JP6015838B2 - Alkoxycinnamic acid ester polymer and retardation film using the same - Google Patents

Description

  The present invention relates to a novel alkoxycinnamic acid ester polymer and a retardation film using the same, and more specifically, it has excellent productivity and has a high out-of-plane retardation even in a thin film. The present invention relates to a novel alkoxycinnamate polymer suitable for a retardation film, particularly an optical compensation film for a liquid crystal display device.

  A liquid crystal display is widely used as a most important display device in a multimedia society, such as a mobile phone, a computer monitor, a notebook computer, and a television.

  Many optical films are used for improving the display characteristics of the liquid crystal display. In particular, the retardation film plays a major role in improving contrast and compensating for color tone when viewed from the front or obliquely. As the conventional retardation film, polycarbonate or cyclic polyolefin is used, and these polymers are polymers having positive birefringence. Here, the sign of birefringence is defined as shown below.

  The optical anisotropy of the polymer film molecularly oriented by stretching or the like can be represented by a refractive index ellipsoid shown in FIG. Here, the refractive index in the fast axis direction in the film plane when the film is stretched is represented by nx, the refractive index in the film in-plane direction orthogonal thereto is represented by ny, and the refractive index in the thickness direction of the film is represented by nz. The fast axis indicates an axial direction having a low refractive index in the film plane.

  Negative birefringence means that the stretching direction is the fast axis direction, and positive birefringence means that the direction perpendicular to the stretching direction is the fast axis direction.

  That is, in the uniaxial stretching of the polymer having negative birefringence, the refractive index in the stretching axis direction is small (fast axis: stretching direction), and in the uniaxial stretching of the polymer having positive birefringence, the axial direction perpendicular to the stretching axis. Has a small refractive index (fast axis: direction perpendicular to the stretching direction).

  Many polymers have positive birefringence. As a polymer having negative birefringence, there are acrylic resin and polystyrene. However, acrylic resin has a small retardation, and the properties as a retardation film are not sufficient. Since polystyrene has a large photoelastic coefficient in the low-temperature region, it has a problem of stability of phase difference such as phase difference being changed by a slight stress, and a practical problem of low heat resistance, and is not used at present. .

  A stretched polymer film exhibiting negative birefringence has a high refractive index in the thickness direction of the film and becomes an unprecedented retardation film. (VA-LCD), in-plane oriented liquid crystal display (IPS-LCD), reflective liquid crystal display (reflective LCD), etc., useful as a retardation film for compensating viewing angle characteristics and a viewing angle compensation film for a deflection plate There is a strong market demand for retardation films having negative birefringence.

  A method for producing a film has been proposed in which a polymer having positive birefringence is used to increase the refractive index in the thickness direction of the film. One is a treatment method (for example, Patent Documents 1 to 3) in which a heat-shrinkable film is bonded to one side or both sides of a polymer film, the laminate is subjected to a heat stretching treatment, and a shrinkage force is applied in the film thickness direction of the polymer film. Reference). In addition, a method of uniaxial stretching in a plane while applying an electric field to a polymer film has been proposed (see, for example, Patent Document 4).

  In addition, a retardation film composed of fine particles having negative optical anisotropy and a transparent polymer has been proposed (for example, see Patent Document 5).

  However, the methods proposed in Patent Documents 1 to 4 have a problem that productivity is inferior because the manufacturing process becomes very complicated. Also, the control of the uniformity of the phase difference and the like is extremely difficult as compared with the conventional control by stretching.

  When polycarbonate is used as the base film, the photoelastic coefficient at room temperature is large and the phase difference is changed by a slight stress, so that there is a problem in the stability of the phase difference. Furthermore, there is a problem that the wavelength dependence of the phase difference is large.

  The retardation film obtained in Patent Document 5 is a retardation film that exhibits negative birefringence by adding fine particles having negative optical anisotropy. From the viewpoint of simplification of production method and economical efficiency, fine particles are obtained. There is a need for retardation films that do not require the addition of.

  Moreover, the fumaric-acid diester type resin and the film which consists of it are proposed (for example, refer patent documents 6-10).

  Further, a diisopropyl fumarate-cinnamic acid derivative copolymer comprising a diisopropyl fumarate residue unit and a cinnamic acid residue unit or a cinnamic acid ester residue unit having an alkyl group having 1 to 6 carbon atoms, and A retardation film using the diisopropyl fumarate-cinnamic acid derivative copolymer has been proposed (see, for example, Patent Document 11).

  Further, a fumaric acid diester residue unit, a cinnamic acid ester residue unit having an alkyl group having 1 to 6 carbon atoms, and a polyfunctional monomer residue unit having two or more radical polymerizable functional groups An acid diester-cinnamic acid ester copolymer and a retardation film using the fumaric acid diester-cinnamic acid ester copolymer have been proposed (see, for example, Patent Document 12).

Japanese Patent No. 2818983 JP-A-5-297223 JP-A-5-323120 JP-A-6-88909 JP 2005-156862 A JP 2008-112141 A JP 2012-032784 A WO2012 / 005120 JP 2008-129465 A JP 2006-193616 A WO2014 / 013982 WO2014 / 084178

  Although the fumaric acid diester-based resin proposed in Patent Documents 6 to 10 and a film made thereof have a high out-of-plane retardation, at present, a film having a higher out-of-plane retardation is also present in a thin film. It has been demanded.

  Although the diisopropyl fumarate-cinnamic acid derivative-based copolymer proposed in Patent Document 11 exhibits a higher out-of-plane retardation than the resins proposed in Patent Documents 6 to 10, it is more excellent in productivity and more There is a need for polymers obtained in high yield. Moreover, although the retardation film proposed in Patent Document 11 has a high out-of-plane retardation in a thin film, a film having a higher out-of-plane retardation in a thin film is also required.

  The fumaric acid diester-cinnamic acid ester copolymer proposed in Patent Document 12 is excellent in productivity and can be obtained in a high yield. However, when it is used as a film, it has an out-of-plane retardation higher than that of Patent Document 11. There is a need for a polymer that is excellent in productivity and has a higher out-of-plane retardation.

  An object of the present invention is to provide a novel alkoxycinnamic acid ester polymer suitable for a retardation film which is a polymer excellent in productivity and has a high out-of-plane retardation even in a thin film and excellent in optical properties. There is.

  As a result of intensive studies to solve the above problems, the present inventors have found that a specific alkoxycinnamic acid ester polymer can solve the above problems, and have completed the present invention.

  That is, the present invention relates to an alkoxycinnamic acid ester polymer characterized by containing an alkoxycinnamic acid ester residue unit represented by the general formula (1) and a retardation film using the same. .

(Here, R ₁ represents a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group, and R ₂ represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group, or 3 carbon atoms. ) Represents a cyclic alkyl group of -6, and n represents an integer of 1-5.
Hereinafter, the alkoxycinnamate polymer suitable for the retardation film of the present invention will be described in detail.

  The alkoxycinnamate ester polymer of the present invention is an alkoxycinnamate ester polymer containing an alkoxycinnamate residue unit represented by the general formula (1). And the alkoxycinnamic ester polymer of the present invention comprises a specific alkoxycinnamic ester residue unit, thereby expressing a high out-of-plane retardation even in a thinner film, and It is characterized by a high polymerization pass-through rate of the monomer and excellent productivity.

(Here, R ₁ represents a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group, and R ₂ represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group, or 3 carbon atoms. ) Represents a cyclic alkyl group of -6, and n represents an integer of 1-5.
R ₁ in the general formula (1) of the present invention represents a linear or branched alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a hexyl group, and a dodecyl group. N is an integer of 1-5. Also, _{R 2} in the general formula (1) of the present invention is a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group, or cyclic alkyl group having 3 to 6 carbon atoms, 1 to 12 carbon atoms Examples of the linear alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group, and a branched alkyl group having 1 to 12 carbon atoms. Examples of the group include an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Examples of the cyclic alkyl group having 3 to 6 carbon atoms include a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group. Is mentioned. Among these, since the alkoxycinnamate polymer exhibits a high out-of-plane retardation, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- A butyl group and a cyclohexyl group are preferred.

  Specific examples of the alkoxycinnamate residue unit represented by the general formula (1) include a methoxycinnamate residue unit, an ethoxycinnamate residue unit, and a propoxycinnamate residue unit. Hexoxycinnamate residue units, dodeoxycinnamate residue units, and the like. Among these, since a high phase difference is expressed, a methoxycinnamate residue unit and an ethoxycinnamate residue unit are preferable, and a 4-methoxycinnamate residue unit is more preferable.

  In the present invention, as the methoxycinnamate ester residue unit, for example, 2-methoxycinnamate methyl residue unit, 2-methoxycinnamate ethyl residue unit, 2-methoxycinnamate n-propyl residue Unit: 2-methoxycinnamic acid isopropyl residue unit, 2-methoxycinnamic acid n-butyl residue unit, 2-methoxycinnamic acid sec-butyl residue unit, 2-methoxycinnamic acid tert-butyl residue Units: 2-methoxycinnamate cyclohexyl residue unit, 3-methoxycinnamate methyl residue unit, 3-methoxycinnamate ethyl residue unit, 3-methoxycinnamate n-propyl residue unit, 3- Isopropyl methoxycinnamate residue unit, 3-methoxycinnamic acid n-butyl residue unit, 3-methoxycinnamic acid sec-butyl residue unit, 3-methoxycinnamic acid tert- Chyl residue unit, 3-methoxycinnamate cyclohexyl residue unit, 4-methoxycinnamate methyl residue unit, 4-methoxycinnamate ethyl residue unit, 4-methoxycinnamate n-propyl residue unit 4-methoxycinnamic acid isopropyl residue unit, 4-methoxycinnamic acid n-butyl residue unit, 4-methoxycinnamic acid sec-butyl residue unit, 4-methoxycinnamic acid tert-butyl residue unit 4-methoxycinnamate cyclohexyl residue unit, 2,3-dimethoxycinnamic acid methyl residue unit, 2,3-dimethoxycinnamic acid ethyl residue unit, 2,3-dimethoxycinnamic acid n-propyl residue Base unit, isopropyl residue unit of 2,3-dimethoxycinnamic acid, n-butyl residue unit of 2,3-dimethoxycinnamic acid, sec-butyl residue unit of 2,3-dimethoxycinnamic acid, , 3-Dimethoxycinnamic acid tert-butyl residue unit, 2,3-dimethoxycinnamic acid cyclohexyl residue unit, 2,4-dimethoxycinnamic acid methyl residue unit, 2,4-dimethoxycinnamic acid ethyl residue Group unit, 2,4-dimethoxycinnamic acid n-propyl residue unit, 2,4-dimethoxycinnamic acid isopropyl residue unit, 2,4-dimethoxycinnamic acid n-butyl residue unit, 2,4- Dimethoxycinnamic acid sec-butyl residue unit, 2,4-dimethoxycinnamic acid tert-butyl residue unit, 2,4-dimethoxycinnamic acid cyclohexyl residue unit, 2,5-dimethoxycinnamic acid methyl residue Unit, ethyl 2,5-dimethoxycinnamate residue unit, 2,5-dimethoxycinnamic acid n-propyl residue unit, 2,5-dimethoxycinnamate isopropyl residue unit, 2,5- Dimethoxycinnamic acid n-butyl residue unit, 2,5-dimethoxycinnamic acid sec-butyl residue unit, 2,5-dimethoxycinnamic acid tert-butyl residue unit, 2,5-dimethoxycinnamic acid cyclohexyl Residue unit, methyl 2,6-dimethoxycinnamate residue unit, ethyl 2,6-dimethoxycinnamate residue unit, 2,6-dimethoxycinnamic acid n-propyl residue unit, 2,6-dimethoxy Isopropyl cinnamate residue unit, 2,6-dimethoxycinnamic acid n-butyl residue unit, 2,6-dimethoxycinnamic acid sec-butyl residue unit, 2,6-dimethoxycinnamic acid tert-butyl residue Group unit, cyclohexyl residue unit of 2,6-dimethoxycinnamic acid, methyl residue unit of 3,4-dimethoxycinnamate, ethyl residue unit of 3,4-dimethoxycinnamic acid, 3,4-dimeth Cinnamic acid n-propyl residue unit, 3,4-dimethoxycinnamic acid isopropyl residue unit, 3,4-dimethoxycinnamic acid n-butyl residue unit, 3,4-dimethoxycinnamic acid sec-butyl residue Base unit, tert-butyl residue unit of 3,4-dimethoxycinnamate, cyclohexyl residue unit of 3,4-dimethoxycinnamate, methyl residue unit of 3,5-dimethoxycinnamate, 3,5-dimethoxysilicate Ethyl cinnamate residue units, 3,5-dimethoxycinnamate n-propyl residue units, 3,5-dimethoxy cinnamate isopropyl residue units, 3,5-dimethoxy cinnamate isopropyl residue units, 3, 5-dimethoxycinnamic acid n-butyl residue unit, 3,5-dimethoxycinnamic acid sec-butyl residue unit, 3,5-dimethoxycinnamic acid tert-butyl residue unit, 3,5-dimethoxy Toxicinamate cyclohexyl residue unit, 2,3,4-trimethoxycinnamate ethyl residue unit, 2,3,4-trimethoxycinnamate n-propyl residue unit, 2,3,4-trimethoxy Isopropyl cinnamate residue unit, 2,3,4-trimethoxy cinnamate isopropyl residue unit, 2,3,4-trimethoxy cinnamate n-butyl residue unit, 2,3,4-trimethoxy Cinnamic acid sec-butyl residue unit, 2,3,4-trimethoxycinnamic acid tert-butyl residue unit, 2,3,4-trimethoxycinnamic acid cyclohexyl residue unit, 2,3,5- Methyl trimethoxycinnamate residue unit, ethyl 2,3,5-trimethoxycinnamate residue unit, 2,3,5-trimethoxycinnamic acid n-propyl residue unit, 2,3,5- Isopropyl trimethoxycinnamate residue Base unit, 2,3,5-trimethoxycinnamic acid isopropyl residue unit, 2,3,5-trimethoxycinnamic acid n-butyl residue unit, 2,3,5-trimethoxycinnamic acid sec- Butyl residue unit, 2,3,5-trimethoxycinnamic acid tert-butyl residue unit, 2,3,5-trimethoxycinnamic acid cyclohexyl residue unit, 2,3,6-trimethoxy cinnamic acid Methyl residue unit, 2,3,6-trimethoxycinnamic acid ethyl residue unit, 2,3,6-trimethoxycinnamic acid n-propyl residue unit, 2,3,6-trimethoxycinnamic acid Isopropyl residue unit, 2,3,6-trimethoxycinnamic acid isopropyl residue unit, 2,3,6-trimethoxycinnamic acid n-butyl residue unit, 2,3,6-trimethoxycinnamic acid sec-butyl residue unit, 2,3,6-tri Toxycinnamic acid tert-butyl residue unit, 2,3,6-trimethoxycinnamic acid cyclohexyl residue unit, 2,4,5-trimethoxycinnamic acid methyl residue unit, 2,4,5-trimethoxy Ethyl cinnamate residue unit, 2,4,5-trimethoxycinnamic acid n-propyl residue unit, 2,4,5-trimethoxy cinnamate isopropyl residue unit, 2,4,5-trimethoxy N-butyl cinnamate residue unit, 2,4,5-trimethoxycinnamic acid sec-butyl residue unit, 2,4,5-trimethoxycinnamic acid tert-butyl residue unit, 2,4,5 5-trimethoxycinnamic acid cyclohexyl residue unit, 2,4,6-trimethoxycinnamic acid methyl residue unit, 2,4,6-trimethoxycinnamic acid ethyl residue unit, 2,4,6- N-propyl residue of trimethoxycinnamate Units: 2,4,6-trimethoxycinnamic acid isopropyl residue unit, 2,4,6-trimethoxycinnamic acid n-butyl residue unit, 2,4,6-trimethoxycinnamic acid sec-butyl Residue unit, tert-butyl 2,4,6-trimethoxycinnamate residue unit, cyclohexyl residue unit of 2,4,6-trimethoxycinnamate, methyl 3,4,5-trimethoxycinnamate Residue unit, ethyl 3,4,5-trimethoxycinnamate residue unit, n-propyl residue unit of 3,4,5-trimethoxycinnamic acid, isopropyl 3,4,5-trimethoxycinnamate Residue unit, 3,4,5-trimethoxycinnamate n-butyl residue unit, 3,4,5-trimethoxycinnamate sec-butyl residue unit, 3,4,5-trimethoxycinnamate Acid tert-butyl residue unit, 3,4,5-to Rimethoxycinnamate cyclohexyl residue unit, 2,3,4,5-tetramethoxymethyl cinnamate residue unit, 2,3,4,5-tetramethoxyethyl cinnamate residue unit, 2,3,4, 5-tetramethoxycinnamate n-propyl residue unit, 2,3,4,5-tetramethoxycinnamate isopropyl residue unit, 2,3,4,5-tetramethoxycinnamate n-butyl residue Unit: 2,3,4,5-tetramethoxycinnamic acid sec-butyl residue unit, 2,3,4,5-tetramethoxycinnamic acid tert-butyl residue unit, 2,3,4,5- Cyclohexyl residue unit of tetramethoxycinnamate, methyl residue unit of 2,3,4,6-tetramethoxycinnamate, ethyl residue unit of 2,3,4,6-tetramethoxycinnamate, 2,3,4 4,6-tetramethoxycinnamic acid n- Lopyr residue unit, 2,3,4,6-tetramethoxycinnamic acid isopropyl residue unit, 2,3,4,6-tetramethoxycinnamic acid n-butyl residue unit, 2,3,4,6 -Tetramethoxycinnamate sec-butyl residue unit, 2,3,4,6-tetramethoxycinnamate tert-butyl residue unit, 2,3,4,6-tetramethoxycinnamate cyclohexyl residue unit 2,3,5,6-tetramethoxycinnamic acid methyl residue unit, 2,3,5,6-tetramethoxycinnamic acid ethyl residue unit, 2,3,5,6-tetramethoxycinnamic acid n-propyl residue unit, 2,3,5,6-tetramethoxycinnamate isopropyl residue unit, 2,3,5,6-tetramethoxycinnamate n-butyl residue unit, 2,3,5 , 6-Tetramethoxycinnamic acid sec-butyl residue Position, 2,3,5,6-tetramethoxycinnamate tert-butyl residue unit, 2,3,5,6-tetramethoxycinnamate cyclohexyl residue unit, pentamethoxycinnamate methyl residue unit, Pentamethoxycinnamic acid ethyl residue unit, pentamethoxycinnamic acid n-propyl residue unit, pentamethoxycinnamic acid isopropyl residue unit, pentamethoxycinnamic acid n-butyl residue unit, pentamethoxycinnamic acid sec -Butyl residue unit, pentamethoxycinnamic acid tert-butyl residue unit, pentamethoxycinnamic acid cyclohexyl residue unit, and the like.

  Examples of the ethoxycinnamic acid ester residue units include 2-ethoxycinnamic acid methyl residue units, 2-ethoxycinnamic acid ethyl residue units, 2-ethoxycinnamic acid n-propyl residue units, and 2-ethoxycinnamic acid isopropyl units. Residue unit, 2-ethoxycinnamic acid n-butyl residue unit, 2-ethoxycinnamic acid sec-butyl residue unit, 2-ethoxycinnamic acid tert-butyl residue unit, 2-ethoxycinnamic acid cyclohexyl residue unit, 3-ethoxycinnamic acid methyl residue unit, 3-ethoxycinnamic acid ethyl residue unit, 3-ethoxycinnamic acid n-propyl residue unit, 3-ethoxycinnamic acid isopropyl residue unit, 3-ethoxycinnamic acid n-butyl Residue unit, 3-ethoxycinnamic acid sec-butyl residue unit, 3-ethoxycinnamic acid tert-butyl residue unit, -Ethoxycinnamic acid cyclohexyl residue unit, 4-ethoxycinnamic acid methyl residue unit, 4-ethoxycinnamic acid ethyl residue unit, 4-ethoxycinnamic acid n-propyl residue unit, 4-ethoxycinnamic acid isopropyl residue unit 4-ethoxycinnamic acid n-butyl residue unit, 4-ethoxycinnamic acid sec-butyl residue unit, 4-ethoxycinnamic acid tert-butyl residue unit, 4-ethoxycinnamic acid cyclohexyl residue unit, 2, 3 -Methyl diethoxycinnamate residue unit, 2,3-diethoxyethyl cinnamate residue unit, 2,3-diethoxycinnamic acid n-propyl residue unit, 2,3-diethoxycinnamic acid isopropyl residue unit, 2,3 -N-butyl residue unit of diethoxycinnamic acid, sec-butyl residue unit of 2,3-diethoxycinnamic acid, 2,3-diethoxy Tert-butyl cinnamate residue unit, 2,3-diethoxycinnamic acid cyclohexyl residue unit, 2,4-diethoxycinnamic acid methyl residue unit, 2,4-diethoxycinnamic acid ethyl residue unit, 2,4- Diethoxycinnamic acid n-propyl residue unit, 2,4-diethoxycinnamic acid isopropyl residue unit, 2,4-diethoxycinnamic acid n-butyl residue unit, 2,4-diethoxycinnamic acid sec-butyl residue unit, 2,4-diethoxycinnamic acid tert-butyl residue unit, 2,4-diethoxycinnamic acid cyclohexyl residue unit, 2,5-diethoxycinnamic acid methyl residue unit, 2,5-diethoxycinnamic acid ethyl residue unit, 2,5-diethoxycinnamic acid n-propyl residue unit, 2,5-diethoxycinnamic acid isopropyl residue unit, 2,5-diethoxycinnamic leather Acid n-butyl residue unit, 2,5-diethoxycinnamic acid sec-butyl residue unit, 2,5-diethoxycinnamic acid tert-butyl residue unit, 2,5-diethoxycinnamic acid cyclohexyl residue unit, 2, 6-diethoxycinnamic acid methyl residue unit, 2,6-diethoxycinnamic acid ethyl residue unit, 2,6-diethoxycinnamic acid n-propyl residue unit, 2,6-diethoxycinnamic acid isopropyl residue unit, 2, 6-diethoxycinnamic acid n-butyl residue unit, 2,6-diethoxycinnamic acid sec-butyl residue unit, 2,6-diethoxycinnamic acid tert-butyl residue unit, 2,6-diethoxycinnamic acid cyclohexyl residue unit Units: 3,4-diethoxycinnamic acid methyl residue units, 3,4-diethoxycinnamic acid ethyl residue units, 3,4-diethoxycinnamic acid n- Lopyl residue unit, 3,4-diethoxycinnamic acid isopropyl residue unit, 3,4-diethoxycinnamic acid n-butyl residue unit, 3,4-diethoxycinnamic acid sec-butyl residue unit, 3,4-diethoxysilicate Cinnamic acid tert-butyl residue unit, 3,4-diethoxycinnamic acid cyclohexyl residue unit, 3,5-diethoxycinnamic acid methyl residue unit, 3,5-diethoxycinnamic acid ethyl residue unit, 3,5-diethoxysilicate Cinnamic acid n-propyl residue unit, 3,5-diethoxycinnamic acid isopropyl residue unit, 3,5-diethoxycinnamic acid n-butyl residue unit, 3,5-diethoxycinnamic acid sec-butyl residue unit, 3 , 5-Diethoxycinnamic acid tert-butyl residue unit, 3,5-diethoxycinnamic acid cyclohexyl residue unit, 2,3,4-triethoxy Ethyl cinnamate residue unit, 2,3,4-triethoxycinnamic acid n-propyl residue unit, 2,3,4-triethoxy cinnamate isopropyl residue unit, 2,3,4-triethoxy N-butyl cinnamate residue unit, 2,3,4-triethoxycinnamic acid sec-butyl residue unit, 2,3,4-triethoxycinnamic acid tert-butyl residue unit, 2,3,4 4-triethoxycinnamic acid cyclohexyl residue unit, 2,3,5-triethoxycinnamic acid methyl residue unit, 2,3,5-triethoxycinnamic acid ethyl residue unit, 2,3,5- N-propyl triethoxycinnamate residue unit, isopropyl residue unit of 2,3,5-triethoxycinnamic acid, n-butyl residue unit of 2,3,5-triethoxycinnamic acid, 2,3,5 5-triethoxycinnamic acid sec-butyl residue unit, 2 , 3,5-triethoxycinnamic acid tert-butyl residue unit, 2,3,5-triethoxycinnamic acid cyclohexyl residue unit, 2,3,6-triethoxycinnamic acid methyl residue unit, 2 , 3,6-triethoxycinnamic acid ethyl residue unit, 2,3,6-triethoxycinnamic acid n-propyl residue unit, 2,3,6-triethoxycinnamic acid isopropyl residue unit, 2 , 3,6-triethoxycinnamic acid n-butyl residue unit, 2,3,6-triethoxycinnamic acid sec-butyl residue unit, 2,3,6-triethoxycinnamic acid tert-butyl residue Base unit, 2,3,6-triethoxycinnamic acid cyclohexyl residue unit, 2,4,5-triethoxycinnamic acid methyl residue unit, 2,4,5-triethoxycinnamic acid ethyl residue unit 2,4,5-triethoxycinnamic acid -Propyl residue unit, 2,4,5-triethoxycinnamic acid isopropyl residue unit, 2,4,5-triethoxycinnamic acid n-butyl residue unit, 2,4,5-triethoxycinnamic leather Acid sec-butyl residue unit, 2,4,5-triethoxycinnamic acid tert-butyl residue unit, 2,4,5-triethoxycinnamic acid cyclohexyl residue unit, 2,4,6-triethoxy Methyl cinnamate residue unit, 2,4,6-triethoxyethyl cinnamate residue unit, 2,4,6-triethoxycinnamic acid n-propyl residue unit, 2,4,6-triethoxy Isopropyl cinnamate residue unit, 2,4,6-triethoxycinnamic acid n-butyl residue unit, 2,4,6-triethoxycinnamic acid sec-butyl residue unit, 2,4,6- Unit of tert-butyl triethoxycinnamate 2,4,6-triethoxycinnamic acid cyclohexyl residue unit, 3,4,5-triethoxycinnamic acid methyl residue unit, 3,4,5-triethoxycinnamic acid ethyl residue unit, 3, 4,5-triethoxycinnamic acid n-propyl residue unit, 3,4,5-triethoxycinnamic acid isopropyl residue unit, 3,4,5-triethoxycinnamic acid isopropyl residue unit, 3, 4,5-triethoxycinnamic acid n-butyl residue unit, 3,4,5-triethoxycinnamic acid sec-butyl residue unit, 3,4,5-triethoxycinnamic acid tert-butyl residue unit Unit, 3,4,5-triethoxycinnamate cyclohexyl residue unit, 2,3,4,5-tetraethoxymethylcinnamate residue unit, ethyl 2,3,4,5-tetraethoxycinnamate Residue unit, 2,3,4,5-tetra Ethoxycinnamic acid n-propyl residue unit, 2,3,4,5-tetraethoxycinnamic acid isopropyl residue unit, 2,3,4,5-tetraethoxycinnamic acid n-butyl residue unit, 3,4,5-tetraethoxycinnamic acid sec-butyl residue unit, 2,3,4,5-tetraethoxycinnamic acid tert-butyl residue unit, 2,3,4,5-tetraethoxycinnamic leather Acid cyclohexyl residue unit, 2,3,4,6-tetraethoxycinnamate methyl residue unit, 2,3,4,6-tetraethoxyethyl cinnamate residue unit, 2,3,4,6- Tetraethoxycinnamic acid n-propyl residue unit, 2,3,4,6-tetraethoxycinnamic acid isopropyl residue unit, 2,3,4,6-tetraethoxycinnamic acid n-butyl residue unit, 2,3,4,6-tetraethoxycinnax sec-butyl residue unit, 2,3,4,6-tetraethoxycinnamic acid tert-butyl residue unit, 2,3,4,6-tetraethoxycinnamic acid cyclohexyl residue unit, 2,3,5 , 6-Tetraethoxycinnamic acid methyl residue unit, 2,3,5,6-tetraethoxycinnamic acid ethyl residue unit, 2,3,5,6-tetraethoxycinnamic acid n-propyl residue unit 2,3,5,6-tetraethoxycinnamic acid isopropyl residue unit, 2,3,5,6-tetraethoxycinnamic acid n-butyl residue unit, 2,3,5,6-tetraethoxysilicic acid unit Cinnamic acid sec-butyl residue unit, 2,3,5,6-tetraethoxycinnamic acid tert-butyl residue unit, 2,3,5,6-tetraethoxycinnamic acid cyclohexyl residue unit, pentaethoxysilicate Methyl cinnamate residue unit, pe Ethyl taethoxycinnamate residue unit, pentaethoxycinnamic acid n-propyl residue unit, pentaethoxycinnamic acid isopropyl residue unit, pentaethoxycinnamic acid n-butyl residue unit, pentaethoxycinnamic acid sec-butyl Examples thereof include a residue unit, a tert-butyl pentaethoxycinnamate residue unit, and a cyclohexyl residue unit of pentaethoxycinnamic acid.

  Examples of the propoxycinnamic acid ester residue unit include a 2-propoxycinnamic acid methyl residue unit, a 2-propoxycinnamic acid ethyl residue unit, a 2-propoxycinnamic acid n-propyl residue unit, 2- Propoxycinnamic acid isopropyl residue unit, 2-propoxycinnamic acid n-butyl residue unit, 2-propoxycinnamic acid sec-butyl residue unit, 2-propoxycinnamic acid tert-butyl residue unit, 2- Propoxycinnamic acid cyclohexyl residue unit, 3-propoxycinnamic acid methyl residue unit, 3-propoxycinnamic acid ethyl residue unit, 3-propoxycinnamic acid n-propyl residue unit, 3-propoxycinnamic acid Isopropyl residue unit, 3-propoxycinnamic acid n-butyl residue unit, 3-propoxycinnamic acid sec-butyl residue unit, 3-propoxyke Cinnamic acid tert-butyl residue unit, 3-propoxycinnamic acid cyclohexyl residue unit, 4-propoxycinnamic acid methyl residue unit, 4-propoxycinnamic acid ethyl residue unit, 4-propoxycinnamic acid n- Propyl residue unit, 4-propoxycinnamic acid isopropyl residue unit, 4-propoxycinnamic acid n-butyl residue unit, 4-propoxycinnamic acid sec-butyl residue unit, 4-propoxycinnamic acid tert- Butyl residue unit, 4-propoxycinnamate cyclohexyl residue unit, 2,3-dipropoxycinnamate methyl residue unit, 2,3-dipropoxycinnamate ethyl residue unit, 2,3-dipropoxy N-propyl cinnamate residue units, isopropyl residue units of 2,3-dipropoxycinnamic acid, n-butyl residue units of 2,3-dipropoxycinnamic acid, 2,3 Dipropoxycinnamic acid sec-butyl residue unit, 2,3-dipropoxycinnamic acid tert-butyl residue unit, 2,3-dipropoxycinnamic acid cyclohexyl residue unit, 2,4-dipropoxycinnamic leather Acid methyl residue unit, 2,4-dipropoxycinnamic acid ethyl residue unit, 2,4-dipropoxycinnamic acid n-propyl residue unit, 2,4-dipropoxycinnamic acid isopropyl residue unit, 2,4-dipropoxycinnamic acid n-butyl residue unit, 2,4-dipropoxycinnamic acid sec-butyl residue unit, 2,4-dipropoxycinnamic acid tert-butyl residue unit, 2, 4-dipropoxycinnamic acid cyclohexyl residue unit, 2,5-dipropoxycinnamic acid methyl residue unit, 2,5-dipropoxycinnamic acid ethyl residue unit, 2,5-dipropoxycinnamic acid n - Lopyr residue unit, 2,5-dipropoxycinnamic acid isopropyl residue unit, 2,5-dipropoxycinnamic acid n-butyl residue unit, 2,5-dipropoxycinnamic acid sec-butyl residue unit 2,5-dipropoxycinnamate tert-butyl residue unit, 2,5-dipropoxycinnamate cyclohexyl residue unit, 2,6-dipropoxycinnamate methyl residue unit, 2,6-di Propoxycinnamic acid ethyl residue unit, 2,6-dipropoxycinnamic acid n-propyl residue unit, 2,6-dipropoxycinnamic acid isopropyl residue unit, 2,6-dipropoxycinnamic acid n- Butyl residue unit, 2,6-dipropoxycinnamic acid sec-butyl residue unit, 2,6-dipropoxycinnamic acid tert-butyl residue unit, 2,6-dipropoxycinnamic acid cyclohexyl residue unit , , 4-dipropoxycinnamate methyl residue unit, 3,4-dipropoxycinnamate ethyl residue unit, 3,4-dipropoxycinnamate n-propyl residue unit, 3,4-dipropoxycin Isopropyl cinnamate residue unit, 3,4-dipropoxycinnamic acid n-butyl residue unit, 3,4-dipropoxycinnamic acid sec-butyl residue unit, 3,4-dipropoxycinnamic acid tert- Butyl residue unit, 3,4-dipropoxycinnamate cyclohexyl residue unit, 3,5-dipropoxycinnamate methyl residue unit, 3,5-dipropoxycinnamate ethyl residue unit, 3,5 -N-propyl residue unit of dipropoxycinnamate, isopropyl residue unit of 3,5-dipropoxycinnamic acid, isopropyl residue unit of 3,5-dipropoxycinnamic acid, 3,5-dipropoxycinnamic acid n-bu Residue unit, 3,5-dipropoxycinnamic acid sec-butyl residue unit, 3,5-dipropoxycinnamic acid tert-butyl residue unit, 3,5-dipropoxycinnamic acid cyclohexyl residue unit 2,3,4-tripropoxycinnamate ethyl residue unit, 2,3,4-tripropoxycinnamate n-propyl residue unit, 2,3,4-tripropoxycinnamate isopropyl residue unit 2,3,4-tripropoxycinnamate isopropyl residue unit, 2,3,4-tripropoxycinnamate n-butyl residue unit, 2,3,4-tripropoxycinnamate sec-butyl residue Base unit, tert-butyl residue unit of 2,3,4-tripropoxycinnamate, cyclohexyl residue unit of 2,3,4-tripropoxycinnamate, methyl 2,3,5-tripropoxycinnamate residue Base unit 2,3,5-tripropoxycinnamic acid ethyl residue unit, 2,3,5-tripropoxycinnamic acid n-propyl residue unit, 2,3,5-tripropoxycinnamic acid isopropyl residue unit 2,3,5-tripropoxycinnamic acid isopropyl residue unit, 2,3,5-tripropoxycinnamic acid n-butyl residue unit, 2,3,5-tripropoxycinnamic acid sec-butyl residue Base unit, tert-butyl residue unit of 2,3,5-tripropoxycinnamic acid, cyclohexyl residue unit of 2,3,5-tripropoxycinnamic acid residue, methyl 2,3,6-tripropoxycinnamic acid residue Base unit, ethyl 2,3,6-tripropoxycinnamate residue unit, 2,3,6-tripropoxycinnamate n-propyl residue unit, isopropyl 2,3,6-tripropoxycinnamate residue Base unit, 2, , 6-Tripropoxycinnamic acid isopropyl residue unit, 2,3,6-tripropoxycinnamic acid n-butyl residue unit, 2,3,6-tripropoxycinnamic acid sec-butyl residue unit, 2 , 3,6-tripropoxycinnamic acid tert-butyl residue unit, 2,3,6-tripropoxycinnamic acid cyclohexyl residue unit, 2,4,5-tripropoxycinnamic acid methyl residue unit, 2 2,4,5-tripropoxycinnamic acid ethyl residue unit, 2,4,5-tripropoxycinnamic acid n-propyl residue unit, 2,4,5-tripropoxycinnamic acid isopropyl residue unit, 2 , 4,5-Tripropoxycinnamic acid isopropyl residue unit, 2,4,5-tripropoxycinnamic acid n-butyl residue unit, 2,4,5-tripropoxycinnamic acid sec-butyl residue unit , 2, , 5-tripropoxycinnamate tert-butyl residue unit, 2,4,5-tripropoxycinnamate cyclohexyl residue unit, 2,4,6-tripropoxycinnamate methyl residue unit, 2,4 , 6-Tripropoxycinnamic acid ethyl residue units, 2,4,6-tripropoxycinnamic acid n-propyl residue units, 2,4,6-tripropoxycinnamic acid isopropyl residue units, 2,4 , 6-Tripropoxycinnamic acid isopropyl residue unit, 2,4,6-tripropoxycinnamic acid n-butyl residue unit, 2,4,6-tripropoxycinnamic acid sec-butyl residue unit, 2 , 4,6-tripropoxycinnamic acid tert-butyl residue unit, 2,4,6-tripropoxycinnamic acid cyclohexyl residue unit, 3,4,5-tripropoxycinnamic acid methyl residue unit, 3 , 4 , 5-tripropoxycinnamate ethyl residue unit, 3,4,5-tripropoxycinnamate n-propyl residue unit, 3,4,5-tripropoxycinnamate isopropyl residue unit, 3,4 , 5-tripropoxycinnamic acid isopropyl residue unit, 3,4,5-tripropoxycinnamic acid n-butyl residue unit, 3,4,5-tripropoxycinnamic acid sec-butyl residue unit, 3 , 4,5-Tripropoxycinnamate tert-butyl residue unit, 3,4,5-Tripropoxycinnamate cyclohexyl residue unit, 2,3,4,5-tetrapropoxycinnamate methyl residue unit 2,3,4,5-tetrapropoxycinnamate ethyl residue unit, 2,3,4,5-tetrapropoxycinnamate n-propyl residue unit, 2,3,4,5-tetrapropoxysilicate unit Isopropyl cinnamate Residue unit, 2,3,4,5-tetrapropoxycinnamic acid n-butyl residue unit, 2,3,4,5-tetrapropoxycinnamic acid sec-butyl residue unit, 2,3,4, 5-tetrapropoxycinnamate tert-butyl residue unit, 2,3,4,5-tetrapropoxycinnamate cyclohexyl residue unit, 2,3,4,6-tetrapropoxycinnamate methyl residue unit, 2,3,4,6-tetrapropoxycinnamate ethyl residue unit, 2,3,4,6-tetrapropoxycinnamic acid n-propyl residue unit, 2,3,4,6-tetrapropoxycinnax Isopropyl acid residue unit, 2,3,4,6-tetrapropoxycinnamic acid n-butyl residue unit, 2,3,4,6-tetrapropoxycinnamic acid sec-butyl residue unit, 4,6-tetrapropoxycinnamic acid ert-butyl residue unit, 2,3,4,6-tetrapropoxycinnamate cyclohexyl residue unit, 2,3,5,6-tetrapropoxycinnamate methyl residue unit, 2,3,5,6 -Tetrapropoxycinnamate ethyl residue unit, 2,3,5,6-tetrapropoxycinnamate n-propyl residue unit, 2,3,5,6-tetrapropoxycinnamate isopropyl residue unit, 2 , 3,5,6-tetrapropoxycinnamic acid n-butyl residue unit, 2,3,5,6-tetrapropoxycinnamic acid sec-butyl residue unit, 2,3,5,6-tetrapropoxysilicate Cinnamic acid tert-butyl residue unit, 2,3,5,6-tetrapropoxycinnamic acid cyclohexyl residue unit, pentapropoxycinnamic acid methyl residue unit, pentapropoxycinnamic acid ethyl residue unit, pentap Roxy cinnamate n-propyl residue unit, pentyl propoxycinnamate residue unit, pentapropoxycinnamate n-butyl residue unit, pentapropoxycinnamate sec-butyl residue unit, pentapropoxycinnamate tert -A butyl residue unit, a pentapropoxycinnamate cyclohexyl residue unit, etc. are mentioned.

  Examples of hexoxycinnamic acid ester residue units include 2-hexoxycinnamic acid methyl residue units, 2-hexoxycinnamic acid ethyl residue units, 2-hexoxycinnamic acid n-propyl residue units, and 2-hexoxycinnamic acid isopropyl units. Residue unit, 2-hexoxycinnamic acid n-butyl residue unit, 2-hexoxycinnamic acid sec-butyl residue unit, 2-hexoxycinnamic acid tert-butyl residue unit, 2-hexoxycinnamic acid cyclohexyl residue unit, 3-hexoxycinnamic acid methyl residue unit, 3-hexoxycinnamic acid ethyl residue unit, 3-hexoxycinnamic acid n-propyl residue unit, 3-hexoxycinnamic acid isopropyl residue unit, 3-hexoxycinnamic acid n-butyl Residue unit, 3-hexoxycinnamic acid sec-butyl residue unit, 3-hexoxyke Cinnamic acid tert-butyl residue unit, 3-hexoxycinnamic acid cyclohexyl residue unit, 4-hexoxycinnamic acid methyl residue unit, 4-hexoxycinnamic acid ethyl residue unit, 4-hexoxycinnamic acid n-propyl residue unit , 4-hexoxycinnamic acid isopropyl residue unit, 4-hexoxycinnamic acid n-butyl residue unit, 4-hexoxycinnamic acid sec-butyl residue unit, 4-hexoxycinnamic acid tert-butyl residue unit, 4-hexoxysilicate Cyclohexyl residue unit, methyl 2,3-dihexoxycinnamate residue unit, ethyl 2,3-dihexoxycinnamate residue unit, 2,3-dihexoxycinnamic acid n-propyl residue unit, 2,3-dihexoxysilicate unit Isopropyl cinnamate residue unit, 2,3-dihexoxycinnamate n-butyl residue unit, 2, 3 Dihexoxycinnamic acid sec-butyl residue unit, 2,3-dihexoxycinnamic acid tert-butyl residue unit, 2,3-dihexycinnamic acid cyclohexyl residue unit, 2,4-dihexoxycinnamic acid methyl residue unit, 2, 4-dihexoxycinnamic acid ethyl residue unit, 2,4-dihexoxycinnamic acid n-propyl residue unit, 2,4-dihexoxycinnamic acid isopropyl residue unit, 2,4-dihexoxycinnamic acid n-butyl residue unit, 2,4-dihexoxycinnamic acid sec-butyl residue unit, 2,4-dihexoxycinnamic acid tert-butyl residue unit, 2,4-dihexoxycinnamic acid cyclohexyl residue unit, 2,5-dihexoxycinnamic acid methyl residue Unit, ethyl 2,5-dihexoxycinnamate residue unit, 2,5-dihexoxycinnamic acid n-group Lopyr residue unit, 2,5-dihexoxycinnamate isopropyl residue unit, 2,5-dihexoxycinnamate n-butyl residue unit, 2,5-dihexoxycinnamate sec-butyl residue unit, 2,5-dihexoxysilicate Cinnamic acid tert-butyl residue unit, 2,5-dihexoxycinnamate cyclohexyl residue unit, 2,6-dihexoxycinnamate methyl residue unit, 2,6-dihexoxycinnamic acid ethyl residue unit, 2,6-dihexoxysilicate N-propyl cinnamate residue unit, isopropyl 2,6-dihexoxycinnamate residue unit, n-butyl residue unit of 2,6-dihexoxycinnamic acid, sec-butyl residue unit of 2,6-dihexoxycinnamic acid, 2 , 6-dihexoxycinnamic acid tert-butyl residue unit, 2,6-dihexoxycinnamic acid cyclohexyl residue unit, , 4-Dihexoxycinnamic acid methyl residue unit, 3,4-dihexoxycinnamic acid ethyl residue unit, 3,4-dihexoxycinnamic acid n-propyl residue unit, 3,4-dihexoxycinnamic acid isopropyl residue unit, 3 , 4-Dihexoxycinnamic acid n-butyl residue unit, 3,4-dihexoxycinnamic acid sec-butyl residue unit, 3,4-dihexoxycinnamic acid tert-butyl residue unit, 3,4-dihexoxycinnamic acid cyclohexyl residue Base unit, 3,5-dihexoxycinnamic acid methyl residue unit, 3,5-dihexoxycinnamic acid ethyl residue unit, 3,5-dihexoxycinnamic acid n-propyl residue unit, 3,5-dihexoxycinnamic acid isopropyl residue Base unit, isopropyl residue unit of 3,5-dihexoxycinnamic acid, n-butyl 3,5-dihexoxycinnamic acid Residue unit, 3,5-dihexoxycinnamic acid sec-butyl residue unit, 3,5-dihexoxycinnamic acid tert-butyl residue unit, 3,5-dihexoxycinnamic acid cyclohexyl residue unit, 2,3,4 -Ethyl trihexoxycinnamate residue unit, 2,3,4-trihexoxycinnamic acid n-propyl residue unit, 2,3,4-trihexoxycinnamic acid isopropyl residue unit, 2, 3,4-trihexoxycinnamic acid isopropyl residue unit, 2,3,4-trihexoxycinnamic acid n-butyl residue unit, 2,3,4-trihexoxycinnamic acid sec-butyl residue Base unit, tert-butyl residue unit of 2,3,4-trihexoxycinnamate, cyclohexyl residue unit of 2,3,4-trihexoxycinnamic acid, 2,3,5-trihexycinnamic bark Acid methyl residue unit 2,3,5-trihexoxycinnamic acid ethyl residue units, 2,3,5-trihexoxycinnamic acid n-propyl residue units, 2,3,5-trihexoxycinnamic acid isopropyl units Residue unit, 2,3,5-trihexoxycinnamic acid isopropyl residue unit, 2,3,5-trihexoxycinnamic acid n-butyl residue unit, 2,3,5-trihexoxysilicate Cinnamic acid sec-butyl residue unit, 2,3,5-trihexoxycinnamic acid tert-butyl residue unit, 2,3,5-trihexoxycinnamic acid cyclohexyl residue unit, 2,3,6 -Methyl trihexoxycinnamate residue unit, ethyl 2,3,6-trihexoxycinnamate residue unit, 2,3,6-trihexoxycinnamic acid n-propyl residue unit, 2, 3,6-trihexoxycinnamic acid isopropyl residue unit, 2, , 6-Trihexoxycinnamic acid isopropyl residue unit, 2,3,6-trihexoxycinnamic acid n-butyl residue unit, 2,3,6-trihexoxycinnamic acid sec-butyl residue Unit: 2,3,6-trihexoxycinnamic acid tert-butyl residue unit, 2,3,6-trihexoxycinnamic acid cyclohexyl residue unit, 2,4,5-trihexoxycinnamic acid Methyl residue unit, 2,4,5-trihexoxycinnamic acid ethyl residue unit, 2,4,5-trihexoxycinnamic acid n-propyl residue unit, 2,4,5-trihexoxy Isopropyl cinnamate residue unit, 2,4,5-trihexoxycinnamic acid isopropyl residue unit, 2,4,5-trihexoxycinnamic acid n-butyl residue unit, 2,4,5- Tri-hexoxycinnamic acid sec-butyl residue unit, 2, , 5-trihexoxycinnamate tert-butyl residue unit, 2,4,5-trihexoxycinnamic acid cyclohexyl residue unit, 2,4,6-trihexoxycinnamic acid methyl residue unit, 2,4,6-Trihexoxycinnamic acid ethyl residue unit, 2,4,6-trihexoxycinnamic acid n-propyl residue unit, 2,4,6-trihexoxycinnamic acid isopropyl residue Base unit, 2,4,6-trihexoxycinnamic acid isopropyl residue unit, 2,4,6-trihexoxycinnamic acid n-butyl residue unit, 2,4,6-trihexoxycinnamic bar Acid sec-butyl residue unit, 2,4,6-trihexoxycinnamic acid tert-butyl residue unit, 2,4,6-trihexoxycinnamic acid cyclohexyl residue unit, 3,4,5- Units of methyl trihexoxycinnamate, 3, 4 , 5-trihexoxycinnamic acid ethyl residue unit, 3,4,5-trihexoxycinnamic acid n-propyl residue unit, 3,4,5-trihexoxycinnamic acid isopropyl residue unit, 3,4,5-trihexoxycinnamic acid isopropyl residue unit, 3,4,5-trihexoxycinnamic acid n-butyl residue unit, 3,4,5-trihexoxycinnamic acid sec- Butyl residue unit, 3,4,5-trihexoxycinnamic acid tert-butyl residue unit, 3,4,5-trihexoxycinnamic acid cyclohexyl residue unit, 2,3,4,5-tetra Hexoxycinnamate methyl residue unit, 2,3,4,5-tetrahexoxycinnamate ethyl residue unit, 2,3,4,5-tetrahexoxycinnamate n-propyl residue unit, 2,3,4,5-tetrahexoxycinnamic acid isopropyl ester Residue unit, 2,3,4,5-tetrahexoxycinnamic acid n-butyl residue unit, 2,3,4,5-tetrahexoxycinnamic acid sec-butyl residue unit, 2,3,4 4,5-tetrahexoxycinnamic acid tert-butyl residue unit, 2,3,4,5-tetrahexoxycinnamic acid cyclohexyl residue unit, 2,3,4,6-tetrahexoxycinnamic acid Methyl residue unit, 2,3,4,6-tetrahexoxycinnamic acid ethyl residue unit, 2,3,4,6-tetrahexoxycinnamic acid n-propyl residue unit, 2,3,4 , 6-tetrahexoxycinnamic acid isopropyl residue unit, 2,3,4,6-tetrahexoxycinnamic acid n-butyl residue unit, 2,3,4,6-tetrahexoxycinnamic acid sec -Butyl residue unit, 2,3,4,6-tetrahexoxycinnamic acid ert-butyl residue unit, 2,3,4,6-tetrahexoxycinnamate cyclohexyl residue unit, 2,3,5,6-tetrahexoxycinnamate methyl residue unit, 2,3,5 1,6-tetrahexoxycinnamic acid ethyl residue unit, 2,3,5,6-tetrahexoxycinnamic acid n-propyl residue unit, 2,3,5,6-tetrahexoxycinnamic acid isopropyl Residue unit, 2,3,5,6-tetrahexoxycinnamic acid n-butyl residue unit, 2,3,5,6-tetrahexoxycinnamic acid sec-butyl residue unit, 2,3, 5,6-tetrahexoxycinnamic acid tert-butyl residue unit, 2,3,5,6-tetrahexoxycinnamic acid cyclohexyl residue unit, pentahexoxycinnamic acid methyl residue unit, pentahexoxy Ethyl cinnamate residue unit, pentahe N-Propyl residue unit of xoxycinnamic acid, isopropyl residue unit of pentahexoxycinnamic acid, n-butyl residue unit of pentahexoxycinnamic acid, sec-butyl residue unit of pentahexoxycinnamic acid, pentahexoxy Examples thereof include a tert-butyl cinnamate residue unit and a cyclohexyl residue unit of pentahexoxycinnamate.

  Examples of dodeoxycinnamic acid ester residue units include 2-dodeoxycinnamic acid methyl residue unit, 2-dodoxycinnamic acid ethyl residue unit, 2-dodoxycinnamic acid n-propyl residue unit, 2-dodoxycinnamic acid isopropyl residue Residue unit, 2-dodeoxycinnamic acid n-butyl residue unit, 2-dodeoxycinnamic acid sec-butyl residue unit, 2-dodoxycinnamic acid tert-butyl residue unit, 2-dodeoxycinnamic acid cyclohexyl residue unit, 3-dodeoxycinnamate methyl residue unit, 3-dodeoxycinnamate ethyl residue unit, 3-dodeoxycinnamate n-propyl residue unit, 3-dodeoxycinnamate isopropyl residue unit, 3-dodeoxycinnamate n-butyl Residue unit, 3-dodecoxycinnamic acid sec-butyl residue unit, 3-dodecoxyke Cinnamic acid tert-butyl residue unit, 3-dodoxycinnamic acid cyclohexyl residue unit, 4-dodoxycinnamic acid methyl residue unit, 4-dodoxycinnamic acid ethyl residue unit, 4-dodoxycinnamic acid n-propyl residue unit , 4-dodeoxycinnamic acid isopropyl residue unit, 4-dodeoxycinnamic acid n-butyl residue unit, 4-dodoxycinnamic acid sec-butyl residue unit, 4-dodoxycinnamic acid tert-butyl residue unit, 4-dodoxycin Cinnamic acid cyclohexyl residue unit, 2,3-didodoxycinnamic acid methyl residue unit, 2,3-didodoxycinnamic acid ethyl residue unit, 2,3-didodoxycinnamic acid n-propyl residue unit, 2,3-didodoxysilicic acid unit Isopropyl cinnamate residue unit, 2,3-didodoxycinnamic acid n-butyl residue unit, 2, 3 Didodeoxycinnamic acid sec-butyl residue unit, 2,3-didodoxycinnamic acid tert-butyl residue unit, 2,3-didodoxycinnamic acid cyclohexyl residue unit, 2,4-didodoxycinnamic acid methyl residue unit, 2, 4-didodoxycinnamic acid ethyl residue unit, 2,4-didodoxycinnamic acid n-propyl residue unit, 2,4-didodoxycinnamic acid isopropyl residue unit, 2,4-didodoxycinnamic acid n-butyl residue unit, 2,4-didodoxycinnamic acid sec-butyl residue unit, 2,4-didodoxycinnamic acid tert-butyl residue unit, 2,4-didodoxycinnamic acid cyclohexyl residue unit, 2,5-didodoxycinnamic acid methyl residue Unit, ethyl 2,5-didodeoxycinnamate residue, 2,5-didodeoxycinnamic acid n-group Lopyr residue unit, 2,5-didodeoxycinnamic acid isopropyl residue unit, 2,5-didodeoxycinnamic acid n-butyl residue unit, 2,5-didodeoxycinnamic acid sec-butyl residue unit, 2,5-didodeoxysilicate Cinnamic acid tert-butyl residue unit, 2,5-didodoxycinnamate cyclohexyl residue unit, 2,6-didodoxycinnamic acid methyl residue unit, 2,6-didodoxycinnamic acid ethyl residue unit, 2,6-didodoxysilicate Cinnamic acid n-propyl residue unit, 2,6-didodoxycinnamic acid isopropyl residue unit, 2,6-didodoxycinnamic acid n-butyl residue unit, 2,6-didodoxycinnamic acid sec-butyl residue unit, 2 , 6-didodeoxycinnamic acid tert-butyl residue unit, 2,6-didodoxycinnamic acid cyclohexyl residue unit, , 4-Didodeoxycinnamic acid methyl residue unit, 3,4-didodoxycinnamic acid ethyl residue unit, 3,4-didodoxycinnamic acid n-propyl residue unit, 3,4-didodoxycinnamic acid isopropyl residue unit, 3 , 4-didodoxycinnamic acid n-butyl residue unit, 3,4-didodoxycinnamic acid sec-butyl residue unit, 3,4-didodoxycinnamic acid tert-butyl residue unit, 3,4-didodoxycinnamic acid cyclohexyl residue Base unit, methyl 3,5-didodeoxycinnamate residue unit, ethyl 3,5-didodeoxycinnamate residue unit, n-propyl residue unit of 3,5-didodeoxycinnamic acid residue, isopropyl 3,5-didodeoxycinnamate residue Base unit, isopropyl residue unit of 3,5-didodoxycinnamic acid, n-butyl 3,5-didodoxycinnamic acid Residue unit, 3,5-didodeoxycinnamic acid sec-butyl residue unit, 3,5-didodeoxycinnamic acid tert-butyl residue unit, 3,5-didodeoxycinnamic acid cyclohexyl residue unit, 2,3,4 -Ethyl tridodeoxycinnamate residue unit, 2,3,4-tridodoxycinnamic acid n-propyl residue unit, 2,3,4-tridodoxycinnamic acid isopropyl residue unit 2,3,4-tridodoxycinnamate isopropyl residue unit, 2,3,4-tridodoxycinnamic acid n-butyl residue unit, 2,3,4-tridodeoxycinnamic acid unit Cinnamic acid sec-butyl residue unit, 2,3,4-tridodecoxycinnamic acid tert-butyl residue unit, 2,3,4-tridodoxycinnamic acid cyclohexyl residue unit, 2,3 , 5-Tridodoxycinnamate methyl residue unit 2,3,5-tridodeoxycinnamic acid ethyl residue unit, 2,3,5-tridodoxycinnamic acid n-propyl residue unit, 2,3,5-tridodeoxycinnamic acid unit Isopropyl cinnamate residue unit, 2,3,5-tridodoxycinnamate isopropyl residue unit, 2,3,5-tridodoxycinnamic acid n-butyl residue unit, 2,3,5 -Sec-butyl residue unit of tridodeoxycinnamic acid, tert-butyl residue unit of 2,3,5-tridodoxycinnamic acid, cyclohexyl residue of 2,3,5-tridodeoxycinnamic acid Base unit, 2,3,6-tridodoxycinnamic acid methyl residue unit, 2,3,6-tridodoxycinnamic acid ethyl residue unit, 2,3,6-tridodeoxycinnamic unit N-propyl cinnamate residue unit, 2,3,6-tridodoxy cinnamate isopropyl residue unit, 2, , 6-Tridodeoxycinnamic acid isopropyl residue unit, 2,3,6-Tridodoxycinnamic acid n-butyl residue unit, 2,3,6-Tridodoxycinnamic acid sec- Butyl residue unit, 2,3,6-tridodeoxycinnamic acid tert-butyl residue unit, 2,3,6-tridodeoxycinnamic acid cyclohexyl residue unit, 2,4,5-tri Dodeoxycinnamic acid methyl residue unit, 2,4,5-tridodoxycinnamic acid ethyl residue unit, 2,4,5-tridodoxycinnamic acid n-propyl residue unit, 2 , 4,5-Tridodoxycinnamic acid isopropyl residue unit, 2,4,5-tridodeoxycinnamic acid isopropyl residue unit, 2,4,5-tridodeoxycinnamic acid n- Butyl residue unit, 2,4,5-tridodoxycinnamic acid sec-butyl residue unit, 2, , 5-tridodeoxycinnamic acid tert-butyl residue unit, 2,4,5-tridodeoxycinnamic acid cyclohexyl residue unit, methyl 2,4,6-tridodeoxycinnamic acid residue Group unit, 2,4,6-tridodeoxycinnamic acid ethyl residue unit, 2,4,6-tridodoxycinnamic acid n-propyl residue unit, 2,4,6-tridode Isopropyl oxycinnamate residue units, 2,4,6-tridodeoxy cinnamate isopropyl residue units, 2,4,6-tridodeoxy cinnamate n-butyl residue units, 2,4 , 6-tridodeoxycinnamic acid sec-butyl residue unit, 2,4,6-tridodeoxycinnamic acid tert-butyl residue unit, 2,4,6-tridodeoxycinnamic acid Cyclohexyl residue unit, 3,4,5-methyl tridodeoxycinnamate residue unit, 3,4 , 5-Tridodeoxycinnamic acid ethyl residue unit, 3,4,5-Tridodoxycinnamic acid n-propyl residue unit, 3,4,5-Tridodoxycinnamic acid isopropyl residue Base unit, 3,4,5-tridodeoxycinnamic acid isopropyl residue unit, 3,4,5-tridodoxycinnamic acid n-butyl residue unit, 3,4,5-tridode Toxiccinnamic acid sec-butyl residue unit, 3,4,5-tridodeoxycinnamic acid tert-butyl residue unit, 3,4,5-tridodeoxycinnamic acid cyclohexyl residue unit, 2 , 3,4,5-tetradodeoxy cinnamate methyl residue unit, 2,3,4,5-tetradodeoxy cinnamate ethyl residue unit, 2,3,4,5-tetradode Toxicinnamic acid n-propyl residue unit, 2,3,4,5-tetradodeoxycinnamic acid isopropyl Residue unit, 2,3,4,5-tetradodeoxycinnamic acid n-butyl residue unit, 2,3,4,5-tetradodoxycinnamic acid sec-butyl residue unit, 2, 3,4,5-tetradodeoxycinnamic acid tert-butyl residue unit, 2,3,4,5-tetradodeoxycinnamic acid cyclohexyl residue unit, 2,3,4,6-tetradone Deoxycinnamic acid methyl residue unit, 2,3,4,6-tetradodoxycinnamic acid ethyl residue unit, 2,3,4,6-tetradodoxycinnamic acid n-propyl residue Unit, isopropyl residue unit of 2,3,4,6-tetradodoxycinnamic acid, n-butyl residue unit of 2,3,4,6-tetradodoxycinnamic acid, 2,3,4, 6-tetradodoxycinnamic acid sec-butyl residue unit, 2,3,4,6-tetradodeoxycinnamic acid ert-butyl residue unit, 2,3,4,6-tetradodeoxycinnamic acid cyclohexyl residue unit, 2,3,5,6-tetradodoxycinnamic acid methyl residue unit, 2,3 , 5,6-tetradodecoxycinnamic acid ethyl residue unit, 2,3,5,6-tetradodeoxycinnamic acid n-propyl residue unit, 2,3,5,6-tetradode Isopropyl oxycinnamate residue unit, 2,3,5,6-tetradodeoxycinnamic acid n-butyl residue unit, 2,3,5,6-tetradodeoxycinnamic acid sec-butyl residue Base unit, tert-butyl residue unit of 2,3,5,6-tetradodoxycinnamic acid, cyclohexyl residue unit of 2,3,5,6-tetradodoxycinnamic acid, pentadodoxysilicate Methyl cinnamate residue units, pentadodeoxy cinnamate ethyl residue units, pentad N-propyl residue unit of deoxycinnamic acid, isopropyl residue unit of pentadodeoxycinnamic acid, n-butyl residue unit of pentadodeoxycinnamic acid, sec-butyl residue unit of pentadodeoxycinnamic acid, Examples thereof include a tert-butyl residue unit of pentadodeoxycinnamic acid, a cyclohexyl residue unit of pentadodeoxycinnamic acid, and the like.

  Among these, since a high phase difference is expressed, 4-methoxycinnamic acid methyl residue unit, 4-methoxycinnamic acid ethyl unit residue, 4-methoxycinnamic acid n-propyl residue unit, 4- Isopropyl methoxycinnamate residue unit, 4-methoxycinnamic acid n-butyl residue unit, 4-methoxycinnamic acid sec-butyl residue unit, 4-methoxycinnamic acid tert-butyl residue unit and 4-methoxycinnamic acid tert-butyl residue unit A methoxycinnamate cyclohexyl residue unit is preferred, and an ethyl 4-methoxycinnamate residue unit is more preferred.

  The alkoxycinnamate ester polymer of the present invention can improve solubility and compatibility while maintaining a high out-of-plane retardation, so that the monomethyl fumarate unit, the monoethyl fumarate unit, the fumarate It preferably contains a fumaric acid monoester residue unit represented by the general formula (2) such as an acid monoisopropyl residue unit.

(Here, R ₃ represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group, or a cyclic alkyl group having 3 to 6 carbon atoms.)
The alkoxycinnamic ester polymer of the present invention may contain other monomer residue units as long as it does not exceed the scope of the present invention. Examples of other monomer residue units include: Styrene residue units such as styrene residue units and α-methylstyrene residue units; (meth) acrylic acid residue units; (meth) methyl acrylate residue units, (meth) ethyl acrylate residue units, (Meth) acrylic acid ester residue units such as butyl (meth) acrylate residue units; vinyl ester residue units such as vinyl acetate residue units and vinyl propionate residue units; acrylonitrile residue units; methacrylonitrile Residue units; vinyl ether residue units such as methyl vinyl ether residue units, ethyl vinyl ether residue units, butyl vinyl ether residue units; diethyl fumarate residue units, fumarate Fumarate residue units other than the fumaric acid monoester residue units represented by the general formula (2) such as diisopropyl residue units; N-methylmaleimide residue units, N-cyclohexylmaleimide residue units, N-phenyl Examples thereof include N-substituted maleimide residue units such as maleimide residue units; one or more selected from olefin residue units such as ethylene residue units and propylene residue units.

  Since the composition of the alkoxycinnamate ester polymer of the present invention has excellent retardation characteristics when used as a retardation film, the alkoxycinnamate residue unit is preferably 10 mol% or more. More preferably, the cinnamate residue unit is 20 mol% or more, the alkoxycinnamate residue unit is more preferably 50 mol% or more, the alkoxycinnamate residue unit is more preferably 60 mol% or more, the alkoxycinnax The acid ester residue unit of 70 mol% or more is most preferable.

  Since the alkoxycinnamate polymer of the present invention has excellent mechanical properties, the number average molecular weight in terms of standard polystyrene obtained from an elution curve measured by gel permeation chromatography (GPC). Is preferably 30,000 to 500,000, more preferably 40,000 to 400,000.

  As a method for producing the alkoxycinnamate ester polymer of the present invention, any method may be used as long as an alkoxycinnamate ester polymer is obtained. For example, radical polymerization of an alkoxycinnamate ester may be performed. It can be manufactured by doing.

  For the radical polymerization, any known polymerization method, for example, bulk polymerization method, solution polymerization method, suspension polymerization method, precipitation polymerization method or emulsion polymerization method can be employed.

  Examples of the polymerization initiator used for radical polymerization include benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, and dicumyl peroxide. , Organic peroxides such as t-butylperoxyacetate, t-butylperoxybenzoate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane; 2,2′-azobis ( 2,4-dimethylvaleronitrile), 2,2′-azobis (2-butyronitrile), 2,2′-azobisisobutyronitrile, dimethyl-2′-azobisisobutyrate, 1,1′-azobis And azo initiators such as (cyclohexane-1-carbonitrile).

  And there is no restriction | limiting in particular as a solvent which can be used in solution polymerization method, suspension polymerization method, precipitation polymerization method, emulsion polymerization method, For example, aromatic solvents, such as benzene, toluene, xylene; Methanol, ethanol, propanol, butanol, etc. Cyclohexane, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, dimethylformamide, isopropyl acetate, water and the like, and mixed solvents thereof.

  Moreover, since the polymerization temperature at the time of performing radical polymerization can be suitably set according to the decomposition temperature of the polymerization initiator and the control of the reaction is easy, it is generally performed in the range of 30 to 150 ° C. It is preferable.

  When an optical film using the alkoxycinnamic acid ester polymer of the present invention is obtained, a retardation film is preferred because it has a high out-of-plane retardation even in a thin film and is excellent in optical properties.

  In the retardation film of the present invention, the refractive index in the fast axis direction in the film plane is nx, the refractive index in the film in-plane direction perpendicular thereto is ny, and the refractive index in the thickness direction of the film is nz. A retardation film characterized in that the relationship is nx ≦ ny <nz. By satisfying nx ≦ ny <nz, the viewing angle of STN-LCD, IPS-LCD, reflective LCD, transflective LCD, etc. The retardation film is excellent in compensation performance. In general, since the control of the three-dimensional refractive index of the film is performed by stretching the film and the like, the manufacturing process and quality control are complicated. However, the retardation film of the present invention is unstretched and has a refractive index in the film thickness direction. Has been found to exhibit a unique behavior of high.

In addition, since the retardation film of the present invention becomes a retardation film having more excellent optical properties, an out-of-plane retardation (Rth) measured at a wavelength of 550 nm represented by the following formula (a) is −100 to − It is preferably 2000 nm, more preferably −100 to −500 nm, and particularly preferably −180 to −500 nm.
Rth = ((nx + ny) / 2−nz) × d (a)
(Here, d indicates the thickness of the film.)
Since the retardation film of the present invention has a high out-of-plane retardation even in a thin film, the absolute value of the relationship between the film thickness and the out-of-plane retardation is preferably 5.5 nm / film thickness (μm) or more, and 6 nm / The film thickness (μm) or more is more preferable, and 8 nm / film thickness (μm) or more is particularly preferable.

  When the retardation film of the present invention is used in a liquid crystal display device, the image quality characteristics are good, and therefore, the light transmittance is preferably 85% or more, and more preferably 90% or more. . The haze (cloudiness) of the retardation film is preferably 2% or less, more preferably 1% or less.

  There is no restriction | limiting in particular as a manufacturing method of the phase difference film of this invention, For example, methods, such as a solution cast method and a melt cast method, are mentioned.

  The solution cast method is a method in which a solution obtained by dissolving an alkoxycinnamic ester polymer in a solvent (hereinafter referred to as a dope) is cast on a support substrate, and then the solvent is removed by heating or the like to obtain a film. is there. In this case, as a method for casting the dope on the support substrate, for example, a T-die method, a doctor blade method, a bar coater method, a roll coater method, a lip coater method, or the like is used. Particularly, industrially, a method in which a dope is continuously extruded from a die onto a belt-like or drum-like support substrate is the most common. Examples of the support substrate used include a glass substrate, a metal substrate such as stainless steel and ferrotype, and a film such as polyethylene terephthalate. In the solution casting method, when forming a film having high transparency and excellent thickness accuracy and surface smoothness, the solution viscosity of the dope is an extremely important factor, preferably 10 to 20000 cPs, More preferably, it is -10000 cPs.

  In this case, the coating thickness of the alkoxycinnamic acid ester polymer is preferably 1 to 200 μm, more preferably 2 to 100 μm, and particularly preferably 3 to 50 μm after drying because the film can be easily handled.

  The melt casting method is a molding method in which an alkoxycinnamic ester polymer is melted in an extruder and extruded from a slit of a T die into a film shape, and then cooled and cooled with a roll or air.

  The retardation film of the present invention can be used by being peeled off from a glass substrate as a base material or another optical film, and can also be used as a laminate with a glass substrate as a base material or another optical film.

  The retardation film of the present invention can be laminated with a polarizing plate to be used as a circular or elliptical polarizing plate, and can be laminated with a polarizer containing polyvinyl alcohol / iodine or the like to form a polarizing plate. is there. Furthermore, the retardation films of the present invention can be laminated with each other or with other retardation films.

  In the retardation film of the present invention, an antioxidant is preferably blended in order to increase the thermal stability of the retardation film itself or during film formation. Examples of the antioxidant include hindered phenolic antioxidants, phosphorus antioxidants, and other antioxidants, and these antioxidants may be used alone or in combination. And since an antioxidant effect | action improves synergistically, it is preferable to use together a hindered antioxidant and phosphorus antioxidant, and in that case, for example with respect to 100 weight part of hindered antioxidant More preferably, the phosphorus-based antioxidant is used in a mixture of 100 to 500 parts by weight. Moreover, as addition amount of antioxidant, since it is excellent in an antioxidant effect | action with respect to 100 weight part of alkoxycinnamate type | system | group polymers which comprise the retardation film of this invention, 0.01-10 weight part is set. Preferably, 0.5 to 1 part by weight is more preferable.

  Furthermore, as an ultraviolet absorber, for example, an ultraviolet absorber such as benzotriazole, benzophenone, triazine, or benzoate may be blended as necessary.

  The retardation film of the present invention is blended with other polymers, surfactants, polymer electrolytes, conductive complexes, inorganic fillers, pigments, antistatic agents, antiblocking agents, lubricants, etc. within the scope of the invention. May be.

  According to the present invention, optical properties such as a contrast film and a viewing angle characteristic compensation film and an antireflection film of a liquid crystal display having a large refractive index in the thickness direction, a large in-plane retardation, and a small wavelength dependency. It is possible to provide an alkoxycinnamic acid ester polymer suitable for a retardation film excellent in the above.

Change in refractive index ellipsoid by stretching

    EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

  In addition, the various physical properties shown by an Example were measured with the following method.

<Composition of alkoxycinnamate polymer>
Using a nuclear magnetic resonance measuring apparatus (manufactured by JEOL, trade name JNM-GX270), it was determined by proton nuclear magnetic resonance spectroscopy ( ¹ H-NMR) spectrum analysis.

<Measurement of number average molecular weight>
Using a gel permeation chromatography (GPC) apparatus (manufactured by Tosoh Corporation, trade name C0-8011 (equipped with column GMH _HR- H)), tetrahydrofuran was measured as a solvent at 40 ° C., and the standard polystyrene equivalent value was obtained. Asked.

<Transparency evaluation method>
The total light transmittance and haze of the film were measured using a haze meter (trade name NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.).

<Measurement of refractive index>
An Abbe refractometer (manufactured by Atago) was used and measured according to JIS K 7142 (1981 version).

<Measurement of retardation and three-dimensional refractive index of film>
Measurement was performed using a fully automatic birefringence meter (trade name KOBRA-WR, manufactured by Oji Scientific Instruments).

Example 1 (Synthesis 1 of alkoxycinnamate ester polymer (methyl 4-methoxycinnamate / 4-methoxycinnamate n-butyl copolymer) 1)
In a glass ampule with a capacity of 75 mL, 50 g (0.26 mol) of methyl 4-methoxycinnamate, 15.2 g (0.065 mol) of n-butyl 4-methoxycinnamate and tert-butylperoxy which is a polymerization initiator 0.38 g (0.0022 mol) of pivalate was added, and after nitrogen substitution and depressurization were repeated, sealing was performed under reduced pressure. The ampoule was placed in a thermostatic bath at 50 ° C. and kept for 96 hours to carry out radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampoule and dissolved with 400 g of tetrahydrofuran. This polymer solution was dropped into 3 L of methanol and precipitated, and then vacuum-dried at 80 ° C. for 10 hours to obtain 15 g of an alkoxycinnamic acid ester polymer (yield: 23%).

  The obtained alkoxycinnamic acid ester polymer was excellent in productivity and thus had a high yield, and the number average molecular weight was 41,000.

Moreover, it is confirmed by ¹ H-NMR measurement that the copolymer composition is 4-methoxycinnamate methyl residue unit / 4-methoxycinnamate n-butyl residue unit = 84/16 (mol%). did.

Example 2 (Synthesis 2 of alkoxycinnamate ester polymer (ethyl 4-methoxycinnamate / diisopropyl fumarate copolymer) 2)
In a glass ampule with a capacity of 75 mL, 50 g (0.24 mol) of ethyl 4-methoxycinnamate, 20.8 g (0.10 mol) of diisopropyl fumarate and 0.40 g of tert-butyl peroxypivalate as a polymerization initiator ( 0.0023 mol) was added, and after nitrogen substitution and depressurization were repeated, the mixture was sealed under reduced pressure. The ampoule was placed in a thermostatic bath at 50 ° C. and kept for 96 hours to carry out radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampoule and dissolved with 400 g of tetrahydrofuran. This polymer solution was dropped into 3 L of methanol and precipitated, and then vacuum-dried at 80 ° C. for 10 hours to obtain 25 g of an alkoxycinnamic ester polymer (yield: 35%).

  The resulting alkoxycinnamic acid ester polymer was excellent in productivity and thus had a high yield, and the number average molecular weight was 47,000.

Moreover, it was confirmed by ¹ H-NMR measurement that the copolymer composition was 4-methoxycinnamate ethyl residue unit / diisopropyl fumarate residue unit = 54/46 (mol%).

Example 3 (Synthesis of alkoxycinnamic ester polymer (isopropyl 4-methoxycinnamate / diethyl fumarate copolymer) 3)
A glass ampule with a capacity of 75 mL was charged with 50 g (0.21 mol) of isopropyl 4-methoxycinnamate, 4.1 g (0.024 mol) of diethyl fumarate and 0.28 g of tert-butyl peroxypivalate as a polymerization initiator ( 0.0016 mol) was added, and after nitrogen substitution and depressurization were repeated, the mixture was sealed under reduced pressure. The ampoule was placed in a thermostatic bath at 50 ° C. and kept for 96 hours to carry out radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampoule and dissolved with 400 g of tetrahydrofuran. This polymer solution was dropped into 3 L of methanol and precipitated, and then vacuum dried at 80 ° C. for 10 hours to obtain 15 g of an alkoxycinnamic acid ester polymer (yield: 27%).

  The resulting alkoxycinnamic ester polymer polymer was excellent in productivity and thus had a high yield, and the number average molecular weight was 43,000.

The copolymer composition was confirmed to be 4-methoxycinnamate isopropyl residue unit / diethyl fumarate residue unit = 90/10 (mol%) by ¹ H-NMR measurement.

Example 4 (Synthesis 4 of alkoxycinnamate ester polymer (ethyl 3,4-dimethoxycinnamate copolymer / N-phenylmaleimide copolymer) 4)
A glass ampule with a capacity of 75 mL was charged with 50 g (0.23 mol) of ethyl 3,4-dimethoxycinnamate, 4.4 g (0.025 mol) of N-phenylmaleimide, and tert-butyl peroxypivalate 0 as a polymerization initiator. .29 g (0.0017 mol) was added, and after nitrogen substitution and depressurization were repeated, the mixture was sealed under reduced pressure. The ampoule was placed in a thermostat at 50 ° C. and kept for 48 hours to carry out radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampoule and dissolved with 400 g of tetrahydrofuran. This polymer solution was dropped into 3 L of methanol and precipitated, and then vacuum-dried at 80 ° C. for 10 hours to obtain 17 g of an alkoxycinnamic ester polymer (yield: 31%).

  The resulting alkoxycinnamic acid ester polymer was excellent in productivity and thus had a high yield, and the number average molecular weight was 78,000.

The copolymer composition was confirmed to be ethyl 3,4-dimethoxycinnamate residue units / N-phenylmaleimide residue units = 82/18 (mol%) by ¹ H-NMR measurement.

Example 5 (Synthesis 5 of alkoxycinnamate ester-based polymer (ethyl 4-ethoxycinnamate / ethyl acrylate copolymer) 5)
A glass ampule with a capacity of 75 mL was charged with 50 g (0.24 mol) of ethyl 4-ethoxycinnamate, 1.3 g (0.013 mol) of ethyl acrylate and 0.30 g (0 of tert-butyl peroxypivalate as a polymerization initiator). .0017 mol) was added, nitrogen substitution and depressurization were repeated, and the mixture was sealed under reduced pressure. The ampoule was placed in a thermostat at 50 ° C. and kept for 48 hours to carry out radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampoule and dissolved with 400 g of tetrahydrofuran. This polymer solution was dropped into 3 L of methanol and precipitated, and then vacuum-dried at 80 ° C. for 10 hours to obtain 9 g of an alkoxycinnamic acid ester polymer (yield: 18%).

  The resulting alkoxycinnamic acid ester polymer was excellent in productivity and thus had a high yield, and the number average molecular weight was 56,000.

The copolymer composition was confirmed by ¹ H-NMR measurement to be 4-ethoxycinnamate ethyl residue unit / ethyl acrylate residue unit = 89/11 (mol%).

Example 6 (Synthesis of alkoxycinnamic ester polymer (n-propyl 4-methoxycinnamate / monoisopropyl fumarate copolymer) 6)
A glass ampule with a capacity of 75 mL was charged with 7 g (0.03 mol) of n-propyl 4-methoxycinnamate, 43 g (0.27 mol) of monoisopropyl fumarate and 1,1 di (tert-butylperoxy) as a polymerization initiator. ) -2-methylcyclohexane 0.42 g (0.0015 mol) was added, and after nitrogen substitution and depressurization were repeated, the mixture was sealed under reduced pressure. The ampule was placed in a constant temperature bath at 70 ° C. and held for 72 hours to carry out radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampoule and dissolved with 400 g of tetrahydrofuran. This polymer solution was dropped into 3 L of methanol and precipitated, followed by vacuum drying at 80 ° C. for 10 hours to obtain an alkoxycinnamic ester polymer (yield: 20%).

  The number average molecular weight of the obtained alkoxycinnamic ester polymer was 42,000.

The copolymer composition was confirmed by ¹ H-NMR measurement to be 4-methoxycinnamic acid n-propyl residue unit / monoisopropyl fumarate residue unit = 12/88 (mol%).

Example 7 (Synthesis of alkoxycinnamic ester polymer (ethyl 2-methoxycinnamate / diethyl fumarate copolymer) 7)
In a glass ampoule having a capacity of 75 mL, 46 g (0.22 mol) of ethyl 2-methoxycinnamate, 4 g (0.02 mol) of diethyl fumarate and 2,5-dimethyl-2,5-di (2 -Ethylhexanoylperoxy) hexane 0.53g (0.0012mol) was put, and after nitrogen substitution and depressurization were repeated, it was sealed under reduced pressure. This ampoule was placed in a constant temperature bath at 60 ° C. and kept for 96 hours to carry out radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampoule and dissolved with 400 g of tetrahydrofuran. This polymer solution was dropped into 3 L of methanol and precipitated, followed by vacuum drying at 80 ° C. for 10 hours to obtain an alkoxycinnamic ester polymer (yield: 37%).

  The number average molecular weight of the obtained alkoxycinnamic ester polymer was 45,000.

The copolymer composition was confirmed by ¹ H-NMR measurement to be 2-methoxycinnamate ethyl residue unit / diethyl fumarate residue unit = 87/13 (mol%).

Example 8 (Synthesis of alkoxycinnamic ester polymer (n-propyl 2,4,6-trimethoxycinnamate / monoethyl fumarate copolymer) 8)
N-Propyl 2,4,6-trimethoxycinnamate 31 g (0.12 mol), monoethyl fumarate 19 g (0.13 mol), toluene 5 g and t-butyl which is a polymerization initiator 0.30 g (0.0017 mol) of peroxypivalate was added, and after nitrogen substitution and depressurization were repeated, the mixture was sealed under reduced pressure. The ampoule was placed in a thermostatic bath at 50 ° C. and kept for 96 hours to carry out radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampoule and dissolved with 400 g of tetrahydrofuran. This polymer solution was dropped into 3 L of methanol and precipitated, and then vacuum-dried at 80 ° C. for 10 hours to obtain an alkoxycinnamic ester polymer (yield: 29%).

  The number average molecular weight of the obtained alkoxycinnamic ester polymer was 40,000.

In addition, the copolymer composition was determined by ¹ H-NMR measurement to be 2,4,6-trimethoxycinnamic acid n-propyl residue unit / monoethyl fumarate residue unit = 51/49 (mol%). confirmed.

Synthesis Example 1 (Synthesis 1 of fumarate diester copolymer (diisopropyl fumarate / di-n-butyl fumarate copolymer) 1)
In a 1 L autoclave equipped with a stirrer, a condenser tube, a nitrogen inlet tube and a thermometer, 1.6 g of hydroxypropylmethylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd., trade name Metrose 60SH-50), 520 g of distilled water, 230 g of diisopropyl fumarate, difumarate di After adding 50 g of n-butyl and 2.1 g of t-butyl peroxypivalate which is a polymerization initiator and carrying out nitrogen bubbling for 1 hour, the suspension is kept at 50 ° C. for 24 hours while stirring at 400 rpm. Polymerization was performed. After cooling to room temperature, the resulting suspension containing the polymer particles was filtered off and washed with distilled water and methanol to obtain a fumaric acid diester copolymer. (Yield: 80%).

  The number average molecular weight of the obtained fumaric acid diester copolymer was 150,000.

The copolymer composition was confirmed to be diisopropyl fumarate residue unit / di-n-butyl fumarate residue unit = 87/13 (mol%) by ¹ H-NMR measurement.

Synthesis Example 2 (Synthesis 2 of Fumarate Diester Copolymer (Diisopropyl Fumarate / Bis-2-ethylhexyl Fumarate Copolymer 2))
In a 1 L autoclave equipped with a stirrer, a condenser tube, a nitrogen inlet tube and a thermometer, 1.6 g of hydroxypropylmethylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd., trade name Metrose 60SH-50), 520 g of distilled water, 196 g of diisopropyl fumarate, bis of fumarate 84 g of 2-ethylhexyl and 1.9 g of t-butyl peroxypivalate as a polymerization initiator were added, nitrogen bubbling was performed for 1 hour, and then the suspension was kept at 50 ° C. for 24 hours while stirring at 400 rpm. Polymerization was performed. After cooling to room temperature, the resulting suspension containing the polymer particles was filtered off and washed with distilled water and methanol to obtain a fumaric acid diester copolymer. (Yield: 66%).

  The number average molecular weight of the obtained fumaric acid diester copolymer was 86,000.

The copolymer composition was confirmed by ¹ H-NMR measurement to be diisopropyl fumarate residue unit / bis2-ethylhexyl fumarate residue unit = 84/16 (mol%).

Synthesis Example 3 (Synthesis of diisopropyl fumarate homopolymer)
After putting 50 g (0.25 mol) of diisopropyl fumarate and 0.27 g (0.0015 mol) of tert-butyl peroxypivalate as a polymerization initiator into a glass ampule with a capacity of 75 mL, and repeating nitrogen substitution and depressurization. Sealed under reduced pressure. The ampoule was placed in a thermostat at 50 ° C. and held for 36 hours to carry out radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampoule and dissolved with 400 g of tetrahydrofuran. This polymer solution was dropped into 3 L of methanol and precipitated, followed by vacuum drying at 80 ° C. for 10 hours to obtain a diisopropyl fumarate homopolymer (yield: 71%).

  The number average molecular weight of the obtained diisopropyl fumarate homopolymer was 118,000.

Synthesis Example 4 (Synthesis of monoisopropyl fumarate homopolymer)
A glass ampule with a capacity of 75 mL is charged with 50 g (0.32 mol) of monoisopropyl fumarate and 0.40 g (0.0015 mol) of 1,1 di (tert-butylperoxy) -2-methylcyclohexane as a polymerization initiator. After repeating nitrogen substitution and depressurization, the mixture was sealed in a reduced pressure state. The ampule was placed in a constant temperature bath at 70 ° C. and held for 72 hours to carry out radical polymerization. After completion of the polymerization reaction, the polymer was taken out from the ampoule and dissolved with 400 g of tetrahydrofuran. This polymer solution was dropped into 3 L of methanol and precipitated, followed by vacuum drying at 80 ° C. for 10 hours to obtain a monoisopropyl fumarate homopolymer (yield: 18%).

  The number average molecular weight of the obtained monoisopropyl fumarate homopolymer was 36,000.

Example 9
Dissolve the alkoxycinnamic acid ester polymer obtained in Example 1 in methyl isobutyl ketone to give a 20% by weight resin solution, cast on a polyethylene terephthalate film with a coater, and dry at 130 ° C. for 10 minutes. Thus, a film using an alkoxycinnamic acid ester polymer having a thickness of 30 μm was obtained.

  The obtained film had a total light transmittance of 90%, a haze of 0.5%, and a refractive index of 1.564.

  The three-dimensional refractive index is nx = 1.5605, ny = 1.5605, nz = 1.5704, and the obtained film has a large refractive index in the thickness direction of nx = ny <nz. . Further, the out-of-plane retardation Rth was negatively large at −297 nm. The ratio between the absolute value of the out-of-plane retardation and the film thickness was 9.9 nm / film thickness (μm).

  From these results, the obtained film has a negative birefringence, a large refractive index in the thickness direction, a large negative out-of-plane retardation, and a high out-of-plane retardation even in a thin film. It was suitable for a phase difference film.

Example 10
By dissolving the alkoxycinnamic acid ester polymer obtained in Example 2 in cyclohexanone to give a resin solution of 20% by weight, casting on a polyethylene terephthalate film with a coater, and drying at 150 ° C. for 10 minutes, A film using an alkoxycinnamic ester polymer having a thickness of 20 μm was obtained.

  The obtained film had a total light transmittance of 92%, a haze of 0.6%, and a refractive index of 1.517.

  The three-dimensional refractive index is nx = 1.5134, ny = 1.5134, nz = 1.5228, and the obtained film has a large refractive index in the thickness direction of nx = ny <nz. . Further, the out-of-plane retardation Rth was as negative as -188 nm. The ratio between the absolute value of the out-of-plane retardation and the film thickness was 9.4 nm / film thickness (μm).

  From these results, the obtained film has a negative birefringence, a large refractive index in the thickness direction, a large negative out-of-plane retardation, and a high out-of-plane retardation even in a thin film. It was suitable for a phase difference film.

Example 11
The alkoxycinnamic acid ester polymer obtained in Example 3 was dissolved in a toluene / methyl isobutyl ketone mixed solvent to give a 20% by weight resin solution, which was cast on a polyethylene terephthalate film by a coater, and 10% at 130 ° C. By partial drying, a film using an alkoxycinnamic ester polymer having a thickness of 20 μm was obtained.

  The obtained film had a total light transmittance of 91%, a haze of 0.6%, and a refractive index of 1.529.

  The three-dimensional refractive index was nx = 1.5259, ny = 1.5259, nz = 1.5361, and the obtained film showed a large value of the refractive index in the thickness direction of nx = ny <nz. . Further, the out-of-plane retardation Rth was as negative as −204 nm. The ratio between the absolute value of the out-of-plane retardation and the film thickness was 10.2 nm / film thickness (μm).

  From these results, the obtained film has a negative birefringence, a large refractive index in the thickness direction, a large negative out-of-plane retardation, and a high out-of-plane retardation even in a thin film. It was suitable for a phase difference film.

Example 12
The alkoxycinnamic ester polymer obtained in Example 4 was dissolved in a toluene / methyl ethyl ketone mixed solvent to give a 20% by weight resin solution, cast on a polyethylene terephthalate film with a coater, and dried at 110 ° C. for 10 minutes. As a result, a film using an alkoxycinnamic ester polymer having a thickness of 30 μm was obtained.

  The obtained film had a total light transmittance of 90%, a haze of 0.7%, and a refractive index of 1.563.

  The three-dimensional refractive index was nx = 1.5602, ny = 1.5602, nz = 1.5689, and the obtained film showed a large value of the refractive index in the thickness direction of the film, nx = ny <nz. . Further, the out-of-plane retardation Rth was as negative as −261 nm. The ratio between the absolute value of the out-of-plane retardation and the film thickness was 8.7 nm / film thickness (μm).

  From these results, the obtained film has a negative birefringence, a large refractive index in the thickness direction, a large negative out-of-plane retardation, and a high out-of-plane retardation even in a thin film. It was suitable for a phase difference film.

Example 13
By dissolving the alkoxycinnamate-based polymer obtained in Example 5 in tetrahydrofuran to give a resin solution of 20% by weight, casting on a polyethylene terephthalate film with a coater, and drying at 70 ° C. for 10 minutes, A film using an alkoxycinnamic ester polymer having a thickness of 25 μm was obtained.

  The obtained film had a total light transmittance of 91%, a haze of 0.5%, and a refractive index of 1.545.

  The three-dimensional refractive index is nx = 1.5420, ny = 1.5420, nz = 1.5506, and the obtained film has a large refractive index in the thickness direction of nx = ny <nz. . Further, the out-of-plane retardation Rth was as negative as −215 nm. The ratio between the absolute value of the out-of-plane retardation and the film thickness was 8.6 nm / film thickness (μm).

  From these results, the obtained film has a negative birefringence, a large refractive index in the thickness direction, a large negative out-of-plane retardation, and a high out-of-plane retardation even in a thin film. It was suitable for a phase difference film.

Example 14
Dissolve the alkoxycinnamic acid ester polymer obtained in Example 6 in cyclopentanone to give a 20% by weight resin solution, cast on a polyethylene terephthalate film with a coater, and dry at 120 ° C. for 10 minutes. As a result, a film using an alkoxycinnamic ester polymer having a thickness of 25 μm was obtained.

  The obtained film had a total light transmittance of 94%, a haze of 0.5%, and a refractive index of 1.427.

  The three-dimensional refractive index was nx = 1.4242, ny = 1.4242, nz = 1.4323, and the obtained film exhibited a large value of refractive index in the thickness direction of nx = ny <nz. . Further, the out-of-plane retardation Rth was as negative as −203 nm. The ratio between the absolute value of the out-of-plane retardation and the film thickness was 8.1 nm / film thickness (μm).

  From these results, the obtained film has a negative birefringence, a large refractive index in the thickness direction, a large negative out-of-plane retardation, and a high out-of-plane retardation even in a thin film. It was suitable for a phase difference film.

Example 15
By dissolving the alkoxycinnamic acid ester polymer obtained in Example 7 in cyclohexanone to give a resin solution of 20% by weight, casting it on a polyethylene terephthalate film with a coater, and drying at 130 ° C. for 10 minutes, A film using an alkoxycinnamic ester polymer having a thickness of 25 μm was obtained.

  The obtained film had a total light transmittance of 91%, a haze of 0.4%, and a refractive index of 1.543.

  The three-dimensional refractive index was nx = 1.5397, ny = 1.5397, nz = 1.5506, and the obtained film exhibited a large value of the refractive index in the thickness direction of nx = ny <nz. . Further, the out-of-plane phase difference Rth was as negative as −273 nm. The ratio between the absolute value of the out-of-plane retardation and the film thickness was 10.9 nm / film thickness (μm).

  From these results, the obtained film has a negative birefringence, a large refractive index in the thickness direction, a large negative out-of-plane retardation, and a high out-of-plane retardation even in a thin film. It was suitable for a phase difference film.

Example 16
Dissolve the alkoxycinnamic ester polymer obtained in Example 8 in methyl isobutyl ketone to give a 20% by weight resin solution, cast on a polyethylene terephthalate film with a coater, and dry at 130 ° C. for 10 minutes. As a result, a film using an alkoxycinnamic ester polymer having a thickness of 25 μm was obtained.

  The obtained film had a total light transmittance of 93%, a haze of 0.5%, and a refractive index of 1.473.

  The three-dimensional refractive index is nx = 1.4699, ny = 1.4699, nz = 1.4793, and the obtained film has a large refractive index in the thickness direction of nx = ny <nz. . Further, the out-of-plane retardation Rth was as negative as −235 nm. The ratio between the absolute value of the out-of-plane retardation and the film thickness was 9.4 nm / film thickness (μm).

  From these results, the obtained film has a negative birefringence, a large refractive index in the thickness direction, a large negative out-of-plane retardation, and a high out-of-plane retardation even in a thin film. It was suitable for a phase difference film.

Comparative Example 1
The fumaric acid diester copolymer obtained in Synthesis Example 1 was dissolved in a toluene / methyl ethyl ketone = 50/50 mixed solvent to form a 20% by weight resin solution, which was cast on a polyethylene terephthalate film by a coater, at 70 ° C. A film having a thickness of 30 μm was obtained by drying for 10 minutes.

  The obtained film had a total light transmittance of 92%, a haze of 0.6%, and a refractive index of 1.472.

  The three-dimensional refractive index was nx = 1.4712, ny = 1.4712, nz = 1.4743, and the obtained film had a large refractive index in the thickness direction of nx = ny <nz. However, the out-of-plane retardation was as small as -93 nm, and the ratio between the absolute value of the out-of-plane retardation and the film thickness was as small as 3.1 nm / film thickness (μm).

Comparative Example 2
The fumaric acid diester copolymer obtained in Synthesis Example 2 was dissolved in a toluene / methyl ethyl ketone = 50/50 mixed solvent to form a 20 wt% resin solution, which was cast on a polyethylene terephthalate film by a coater, at 70 ° C. A film having a thickness of 30 μm was obtained by drying for 10 minutes.

  The obtained film had a total light transmittance of 92%, a haze of 0.6%, and a refractive index of 1.473.

  The three-dimensional refractive index was nx = 1.4723, ny = 1.4723, nz = 1.4738, and the obtained film had a large refractive index in the thickness direction of nx = ny <nz. However, the out-of-plane retardation was as small as −45 nm, and the ratio between the absolute value of the out-of-plane retardation and the film thickness was also as small as 1.5 nm / film thickness (μm).

Comparative Example 3
The diisopropyl fumarate homopolymer obtained in Synthesis Example 3 was dissolved in tetrahydrofuran to give a 22% by weight resin solution, cast on a polyethylene terephthalate film with a coater, and dried at 70 ° C. for 10 minutes to obtain a thickness of 21 μm. Film was obtained.

  The obtained film had a total light transmittance of 93%, a haze of 0.3% and a refractive index of 1.468.

  The three-dimensional refractive index is nx = 1.46889, ny = 1.4689, nz = 1.4723, and the obtained film has a large refractive index in the thickness direction of nx = ny <nz. However, the out-of-plane retardation Rth was as small as −71 nm, and the ratio between the absolute value of the out-of-plane retardation and the film thickness was as small as 3.4 nm / film thickness (μm).

  From these results, the obtained film had negative birefringence and a large refractive index in the thickness direction, but the out-of-plane retardation was small, and even a thin film could not be expected to have a high out-of-plane retardation. Met.

Comparative Example 4
The monoisopropyl fumarate homopolymer obtained in Synthesis Example 4 was dissolved in cyclopentanone to give a 20 wt% resin solution, cast on a polyethylene terephthalate film with a coater, and dried at 120 ° C. for 10 minutes. A film having a thickness of 25 μm was obtained.

  The obtained film had a total light transmittance of 94%, a haze of 0.6%, and a refractive index of 1.410.

  The three-dimensional refractive index is nx = 1.4087, ny = 1.4087, nz = 1.4126, and the obtained film has a large refractive index in the thickness direction of nx = ny <nz. However, the out-of-plane retardation Rth was as small as −97 nm, and the ratio between the absolute value of the out-of-plane retardation and the film thickness was as small as 3.9 nm / film thickness (μm).

  From these results, the obtained film had negative birefringence and a large refractive index in the thickness direction, but the out-of-plane retardation was small, and even a thin film could not be expected to have a high out-of-plane retardation. Met.

nx: Refractive index in the fast axis direction in the film plane.
ny: Refractive index in the film in-plane direction orthogonal to nx.
nz: The refractive index in the thickness direction of the film.

Claims (9)

An alkoxycinnamic ester polymer comprising at least an alkoxycinnamic acid ester residue unit represented by the general formula (1).

(Here, R ₁ represents a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group, and R ₂ represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group, or 3 carbon atoms. ) Represents a cyclic alkyl group of -6, and n represents an integer of 1-5. The alkoxycinnamate ester polymer according to claim 1, comprising 10 mol% or more of an alkoxycinnamate residue unit represented by the general formula (1). The alkoxycinnamate ester polymer according to claim 1 or 2, comprising a fumaric acid monoester residue unit represented by the general formula (2).

(Here, R ₃ represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group, or a cyclic alkyl group having 3 to 6 carbon atoms.) The number average molecular weight of standard polystyrene conversion is 30,000-500,000, The alkoxycinnamate polymer in any one of Claims 1-3 characterized by the above-mentioned. The alkoxycinnamate residue unit is one or more residue units selected from a methoxycinnamate residue unit and an ethoxycinnamate residue unit. The alkoxycinnamate ester polymer according to any one of the above. 6. The alkoxycinnamic acid ester polymer according to claim 1, wherein the alkoxycinnamic acid ester residue unit is a 4-methoxycinnamic acid ester residue unit. The alkoxycinnamate residue unit is 4-methoxycinnamate methyl residue unit, 4-methoxycinnamate ethyl residue unit, 4-methoxycinnamic acid n-propyl residue unit, 4-methoxycinnamate Isopropyl residue unit, 4-methoxycinnamic acid n-butyl residue unit, 4-methoxycinnamic acid sec-butyl residue unit, 4-methoxycinnamic acid tert-butyl residue unit and 4-methoxycinnamic leather unit The alkoxycinnamic acid ester polymer according to any one of claims 1 to 6, wherein the alkoxycinnamic acid ester polymer is selected from the group consisting of acid cyclohexyl residue units. A retardation film using the alkoxycinnamate polymer according to any one of claims 1 to 7. The relationship when the refractive index in the fast axis direction in the film plane is nx, the refractive index in the film in-plane direction orthogonal to it is ny, and the refractive index in the thickness direction of the film is nz is nx ≦ ny <nz. The retardation film according to claim 8, wherein the retardation film is present.

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