TW200946551A - Polyurethane resins containing cycloaliphatic and/or aromatic component and phase difference films using them - Google Patents

Abstract

The present invention provides a polyurethane resin for using in phase difference film, and a phase difference film which exhibits no heat deterioration even experienced the extension process at the temperature above glass transition temperature (Tg), and the phase difference of the extended film will not be decreased as used in summer's high temperature. The polyurethane resin of present invention is characterized in comprising cycloaliphatic and/or aromatic components, and particularly with a glass transition temperature higher than 100 DEG C and lower than 200 DEG C.

Description

[Technical Field] The present invention relates to a polyurethane resin containing an alicyclic component or an aromatic component, and a phase used in a liquid crystal display device or the like using the urethane resin. Poor film.

[Prior Art] A retardation film used in a liquid crystal display device or the like is initially used in the development of a polycarbonate film (Japanese Patent Laid-Open No. Hei 5-113506, etc.). However, polycarbonate has a large photoelastic coefficient, and it is difficult to obtain a film having a uniform phase difference. Therefore, a film in which a phase difference adjuster is added to cellulose triacetate is put into practical use (EP0911656, etc.). However, cellulose acetate (cellul〇setriacetate) still has a problem of poor heat resistance. In order to solve this problem, a cycloolefin-based resin film has been used as a retardation film having high heat resistance (Japanese Patent Laid-Open No. Hei 4_36123, etc.). However, the 'cycloolefin type resin film has a problem that the mechanical strength is low and the film is easily broken. Further, a method of applying a layer having a phase difference function to a film is also known, and a polyamide and a polyamide are proposed as the resin. (曰 This patent is open 2006-58540, etc.). However, when these resins are present alone, the coating property is poor, and it is necessary to provide a bonding layer (primer layer) such as a urethane resin. 200946551 Further, a urethane-based resin coated with the underlayer is proposed as a phase difference film of phase difference (Japanese Patent Laid-Open No. Hei 2-7-328-52, Japanese Patent No. 2007-328053). It has the advantages of excellent coatability and high mechanical strength, but it is generally low in heat. Even if the stretched orientation touches and shows a phase difference, the orientation will be relieved and the phase difference will decrease in the summer. 5 'Proposed to use an optical film having a high (four) thermal ammonia § designation (for example, 'Japanese Patent Laid-Open No. 2005-126665, Japanese Patent Laid-Open No. Hei No. Hei 2 No. 5-225997, Japanese Patent Laid-Open No. 2GG5-272614, Japanese patent system __272615, Japanese patent special bribe - _557). In these optical films, the glass transition degree (Tg, giass transiti〇 temperatuj_e) which exhibits heat resistance of the film is 2 〇〇 c > c or higher = high temperature. In order to express the film phase difference, it is necessary to heat the film to the above step and to reverse the step ′, and at a temperature of 2qqCw, the film may be thermally degraded (e.g., it is difficult to make the film stretch exhibit a phase difference). [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. 2, No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei No. 5-225 " No. 7 [Patent Document 9] Japanese Patent Publication No. 2726! No. 4 [Patent Document ίο] 曰本专利特开2005_272615号SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the invention is to provide a urethane surface grease and a phase difference _ using the resin. It is easy to exhibit a phase difference, and it is practical to change the phase filament, and has a glass transition temperature of a retardation film which is sufficiently heat-resistant. The poly IU measurement of the present invention is characterized in that the frequency emission contains an alicyclic component and/or a component group. With such a configuration, it is possible to provide an ammonia-containing phase difference film having heat resistance. Further, in the polyurethane resin of the present invention, it is preferred that the glass transition temperature (f) is 100 ° C or more and less than 20 (TC). The glass transition temperature is set in the above range Q to be produced at the time of manufacture. It is easy to extend the rainbow, and it is easy to ship the difference, and the phase difference film having sufficient heat resistance is practically changed. The polyurethane resin of the present invention is particularly preferably a diisocyanate having a cyclohexane structure and having The diol having a cyclohexane structure is polymerized. Alternatively, it is preferred to polymerize a diisocyanate having a phenyl group and a diol having a cyclohexane structure.

I 200946551 The above-mentioned polyurethane tree, the compound of the present invention is better or the compound represented by (H).卜ι化予式(化3) (1) ^τΟΟτ-Ο 【化4】 Ο ❹ (1)) It is now possible to make a phase difference by having a structure like a mosquito scale. (4) Her poor Γ The invention is her poor _, which is characterized by the tumbling of the polyurethane, after the _ shape, the exhaustion ί: after the solvent is made into a solution (coating solution), applied to other buckles (溥膜4 ), a phase difference film that is extended. Further, an optical film such as a urethane resin protective film containing the above compound. The polyurethane resin of the present invention has practically sufficient heat resistance and has a glass transition temperature (5) in a temperature range which can be extended without causing thermal deterioration. Therefore, the phase difference of the above-mentioned polyurethane-containing grease is _ The step of extending to the glass transition temperature (5) 2 and extending is not thermally deteriorated, and even if the stretched film is used under the summer (4), the difference will not decrease. 7 200946551 [Embodiment] Hereinafter, the polyurethane resin of the present invention and a phase difference film or an optical film composed of the urethane resin will be described in detail. The present invention is characterized in that it contains more than one alicyclic component and/or aromatic component in its molecule. The above polyurethane resin is obtained by reacting a diisocyanate compound with a diol compound. The diisocyanate compound used in the polyurethane resin is one having an isocyanate group in the molecule, such as '2'4-toluene di isocyanate, 2,6-toluene. Diisocyanate, 1,3-benzenedidecyl-isocyanate δ (1,3-xylylene di isocyanate), 1,4-benzenedidecyl monoisocyanate, 1,5-naphthalene diisocyanate (1,5- Naphthalene diisocyanate ), m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3,-dimethyl-4,4,-diphenylmethane diisocyanate , 4, 4'-diphenyldecane diisocyanate, 2,4'-diphenylmethane diisocyanate, 3,3'-dimethylexyl diisocyanate, 4,4'-biphenylene Isocyanate, 1,6-hexane diisocyanate, isophorone di isocyanate, 4, 4'-dicyclohexylmethane diisocyanate (4, 4' -di cy c 1 ohexy 1 me thane dii socy Ana te), methylene bis(4-cyclohexyl isocyanate), 2, 2, 4-trimethylhexamethylene diisocyanate §, 1, 4-hexamethylene Diisocyanate, bis(2-isocyanateethyl) fumarate, bis(4-isocyanate 200946551 ester cyclohexyl)methane, 6-isopropyl-1,3-phenyl diisocyanate, 4-di Styrene propane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, tetradecyl dinonyl diisocyanate 'norbornane diisocyanate' and the like. Further, the compound of the diisocyanate g used in the present invention may be one type or two or more types. Next, the diol compound used in the present invention will be described. The diol compound used in the present invention is, for example, an aromatic diol, an aliphatic diol or an alicyclic diol. Examples of the aromatic diol include ethylene oxide addition diol of bisphenol A and propylene oxide addition diol bisphenol A butyl butyl bisphenol A. Alkane addition diol, bisphenol F ethylene oxide addition diol, bisphenol F propylene oxide addition diol, bisphenol f butylene oxide addition diol, hydroquinone epoxy Alkylene (Alkylene 0xide) addition diol, naphthoquinone alkylene oxide addition diol, and the like. Examples of the aliphatic diol ′ include ethylene glycol (glycol) propanol, tetramethylene glycol, 1,2-butylene glycol, and isobutylene glycol. Examples of the above-mentioned lipid diol include hydrogenated (tetra) A epoxy epethane addition diol, hydrogenated bis-A propylene propylene addition diol, hydrogenated double hop A epoxidized addition diol, and hydrogenation double Fresh epoxy Ethylene addition diol, hydrogenated double sulphide propylene sulphide plus 9 200946551 into one g, hydrogenated double F epoxide butadiene calcined diol, dicyclopentadiene dimethyl hydrazine 1) a compound, tricyclodecanediethanol (tncycl. decane dimethanc Dle), u-cyclohexane dimethanol, and the like. The glass transition temperature (taken) of the polyurethane resin of the present invention is preferably such that i sail is less than 200 C. If the Tg is lower than the above range, the impurity including the extension of the polyurethane sap is used as the phase difference _ at the high temperature in summer, the phase difference exhibited by the elongation is decreased, and _g_ is used as the phase difference. The function of the film is degraded. Further, when the right Tg is in the above range, when the processing such as the stretching process is heated to the vicinity of the processing, the possibility of thermal deterioration of the resin is high. In particular, the polyurethane resin of the present invention is obtained by polymerizing a diisocyanate having a cyclohexene structure and a diol having a cyclohexane structure. As the above urethane resin, a compound represented by the following chemical formula (I) is particularly preferable. Selecting 4,4,-dicyclohexylmethane monooleic acid vinegar as a diisocyanate having a cyclohexane structure and selecting 1,4-cyclohexyl sulphide as a diol having a cyclohexane structure When a monomer is reacted, a compound represented by the following chemical formula (I) is obtained. [Chemical 5] And 'as a diisocyanate having a cyclohexane structure, the choice of isophorone diazepam is unknown, as a diol having a cyclohexyl structure to select 1,4-cyclohexanedimethanol reaction 200946551 At the time, a compound represented by the following chemical formula (1') 4 was obtained. 【化6】

Further, the polyamine shark of the present invention is particularly preferred to have a polyisocyanate having a silky diisocyanate and a bis-line polymer having a cyclohexanium structure.

Further, as the polyvalent resin which is obtained by polymerizing a diisocyanate having a filament as described above and polymerized with a diol having a cyclohexene, a compound represented by the following chemical formula (n) is particularly preferable. When 4,4, _diphenylcarbazide-' is selected as a diisocyanate having a stupid base, and 1,4-cyclohexanone is selected as a diol having a cycloheximide structure, and a raw material monomer can be obtained. A compound of the following formula (8). 【化6】

(Π) -NH·Expansion. , <^叶士t#明的聚氮|The purpose of the resin is not to turn over the purpose of the invention, but also to make *方知夕7〇 know, fat% polyol, aromatic polyol, polyphenol polyol, Copolymerization (eGpQlymerizati〇n) is carried out on components such as polysulfide vinegar polyol and poly ρ _ _ _ _ polycaprolactone polyol. The weight average molecular weight of the H fat is preferably 5, deleted ~ 1,000, 〇〇〇. If the molecule goes to Lihe 5, 树脂, the resin will easily become brittle and crack. Further, 200946551, when the molecular weight exceeds 1,000,000 Å, the meltability becomes very rfj when molten resin or a solution is formed, and it becomes difficult to form. Next, a method of producing the polyurethane resin of the present invention will be explained. As a method of producing the polyurethane resin of the present invention, a usual method can be used, and any method can be selected depending on the type of the diisocyanate compound and the diol compound of the monomer compound. For example, a method in which a diisocyanate compound or a diol compound of a monomer compound is dissolved in a solvent, mixed and reacted, and a reactant is precipitated can be selected. © In this state, as the solvent of the monomer compound, a solvent which can dissolve the monomer compound used at a desired concentration can be appropriately selected. For example, a hydrocarbon solvent such as benzene or hexyl alcohol; ketone, methyl isobutyl gjg, cyclohexanone (CyCi〇hexanone), fluorenylcyclohexane; a ketone solvent such as a ketone; an ether solvent such as tetrahydrofuran or l2-dimethoxyethane; a halogenated solvent such as a gas imitation; An ester solvent such as methyl acetate, butyl phthalate or propyl phthalate ( pr〇pylene giyc〇im〇n〇methylether acetate); n,N-dimercaptocarboxamide (1) ^, 1^- dimethylformamide) and other amide-based solvents, and sulfoxide-based solvents such as dimethylsulfoxide. In the present step, it is preferred to use a guanamine-based solvent such as dimethylformamide. Further, as the solvent used in the present aspect, a single solvent may be used, and 12 200946551 may be a mixed solvent of a plurality of solvents. The retardation film obtained in 1 and the method of producing the polyaminoester of the present invention will be described below. The fat, the braided material, the mono-layer film of the sulphuric acid, or the layered film of the 相位 Π Π 之 之 之 之 之 之 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为After the broadcast method is heard, the method of the paste obtained by the == stretching method: the step of the scaly method rw, the money tree solution in the solvent, and the step of coating the surface, the above coating liquid and the dry tree _ The step of forming the sheet, and (6) the method of extending the step of extending the resin sheet. First, a method for producing an early layer film of a retardation film obtained by the invention of the invention can be described. When manufactured by the melt-broadcasting method, the fat is supplied to the uniaxial or two-axis extruder, and the degree of resin drilling can be extruded by the extruder and added at a temperature at which the decomposition temperature of the resin is not full. In the form of flakes. The extruded resin is cooled to form a resin crucible by controlling the temperature near the glass transition temperature (Tg) of the resin or below. The obtained resin sheet 'sends the phase difference of the film by the arrangement of the polyurethane-fat material molecules contained therein, and is sent to the stretching step. Since the stretching step and the case of the solution_method described later are omitted, the description thereof is omitted here. 13 200946551 The resin sheet may contain other compounds than the urethane resin as long as it does not impair the object of the present invention. For example, it may be blended with a known thermoplastic resin, an elastomeric elastomer, an elastomeric polymer, an organic fine particle, an inorganic fine particle, an antioxidant, an ultraviolet absorber, a mold release agent, a flame retardant, an antibacterial agent, a wood powder, and an even Mixture, petroleum resin, plasticizer, colorant, lubricant, antistatic agent, Shixia oil, foaming agent. Further, in the case of the granule washing and casting method, first, the above-mentioned polyurethane spray is dissolved in a solvent to adjust the coating liquid (step (A)). The solvent to be used in the case of dissolving the above-mentioned polyurethane resin is not particularly limited, and examples thereof include a ketone solvent such as benzene or hexyl ketone; decyl ethyl ketone and methyl isobutyl ketone; , cyclohexanone, mercaptocyclohexanone solvent; tetrahydrofuran, 1,2-dimethoxyethyl ether solvent; gas-like, two-gas calcination and other tooth-based burning solvent; [Acrylic acid alone, propylene glycol monodecyl ketone acetate solvent such as vinegar; guanamine solvent such as N,N-dimethyl decylamine; and a hardening solvent such as dimethyl sulfene. Further, the solvent may be a solvent containing a single solvent or a mixed solvent of a plurality of solvents. If the coating liquid is not in the form of a foreign product, the polyurethane resin and other compounds other than the solvent may be added. H may also be added with a known thermoplastic resin: hot elastomer, rubbery polymer, organic fine particles, inorganic fine particles. , anti-deuteration, UV absorber, mold release agent, flame retardant coupling agent, stone wheel, enamel, coloring system, anti-^ 2 200946551 foaming agent. The concentration of the polyamine (tetra) lipid component in the coating liquid is usually 5% (10% by weight), 乂仏1 to 50% by weight, and further preferably 5 to 35% by weight. When the resin component concentration is less than the above range, a resin thin plate having a sufficient thickness may not be obtained, and it may not be obtained due to foaming accompanying the melting of the sugar. _. On the other hand, if the concentration of the ageing component exceeds the above-mentioned range, the gambling of the solution is too high, and sometimes the resin film having a uniform thickness or a uniform surface state cannot be obtained. ν and 'the dryness of the coating solution at room temperature, usually Η, _, _ 咖 · $, preferably Η) ~ said, _ mPa · s, and more preferably (10) ~ printed, _ café S ' Especially good is 1, 〇〇〇 ~ 40, 〇〇〇mpa · s. When the coating liquid is adjusted, the temperature at which the solvent dissolves the polyurethane resin may be room temperature or high temperature. With a full secret, Saki has a uniform solution. Further, it is possible to remove the gas remaining in the solution by means of heating, standing, or the like as needed. Further, as needed, a coloring agent such as a dye 'pigment may be used in the solution at the time of coloring. Further, in order to improve the smoothness of the surface of the film, a leveling agent may be added. Such a leveling agent' is a usual leveling agent: it is not particularly limited, and for example, a nonionic (n〇ni〇nic) surfactant, a special acrylic resin leveling agent, and a polyfluorene can be used. Oxygen leveling agent. Next, the coating (four) of the coating is applied to a suitable substrate to be dried to obtain a bismuth resin sheet (step (B)). u 15 200946551 The method of coating is not particularly limited as long as it can apply a specific amount of the coating liquid to the substrate. Examples of such a coating method include a grazing coat method, a reverse coat method, a knife coat method, and a dip c〇at meth method. 〇d), spray coat method, air knife method (air_knife c〇at method), spin coat method, report method (r〇uc〇at method), printing method (print Method)' dip coating method (dip c〇atmg meth〇d), curtain coating method, die coating method (die c〇at meth〇d), cast coating method, bar coating Method (bar c〇at meth〇d), extrusion coating method, E-coating method, and the like. As a suitable substrate for coating the coating liquid, for example, a metal drum, a steel belt, a polyethylene terephthalate (10), a (10) (four) ephthaiate, PET), a polyethylene naphthalate Two kinds of vinegar (can (also known as ahahalate, remuneration) and other polyester film, polytetrafluoroethylene (polytetrafluoroethylene). For the drying method of the coating liquid, a drying method which is usually used, such as a heating dry method and a vacuum drying method, can be used. Further, the drying method of the present aspect is not limited to the single-method. For example, the drying method may be sequentially changed by reducing the amount of solvent remaining in the coating, and the drying method may be employed. Dry, the temperature is not particularly limited, and is preferably (9). c~(10). c or so. "After drying, the coating film is peeled off from the substrate to obtain a resin sheet. In 200946551, the phase difference of the binding film of the money-containing material is arranged, and the elongation step (step (〇) The fine ___ (4) Lin reinterpreted the continuation of this issue « Syria (four) 駄 财 之 之 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位 相位Uniaxial extension or -^ ❹ ❹ can be used as a method, • can be::: two-length _ extension method' tenter stretching method (TenterSt·^ Tubular stretching method (.) = extension processing method At the time of the closure of the two-way extension, the extension of the two-handed or the bill of lading may be carried out, and the extension direction of the treatment may be performed in the same direction as the extension direction. At this time, the two extension axes intersect. The desired characteristics of the optical film are determined, and = the root is in the range of 120 to 60 degrees. ',,, <疋', but the 延伸 usually extends at a speed of uniaxial stretching, usually 卜5, coffee $ 疋5 〇~to (four) points, and more preferably (10)~U_ points. The extension speed of the good two-axis extension processing method The direction of extension can also be = usually 1~5, _minute' is preferably 5. ~ ^ 疋 疋 (10) ~ U _ / min, especially good is 1 〇〇 ~ 5 points. Depending on the purpose, it is particularly limited, but it is usually UHG times, preferably 1 () 3 to 5 times, ^ 200946551 is preferably 1. 03 to 3 times. If the stretching ratio exceeds the above range, In some cases, the phase difference of the film obtained by the method is difficult to be obtained. 0. As the extension processing temperature, as in the case of f, it is preferable to use the film which is broken above the glass transition temperature and below the melting point. The state of the domain is extended. The stretched film can be cooled after the stretching process, but the film is kept at least ι sec or more in a temperature environment of the resin film HC~Tg, preferably 30 seconds to 60 seconds. It is better to carry out the cooling after the sub-segment (9). Therefore, the 薄膜 〇 〇 〇 _ 魏 魏 魏 魏 较 较 较 较 较 较 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏 魏Film, a method for producing a multilayer film. Further, as a multilayer of the present invention, the second layer The structure may be a three-layer structure, and may have three or more layers. As a method for producing the multilayer film, (i) a plurality of resin sheets obtained by a melt extrusion method or a solvent washing method may be mentioned. a method of laminating, forming a laminate, and then stretching the laminate to form a multilayer film; (n) coating the coating solution with a coating liquid and drying it, and then coating the coating liquid Drying, repeating the operation to form a laminated body', and then stretching the laminated body into a multilayer film; (ill) coating and drying the coating liquid on a transparent substrate to form a laminate, and thereafter, The laminate is stretched to obtain a multilayer film method or the like. A method (i) for producing the above multilayer film will be described. First, two or more sheets of paper are prepared in the same manner as the one-layer film production method. The tree slabs manufactured by the method of 2009 200951 are laminated to each other to obtain a laminate. In such a laminate, a common layer of the primer or the bottom layer may be added between the sheets. * Spear] The above-mentioned laminated layer is extended in the same manner as described above to prepare a multilayer thin film. In the same manner as the above-mentioned single-layer film production method, the money of the present invention is dissolved in a solvent, and the coating liquid is finely coated, coated on a substrate, and dried to obtain a resin sheet. . Thereafter, the coating liquid was applied onto the resin sheet, and dried in the same manner to form a two-layer laminate. Thereafter, the laminate was stretched in the same manner as above to obtain a two-layer retardation film. Further, a film of three or more layers can be produced by repeating the above coating and drying steps. In the method (iii) for producing a multilayer film, the coating liquid adjusted on the transparent substrate (thin sheet, film, or the like) in the same manner as described above may be applied and dried to form a laminate. The laminate is stretched into a multilayer film. As the transparent substrate, the polyurethane resin of the present invention or a resin material which is usually used can be used. For example, a cellulose derivative (eeiiui〇se derivative), a cycloolefin resin, a polydecyl methacrylate, a polyvinyl alcohol, a polyamine, a polyallyl Polyallylate, polyethylene terephthalate, polyfluorene 19 200946551 (polysulphone), polystyrene (P〇iy ether sulfones), amorphous poly (m〇n) hous polyolefin), Modified acrylic polymer, polystyrene, epoxy resin, polycarbonate, polyester, and the like. Further, the thickness of the retardation film of the present invention is not particularly limited, and is usually from about 50 /zm to 500 //m. [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the following examples. (Evaluation Analysis Method) The evaluation analysis method used in the present example is as follows. (1) Heat resistance of resin The differentially-packed heat analysis (DSC) was used to evaluate the glass transition temperature (Tg) measured at a temperature rise of 2{rc/min.

(2) Weight average molecular weight U (ge[ permeation Chromatography &gt; GPC) is just determined and calculated. (3) Optical properties of solvent-cast film: The resin is dissolved in a solvent, coated on a grease-coated plate, and dried and then peeled off to obtain a film having a glass transition temperature of +2 (the temperature of rc is uniaxially stretched twice, and then Optical characteristics 20 200946551 • Appearance: Visually evaluate the appearance of defects. • Phase difference: The front and thickness directions are measured by an ellipsometry device (K〇BLA wpRXY2〇2〇, prince measurement αα (manufactured by Yuet)) The phase difference is converted into a film thickness of 1 。. Phase difference retention ratio: The retention ratio of the retardation film to the phase difference after heating for 3 days at TC temperature for 3 days is calculated according to the following equation. Rate = force ° phase difference after heat (nm) / phase difference before heating (nm) χ © 100 (%) (4) Optical properties of the melt-extruded film The resin is supplied to the extruder at a temperature of 225t. The die was extruded to produce an unstretched film. Then, after the uniaxial stretching of the glass at a temperature of 15 t: the uniaxial extension was performed twice, the following optical characteristics were evaluated. • Appearance: visually evaluated whether the appearance was defective or not. ❹ • Phase difference: ellipsoid The circular polarization measuring device (K〇BLA wpRXY2〇2〇, manufactured by Oji Scientific Instruments Co., Ltd.) measures the phase difference between the front side and the thickness direction. The phase difference is converted into a film thickness of 1 。. • Phase difference retention rate: The following formula is used to calculate the retention ratio of the retardation film to the phase difference after heating for 5 hours at TC temperature for 500 hours. Phase difference scale = add her difference (nm) / add back phase difference ((10)) X 100 (8) ( 5) Film strength 21 200946551 Evaluation Whether the stretched film was bent at a direction perpendicular to the extending direction at room temperature was observed. (6) Coating property of the film The resin was dissolved in a solvent and applied to a cellulose triacetate film to The coated surface after drying was visually observed. <Example 1> 45.2 parts by weight of 4,4,-dicyclohexyldecane diisodecanoic acid vinegar was added to the reaction vessel, and 240 parts by weight of dimethylformamide was further added thereto. This was dissolved. Then, while stirring the solution, a solution of 24.8 parts by weight of i, 4_cyclohexanol dioxime dissolved in 40 parts of 1 part of dimethylformamide was added slowly. After the completion, react at 4 ° C for 4 hours, will The liquid was poured into decyl alcohol to precipitate the formed resin, and the precipitated resin was vacuum dried at a temperature of 8 (TC). The NMR spectrum of the resin prepared as described above is shown in Fig. The results of molecular weight, optical properties, strength, and coatability are shown in Table &lt;Example 2 &gt; ^ 44.4 parts by weight of 4,4,-diphenylnonane diisocyanate was added to the reaction vessel. 240 parts by weight of dimethyl decylamine and dissolved. Then, while stirring the solution, slowly add 25.59 parts by weight of 1,4-cyclohexanedimethanol in 40 parts by weight of dimethylformamidine. a solution in an amine. After completion of the addition, the reaction was carried out for 4 hours at a temperature of 13 ° C, and the reaction liquid was poured into methanol t to precipitate a resin formed. The precipitated resin was vacuum dried at a temperature of 8 (TC). 22 200946551

The results of characteristics, strength, and coatability are shown in Table j. Evaluation of heat resistance, molecular weight, and optical <Example 3>

After removing the solvent under a reduced pressure of about 5 Torr at ° C, the reaction vessel was heated to 220 to eject the resin from the reaction vessel to pelletize. The heat resistance, molecular weight, optical properties, strength, and coating properties of the resin are shown in Table 1. &lt;Example 4&gt; 7 〇·83 parts by weight of 1,4-cyclohexanedimethanol was placed in a reaction vessel, 120 parts by weight of dimethyl decylamine was added as a solvent, and heated to a pressure of u〇 in a nitrogen atmosphere. t. Then, 108.08 parts by weight of isophorone diisocyanate was added. After the end of the addition, the reaction was carried out at a temperature of 130 ° C for 25 hours. The obtained reaction solution was heated to 2 Torr (rc, and the solvent was removed under reduced pressure, and the resin was taken out. The heat resistance, molecular weight, film optical properties, strength, and coatability of the resin are shown in Table 1. <Comparative Example 1 &gt; 23 200946551 Commercially available urethane resin (HUX320, manufactured by ADEKA Co., Ltd.), heat resistance, molecular weight, optical properties, strength, and coatability were evaluated in the same manner as in the examples. The results are shown in Table 1. <Comparative Example 2) Commercially available cyclic olefin resin (TOPAS 6013 manufactured by Polyplastics Co., Ltd.) was evaluated for heat resistance, molecular weight, optical properties, strength, and applicability in the same manner as in the examples. The results are shown in Table 1.

24 200946551

oG [5 coatability-tri^ strength 1 .. 1 no cracking without cracking - no cracking i _ . _ 1 no cracking no cracking cracking optical property 1 phase difference retention ratio (%) __—— — 1 thickness direction CD 〇〇* CO CD LO CD CZ? CD 1 i front 1 〇〇〇〇cn&gt;cn&gt; s phase difference (nm) / thickness / zm thickness direction CD LO C&lt;1 ο r &lt; CO 1490 § 1380 front ο inch Cz&gt; H CO 1460 s cz&gt; CO 03 Appearance is good 岽jss*L Weight average molecular weight (Mw) 33000 35000 26000 18000 Unable to measure 114000 Pairs of heat (glass transition temperature (Tg)) (°C) csa C&lt;I 1 &gt T-&lt; οα 1 &lt; CD (NI i _H less than 40 &lt; 3) CO &gt;&quot; 1 Sample Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 200946551 Ming's polyurethane resin of the present invention can provide a retardation film, VIII, glass transition temperature (Tg) of more than 100C, less than 2 〇〇 °c, even after heating to glass transition temperature (Tg) Above and extending the steps, the film will not be thermally degraded, and even in summer cars After extending the case of using a thin film, the retardation will not decrease. Further, the present invention has excellent optical characteristics and is excellent in the field of view compensation effect. Therefore, it is suitable as a field-of-view compensation film (view c〇fflpensati〇n mm) used in a liquid crystal display such as a large Weijing TV. In addition, it can also be used as, for example, a mobile phone, a digital information terminal, a pocket bell, a navigation system, a vehicle liquid crystal display, a liquid crystal monitor, and a dimming plate (Hght Yang).咐), 〇a An optical film used for various liquid crystal display elements, electroluminescence display elements, or touch panels, such as a display for a device and a display for an AV device. Further, it can also be used as a wave plate used in optical disk recording and reproducing apparatuses such as CDs, CD-Rs, MDs, MOs, and DVDs. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an NMR spectrum of a polyurethane resin according to an embodiment of the present invention. [Main component symbol description] 26

Claims (1)

200946551 VII. Patent application scope: 1. A polyurethane grease containing alicyclic components and/or aromatic components. 2. For example, the polyurethane resin described in the above item, less than 20 (rc. Pregnancy ▲ degree is 3 · as claimed in the scope of patent application), the structure of diisocyanate and having a cyclohexane structure The diol is obtained by polymerizing the diol according to the first aspect of the invention, which is obtained by polymerizing a diol having a stupid red diisocyanate and a cyclohexane structure. The polyurethane resin compound according to any one of the preceding claims, which is represented by the following chemical formula (J). !-〇,〇^-士 (I) 6. If you apply for the special (4) item or the item 4 of the fourth item, the product is represented by the following chemical formula (Π). [Chemical Formula 2] (Π) 7. A retardation film comprising the polyurethane resin according to any one of claims 1-6. 8. If the phase difference _ described in the scope of patent application 胄 7 is _, it is formed by stretching the poly-glycol vine resin into a sheet of 2009, 2009, 451, 051. 9. The retardation film according to claim 7, wherein the polyurethane resin is dissolved in a solvent as a coating liquid, and then coated on a transparent substrate and stretched. 10. An optical film comprising the polyurethane resin according to any one of claims 1 to 6 of the patent application. Q 28