JP6062680B2 - Antifouling hard coat and antifouling hard coat precursor - Google Patents

Description

  The present disclosure relates to an antifouling hard coat and an antifouling hard coat precursor.

  Hard coats are used to protect the surfaces of various hard and flexible materials. Hard coats are required to have excellent scratch resistance and impact resistance, and optical properties are required for transparent materials. There is also a strong demand for imparting antifouling properties to the hard coat surface.

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

  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

  The antifouling property of the hard coat tends to decrease with wear of the hard coat surface. Therefore, it is still desired to further improve the durability of the antifouling hard coat. Accordingly, an object of the present disclosure is to provide a hard coat and a hard coat precursor that have excellent scratch resistance and high antifouling durability.

  According to an embodiment of the present disclosure, a hard coat 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, 10% to 50% by weight 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, and 60 nm to 400 nm. The ratio of the average particle size of nanoparticles having an average particle size in the range to 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, and the binder is A hard coat comprising a multifunctional fluorinated (meth) acrylic compound, its reaction product, or a combination thereof is provided.

  According to another embodiment of the present disclosure, a hard coat precursor comprising a mixture of nanoparticles and a binder, wherein the nanoparticles constitute 40% to 95% by weight of the total weight of the nanoparticles and the binder 10% to 50% by mass of the nanoparticles have an average particle size ranging from 2 nm to 200 nm, and 50% to 90% by mass of the nanoparticles have an average particle size ranging from 60 nm to 400 nm. The ratio of the average particle diameter of nanoparticles having an average particle diameter in the range of 60 nm to 400 nm and the average particle diameter of nanoparticles having an average particle diameter in the range of 2 nm to 200 nm is in the range of 2: 1 to 200: 1. A hard coat precursor is provided wherein the binder comprises a multifunctional fluorinated (meth) acrylic compound.

  The antifouling hard coat of the present disclosure highly filled with nanoparticles exhibits both excellent scratch resistance and impact resistance while maintaining optical transparency. And since the binder contains a polyfunctional fluorinated (meth) acrylic compound, its reaction product, or a combination thereof, it prevents adhesion of fingerprints, oils and fats, dust, dirt, etc. Can be easily washed, and the durability of the antifouling property can be enhanced. Moreover, such an antifouling hard coat can be formed using the antifouling hard coat precursor of the present disclosure.

  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 schematic diagram of the 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 hard coat according to an embodiment of the present disclosure includes a mixture of nanoparticles and a binder, the binder including a multifunctional fluorinated (meth) acrylic compound, a reaction product thereof, or a combination thereof.

  Typical binders contained in the hard coat include a resin obtained by polymerizing a curable monomer and / or a curable oligomer, a resin obtained by polymerizing a 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 hard coat binder is typically about 5% to about 60% by weight of the total weight of the hard coat, and in some embodiments, about 10% to about 40%, or about 15%. % To about 30% by mass. According to the present disclosure, a hard coat can be formed even if the amount of the binder is relatively small.

  If necessary, the hard coat may be further cured with other curable monomers or curable oligomers. 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 comprises from about 40% to about 95% by weight of the total weight of the hardcoat, and in some embodiments, from about 60% to about 90% of the total weight of the hardcoat. It constitutes about 70% by weight 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, using such a silica sol more accurately controls the packing rate of the nanoparticles in the hard coat, and achieves the desired characteristics. The hard coat which has 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 with different sizes, the hard coat can be filled with a large amount of nanoparticles to increase the hardness of the hard coat.

  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 hard coat can be obtained that combines the desired transparency and hardness.

  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 are loaded into the hard coat and to adjust the transparency and hardness of the resulting hard coat Can do.

  The thickness of the hard coat generally ranges from about 80 nm to about 30 μm (in some embodiments, from about 200 nm to about 20 μm, or from about 1 μm to about 10 μm), but with a thickness outside these ranges Even if it exists, it may be useful. By using a mixture of nanoparticles of different sizes, a thicker and harder hard coat may be obtained.

  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.

  The antifouling hard coat binder of the present disclosure includes a polyfunctional fluorinated (meth) acrylic compound, a reaction product thereof, or a combination thereof, thereby imparting antifouling property to the hard coat surface and cleaning. Ease (for example, fingerprint adhesion prevention, oil prevention, dust prevention and / or antifouling function) is improved. 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, the coefficient of friction on the hard coat surface 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.

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. 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 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 strongly bonded to the hard coat to increase the antifouling durability, while the perfluoroether portion between the (meth) acrylic groups is present on the hard coat surface. It is considered that it can easily migrate and be oriented in the in-plane direction, and as a result, the antifouling property can be sufficiently exhibited.

  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 hard coat is more firmly held by the interaction with the particles, 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. It can be suitably used for an antifouling hard coat.

  Multifunctional fluorinated (meth) acrylic compounds and their reaction products are, for example, nanoparticles, curable monomers and curable when the reaction product is considered the corresponding multifunctional fluorinated (meth) acrylic compound From about 0.01 parts by weight to about 20 parts by weight (in some embodiments, from about 0.1 parts by weight to about 10 parts by weight, or from about 0.2 parts by weight to about 5 parts by weight, based on a total of 100 parts by weight of oligomers. In the range of (part by mass), it is contained in the binder.

  If necessary, the hard coat binder may further contain known additives such as UV absorbers, anti-fogging agents, leveling agents, UV reflectors, anti-static agents, or other agents that add a cleaning facilitating function. May be included.

  In some embodiments, a UV absorber is included in the hard coat binder. 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 absorbability of the hard coat 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 hardcoat comprising a UV absorber can achieve UV transmission of less than 3%.

  In some embodiments, an antifogging agent is included in the hardcoat binder. 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).

  A hard coat precursor that can be used to form a hard coat includes a mixture of the above nanoparticles, a curable monomer and / or a curable oligomer, and a binder containing a polyfunctional fluorinated (meth) acrylic compound, a reaction initiator And, if necessary, the above-mentioned addition of a solvent such as methyl ethyl ketone (MEK) or 1-methoxy-2-propanol (MP-OH), an ultraviolet absorber, an antifogging agent, a leveling agent, an ultraviolet reflector, an antistatic agent, etc. Contains agents. 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, and the binder is multifunctional fluorinated (meta) Contains acrylic compounds.

  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 can be formed on the substrate.

  Typical substrates to which the antifouling hard coat of the present disclosure is applied include films, plastics (polymer plates), plate glass, metal sheets and the like. The film 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%. Typical films include polyolefin (for example, polyethylene (PE), polypropylene (PP), etc.), polyurethane, polyester (for example, polyethylene terephthalate (PET)), poly (meth) acrylate (for example, polymethyl methacrylate (PMMA)). Etc.), polyvinyl chloride, polycarbonate, polyamide, polyimide, phenolic resin, cellulose diacetate, cellulose triacetate, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile butadiene styrene copolymer (ABS), epoxy, polyacetate, or glass Is mentioned. The plastic (polymer plate) may be transparent or opaque. Typical plastics (polymer plates) include polycarbonate (PC), polymethyl methacrylate (PMMA), styrene-acrylonitrile copolymer, acrylonitrile butadiene styrene copolymer (ABS), a blend of PC and PMMA, or a laminate of PC and PMMA. What was formed is mentioned. The metal sheet may be flexible or rigid. In the present disclosure, “flexible metal sheet” means a metal sheet that can be subjected to mechanical stress such as bending or stretching without significant irreversible changes, and “rigid metal sheet” Means a metal sheet that cannot be subjected to mechanical stresses such as bending or stretching without significant irreversible changes. Exemplary flexible metal sheets include those made from aluminum. Exemplary rigid metal sheets include those made from aluminum, nickel, nickel-chromium, and stainless steel.

  The thickness of the film ranges from about 5 μm to about 500 μm (in some embodiments, from about 10 μm to about 200 μm, or from about 25 μm to about 100 μm). The thickness of the plastic (polymer plate) ranges from about 0.5 mm to about 10 cm (in some embodiments, from about 0.5 mm to about 5 mm, or from about 0.5 mm to about 3 mm). The thickness of the glass sheet or metal sheet ranges from about 5 μm to about 500 μm, or from about 0.5 mm to about 10 cm (in some embodiments, from about 0.5 mm to about 5 mm, or from about 0.5 mm to about 3 mm). It is. These substrates may be usefully used even if they have a thickness outside the above range.

  Hard coats can be applied to multiple surfaces of the substrate. A plurality of hard coat layers can also be applied to the surface of the substrate.

  In some embodiments, the surface of the substrate is primed or a primer layer is disposed on the surface of the substrate to improve the adhesion between the hard coat and the substrate. The primer treatment or the primer layer is particularly effective particularly when the substrate contains a hardly adhesive material such as polypropylene or polyvinyl chloride or is a metal sheet.

  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 is a polypropylene film, 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.

  If necessary, an article having the hard coat of the present disclosure may have an adhesive layer. The adhesive layer can be disposed, for example, on the surface of the opposite substrate as viewed from the hard coat. As the adhesive layer, rubber-based, acrylic-based, polyurethane-based, polyolefin-based, polyester-based, and silicone-based adhesives or pressure-sensitive adhesives known in this technical field can be used. The adhesive layer may be formed by applying or extruding the adhesive and the pressure-sensitive adhesive directly to the substrate, and the adhesive layer formed by applying it to a release liner or the like may be laminated and transferred to the substrate.

  The thickness of the adhesive layer comprising the adhesive or pressure sensitive adhesive generally ranges from about 1 μm to about 100 μm (in some embodiments, from about 5 μm to about 75 μm, or from about 10 μm to about 50 μm). The adhesive or pressure sensitive adhesive may contain the above-described UV absorber.

  If necessary, a release liner or a protective liner known in the art may be applied on the hard coat and / or the adhesive layer. As the release liner, those known in this technical field in which a paper or a polymer film is treated with silicone or the like can be used.

  The antifouling hard coat of the present disclosure includes, for example, an optical display (for example, a cathode ray tube (CRT), a light emitting diode (LED) display), a plastic card, a camera lens or body, a fan, a door knob, a faucet handle, a mirror, And household appliances such as vacuum cleaners or washing machines; devices such as personal digital assistants (PDAs), mobile phones, liquid crystal display (LCD) panels, touch-sensitive screens and removable computer screens, and the bodies of such devices, etc. Useful in. The antifouling hard coat of the present disclosure is also useful, for example, for furniture, doors and windows, toilets and bathtubs, interior / exterior of vehicles, lenses (camera or glasses), or photovoltaic panels (solar panels). There can be.

  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 properties of the hard coat of the present disclosure were evaluated according to the following methods. The hard coat was formed by applying a hard coat precursor to a substrate and irradiating it with ultraviolet rays, and was evaluated in a state of being supported on the substrate.

1. Pencil Hardness Based on JIS K5600-5-4 (1999), the pencil hardness of the hard coat surface formed on the substrate using a weight of 750 g was determined.

2. Optical properties The haze of the hard coat was measured using a haze meter NDH-5000W (obtained from Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7136 (2000).

3. Contact angle A contact angle meter (obtained from Kyowa Interface Science Co., Ltd. as a product name “DROPMASTER FACE”) was used, and the water contact angle of the hard coat surface was measured 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.

4). Ink repellency test Using an oil-based magic (Mckey (black), obtained from Zebra Corporation), a straight line was drawn on the hard coat and the appearance was visually observed. Samples that repel ink and did not become lines were good, and samples that could draw lines without repelling were considered bad.

5. Abrasion Resistance Test The scratch resistance of the hard coat was evaluated by measuring optical properties and water contact angle after the abrasion resistance test. In the fabric abrasion resistance test, a 32 mm wide JIS test cotton fabric (obtained from the Japan Industrial Standards Committee) was used at a load of 500 g, and in a steel wool abrasion resistance test, 32 mm square # 0000 steel wool was used at a load of 1 kg. The hard coat surface is polished 200 times (cycle) at a stroke of 60 cycles / minute. FIG. 2 shows a schematic diagram of an abrasion resistance test apparatus 60 (rubbing tester IMC-157C, available 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 fabric or steel wool 64 via the stylus 62, and the stage 61 is reciprocated to polish the surface of the sample. The abrasion resistance test simulates scratching during wiping and cleaning.

  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)>
11.34 g of sol 1, 5.88 g of sol 2, 2.25 g of Ebecryl 4858, and 0.25 g of SR340 were mixed. 0.20 g of Irgacure 2959 as photopolymerization initiator and 0.001 g of BYK-UV3500 as leveling agent were added to the mixture. Next, 1-methoxy-2-propanol was added to adjust the solid content to 50% by mass to prepare a hard coat precursor HC-1.

<Preparation of hard coat precursor (HC-2)>
11.34 g of sol 1, 5.88 g of sol 2, 2.25 g of Ebecryl 4858, and 0.25 g of SR340 were mixed. 0.17 g HFPO urethane acrylate as an antifouling agent, 0.1 g Irgacure 2959 as a photopolymerization initiator, and 0.001 g 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% by mass to prepare a hard coat precursor HC-2. HFPO urethane acrylate is a monofunctional fluorinated (meth) acrylic compound.

<Preparation of hard coat precursor (HC-3 to HC-8)>
Hard coat precursors HC-3 to HC-8 were prepared in the same manner as HC-2 with the formulation described in Table 2. HC-6 to HC-8 use Kayarad UX-5000 as an acrylate oligomer, and HC-4, HC-5 and HC-8 use KY-1203 as a polyfunctional (meth) acrylic compound (antifouling agent) did.

  The composition of HC-1 to HC-8 is shown in Table 2.

<Example 1>
A PMMA substrate (Acrylite L-001, 100 × 53 × 2 mm, obtained from Mitsubishi Rayon Co., Ltd.) was fixed on a stainless steel table with level adjustment. The hard coat precursor HC-4 was applied to a PMMA substrate using a Mayer rod # 16 and dried 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 10 times (irradiation amount: about 1400 mJ / cm ² ) at a line speed of 13 m / min in a nitrogen atmosphere. The thickness of the hard coat was about 10 μm. In this way, the hard coat of Example 1 was formed on the PMMA substrate.

<Examples 2 and 3 and Comparative Example 1-5>
A hard coat was formed on the PMMA substrate in the same manner as in Example 1 using the hard coat precursors HC-1 to HC-3 and HC-5 to HC-8.

  The results of evaluating these hard coats are shown in Tables 3 and 4.

  As shown in Table 3, hard coats (Examples 1 and 2: KY-1203, Comparative Examples 2 and 3: HFPO urethane acrylate) containing a fluorinated (meth) acrylic compound as an antifouling agent are also fluorinated (meth) acrylic. The pencil hardness was 8H, which was equivalent to that of the hard coat containing no compound (Comparative Example 1). Addition of an appropriate amount of fluorinated (meth) acrylic compound did not affect the pencil hardness of the hard coat. The water contact angle increased with the addition of the fluorinated (meth) acrylic compound. HC-4 (Example 1) and HC-5 (Example 2) showed good ink repellency even after the fabric abrasion resistance test. On the other hand, with HC-3 (Comparative Example 3) in which the amount of HFPO urethane acrylate as an antifouling agent was increased, ink repellency was poor after the fabric abrasion resistance test.

  Table 4 shows the results of a steel wool abrasion resistance test in addition to the fabric abrasion resistance test. For the fabric abrasion resistance test, the water contact angle and ink repellency before and after the test were compared, and for the steel wool abrasion resistance test, the water contact angle, ink repellency and optical characteristics before and after the test were compared. HC-7 (Comparative Example 5) and HC-8 (Example 3) showed water contact angles greater than 100 degrees and good ink repellency both at the initial stage and after the fabric abrasion resistance test. As a urethane acrylate oligomer, the hard coat of Example 2 containing UX-5000, a multifunctional acrylate having multiple acrylate groups, had a higher scratch resistance than the hard coat of Example 3 containing Ebecryl 4858.

Steel wool wear resistance was improved by the addition of fluorinated (meth) acrylic compounds. The change in haze value (Δhaze) after the steel wool abrasion resistance test of HC-7 (Comparative Example 5) and HC-8 (Example 3) was less than 0.1%. The fluorinated (meth) acrylic compound reduced the coefficient of friction on the hard coat surface and improved the steel wool wear resistance of the hard coat. In particular, HC-8 (including Example 8, KY-1203) had excellent scratch resistance and high durability with respect to antifouling properties. HC-8 ink repellency did not change even after the steel wool abrasion resistance test. The hard coat containing a polyfunctional fluorinated (meth) acrylic compound having a siloxane unit had higher antifouling durability than that containing a monofunctional fluorinated (meth) acrylic compound.
The present disclosure also includes:
[1] A hard coat comprising a mixture of nanoparticles and a binder,
The nanoparticles constitute 40 mass% to 95 mass% of the total mass of the hard coat,
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. The hard coat, wherein the binder comprises a polyfunctional fluorinated (meth) acrylic compound, a reaction product thereof, or a combination thereof.
[2] The hard coat according to aspect 1, wherein the nanoparticles are surface-modified nanoparticles.
[3] The hard coat according to any one of the above aspects 1 or 2, wherein the polyfunctional fluorinated (meth) acrylic compound is a perfluoroether compound having two or more (meth) acrylic groups.
[4] The hard coat according to any one of the above aspects 1 to 3, wherein the polyfunctional fluorinated (meth) acrylic compound has three or more (meth) acrylic groups.
[5] The hard coat according to any one of the above aspects 1 to 4, wherein the nanoparticles are inorganic oxide nanoparticles, and the multifunctional fluorinated (meth) acrylic compound contains a siloxane unit.
[6] The hard coat according to the above aspect 5, wherein the nanoparticles are silica nanoparticles.
[7] The hard coat according to any one of the above aspects 5 and 6, wherein the polyfunctional fluorinated (meth) acrylic compound contains a cyclic siloxane unit.
[8] The hard coat according to any one of the above aspects 1 to 7, wherein the binder further contains an ultraviolet absorber.
[9] A hard coat precursor comprising a mixture of nanoparticles and a binder,
The nanoparticles constitute 40 mass% to 95 mass% of the total mass of the nanoparticles and the binder,
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. A hard coat precursor, wherein the binder comprises a polyfunctional fluorinated (meth) acrylic compound.

60 Abrasion Resistance Test Device 61 Stage 62 Stylus 63 Weight 64 Fabric or Steel Wool

Claims (9)

A method of manufacturing a hard coat comprising nanoparticles child Contact and binder,
Before SL nanoparticles constitute 40 wt% to 95 wt% of the total mass of the hard coat,
The method
Nanoparticles having an average particle size ranging from 2 nm to 200 nm , from 10% to 50% by weight , based on the total weight of the nanoparticles,
Nanoparticles having an average particle size in the range of 60 nm to 400 nm , 50% to 90% by weight , based on the total weight of the nanoparticles, and
The multifunctional fluorinated (meth) acrylic compound containing Muba Indah,
To obtain a hard coat precursor,
Coating the hard coat precursor on a substrate to form a hard coat;
Including
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. A method for producing a hard coat. The method of claim 1, wherein the nanoparticles are surface modified nanoparticles. The method according to claim 1 or 2, wherein the polyfunctional fluorinated (meth) acrylic compound is a perfluoroether compound having two or more (meth) acrylic groups. The method according to any one of claims 1 to 3, wherein the polyfunctional fluorinated (meth) acrylic compound has 3 or more (meth) acrylic groups. The method according to any one of claims 1 to 4, wherein the nanoparticles are inorganic oxide nanoparticles, and the polyfunctional fluorinated (meth) acrylic compound comprises a siloxane unit. The method of claim 5, wherein the nanoparticles are silica nanoparticles. The method according to claim 5 or 6, wherein the polyfunctional fluorinated (meth) acrylic compound comprises a cyclic siloxane unit. The method according to claim 1, wherein the binder further comprises an ultraviolet absorber. A method of manufacturing a hard coat precursor containing nanoparticles child Contact and binder,
Before SL nanoparticles constitute 40 wt% to 95 wt% of the total weight of the nanoparticles and the binder,
The method
Wherein 10 wt% to 50 wt% based on the total mass of nanoparticles, nanoparticles that have a mean particle size in the range of 2 nm to 200 nm,
50% to 90% by weight based on the total mass of the nanoparticles, nanoparticles that have a mean particle size in the range of 60Nm～400nm, and
The multifunctional fluorinated (meth) acrylic compound containing Muba Indah,
Including combining
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. A method for producing a hard coat precursor.

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