TW200927487A - Norbornene-based resin film with hard coating layer and manufacturing method of norbornene-based resin film with hard coating layer - Google Patents

Abstract

The present invention provides a manufacturing method that employs a simple process to manufacture a norbornene-based resin film having excellent optical properties, having sufficient surface hardness, and having a hard coating layer, and a norbornene-based resin film having a hard coating layer. The present invention provides a manufacturing method of norbornene-based resin film with hard coating layer, which is characterized by comprising a step of forming a norbornene-based resin substrate film, and a step of forming a hard coating layer containing at least two organic ingredients, the hard coating layer being subjected to phase separation, and the present invention also provides a norbornene-based resin film with hard coating layer.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an original borneol-based resin film having a hard coat layer and a method for producing the same. More specifically, it relates to a norbornene film which has a phase-separated hard coat layer as a base film of a raw borneol resin film and a method for producing the same. ^ [Prior Art] Since the original borneol-based resin is excellent in transparency, heat resistance, and chemical resistance, it has attracted attention as a material for various optical parts. In particular, it has a performance suitable for use as an optical film. For example, a polarizing film in which an original borneol-based resin sheet is laminated as a protective layer on a polarizing film has been proposed (see Patent Document 1). However, the optical film obtained from the original borneol-based resin has insufficient surface hardness, and when used for a protective layer for a polarizing film, a retardation film, and a display element φ plate, damage is likely to occur, and optical properties due to the damage are caused. Falling and other issues. In order to overcome this problem, it is attempted to form a hard coat layer composed of a violet outer-line curable resin or the like on the surface of the film (see Patent Document 2). However, since the adhesion to the hard coat layer is insufficient, even if hard is provided The coating does not sufficiently exhibit the problem of surface hardness. So far, a laminate which can maintain excellent optical properties of the original borneol-based resin and which can improve surface hardness has been developed. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A raw borneol-based resin film having a hard coat layer having excellent optical properties and having sufficient surface hardness, which is a problem associated with the prior art, and a method for producing the same. [Means for Solving the Problem] The original borneol-based resin film having a hard coat layer of the present invention is characterized in that a specific hard coat layer is laminated on a film of the original borneol-based resin base material, and the specific hard coat layer is a phase. Separation. The above specific hard coat layer is preferably formed by a coating composition containing (a) a polymer component having a structural unit containing an alicyclic structure, and (b) a coating composition containing a curable monomer component. The film of the original borneol-based resin base material preferably contains an ultraviolet absorber. Further, the original borneol-based resin film having a hard coat layer of the present invention preferably has a center line average roughness of 0 on the surface of the specific hard coat layer. The unevenness of 1 to 20.0 μm. The method for producing a hard-coated ortho-ene resin film of the present invention is characterized in that it has a step of forming a base film from an original borneol-based resin, and the obtained raw borneol-based resin base The step of forming a hard coat layer (hereinafter also referred to as "specific coating") having at least two kinds of organic components is formed on the material film, and the specific coating layer is phase-separated. -6- 200927487 The above-mentioned raw borneol-based resin base film preferably contains an ultraviolet absorber 〇 - Further, it is preferred to subject the surface of the original borneol-based resin base film to a plasma treatment to form a hard coat layer. Further, the above-mentioned original borneol-based resin base film is preferably obtained by melt-molding an original borneol: an olefin-based resin. Further, the method for producing a thin film of the original borneol-based resin substrate having a hard coat layer of the present invention may further have a step of extending the film of the original borneol-based resin base material. According to the present invention, it is possible to obtain a raw borneol-based resin film having a hard coat layer having excellent optical properties, excellent adhesion to an original borneol-based resin base film, and having sufficient surface hardness. [Embodiment] Hereinafter, the present invention will be specifically described. H The base film having a hard coat layer according to the present invention has a base film composed of an original borneol-based resin film, and a specific coating layer is laminated on the original borneol resin base film. <Original borneol-based resin base film> The original borneol-based resin constituting the original borneol-based resin base film used in the present invention is (co)polymerized with a monomer composition containing at least one of the ornidylene-based compounds. The resin is formed, and a resin obtained by hydrogenating the resin as needed may be used. 200927487 (monomer composition) The raw borneol compound which is contained in the above monomer composition is, for example, a norbornene compound represented by the following formula (1).

In the formula (1), R1 to R4 each independently represent a hydrogen atom; a halogen atom; or a valent group of oxygen, nitrogen, sulfur or hydrazine. The above monovalent group is exemplified by a monovalent organic group, a cyano group, an amine group and the like. Further, the monovalent organic group is exemplified by a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms which may have a linking group containing oxygen, nitrogen, sulfur or hydrazine. X means 〇 or an integer from 1 to 3, and y means 〇 or! Further, R1 and R2, or R3 and R4 may be bonded to each other to form an alkylene group, or R1 and R2, R3 and R4 or R2 and R3 may be bonded to each other to form a monocyclic or polycyclic carbon ring, or a single ring or more Heterocyclic ring. Here, "the ruler 1 and the ruler 2 are bonded to each other to form an alkylene group" means that any of R1 and R2 is detached, and the remaining group is bonded to the ring structure by a double bond (the following formula (1 ')). The same is true for R3 and R4. Further, the above carbocyclic or heterocyclic ring is exemplified by an alicyclic or aromatic ring. -8- 200927487

The original borneol compound represented by the above formula (1) may be used singly or in combination of two or more kinds. The original borneol compound represented by the above formula (1) can be exemplified by the following compounds, but is not limited thereto. Bicyclo[2·2·Πhept-2-ene (formylbornene) 5-methyl-bicyclo[2.2.1]hept-2-ene 5-ethyl-bicyclo[2.2.1]hept-2-ene 5 -cyclohexyl-bicyclo[2.2.1]hept-2-iso-5-phenyl-bicyclo[2.2.1]hept-2-ene 5-(4-biphenyl)-bicyclo[2 2丨]hept_2 _ene® 5_methoxycarbonyl-bicyclo[2.2.1]hept-2-ylidene 5-phenoxycarbonyl-bicyclo[2.2.1]heptan-2_jing: 5-phenoxyethylcarbonyl-bicyclic [2·21]hept-2-ene, 5-phenylcarbonyloxy-bicyclo[2.2.1]hept-2-ene-5-methyl-5-methoxycarbonyl-bicyclo[2 2 ^h-^ Alkene 5-methyl-5-phenoxy-based bicyclo [2 2m dilute 5-methyl-5-phenoxyethyl pseudo-bicyclo[221]hept-2-ene 5-vinyl-bicyclo[2.21 Geng_2_ene 5-ethylene-bicyclo[2.2.1]hept-2-ene 5,5-dimethyl-bicyclo[2.21]hept-2-ene 200927487 5.6-dimethyl-bicyclo[2.2 .1]hept-2-ene 5-fluoro-bicyclo[2.2.1]hept-2-ene 5-chloro/bicyclo[2.2.1]hept-2-ene 5-bromo-bicyclo[2·2·1] Hept-2-ene 5.6-difluoro-bicyclo[2.2.1]hept-2-ene 5.6-dichloro-bicyclo[2.2.1]hept-2-ene

5.6-Dibromo-bicyclo[2.2.1]hept-2-ene 5-hydroxy-bicyclo[2.2.1]hept-2-ene 5-hydroxyethyl-bicyclo[2.2.1]hept-2-ene-5- Cyano-bicyclo[2.2.1]hept-2-ene-5-amino-bicyclo[2.2.1]hept-2-enetricyclo[4.3.0.12]]-3-ene tricyclo[4.3.0. I2 5]undecyl-3-ene 7-methyl-tricyclo[4.3.0.I2 5]non-3-ene 7-ethyl-tricyclo[4.3.0.I25]non-3-ene 7 -cyclohexyl-tricyclo[4.3.0.I25]non-3-ene 7-phenyl-tricyclo[4.3.0.I25]non-3-ene 7-(4-biphenylyl)-tricyclo[ 4.3.0.I25] indole-3-ene 7,8-dimethyl-tricyclo[4.3.0.I2·5]non-3-ene 7,8,9-trimethyl-tricyclo[4.3. 0.125] indole-3-ene 8-methyl·tricyclo[4.3.0.I2'5]undec-3-ene 8-phenyl-tricyclo[4.3.0.I2·5]undecane- 3-ene 7-fluoro-tricyclo[4.3.0.I25]non-3-ene 7-chloro-tricyclo[4.3.0.I2 5]indole-3-ene-10-200927487 7-bromo-tricyclic [4.3.0.12.5] Indole-3-ene 7,8-dichloro-tricyclo[4.3.0.125] indole-3-ene 7,8,9- =chlorotricyclo[4.3.0. I25]癸- 3-ene 7-chloromethyl-tricyclo[4.3.0.I2·5]non-3-ene 7-dichloromethyl-tricyclo[4.3.0.I2'5]non-3-ene 7- Trichloromethyl-tricyclo[4.3.0.125]non-3-ene 7-hydroxy-tricyclo[4.3.0.12·5]non-3-ene 7-cyano-tricyclo[4.3.0.125]癸-3 -ene 7-amine -Tricyclo[4.3.0.125]indole-3-enetetracyclo[4·4·0.125,17'1()]dodecane-3-ene pentacycle [7.4.0.12 5,18'11,07'12 ] pentadecan-3-ene hexacyclo[8.4.0.12 5,17'14,19'12,08,13]heptadecan-3-ene 8-methyl-tetracyclo[4_4.0·12·5 ,17,1()]dodecane-3-ene 8-ethyl-tetracyclo[4.4.0.12 5,17'1Q]dodec-3-enyl 8-cyclohexyl-tetracyclo[4.4.0.125, 17'1()]dodecyl-3-ene 8-phenyl·tetracyclo[4.4.0.125,17,1Q]dodec-3-ene-8-(4-biphenyl)-tetracyclo[4.4 .0.125,17,1()]dodecane-3-ene 8-methoxycarbonyl·tetracyclo[4.4.0.12·5,Γ'1()]dodec-3-ene-8-phenoxy Carbonyl-tetracyclo[4.4.0.125,17,1Q]dodec-3-ene-8-phenoxyethylcarbonyl-tetracyclo[4.4.0.125,17'1()]dodec-3-ene8 -phenylcarbonyloxy-tetracyclo[4.4.0.12·5,17'1()]dodec-3-ene-8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.12'5, L7,1()]dodecane-3-ene 8-methyl-8-phenoxycarbonyl-tetracyclo[4.4.0.125,17'1()]dodecane-3- -11 - 200927487 ene 8 -Methyl-8-phenoxyethylcarbonyl-tetracyclo[4.LO.l25,〗 7,1 G] 12th hospital-3 - suspected 8-vinyl-tetracyclic [4.4.0.12'5,17 '1G' Dialkyl-3-ene 8-ethylene-tetracyclo[4.4.0.125,17'1Q]dodecane-3-ene: 8,8-dimethyl-tetracyclo[4.4.0_125,17'1 ( )]Dodecane-3-ene-8,9-dimethyl-tetracyclo[4.4.0_125,17,1()]dodecane-3-ene φ 8-fluoro-tetracyclo[4.4.0.12 5 , 17'1()] dodec-3-ene 8-chloro-tetracyclo[4.4.0.12 5,17'1()]dodec-3-ene 8-bromo-tetracyclo[4.4.0.12 5 ,17,1G]dodecane-3-ene 8.8-dichloro-tetracyclo[4.4.0_12 5,17'1()]dodecane-3-ene 8.9-dichloro-tetracyclo[4·4· 0.12 5,17'1()]dodecane-3-ene 8.8.9.9-tetrachloro-tetracyclo[4.4.0.125,17'1()]dodec-3-ene-8-hydroxy-tetracyclo[ 4·4.0·12·5,Γ'1()]dodecane·3-ene 8-hydroxyethyl-tetracyclo[4·4·0.125,17'1()]dodecane-3-ene Q 8-methyl-8-hydroxyethyltetracyclo[4.4.〇.12 5,17'1g]dodecane-3-can 8-cyano-tetracyclo[4.4.0.125,17'1()]Te Dialkyl-3-ene: 8-amino-tetracyclo[4_4.0.12_5,17'1Q]dodec-3-ene. The type and amount of the ornidylene-based compound used in the present invention are appropriately selected depending on the properties of the resin required. The original borneol-based compound represented by the above formula (1) preferably has at least one selected from the group consisting of an oxygen atom, a nitrogen atom, and sulfur in view of excellent adhesion to the other material or adhesion. The structure of at least one atom of atoms and sand atoms (hereinafter referred to as "polar structure") is -12-200927487. In particular, in the above formula (1), R1 and R2 are a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 3, preferably a hydrogen atom or a methyl group, and the water absorption (wet) property of the obtained resin is lowered, and the ultraviolet absorber is used. In the viewpoint of excellent compatibility, it is preferred that either R 2 or R 4 is a compound having a polar structure and the other is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. In addition, the original borneol compound having a polar structure: the group represented by the following formula (2) can be used. The obtained resin has a good balance between heat resistance and water absorption (wet), and is preferably - (CH2) zCOOR (2) In the formula (2), 'R represents a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms, and z represents an integer of 0 or 1 to 10. In the above formula (2), since the smaller the z is, the higher the glass transition temperature of the hydride of the obtained polymer is, the more excellent the heat resistance is. Therefore, z is preferably an integer of 〇 or 1 to 3, and 2 is 〇. The monomer is preferred in terms of its ease of synthesis. Further, in the above formula (2), the higher the carbon number, the more the water absorption (wet) property of the hydride of the polymer obtained by φ decreases, but the glass transition temperature tends to decrease, so that heat resistance is maintained. Sexuality: It is preferably a hydrocarbon group having 1 to 10 carbon atoms, and particularly preferably a hydrocarbon group having 1 to 6 carbon atoms. In the above formula (1), the carbon atom bonded to the group represented by the above formula (2) is bonded to an alkyl group having 1 to 3 carbon atoms, particularly a methyl group, in terms of heat resistance and water absorption (wet). It is preferable from the viewpoint of the balance of sex. Further, in the above formula (1), the compound wherein X is 0 or 1 and y is 1 has high reactivity, can obtain a polymer in a high yield, and can obtain a polymer having high heat resistance-13-200927487 hydride, and further It is easy to use in the industry and is more suitable. When the ornidylene-based resin used in the present invention is obtained, a monomer copolymerizable with the above-mentioned ortho-ene-based compound can be contained in the monomer composition and polymerized in a range that does not impair the effects of the present invention. The copolymerizable monomer may, for example, be a cyclic olefin such as cyclobutene, cyclopentene, cyclohexene, cyclooctene or cyclodecene; 1,4-cyclooctadiene or dicyclopentadiene; a non-conjugated cyclic polyene such as cyclododecanetriene. These copolymerizable monomers may be used singly or in combination of two or more kinds (polymerization method). The polymerization method of the norbornene-based resin used in the present invention is as long as the monomer composition containing the above-mentioned ortho- borneene-based compound can be polymerized. However, it is not particularly limited, but it can be polymerized by, for example, ring-opening polymerization or addition polymerization. ❹ (1) Ring-opening polymerization The production of a polymer by ring-opening polymerization can be carried out by a ring-opening polymerization reaction of a conventional norbornene-based compound, and a polymerization catalyst, a solvent for polymerization, and optionally The molecular weight modifier is produced by ring-opening polymerization of a monomer composition containing the above-mentioned norbornene-based compound. (a) Polymerization catalyst In the present invention, the polymerization of the monomer composition by ring-opening (co)polymerization is preferably carried out in the presence of a metathesis reaction catalyst. -14- 200927487 The metathesis reaction catalyst may be a conventional catalyst, specifically a catalyst composed of the following: (A) a compound selected from at least one of compounds having W, Mo and Re (hereinafter referred to as a compound) (A)), and (B) are elements of Group IA of the Periodic Table with Derming (eg, Li ', Na, K, etc.), Group IIA elements (eg, Mg, Ca, etc.), Group IIB elements (eg, Zn, Cd, Hg) Or a compound of the lanthanum element (for example, B, A1, etc.), an IVA group element (for example, Si, Sn, Pb, etc.), or a group IVB element (for example, Ti, ruthenium, etc.) is selected from the group consisting of the element and carbon. At least one compound (hereinafter referred to as a compound (Β)) which is a bond or a compound of at least one of the elements bonded to hydrogen. Further, as the additive (C) for improving the activity of the catalyst, an alcohol, an aldehyde, a ketone, an amine or the like can be suitably used. For example, the following (1) to (9)·(1) monomers boron, BF3, or the like can be used. a non-organometallic compound of boron such as BC13, B(0-n-C4H9)3, (C2H5〇3)2 0 , BF, B203, H3B〇3, etc.

Non-organometallic compounds such as Si(OC2H5)4; (2) Alcohols, hydrogen peroxides and peroxides; _ (3) water; (4) oxygen; (5) aldehydes and ketones a carbonyl compound and a polymer thereof; (6) a cyclic ether such as ethylene oxide, epichlorohydrin or oxetane; (7) hydrazine, hydrazine-diethylformamide, hydrazine, hydrazine-bis An amine such as decylamine such as methyl acetamide, an amine such as aniline, morpholine or piperidine or an azo compound such as azobenzene; -15- 200927487 (8) N-nitrosodimethylamine, N-nitrous oxide An N-nitroso compound such as a diphenylamine; (9) a compound containing an S-C1 or N-C1 group such as trichlorocyanate, N-chloroammonium imine or phenylsulfenyl chloride . The metathesis reaction catalyst is preferably used in an amount such that the molar ratio of the above compound (A) to all monomers to be polymerized (compound (A): all monomers) is usually 1:500 to 1:50,000, preferably 1: 1,000~1: 10,000. The ratio of the compound (A) to the compound (B) (the compound (A): the compound (B)) is preferably from 1:1 to 1:50, preferably from 1:2 to 1:30, in terms of metal atomic ratio. The ratio of the compound (A) to the compound (C) (compound (C): compound (A)) is preferably 0.005:1 to 15:1, preferably 0.05:1 to 7:1 in terms of a molar ratio. ❹ (b) The solvent used in the ring-opening polymerization of the polymerization solvent is such that the monomer composition or the catalyst or the like which is supplied to the polymerization can be dissolved without deactivating the catalyst, and the open-loop polymerization can be produced. The substance is dissolved, but is not particularly limited, and examples thereof include alkane such as pentane, hexane, heptane 'octane, decane, and decane; cyclohexane, cycloheptane, cyclooctane, and decalin. Naphthenes such as norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, dichloromethane, dichloroethane, hexamethylene dibromide Halogenated compounds such as chloroform and tetrachloroethane; halogenated aryl compounds such as benzene; ethyl acetate, n-butyl acetate-16-200927487, isobutyl acetate, methyl propionate, dimethoxyethane, etc. Saturated: ethers such as dibutyl ether, tetrahydrofuran, and dimethoxyethane are used singly or in combination of two or more. Further, in addition to the solvent orthoenic compound, the copolymerizable monomer, and/or the metathesis solvent, a solution constituting the molecular weight modifier may be used; the solvent is preferably used as a solvent and a monomer group for polymerization. The amount ratio (solvent: monomer composition) is usually 1:1 to 10:1 carboxylate. These may cause the above catalyst to dissolve the solvent. The weight of the product, preferably

(C) Molecular weight modifier The molecular weight of the obtained ring-opening polymer can also be adjusted depending on the polymerization temperature and the type of the solvent, but the molecular weight regulator can also be adjusted in a coexistence. Suitable molecular weight modifiers are, for example, α-olefins such as ethylene, propylene, pentene, 1-hexene, 1-heptene, 1-octene, decene- decene, and the like; Aromatic ethylene compounds such as methyl styrene, 2_ storage, and 4-ethyl benzene, etc., which are 丨-butene and 丨-hexene. These molecular weight modifiers may be used alone or in combination of two or more. The molecular weight modifier is used in an amount of usually 0.005 to 0.6 mol per mol of the ring-opening polymer, preferably 〇〇1 (d) other polymerization conditions, catalyst species and reaction olefins, 1-butyl , the best use or mixed reaction of 1-decene, methyl benzene, etc. -0.5 moles -17- 200927487 The above ring-opening polymer can ring-open the above-mentioned raw borneol compound or make the original borneol thin The compound is ring-opened and copolymerized with a copolymerizable monomer to obtain 'but a co-heptadiene compound such as polybutadiene or polyisoprene, a styrene-butadiene copolymer, or an ethylene-non- In the presence of an unsaturated hydrocarbon-based polymer such as a conjugated diene copolymer or a polynorbornene containing two or more carbon-carbon double bonds in the main chain, the ortho-ene compound is contained. The monomer composition is ring-opened and polymerized. (2) Addition polymerization Polymerization by addition (co)polymerization can be carried out by a conventional addition polymerization reaction of a raw borneol compound, and a polymerization catalyst or, as the case may be, a solvent for polymerization reaction can be used. And a molecular weight modifier according to the case, and the monomer composition containing the above-mentioned norbornene-based compound is produced by addition polymerization. Q (Hydrogenation Reaction) The polymer obtained by the above ring-opening polymerization has an olefin : a hydrocarbon unsaturated bond in its molecule. Further, in the above-mentioned addition polymerization reaction, there is also a case where the polymer has an olefinic unsaturated bond in its molecule. Since the olefinic unsaturated bond present in the polymer molecule is degraded by discoloration or gelation over time, it is preferred to carry out a hydrogenation reaction to change the olefinic unsaturated bond to a saturated bond. The hydrogenation reaction can be carried out by a conventional method, and a conventional hydrogenation catalyst is added to a polymer solution containing an olefinic unsaturated bond at a normal pressure of from -18 to 200927487 to 300 atm, preferably from 3 to 200 atm. The hydrogen gas is reacted at 0 to 200 ° C, preferably at 20 to 180 ° C. The hydrogenation rate of the hydrogenated polymer is usually 50% or more, preferably 70% or more, more preferably 90% or more, more preferably 98% or more, still more preferably 99% or more, as measured by W-NMR at 500 MHz. The higher the hydrogenation rate, the more excellent the stability of the hydrogenated polymer to heat or light, and it is preferable to obtain long-term stability characteristics when used as a molded body. When the polymer obtained by the above method has an aromatic group in its molecule, the aromatic group does not cause deterioration such as discoloration or gelation over time, and is not advantageous for obtaining mechanical properties or optical properties. This aromatic group does not require the necessary hydrogenation. As the hydrogenation catalyst, a user can be used in the hydrogenation reaction of a conventional olefinic compound. The hydrogenation catalyst can be exemplified by a heterogeneous catalyst and a homogeneous catalyst. The heterogeneous catalyst may be a solid catalyst in which a noble metal such as palladium, lead, nickel, ruthenium or osmium is supported on a carrier such as carbon, ruthenium oxide, aluminum oxide or titanium oxide. The homogeneous catalyst can be exemplified by nickel naphthenate/triethylammonium, nickel acetoxyacetate/triethylammonium, cobalt octoate/n-butyllithium, dichlorotitanium dichloride/. diethylammonium monochloride , barium acetate, chloroform (triphenylphosphine) ruthenium, dichloro ginseng (triphenylphosphine) ruthenium, chlorohydrocarbonyl carbonyl (triphenylphosphine) ruthenium, dichlorocarbonyl ginseng (triphenylphosphine) ruthenium and the like. These catalysts may be in the form of powder or granules. These hydrogenation catalysts are usually used in a ratio of the weight ratio of the ring-opening polymer to the hydrogenation catalyst (open-loop polymer: hydrogenation catalyst) of 1:1 χ 10_6 to 1:2. -19- 200927487 (Characteristics of original borneol-based resin)

The raw borneol-based resin used in the present invention has a viscosity U]inh of preferably 0·2 to 2.0 dl/g at 30 ° C, more preferably 〇.4 to 0.85 dl/g, more preferably Determination by gel permeation chromatography: The number average molecular weight (Μη) of the olefin is preferably from 5,000 to 100. 10,000 to 500,000, preferably from 15,000 to 250,000, and the weight average: ^ is preferably from 10,000 to 2 million, preferably It is 20,000 to 1 million, the most tens of thousands. Intrinsic viscosity [7?] inh, number average molecular weight, and weight In the above range, the original borneol resin is excellent in mechanical strength and is easily damaged by the original borneol-based resin base film. Further, the glass transition of the above-mentioned raw borneol-based resin is usually at most 120 ° C, preferably at least 130 ° C. Tg is a raw substrate film which is highly reliable even after long-term use. φ (ultraviolet absorber): In the present invention, it is preferred to add an agent to the original borneol-based resin. The ultraviolet ray absorbing agent reduces the discoloration or transparency of the active radical species caused by the deterioration of the olefinic resin by absorbing ultraviolet rays. Further, the original borneol-based resin film is used as the retardation film or the offset prevents the transmission of ultraviolet light toward the polarizing film to prevent the bias. The ultraviolet absorbing agent can be arbitrarily used in the conventional chloroform of chloroform)·35 〜l.〇dl/g, converted into polyphenylene ketone, more preferably 1 sub-quantity (M w ), preferably 30,000 to 50 When the average molecular weight is obtained, the temperature at which the temperature is not allowed to pass (Tg) is within the above range, and the borneol-based resin is added to the ultraviolet ray to form a raw material, and the raw material is prevented from deteriorating, and the light absorbing agent is deteriorated when the light-protective film having a hard coat layer is deteriorated, but - 20-200927487 It is preferable to use a high molecular weight benzotriazole-based ultraviolet absorber which is excellent in compatibility with the original borneol-based resin and has low volatility. The melting point of the benzotriazole-based ultraviolet absorber is preferably a Tg-35°c~Tg+75°c, preferably Tg-30°C~Tg for the glass transition temperature (Tg) of the original borneol-based resin. + 70 ° C. When the melting point is lower than Tg - 35 ° C, the ultraviolet absorbing: the volatility of the collecting agent increases, and there is a problem that the ultraviolet absorbing agent or its decomposition product adheres to a film or a film forming machine. On the other hand, when the melting point is higher than 0 Tg + 75 ° C, the ultraviolet absorber will bleed out of the surface of the film during film formation, and it is easy to adhere due to high melting point and insolubilization on the surface during the formation cooling. Problems on the surface of the roll or film" The benzotriazole-based ultraviolet absorber is exemplified by, for example, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6- [2H-benzotriazol-2-yl]phenol], 2-(211-1,2,3-benzotriazol-2-yl)-4,6-di-t-butylphenol, 2-( 2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-[2 '-Hydroxy-3',5'-bis-(α,α-di-φ-methylbenzyl)phenyl]-211-benzotriazole, 2-[2'-hydroxy-3'-(1-A Base - 1-phenylethyl)-5'-(1,1,3,3-tetramethylbutyl)-benzotriazole and the like. : Among these, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-[2Η-benzotriazol-2-yl]phenol] Most suitable. The amount of the ultraviolet absorber added is usually 0.1 to 1 part by weight, preferably 0.1 to 5 parts by weight, based on 1 part by weight of the original borneol-based resin. If the amount of the ultraviolet absorber added is less than 0.1 part by weight, a sufficient ultraviolet absorbing effect cannot be seen, and it is difficult to exhibit the effects of the present invention. Further, when it exceeds 20 parts by weight, there is a problem that the light in the visible light region of the resulting film is transmitted through the -21 - 200927487 rate. Further, the ratio of the benzotriene in the total ultraviolet absorbing agent is usually 1% by weight or more, preferably 50% (other components). In the present invention, an anti-addition resistance can be further added to the resin which does not impair the effects of the present invention. The additive antioxidant of an oxidizing agent or the like is exemplified by, for example, 2,6-di-third bis 2,2'-dioxy-3,3'-di-tert-butyl-5,5'-dimethyl [methylene- 3-(3,5-Di-tert-butyl-4-hydroxyphenyl group) When a film is produced by a solution casting method described later, a flow-through agent or an antifoaming agent may be added to make the resin thin. In the production of the original φ film used in the present invention, it is mixed with a raw borneol-based resin or the like, and the olefin-based resin is added and preliminarily formulated. The characteristics of the vine are appropriately selected, but usually with respect to the original borneol system. It is 0.01 to 5.0 parts by weight, preferably 0.05 to (the method for producing the original borneol-based resin base film). The original borneol-based resin substrate used in the present invention is a thin borneol-based resin or contains the above-mentioned raw borneol. The resin composition of the agent is melt-extrusion molding, or the amount of the silicon-based ultraviolet absorber is 以i is surrounded by the original borneol enelate "yl-4-methylphenol, j diphenylmethane, hydrazine" propionate] methane, etc.: the production of the film of the olefinic resin substrate f becomes: a olefinic system Resin substrate or in the production of raw ice: the amount is based on 100 parts by weight of the desired resin. 2 parts by weight. The film can be formed by casting the above-mentioned resin and the above-mentioned additive in a solvent by -22-200927487. (A) melt-forming The film of the norbornene-based resin base material used in the present invention may be composed of the above-mentioned ortho-ene base-based resin or a resin containing the above-mentioned raw borneol-based resin and the above-mentioned additive: additive The product is melt-molded and molded. In this case, since the method is simple, the equipment cost is low, and since the solvent is not used, the cost is low, and the melt extrusion molding is particularly suitable from the viewpoint of less waste. The thickness of the original borneol-based resin base film used in the present invention is not particularly limited, but is usually 5 to 500 μm, preferably 10 to 150 μm, more preferably 20 to 100 μm. When the thickness of the film is in the above range Internal time A film having sufficient strength and a film having excellent birefringence, transparency, and good appearance can be obtained. The light transmission property of the original borneol-based resin base film used in the present invention is usually 80% or more, preferably. It is 85% or more, more preferably 90% or more. : (Microbial treatment) • The original borneol-based resin base film used in the present invention may be subjected to surface treatment in order to improve adhesion to a specific coating layer. The surface treatment is exemplified by a primer treatment, a plasma treatment, a corona treatment, an alkali treatment, a coating treatment, etc. In the above surface treatment, in particular, by using a plasma treatment, a film of a water-borne olefinic resin base film can be obtained. Close to the specific coating. In the surface treatment, especially the atmospheric pressure (normal pressure) plasma -23-200927487 is preferably treated, and may be a rare gas such as helium or argon or a discharge gas such as nitrogen or air, and if necessary, a kind of The above reaction gases such as oxygen, hydrogen, nitrogen, carbon monoxide, carbon dioxide, nitrogen monoxide, nitrogen dioxide, water vapor, methane, and tetrafluoromethane are surface-modified. For example, the plasma treatment can be carried out on the surface of the original borneol-based resin-based film according to the method described in JP-A-2000-3 5 67 1 . φ (Extension treatment) The original borneol-based resin base film used in the present invention can be used as a retardation film by applying an elongation treatment. As a method of the elongation treatment, a method of subjecting the original borneol-based resin film to uniaxial stretching or biaxial stretching is used. In the uniaxial stretching treatment, the stretching speed is usually from 1 to 5,000%/min, preferably from 50 to 1,000%/min, more preferably from 1 to 〇〇〇, 〇〇〇%/min. In the biaxial stretching, the method of the Φ method for simultaneously performing the stretching treatment in the two directions or the method of extending the treatment in the direction different from the direction of the stretching treatment after the one-axis stretching treatment can be used. In this case, the angle of intersection of the two extension axes is appropriately determined depending on the characteristics required for the intended optical film (phase difference film). The determination is not particularly limited, but is usually in the range of 60 to 120 degrees. Further, the stretching speed is usually from 1 to 5,000%/min, preferably from 50 to 1,000%/min, more preferably from 100 to 1,000%/min, most preferably from 100 to 500%/min, and the stretching directions may be the same. It can also be different. The temperature of the elongation treatment is not particularly limited, but the glass transition temperature (Tg) of the original borneol-based resin used is Tg ± 30 ° C, preferably -24 - 200927487.

When Tg ± 15 ° C, more preferably in the range of Tg - 5 ° C to Tg + 15 ° C, by setting the stretching treatment temperature within the above range, occurrence of unevenness in phase difference in the obtained stretched film can be suppressed. Further, it is preferable from the viewpoint of easy control of the refractive index ellipsoid. The stretching ratio is not particularly limited as long as the characteristics required for the optical film to be used are appropriate, and is usually 1. 〇 1 to 1 〇, preferably 1.03-5 times, more preferably 1.03 to 3 times. When the stretching ratio is within the above range, the phase difference of the obtained stretched film can be easily controlled. The stretched film can be directly cooled, but is preferably maintained at a temperature of Tg-20 ° C to Tg for at least 10 seconds, preferably 30 seconds to 60 minutes, more preferably 1 to 60 minutes, and then cooled. According to this, it is possible to obtain a retardation film which has a small change in the phase difference of transmitted light and which is stable over time. The film subjected to the stretching treatment as described above can impart a phase difference with the transmitted light as a result of the orientation of the molecules by the stretching treatment, but the phase difference can be controlled by the stretching ratio, the stretching temperature or the film thickness. <Specific Coating> The specific coating used in the present invention is characterized by having at least two kinds of organic components which are phase separated. With such a configuration, the surface of the specific coating layer usually has irregularities, and the center line average roughness of the unevenness is usually 〇·1 to 1 · Ομηι, preferably 〇·1 5 to 0.8 μm. By providing irregularities on the surface, the specific coating imparts anti-glare properties in addition to imparting high hardness. The preferred glare-reducing property is that the original borneol-based resin film of the hard coat layer of the present invention has a haze of 5 to 65 and a total light transmittance of -25 to 200927487 8 0 to 9 8 %. The performance of the feature. The specific coating layer is usually not particularly limited as long as the obtained hard coat layer is separated, but a hard coat composition having at least two types of organic components may be coated on the original norbornene base film (hereinafter referred to as "specific hard". The coating composition ") is formed into a coating film by drying or photohardening. : The above-mentioned at least two types of organic components are hard to be compatible with each other: the coating state is a combination of phase-separated organic components, and is dried or hardened to form a non-stick coating film, and is not particularly limited. The coating composition may be phase separated or may be homogeneous in the solvent but separated after drying. For example, a combination of a plurality of different types of polymers, a combination of a polymer and a curing monomer, a combination of a plurality of different types of curing monomers, and the like. Further, the term "curable single system herein means a photocurable monomer and a thermosetting monomer", but it is preferably a photocurable monomer from the viewpoint of a short curing time. The polymer is exemplified by a styrene resin, a (meth)acrylic resin, an organic acid vinyl ester resin, an ethene ether resin, a halogen-containing resin, an olefin resin, and an original. Norbornene 'polycarbonate resin, polyester resin, polyamine resin, # Μ plastic polyurethane resin, poly maple resin, polyphenylene ether resin * 'cellulose derivative, 矽Oxygen resin, rubber or elastomer (diene rubber such as polybutadiene or polyisoprene, styrene-butadiene copolymer, propylene-butadiene copolymer, acrylic rubber, amine based Acid ester rubber, silicone rubber, etc.). (a) Polymer component having a structural unit containing an alicyclic structure -26- ❹ 200927487

It is known that a combination of components other than SP is known as a phase j, and a polymer having a structural unit containing an alicyclic structure for a hardenable monomer component such as an acryloxy group, a methacrylic group, or a methacrylamide group. Combination - can. These alicyclic structures are preferably isobornyl groups. The alicyclic structure may be represented by a polymerizable monomer having an isobornyl group, and the I alicyclic structure may exhibit a structural unit with the original borneol-based resin substrate I © having the above alicyclic structure in units of β-constituting units as 100% by weight. In the case where the structural unit having 50 parts by weight of 60 to 95% by weight and preferably 75 to 90 parts by weight is in the above range, the adhesion to the original ice > film is good. (b) Curable monomer The above (b) curable monomer is preferably a monomer which is photopolymerizable by radical polymerization. Terminal-unsaturated groups such as a decyleneoxy group, a methacryloxy group, a acrylamide group, a vinyl ether group, or a vinyl group, and the photocurability (light-polymerization property) In principle, it is preferred to use a photopolymerizable monomer having a molecular terminal or a methacryloxy group, or a carboxylic acid ester, and it is preferred to use a phthalocyanate having 2 to 6 functional groups. The means for the separation is generally i-oxyl or acrylamide, and the above-mentioned (a) is a phase-separated polymerization which is a ring-like structure. In addition, the good adhesion of the film is introduced: the entire structure of the polymer - 99% by weight, preferably t%. The alicyclic olefin-based resin substrate having a weak end having an unsaturated bond, for example, a monomer having a terminal group of propylene and methacrylamide as a terminal group) and a propylene having a hardened substance The methoxy group, ie, (meth) propylene (meth) propylene -27- 200927487 can be specifically exemplified as 1,3 - butanediol di(meth) acrylate, 1,4-butanediol bis (A) Acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, octyl Alcohol di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, bisphenol A: ethylene oxide 2 molar addition di(meth) acrylate, bisphenol F ethylene oxide 4 molar addition di(meth) acrylate, trimethylolpropane tri φ (meth) acrylate, pentaerythritol Tris(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene glycol diglycidyl ether, (meth)acrylic acid 2 molar addition (representing an addition reaction of acrylic acid or methacrylic acid). The following 2 molar additions are also of the same meaning), 1,2-propanediol diglycidyl ether, (meth)acrylic acid 2 molar addition, U6_hexanediol diglycidyl ether (meth)acrylic acid 2 molar addition, hydrogenated bisphenol A glycidyl ether _ (meth)acrylic acid 2 molar addition, bisphenol A diglycidyl ether · (meth)acrylic acid 2 molar addition, trioxindole Methylpropane triglycidyl ether, (meth)acrylic acid 3 molar addition, etc. as an aliphatic or alicyclic family Aromatic polyfunctional (meth) acrylic: ester of acid exemplified. When a photocurable monomer is used as a component of a specific coating composition, a photopolymerization initiator is usually added to the composition. As the photopolymerization initiator, not only the compounds defined in the present invention, but also photopolymerization initiators generally used, that is, acetophenones, benzophenones, diethyl ketones, benzyl groups can also be used. Classes, benzoin, benzoin ethers, benzyl dimethyl ketals, benzoin benzoates, hydroxyphenyl ketones, amino phenyl ketones, etc. 羯-28- 200927487 The compound is a photopolymerization initiator, a thiuram sulfide organic sulfur compound photopolymerization initiator, a mercapto oxygen compound photopolymerization initiator, and the like. The plurality of agents in the present invention may be used singly or in combination of two or more. Further, an organic solvent, a surfactant, an antioxidant, a chelating agent, or the like which is compatible with the component may be further added to the specific coating composition. 0 The specific coating composition is obtained by mixing the above components to obtain a specific coating layer on the original norbornene-based base film, and after drying as needed, it is preferably irradiated with purple. The film thickness of the special coating layer is not particularly limited, but if the surface hardness of the film thickness is too large, the substrate is likely to be wound, usually 〇5 to 25 μm, preferably 2 to 15 μm. When the film is surrounded, a laminate having sufficient hardness can be obtained, and a laminate having good Q, transparency, and appearance can be obtained. The center line of the specific coating is measured by a confocal microscope: 0.01 to 10. Ομιη, preferably 0.1 to 5 μιη, the most " _ bump. The centerline average roughness of a particular coating is on

Coexistence of exhibiting high surface hardness and suppressing curling I < original borneol-based resin film having a hard coat layer> Laminating of a raw layer of a norbornene-based resin-based resin substrate having a hard coat layer of the present invention Specific coatings, organic phosphating species such as phosphines such as thioxanthone and the like are photopolymerized to start the above two types of organic agents and absorb ultraviolet rays. Coating the radiation line such as the specific coating outer line is too thin to obtain a defect such as koji, and therefore the thickness is within the range of 0.1 to 3 μm when the birefringence average roughness is generally obtained in the above range. good. The fat film is applied to the raw ice without damaging the original borneol -29-200927487. The olefin resin base film has the effect of greatly improving the surface hardness under the birefringence, transparency and heat resistance. In particular, the original borneol-based resin base film obtained by melt extrusion molding has excellent properties such as productivity, phase difference exhibitability, and film thickness precision, and particularly has a problem of a decrease in surface hardness, but the present invention has a hard - The coating of the original borneol-based resin film, even if a film obtained by melt extrusion molding is used as the original borneol-based resin base film, has a significant improvement in surface hardness of 0. Further, the original borneol-based resin film having a hard coat layer of the present invention is characterized in that the original borneol-based resin base film is highly adherent to a specific coating layer. In particular, the original borneol-based resin film having a hard coat layer of the present invention is preferably used for optical applications, and a UV absorber is preferably added to the film of the original borneol-based resin substrate, but a film containing an ultraviolet absorber is particularly hard. The coating lacks the problem of adhesion. The original norbornene-based resin film having a hard coat layer of the present invention has a high adhesion to a specific coating layer even if a film having an ultraviolet absorber is used as a film of the original borneol φ olefin resin base material, and the surface is greatly improved. The amazing effect of hardness. The lead of the surface of the original borneol-based resin film having a hard coat layer of the present invention. The pen hardness is usually 2H or more, preferably 3H or more. Further, the total light transmittance is preferably 80% or more, preferably 90% or more. Further, since the plasma treatment is carried out, it is possible to obtain a laminate having a high adhesion to the substrate having a cross-cut adhesion of 1 Å/100 in the method described in JIS K5600. [Examples] -30-200927487 The present invention will now be described by way of examples, but the invention is not limited by the examples. Further, the following "parts" means "parts by weight" unless otherwise specified. In addition, various evaluations were carried out in the following manner. : <glass transition temperature (Tg) > Using a differential scanning card meter (DSC) manufactured by SEIKO INSTRUMENT Co., Ltd., the glass transition temperature was measured at a temperature increase rate of 20 ° C /min in nitrogen (hereinafter also referred to as " Tg"). <Total Light Transmittance> The total light transmittance was measured using a spectrophotometer V73 00 manufactured by JASCO Corporation. <Haze (haze)> 雾 Haze was measured by a method described in JIS K7105 using a haze meter HZ-2 (manufactured by SUGA Testing Co., Ltd.). <Adhesiveness (checkerboard peeling test)> It was measured by the method described in JIS-D0202 using Sai Lulu tape ("CT24", manufactured by NICHIIBAN Co., Ltd.). <Pencil hardness> Measured under a load of 500 g by the method described in JIS K5600. -31 - 200927487 <uv transmission rate> The UV transmittance was measured at a wavelength of 380 nm using the HIGHTECHNOLOGY company U33 10" - < centerline roughness > ' Using LASERTEC's confocal microscope "φ", The center roughness Ra was measured. [Synthesis Example 1] (Synthesis of raw borneol-based resin)

227.5 parts of 8-mercapto-8-methoxy[4·4·0·12'5·17'1()]-3-dodecene and 22.5 parts of bis, 18 parts of 1-hexene (molecular weight adjustment) The solvent and the solvent for the 750 injury reaction were fed into a reaction vessel purged with nitrogen and heated to 60 °C. Next, 0.62 parts of triethylammonium I / liter), 3.7 parts of third butanol / methanol modified • Butanol: methanol: tungsten = 0.35 mole: 〇. 3 mole: 1, liquid ( The concentration 〇·〇5 mol/liter) was added to the reaction vessel, and the system was subjected to heating and stirring at 80 ° C for 3 hours to obtain a ring-opening copolymer solution. The polymerization was carried out in 4,000 parts of the thus obtained ring-opening jersey and 0.48 parts of the solution of RuHC1(CO)[P(C6H5)3]3 polymer and at a hydrogen pressure of 100 kg/cm2. OPTELICS C130

Alkyl carbonyl tetracyclic ring [2.2.1] hept-2-ene toluene (in a ring-opening polymerization, and a solution of the solution of benzene solution (1 · 5 mo hexachlorochloride (third molar) in toluene) In the ring-opening polymerization, the conversion rate is 97%. The solution is fed to the autoclave and heated under the conditions of the ring-opening reaction temperature of 160 ° C -32 - 200927487 for 3 hours for hydrogenation. The reaction solution (hydrogenated polymer solution) is cooled to 'release hydrogen pressure. The reaction solution is poured into a large amount of methanol to separate and recover the coagulum' and dried to obtain a hydrogenated cyclic olefin resin A. The resin A has a Tg of 140°. C. Further, the Μη, Mw, and Mw/Mn converted to polystyrene by the GPC method were 24,000, 67,000, 2, and 8, respectively, and the intrinsic viscosity (β) was 0.4 9 dl/g. 1 10 ( g · 25 μm / m 2 · 24 hr ) ° [Preparation Example 1] <Formation of original borneol-based resin base film> Using a biaxial extruder, the ratio of the resin A to 100 parts was 0.3 parts. (Pentaerythritol 肆-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate: melting point 115 ° C) '1.5 parts of benzotriazole compound (2,2'-methylenebis[4-( 1,1,3,3-tetramethylbutyl)-6- ( 2H-benzotriene) Zyridin-2-yl)phenol]: melting point 199 ° C), after melt-kneading in 2701, it is extruded into strands, and after passing through water, it is passed through a feed die to obtain granules. The obtained granules are subjected to nitrogen at 100 ° C. After circulating and dehumidifying and drying for 3 hours, it was sent to the feed port to melt at a resin temperature of 270 ° C by a uniaxial extruder of a spiral of 75 mm φ. The molten resin was heated to 280 by a double-shaft discharge type gear pump. The polymer filter (mesh 5 μιη) is guided to a 700 mm wide coat hanger nozzle. The resin flowing from the die falls onto the 250 mm φ casting roll and is pressed 'and along the level for the casting roll axis After the two cooling rolls are pressed, the strip is peeled off -33-200927487 and taken up to obtain a film of 80 μm thick (Α·1). Using a plasma processor (manufactured by Sekisui Chemical Co., Ltd.), the film (Α- 1) Plasma treatment was carried out at a frequency of 10 kHz under a nitrogen atmosphere to obtain a film (A-2). The surface tension of the obtained film (A-2) was 73 mN/m (wetting test determination) [Preparation Example 2] <Formation of original borneol-based resin base film> A film (a-Ι) having a thickness of 80 μπα was obtained in the same manner as in Production Example 1 except that the benzotriazole-based compound was not used. The film (a-1) was also subjected to a plasma treatment in the same manner as in Preparation Example 1 to obtain a film (a-2). The surface tension of the obtained film (a-2) was 73 mN/m (measured by a wetness test). [Preparation Example 1] <Preparation of Specific Coating Composition 1> 〇 Mixing: 147.2 g of isophorone methacrylate, 2.8 g of methyl methacrylate, 4.0 g of ethyl hydroxyacrylate, 1 〇. a mixture of gram methacrylic acid and 1 600 gram of propylene glycol monomethyl ether. The mixture was mixed with 20.0 g of propylene glycol monomethyl ether solution containing 2 g of t-butylperoxy-2-ethylhexanoate at a constant rate for 3 hours at the same time. The tube, the cooling tube and the dropping funnel were reacted in a 1 liter reaction vessel in 200.0 g of propylene glycol monomethyl ether heated to 110 ° C under nitrogen for 'subsequent' reaction at 110 ° C for 30 minutes. Subsequently, 17 g of a propylene glycol monomethyl ether solution -34 - 200927487 containing 2 g of tributylperoxy-2-ethylhexanoate was added dropwise and reacted at lio ° C for 30 minutes. To the reaction solution, a solution of 1.5 g of tetrabutylammonium bromide and 0.1 g of hydroquinone in 5_0 g of propylene glycol monomethyl ether was added, and while air bubbles were introduced, 17.3 g of methacrylic acid was added dropwise within 1 hour. A solution of glyceride and 5 g of propylene glycol monomethyl ether was further reacted for 5 hours to obtain a polymer having a number average molecular weight of 8,800 and a weight average molecular weight of 18,000. 5 parts by weight of the obtained polymer, 75 parts by weight of dipentaerythritol hexaacrylate, and 5 parts by weight of a photopolymerization initiator 2,4,6-trimethylbenzylidene 2 as propylene glycol monomethyl ether as a solvent Phenylphosphine oxide and 1 part by weight of the perfluoroalkyl group-containing oligomer were adjusted to have a nonvolatile content of 23% by weight to obtain a specific coating composition 1. [Preparation Example 2] <Preparation of Specific Coating Composition 2> A mixture of 171.6 g of isophorone methacrylate, 2.6 g of methyl methacrylate, and 9.2 g of methacrylic acid was mixed. The mixture was added to a solution of 1.8 g of propylene glycol monomethyl ether containing 1.8 g of t-butylperoxy-2-ethylhexanoate at a constant rate over 3 hours. The device was equipped with a stirring blade and a nitrogen introduction tube. , in a 1 liter reaction vessel of a cooling tube and a dropping funnel, heated to 33 gram of propylene glycol monomethyl ether in a nitrogen atmosphere, and then reacted at 1 l 〇 ° C for 30 minutes. . Subsequently, a solution of 10.7 g of propylene glycol monomethyl ether containing 0.2 g of t-butylperoxy-2-ethylhexanoate was added dropwise, and 5.0 g of tetrabutylammonium bromide and 0.1 g of hydroquinone were added thereto. A solution of 22.4 g of 4-hydroxybutyl acrylate glycidyl ether and -35-200927487 5.0 g of propylene glycol monomethyl ether was added dropwise to the propylene glycol monomethyl acid solution while introducing air bubbles over 2 hours. After reacting for 5 hours, a polymer having a number average molecular weight of 5,500 and a weight average molecular weight of 18,000 was obtained. 5 parts by weight of the obtained polymer, 50 parts by weight of pentaerythritol triacrylate, 50 parts by weight of polyethylene glycol #2 00 diacrylate, and 13 parts by weight of photopolymerization initiator 2-methyl-1 [4- (Methylthio)phenyl]-2-morpholinylpropan-1-one: mixed in a solvent methyl isobutyl ketone, adjusted to a nonvolatile content of 60% by weight *., to obtain a specific coating composition 2 . ❹ [Comparative formulation example] <Preparation of coating composition> 250 parts of glycidyl methacrylate and 1.3 parts of laurel are fed into a reaction apparatus equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube. After the base thiol, 1, butyl butyl acetate and 7.5 parts of 2,2'-azobisisobutyronitrile, the temperature in the system is raised to about 90 ° C in about 1 hour under a nitrogen stream, and the temperature is maintained. 1 hour. Next, a mixed solution of 750 parts of glycidyl methacrylate, 3.7 parts of lauryl mercaptan and 22.5 parts of 2,2'-azobisisobutyronitrile was fed in a dropping funnel, and the mixture was allowed to flow under a nitrogen stream. The mixture was added dropwise to the system over about 2 hours, and after incubation at the same temperature for 3 hours, 1 part of 2,2'-azobisisobutyronitrile was fed and incubated for 1 hour. Subsequently, the temperature was raised to 120 ° C and kept for 2 hours. The weight average molecular weight of the obtained polymer was 1,900 (in terms of GPC to styrene). After cooling to 60 ° C, the nitrogen introduction tube was replaced by an air introduction tube, and 5 07 parts of acrylic acid, 2 · hydrazine hydroquinone monomethyl ether and 5.4 parts of triphenyl phosphine were fed and mixed, and then heated under air bubbles. To 1 1 〇 °C. After 8 hours of incubation at the same temperature, 1.4 parts of hydroquinone monomethyl ether of -36-200927487 was fed, and after cooling, ethyl acetate was added to make the nonvolatile content 50%, and a paint was obtained. Mix 5 parts of trimethylolpropane triacrylate and 25 parts of polyfunctional urethane amide in 25 parts of this paint (manufactured by Arakawa Chemical Co., Ltd., trade name "BEAMSET 5 5 7"), and the solid content of the ethyl acetate was adjusted to 50%, and 1-hydroxy-cyclohexyl phenyl ketone as a photopolymerization initiator was added to the solid content of 5% of the formulation, and after dissolution, The solid content concentration was adjusted to 80% with ethyl acetate to prepare an ultraviolet curable composition. 65.1 parts of the ultraviolet curable composition, 25.8 parts of methyl ethyl ketone, and 9.17 parts of cerium oxide (AEROSIL (average particle diameter: about 12 nm) were blended in an open barrel for stirring (about 40 cm in inner diameter and 58 cm in inner side). ), manufactured by AERO SIL Co., Ltd., and dispersed and stirred for 150 minutes with a stirring blade having a diameter of about 11 cm. Subsequently, it was diluted with methyl ethyl ketone to obtain a coating composition having a solid content of 40%. 〇 [Example 1] The coating composition 1 obtained in Formulation Example 1 was applied onto the surface of the film (A-2 4 ) obtained in Preparation Example 1 using a coating bar (NCL18) at an ambient temperature of 23 t. The solvent was dried by heating at 50 ° C for 10 minutes to make the film thickness 6 μm. Subsequently, a coating was formed by exposure to an ultrahigh pressure mercury lamp with an ultraviolet ray of 1 J/cm 2 to obtain a raw borneol-based resin film (B-1) having a hard coat layer. The evaluation results are shown in Table 1. [Example 2] -37-200927487 An original borneol-based resin film (B-2) having a hard coat layer was obtained as in Example 1 except that the film (a-2) obtained in Preparation Example 2 was used. The evaluation results are shown together in Table 1. [Example 3] An original borneol-based resin film (B-3) having a hard coat layer was obtained as in Example 1 except that the film (A-1) obtained in Preparation Example 1 was used. The evaluation results are shown together in Table 1. [Example 4] The coating composition 2 obtained in Formulation Example 2 was applied onto the surface of the film (A-2) obtained in Preparation Example 1 at a temperature of 23 ° C using a coating bar (No. 5). The solvent was removed by heating at 80 ° C to make the film thickness 4 μηη. Then, a coating layer was formed by exposure to an ultrahigh pressure mercury lamp with an ultraviolet ray of 1 J/cm 2 to obtain a raw borneol-based resin film (B-4) having a hard coat layer. The evaluation results are shown in Table 1. [Comparative Example] Using the film (A-1) obtained in Preparation Example 1, the coating composition obtained in the comparative formulation was applied by gravure printing, dried at 8 (TC for 6 () seconds, and irradiated for 1 5 /cm2 of ultraviolet rays, and hardened to form a film coating of 4 μm, to obtain a film (b) having a hard coat layer. The evaluation results are shown together in Table 1. -38- 200927487 [Table 1] ί _ Comparative Example 1 2 3 4 Evaluation film Β-1 Β-2 B-3 B-4 b Film formation film Α-2 a-2 A-1 A-2 A-1 Plasma treatment has yi, with or without Hardcoat Specific Coating Composition 1 Specific Coating Composition 1 Specific Coating Composition 1 Specific Coating Composition 2 Coating Composition Total Light Transmittance (%) 96.5 95.8 96.6 93.7 91.8 Haze 39.8 41.5 43.2 8.9 7.8 Pencil hardness 3Η 3H 2H 2H HB Period disc peeling test 100/100 100/100 32/100 100/100 58/100 UV transmittance (%) 2.9 89.5 3.1 3.0 3.1 Center line average roughness (μιη) 1.9 1.9 1.8 1.0 In the above embodiment, the hard coat film composed of the present invention exhibits high pencil hardness and high total light transmittance, and is excellent in confirmation. With the present invention can be expected to provide a touch panel or the like suitable for an optical film polarizing plate, etc. Excellent Good substrate. -39-

Claims (1)

200927487 X. Patent Application No. 1. A raw borneol-based resin film having a hard coat layer, which is characterized in that a hard coat layer having at least two organic components is formed on a film of an original borneol-based resin base material, and The hard coat layer is phase separated. 2. The method according to claim 1, wherein the hard coat layer is composed of a polymer component containing (a) a structural unit having a structure containing a alicyclic ring; b) A coating composition containing a curable monomer in an amount of 0. 3. The raw borneol-based resin film having a hard coat layer according to claim 1 or 2, wherein the (a) structural unit containing an alicyclic structure having a polymer component having a structural unit of an alicyclic structure contains The amount is 50 to 99% by weight in terms of 100% by weight of all the constituent units of the polymer. 4. The raw ice sheet-like resin film having a hard coat layer according to the first to third aspects of the patent application, wherein the raw borneol-based resin film contains an ultraviolet absorber. 0. The original borneol-based resin film having a hard coat layer according to the first to fourth aspects of the patent application, wherein the surface of the hard coat layer has a center line average. The roughness is 〇.1~1〇.〇μηι Bump. 6. A method for producing a raw layer of a norbornene-based resin film having a hard coat layer, comprising the steps of: forming a film of an original borneol-based resin base material, and forming a film of the obtained norbornene-based resin base material a step of hard coating of at least two organic components, and the hard coat layer is phase separated. 7. The method for producing a hard-coated original borneol-based resin film according to claim 6, wherein the raw borneol-based resin base film contains -40-200927487 having an ultraviolet absorber. 8. The method for producing a hard-coated raw ice-ene-based resin film according to claim 6 or 7, wherein the surface of the original borneol-based resin substrate film is subjected to a charge-receiving treatment to form a hard coat layer . 9. The method for producing a hard-coated base ice-sheetene resin film according to the sixth to eighth aspect of the patent application, wherein the raw borneol-based resin substrate thin film is melted and extruded by the original borneol resin And formed. 0. The method for producing a raw borneol film having a hard coat layer according to the sixth to ninth aspect of the invention, which further comprises a step of extending the film of the original borneol-based resin base material. ❹ -41 - 200927487 VII. Designated representative map: (1) The representative representative of the case is: None (2), the representative symbol of the representative figure is a simple description: None 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none -4-