TW201217459A - Urethane resin for phase difference films and phase difference film - Google Patents

Abstract

The present invention addresses the problem of providing a phase difference film having high heat resistance, which is capable of uniform polarized light conversion across a broad wavelength region and has good phase difference-generating ability, and resins that use said films. The problem can be solved by a urethane resin for phase difference films that comprises diisocyanate structural units represented by formula (I): [In the formula, X is as described in the Specifications] and fluorene structural units represented by formula (II): [In the formula, R1 to R3, l, m and n are as described in the Specifications], and by a phase difference film comprising said resin.

Description

201217459 6. TECHNOLOGICAL FIELD OF THE INVENTION The present invention relates to a urethane resin for a retardation film having a constituent unit containing an alicyclic moiety and a constituent unit containing a hydrazine moiety, and the amine A phase difference film of a urethane resin. [Prior Art] A polycarbonate film is used in the initial stage of development of a retardation film used in a liquid crystal display device or the like (for example, Patent Document 1). However, the photoelastic coefficient of polycarbonate is large, so that it is difficult to obtain a film having a uniform phase difference. A reflective or semi-transmissive liquid crystal display device used for mobile device applications or the like is required to have a film having a small dispersion of a phase difference which can perform the same polarization conversion in a wide wavelength range. However, the wavelength dispersion of the polycarbonate film is large, so that the same polarization conversion cannot be performed in a wide wavelength range. Therefore, a film obtained by adding a phase difference adjusting agent to triacetyl cellulose is put into practical use (for example, Patent Document 2). However, triacetyl cellulose has a problem of poor heat resistance. In order to solve this problem, a phase difference film having a high heat resistance and a small wavelength dispersion is formed of a cycloolefin resin (for example, Patent Document 3). However, the film formed of the cycloolefin-based resin has low phase difference property and cannot increase the phase difference. Therefore, in order to obtain a predetermined retardation film, it is necessary to have a certain thickness, so that it is difficult to make the film thin. In the 'organic EL display device', the light from the outside of the display device 201217459 is reflected inside, and then disappears outside, so there is a problem of significantly reducing the contrast. The countermeasure adopted is to use the combined phase outside the display device. A thin film of a λ/4 plate and a polarizing plate of a polarizing plate to block light reflected outside the display device, and the wavelength dispersion of the λ/4 plate used at this time is relative to the phase of the entire wavelength λ of the visible light field. The difference is λ/4, that is, the wavelength dispersion needs to be inverse wavelength dispersion in contrast to polycarbonate or the like. CITATION LIST PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT DISCLOSURE OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION An object of the present invention is to provide a retardation film suitable for use in a reflective and transflective liquid crystal display device used in mobile device applications and the like. Therefore, the subject is to provide a higher heat resistance, and the same polarization conversion can be performed in a wider wavelength range, and the shorter the wavelength of the light, the smaller the phase difference, and the polarization conversion of the reverse wavelength dispersion can be performed, and the polarization can be made higher. A retardation film having a phase difference found and a resin used for the film. The method for solving the problem has been found by the present inventors, and it has been found that a retardation film of a urethane-6-201217459 resin having a constituent unit containing an alicyclic moiety and a constituent unit containing a hydrazine moiety can be used. The above issues. That is, the present invention includes the following items. (1) A urethane resin for a retardation film having the general formula I: [Chemical Formula 1]

[wherein, X is a cycloalkyl group, an alkylene alkyl group, a cycloalkyl group, an alkyl group, an alkyl group, an alkyl group, or a bicycloalkyl group. The diisocyanate represented by the at least one substituent selected from the group consisting of halogen, Ci-6 alkyl or C!-6 alkoxy group), and the general formula II:

Wherein R1 is independently alkyl, cycloalkyl, aryl or aryl extended 201217459 alkyl; 1 is 0 or 1; R2 is independently of halogen, Cm alkyl or Cu alkoxy; m An integer of 0 to 4; R3 is independently a halogen, a Ci.6 alkyl group or a (:1-6 alkoxy group; η is an integer of 0 to 4), and represents a unit of 芴. (2) as (1) The urethane resin for the retardation film described, wherein X is a cyclohexyl group, a Ci-3 alkylene group, a cyclohexyl group, a Cm alkyl group, and a Cm alkyl group. Ch alkyl- or dicyclohexyl (which may be substituted by Cm alkyl), R1 is independently of each other Ci-3 alkyl '1 is 1, m and η are 0. (3) as (1) or (2) The urethane resin used for the retardation film described, wherein the diisocyanate represented by the general formula I is a unit derived from dicyclohexylmethane-4,4'-diisocyanate or isophorone Isocyanate, cyclohexyl diisocyanate, or 1,3-bis(isocyanatomethyl)cyclohexane. (4) A retardation film as described in any one of (1) to (3) Amino group The ethyl ester resin 'wherein the oxime constituent unit represented by the general formula II is from 9,9-bis[4-(hydroxy C..3 alkoxy)phenyl]anthracene. (5) as (1) to (4) Any of the urethane resins for the retardation film described in any one of the above, wherein -8 - 201217459 is a general formula III: [Chemical 3] m -0-Y-〇 [wherein γ is a ring An alkyl group, an alkyl group alkyl group, a cycloalkyl group alkyl alkyl group, an alkyl group alkyl group alkyl group, or a bicycloalkyl group (this can be halogen, (^.6) The diol composition unit represented by the alkyl group or at least one substituent selected from the group consisting of C and -6 alkoxy groups. (6) The amine group for the retardation film as described in (5) An ethyl formate resin, wherein γ is a cyclohexyl group, a Cl.3 alkylene group, a cyclohexyl group, a Ci.3 alkyl group, a hexyl group, a Cu3 alkyl group, a hexyl group, an alkyl group, or (6) A urethane resin for a retardation film as described in (5) or (6), wherein the diol constituent unit represented by the general formula III is derived from 1,4-cyclohexane Alkanediethanol, 1,4-cyclohexanediol, or 4,4 - a urethane resin for a retardation film according to any one of (1) to (7), wherein X is a cyclohexyl group (may be (^.3) When the alkyl group is substituted, and the isocyanate moiety of one of the diisocyanate constituent units is one position with respect to the bonding position of the above-mentioned cyclohexyl group, the bonding position of the other isocyanate moiety is 2, 3, 5 Or a 6-position; 乂 is an alkylcyclohexylene group (which may be substituted by a Ch alkyl group), and the isocyanate moiety of one of the diisocyanate 201217459 acid ester units is 1 position with respect to the bonding position of the front part The other isocyanate is bonded to the G.3 alkylene moiety at the 2-position, the 3-position, or the oxime is an alkyl group, and the diisocyanate constitutes a unit. When one of the isocyanic acid groups of one of the isocyanic acid groups is in the 1-position relative to the above-mentioned ring-extension group, the bonding position of the other alkyl group in which the isocyanate moiety is bonded is 2 and 3 positions. , a 5- or 6-position (9) amine resin for a retardation film as described in (8), wherein the general formula I The diisocyanate is represented by a monophorone diisocyanate or a 1,3-bis (isocyanatomethylhydrazine (10) such as the phase difference ethyl formate resin described in (8) or (9), wherein Having the general formula IV: [Chemical 4] The 5- or 6-position of the ring-bonding moiety; the C 1 - 3-based ester-bonding moiety-bonding moiety 3 - C 1 -3 Ο Ethyl formate is an amine group derived from a hetero group) cyclohexane film

The diisocyanate constituent unit represented by an alkyl group (all [wherein 'X' is a Cl-IQ stretching base or a stretching base oxy group having 2 to 10 carbons). The urethane (11) is a phase difference film as described in (1 〇) -10- 201217459 ester resin, wherein the diisocyanate represented by the general formula IV is a unit derived from hexamethylene diisocyanate. (1) The urethane resin for a retardation film according to any one of (1) to (1), wherein the glass transition temperature is from 100 to 200 〇C ° (13). A poor film which is a urethane resin containing a retardation film as described in any one of (1) to (12). (14) A retardation film as described in (13), wherein the following formula is used:

Re= ( nx-ny ) xD wavelength dispersion = Re ( 449 ) _ /Re ( 54 8.7 ) [wherein nx is the refractive index of the retardation axis direction when the refractive index in the plane of the phase difference film is the largest; ny is orthogonal a refractive index in the direction of the aforementioned retardation axis; D is a thickness (nm) of the retardation film;

Re is the in-plane phase difference, Re ( 449 ) is the in-plane phase difference of the light having a wavelength of 449 nm, and Re ( 548.7 ) is the in-plane phase 'difference of the light having a wavelength of 548.7 nm. The wavelength dispersion is less than 1.02. The present specification is the basis of the priority of the present application, and is included in the description of the specification and/or drawings of Japanese Patent Application No. 20 10-1 75730. Advantageous Effects of Invention -11 - 201217459 The present invention can provide a retardation film suitable for use in a reflective or semi-transmissive liquid crystal display device used for mobile machine applications and the like. More specifically, it is possible to provide a phase difference film which has high heat resistance, performs the same polarization conversion in a wide wavelength range, and can obtain a high phase difference discovery property, and a resin used for the above film. Mode for Carrying Out the Invention The present invention will be described in detail below. The "alkylene group" of the present invention means a divalent group formed by the loss of two hydrogen atoms from a carbon atom of an alkane, and is generally represented by -CnH2n- (η is a positive integer). The alkylene group may be linear or branched. Further, the so-called alkylene group formed by the loss of two hydrogen atoms from the same carbon atom also includes the alkylene group of the present invention. The alkylene group of the present invention is preferably a 6-alkyl group, particularly preferably a Ci-3 alkylene group. For example, methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like. The "cycloalkylene group" of the present invention means a divalent group formed by the loss of two hydrogen atoms in a carbon atom of an alkane, and is generally -CmH2in.2-(m is a positive integer of 3 or more, forming a ring) Said. The so-called cycloalkylene group formed by the loss of two hydrogen atoms from the same carbon atom is also included in the cycloalkylene group of the present invention. The cycloalkylene group of the present invention is preferably a C3-1G cycloalkylene group, particularly preferably a C5-8 cycloalkylene group. For example, a cyclic propyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclodextyl group, and the like. In the present invention, the "base of the base of the hospital" refers to the carbon atom of the base portion of the courtyard base chain and the carbon atom of the cycloalkane portion respectively lose one hydrogenogen-12-201217459 The valence group is generally represented by -CnH2n-CmH2m-2- (η is a positive integer; m is a positive integer of 3 or more, forming a ring). The alkyl moiety may be linear or branched. The alkylene alkylene group of the present invention is preferably a Cu alkylene group C3-1G cycloalkylene group, particularly preferably a Ci-3 alkylene group C5.8 cycloalkylene group. For example, a methylcyclohexyl group, a methyl group, a hexyl group, a methyl group, a heptyl group, an ethyl group, a pentyl group, an ethyl group, a hexyl group, an ethyl group, a heptyl group, and a propylene group. The base ring is pentyl group, the propyl ring is extended to the hexyl group, the propyl ring is extended to the heptyl group, and the like. The "cycloalkylenealkylcycloalkylene group" of the present invention means a divalent group formed by the loss of one hydrogen atom per carbon atom of two cycloalkyl portions of a bicycloalkylalkane, generally -CmHh.rCnHh-CmHh-y (where η is a positive integer; m is a positive integer of 3 or more, forming a ring). The alkane moiety may be linear or branched. The cycloalkylenealkylcycloalkylene group of the present invention is preferably a C3-I()cycloalkylene group (^.6 alkylene C3_1G cycloalkylene group, particularly preferably a C5_8 cycloalkylene alkylene alkyl group) (: 5-8 cycloalkylene group. For example, a cyclopentyl group stretching methyl ring pentyl group, a cyclohexyl group stretching methyl ring extension hexyl group, a ring stretching heptyl group stretching methyl ring stretching heptyl group, a ring extending pentylene group B a pentyl group, a cyclohexyl group, an ethyl group, a hexyl group, a ring, a heptyl group, an ethyl group, a heptyl group, a pentyl group, a propyl group, a pentyl group, a cyclohexyl group, a propyl ring, a hexyl group, and a ring extension. The heptyl propyl ring is extended to a heptyl group, etc. The "alkyl extended alkylalkylene group" of the present invention means that the carbon atoms of the two alkyl portions of the dialkylcycloalkane are each lost by one hydrogen atom. The divalent group 'is generally represented by -CnH2n-CmH2m_2-CnH2n- (n is a positive integer; m is a positive integer of 3 or more, forming a ring). The alkyl moiety may be linear-13-201217459 or branched. The alkylene alkylene alkylene group of the present invention is preferably a C6 alkyl group C3.1Q cycloalkylene group (^.6 alkylene group, particularly preferably (^.3 alkylene group C5-8). Cycloalkyl C! -3 alkylene. For example, stretching The base ring is extended to the methyl group, the methyl group is extended to the methyl group, the methyl group is extended to the methyl group, the methyl group is extended to the methyl group, the ethyl group is extended to the ethyl group, and the ethyl group is extended to the ethyl group. The base ring is extended to ethyl, the propyl ring is extended to the pentyl group, the propyl group is extended to the propyl group, the propyl group is extended to the propyl group, and the like. The "bicycloalkylene group" of the present invention is The divalent group formed by the loss of one hydrogen atom in each of the carbon atoms of the two cycloalkane portions of the bicycloalkane is generally -CmH2in-2-CmH2in-2- (m is a positive integer of 3 or more, The ring-forming alkyl group of the present invention is preferably a c3_1Q cycloalkyl group c3.1G cycloalkylene group, particularly preferably (: 5.8 cycloalkylene C5-8 cycloalkylene group. For example, a ring The pentyl group is a pentyl group, a cyclohexyl group, a heptyl group, a heptyl group, and a heptyl group. The "aryl group" of the present invention means that a group of aromatic hydrocarbons loses two hydrogen atoms. The aryl group may be a monocyclic ring or a condensed ring. The exoaryl group of the present invention is, for example, a phenyl group, a naphthyl group, a phenylene group, or the like. Alkyl The carbon atom of the alkyl moiety and the carbon atom of the aromatic hydrocarbon moiety each lose a divalent group formed by one hydrogen atom. The alkyl moiety may be a chain or a branched chain, and the aromatic hydrocarbon moiety may be a monocyclic ring or a condensed ring. The exoarylalkyl group of the invention is preferably an aryl group C, .6 alkyl group, particularly preferably an exoaryl C! -3 alkyl group. For example, a phenyl group stretching methyl group, a stretching phenyl group -14-201217459 Ethyl, anthranylmethyl, methyl naphthyl, ethyl phenyl, methyl phenyl, ethyl phenyl, etc. 1. ethyl urethane for retardation film

The urethane used for the retardation film of the present invention is of the general formula I

[Chemical 5]

[wherein, X is a cycloalkyl group, an alkylene alkyl group, a cycloalkyl group, an alkyl group, an alkyl group, an alkyl group, or a bicycloalkyl group. a diisocyanate group represented by at least one substituent selected from a group consisting of a halogen, a Ci-6 alkyl group and an alkoxy group), and a general formula 11 · [Chem. 6] 201217459 [wherein R 1 is independently alkyl, alkyl, aryl or aryl; 1 is 0 or 1; R 2 is independently of halogen, C, -6 alkyl ' or alkoxy; m An integer of 0 to 4; R3 is independently a halogen, a Cu alkyl group, or a Cu alkoxy group, and η is an integer of 0 to 4, which is represented by a unit of 芴. The urethane used for the retardation film of the present invention may have a general formula: in addition to the diisocyanate constituent unit represented by the general formula I and the oxime constituent unit represented by the general formula ΠΙ: [Chemical Formula 7] Υ is a cycloalkyl group, an alkyl group alkyl group, a cycloalkyl group alkyl group alkyl group, an alkyl group alkyl group alkyl group, or a bicycloalkyl group (such a halogen, C The diol is a unit of the diol represented by at least one substituent selected from the group consisting of an alkyl group and a Ci -6 alkoxy group. When the diol constituent unit represented by the general formula III is used, the ratio of the oxime unit to the yttrium unit and the diol unit may be a ratio of the phase difference film produced from the amine-16-201217459 carboxylic acid ethanol. By the following formula:

Re= ( nx-ny ) xD wavelength fraction = Re( 449 ) /Re ( 548.7 ) [wherein ^ is the refractive index of the retardation axis direction when the refractive index in the plane of the retardation film is the largest; ny is orthogonal to the foregoing The refractive index in the direction of the slow axis; D is the thickness (nm) of the retardation film;

Re is the in-plane phase difference, Re ( 449 ) is the in-plane phase difference of the light having a wavelength of 449 nm, and Re ( 548.7 ) is the in-plane phase difference of the light having a wavelength of 548 · 7 η π ι. The wavelength dispersion obtained is less than 1.02. Limited, but especially preferably 3 Omol%. Further, the urethane resin may have any other constituent unit within the range in which the effects of the present invention are not impaired. The weight average molecular weight (Mw) of the urethane resin of the present invention is not particularly limited, and is preferably 200,000 to 5,000, particularly preferably 100,000 to 1 Torr, and most preferably 50,000 to 20,000. The weight average molecular weight can be determined by gel permeation chromatography (GPC). The glass transition temperature (Tg) of the ethyl urethane of the present invention is preferably from 100 to 200 °C, particularly preferably from 120 to 180 °C. The glass transition temperature can be determined by differential scanning calorimetry (D S C ). When the glass transition temperature is less than 1 〇 〇 °c, it is not preferable to store the retardation film made of the urethane resin at a high temperature or the like. When the glass transition temperature exceeds 200 ° C, it is difficult to carry out processing such as stretching, and it is difficult to produce a retardation film 201217459. 2. Diisocyanate constituent unit In one embodiment of the present invention, the diisocyanate constituent unit represented by the general formula I is X. Cyclohexyl, 1.3 alkyl Cyclohexyl, cyclohexyl hexyl hydrazide alkyl hexyl group, Ci_3 alkyl Cycloalkyl hexyl group, or bicyclohexyl group (this can be halogen, < At least one substituent selected from the group consisting of a ^6 alkyl group and a Q-6 alkoxy group). In a preferred embodiment of the present invention, X is a cyclohexyl group, a methyl group extending to a hexyl group, a ring-extension hexyl group, a methyl group extending a hexyl group, a methyl group extending a hexyl group, or a bicyclohexyl group (such Can be substituted by Cu alkyl). In a particularly preferred embodiment of the present invention, X is a cyclo-extension-methyl-extension-hexyl group, a cyclohexyl group, a Cu-alkyl-cyclohexyl group, or a Cm-alkyl-alkyl-extension hexyl C i ·3 alkyl group (this Etc. can be replaced by c! d alkyl). In particular, when the urethane used for the retardation film of the reverse wavelength dispersion is formed, it is preferred that 'X is a cyclohexyl group (which may be substituted by a Ci. 3 alkyl group), and the isocyanate moiety of one of the diisocyanate constituent units is relatively When the bonding position of the ring-extension hexyl group is 1 position, the bonding position of the other isocyanate moiety is 2, 3 '5 or 6 position; X is an alkylene group hexyl group (can be Cu alkyl group) When the substitution position of the one of the diisocyanate constituent units is the same as the bonding position of the above-mentioned cyclohexyl moiety, the bonding of the other alkyl group of the isocyanate moiety bonded to the other isocyanate moiety The position is 2, 3, 5 or 6; X is ¢: ^3 alkylcyclohexylhexyl-6-3 alkyl (can be substituted by mc!.3), and the diisocyanate constitutes the unit -方分异氤-18- 201217459 The other one of the isocyanate moiety bonded to one of the 0.3 alkyl groups of the ester moiety is bonded to the above ring, and the other isocyanate moiety is bonded to the other alkyl group. The part of the bonding position is 2, 3, 5 or 6 bits. It is particularly preferred that the two isocyanate moieties are directly or indirectly bonded to the cyclohexyl group in the relationship of the 1, 3 position. Further, the urethane resin of the present invention preferably contains a general formula IV in the form of a copolymerization: [in the formula, an alkylene group or an alkyloxyalkylene group (all having 2 to 10) The other diisocyanate represented by carbon) is a unit. In this way, the Tg can be reduced to a forming process such as extension. In one embodiment of the present invention, X' is a c4-8 alkylene group or an alkyloxyalkylene group (all having 4 to 8 carbons), preferably C4-8, in the unit of diisocyanate represented by the general formula IV. Alkyl groups, especially good for the base. A diisocyanate compound for producing a urethane resin having a diisocyanate constituent unit represented by the general formula, for example, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, cyclohexyldiyl Isocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and the like. Preferably, such as dicyclohexylmethane-4,4'-diisocyanate, the reverse wavelength dispersibility of the ethyl carbamate is preferably, for example, isophorone diisocyanate, and 1,3 -bis ( -19- 201217459 Isocyanatomethyl)cyclohexane. These diisocyanate compounds may be used alone or in combination of plural kinds. Further, in order to facilitate the extension processing, it is preferable to form the diisocyanate-constituting unit compound represented by the general formula iv as 'hexamethylene diisocyanate. 3. 芴 constituting unit In one embodiment of the present invention, in the oxime structure represented by the general formula II, R' is independently a Cu alkyl group and 1 is 1. In a preferred embodiment of the present invention, R1 is an exoethyl group and 1 is 1. In an embodiment of the present invention, R2 and R3 are each a Ci-3 alkyl group in the fluorene unit, and 111 and 11 are independently from each other to 2 The integer. In a preferred embodiment of the invention, m and η are both zero. A compound for producing a urethane resin having the above oxime constituent unit, for example, 9,9-bis[4-(hydroxycu-alkoxy)phenyl]anthracene, such as 9,9·bis[4-(2-hydroxyl) Ethoxy)phenyl]anthracene. These medicinal substances may be used alone or in combination of plural kinds. 4. Glycol constituent unit In one embodiment of the present invention, in the diol configuration represented by the general formula, Y is a cyclohexyl group, a Cm alkyl group, a cyclohexyl group, a cyclohexyl C alkyl group, and a C group. .3 alkyl-terminated hexyl hydrazine-3 stretching, or hexyl (which may be substituted by at least one substituent selected by halogen, C^6 alkyl and ί^6 alkoxy) . In a preferred embodiment of the present invention, γ is a ring-extension hexyl group, and the unit is only used to make it stand alone, and the base ring is -20-201217459. Stretching a methyl ring to extend a hexyl group, stretching a methyl ring to extend a hexyl group to form a methyl group, or a bicyclohexyl group (which may be substituted by a C..3 alkyl group). In a particularly preferred embodiment of the invention, Y is a methyl-extended methyl group. A diol compound for producing a urethane resin having the above diol constituent unit such as '丨, 4_cyclohexane dimethanol, 1,4-cyclohexanediol, or 4,4'-dicyclohexane The alcohol is preferably, for example, 1,4·cyclohexanedimethanol. These diol compounds may be used singly or in combination of plural kinds. 5. Phase difference film The phase difference film of the present invention can be produced from the above urethane resin. The retardation film may contain other optional components within the range which does not impair the effects of the present invention. The method for producing the retardation film is not particularly limited, and various known methods can be used. For example, 'the urethane resin is dissolved in a solvent and then coated on a support, and then dried and extended, or the urethane resin is supplied to an extruder, and then extruded into a film by a T die. The method of stretching, and the like. The in-plane retardation (Re) of the retardation film of the present invention is preferably from 1 Å to 2,000 nm in terms of thickness ΙΟΟμηη, and particularly preferably from 300 Å to 1,500 nm. When the in-plane phase difference is less than 100 nm, the phase difference film needs to be thickened, and the result is small and lightweight retrograde with the mobile machine. Further, when the in-plane retardation exceeds 200 nm, the thickness of the film is too thin to be processed. The in-plane phase difference can be expressed by the following formula: -21 - 201217459

Re= ( nx-ny ) xD [wherein nx is the refractive index of the retardation axis direction when the refractive index in the plane of the retardation film is the largest: 'ny is the refractive index orthogonal to the direction of the aforementioned slow phase axis; D is The thickness (nm) of the retardation film was determined. The retardation film in the thickness direction of the retardation film of the present invention is preferably in the range of 1 〇〇 to 2000 nm in thickness ΙΟΟμηι, and particularly preferably in the range of 3 00 to 1 500 00 nm. : Thickness direction phase difference (Re') = (nx-nz) XD [wherein, nx is the refractive index in the retardation axis direction when the refractive index in the retardation film is the largest: nz is the refractive index in the thickness direction of the retardation film Rate; D is the thickness (nm) of the retardation film. The wavelength dispersion of the retardation film of the present invention is the same as the polarization conversion in the wider wavelength range, preferably less than 1·〇2. It is preferably 0.9 or more and less than 1.02, more preferably 0.95 or more and 1.01 or less. The wavelength dispersion can be expressed by the following formula: Wavelength dispersion l=Re ( 449 ) /Re ( 5 4 8.7 ) [In the formula, -22- 201217459

Re ( 449 ) is the in-plane phase difference of light having a wavelength of 449 nm;

Re (548.7) is obtained by in-plane retardation of light having a wavelength of 548.7 nm]. Further, in order to form a film having a reverse wavelength dispersibility, the wavelength dispersion of the retardation film is preferably 0.7 or more and 0.95 or less, and particularly preferably about 0.81. The retardation film of the present invention can reduce the film thickness of the film in order to improve the phase difference. For example, the film thickness is preferably from 5 to 50 μm, particularly preferably from 10 to 30 μm. [Embodiment] EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the technical scope of the present invention is not limited thereto. . Evaluation Analysis Method The evaluation analysis method used in the present embodiment is as follows. (1) Heat resistance of resin The glass transition temperature (Tg) measured at a temperature rise of 20 ° C / min was evaluated by differential scanning calorimetry (DSC). (2) Weight average molecular weight (Mw) Measured by gel permeation chromatography (G P C ). (3) Optical properties of solvent-cast film The resin was dissolved in a solvent and applied to a fluororesin-coated plate. The film which was peeled off after drying was subjected to a uniaxial elongation of 2 times at a glass transition temperature of +10 to 25 ° C. -23 - 201217459 After stretching, the following optical characteristics were evaluated. (i) Phase difference The phase difference between the in-plane and thickness directions of the light having a wavelength of 5 8 9.3 nm was measured using an ellipsometry apparatus (KOBLA WPRXY2020, manufactured by Five-Piece Measurer). The phase difference is converted to the thickness of the film ΙΟΟμηι. (ii) Wavelength dispersion The in-plane phase difference [R ( 449 ) and R ( 5 48.7 ) with respect to a light having a wavelength of 449 nm and a light of 548.7 nm was measured using an ellipsometry apparatus (KOBLA WPRXY2020, manufactured by a five-segment measuring device). ], to find the wavelength dispersion [R ( 449 ) / R ( 54 8.7 )]. Example 1 9,9-bis[4-(2-hydroxyethoxy)phenyl]anthracene (23.9 parts by weight), and 1,4-cyclohexanedimethanol (18.4 parts by weight) were placed in a reaction vessel. Dimethylformamide (60 parts by weight) was added to dissolve it. Next, dicyclohexylmethane-4,4'-diisocyanate (47.7 parts by weight) was gradually added while stirring the solution. After the completion of the addition, the reaction was carried out at 130 ° C for 1 hour, followed by heating to 22 CTC, and the solvent was removed under reduced pressure. The heat resistance, molecular weight and optical properties of the obtained resin were evaluated, and the results are shown in Table 1. Examples 2 and 3 were changed to 9,9-bis[4-(2-hydroxyethoxy)phenyl]-24-201217459 hydrazine, 1,4-cyclohexanedimethanol, and dicyclohexyl group according to Table 1. A resin was prepared in the same manner as in Example 1 except for methane-4,4'-diisocyanate. The heat resistance, molecular weight and optical properties of the obtained resin were evaluated, and the results are shown in Table 1. Comparative Example 1 1,4-cyclohexanedimethanol (31.9 parts by weight) was placed in a reaction vessel, and dimethylformamide (60 parts by weight) was added thereto to dissolve. Next, dicyclohexylmethane-4,4-diisocyanate (58.1 parts by weight) was gradually added while stirring the solution. After the completion of the addition, the reaction was carried out at 130 ° C for 4 hours, followed by heating to 220 ° C, and the solvent was removed under reduced pressure. The results of evaluating the heat resistance, molecular weight and optical properties of the obtained resin are shown in Table 1. Comparative Example 2 The film was formed by uniaxially stretching a film formed of a cycloolefin-based resin (曰Jeol (registered trademark) film manufactured by Benjamin Co., Ltd.) in the same manner as in Example 1. Comparative Example 3 A polycarbonate resin (Mitsubishi Ngini's product number Η4000) was supplied to an extruder, and a film was extruded at 280 ° C by a die, and then uniaxially stretched as in Example 1, and then evaluated. Optical properties. -25-201217459 [Table 1] Item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Raw material (parts by weight) 9,9-bis[4-(2-hydroxyethoxy)benzene Base 1芴23.9 35.6 56.3 0 Cycloolefin resin film Polycarbonate film 1,4-cyclohexanedimethanol 18.4 11.7 0 31.9 —Cyclohexylmethane-4,-diisocyanate 47.7 42.6 33.7 58.1 Glassy temperature (Tg) 137 144.9 158 125 135 150 Weight average molecular weight _) 31000 33000 41000 260(10) . ί Single film extension prison (. 〇155 170 175 140 155 160 Optical properties of the film In-plane phase difference (nm) Γ 1080 670 "440 1460 200 440 Thickness direction phase difference (nm) 1080 750 440 1490 190 460 Wave cake dispersion IRe (449) / Re (548.7)] 1·00 0.99 0.95 1.02 1.00 1.07 Amino urethane resin without hydrazine skeleton (Comparative example) 1) In the polycarbonate film (Comparative Example 3), since the wavelength dispersion of the film is large, 1_〇2 and 1.07, respectively, it is difficult to perform the same polarization conversion in a wide wavelength range, and the cycloolefin system is also used. In the film formed by the resin (Comparative Example 2), the wavelength dispersion of the film was as small as 1.0, but doubled When the phase difference is small, it is difficult to form a thin phase difference film. On the other hand, in the urethane resin of the present invention (Examples 1 to 3), the glass transition temperature is higher than 100 ° C. The heat resistance is excellent, and the wavelength dispersion of the film is less than 1.02, and the phase difference at the time of double stretching is large. Therefore, a thin retardation film which can perform the same polarization conversion in a wide wavelength range can be formed. 9,9-bis[4-(2-hydroxyethoxy)phenyl]anthracene (50.7 parts by weight), and 1,4-cyclohexanedimethanol (7.1 parts by weight) were placed in a reaction vessel -26- 201217459, dimethylformamide (60 parts by weight) was added for dissolution. Secondly, isophorone diisocyanate (18.3 parts by weight) and hexamethylene diisocyanate (13.9 parts by weight) were gradually added while stirring the solution. After the end of the addition, the reaction was carried out at 130 ° C for 16 hours, followed by heating to 160 t, and the solvent was removed under reduced pressure. Examples 5 to 8 were changed to 9,9-bis[4-(2-hydroxyethoxy) according to Table 2. Phenyl] hydrazine, 1,4-cyclohexanedimethanol, isophorone diisocyanate, and hexamethylene diisocyanate 4 to produce a resin. The resulting heat-resistant resin evaluation, and the optical properties of the outer molecular weight esters with Example 1. The results shown in Table 2. Further, the phase difference R0 with respect to the light of 749.4 nm and the phase difference R0 with respect to the light of the wavelength of 59.39.3 nm were measured from the wavelength of 449 nm, and the wavelength dispersion characteristic (R/R0) was obtained. The result is shown in Figure 1. [Table 2] Item Example 4 Example 5 Example 6 Example 7 Example 8 Starting material (parts by weight) 9,9, bis[4-(2-diabaseethoxy)phenyl 1芴50.7 54.9 56, 9 58.8 62.3 1,4-cyclohexane-methanol 7.1 4.5 3.3 2.2 0 crystalphorone diisocyanate 18.3 17.4 17.0 16.6 15.8 Hexamethylene monoisocyanate 13.9 13.2 12.8 12.5 1L9 glass transition temperature (Tg) 120.5 125.5 128.2 131.1 132.8 Weight average molecular weight (Mw) 44000 45000 40000 39000 30000 Thin surface ether (. 〇135 140 140 145 150 Optical properties of the film In-plane phase difference (nm) 151 65 62 42 29 Thickness direction phase difference (nm) 142 48 43 42 30 Wavelength dispersion 丨Re(449)/Re(548.7)] 0. 85 0.82 0.77 0,78 0. 56 The wavelength dispersion of the film in the urethane resin of Examples 4 to 8 was reduced to 〇. It is expressed as inverse wavelength dispersion. Further, the wavelength dispersion [Re ( 449 ) /Re ( 548.7 )] of the wide band λ/4 plate whose phase -27-201217459 is λ/4 with the overall wavelength λ is 0.81, and The wavelength dispersion of Examples 5 to 8 is equal to or lower than the wavelength dispersion of the wide band λ/4 plate. (4) The phase difference of the high-magnification stretch film will be tree After being dissolved in a solvent, it is applied to a fluororesin coated plate. After drying and stripping the film at a glass transition temperature of +10 to 25 t, three times of uniaxial stretching is performed, and the above evaluation method (3)(i) is used. The phase difference was evaluated. Results The high-magnification stretching films of the urethane resins of Examples 4 and 5 had a high phase difference of 310 nm and 232 nm, respectively, that is, a wide-band λ/4 plate was formed (wavelength at 59.83 nm). The thickness of the phase difference is 147.3 nm), each of which is 48 μπι, 63 μηη, which has sufficient thinness to be mounted on the mobile device. This specification is to be directly referred to and incorporated in all publications, patents and patent applications cited in this specification. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the wavelength dispersion characteristics (R/R0) of the film of the urethane resin of Examples 4 to 8 and the wide band λ/4 plate.

Claims (1)

201217459 VII. Patent application scope: 1. A kind of amino group for phase difference film. General formula I: [Chemical 1] Ο 〇HH Η II --c-Ν-χ-Ν-c-- [where X is a cycloalkylene group, an alkylene group alkylalkylene group, an alkylcycloalkylene group (which may be substituted by at least one substituent of halogen, Ci.6 alkyl and C)] Diisocyanate constitutes a unit of the general formula II: an ethyl ester resin which is selected from the group consisting of a pendant alkyl group, a cycloalkyl group, a dicycloalkyl group, and a -6 alkoxy group. [Chemical 2] II [wherein, the aryl group, the aryl group or the aryl group R1 are independently alkyl and ring alkyl; -29-201217459 1 is 0 or 1; R2 is independently halogen, <^·6 a group, or a c,.6 alkoxy group; m is an integer from 0 to 4; R3 is independently of each other a halogen, a <^.6 alkyl group, or a Cm alkoxy group; η is an integer from 0 to 4;芴 constitutes a unit. 2. A urethane resin for a retardation film according to the first aspect of the invention, wherein X is a cyclohexyl group, a Cm alkyl group, a cyclohexyl group, a cyclohexyl group, a Cw alkyl group, and a Cw extension. The alkyl ring extends to a Cw alkyl group, or a bicyclohexyl group (which may be substituted by a Cm alkyl group), R1 is independently alkyl, and 1 is 1, m and η are 0. 3. The urethane resin for a retardation film according to claim 1 or 2, wherein the diisocyanate represented by the general formula I is a unit derived from dicyclohexylmethane-4,4'-diisocyanate, Isophorone diisocyanate, cyclohexyl diisocyanate, or 1,3-bis(isocyanatomethyl)cyclohexane. 4. The urethane resin for a retardation film according to any one of claims 1 to 3, wherein the oxime constituent unit represented by the general formula II is from 9,9-bis[4-(hydroxyl) Ch3 Institute of oxy)phenyl] hydrazine. 5. A urethane resin for a retardation film according to any one of claims 1 to 4, which further has a general formula III: -30-201217459 [Chemical 3] [wherein, Y is a cycloalkyl group, an alkylene alkyl group, a ring alkyl group, an alkyl group, an alkyl group or an alkyl group, or a ring. The diol is represented by a diol represented by at least one substituent selected from the group consisting of halogen, Cw alkyl and Ci. 6 alkoxy. 6. A urethane resin for use in a retardation film according to item 5 of the patent application, wherein Y is a cyclohexyl group, a C!.3 alkylene group, a cyclohexyl group, and a C alkyl group. The cyclohexyl group, the Cm alkyl group, the hexyl group, the Ci.3 alkyl group, or the bicyclohexyl group. 7. The urethane resin for a retardation film according to claim 5 or 6, wherein the diol constituent unit represented by the general formula 来自 is derived from 1,4-cyclohexanedimethanol, 1, 4 - cyclohexanediol or 4,4'-dicyclohexanediol. 8. The urethane resin for a retardation film according to any one of claims 1 to 7, wherein X is a cyclohexyl group (which may be substituted by a Clo alkyl group), and the diisocyanate constitutes one of the units When the isocyanate moiety is in the 1-position position relative to the ring-extension hexyl group, the other isocyanate moiety is bonded to the 2-position, 3-position, 5-position or 6-position; (may be substituted by 6.3 alkyl group), and the isocyanate moiety of one of the diisocyanate constituent units is 1 position with respect to the bonding position of the above-mentioned cyclohexyl moiety, and the other isocyanate moiety is bonded to -31 - 201217459 The bonding position of the alkyl group of the above c, -3 is 2 or 3 positions: or 乂 is an alkyl group, an alkyl group (which may be C, substituted), and a diisocyanate unit When one of the isocyanate groups of one of the isocyanate i is in the 1-position with respect to the above-mentioned cyclic alkyl moiety, the other alkyl moiety of the other isocyanate moiety is bonded to the 2-position and the 3-position. , 5 or 6 digits. 9. The month for the retardation film of claim 8: ethyl ester resin, wherein the diisocyanate structure represented by the general formula I is derived from isophorone diisocyanate or 1,3 -bis (isocyanato) ί Cyclohexane. 10. A phase difference film of ethyl formate resin according to claim 8 or 9 of the patent application, wherein the other formula IV: [Chemical 4] Ο 〇 - C ΐ X, -N C- - ^ [wherein ' (1.|() alkyl, or alkylene oxide has 2 to 10 carbons)] represents the diisocyanate constituent unit. 1 1 · as claimed The phase difference film of the item 0 is an acid ethyl ester resin, wherein the diisocyanate represented by the general formula IV is derived from hexamethylene diisocyanate. • 5 or 6.3 fluorenyl group is bonded to the ίβ bond junction h The formula I C is 3 carboxylic acid I unit is ί methyl) 3 amine group (full amine base unit - 32 - 201217459 1 2. The phase of any one of claims 1 to 1 a urethane resin for a poor film, wherein the glass transition temperature is from 1 〇〇 to 200 ° C 〇 13. a retardation film, A urethane resin for use in a retardation film according to any one of claims 1 to 12. 14. A retardation film according to claim 13 wherein the following formula: Re = ( nx-ny ) xD wavelength dispersion = Re( 449 ) /Re( 548.7 ) [wherein nx is the refractive index of the retardation axis direction when the refractive index in the plane of the phase difference film is the largest; ny is orthogonal to the aforementioned delay The refractive index in the direction of the phase axis; D is the thickness of the phase difference film (nm); Re is the in-plane phase difference, and Re ( 449 ) is the in-plane phase difference of the light having a wavelength of 44 9 nm ' Re ( 548 _7 ) is the wavelength 548.7 The in-plane phase difference of the light of nm] The wavelength dispersion obtained is less than 1.02. -33-