TW200837160A - Anti-glare hard coating solution and hard coating film with high hardness using the same - Google Patents

Abstract

The present invention provides a hard coating solution, and a hard coating film formed by coating the processing solution. The hard coating film has a very good hardness, curl-endurance, weather-endurance, transparency, wearing-endurance, anti-glare property, and anti-contamination property. The processing solution comprises: the inorganic silicon particles generated by associating the polysiloxane compound containing poly-acrylate with the hydroxyl group on the surface of silicon particles chemically; poly-acrylate; the initiator; and the silicon micro-particles.

Description

[Technical Field] The present invention relates to an anti-glare surface-hardening treatment liquid and a high-hardness surface-hardened treatment film using the treatment liquid. [Prior Art] Conventionally, a surface hardened film is used for various display panels for the purpose of protecting a surface or the like; for example, a liquid crystal display (LCD), a plasma display (PDP), a cathode ray tube (CRT), and electricity. A panel such as an excitation light display (EL). In addition to surface hardening, it is also easy to remove fingerprints or display labels (ie, antifouling properties). /乍 is a material for forming a surface-hardened film, and in the case of using only the organic substance itself, such as a polyester resin, an acrylic resin, a urethane acrylate, and an epoxy acrylate-based hardening type acrylic surface-hardening material, It is impossible to show sufficient surface protection properties as a surface hardened film. Therefore, in order to improve high hardness and wear resistance, various inorganic surface treatment liquids containing phthalic acid gel particles (which are ..., organic substances) have been used for the surface-hardened film. μ ★ However, it still does not need to deal with the surface hardening film used for the protection of the panel device. These items include the precipitation of the citrate particles generated by the modification of the organic substances in the surface, and the gelation caused by the gelation. Stability issues, hardening, optical transparency and adhesion. Further, if the thickness of the conventional surface-hardened film is increased in order to increase the hardness, the thickness of the obtained surface hardening treatment may increase, but conversely, peeling of the surface-hardened layer may occur, and hardening may occur. Shrinkage, hot and wet shrinkage causes the surface hardening _ the curl _) which is rolled up at the end of the film becomes large, and causes the handling of the miscellaneous. Furthermore, the f-filament hardening treatment 200837160 The film also has a problem that the visibility of the display is lowered due to reflection of external light. SUMMARY OF THE INVENTION In order to improve the problems of the prior art described above, an object of the present invention is to provide an anti-glare surface-hardening treatment liquid and a high-hardness surface-hardening treatment film using the treatment liquid, which is not enough to maintain the display device The general physical properties required for the surface-hardened film for protection are provided to provide high-hardness surface hardening treatment, and it is also possible to suppress the occurrence of peeling and curling of the surface-hardened layer, and to have uniform prevention by containing ruthenium particles. Dizziness. In order to achieve the above object, the present invention provides an anti-glare surface-hardening treatment liquid 'comprising (A) chemically containing the following [chemical formula η polymerization (the polymerization of the two dilute vinegars is combined with the surface of the heterosis) There are inorganic Shixia particles in the base class; (Β) polymerization (inter- acrylate; (c) initiator; and (9) Shixi microparticles, [Chemical Formula 1]

In the above formula, η is an integer of 1 to 3, and imaginary and R2 are each independently and represent an aliphatic or aromatic hydrocarbon having a carbon number of 1 1 G, and R 3 represents a carbon number of 1 or 1 with or without a hetero atom. 1〇 of the fat or (4) group of hydrocarbons, R4 is a linear or branched hydrocarbon containing or not containing linear, branched or ring-shaped atoms, γ means with or without An aliphatic or aromatic hydrocarbon having a hetero atom having 7 to 10 carbon atoms having a ruthenium b base of 2 10 (m-) propylene. Further, the antiglare hardening treatment liquid provided is characterized in that it is excited with respect to the weight of the surface hardening treatment liquid, and the inorganic impurities 200837160 contained in the mixture are 5 to 50 篁❻/〇, the polymerization. The acrylic vinegar is 5 to 4% by weight, the photoinitiator is 〇1 to 10% by weight, and the cerium microparticles are U0% by weight. Further, the antiglare surface hardening treatment liquid is characterized in that the average particle diameter of the ruthenium microparticles is in the range of 1 to ΙΟμηη. This Chemical Formula 1 is defined by the following Chemical Formula 2, [Chemical Formula 2]

(R2)n-3〆 (RlO)r

Si — R3

κ κι Η || n-r5-n-^ο-γ In the above formula, 11, ruler 1, ruler 2, ^ and ¥ are the same as before, 115 is with or without linear, divergent ( A branched or cyclic aliphatic or aromatic hydrocarbon having a hetero atom of from 1 to 13 carbon atoms. The present invention provides an anti-glare surface-hardening treatment film comprising a surface-hardening treatment layer which is applied to a transparent substrate by an anti-glare surface-hardening treatment liquid according to any one of claims K4. It is formed by hardening one side or both sides. Further, the transparent substrate is a triaCetylcellulse film or a cycloolefin derivative film. The present invention provides an anti-glare surface-hardening treatment film which is a high-hardness surface-hardening treatment film having a cross-linked surface-hardened treatment layer, which is characterized in that it is surface-hardened by a cross-linked bridge. In the layer, the structure in which the ruthenium particles are chemically combined in the bridge network and the ruthenium particles which are independent of each other and the bridge network exist simultaneously, and the thickness of the surface hardened layer is 5 to 3 〇 μηη, and the curl property is Below i5mm. 200837160

Further, the present invention provides an anti-glare surface-hardening treatment film characterized in that, in the bridge network, there is a nozzle compound containing the polymerized (meth)acrylic acid vinegar of the following formula 1 and the dopant is chemically The method combines the structure of Qingcheng, the integer of 'η疋1 to 3 in the upper formula i, Ri, & respectively, and represents the monthly aliphatic or aromatic tantalum carbide with a carbon number of 1 mountain 10, & Or does not contain the heterogeneous = sub-slave atomic number 1~1Q of the fat-rich fresh hydrogen carbide, which is or does not ^ 3 ^^^lnear)"^^^(branched)^^^(cyc^^^^ 1 ^15 2 atomic fat female or family hydrocarbon, Y means aliphatic or with or without a hetero atom having a carbon number of 7 to 8 () Further, the present invention relates to a polarizing plate of the present invention, which comprises the above-mentioned anti-glare surface-hardening treatment film. The present invention is provided with a sturdy surface-hardened enamel film. The thief-like surface hardening treatment of the invention and the high hardness and surface hardening treatment using the treatment liquid _ providing adhesion, antifouling property, thief property, abrasion resistance Further, the surface hardening treatment liquid of the present invention has a high rate of hardening, and therefore has excellent productivity. [Embodiment] Hereinafter, the present invention will be described in detail. First, the anti-glare surface-hardening treatment liquid is described. Let the package = two: = sign; in the 'contained, chemical-based person's private 4 main &] poly a (m-) acrylate polymerized decane compound knot; · (Initiating the production of inorganic impurities by the base; (B) Polymerization (m), propyl hydrazine® 曰, (L) initiator; and (D) 矽 microparticles,

[Chemical Formula 1J (R1〇)r N — R4-〇

In the V 2 county formula, 'n is an integer from 1 to 3'. The illusion and the illusion are independent and represent the carbon thief or the material tree, the R3 wire contains or does not contain the aliphatic or aromatic hydrocarbon of the same 1, and R4 is the inclusion or A non-discriminating or ring-shaped (CyCliC) aliphatic or trivalent hydrocarbon having a hetero atom of 1 to 15 carbon atoms, and a gamma-ray containing or not containing a functional group of 2 to Η) The number of carbon atoms is 7 to 8 aliphatic or aromatic hydrocarbons. In the present invention, inorganic Shih-ray particles are chemically bonded to the above-mentioned [chemical formula = poly (4) Wei compound) Although the surface of the chlorine emulsion is not limited by the inorganic impurities, the weight of the surface is hard to be treated. It is preferable to use a Wei gum solution dispersed in an organic solvent towel as the organic solvent, and as the organic solvent, a ketone top and a mercapto isobutyl ketone, and an alcohol can be used. The isopropanol and medium, in terms of dispersibility and stability, the expectation is methyl isobutyl ketone. Glue solution, the market is sold by Ding Gang Shi Xi solution (mek_st, day 200837160 chemical production, average particle size 22nm, general genus), Wei traiti (A_yl TT600 'A Yi yl system' particle average size tear m ), methyl isobutyl ketone solution (MIBK-ST, Nissan Chemical's average particle size 22nm, Shixi content 3〇%), isopropanol stone solution _ initial, average particle size 22 calendar, 7 content 骂And so on, any of at least one of them can be used. In addition, although the average particle size of the particle is not limited, it can be used in the range of 1 〇 nm to 1 〇〇 nm; when applied to a transparent film formed by hardening, the expected value is 10 nm 50 nm. In the case of the run-up coffee, the transparency is also reduced, and the situation in which the surface hardening is poor is formed. Further, when the particle diameter is less than 10 nm, the hardness of the surface hardening treatment tends to deteriorate. The polymerized alkane compound containing a polymerized (10) decenoic acid ester and bonded to the hetero atom table _hydroxyl group is represented by the aforementioned [chemical formula 丨]. The integers of the ages 1 to 3, &, & respectively, indicate that the carbon protozoa indicates an aliphatic or aromatic hydrocarbon having or having no heterofunctional functional groups of 2 to ω. Ding number / 80 of different atoms if you want to give - for example, pure _ words, ^ 2 Yang 疋 methyl 6 base, isopropyl, propyl, ethyl, isopropyl, propyl, butyl: = R3 can The structure of a hetero atom such as a methyl group or a group. There is no restriction on the ether ke in the soil s疋/, and the K is not limited, but the structure of the chemistry is _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 200837160 [Chemical Formula 2] (Rl〇)r

Si-r3-

•N

O JH (R2)n-3〆N —R5 γ 2 In the above formula, ' 11 ' Rl ' R2 ' R3 and Y are the same as before, 115 is with or without linear, branched or A cydic aliphatic or aromatic hydrocarbon having a hetero atom of 1 to 13 carbon atoms. That is, it is reported as a compound of the invention to cause the polymerization of the hydroxyl group-containing (m-)-propylglycolic acid (7) to be reacted with the cerium oxide compound to produce. As a desired product of the triisocyanate compound, it may be 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylene diisocyanate, 1,4-xylene Different purpose, with naphthalene: isocyanide, m phenylene: isophthalic acid vinegar, P. phenyl diisocyanide, 3,3, dimethyl _4,4, _diphenyl carbaryl Cyanic acid vinegar, 4,4_ a base of carbaryl diisocyanate, 3,3-dimethylphenyl diisocyanate, 4,4_diphenylene di = diisofine, different Buddha Ketone diisofine, methylene (4-loroyliso-amp; grade), 2,2,4·trimethylhexadienyl _ 2 酉) fumaric acid, 6-isopropyl heart 3 benzene Isocyanic acid, 4 (burning = = vinegar, U · bis (methyl isocyanic acid), tetramethyl: ... heterogeneous and other beautiful stone containing a functional group number of 2 ~ 1G (marginal acid vinegar = System, but by the chemical formula! 仏 and γ hair; ^ = should be selected to have a hydroxyl group in the polymerization (between the best. 卞 is the reverse as an example, may be pure ethyl propylene Acid, (10) propyl propylene acrylate 200837160 acid, 2- butyl butyl acrylate, 2- carbyl _3 oxy phenyl propyl acrylate, M butane diol single acrylic , burnt (nyl phosphoric acid (meth)acrylate, 4_cyclohexyl (meth)acrylic acid, 1,6-hexanediol mono(meth)acrylic acid, neopentyl glycol mono(meth)acrylic acid, trihydroxyl Methylpropane (meth)acrylic acid, trimethylolethane (meth)acrylic acid, pentaerythritol (meth)acrylic acid, and diisoamyltetraol (meth)acrylic acid, etc. In this specification, -) Acrylate means acrylic acid or / and m-acrylic acid. The polymerized decane compound containing a polymeric (m-) acrylate is not limited, but is used in a weight ratio of 5:1 to 1:4. Preferably, the polymerized (m-) acrylate group of the present invention contained in the surface hardening treatment liquid may contain diisoamyl hexaol (mercapto) acrylic acid, diisoprene Alcohol (meth)acrylic acid, pentaerythritol (meth)acrylic acid, ditrimethylolpropane tetra(meth)acrylic acid, (meth)acrylic acid, trimethylolpropanol (?) acrylic vinegar, Triglyceride (meth)acrylic acid, tris(2-hydroxyethyl)isocyanuric acid tris(meth)acrylic acid, ethylene glycol dimethyl (meth)acrylic acid, propylene glycol ( Methyl)acrylic acid, ^-butanediol di(methyl)propanoid: 1,4-butanediol di(methyl)propionic acid, ... hexanediol di(methyl)propionic acid, neopentyl Diol di(meth)acrylic acid, diethylene glycol di(meth)acrylic acid, triethylene glycol di(meth)acrylic acid, dipropylene glycol di(methyl)propyl-, di(tetra)cyanate di(acrylic acid, anthracene) Ethyl (meth)acrylic acid, propyl (meth) acrylate, butyl acrylate, isooctyl (meth) acrylate, stearic acid (meth) acrylate, phenoxyethyl (methyl)propionic acid or the like - a plurality of types of polymerization (m-) propylene. The use thereof is not limited, but is 5 to 4 ° / Torr per surface weight of the surface hardening treatment liquid, and is expected It is preferably 1 〇 to 3 wt%. The present invention is limited as a sub-selection in the field of initiation of the surface hardening treatment liquid, and may be, for example, methyl thio) phenyl] 2 oxazepine acetonide, diphenyl. Ketone benzomethanthenone, upper hydroxyl group 12 200837160 -2-methyl-1-phenyl-1, 4-hydroxycyclopropanone, dimethoxy 2,phenyl phenyl benzene, Antra ANTHRAQUINONE, hydrazine, triphenylamine, carbazole, 3_mercaptophenyl benzene, 4 benzyl chloroketone, 4,4-didecyloxy acetophenone, 4,4-diaminodiphenyl The ketone, the hydroxycyclophenyl hydrazine and the like are mixed or mixed. The amount of use is on the surface, and when the treatment liquid is α1 to 1% by weight per 100 parts by weight, and the case is less than 〇Λ% by weight, the curing rate is slow. In the case of more than 1% by weight, the degree of bridging is lowered and the mechanical strength is also low.曰 In the present invention, by adding #microparticles to the surface hardening treatment liquid to form the surface unevenness 3, it is possible to provide excellent and uniform antiglare property in terms of antifouling property. The diameter of the heterogeneous particles (4) scattered in the predecessor's hard-core financial management is ϊ^111 ‘the ones are 1~_. The particle (4) is unshaped _, and if it is 1 () handsome, the surface is thicker, and the image quality is also shown. The amount of the particle added is relative to the weight of the wire hardening treatment. % is set, and the expected one is 3 to 2 (% by weight). If it is added when there is a picture: one, it will be used to remove the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Can be methyl isobutyl _, its; alcohol n-butanol, etc.), _ member (butanone, methyl butyl ketone, can be added !.!; heavy denier relative to 100 weight ratio of the surface-hardening treatment liquid in the tearing acid Colloidal particles 13 200837160 In addition to the above substances, it is also possible to use an antioxidant, a UV absorber, a photo-agglomerating agent, a thermal polymerizing inhibitor, a leveling agent, a surfactant, and the same day in the same day using the surface hardening treatment liquid. Further, the present invention provides an anti-glare surface-hardening treatment film. The anti-glare surface-hardening treatment film of the present invention is characterized in that it has an anti-glare property and is bridged ( The surface hardening layer of cr〇ss_Unked) is integrated in the bridge network in the cross-linked surface hardening layer, and the anti-glare surface hardening is taken as an example. The treatment film may be obtained by applying the aforementioned anti-glare surface hardening treatment liquid to After the base material is formed, by letting the ruthenium particles and the former ship material 1 aggregate and combine the age and the hybrid bridge, the stone ray particles are chemically combined in the bridge network to provide high hardness and solve the peeling, In addition, the surface hardened layer of the bridge (cr〇ss_linked) is chemically combined with the formed structure and the tantalum particles independently of the bridge network. The surface irregularities are formed by using the fine particles, so that excellent and uniform anti-glare property can be provided in terms of antifouling properties. As the transparent substrate, any transparent plastic film can be used, and for example, norbornene or a cyclopentene-based monomer, a cycloolefin derivative having a unit of a cycloolefin, a cellulose, that is, a cellulose diacetate, a cellulose triacetate, a butyl acetate, an isobutyl cellulose acetate , vinyl sister ethylene acetate copolymer, propionyl cellulose, cellulose butyl phthalate, cellulose acetate propionate, or polycyclic olefin, polyester, polystyrene, polyamine, polyether Imine, polyacrylate, polyamidamine, polyethersulfone, polyfluorene, polyethylene, polypropylene, polyethylene, polyvinylidene chloride, polyvinyl alcohol, polyvinyl alcohol, polyfluorene, poly_ Hole, poly style, polymethyl methacrylate, poly(p-phenylene terephthalate), polybutylene terephthalate, acid ethane II 200837160 ester, polycarbonate, polyurethane An unstretched uniaxial or biaxially stretched film may be used as the at least one of a thermoplastic polymer such as an ester or an epoxy. Among them, a uniaxial or biaxially oriented polycondensation which is excellent in transparency and heat resistance is desired. An ester film, a difficult-to-diffuse and heterogeneous, and capable of riding a large-sized cycloolefin derivative film, a polymethyl methacrylate film, and a triacetate fiber which is not transparent and optically anisotropic. It is fine in age and can be used in scales. The thickness of the transparent base film is not limited, but is 8 to 1 μm, and is desirably 40 to 100 μm. When the transparent base film is 8 or less, the strength is lowered, and the addition property is deteriorated. On the other hand, if it is touched (four) or more, problems such as low transparency and an increase in weight of the polarizing plate occur. . In the present invention, as for the coating of the surface-hardened film, a coating can be used! § (die coater), air knife (air), inverter (Γ6ν_(7)(6)spray, tool (10), casting), gravure printing (a) (spin), spin coating, etc. The coating method is applied in an appropriate manner. The thickness of the female _ cloth on the surface hardening is generally 〇·1~50μπι 'if the wetness is desired, and the desired one is 3~2_. After coating The composition is dried by evaporation of 3V to crater (10) for 1 second to 2 hours, and desired for 5 hours for 2 hours, and then cured by uv light irradiation and the amount of light irradiation is about 〇〇1~1〇J/cm2, the expected one is Ο"]Qi^ As in (4), the thief-like surface hardening _ has excellent high hardness = wear resistance, weather resistance, anti-fouling, anti- High transparency in glare and optics, extremely fast speed and excellent productivity. The film curled after hardening is 15mm or less, which is excellent. The table is also - 15 200837160 The aforementioned polarizer has no lion (4) J, but the type of tanning system can be given as a polarizing plate, which can be used, for example, in a polyethyl alcohol film and a vinyl acetate system. In order to forget a hydrophilic polymer such as a film, a film formed by uniaxially stretching a dichroic substance such as a smear, a degaussing treatment of polystyrene or a dechlorination treatment of polychlorinated ethylene In the case of a maternity alignment film, etc., a polarizing plate made of a polyvinyl alcohol film and a dichroic substance such as J0D is desirable. The thickness of these polarizing plates is not limited, but is one degree. Further, the present invention provides a t-type and a display device to which the above-described anti-glare surface-hardening film is applied. The polarizing plate on which the anti-glare surface hard-treated film of the present invention is formed is incorporated in a display device. In this way, it is possible to manufacture a display device of the present invention which is excellent in visibility, and the anti-glare surface-hardening treatment film of the present invention can be mounted on a window of a display device. The surface hardened film is expected to be used in a reflective type, a transmissive type, a semi-transmissive type LCD or TN type, an STN type, an 0CB type, a Han type, a VA type, and an ιρ. In addition, the 'anti-glare surface hardening treatment of the present invention』 = ^Electrical display Various display devices such as a device, a field emission display, an organic EL display, and an electronic paper. Xing Ding... The present day and the moon can be understood by the following figures and detailed descriptions, but the description of the examples is only For the sake of clarity _ this case, _ to limit the patent scope of this case. Acid my 矽 矽 化合物 compound (Synthesis Example 1) Weight ratio ^ 2G · 6 @ 异佛_Diisocyanate S is designed to G ° C - hour缓16 200837160 Dropped into a double [3-(trimethoxy)propyl]amine with a weight ratio of 14.2, the weight ratio of 鼠·2 of tin sulphate is dissolved in the _ minus the difference in the drink, the weight will be The foreign body tetraol acrylic acid having a ratio of 71.4 was slowly dropped into the solution at - hour, and after the dropwise addition, the temperature was raised to 6 ° C and stirred for three hours. Regarding the infrared absorption spectrum absorption peak of the product, it can be confirmed that RHC-〇)_NH-] is 1720 cm, and then [stomach 〇]__ peak is 1660 cm'1 ° (Synthesis Example 2) 异 Will weighs 20.6 by weight The keto-diisocyanate was slowly added dropwise under the armpit for one hour to a double [3_(trimethoxy)propyl]amine having a weight ratio of 14.2, and a tin cyanide solution having a weight ratio of 〇2. Stirring at 25t, mixing diisopentaerythritol/hexamethylene acid with a weight ratio of 125.6 at 3 〇〇c slowly into the solution for one hour, and increasing the temperature to 6 after doubling (TC stirring) Three hours. Regarding the absorption peak of the infrared spectrum spectrum of the product, it can be confirmed that [_N_(C_0> NH_] is 'the peak value is 1660 cm-1 〇 (Synthesis Example 3). The weight ratio is 20 and 6 is corrected. Cyanate vinegar slowly drip into the weight ratio of double [3_(trimethoxy)propene fine, the ratio of 〇1 of cyanic acid tanning towel in the underarm for one hour. The foreign body tetraol acrylic acid having a weight ratio of 9 L5 was slowly dropped into the solution at -hour, and after the dropwise addition, the temperature was raised to 60 ° C and stirred for three hours. The infrared absorption spectrum of the object absorbs the peak value, and it can be confirmed that [_N_(C 0)_顺_] is the job ^, and then the [pass one (7) simple] peak value is 1660cm 1 〇 17 200837160 (Synthesis Example 4) The reset ratio is 20 1,6_n-hexane diisocyanate was slowly dropped into a bis(3_(trioxo)propyl)amine having a weight ratio of 18·28 and a tin cyanide solution having a weight ratio of 〇1 under an hour. After the solution was stirred at 25 ° C for 3 minutes, the solution was slowly dropped into the solution at a weight ratio of 160.09 diisopentaerythritol / hexaacrylic acid at 3 Torr for one hour, and the temperature was dropped after the dropwise addition. Raise to 6 (r (^4 stir for three hours.) Regarding the infrared absorption spectrum absorption peak of the product, you can discard [-Ν_((:_0)_ΝΗ·] to 1720cm-1, followed by [_0-(c-〇) -NH_] peak value of I660 cm_1 〇 Colloidal production of inorganic cerium particles (Production Example 1) A polymerized decane compound (synthesis example 1) containing a polymerized (m-) acrylate having a weight ratio of 8·7, and a weight ratio of 91.3 Butanone solution (ΜΕΚ-ST, Nissan Chemical, 30% yttrium), methanol with a weight ratio of 〇·2, and distilled water with a weight ratio of 〇1 at 8 ° C, under nitrogen After mixing for three hours, methyl n-butanone having a weight ratio of 14 was added, and the mixture was stirred for one hour at 80 ° C under a nitrogen atmosphere to obtain colloidal inorganic particles. (Production Example 2) Except that the synthesis example 2 was used. The product was carried out in the same manner as in Production Example 1 except that the polymerized decane compound containing a polymer (inter) acrylate was used. (Production Example 3) Except that the product produced in Synthesis Example 3 was used. The procedure was carried out in the same manner as in the production example except that the polymerization (the methacrylate-based polymerized decane compound) was contained. 18 200837160 (Production Example 4) The same procedure as in Production Example 1 was carried out except that the product produced in Synthesis Example 4 was used as a polymerized decane compound containing a polymerized (m-) acrylate. (Example 1) A colloid having a weight ratio (solvent content) of 69.8 was added with inorganic cerium particles (manufacturing example, diisopentyl alcohol/hexaacrylic acid (DPHA, manufactured by NK) having a weight ratio of 12.6, and a weight ratio of 12.6. Isopentyl alcohol/tetraacrylic acid (manufactured by NK), 丨_cyclohexyl hexyl phenyl ketone (manufactured by CIBA-GEIGY CO. LTD.) in a weight ratio of 〇5 ^ 2_曱基·1 ·[4·(decylthio)benzene]2_oxazepineacetone] (q[BA-GEIGY c〇LTD), 6μηη矽 particles with a weight ratio of 3, and a leveling agent with a weight ratio of 〇·3 GUde 410 (manufactured by DegUS Sa) was stirred for one hour, and the resultant was applied onto a transparent base film (80 μηι, TAC) by a roll to form a humidity film having a thickness of i4 gm, and after drying for one minute, 720 mJ/ was used. Cm2 was hardened to produce a high-hardness surface-hardened film. (Example 2) The same procedure as in Example 1 was carried out except that the product produced in Production Example 2 was used as a colloid and inorganic stone particles were used. (Example 3) Except that the product produced in Production Example 3 was used as a colloid, and the inorganic ceramsite particles were used, 1 was carried out in the same manner. (Example 4) Except that the product produced in Production Example 4 was used as the colloid and the inorganic granules were used, the rest were carried out in the same manner as in Example 1. (Example 5 ' 19 200837160 The same procedure as in Example 1 was carried out except that a humidity film having a thickness of 9 Å was applied on a transparent substrate film (TAC). (Comparative Example 1) A colloid having a reduction ratio (solvent content) of 69·2 was inorganic cerium particles (MIBK-ST' Nissan Chemical Co., Ltd.), and a weight ratio of 29.7 diisopropanol/hexaacrylic acid (manufactured by νK) '1-hydroxycyclohexylhexyl phenyl ketone (manufactured by Ciba_geigy CO. LTD.) having a weight ratio of 1 and a fluorinated surfactant (fc (10) having a weight ratio of qi,

The surface hardening treatment liquid of Ltd) is applied onto a transparent substrate film (8 μm, tac) by a roll to form a humidity film having a thickness of 14 μm, and after drying for one minute, it is hardened by using 720 mJ/cm 2 to produce High hardness surface hardened film. (Comparative Example 2) A colloid having a reset ratio (solvent content) of 67·5 was inorganic cerium particles (MIBK-ST' Nissan Chemical Co., Ltd.), and diisopentaerythritol/hexaacrylic acid having a weight ratio of 28.9 (manufactured by Nippon Co., Ltd.) ), a 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba_geigy CO. LTD.) having a weight ratio of ΐ·〇, a fluorine-based surfactant (FC34(), 3M c〇. Ltd), and a weight ratio The surface hardening treatment liquid of the 6 μιη stone-like fine particles having a ratio of 2.5 was applied onto a transparent base film (8 μηηι, TAC) by a roll to form a film having a thickness of 14 μm, and dried for one minute, and then used for 720 mJ. /cm2 hardens it to produce a high-hardness surface-hardened film. (Comparative Example 3) The same procedure as in Comparative Example 2 was carried out except that a ruthenium polymerizable acrylic polymer (4D5-15' DSMCo. Ltd) having a weight ratio of 67.5 was used. (Comparative Example 4) The same procedure as in Comparative Example 2 was carried out except that a siloxane-based surfactant (BYK-325, manufactured by BYK Co., Ltd.) 20 200837160 was used as the fluorocarbon surfactant. . The surface hardening treatment solutions of the respective examples and comparative examples were produced, and then applied to a transparent base film, followed by drying, and the surface hardened film subjected to the ultraviolet curing process was used as a protection for the JOD-based absorption dichroic polarizing film. The layer is used to produce a polarizing film, and as a result, a polarizing film having a surface protection function capable of maintaining the aforementioned characteristics and having high practicality can be obtained. Evaluation of physical properties (1) Transmittance and haze A spectrophotometer (HZ-1, manufactured by Japan's SUGA Co., Ltd.) was used to measure total light transmittance (Hatra) and haze. (2) Anti-glare indication, 50% using HdCM], manufactured by Japan's SUGA Co., Ltd.) The penetration sharpness of the optical rod 2 mm was measured in the mode, and the value of the measured data = that the anti-glare property was Hey. When the evaluation is performed here, less than 5 % is expressed by 以上 above, but less than 70% is represented by Δ, and 70% or more is represented by X. (3) Wrong pen hardness using a pencil hardness machine (PHT, Korea SUKB〇SCIENCE) 500g to determine the wrong pen hardness. Using Mitsubishi's wrong pen, five times for one & = negative, if the damage is more than two It is judged to be defective., Hard damage: οοκ Damage: 1 OK Damage: 2 or more NG (4) Rub resistance 21 200837160 Using a steel wool tester (WT-LCM100, manufactured by Korea PROTECH Co., Ltd.) under lkg/(2cmx2cm) Move back and forth ten times to test wear resistance. Use #0000 steel wool. A: 0 scratches A': 1~10 scratches B: 11~20 scratches C: 21~30 scratches D·· 31 or more Scratch (5) Adhesiveness After eleven lines are drawn in the longitudinal direction and the lateral direction at intervals of linm on the surface on which the film is applied to form one square square shape, the glue is used (CT_24, manufactured by NICHffiAN Co., Ltd., Japan) Three peel tests were performed, and three squares of one square were tested and the average value was recorded. The adhesion was recorded as follows. Adhesion = n/100 η · Undivided square in the whole square Quantity 100: The number of all squares is correct. Recorded as 1(8)"〇〇. (6) Curl The sample was cut into squares of A4 size (29.7x21.0cm) and applied to a flat glass plate, and the film-coated surface was placed on it, in the pit, 5 〇%rh measures the distance from the four corners of the glass plate and calculates the average value. (7) Fingerprint wiping (antifouling) The cleaning paper is used by ten testers on the film-coated surface (dean paperXULTIMA Π 'HANSONG) Wipe gently ten times and visually wipe the 22 200837160. A: No wiping marks are left. B: Some residual wiping marks. C: Residual wiping marks. (8) Weather resistance using Sunshine weatherability (Japan SUGA test machine) 300 hours After that, the state of the surface of the sample was observed with the naked eye. A: No change in surface B: Thickened surface C: Surface dissolved [Table 1]

Example 1 Example 2 Example 3 Example 4 Example 5 Total light transmittance (%) 91.4 90.2 91.2 91.3 90.2 Haze (%) 13.8 14.2 13.9 14.8 25.5 Anti-glare 〇〇〇〇〇 pencil hardness 3H 4H 3H 4H 2H Abrasion A, A, AA, A, Adhesive 100/100 100/100 100/100 100/100 100/100 Curly good Good Very good Good Very good Finger rubbing ABABA 23 200837160

Finance A A A A A

[Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Total light transmittance (%) 92.3 90.4 90.4 90.1 Haze (%) 0.3 18.7 16.4 20.1 Anti-glare X 〇〇〇 Pencil hardness Η Η 2Η Η擦 性 CC Β D Adhesive 100/100 99/100 100/100 85/100 Bad defect, bad defect, bad fingerprint wiping CC Β C Weather resistance Β Β Β C [Simple description] None. [Main component symbol description] None 0 24

Claims (1)

200837160 X. Patent application scope: 1. An anti-glare surface hardening treatment with 16 plus CGating) liquid, comprising (4) a polymeric calcining compound chemically obtained by chemical polymerization (intermediate formula 1) , (<>> produced by the hydroxyl group on the surface of the Shixi particle; inorganic granules; (9) polymerized (meth) acrylate; (C) initiator; and (D) bismuth microparticles, [Chemical Formula 1] The integers of the above-mentioned towels η 疋 1 to 3, &, & respectively, represent the aliphatic or aromatic hydrocarbon having a carbon number of 0, and & represents an aliphatic group containing or not containing a heterogeneous hetero atom. Or aromatic hydrocarbon, Y means that the package is never wrapped and ancient The atomic carbon number is 1~1G _ or aromatic hydrocarbon, R4 is or does not contain linear (Unear), divergent gamma _ _ (4) 25 200837160 Climbing / (Rl〇)n\ \ 〇ο Si — R〇-η-μ__Ν Η Η || \ (R2)n/ Γ N-R5-N-^〇-Y \ Λ The above formula is the same as the above, and the heart contains or does not contain linear, divergent An aliphatic or aromatic hydrocarbon having a branched or cydic hetero atom having 1 to 13 carbon atoms. An anti-glare surface-hardening treatment film comprising a surface-hardening treatment layer which is applied to a transparent substrate by the anti-glare surface-hardening treatment liquid according to any one of the claims It is formed by hardening one side or both sides. 6. An anti-glare hardfacing film according to the 5th patent scope of May, which is characterized in that it is a film of a triacetylcellulose film or a cy cloolefin derivative. 7. An anti-glare hardfacing film which is a high-hardness surface-hardened film having a surface hardened layer of a bridge (four) and a toe, characterized in that it is hardened on the cross-linked surface. In the treatment layer, the bridge and the inner stone particles in the network are chemically separated from each other and the bridge network is independent of each other (10) microparticles, the thickness of the surface hardened layer is 5~3〇μηη, curl (curi The characteristic is 15mm or less. 8. The anti-glare hardfacing film according to claim 7 of the invention, characterized in that in the bridge network, there is a polymerization (the polymeric decane compound of the following formula i) and the ruthenium particles chemically The way the structure is formed, 曰[Chemical Formula 1] 26 200837160 (Ri〇>(R2)n-3" N - R4 - In the above formula, n is an integer from 1 to 3, and Ri and R2 are each independently and represent a Liner surface hydrocarbon having 1 to 10 carbon atoms, & represents a carbon atom with or without heterogeneous The number of W0's fat scented surface hydrogen, & is included or not ^((linear).^^(bra^ ΐ thief _ family hydrocarbon, γ silk package repair has a moon 匕 ^ f ★ (between The pro- vine vinegar-based carbon source is 7 to 80% of the atomic scorpion scorpion fat or the scented scented hydrocarbon. The chemistry is reversed, and it has the anti-glare surface hardness of the 7th or 8th patent application scope. ·-Display device, straight hardening treatment_.~ Apply for patent anti-glare surface 27 or 8