JP2016145290A - Alkoxycinnamic acid ester-acrylate copolymer and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel alkoxycinnamic acid ester-acrylate copolymer with high molecular weight having excellent toughness even when making a film and an efficient manufacturing method.SOLUTION: There is provided an alkoxycinnamic acid ester-acrylate copolymer containing an alkoxycinnamic acid ester unit and polyfunctional acrylate unit having a urethane bond and optionally a fumaric diester unit or an N-substituted maleimide unit as other monomers. There is provided a manufacturing method of the alkoxycinnamic acid ester-acrylate copolymer by conducting a radical polymerization reaction of 100 mol% of total monomer containing the alkoxycinnamic acid ester of 50 to 99.99 mol%, the polyfunctional acrylate unit having the urethane bond of 0.01 to 1 mol% and other monomers of 0 to 49.99 mol% in a presence of a radical polymerization initiator of 0.001 to 5 mol%. There is provided the alkoxycinnamic acid ester-acrylate copolymer having weight average molecular weight in terms of standard polystyrene of 120000 to 1000000.SELECTED DRAWING: None

Description

  The present invention relates to a novel alkoxycinnamate-acrylate copolymer and a method for producing the same, and more specifically, a novel alkoxycinnamate having a high molecular weight that can be applied to a film having excellent toughness. The present invention relates to an ester-acrylate copolymer and a method for efficiently producing the same.

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.
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. For example, a super twist nematic liquid crystal display (STN-LCD) or a vertical alignment liquid crystal display (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. Further, even when the film is a thin film, there is a demand for a polymer that exhibits a high out-of-plane retardation while maintaining the properties as a film.

  An object of the present invention is to provide a novel high-molecular-weight alkoxycinnamate-acrylate copolymer that exhibits a high retardation in a thin film even when used as a film and has excellent toughness, and a method for efficiently producing the same. There is to do.

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

  That is, the present invention includes an alkoxycinnamic acid ester-acrylate characterized by comprising an alkoxycinnamic acid ester residue unit represented by the general formula (1) and a polyfunctional acrylate residue unit having a urethane bond. The present invention relates to a copolymer and a method for producing the same.

（ここで、Ｒ_１は炭素数１〜１２の直鎖状アルキル基または分岐状アルキル基を示し、Ｒ_２は炭素数１〜１２の直鎖状アルキル基、分岐状アルキル基、または炭素数３〜６の環状アルキル基を示し、ｎは１〜５の整数を示す。）
以下、本発明のアルコキシケイ皮酸エステル−アクリレート共重合体について詳細に説明する。

(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-acrylate copolymer of the present invention will be described in detail.

  The alkoxycinnamate-acrylate copolymer of the present invention comprises an alkoxycinnamate containing an alkoxycinnamate residue unit represented by the general formula (1) and a polyfunctional acrylate residue unit having a urethane bond. It is an acid ester-acrylate copolymer. And the alkoxycinnamate-acrylate copolymer of the present invention comprises a specific alkoxycinnamate residue unit, so that a high out-of-plane retardation is expressed even in a thin film. To do. In addition, the alkoxycinnamate-acrylate copolymer of the present invention contains the alkoxycinnamate residue unit, so that the polymerization pass rate of the monomer when it becomes a polymer is high, and the production It is characterized by excellent properties.

（ここで、Ｒ_１は炭素数１〜１２の直鎖状アルキル基または分岐状アルキル基を示し、Ｒ_２は炭素数１〜１２の直鎖状アルキル基、分岐状アルキル基、または炭素数３〜６の環状アルキル基を示し、ｎは１〜５の整数を示す。）
本発明の一般式（１）におけるＲ_１は炭素数１〜１２の直鎖状または分岐状のアルキル基を示し、例えば、メチル基、エチル基、プロピル基、イソプピル基、ヘキシル基、ドデシル基等が挙げられ、ｎは１〜５の整数である。また、本発明の一般式（１）におけるＲ_２は、炭素数１〜１２の直鎖状アルキル基、分岐状アルキル基、または炭素数３〜６の環状アルキル基を示し、炭素数１〜１２の直鎖状アルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基等が挙げられ、炭素数１〜１２の分岐状アルキル基としては、例えば、イソプロピル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基等が挙げられ、炭素数３〜６の環状アルキル基としては、例えば、シクロプロピル基、シクロブチル基、シクロヘキシル基等が挙げられる。これらの中でも、アルコキシケイ皮酸エステル−アクリレート共重合体が高い面外位相差を発現することから、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、シクロヘキシル基が好ましい。

(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-acrylate copolymer exhibits a high out-of-plane retardation, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, A tert-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 unit, 3,5-dimethoxycinnamate n-propyl residue unit, 3,5-dimethoxycinnamate isopropyl residue unit, 3,5-dimethoxycinnamate n-butyl residue unit, 3,5-dimethoxycinnamic acid sec-butyl residue unit, 3,5-dimethoxycinnamic acid tert-butyl residue unit, 3,5-dimethoxycinnamic acid cyclohexyl residue unit, -Methyl trimethoxycinnamate residue unit, ethyl 2,3,4-trimethoxycinnamate residue unit, 2,3,4-trimethoxycinnamic acid n-propyl residue unit, 2,3,4 -Isopropyl trimethoxycinnamate residue unit, n-butyl residue unit of 2,3,4-trimethoxycinnamic acid, sec-butyl residue unit of 2,3,4-trimethoxycinnamic acid, 2,3 , 4-trimethoxycinnamic acid tert-butyl residue unit, 2,3,4-trimethoxycinnamic acid cyclohexyl residue unit, 2,3,5-trimethoxycinnamic acid methyl residue unit, 2,3 , 5-trimethoxycinnamic acid ethyl residue unit, 2,3,5-trimethoxycinnamic acid n-propyl residue unit, 2,3,5-trimethoxycinnamic acid isopropyl residue unit, 2,3 , 5-Trimethoxycinnamate n-butyl residue Unit, sec-butyl residue unit of 2,3,5-trimethoxycinnamic acid, tert-butyl residue unit of 2,3,5-trimethoxycinnamic acid, cyclohexyl 2,3,5-trimethoxycinnamic acid Residue unit, methyl 2,3,6-trimethoxycinnamate residue unit, ethyl 2,3,6-trimethoxycinnamate residue unit, n-propyl 2,3,6-trimethoxycinnamate 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-trimethoxycinnamate tert-butyl residue unit, 2,3,6-trimethoxycinnamate cyclohexyl residue unit, 2,4,5-trimethoxycinnamate Acid methyl residue unit, 2,4,5-tri Toxic ethyl cinnamate residue unit, 2,4,5-trimethoxy cinnamate 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 unit of trimethoxycinnamate, isopropyl residue unit of 2,4,6-trimethoxycinnamate, n-butyl residue unit of 2,4,6-trimethoxycinnamate, 2,4,6 6-trimethoxycinnamate sec-butyl residue Unit, tert-butyl residue unit of 2,4,6-trimethoxycinnamate, cyclohexyl residue unit of 2,4,6-trimethoxycinnamate, methyl residue of 3,4,5-trimethoxycinnamate Unit, ethyl 3,4,5-trimethoxycinnamate residue unit, 3,4,5-trimethoxycinnamic acid n-propyl residue unit, 3,4,5-trimethoxycinnamic acid isopropyl residue Unit: 3,4,5-trimethoxycinnamic acid n-butyl residue unit, 3,4,5-trimethoxycinnamic acid sec-butyl residue unit, 3,4,5-trimethoxycinnamic acid tert -Butyl residue unit, 3,4,5-trimethoxycinnamate cyclohexyl residue unit, 2,3,4,5-tetramethoxymethyl cinnamate residue unit, 2,3,4,5-tetramethoxy Ethyl cinnamate residue units, 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-tetramethoxycinnamate n-propyl residue unit, 2,3,4,6-tetramethoxycinnamate isopropyl residue unit, 2,3,4,6-tetramethoxycinnamate n-butyl Residue unit, 2,3,4,6-tetrameth Cinnamic acid sec-butyl residue unit, 2,3,4,6-tetramethoxycinnamic acid tert-butyl residue unit, 2,3,4,6-tetramethoxycinnamic acid 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 unit, 2,3,5,6-tetramethoxycinnamic acid tert-butyl residue unit, 2,3,5,6-tetramethoxycinnamic acid cyclohexyl residue unit, Methyl pentamethoxycinnamate residue Unit, ethyl pentamethoxycinnamate residue unit, pentamethoxycinnamic acid n-propyl residue unit, pentamethoxycinnamate isopropyl residue unit, pentamethoxycinnamate n-butyl residue unit, pentamethoxycinnamate Examples include acid sec-butyl residue units, pentamethoxycinnamate tert-butyl residue units, pentamethoxycinnamate cyclohexyl residue units, 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 Methyl cinnamate residue unit, 2,3,4-triethoxyethyl cinnamate residue unit, 2,3,4-triethoxycinnamic acid n-propyl residue unit, 2,3,4-triethoxy Isopropyl cinnamate residue unit, 2,3,4-triethoxycinnamic acid n-butyl residue unit, 2,3,4-triethoxycinnamic acid sec-butyl residue unit, 2,3,4 Tert-butyl triethoxycinnamate residue unit, cyclohexyl residue unit of 2,3,4-triethoxycinnamic acid, methyl residue unit of 2,3,5-triethoxycinnamic acid, 2,3,5- Ethyl triethoxycinnamate residue units, 2,3,5-triethoxycinnamic acid n-propyl residue units, 2,3,5-triethoxycinnamic acid isopropyl residue units, 2,3,5- N-butyl triethoxycinnamate units, 2, 3, 5 -Sec-butyl residue unit of triethoxycinnamic acid, tert-butyl residue unit of 2,3,5-triethoxycinnamic acid, cyclohexyl residue unit of 2,3,5-triethoxycinnamic acid, 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 unit, 2,3,6-triethoxycinnamic acid cyclohexyl residue unit, 2,4,5-triethoxycinnamic acid methyl residue unit, 2 , 4,5-Triethoxycinnamic acid Chill residue unit, 2,4,5-triethoxycinnamic acid n-propyl residue unit, 2,4,5-triethoxycinnamic acid isopropyl residue unit, 2,4,5-triethoxycinnamic acid n-butyl residue unit, 2,4,5-triethoxycinnamic acid sec-butyl residue unit, 2,4,5-triethoxycinnamic acid tert-butyl residue unit, 2,4,5-tri Ethoxycinnamate cyclohexyl residue unit, 2,4,6-triethoxycinnamic acid methyl residue unit, 2,4,6-triethoxycinnamic acid ethyl residue unit, 2,4,6-triethoxysilicate N-propyl cinnamate residue unit, isopropyl residue unit of 2,4,6-triethoxycinnamic acid, n-butyl residue unit of 2,4,6-triethoxycinnamic acid unit, 2,4,6-tri Ethoxycinnamic acid sec-butyl residue unit, 2, 4, -Tert-butyl triethoxycinnamate residue unit, cyclohexyl residue unit of 2,4,6-triethoxycinnamic acid, methyl residue unit of 3,4,5-triethoxycinnamic acid residue, 3,4,5 -Ethyl triethoxycinnamate residue units, 3,4,5-triethoxycinnamic acid n-propyl residue units, 3,4,5-triethoxycinnamic acid isopropyl residue units, 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, 3 , 4,5-Triethoxycinnamic acid cyclohexyl residue unit, 2,3,4,5-tetraethoxycinnamic acid methyl residue unit, 2,3,4,5-tetraethoxycinnamic acid ethyl residue unit 2,3,4,5-tetraethoxy N-propyl cinnamate residue unit, 2,3,4,5-tetraethoxycinnamic acid isopropyl residue unit, 2,3,4,5-tetraethoxycinnamic acid n-butyl residue unit, 2, 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-tetraethoxycinnamic acid se -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-tetraethoxycinnamic leather Acid sec-butyl residue unit, 2,3,5,6-tetraethoxycinnamic acid tert-butyl residue unit, 2,3,5,6-tetraethoxycinnamic acid cyclohexyl residue unit, pentaethoxycinnamic Methyl acid residue unit, pentae Ethyl xycinnamate 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, n-butyl residue unit of 3,5-dipropoxycinnamic acid, 3,5-dipropoxysilicate Cinnaic acid sec- Chill residue unit, 3,5-dipropoxycinnamate tert-butyl residue unit, 3,5-dipropoxycinnamate cyclohexyl residue unit, 2,3,4-tripropoxycinnamate methyl 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-tripropoxycinnamic acid n-butyl residue unit, 2,3,4-tripropoxycinnamic acid sec-butyl residue unit, 2,3,4-tripropoxycinnamic acid tert- Butyl residue unit, 2,3,4-tripropoxycinnamic acid cyclohexyl residue unit, 2,3,5-tripropoxycinnamic acid methyl residue unit, 2,3,5-tripropoxycinnamic acid ethyl residue Base unit, 2, 3,5-tripropoxycinnamic acid n-propyl 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 unit, 2,3,5-tripropoxycinnamic acid tert-butyl residue unit, 2,3,5-tripropoxycinnamic acid cyclohexyl residue unit Unit, 2,3,6-tripropoxycinnamate methyl residue unit, 2,3,6-tripropoxycinnamate ethyl residue unit, 2,3,6-tripropoxycinnamate n-propyl residue Unit, isopropyl residue unit of 2,3,6-tripropoxycinnamic acid, n-butyl residue unit of 2,3,6-tripropoxycinnamic acid, sec-butyl 2,3,6-tripropoxycinnamic acid Residue units, 2, , 6-tripropoxycinnamate tert-butyl residue unit, 2,3,6-tripropoxycinnamate cyclohexyl residue unit, 2,4,5-tripropoxycinnamate methyl residue unit, 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 n-butyl residue unit, 2,4,5-tripropoxycinnamic acid sec-butyl residue unit, 2,4,5-tripropoxycinnamic acid tert-butyl residue unit 2,4,5-tripropoxycinnamic acid cyclohexyl residue unit, 2,4,6-tripropoxycinnamic acid methyl residue unit, 2,4,6-tripropoxycinnamic acid ethyl residue unit, 2 , 4,6 N-propyl residue unit of tripropoxycinnamic acid, isopropyl residue unit of 2,4,6-tripropoxycinnamic acid, n-butyl residue unit of 2,4,6-tripropoxycinnamic acid, 2,4,4 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-tripropoxycinnamate methyl residue unit, 3,4,5-tripropoxycinnamate ethyl residue unit, 3,4,5-tripropoxycinnamate n-propyl 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- Tert-butyl tripropoxycinnamate residue unit, 3,4,5-tripropoxycinnamate cyclohexyl residue unit, 2,3,4,5-tetrapropoxycinnamate methyl residue unit, 2,3,5 4,5-tetrapropoxycinnamic acid ethyl residue unit, 2,3,4,5-tetrapropoxycinnamic acid n-propyl residue unit, 2,3,4,5-tetrapropoxycinnamic acid isopropyl 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 units, 2,3,4,5-tetrapropoxycinnamate cyclohexyl residue units, 2,3,4,6-tetrapropoxycinnamate methyl residue units, 2, 3,4,6 Ethyl tetrapropoxycinnamate residue units, 2,3,4,6-tetrapropoxycinnamate n-propyl residue units, 2,3,4,6-tetrapropoxycinnamate isopropyl residue units, 2, 3,4,6-tetrapropoxycinnamate n-butyl residue units, 2,3,4,6-tetrapropoxycinnamate sec-butyl residue units, 2,3,4,6-tetrapropoxycinnax Acid tert-butyl residue unit, 2,3,4,6-tetrapropoxycinnamate cyclohexyl residue unit, 2,3,5,6-tetrapropoxycinnamate methyl residue unit, 2,3,5 6-tetrapropoxycinnamic acid ethyl residue unit, 2,3,5,6-tetrapropoxycinnamic acid n-propyl residue unit, 2,3,5,6-tetrapropoxycinnamic acid 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-tetrapropoxycinnamic acid tert-butyl Residue unit, cyclohexyl residue unit of 2,3,5,6-tetrapropoxycinnamate, methyl residue unit of pentapropoxycinnamate, ethyl residue unit of pentapropoxycinnamate, n-propyl pentapropoxycinnamate Residual unit, isopropyl pentapropoxycinnamate residue unit, n-butyl pentapropoxycinnamate residue unit, sec-butyl pentapropoxycinnamate residue unit, tert-butyl pentapropoxycinnamate residue unit, Examples include a cyclohexyl residue unit of pentapropoxycinnamic acid.

  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, methyl 3,5-dihexoxycinnamate residue unit, ethyl 3,5-dihexoxycinnamate residue unit, n-propyl residue unit of 3,5-dihexoxycinnamic acid residue, isopropyl 3,5-dihexoxycinnamate residue Base unit, n-butyl residue unit of 3,5-dihexoxycinnamic acid, sec- 3,5-dihexoxycinnamic acid sec- Til residue unit, 3,5-dihexoxycinnamate tert-butyl residue unit, 3,5-dihexoxycinnamate cyclohexyl residue unit, 2,3,4-trihexoxycinnamate methyl residue unit, 2, 3,4-trihexoxycinnamic acid ethyl residue unit, 2,3,4-trihexoxycinnamic acid n-propyl 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 unit, 2,3,4-trihexoxycinnamic leather Acid tert-butyl residue unit, 2,3,4-trihexoxycinnamate cyclohexyl residue unit, 2,3,5-trihexoxycinnamate methyl residue unit, 2,3,5-trihex Soxycinnamate ethyl residue unit, 2, 3,5-trihexoxycinnamic acid n-propyl residue unit, 2,3,5-trihexoxycinnamic acid isopropyl residue unit, 2,3,5-trihexoxycinnamic acid n-butyl residue Base unit, 2,3,5-trihexycinnamic acid sec-butyl residue unit, 2,3,5-trihexycinnamic acid tert-butyl residue unit, 2,3,5-trihexoxy Cyclohexyl cinnamate residue unit, 2,3,6-trihexoxycinnamic acid methyl residue unit, 2,3,6-trihexoxycinnamic acid ethyl residue unit, 2,3,6-trihex N-propyl residue unit of oxycinnamic acid, isopropyl residue unit of 2,3,6-trihexoxycinnamic acid, n-butyl residue unit of 2,3,6-trihexycinnamic acid, 2,3 , 6-trihexoxycinnamic acid sec-butyl residue unit, 2, , 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-trihexoxycinnamic acid isopropyl residue Base unit, 2,4,5-trihexoxycinnamic acid n-butyl residue unit, 2,4,5-trihexoxycinnamic acid sec-butyl residue unit, 2,4,5-trihexoxy Tert-butyl cinnamate residue unit, 2,4,5-trihexoxycinnamic acid cyclohexyl residue unit, 2,4,6-trihexoxycinnamic acid methyl residue unit, 2,4,6- Ethyl trihexoxycinnamate residue units, 2, 4, 6 N-propyl residue unit of trihexoxycinnamic acid, isopropyl residue unit of 2,4,6-trihexoxycinnamic acid, n-butyl residue unit of 2,4,6-trihexycinnamic acid 2 , 4,6-trihexoxycinnamic acid sec-butyl residue unit, 2,4,6-trihexoxycinnamic acid tert-butyl residue unit, 2,4,6-trihexoxycinnamic acid cyclohexyl Residue units, methyl units of 3,4,5-trihexoxycinnamic acid residues, ethyl units of 3,4,5-trihexoxycinnamic acid residues, 3,4,5-trihexoxycinnamic acid n-propyl residue unit, 3,4,5-trihexoxycinnamate isopropyl residue unit, 3,4,5-trihexoxycinnamate n-butyl residue unit, 3,4,5-tri Hexoxycinnamic acid sec-butyl residue unit, 3,4,5- Tert-butyl trihexoxycinnamate residue unit, 3,4,5-trihexoxycinnamic acid cyclohexyl residue unit, 2,3,4,5-tetrahexoxycinnamic acid methyl residue unit, 2 , 3,4,5-tetrahexoxycinnamic acid ethyl residue unit, 2,3,4,5-tetrahexoxycinnamic acid n-propyl residue unit, 2,3,4,5-tetrahexoxy Isopropyl cinnamate residue unit, 2,3,4,5-tetrahexoxycinnamic acid n-butyl residue unit, 2,3,4,5-tetrahexoxycinnamic acid sec-butyl residue unit, 2,3,4,5-tetrahexoxycinnamate tert-butyl residue unit, 2,3,4,5-tetrahexoxycinnamate cyclohexyl residue unit, 2,3,4,6-tetrahex Methyl oxycinnamate residue unit, 2,3,4,6 Tetrahexoxycinnamate ethyl residue unit, 2,3,4,6-tetrahexoxycinnamate n-propyl residue unit, 2,3,4,6-tetrahexoxycinnamate 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 -Tert-butyl tetrahexoxycinnamate residue unit, 2,3,4,6-tetrahexoxycinnamate cyclohexyl residue unit, methyl 2,3,5,6-tetrahexoxycinnamate residue Unit, 2,3,5,6-tetrahexoxycinnamic acid ethyl residue unit, 2,3,5,6-tetrahexoxycinnamic acid n-propyl residue unit, 2,3,5,6- Tetrahexoxycinnamate isopropyl residue units, 2, 3, 5 6-tetrahexoxycinnamic acid n-butyl residue unit, 2,3,5,6-tetrahexycinnamic acid sec-butyl residue unit, 2,3,5,6-tetrahexycinnamic acid tert-butyl residue unit, 2,3,5,6-tetrahexoxycinnamate cyclohexyl residue unit, pentahexoxycinnamate methyl residue unit, pentahexoxycinnamate ethyl residue unit, pentahex Soxycinnamic acid n-propyl residue unit, pentahexoxycinnamic acid isopropyl residue unit, pentahexoxycinnamic acid n-butyl residue unit, pentahexoxycinnamic acid sec-butyl residue unit, pentahex Examples thereof include tert-butyl residue unit of oxycinnamic acid and cyclohexyl residue unit of pentahexoxycinnamic acid.

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, 3,5-didodeoxycinnamic acid n-butyl residue unit, 3,5-didodeoxycinnamic acid sec- Chill residue unit, 3,5-didodeoxycinnamic acid tert-butyl residue unit, 3,5-didodoxycinnamic acid cyclohexyl residue unit, 2,3,4-tridodoxycinnamic acid methyl residue unit, 2 , 3,4-tridodeoxycinnamic acid ethyl residue unit, 2,3,4-tridodoxycinnamic acid n-propyl residue unit, 2,3,4-tridodeoxycinnamic acid unit Isopropyl residue unit, 2,3,4-tridodoxycinnamic acid n-butyl residue unit, 2,3,4-tridodeoxycinnamic acid sec-butyl residue unit, 2,3,4 -Tert-butyl tridodoxycinnamate residue unit, 2,3,4-tridodoxycinnamic acid cyclohexyl residue unit, 2,3,5-tridodoxycinnamic acid methyl residue unit 2,3,5-tridodoxy ethylcinnamate residue units, 2, 3,5-tridodeoxycinnamic acid n-propyl residue unit, 2,3,5-tridodoxycinnamic acid isopropyl residue unit, 2,3,5-tridodeoxycinnamic acid n -Butyl residue unit, 2,3,5-tridodoxycinnamic acid sec-butyl residue unit, 2,3,5-tridodeoxycinnamic acid tert-butyl residue unit, 2,3, 5-tridodeoxycinnamic acid cyclohexyl residue unit, 2,3,6-tridodoxycinnamic acid methyl residue unit, 2,3,6-tridodoxycinnamic acid ethyl residue unit, 2,3,6-tridodoxycinnamic acid n-propyl residue unit, 2,3,6-tridodeoxycinnamic acid isopropyl residue unit, 2,3,6-tridodeoxycinnamic leather Acid n-butyl residue unit, 2,3,6-tridodoxycinnamic acid sec-butyl residue unit, 2, , 6-tridodeoxycinnamic acid tert-butyl residue unit, 2,3,6-tridodeoxycinnamic acid cyclohexyl residue unit, 2,4,5-tridodeoxycinnamic acid methyl residue Basic unit, 2,4,5-tridodeoxycinnamic acid ethyl residue unit, 2,4,5-tridodoxycinnamic acid n-propyl residue unit, 2,4,5-tridode Isopropyl cinnamate residue units, 2,4,5-tridodecoxycinnamic acid n-butyl residue units, 2,4,5-tridodoxycinnamic acid sec-butyl residue units, 2 , 4,5-Tridodeoxycinnamic acid tert-Butyl residue unit, 2,4,5-Tridodoxycinnamic acid cyclohexyl residue unit, 2,4,6-Tridodoxycinnamic acid Methyl residue unit, 2,4,6-tridodoxycinnamic acid ethyl residue unit, 2,4,6 Tridodeoxycinnamic acid n-propyl residue unit, 2,4,6-tridodoxycinnamic acid isopropyl residue unit, 2,4,6-tridodoxycinnamic acid n-butyl residue Unit, 2,4,6-tridodeoxycinnamic acid sec-butyl residue unit, 2,4,6-tridodeoxycinnamic acid tert-butyl residue unit, 2,4,6-trido Deoxycinnamic acid cyclohexyl residue unit, 3,4,5-tridodoxycinnamic acid methyl residue unit, 3,4,5-tridodoxycinnamic acid ethyl residue unit, 3,4, 5-Tridodeoxycinnamic acid n-propyl residue unit, 3,4,5-Tridodoxycinnamic acid isopropyl residue unit, 3,4,5-Tridodoxycinnamic acid n-butyl Residue unit, 3,4,5-tridodoxycinnamic acid sec-butyl residue unit, 3,4,5- Tert-Butyl tridodoxycinnamate residue unit, 3,4,5-tridodoxycinnamic acid cyclohexyl residue unit, methyl 2,3,4,5-tetradodoxycinnamic acid residue Unit, ethyl unit of 2,3,4,5-tetradodeoxycinnamic acid residue, 2,3,4,5-tetradodoxycinnamic acid n-propyl residue unit, 2,3,4, 5-tetradodoxycinnamic acid isopropyl residue unit, 2,3,4,5-tetradodoxycinnamic acid n-butyl residue unit, 2,3,4,5-tetradodeoxycinnamic leather Acid sec-butyl residue unit, 2,3,4,5-tetradodoxycinnamic acid tert-butyl residue unit, 2,3,4,5-tetradodoxycinnamic acid cyclohexyl residue unit, 2,3,4,6-tetradodoxymethylcinnamate residue unit, 2,3,4,6 Tetradodeoxycinnamic acid ethyl residue unit, 2,3,4,6-tetradodoxycinnamic acid n-propyl residue unit, 2,3,4,6-tetradodoxycinnamic acid isopropyl Residue unit, 2,3,4,6-tetradodeoxycinnamic acid n-butyl residue unit, 2,3,4,6-tetradodoxycinnamic acid sec-butyl residue unit, 2, 3,4,6-tetradodeoxycinnamic acid tert-butyl residue unit, 2,3,4,6-tetradodeoxycinnamic acid cyclohexyl residue unit, 2,3,5,6-tetradone Deoxycinnamic acid methyl residue unit, 2,3,5,6-tetradodoxycinnamic acid ethyl residue unit, 2,3,5,6-tetradodoxycinnamic acid n-propyl residue Unit, 2,3,5,6-tetradodoxy cinnamate isopropyl residue unit, 2,3,5 6-tetradodoxycinnamic acid n-butyl residue unit, 2,3,5,6-tetradodoxycinnamic acid sec-butyl residue unit, 2,3,5,6-tetradodeoxy Tert-butyl cinnamic acid residue unit, 2,3,5,6-tetradodeoxycinnamic acid cyclohexyl residue unit, pentadodeoxycinnamic acid methyl residue unit, pentadodoxycinnamic acid ethyl Residue unit, pentadodeoxycinnamate n-propyl residue unit, pentadodeoxycinnamate isopropyl residue unit, pentadodeoxycinnamate n-butyl residue unit, pentadodeoxycinnamate Examples include acid sec-butyl residue units, pentadodeoxycinnamic acid tert-butyl residue units, pentadodeoxycinnamic acid cyclohexyl residue units, 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, 4- A methoxycinnamate cyclohexyl residue unit is preferred, and an ethyl 4-methoxycinnamate residue unit is more preferred.

  Further, the residue unit of the polyfunctional acrylate having a urethane bond may be any residue unit of a polyfunctional acrylate including a portion having a urethane bond and a portion having two or more acrylate units. When the alkoxycinnamate-acrylate copolymer of the present invention comprises a residue unit of a polyfunctional acrylate having a urethane bond, it is possible to achieve higher molecular weight and to become a polymer. The monomer has a high polymerization conversion rate and is excellent in productivity efficiency. Moreover, when the obtained alkoxycinnamic ester-acrylate copolymer is used as a film, the film is excellent in toughness. Here, when it is a residue unit of a polyfunctional acrylate that does not have a urethane bond, it may be difficult to obtain a high molecular weight polymer, and the resulting film may have problems such as poor toughness. .

  The polyfunctional acrylate having a urethane bond of the present invention is preferably a bifunctional acrylate because the molecular weight can be easily controlled. In addition, the polyfunctional acrylate having a urethane bond of the present invention is preferably a polyfunctional acrylate having a urethane bond including a polyester skeleton and / or a polyether skeleton, because a resin having particularly high toughness can be obtained.

  The polyfunctional acrylate having a urethane bond for inducing the residue unit is, for example, a method of producing by urethanation reaction of an acrylate having an isocyanate group and a polyalcohol, an acrylate having a hydroxyl group, and a polyisocyanate. It can be obtained by a method of producing by urethanization reaction. Examples of acrylates having an isocyanate group include 2-acryloyloxyethyl isocyanate, 3-acryloyloxypropyl isocyanate, 4-acryloyloxybutyl isocyanate, 5-acryloyloxypentyl isocyanate, 6-acryloyloxyhexyl isocyanate, and 3-acryloyloxy. Examples of the polyalcohol include ethylene glycol, propylene glycol, 1,4-butanediol, glycerin, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Examples of acrylates having a hydroxyl group include hydroxyethyl acrylate, polyethylene glycol acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate. Examples of polyisocyanates include hexamethylene diisocyanate. Nert, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate, bis (isocyanatomethyl) norbornane, hexamethylene diisocyanate trimer, and the like. The polyfunctional acrylate having a urethane bond includes, for example, a reaction product of hydroxyethyl acrylate and hexamethylene diisocyanate, a reaction product of hydroxyethyl acrylate and bis (4-isocyanatocyclohexyl) methane, hydroxy Reaction product of ethyl acrylate and isophorone diisocyanate, reaction product of 2-hydroxypropyl acrylate and bis (isocyanatomethyl) norbornane, reaction product of polyethylene glycol acrylate and hexamethylene diisocyanate, polyethylene glycol acrylate Product of bis (4-isocyanatocyclohexyl) methane with polyethylene glycol acrylate and isophorone diisocyanate, pentaerythritol Reaction product of reacrylate and hexamethylene diisocyanate, reaction product of pentaerythritol triacrylate and isophorone diisocyanate, reaction product of dipentaerythritol pentaacrylate and hexamethylene diisocyanate trimer, etc. These may be one or two or more of them.

  Moreover, the polyfunctional acrylate which has this urethane bond is a commercial item, for example, (trade name) U-2PPA (made by Shin-Nakamura Chemical Co., Ltd.), (trade name) U-6HA (Shin-Nakamura chemical industry ( Co., Ltd.), (trade name) UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), (trade name) UA-NDP (manufactured by Shin-Nakamura Chemical Co., Ltd.), (trade name) U-108A (new) (Product name) UA-511 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), (product name) UA-4200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), (product name) UA -340P (manufactured by Shin-Nakamura Chemical Co., Ltd.), (product name) UA-6200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), (product name) U-108 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), ( Product name: UA-512 (manufactured by Shin-Nakamura Chemical Co., Ltd.), (product name) UA-7000 (Shin-Nakamura Chemical Industry) (Trade name) UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), (trade name) M-1200 (manufactured by Toagosei Co., Ltd.), (brand name) M-1600 (Toagosei) Co., Ltd.), (trade name) M-1960 (manufactured by Toagosei Co., Ltd.) and the like are available.

  The alkoxycinnamate-acrylate copolymer may contain other monomer residue units as long as the scope of the present invention is not exceeded. 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 unit; vinyl ether residue unit such as methyl vinyl ether residue unit, ethyl vinyl ether residue unit, butyl vinyl ether residue unit; N-methylmaleimide residue N-substituted maleimide residue units such as N-cyclohexylmaleimide residue units and N-phenylmaleimide residue units; olefin residue units such as ethylene residue units and propylene residue units; di-n-fumarate Examples thereof include one or more selected from fumaric acid diester residue units such as a butyl residue unit, a diisopropyl fumarate residue unit, and a bis (2-ethylhexyl) fumarate residue unit.

  The composition of the alkoxycinnamate-acrylate copolymer of the present invention is a high molecular weight alkoxycinnamate-acrylate copolymer having excellent solubility in solvents and the like, and excellent strength and the like when used as a film. Therefore, 50 to 99.99 mol% of alkoxycinnamate ester residue units, 0.01 to 1% of residue units of polyfunctional acrylate having a urethane bond, and other monomer residue units of 0 to 49 99 mol% is preferred, alkoxycinnamate residue units 60-90 mol%, polyfunctional acrylate residue units 0.01-0.5 mol% having a urethane bond, and other monomer residues The base unit of 0 to 39.99 mol% is more preferable.

  Since the alkoxycinnamate-acrylate copolymer of the present invention is excellent in mechanical properties and strength when formed into a film, it is determined from an elution curve measured by gel permeation chromatography (GPC). The weight average molecular weight obtained in terms of standard polystyrene is preferably 120,000 to 1,000,000, more preferably 140,000 to 700,000, and more preferably 150,000 to 500,000. Particularly preferred.

  The alkoxycinnamate-acrylate copolymer of the present invention may be produced by any method as long as the alkoxycinnamate-acrylate copolymer is obtained. For example, the alkoxycinnamate ester may be used. And it can manufacture by performing radical polymerization etc. of the polyfunctional acrylate which has a urethane bond. Here, examples of the polyfunctional acrylate having a urethane bond include a compound that derives a residue unit of the polyfunctional acrylate having a urethane bond.

  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. Alcohol-acrylate solvent; cyclohexane; dioxane; tetrahydrofuran; acetone; methyl ethyl ketone; dimethylformamide; isopropyl acetate; water and the like.

  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.

  Furthermore, when producing the alkoxycinnamate-acrylate copolymer of the present invention, it becomes possible to more efficiently produce a higher molecular weight alkoxycinnamate-acrylate copolymer, 100 mol of total monomers including alkoxycinnamate 50 to 99 mol%, polyfunctional acrylate having urethane bond 0.01 to 1 mol%, and other monomers 0 to 49.99 mol% %, The radical polymerization reaction is preferably performed in the presence of 0.001 to 5 mol% of a radical polymerization initiator.

  When an optical film using the alkoxycinnamate-acrylate copolymer of the present invention is obtained, a thin film having a high out-of-plane retardation even in a thin film and excellent in optical properties can be used as a retardation film. preferable.

  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.

  In the solution casting method, a solution in which an alkoxycinnamic ester-acrylate copolymer is dissolved 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 the method. 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 alkoxycinnamate-acrylate copolymer is preferably 1 to 200 μm, more preferably 5 to 100 μm, particularly preferably 10 to 50 μm after drying because the film can be easily handled. is there.

  The melt casting method is a molding method in which an alkoxycinnamic ester-acrylate copolymer 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 ester-acrylate copolymers which comprise the retardation film of this invention, 0.01 to 10 weight Part is preferable, and 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.

  The alkoxycinnamate-acrylate copolymer of the present invention is excellent in solubility in a solvent and can be formed into a film by a method such as solution casting, and the film has excellent film strength and the like.

  Since the present invention has a high molecular weight, a novel alkoxycinnamate-acrylate copolymer having excellent properties when used as a film or the like and a method for efficiently producing the alkoxycinnamate-acrylate copolymer are disclosed. It is to provide.

  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-acrylate copolymer>
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 weight 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-acrylate copolymer (ethyl 4-methoxycinnamate / 4-methoxyhexamate 2-ethylhexyl / acrylate copolymer) 1)
Ethanol 4-methoxycinnamate 50g (0.26mol), 2-methoxyhexyl 4-methoxycinnamate 15.2g (0.065mol), 75mL glass ampoule, urethane as polyfunctional acrylate having urethane bond Acrylate compound (trade name) UA-4200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.21 g (1.6 × 10 ⁻⁴ mol (0.050 mol%)) 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 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 acid ester-acrylate copolymer (yield: 26%).

  The obtained alkoxycinnamic ester-acrylate copolymer had a weight average molecular weight of 153,000.

The copolymer composition was determined by ¹ H-NMR measurement to be 4-methoxycinnamate ethyl residue units / 4-methoxycinnamate 2-ethylhexyl residue units / acrylate residue units = 83.96 / 15.99. /0.05 (mol%).

  An alkoxycinnamate-acrylate copolymer is dissolved in methyl isobutyl ketone to form a 15% by weight resin solution, cast on a 10 cm × 10 cm polyethylene terephthalate film by a coater, and dried at 130 ° C. for 10 minutes. A transparent film using an alkoxycinnamic ester-acrylate copolymer having a thickness of 30 μm was obtained. When the retardation of the obtained film was measured, the out-of-plane retardation Rth was as negative as −251 nm, and the absolute value of the film thickness and the out-of-plane retardation was 8.4 nm / film thickness (μm). . Furthermore, when this film was bent and subjected to a bending test in which the ends were brought into contact with each other, no cracks were found in the alkoxycinnamate-acrylate copolymer layer, and the film was excellent in toughness.

Example 2 (Synthesis 2 of alkoxycinnamate-acrylate copolymer (ethyl 4-methoxycinnamate / diisopropyl fumarate / acrylate copolymer) 2)
A glass ampoule with a capacity of 75 mL, 50 g (0.24 mol) of ethyl 4-methoxycinnamate, 20.8 g (0.10 mol) of diisopropyl fumarate, a urethane acrylate compound (trade name) as a polyfunctional acrylate having a urethane bond UA-4200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.54 g (4.2 × 10 ⁻⁴ mol (0.120 mol%)) 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 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 25 g of an alkoxycinnamic acid ester-acrylate copolymer (yield: 34%).

  The weight average molecular weight of the obtained alkoxycinnamic ester-acrylate copolymer was 184,000.

In addition, as a result of ¹ H-NMR measurement, the copolymer composition was as follows: ethyl 4-methoxycinnamate residue unit / diisopropyl fumarate residue unit / acrylate residue unit = 54.81 / 45.07 / 0.12 (mol) %).

  The obtained alkoxycinnamic ester-acrylate copolymer was made into a film by the same method as in Example 1, and the phase difference was measured. As a result, the out-of-plane retardation Rth was as negative as −258 nm, and the film thickness and surface The absolute value of the outer phase difference was 8.6 nm / film thickness (μm). Furthermore, when the bending test of this film was implemented, the obtained transparent film was excellent in toughness with no occurrence of cracks.

Example 3 (Synthesis 3 of alkoxycinnamate-acrylate polymer (isopropyl 4-methoxycinnamate / diethyl fumarate / acrylate copolymer) 3)
A glass ampoule with a capacity of 75 mL, 50 g (0.21 mol) of isopropyl 4-methoxycinnamate, 4.1 g (0.024 mol) of diethyl fumarate, a urethane acrylate compound (trade name) as a polyfunctional acrylate having a urethane bond 0.5-6 g (4.3 × 10 ⁻⁴ mol (0.182 mol%)) of U-6HA (manufactured by Shin-Nakamura Chemical Co., Ltd.) 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 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 acid ester-acrylate copolymer (yield: 31%).

  The resulting alkoxycinnamic ester-acrylate copolymer had a weight average molecular weight of 195,000.

The copolymer composition was determined by ¹ H-NMR measurement to be 4-methoxycinnamate isopropyl residue unit / diethyl fumarate residue unit / acrylate residue unit = 89.86 / 9.96 / 0.18 (mol) %).

  The obtained alkoxycinnamic ester-acrylate copolymer was made into a film by the same method as in Example 1 and measured for retardation. As a result, the out-of-plane retardation Rth was as negative as −261 nm, and the film thickness and surface The absolute value of the outer phase difference was 8.7 nm / film thickness (μm). Furthermore, when the bending test of this film was implemented, the obtained transparent film was excellent in toughness with no occurrence of cracks.

Example 4 (Synthesis 4 of alkoxycinnamate-acrylate copolymer (ethyl 3,4-dimethoxycinnamate copolymer / N-phenylmaleimide / acrylate copolymer) 4)
In a glass ampule with a capacity of 75 mL, 50 g (0.23 mol) of ethyl 3,4-dimethoxycinnamate, 4.4 g (0.025 mol) of N-phenylmaleimide, a urethane acrylate compound (polyfunctional acrylate having a urethane bond) Trade name: UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.22 g (1.8 × 10 ⁻⁴ mol (0.070 mol%)) and tert-butyl peroxypivalate 0 which is 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 ampule was placed in a thermostatic bath at 50 ° C. and kept for 24 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 16 g of an alkoxycinnamic acid ester-acrylate copolymer (yield: 30%).

  The resulting alkoxycinnamic ester-acrylate copolymer had a weight average molecular weight of 195,000.

In addition, the copolymer composition was determined by ¹ H-NMR measurement to be 3,4-dimethoxycinnamic acid ethyl residue unit / N-phenylmaleimide residue unit / acrylate residue unit = 81.95 / 17.98 / 0. It was confirmed to be 07 (mol%).

  The obtained alkoxycinnamic ester-acrylate copolymer was made into a film by the same method as in Example 1, and the phase difference was measured. As a result, the out-of-plane retardation Rth was negatively large at −254 nm, The absolute value of the outer phase difference was 8.5 nm / film thickness (μm). Furthermore, when the bending test of this film was implemented, the obtained transparent film was excellent in toughness with no occurrence of cracks.

Example 5 (Synthesis 5 of alkoxycinnamate-acrylate copolymer (ethyl 4-ethoxycinnamate / ethyl acrylate / acrylate copolymer) 5)
A glass ampoule with a capacity of 75 mL, 50 g (0.24 mol) of ethyl 4-ethoxycinnamate, 1.3 g (0.013 mol) of ethyl acrylate, and a urethane acrylate compound (trade name) UA as a polyfunctional acrylate having a urethane bond -4200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.40 g (3.1 × 10 ⁻⁴ mol (0.120 mol%)) and tert-butyl peroxypivalate 0.30 g (0 .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 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, and then vacuum-dried at 80 ° C. for 10 hours to obtain 12 g of an alkoxycinnamic acid ester-acrylate copolymer (yield: 24%).

  The resulting alkoxycinnamic ester-acrylate copolymer had a weight average molecular weight of 194,000.

The copolymer composition was determined by ¹ H-NMR measurement to be 4-ethoxycinnamic acid ethyl residue unit / ethyl acrylate residue unit / acrylate residue unit = 88.93 / 10.95 / 0.12 (mol%) ) Confirmed.

  The obtained alkoxycinnamic ester-acrylate copolymer was made into a film by the same method as in Example 1 and measured for retardation. As a result, the out-of-plane retardation Rth was as negative as −257 nm, The absolute value of the outer phase difference was 8.6 nm / film thickness (μm). Furthermore, when the bending test of this film was implemented, the obtained transparent film was excellent in toughness with no occurrence of cracks.

Comparative Example 1
9 g of 4-methoxycinnamic acid-4-methoxycinnamic acid 2-ethylhexyl copolymer was obtained in the same manner as in Example 1 except that the polyfunctional acrylate having a urethane bond was not used. (Rate: 14%).

The resulting ethyl 4-methoxycinnamate-4-methoxyhexyl 2-methoxyhexyl copolymer had a low weight average molecular weight of 53,000. ^The copolymer composition obtained by ¹ H-NMR measurement was 4-methoxycinnamate ethyl residue unit / 4-methoxycinnamate 2-ethylhexyl residue unit = 84/16 (mol%). .

  The obtained alkoxycinnamic ester copolymer was made into a film by the same method as in Example 1, and when this film was subjected to a bending test, the alkoxycinnamic ester copolymer layer was quickly applied with bending stress. Cracks occurred.

Comparative Example 2
14 g of 4-methoxycinnamate ethyl diisopropyl fumarate copolymer was obtained in the same manner as in Example 2 except that the polyfunctional acrylate having a urethane bond was not used (yield: 20%).

The weight-average molecular weight of the obtained 4-methoxycinnamate ethyl isopropyl fumarate copolymer was as low as 63,000. ^The copolymer composition obtained by ¹ H-NMR measurement was ethyl 4-methoxycinnamate residue unit / diisopropyl fumarate residue unit = 54/46 (mol%).

  The obtained alkoxycinnamic ester copolymer was made into a film by the same method as in Example 1, and when this film was subjected to a bending test, the alkoxycinnamic ester copolymer layer was quickly applied with bending stress. Cracks occurred.

Comparative Example 3
9 g of 4-methoxycinnamate isopropyl-fumarate copolymer was obtained in the same manner as in Example 3 except that the polyfunctional acrylate having a urethane bond was not used (yield: 16%).

The obtained 4-methoxycinnamate-diethyl fumarate copolymer had a low weight average molecular weight of 60,000. ^The copolymer composition obtained by ¹ H-NMR measurement was 4-methoxycinnamate isopropyl residue unit / diethyl fumarate residue unit = 90/10 (mol%).

  The obtained alkoxycinnamic ester copolymer was made into a film by the same method as in Example 1, and when this film was subjected to a bending test, the alkoxycinnamic ester copolymer layer was quickly applied with bending stress. Cracks occurred.

Comparative Example 4
9 g of ethyl 3,4-dimethoxycinnamate-N-phenylmaleimide copolymer was obtained in the same manner as in Example 4 except that the polyfunctional acrylate having a urethane bond was not used (yield: 17 %).

The weight average molecular weight of the obtained 3,4-dimethoxycinnamic acid ethyl-N-phenylmaleimide copolymer was as low as 94,000. The copolymer composition obtained by ¹ H-NMR measurement was ethyl 3,4-dimethoxycinnamate residue unit / N-phenylmaleimide residue unit = 82/18 (mol%).

  The obtained alkoxycinnamic ester copolymer was made into a film by the same method as in Example 1, and when this film was subjected to a bending test, the alkoxycinnamic ester copolymer layer was quickly applied with bending stress. Cracks occurred.

Comparative Example 5
Except not using the polyfunctional acrylate having a urethane bond, 5 g of 4-ethoxycinnamic acid ethyl acrylate copolymer was obtained in the same manner as in Example 5 (yield: 10%).

The obtained ethyl 4-ethoxycinnamate-ethyl acrylate copolymer had a low weight average molecular weight of 78000. The copolymer composition obtained by ¹ H-NMR measurement was 4-ethoxycinnamic acid ethyl residue unit / ethyl acrylate residue unit = 89/11 (mol%).

  The obtained alkoxycinnamic ester copolymer was made into a film by the same method as in Example 1, and when this film was subjected to a bending test, the alkoxycinnamic ester copolymer layer was quickly applied with bending stress. Cracks occurred.

Claims (12)

An alkoxycinnamate-acrylate copolymer comprising at least an alkoxycinnamate residue unit represented by the general formula (1) and a polyfunctional acrylate residue unit having a urethane bond.

(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. 50 to 99.99 mol% of alkoxycinnamate ester residue units, 0.01 to 1 mol% of residue units of polyfunctional acrylate having a urethane bond, and 0 to 49.99 mol of other monomer residue units The alkoxycinnamate-acrylate copolymer according to claim 1, comprising: The alkoxycinnamate-acrylate copolymer according to claim 1 or 2, wherein the weight average molecular weight in terms of standard polystyrene is 120,000 to 1,000,000. The alkoxycinnamate residue unit is one or more residue units selected from a methoxycinnamate residue unit and an ethoxycinnamate residue unit. The alkoxycinnamate-acrylate copolymer according to any one of the above. The alkoxycinnamate-acrylate copolymer according to any one of claims 1 to 4, wherein the alkoxycinnamate residue unit is a 4-methoxycinnamate 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 alkoxycinnamate-acrylate copolymer according to any one of claims 1 to 5, which is any one selected from the group consisting of acid cyclohexyl residue units. The polyfunctional acrylate having a urethane bond is a bifunctional acrylate, and the alkoxycinnamate-acrylate copolymer according to any one of claims 1 to 6. The alkoxycinnamate-acrylate copolymer according to any one of claims 1 to 7, wherein the polyfunctional acrylate having a urethane bond includes a polyester skeleton and / or a polyether skeleton. Total monomer containing alkoxycinnamate 50 to 99.99 mol%, polyfunctional acrylate having urethane bond 0.01 to 1 mol%, other monomers 0 to 49.99 mol% A method for producing an alkoxycinnamic acid ester-acrylate copolymer, wherein a radical polymerization reaction is carried out in the presence of 0.001 to 5 mol% of a radical polymerization initiator as 100 mol%. A film using the alkoxycinnamate-acrylate copolymer according to any one of claims 1 to 8. A retardation film using the film according to claim 10. 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 11, wherein the retardation film is present.