-dimensional shape such as a film, a sheet, a plate, or a molded product, and may be flexible or rigid. In this disclosure, “flexible substrate” means a substrate that can be subjected to mechanical stresses such as bending or stretching without significant irreversible changes, and “rigid substrate” Means a substrate that cannot be subjected to mechanical stress such as bending or stretching without significant irreversible changes. Since the hard coat layer of the present disclosure is highly filled with nanoparticles and has a sufficient hardness even if it is relatively thin, it can be advantageously applied to a flexible substrate.

  The substrate may be transparent or opaque. In the present disclosure, “transparent” means that the total light transmittance in the visible light region (380 nm to 780 nm) is 90% or more, and “opaque” means the total light transmittance in the visible light region (380 nm to 780 nm). Is less than 90%. Since the hard coat layer of the present disclosure has high optical transparency, it can be advantageously applied to a transparent substrate.

  The hard coat layer may be disposed on a part of the surface of the substrate, or the hard coat layer may be disposed on a plurality of surfaces of the substrate. A plurality of hard coat layers can also be applied to the surface of the substrate. The protective device may include a plurality of substrates having a hard coat layer.

  In some embodiments, the surface of the substrate is primed or a primer layer is disposed on the surface of the substrate in order to improve the adhesion between the hard coat layer and the substrate. The primer treatment or the primer layer is particularly effective particularly when the base material contains a poorly adhesive polymer material such as polypropylene or polyvinyl chloride, or a metal material. In these embodiments, the first surface of the substrate has a primer-treated surface or a primer layer disposed thereon, and the first surface of the substrate and the hard coat layer are interposed via the primer-treated surface or primer layer. Are joined.

  Primer treatment is known in the art, and examples include surface treatment such as plasma treatment, corona discharge treatment, flame treatment, electron beam irradiation, surface roughening, ozone treatment, chemical oxidation treatment using chromic acid or sulfuric acid. It is done.

  As a material for the primer layer, for example, a (meth) acrylic resin (a (meth) acrylate homopolymer, a copolymer of two or more (meth) acrylates, or a copolymer of (meth) acrylate and another polymerizable monomer) Coalesced), urethane resin (for example, two-component curable urethane resin composed of polyol and isocyanate curing agent), (meth) acryl-urethane copolymer (for example, acrylic-urethane block copolymer), polyester resin, butyral resin , Chlorinated polyolefins such as vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, chlorinated polyethylene, chlorinated polypropylene, and copolymers and derivatives thereof (for example, chlorinated ethylene-propylene copolymer, Chlorinated ethylene-vinyl acetate copolymer, acrylic modified chlorinated Polypropylene, maleic acid-modified chlorinated polypropylene anhydride, urethane-modified chlorinated polypropylene) and the like. When the substrate comprises polypropylene, it is advantageous that the primer layer comprises chlorinated polypropylene or modified chlorinated polypropylene.

  The primer layer can be formed by applying a primer solution prepared by dissolving the above resin in a solvent by a method known in the art and drying it. The thickness of the primer layer generally ranges from about 0.1 μm to about 20 μm (in some embodiments, from about 0.5 μm to about 5 μm).

  As needed, the base material may have a printing layer, a colored layer, a metal thin film layer, etc. which have a desired pattern in the inside or the surface.

  As protective equipment of the present disclosure, for example, eye protection such as protective glasses, goggles, respiratory protection equipment such as face shield, dust mask, gas mask, and sound protection equipment such as earmuffs, etc. However, it may be worn on other parts of the body.

  For example, in the case of eye protectors such as protective glasses and goggles, a hard coat layer can be disposed on the outside, inside or both surfaces of the lens. The hard coat layer disposed on the inner surface of the lens may contain an antifogging agent. The hard coat layer may be disposed only on the outer surface of the lens, and the inner surface of the lens may be subjected to an antifogging treatment known in the art.

  For example, in the case of respirators such as face shields, dust masks, gas masks, or soundproof protectors such as earmuffs, a hard coat layer may be placed on the surface of transparent parts such as lenses and visors. Further, a hard coat layer may be disposed on the outer surface of the protective device main body, cup, headband or the like. In an embodiment, a respiratory protective device in which a transparent film having a hard coat layer of the present disclosure or a laminate of such a transparent film is attached to a surface of a lens, a visor, or the like may be used. In this embodiment, by removing the scratched used film and applying a new film having a hard coat layer, the protective device can be used for a long time at a low cost without changing the lens or the visor. . Examples of such respiratory protective equipment and soundproof protective equipment are shown in FIGS. The face shield 10 shown in FIG. 2 protects an operator's head and face, and includes a visor 12 made of a transparent base material made of polycarbonate and a protective cap 14 having an opaque base material such as polypropylene on the outer surface. Yes. A hard coat layer can be disposed on the surface of the visor 12, the protective cap 14, or both. 3, a hard coat layer can be disposed on the surface of the lens 22, and a hard coat layer may be disposed on the outer surface of the gas mask body. The earmuff 30 of FIG. 4 includes two cups 32 connected by a headband 34. For example, a hard coat layer can be disposed on the surface of the cup 32.

  In the following examples, specific embodiments of the present disclosure are illustrated, but the present invention is not limited thereto. All parts and percentages are by weight unless otherwise specified.

<Evaluation method>
The characteristics of the hard coat layer applied to the protective device of the present disclosure were evaluated according to the following methods.

1. Steel Wool Abrasion Resistance Test One of the scratch resistances of the hard coat layer was evaluated by changes in haze and total light transmittance after the steel wool abrasion resistance test. In the steel wool abrasion resistance test, 27 mm square # 0000 steel wool was used, and the surface of the hard coat layer formed on the polycarbonate substrate was loaded with a load of 2.0 kg, a stroke of 85 mm, and a speed of 60 cycles / minute. Polish 200 times (cycle). FIG. 5 shows a schematic diagram of a steel wool wear resistance test apparatus 60 (rubbing tester IMC-157C, obtained from Imoto Seisakusho Co., Ltd.). Here, the sample 10 is fixed on the stage 61, the load of the weight 63 is applied to the steel wool 64 via the stylus 62, the surface of the sample is polished by reciprocating the stage 61, and then the optical characteristics of the sample are measured. It was measured. The steel wool abrasion resistance test simulates scratching during wiping and cleaning.

2. Sand Drop Abrasion Resistance Test One of the scratch resistances of the hard coat layer was evaluated by changes in haze and total light transmittance after the sand drop abrasion resistance test according to JIS T 8147 (2003). As the scratch resistance of the plastic lens for protective equipment, the haze after the sand drop wear resistance test is required to be less than 8%. FIG. 6 shows a schematic diagram of a sand drop wear resistance test apparatus 70 based on JIS T 8147 (2003). A black silicon carbide abrasive C # 80 specified in JIS R 6111 is put into the hopper 71, and the abrasive is applied to the surface of the sample fixed to the sample holder 75 in the abrasive receiver 73 through the guide pipe 72 from a height of 635 mm. Drop it. While the abrasive is dropped, the sample is rotated by rotating the sample holder 75 by the electric motor 76 and the belt 77 protected by the shielding plate 74. The numerical value of FIG. 5 is the dimension of each part of the apparatus expressed in millimeters. The falling amount of the abrasive was 60 to 80 g / min, and the total amount was 400 g. After dropping the abrasive, dust was removed from the surface of the hard coat layer and the optical properties of the sample were measured.

3. Adhesion test The adhesion of the hard coat layer to the substrate was evaluated by a cross-cut test based on JIS K5600. A 5 × 5 grid and an adhesive tape (obtained from Nitto Denko Co., Ltd. under the trade name “NICHIBAN”) were used.

4). Optical properties (haze and total light transmittance)
The haze and total light transmittance of the sample were measured using a haze meter NDH-5000W (obtained from Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7136 (2000) and JIS K 7361-1 (1997), respectively. It was measured.

5. Contact angle A contact angle meter (obtained from Kyowa Interface Science Co., Ltd. as a product name “DROPMASTER FACE”) was used to measure the water contact angle of the hard coat layer surface formed on the polycarbonate substrate by the Sessile Drop method. For static measurements, the droplet volume was 4 μL. The water contact angle value was calculated from the average measured five times. A surface having a water contact angle exceeding 100 degrees can easily remove fingerprints, paints, fats and oils, and the like adhering to the surface.

  The reagents and raw materials used in this example are shown in Table 1 below.

<Preparation of surface-modified silica sol (sol 1)>
A surface-modified silica sol (“sol 1”) was prepared as follows. 5.95 g SILQUEST A174 and 0.5 g PROSTAB were added to a mixture of 400 g NALCO 2329 and 450 g 1-methoxy-2-propanol in a glass bottle and stirred for 10 minutes at room temperature. The glass bottle was sealed and placed in an 80 ° C. oven for 16 hours. Water was removed from the resulting solution with a rotary evaporator at 60 ° C. until the solid content of the solution was close to 45% by mass. 200 g of 1-methoxy-2-propanol was added to the resulting solution and then the remaining water was removed using a rotary evaporator at 60 ° C. The latter step was repeated twice to remove more water from the solution. Finally, the SiO ₂ sol containing surface-modified SiO ₂ nanoparticles with an average particle size of 75 nm, with the addition of 1-methoxy-2-propanol to adjust the concentration of all SiO ₂ nanoparticles to 45% by weight. (Hereinafter referred to as sol 1).

<Preparation of surface-modified silica sol (sol 2)>
A surface-modified silica sol (“sol 2”) was prepared as follows. Surface modified SiO ₂ nanoparticles with an average particle size of 20 nm were modified in the same manner as sol 1 except that 400 g NALCO 2327, 25.25 g SILQUEST A174 and 0.5 g PROSTAB were used. An SiO ₂ sol containing 45% by mass (hereinafter referred to as sol 2) was obtained.

<Preparation of hard coat precursor (HC-1)>
108.33 g of sol 1, 58.33 g of sol 2, 22.5 g of SR399, and 2.5 g of SR340 were mixed. 2.00 g Irgacure 2959 as photopolymerization initiator and 0.01 g BYK-UV3500 as leveling agent were added to the mixture. Next, 1-methoxy-2-propanol was added to adjust the solid content to 50.5% by mass to prepare a hard coat precursor HC-1.

<Preparation of hard coat precursor (HC-2)>
108.33 g of sol 1, 58.33 g of sol 2, and 25.0 g of Kayrad UX-5000 were mixed. 2.5 g of KY-1203 as an antifouling agent, 2.00 g of Irgacure 2959 as a photopolymerization initiator, and 0.01 g of BYK-UV3500 as a leveling agent were added to the mixture. Next, 1-methoxy-2-propanol was added to adjust the solid content to 50.1% by mass to prepare a hard coat precursor HC-2.

  The composition of HC-1 and HC-2 is shown in Table 2.

<Comparative Example 1>
An untreated polycarbonate substrate (100 × 53 × 1 mm, obtained from Mitsubishi Gas Chemical Co., Ltd. under the trade name “Iupilon NF-2000”) was used as Comparative Example 1.

<Example 1>
A polycarbonate substrate (100 × 53 × 1 mm, obtained from Mitsubishi Gas Chemical Co., Ltd. under the trade name “Iupilon NF-2000”) was fixed on a glass plate with level adjustment. Hard coat precursor HC-1 was applied to a polycarbonate substrate using Mayer rod # 16 and dried in air at 60 ° C. for 5 minutes. Next, Fusion UV System Inc. The H-bulb (DRS model) was used to irradiate the coated surface with ultraviolet rays (UV-A) in a nitrogen gas atmosphere so that the total irradiation amount was 900 mJ / cm ² . The thickness of the hard coat layer was 9.5 μm. In this way, the hard coat layer of Example 1 was formed on the polycarbonate substrate.

<Example 2>
A polycarbonate substrate (100 × 53 × 1 mm, obtained from Mitsubishi Gas Chemical Co., Ltd. under the trade name “Iupilon NF-2000”) was fixed on a glass plate with level adjustment. The hard coat precursor HC-2 was applied to a polycarbonate substrate using a Mayer rod # 16 and dried in air at 60 ° C. for 5 minutes. Next, using a UV irradiation device (high pressure mercury lamp, 3 kW, 10.3 A, 500 V, obtained from Eye Graphics Co., Ltd.), once in air, the irradiation amount is 400 mJ / cm ^{2 in} total. The coated surface was irradiated with ultraviolet rays (UV-A). The thickness of the hard coat layer was 9.5 μm. In this way, the hard coat layer of Example 2 was formed on the polycarbonate substrate.

  The results of evaluating these hard coat layers are shown in Table 3.

  In both Example 1 and Example 2, the adhesion at the interface between the polycarbonate substrate and the hard coat layer was excellent, and no peeling of the hard coat layer was observed in the adhesion test.

  The initial haze and total light transmittance of Examples 1 and 2 were less than 1% and 90% or more, respectively, and had high transparency equivalent to that of an untreated polycarbonate substrate (Comparative Example 1). This indicates that the protective article of the present disclosure is particularly suitable for optical applications such as protective glasses and goggles.

  After the sand drop abrasion resistance test, the haze of the untreated polycarbonate substrate (Comparative Example 1) increased to 40.64%, but less than 8% for the hard-coated polycarbonate substrates (Example 1 and Example 2). Scratches were hardly observed by visual inspection.

  After the steel wool abrasion resistance test, the haze of the untreated polycarbonate substrate (Comparative Example 1) increased to 24.34%, whereas the hard-coated polycarbonate substrate (Examples 1 and 2) was less than 1%. It was. In Examples 1 and 2, the total light transmittance was maintained at 90% or more, and scratches were hardly observed by visual inspection.

  The hard coat layer (Example 2) containing an antifouling agent (KY-1203: polyfunctional fluorinated (meth) acrylic compound) exhibits a water contact angle exceeding 100 degrees on its surface, and even after a steel wool abrasion resistance test A water contact angle exceeding 90 degrees was shown.

DESCRIPTION OF SYMBOLS 10 Face shield 12 Visor 14 Protection cap 20 Gas mask 22 Lens 30 Earmuff 32 Cup 34 Headband 60 Steel wool abrasion resistance test device 61 Stage 62 Stylus 63 Weight 64 Steel wool 70 Sand drop abrasion resistance test device 71 Hopper 72 Guide pipe 73 Grinding Material holder 74 Shield plate 75 Sample holder 76 Electric motor 77 Belt

Claims (13)

A protective device comprising a substrate having a first surface, and a hard coat layer disposed on the first surface of the substrate, the hard coat layer comprising a mixture of nanoparticles and a binder;
The nanoparticles constitute 40% by mass to 95% by mass of the total mass of the hard coat layer,
10% to 50% by weight of the nanoparticles have an average particle size in the range of 2 nm to 200 nm, 50% to 90% by weight of the nanoparticles have an average particle size in the range of 60 nm to 400 nm, The ratio of the average particle size of nanoparticles having an average particle size in the range of 60 nm to 400 nm and the average particle size of nanoparticles having an average particle size in the range of 2 nm to 200 nm is in the range of 2: 1 to 200: 1. ,Protective equipment.   The protective device of claim 1, wherein the nanoparticles are surface-modified nanoparticles.   The protective device according to claim 1, wherein the protective device is attached to a head or a face.   The protector as described in any one of Claims 1-3 in which the said binder contains a fluorinated (meth) acryl compound, its reaction product, or those combination.   The protector as described in any one of Claims 1-4 in which the said binder contains an anti-fogging agent.   The protector as described in any one of Claims 1-5 in which the said base material contains the material selected from the group which consists of a polycarbonate, a polymethylmethacrylate, a polyethylene terephthalate, and a polypropylene.   The protector as described in any one of Claims 1-6 whose said base material is transparent.   The protector as described in any one of Claims 1-7 in which the said base material has flexibility.   The first surface of the substrate has a primer-treated surface or a primer layer disposed thereon, and the first surface of the substrate and the hard coat layer are interposed via the primer-treated surface or the primer layer. The protector as described in any one of Claims 1-8 currently joined.   The protector as described in any one of Claims 1-9 whose said protector is goggles.   The protector as described in any one of Claims 1-9 whose said protector is a respiratory protector.   The protector as described in any one of Claims 1-9 whose said protector is an earmuff.   The protector as described in any one of Claims 1-9 whose said protector is a visor.

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