JP6500472B2 - Alkoxycinnamic acid ester-acrylate copolymer and method for producing the same - Google Patents

Description

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

Liquid crystal displays are widely used as the most important display devices in the multimedia society, including mobile phones, computer monitors, laptop computers, and televisions. Many optical films are used for liquid crystal displays in order to improve display characteristics. In particular, retardation films play an important role in improving the contrast when viewed from the front or obliquely and compensating the color tone. As the conventional retardation film, polycarbonate and cyclic polyolefin are used, and these polymers are all polymers having positive birefringence.
Many macromolecules have positive birefringence. As a polymer having negative birefringence, there are acrylic resin and polystyrene, but the acrylic resin has a small retardation and the characteristics as a retardation film are not sufficient. Polystyrene has not been used at present because it has a problem of stability of phase difference such as change of phase difference due to slight stress due to large photoelastic coefficient in low temperature region, and practical problem of low heat resistance. .

  A stretched film of a polymer exhibiting negative birefringence has a high refractive index in the thickness direction of the film, and becomes an unconventional retardation film. For example, a super twist nematic liquid crystal display (STN-LCD) or a vertical alignment liquid crystal display (VA-LCD), useful as a retardation film for compensating the viewing angle characteristics of displays such as in-plane oriented liquid crystal display (IPS-LCD), reflective liquid crystal display (reflective LCD), etc. There is a strong market demand for retardation films that have negative birefringence.

  There has been proposed a method for producing a film in which the refractive index in the thickness direction of the film is increased using a polymer having positive birefringence. First, a heat-shrinkable film is adhered to one side or both sides of a polymer film, and the laminate is heat-stretched to apply a shrinking force in the film thickness direction of the polymer film (for example, Patent Documents 1 to 3) See). In addition, a method of uniaxially 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 (see, for example, Patent Document 5).

  However, the methods proposed in Patent Documents 1 to 4 have a problem of low productivity because the manufacturing process becomes very complicated. Further, control of the uniformity of the retardation and the like becomes significantly more 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 changes due to a slight stress, so there is a problem in the stability of the phase difference. Furthermore, there is also a problem in which the wavelength dependency 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, and from the viewpoint of simplification of the production method and economy, the fine particles There is a need for a retardation film that does not require the addition of.

  Moreover, fumaric-acid diester type-resin and the film consisting thereof are proposed (for example, refer patent documents 6-10).

  Further, a diisopropyl fumarate-cinnamic acid derivative-based copolymer comprising a fumaric acid diisopropyl 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, A retardation film using the diisopropyl fumaric acid-cinnamic acid derivative copolymer has been proposed (see, for example, Patent Document 11).

  Furthermore, a fumaric acid diester residue unit, a fumaric acid residue unit of a cinnamic acid ester residue unit having an alkyl group having 1 to 6 carbon atoms, and a residue unit of a polyfunctional monomer having two or more radically 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).

Patent No. 2818983 Unexamined-Japanese-Patent No. 5-297223 Unexamined-Japanese-Patent No. 5-323120 Japanese Patent Laid-Open No. 6-88909 JP 2005-156862 A JP, 2008-112141, A JP 2012-032784 A WO 2012/005120 JP 2008-129465 A JP, 2006-193616, A WO 2014/013982 WO 2014/084178 gazette

  Although the fumaric acid diester resin and the film comprising the same proposed in Patent Documents 6 to 10 have high out-of-plane retardation, films having higher out-of-plane retardation even in thin films are currently available. It has been demanded.

  Although the fumaric acid diisopropyl-cinnamic acid derivative type copolymer proposed by patent document 11 expresses out-of-plane phase difference higher than the resin proposed by patent documents 6-10, it is more excellent in productivity and more There is a need for polymers obtained in high yields. Moreover, although the retardation film proposed by patent document 11 has high out-of-plane phase difference in a thin film, the film which has higher out-of-plane phase difference is further calculated | required also in a thin film.

  Although the fumaric acid diester-cinnamic acid ester copolymer proposed in Patent Document 12 is excellent in productivity and obtained in a high yield, in the film having an out-of-plane retardation higher than that of Patent Document 11 when formed into a film There is a need for polymers having excellent productivity and higher out-of-plane retardation. In addition, even when the film is a thin film, a polymer that exhibits high out-of-plane retardation while maintaining the characteristics of the film is required.

  An object of the present invention is to provide a novel alkoxycinnamic acid ester-acrylate copolymer of high molecular weight which exhibits high phase difference in a thin film even when formed into a film, and has excellent toughness, and a method of efficiently manufacturing the same. It is to do.

  MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors discover that a specific alkoxy cinnamate ester-acrylate copolymer can solve the said subject, and came to complete this invention.

  That is, the present invention comprises an alkoxycinnamic acid ester-acrylate comprising an alkoxycinnamic acid ester residue unit represented by the general formula (1) and a residual unit of a polyfunctional acrylate 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。

(Wherein, 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 -6 cyclic alkyl group is shown, n is an integer of 1-5.)
Hereinafter, the alkoxy cinnamate ester-acrylate copolymer of the present invention will be described in detail.

  An alkoxycinnamic acid ester-acrylate copolymer according to the present invention comprises an alkoxycinnamic acid ester residue unit represented by the general formula (1) and an alkoxycinate residue of a polyfunctional acrylate having a urethane bond. It is an acid ester-acrylate copolymer. And, the alkoxycinnamic acid ester-acrylate copolymer of the present invention is characterized by expressing high out-of-plane retardation even in a thin film by containing a specific alkoxycinnamic acid ester residue unit. It is In addition, the alkoxycinnamic acid ester-acrylate copolymer of the present invention contains the alkoxycinnamic acid ester residue unit, so that the polymerization transfer-through rate of the monomer when it becomes a polymer is high, and the production is It is characterized by being excellent in sex.

（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。

(Wherein, 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 -6 cyclic alkyl group is shown, n is 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, a dodecyl group, etc. N is an integer of 1 to 5; R ₂ in the general formula (1) of the present invention 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, and has 1 to 12 carbon atoms Examples of the linear alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group and the like, and branched alkyl having 1 to 12 carbon atoms Examples of the group include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and the like, and as the cyclic alkyl group having 3 to 6 carbon atoms, for example, cyclopropyl group, cyclobutyl group, cyclohexyl group and the like Can be mentioned. Among these, since an alkoxycinnamic acid ester-acrylate copolymer expresses high out-of-plane retardation, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, A tert-butyl group and a cyclohexyl group are preferable.

  As the alkoxycinnamic acid ester residue unit represented by the general formula (1), for example, methoxycinnamic acid ester residue unit, ethoxycinnamic acid ester residue unit, propoxycinnamic acid ester residue unit And hexoxycinnamic acid ester residue units, dodetoxycinic acid ester residue units, and the like. Among these, a methoxycinnamic acid ester residue unit and an ethoxycinnamic acid ester residue unit are preferable, and a 4-methoxycinnamic acid ester residue unit is more preferable, because high retardation is expressed.

  In the present invention, as a methoxycinnamic acid ester residue unit, for example, methyl 2-methoxycinnamic acid residue unit, ethyl 2-methoxycinnamic acid residue unit, n-propyl 2-methoxycinnamic acid residue unit 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-methoxycinnamic acid cyclohexyl residue unit, 3-methoxycinnamic acid methyl residue unit, 3-methoxycinnamic acid ethyl residue unit, 3-methoxycinnamic acid n-propyl residue unit, 3- Methoxycinnamic acid isopropyl residue unit, 3-methoxycinnamic acid n-butyl residue unit, 3-methoxycinnamic acid sec-butyl residue unit, 3-methoxycinnamic acid tert- Chil residue unit, 3-methoxycinnamic acid cyclohexyl residue unit, 4-methoxycinnamic acid methyl residue unit, 4-methoxycinnamic acid ethyl residue unit, 4-methoxycinnamic acid 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-methoxycinnamic acid cyclohexyl residue unit, 2,3-dimethoxycinnamic acid methyl residue unit, 2,3-dimethoxycinnamic acid ethyl residue unit, n-propyl 2,3-dimethoxycinnamic acid residue Group unit, 2,3-dimethoxycinnamic acid isopropyl residue unit, 2,3-dimethoxycinnamic acid n-butyl residue unit, 2,3-dimethoxycinnamic acid sec-butyl residue unit, 1, 3-Dimethoxycinnamic acid tert-butyl residue unit, 2,3-dimethoxycinnamic acid cyclohexyl residue unit, 2,4-dimethoxycinnamic acid methyl residue unit, ethyl 2,4-dimethoxycinnamic acid residue Group unit, n-propyl residue unit of 2,4-dimethoxycinnamic acid, isopropyl residue unit of 2,4-dimethoxycinnamic acid, n-butyl residue unit of 2,4-dimethoxycinnamic acid, 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 Units, ethyl 2,5-dimethoxycinnamate residue units, n-propyl residue units of 2,5-dimethoxycinnamate, isopropyl isopropyl 2,5-dimethoxycinnamate units, 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, n-propyl 2,6-dimethoxycinnamate residue unit, 2,6-dimethoxy Isocinnamic acid isopropyl 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, 2,6-dimethoxycinnamic acid cyclohexyl residue unit, 3,4-dimethoxycinnamic acid methyl residue unit, 3,4-dimethoxycinnamic acid residue unit, 3,4-dimetho N-propyl residue unit of cinnamate, isopropyl residue unit of 3,4-dimethoxycinnamic acid, n-butyl residue unit of 3,4-dimethoxycinnamic acid, sec-butyl residue of 3,4-dimethoxy cinnamic acid Group unit, 3,4-dimethoxycinnamic acid tert-butyl residue unit, 3,4-dimethoxycinnamic acid cyclohexyl residue unit, 3,5-dimethoxycinnamic acid methyl residue unit, 3,5-dimethoxysilicone Ethyl cyanate residue unit, 3,5-dimethoxycinnamic acid n-propyl residue unit, 3,5-dimethoxycinnamic acid isopropyl residue unit, 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-dimethoxycinnamic acid cyclohexyl residue unit, 2,3, Methyl trimethoxycinnamate residue unit, ethyl 2,3,4-trimethoxycinnamate residue unit, n-propyl residue unit of 2,3,4-trimethoxycinnamate 2,3, 4 -Trimethoxycinnamic acid isopropyl residue unit, 2,3,4-trimethoxycinnamic acid n-butyl residue unit, 2,3,4-trimethoxycinnamic 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-trimethoxycinnamic acid methyl residue unit, 2,3 Ethyl 5,5-trimethoxycinnamate residue unit, n-propyl residue unit 2,3,5-trimethoxycinnamic acid residue, 2,3,5-trimethoxycinnamic acid isopropyl residue unit 2,3 3,5-Trimethoxycinnamic acid n-butyl residue Unit, 2,3,5-trimethoxycinnamic acid sec-butyl residue unit, 2,3,5-trimethoxy cinnamic acid tert-butyl residue unit, 2,3,5-trimethoxy cinnamic acid cyclohexyl 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-trimethoxy cinnamic acid sec -Butyl residue unit, 2,3,6-trimethoxycinnamic acid tert-butyl residue unit, 2,3,6-trimethoxycinnamic acid cyclohexyl residue unit, 2,4,5-trimethoxycinnum Acid methyl residue unit, 2,4,5-tri Ethyl toxicinnamate residue unit, 2,4,5-trimethoxycinnamic acid n-propyl residue unit, 2,4,5-trimethoxycinnamic acid isopropyl residue unit, 2,4,5-trimethoxy N-butyl cinnamate residue unit, 2,4,5-trimethoxycinnamic acid sec-butyl residue unit, 2,4,5-trimethoxy cinnamic acid tert-butyl residue unit, 2,4,4, 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- Trimethoxycinnamic acid n-propyl residue unit, 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, 2,4,6-trimethoxycinnamic acid tert-butyl residue unit, 2,4,6-trimethoxycinnamic acid cyclohexyl residue unit, 3,4,5-trimethoxycinnamic acid methyl residue Unit, 3,4,5-trimethoxycinnamic acid residue unit, 3,4,5-trimethoxycinnamic acid n-propyl residue unit, 3,4,5-trimethoxycinnamic acid isopropyl residue Unit, n-butyl residue unit of 3,4,5-trimethoxycinnamic acid, sec-butyl residue unit of 3,4,5-trimethoxycinnamic acid, tert 3,4,5-trimethoxy cinnamic acid -Butyl residue unit, 3,4,5-trimethoxycinnamic acid cyclohexyl residue unit, 2,3,4,5-tetramethoxycinnamic acid methyl residue unit, 2,3,4,5-tetramethoxy Ethyl cinnamate residue unit, 2, 3, 4 5-tetramethoxycinnamic acid n-propyl residue unit, 2,3,4,5-tetramethoxycinnamic acid isopropyl residue unit, 2,3,4,5-tetramethoxycinnamic acid 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- Tetramethoxycinnamic acid cyclohexyl residue unit, 2,3,4,6-tetramethoxycinnamic acid methyl residue unit, 2,3,4,6-tetramethoxycinnamic acid ethyl residue unit, 2,3, N-Propyl residue unit of 4,6-tetramethoxycinnamic acid, isopropyl residue unit of 2,3,4,6-tetramethoxycinnamic acid, n-butyl 2,3,4,6-tetramethoxycinnamic acid Residue unit, 2,3,4,6-tetrameth 2, 2-, 2-, 4-, 2-, 4-, 4-, 2-, 4-, 2-, 4-, 4- or 5-methoxycinnamic acid tert-butyl residue unit, 2, 3, 4, 6- tetramethoxycinnamic acid cyclohexyl residue unit, 2, Methyl 3,5,6-tetramethoxycinnamate residue unit, ethyl 2,3,5,6-tetramethoxycinnamate residue unit, n-propyl 2,3,5,6-tetramethoxycinnamate Residue unit, 2,3,5,6-tetramethoxycinnamic acid isopropyl residue unit, 2,3,5,6-tetramethoxycinnamic acid n-butyl residue unit, 2,3,5,6- Sec-butyl residue unit of tetramethoxycinnamic acid, tert-butyl residue unit of 2,3,5,6-tetramethoxy cinnamic acid, cyclohexyl residue unit of 2,3,5,6-tetramethoxy cinnamic acid, Methyl pentamethoxycinnamate residue Unit, ethyl pentamethoxycinnamate residue unit, pentamethoxycinnamic acid n-propyl residue unit, pentamethoxycinnamic acid isopropyl residue unit, pentamethoxycinnamic acid n-butyl residue unit, pentamethoxycinnamate Examples include acid sec-butyl residue units, pentamethoxycinnamic acid tert-butyl residue units, pentamethoxy cinnamic acid cyclohexyl residue units, and the like.

  As ethoxycinnamate ester residue units, for example, methyl 2-ethoxycinnamate residue unit, ethyl 2-ethoxycinnamate residue unit, n-propyl 2-ethoxycinnamate residue unit, isopropyl 2-ethoxycinnamate 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, Methyl 3-ethoxycinnamate, ethyl 3-ethoxycinnamate, n-propyl 3-ethoxycinnamate, isopropyl 3-ethoxycinnamate, n-butyl 3-ethoxycinnamate 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, ethyl 2,3-diethoxycinnamate residue unit, n-propyl residue unit of 2,3-diethoxycinnamate residue, isopropyl isopropyl 2,3-diethoxycinnamate residue unit, 2,3 -Diethoxycinnamic acid n-butyl residue unit, 2,3-diethoxycinnamic acid sec-butyl residue unit, 2,3-dietoki Cinnamate tert-butyl residue unit, 2,3-diethoxycinnamate cyclohexyl residue unit, 2,4-diethoxycinnamate methyl residue unit, 2,4-diethoxycinnamate 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, ethyl 2,5-diethoxycinnamic acid residue unit, 2,5-Diethoxycinnamic acid n-propyl residue unit, 2,5-diethoxycinnamic acid isopropyl residue unit, 2,5-diethoxycinnum Acid n-butyl residue unit, 2,5-diethoxycinnamic acid sec-butyl residue unit, 2,5-diethoxy cinnamic acid tert-butyl residue unit, 2,5-diethoxy cinnamic acid cyclohexyl residue unit, 2, Methyl 6-diethoxycinnamate, ethyl 2,6-diethoxycinnamate, n-propyl 2,6-diethoxycinnamate, isopropyl 2,6-diethoxycinnamate 2, 6-diethoxycinnamic acid n-butyl residue unit, 2,6-diethoxy cinnamic acid sec-butyl residue unit, 2,6-diethoxy cinnamic acid tert-butyl residue unit, 2,6-diethoxy cinnamic acid cyclohexyl residue Unit, methyl 3,4-diethoxycinnamate residue unit, ethyl 3,4-diethoxycinnamate residue unit, 3,4-diethoxycinnamic acid n- Ropyl residue unit, 3,4-diethoxycinnamic acid isopropyl residue unit, 3,4-diethoxy cinnamic acid n-butyl residue unit, 3,4-diethoxy cinnamic acid sec-butyl residue unit, 3,4-diethoxy silica Ternary acid tert-butyl residue unit, 3,4-diethoxycinnamate cyclohexyl residue unit, 3,5-diethoxycinnamate methyl residue unit, 3,5-diethoxycinnamate residue unit, 3,5-diethoxy silica N-Propyl residue unit, 3,5-diethoxycinnamic acid isopropyl residue unit, 3,5-diethoxy cinnamic acid n-butyl residue unit, 3,5-diethoxy cinnamic acid sec-butyl residue unit, 3 3,5-Diethoxycinnamic acid tert-butyl residue unit, 3,5-diethoxycinnamic acid cyclohexyl residue unit, 2,3,4-triethoxy Methyl benzoate residue unit, Ethyl 2,3,4-triethoxycinnamate residue unit, 2,3,4-Triethoxycinnamic acid n-propyl residue unit, 2,3,4-Triethoxy Isocinnamic acid isopropyl residue unit, 2,3,4-triethoxycinnamic acid n-butyl residue unit, 2,3,4-triethoxycinnamic acid sec-butyl residue unit, 2,3,4- Triethoxycinnamic acid tert-butyl residue unit, 2,3,4-triethoxycinnamic acid cyclohexyl residue unit, 2,3,5-triethoxy cinnamic acid methyl residue unit, 2,3,5- Ethyl triethoxycinnamate residue unit, 2,3,5-triethoxycinnamic acid n-propyl residue unit, 2,3,5-triethoxycinnamic acid isopropyl residue unit, 2,3,5- Triethoxycinnamic acid n-butyl residue unit, 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 Methyl 6,6-triethoxycinnamate residue unit, ethyl 2,3,6-triethoxycinnamate residue unit, n-propyl residue unit 2,3,6-triethoxycinnamate, 2,3 2, 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 2,3,6-triethoxycinnamic acid tert-butyl residue unit, 2,3,6-triethoxycinnamic acid cyclohexyl residue unit, 2,4,5-triethoxycinnamate methyl residue unit, 2 , 4,5-Triethoxycinnamic acid Chill residue unit, n-propyl residue unit of 2,4,5-triethoxycinnamic acid, isopropyl residue unit of 2,4,5-triethoxycinnamic acid, 2,4,5-triethoxycinnamic acid n-Butyl residue unit, 2,4,5-triethoxycinnamic acid sec-butyl residue unit, 2,4,5-triethoxy cinnamic acid tert-butyl residue unit, 2,4,5-tri Ethyloxycinnamate cyclohexyl residue unit, 2,4,6-triethoxycinnamate methyl residue unit, 2,4,6-triethoxycinnamate ethyl residue unit, 2,4,6-triethoxy silica N-propyl molybdate residue unit, 2,4,6-triethoxycinnamic acid isopropyl residue unit, 2,4,6-triethoxy cinnamic acid n-butyl residue unit, 2,4,6-triethyl residue unit Ethoxycinnamic acid sec-butyl residue unit, 2,4, -Triethoxycinnamic acid tert-butyl residue unit, 2,4,6-triethoxycinnamic acid cyclohexyl residue unit, 3,4,5-triethoxycinnamic acid methyl residue unit, 3,4,5 Ethyl triethoxycinnamate residue unit, n-propyl residue unit of 3,4,5-triethoxycinnamic acid, isopropyl residue unit of 3,4,5-triethoxycinnamic acid, 3,4,5 N-Butyl residue unit of triethoxycinnamic acid, sec-butyl residue unit of 3,4,5-triethoxycinnamic acid, tert-butyl residue unit of 3,4,5-triethoxycinnamic acid, 3 1,4,5-Triethoxycinnamate cyclohexyl residue unit, 2,3,4,5-tetraethoxycinnamate methyl residue unit, 2,3,4,5-tetraethoxycinnamate residue unit 2,3,4,5-Tetraetoki N-propyl residue unit of cinnamate, isopropyl residue unit of 2,3,4,5-tetraethoxycinnamic acid, n-butyl residue unit of 2,3,4,5-tetraethoxy cinnamate, 2, 3,4,5-Tetraethoxycinnamic acid sec-butyl residue unit, 2,3,4,5-tetraethoxycinnamic acid tert-butyl residue unit, 2,3,4,5-tetraethoxycinnamate Acid cyclohexyl residue unit, methyl 2,3,4,6-tetraethoxycinnamate residue unit, ethyl 2,3,4,6-tetraethoxycinnamate residue unit 2,3,4,6- N-propyl residue unit of tetraethoxycinnamic acid, isopropyl residue unit of 2,3,4,6-tetraethoxycinnamic acid, n-butyl residue unit of 2,3,4,6-tetraethoxycinnamic acid, 2,3,4,6-tetraethoxycinnamic acid se -Butyl residue unit, 2,3,4,6-tetraethoxycinnamic acid tert-butyl residue unit, 2,3,4,6-tetraethoxy cinnamic 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-tetraethoxycinnamate Acid sec-Butyl Residue Unit, 2,3,5,6-Tetraethoxycinnamate tert-Butyl Residue Unit, 2,3,5,6-Tetraethoxycinnamic Acid Cyclohexyl Residue Unit, Pentaethoxycinnamate Acid methyl residue unit, pentae Ethyl xyl cinnamate residue unit, n-propyl residue unit of pentaethoxycinnamic acid, isopropyl residue unit of pentaethoxy cinnamic acid, n-butyl residue unit of pentaethoxy cinnamic acid, sec-butyl pentaethoxy cinnamic acid A residue unit, a penta-ethoxy cinnamic acid tert-butyl residue unit, a pentaethoxy cinnamic acid cyclohexyl residue unit, etc. are mentioned.

  Examples of propoxycinnamic acid ester residue units include 2-propoxy cinnamic acid methyl residue units, 2-propoxy cinnamic acid ethyl residue units, 2-propoxy cinnamic acid n-propyl residue units, 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- Propoxycinnamate 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, n-butyl residue unit of 3-propoxycinnamic acid, sec-butyl residue unit of 3-propoxy cinnamic acid, 3-propoxy group Ternary 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-propoxy cinnamic acid tert- Butyl residue unit, 4-propoxycinnamic acid cyclohexyl residue unit, 2,3-dipropoxy cinnamic acid methyl residue unit, 2,3-dipropoxy cinnamic acid residue unit, 2,3-dipropoxy N-propyl cinnamate residue unit, 2,3-dipropoxycinnamic acid isopropyl residue unit, 2,3-dipropoxy cinnamic acid n-butyl residue unit, 2, 3 Dipropoxycinnamic acid sec-butyl residue unit, 2,3-dipropoxy cinnamic acid tert-butyl residue unit, 2,3-dipropoxy cinnamic acid cyclohexyl residue unit, 2,4-dipropoxy cinnamic acid 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, N-Butyl residue unit of 2,4-dipropoxycinnamic acid, sec-butyl residue unit of 2,4-dipropoxy cinnamic acid, tert-butyl residue unit of 2,4-dipropoxy cinnamic acid, 2, 4-dipropoxycinnamic acid cyclohexyl residue unit, 2,5-dipropoxy cinnamic acid methyl residue unit, 2,5-dipropoxy cinnamic acid ethyl residue unit, 2,5-dipropoxy cinnamic acid n - Ropyl residue unit, 2,5-dipropoxycinnamic acid isopropyl residue unit, 2,5-dipropoxy cinnamic acid n-butyl residue unit, 2,5-dipropoxy cinnamic acid sec-butyl residue unit 2,5-dipropoxycinnamic acid tert-butyl residue unit, 2,5-dipropoxy cinnamic acid cyclohexyl residue unit, 2,6-dipropoxy cinnamic acid methyl residue unit, 2,6-di Ethyl propoxycinnamate residue unit, 2,6-dipropoxycinnamic acid n-propyl residue unit, 2,6-dipropoxy cinnamic acid isopropyl residue unit, 2,6-dipropoxy cinnamic acid n- Butyl residue unit, sec-butyl residue unit of 2,6-dipropoxycinnamic acid, tert-butyl residue unit of 2,6-dipropoxy cinnamic acid, cyclohexyl residue unit of 2,6-dipropoxy cinnamic acid , Methyl 4-dipropoxycinnamate residue unit, ethyl 3,4-dipropoxy cinnamate residue unit, n-propyl residue unit of 3,4-dipropoxy cinnamic acid, 3,4- dipropoxy cinnamate Isopropyl isopropyl residue unit, 3,4-dipropoxycinnamic acid n-butyl residue unit, 3,4-dipropoxy cinnamic acid sec-butyl residue unit, 3,4- dipropoxy cinnamic acid tert- Butyl residue unit, 3,4-dipropoxycinnamic acid cyclohexyl residue unit, 3,5-dipropoxy cinnamic acid methyl residue unit, 3,5-dipropoxy cinnamic acid residue unit, 3,5 N-Propyl residue unit of dipropoxycinnamic acid, isopropyl residue unit of 3,5-dipropoxycinnamic acid, n-butyl residue unit of 3,5-dipropoxycinnamic acid, 3,5-dipropoxy cinnamate Skin acid sec- Chil residue unit, 3,5-dipropoxycinnamic acid tert-butyl residue unit, 3,5-dipropoxy cinnamic acid cyclohexyl residue unit, 2,3,4- tripropoxy cinnamic acid residue unit Ethyl 2,3,4-tripropoxycinnamate residue unit n-propyl residue unit 2,3,4-tripropoxycinnamate residue isopropyl group 2,3,4-tripropoxycinnamic acid residue unit 2,3,4-Tripropoxycinnamic acid n-butyl residue unit, 2,3,4-tripropoxy cinnamic acid sec-butyl residue unit, 2,3,4- tripropoxy cinnamic acid tert- Butyl residue unit, 2,3,4-tripropoxycinnamic acid cyclohexyl residue unit, 2,3,5-tripropoxy cinnamic acid methyl residue unit, ethyl 2,3,5-tripropoxy cinnamic acid 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-tripropoxy cinnamic acid tert-butyl residue unit, 2,3,5-tripropoxy cinnamic acid cyclohexyl residue Unit, methyl 2,3,6-tripropoxycinnamate residue unit, ethyl 2,3,6-tripropoxycinnamate residue unit, n-propyl 2,3,6-tripropoxycinnamic acid residue unit Unit, 2,3,6-tripropoxycinnamic acid isopropyl residue unit, 2,3,6-tripropoxycinnamic acid n-butyl residue unit, 2,3,6-tripropoxy cinnamic acid sec-butyl Residue unit, 2, , 6-tripropoxycinnamic acid tert-butyl residue unit, 2,3, 6-tripropoxy cinnamic acid cyclohexyl residue unit, 2,4,5- tripropoxy cinnamic acid methyl residue unit, 2,4 Ethyl 5,5-tripropoxycinnamate residue unit, n-propyl residue unit 2,4,5-tripropoxycinnamic acid residue, 2,4,5-tripropoxycinnamic acid isopropyl residue unit, 2,4 N-Butyl residue unit of 5,5-tripropoxycinnamic acid, sec-butyl residue unit of 2,4,5-tripropoxy cinnamic acid, tert-butyl residue unit of 2,4,5-tripropoxy cinnamic acid 2,4,5-tripropoxycinnamic acid cyclohexyl residue unit, 2,4,6-tripropoxy cinnamic acid methyl residue unit, 2,4,6-tripropoxy cinnamic acid 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-tripropoxy cinnamic acid tert-butyl residue unit, 2,4,6-tripropoxy cinnamic acid cyclohexyl residue unit, 3 ,, Methyl 4,5-tripropoxycinnamate residue unit, Ethyl 3,4,5-tripropoxycinnamate residue unit, n-Propyl residue unit of 3,4,5-tripropoxycinnamic acid 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- Tripropoxycinnamic acid tert-butyl residue unit, 3,4,5-tripropoxycinnamic acid cyclohexyl residue unit, 2,3,4,5-tetrapropoxycinnamic acid methyl residue unit, 2,3, Ethyl 4,5-tetrapropoxycinnamate residue unit, 2,3,4,5-tetrapropoxycinnamic acid n-propyl residue unit, 2,3,4,5-tetrapropoxycinnamic acid isopropyl residue Unit, n-butyl residue unit of 2,3,4,5-tetrapropoxycinnamic acid, sec-butyl residue unit of 2,3,4,5-tetrapropoxy cinnamic acid, 2,3,4,5- Tetrapropoxycinnamic acid tert-butyl residue unit, 2,3,4,5-tetrapropoxycinnamic acid cyclohexyl residue unit, 2,3,4,6-tetrapropoxy cinnamic acid methyl residue unit, 2, 3, 4, 6 Ethyl tetrapropoxycinnamate residue unit, n-propyl residue unit of 2,3,4,6-tetrapropoxycinnamic acid residue, isopropyl isopropyl 2,3,4,6-tetrapropoxycinnamate residue unit, 2, 3,4,6-Tetrapropoxycinnamic acid n-butyl residue unit, 2,3,4,6-tetrapropoxycinnamic acid sec-butyl residue unit, 2,3,4,6-tetrapropoxy cinnamic acid Acid tert-butyl residue unit, 2,3,4,6-tetrapropoxycinnamic acid cyclohexyl residue unit, 2,3,5,6-tetrapropoxy cinnamic acid methyl residue unit, 2,3,5, 6-tetrapropoxycinnamate 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-tetrapropoxy cinnamic acid tert-butyl Residue unit, 2,3,5,6-tetrapropoxy cinnamic acid cyclohexyl residue unit, pentapropoxy cinnamic acid methyl residue unit, pentapropoxy cinnamic acid ethyl residue unit, n-propyl pentapropoxy cinnamic acid Residue unit, pentapropoxy cinnamic acid isopropyl residue unit, pentapropoxy cinnamic acid n-butyl residue unit, pentapropoxy cinnamic acid sec-butyl residue unit, pentapropoxy cinnamic acid tert-butyl residue unit, Pentapropoxy cinnamic acid cyclohexyl residue unit etc. are mentioned.

  As a hexoxycinnamate ester residue unit, for example, methyl 2-hexoxycinnamate residue unit, ethyl 2-hexoxycinnamate residue unit, n-propyl 2-hexoxycinnamate residue unit, isopropyl 2-hexoxycinnamate Residue unit, n-butyl residue unit of 2-hexoxycinnamic acid, sec-butyl residue unit of 2-hexoxycinnamic acid, tert-butyl residue unit of 2-hexoxycinnamic acid, cyclohexyl residue unit of 2-hexoxycinnamic acid, Methyl 3-hexoxycinnamate residue unit, ethyl 3-hexoxycinnamate residue unit, n-propyl residue unit of 3-hexoxycinnamic acid, isopropyl residue unit of 3-hexoxycinnamic acid, n-butyl 3-hexoxycinnamic acid Residue unit, 3-hexoxycinnamic acid sec-butyl residue unit, 3-hexoxykeate Ternary 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-hexoxy cinnamate Cyclohexyl residue unit, 2,3-dihexoxycinnamic acid methyl residue unit, 2,3-dihexoxycinnamic acid ethyl residue unit, 2,3-dihexoxycinnamic acid n-propyl residue unit, 2,3-dihexoxy cinnamate Isopropyl residue unit, 2,3-Dihexoxycinnate residue unit, 2, 3 Dihexoxycinnamic acid sec-butyl residue unit, 2,3-dihexoxycinnamic acid tert-butyl residue unit, 2,3-dihexoxycinnamic 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-P Ropyl residue unit, 2,5-dihexoxycinnamic acid isopropyl residue unit, 2,5-Dihexoxy cinnamic acid n-butyl residue unit, 2,5-Dihexoxy cinnamic acid sec-butyl residue unit, 2,5-Dihexoxy cinnamate Ternary acid tert-butyl residue unit, 2,5-Dihexoxycinnamic acid cyclohexyl residue unit, 2,6-Dihexoxycinnamic acid methyl residue unit, 2,6-Dihexoxycinnamic acid residue unit, 2,6-Dihexoxycinoxy acid N-Propyl residue unit, 2,6-Dihexoxycinnamic acid isopropyl residue unit, 2,6-Dihexoxy cinnamic acid n-butyl residue unit, 2,6-Dihexoxy cinnamic acid sec-butyl residue unit, 2 , 6-Dihexoxycinnamic acid tert-butyl residue unit, 2,6-dihexoxycinnamic acid cyclohexyl residue unit, 1, 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 Group unit, methyl 3,5-dihexoxycinnamate residue unit, ethyl 3,5-dihexoxycinnamate residue unit, n-propyl residue unit of 3,5-dihexoxycinnamate residue, isopropyl 3,5-dihexoxycinnamate residue Group unit, 3,5-Dihexoxycinnamic acid n-butyl residue unit, 3,5-Dihexoxycinnamic acid sec- 2, 2, 3, 4-trihexoxycinnamate methyl residue units, 2, 3, 4-trihexoxycinnamate methyl group units Ethyl 3,4-trihexoxycinnamate residue unit, n-propyl residue unit of 2,3,4-trihexoxycinnamic acid residue, isopropyl residue unit of 2,3,4-trihexoxycinnamic acid residue 2,3,4-Trihexoxycinnamic acid n-butyl residue unit, 2,3,4-trihexoxycinnamic acid sec-butyl residue unit, 2,3,4-trihexoxy cinnamate Acid tert-butyl residue unit, 2,3,4-trihexoxycinnamic acid cyclohexyl residue unit, 2,3,5-trihexoxycinnamic acid methyl residue unit, 2,3,5-trihexene Ethyl soxicinnamate 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 Group unit, 2,3,5-trihexoxycinnamic acid sec-butyl residue unit, 2,3,5-trihexoxycinnamic acid tert-butyl residue unit, 2,3,5-trihexoxy group Cinnamic acid cyclohexyl residue unit, 2,3, 6-trihexoxycinnamic acid methyl residue unit, 2, 3, 6- trihexoxy cinnamic acid residue unit, 2, 3, 6- trihexene N-Propyl residue unit of soxicinnamate, isopropyl residue unit of 2,3,6-trihexoxycinnamic acid, n-butyl residue unit of 2,3,6-trihexoxycinnamic acid, 2,3 , 6-trihexoxycinnamic acid sec-butyl residue unit, 2, 6, 6-trihexoxycinnamic acid tert-butyl residue unit, 2,3, 6-trihexoxycinnamic acid cyclohexyl residue unit, 2,4, 5-trihexoxycinnamic acid methyl residue unit, Ethyl 2,4,5-trihexoxycinnamate residue unit, n-propyl residue unit of 2,4,5-trihexoxycinnamate residue, isopropyl 2,4,5-trihexoxycinnamate residue Group unit, n-butyl residue unit of 2,4,5-trihexoxycinnamic acid, sec-butyl residue unit of 2,4,5-trihexoxycinnamic acid, 2,4,5-trihexoxy group Cinnamic acid tert-butyl residue unit, 2,4,5-trihexoxycinnamic acid cyclohexyl residue unit, 2,4,6-trihexoxycinnamic acid methyl residue unit, 2,4,6- Ethyl trihexoxycinnamate residue unit, 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-trihexoxycinnamic acid, 2 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 unit, methyl 3,4,5-trihexoxycinnamate residue unit, ethyl 3,4,5-trihexoxycinnamate residue unit, 3,4,5-trihexoxycinnamic acid n-Propyl residue unit, 3,4,5-Trihexoxycinnamic acid isopropyl residue unit, 3,4,5-Trihexoxycinnamic acid n-butyl residue unit, 3,4,5-Tri Hexoxycinnamic 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-tetrahexoxycinnamic acid methyl residue unit, 2 Ethyl 3,4,5-tetrahexoxycinnamate residue unit, 2,3,4,5-tetrahexoxycinnamic acid n-propyl residue unit 2,3,4,5-tetrahexoxy Isopropyl cinnamate residue unit, n-butyl residue unit of 2,3,4,5-tetrahexoxycinnamic acid, sec-butyl residue unit of 2,3,4,5-tetrahexoxycinnamic acid, 2,3,4,5-Tetrahexoxycinnamic acid tert-butyl residue unit, 2,3,4,5-Tetrahexoxycinnamic acid cyclohexyl residue unit, 2,3,4,6-tetrahexene Soxicinnamate methyl residue unit, 2, 3, 4, 6 Ethyl tetrahexoxycinnamate residue unit, n-propyl residue unit of 2,3,4,6-tetrahexoxycinnamic acid, isopropyl residue unit of 2,3,4,6-tetrahexoxycinnamic acid 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 tert-butyl residue unit, 2,3,4,6-tetrahexoxycinnamic acid cyclohexyl residue unit, 2,3,5,6-tetrahexoxycinnamic acid methyl residue Units, ethyl 2,3,5,6-tetrahexoxycinnamate residue units, 2,3,5,6-tetrahexoxycinnamic acid n-propyl residue units 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-tetrahexoxy cinnamic acid cyclohexyl residue unit, pentahexoxy cinnamic acid methyl residue unit, pentahexoxy cinnamic acid residue unit, pentahex N-Propyl residue unit of soxicinnamate, isopropyl residue unit of pentahexoxycinnamic acid, n-butyl residue unit of pentahexoxycinnamic acid, sec-butyl residue unit of pentahexoxycinnamic acid, pentahexene Examples thereof include a tert-butyl residue unit of soxcinnamic acid, a cyclohexyl residue unit of pentahexoxycinnamic acid, and the like.

As dodeto cinnamate ester residue unit, for example, methyl 2-dodetocinnamate residue unit, ethyl 2-dodetocinnamate residue unit, n-propyl 2-dodetocinnamate residue unit, isopropyl 2-dodetocinnamate Residue unit, 2-dodoxycinnamic acid n-butyl residue unit, 2-dodoxycinnamic acid sec-butyl residue unit, 2-dodoxycinnamic acid tert-butyl residue unit, 2-dodoxycinnamic acid cyclohexyl residue unit, Methyl 3-dodeoxycinnamate residue unit, ethyl 3-dodeoxycinnamate residue unit, n-propyl residue unit of 3-dodeoxycinnamate, isopropyl residue unit of 3-dodeoxycinnamic acid, n-butyl 3-dodeoxycinnamic acid Residue unit, 3- dodetoxic acid sec-butyl residue unit, 3-dodetoxike Ternary tert-butyl residue unit, 3-dodeoxycinnamic acid cyclohexyl residue unit, 4-dodeoxycinnamic acid methyl residue unit, 4-dodeoxycinnamic acid ethyl residue unit, 4-dodeoxycinnamic acid n-propyl residue unit 4- dodetoxycinnamic acid isopropyl residue unit, 4- dodetoxycinnamic acid n-butyl residue unit, 4- dodetoxycinnamic acid sec-butyl residue unit, 4- dodetoxycinnamic acid tert-butyl residue unit, 4- dodoxycinnamic acid unit Cyclohexyl residue unit, 2,3-dido deoxycinnamic acid methyl residue unit, 2,3-dido deoxy cinnamic acid ethyl residue unit, 2,3-dido deoxy cinnamic acid n-propyl residue unit, 2,3-dido deoxy cinnamate Isopropyl residue unit, 2,3-Zide detoxic acid n-butyl residue unit, 2, 3 Sec-butyl residue unit of dododexycinnamic acid, tert-butyl residue unit of 2,3-didodoxycinnamic acid, cyclohexyl residue unit of 2,3-didodoxycinnamic acid residue, methyl 2,4-didodeoxycinnamic acid residue unit, 2, Ethyl 4-zidodeoxycinnamic acid residue unit, n-propyl residue unit of 2,4-zidodeoxycinnamic acid unit, isopropyl residue unit of 2,4-zidodoxycinnamic acid residue, n-butyl residue unit of 2,4-zidodoxycinnamic acid unit, 2,4-Zide detoxycinnamic acid sec-butyl residue unit, 2,4-zido detoxycinnamic acid tert-butyl residue unit, 2,4-zidodetoxycinnamic acid cyclohexyl residue unit, 2,5-zidodoxycinnamic acid methyl residue Unit, ethyl 2,5-zidodeoxycinnamate residue unit, 2,5-zidodeoxycinnamic acid n-p Ropyl residue unit, 2,5-zidodeoxycinnamic acid isopropyl residue unit, 2,5-zidodoxycinnamic acid n-butyl residue unit, 2,5-zidodetoxycinnamic acid sec-butyl residue unit, 2,5-zidodexoxylic acid unit Ternary acid tert-butyl residue unit, 2,5-dido deoxycinnamic acid cyclohexyl residue unit, 2,6-dido deoxy cinnamic acid methyl residue unit, 2,6-dido deoxy cinnamic acid ethyl residue unit, 2,6-dido dexitone N-propyl molybdate residue unit, 2,6-dido deoxycinnamic acid isopropyl residue unit, 2,6-dido deoxy cinnamic acid n-butyl residue unit, 2,6-dido deoxy cinnamic acid sec-butyl residue unit, 2 , 6- zido detoxicinamic acid tert-butyl residue unit, 2, 6-zido detoxycinnamic acid cyclohexyl residue unit, Methyl 4-, 4- dode-de-cinnamate residue unit, 3,4- do-de-de- cinnamate residue unit, 3,4- do-de-de- cinnamate residue unit, n- propyl residue unit, 3, 4- do-de-deoxy cinnamate isopropyl residue unit, 3 , 4-Zide detoxycinnamic acid n-butyl residue unit, 3,4-zido detoxycinnamic acid sec-butyl residue unit, 3,4-zidodetoxycinnamic acid tert-butyl residue unit, 3,4-zidodoxycinnamic acid cyclohexyl residue Group unit, methyl 3,5-didodeoxycinnamate residue unit, ethyl 3,5-didodeoxycinnamate residue unit, n-propyl residue unit of 3,5-didodecycinamic acid residue, isopropyl 3,5-didodeoxycinnamic acid residue Group unit, 3,5-dido deoxycinnamic acid n-butyl residue unit, 3,5-dido deoxycinnamic acid sec- Tyl residue unit, 3,5-didodeoxycinnamic acid tert-butyl residue unit, 3,5-didodetoxycinnamic acid cyclohexyl residue unit, 2,3,4-tridodoxycinnamic acid methyl residue unit, 2 , 3, 4- toldo deoxycinnamic acid residue unit, 2, 3, 4- toldo deoxycinnamic acid n-propyl residue unit, 2, 3, 4- toldo deoxycinnamic acid Isopropyl residue unit, n-butyl residue unit of 2,3,4-tridodeoxycinnamic acid, sec-butyl residue unit of 2,3,4-tridodeoxycinnamic acid, 2,3,4 -Tridodetoxincinnamic acid tert-butyl residue unit, 2,3,4-tridodeoxycinnamic acid cyclohexyl residue unit, 2,3,5-tridodeoxycinnamic acid methyl residue unit Ethyl 2,3,5 tolydodecinnamate residue units 2, N-Propyl residue unit of 3,5-tolydetodoxycinnamic acid, isopropyl residue unit of 2,3,5-tolytodoxycinnamic acid, n, 2,3,5-tolydoxycinnamic acid n -Butyl residue unit, 2,3,5-tridodeoxycinnamic acid sec-butyl residue unit, 2,3,5-tridodeoxycinnamic acid tert-butyl residue unit, 2,3, 5-tridodetocinnamic acid cyclohexyl residue unit, 2,3, 6-tridodeoxycinnamic acid methyl residue unit, 2,3, 6-tridodetocincinic acid residue unit, N-Propyl residue unit of 2,3,6-toridodexincinnamate, isopropyl residue unit of 2,3,6-toridodexinocinnamic acid, 2,3,6-toridodexic acid shell Acid n-Butyl Residue Unit, 2,3,6-Tridodetocinnamate sec-Butyl Residue Unit, 2, , 6- toldo deoxycinnamic acid tert-butyl residue unit, 2,3, 6 toldo deoxycinnamic acid cyclohexyl residue unit, methyl 2,4,5- tolido deoxycinnamic acid residue Group unit, ethyl 2,4,5-tolydo decinnamate residue unit, 2,4,5- tolydo deoxycinnamic acid n-propyl residue unit, 2,4,5-tolyde group Toxycinamic acid isopropyl residue unit, 2,4,5-tolydodexycinnamic acid n-butyl residue unit, 2,4,5-tolydodoxycinnamic acid sec-butyl residue unit, 2 1,4,5-tolydetodoxycinnamic acid tert-butyl residue unit, 2,4,5-tolydodoxycinnamic acid cyclohexyl residue unit, 2,4,6-tolydodoxycinnamic acid Methyl residue unit, Ethyl 2,4,6-tridodeoxycinnamate residue unit, 2,4,6 N-Propyl residue unit of toldo deoxycinnamic acid, n-propyl residue unit of 2,4,6-tolodotoxycinnamic acid, n-butyl residue of 2,4,6- toldodeoxycinnamic acid Unit, 2,4,6-tolydetoxicinamic acid sec-butyl residue unit, 2,4,6-tolydodoxycinnamic acid tert-butyl residue unit, 2,4,6-tolyde Deoxycinnamic acid cyclohexyl residue unit, 3,4,5-tolydo detoxycinnamic acid methyl residue unit, 3,4,5-tolydodoxycinnamic acid residue unit, 3,4, N-Propyl residue unit of 5-tolydo deoxycinnamic acid, isopropyl residue unit of 3,4,5-tolydo deoxycinnamic acid, n-butyl 3,4,5-tolydo dehydroxycinnamic acid Residue unit, 3,4,5-tridodecinoxylic acid sec-butyl residue unit, 3,4,5- Tri-do-de-t-cinnamic acid tert-butyl residue unit, 3,4,5-trido-de-t-cinnamic acid cyclohexyl residue unit, 2,3,4,5-tetra-do-do-to-cinnamate methyl acid residue Unit, ethyl 2,3,4,5-tetradodetocinnamate residue unit, 2,3,4,5-tetradodetocinnamic acid n-propyl residue unit, 2,3,4, 5-tetradodetoxinic acid isopropyl residue unit, 2,3,4,5-tetradodetoxycinnamic acid n-butyl residue unit, 2,3,4,5-tetradodetoxycinnum skin Acid sec-butyl residue unit, 2,3,4,5-tetradodetoxinocinnamate tert-butyl residue unit, 2,3,4,5-tetradodetoxinocinnamate cyclohexyl residue unit, Methyl 2,2,4,6-tetradodetocinnamate residue unit 2,3,4,6 Ethyl tetra dodetocinnamate residue unit, n-propyl residue unit with 2,3,4,6-tetradodetocinnamic acid, isopropyl 2,3,4,6-tetradodetocinnamate Residue unit, n-butyl residue unit of 2,3,4,6-tetradodetoxycinnamic acid sec-butyl residue unit of 2,3,4,6-tetradodetoxycinnamic acid, 2, 3,4,6-Tetradodetoxycinnamic acid tert-butyl residue unit, 2,3,4,6-tetradodetoxycinnamic acid cyclohexyl residue unit, 2,3,5,6-tetrad Methyl detoxin cinnamic acid residue unit, ethyl 2,3,5,6-tetra-do-de-toxycinnamic acid residue unit, n-propyl residue of 2,3,5,6--tetra-do-de-toxycinnamic acid 2,3,5,6-Tetradodecinoxylic acid isopropyl residue unit 2,3,5 N-Butyl residue unit of 6-tetradodetoxycinnamic acid, sec-butyl residue unit of 2,3,5,6-tetradodetoxycinnamic acid, 2,3,5,6-tetradodoxy Cinnamic acid tert-butyl residue unit, 2,3,5,6-tetradodetoxycinnamic acid cyclohexyl residue unit, pentadodetoxinic acid methyl residue unit, pentadodetoxycinium ethylate Residue unit, n-propyl residue unit of pentadodexycinnamic acid, isopropyl residue unit of pentadodexoxycinnamate, n-butyl residue unit of pentadodexycinnamic acid, pentadotetoxycne skin Examples of the acid sec-butyl residue unit, pentadodecoxycinnamic acid tert-butyl residue unit, pentadodecoxycinnamic acid cyclohexyl residue unit and the like can be mentioned.
Among these, methyl 4-methoxycinnamate residue unit, ethyl 4-methoxycinnamate unit residue, 4-methoxycinnamic acid n-propyl residue unit, 4- 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- The methoxy cinnamic acid cyclohexyl residue unit is preferable, and the 4-methoxy cinnamic acid ethyl residue unit is more preferable.

  Moreover, as a residue unit of the polyfunctional acrylate having a urethane bond, any residue unit of a polyfunctional acrylate including a moiety having a urethane bond and a moiety having two or more acrylate units may be used. And, the alkoxycinnamic acid ester-acrylate copolymer of the present invention can achieve higher molecular weight by containing the residue unit of the polyfunctional acrylate having a urethane bond, and can be a polymer. The polymerization conversion ratio of the monomer of (1) is also high, and the efficiency of productivity is also excellent. In addition, when the obtained alkoxycinnamic acid ester-acrylate copolymer is used as a film, it becomes a film excellent in toughness. Here, when it is a residual unit of a polyfunctional acrylate having no urethane bond, the polymer obtained may have problems such as difficulty in achieving high molecular weight and the resulting film being inferior in toughness. .

  The multifunctional acrylate having a urethane bond of the present invention is preferably a difunctional acrylate because molecular weight can be easily controlled. Further, the polyfunctional acrylate having a urethane bond of the present invention is preferably a polyfunctional acrylate having a urethane bond containing a polyester skeleton and / or a polyether skeleton, since a resin having a particularly high toughness can be obtained.

  The polyfunctional acrylate having a urethane bond for inducing the residual unit is, for example, a method of producing by a urethanization reaction of an acrylate having an isocyanate group and a polyalcohol, an acrylate having a hydroxyl group and a polyisocyanate It is possible to obtain by the method of producing by the urethanization reaction of As acrylates having an isocyanate group, for example, 2-acryloyloxyethyl isocyanate, 3-acryloyloxypropyl isocyanate, 4-acryloyloxybutyl isocyanate, 5-acryloyloxypentyl isocyanate, 6-acryloyloxyhexyl isocyanate, 3-acryloyloxy Phenyl isocyanate, 4-acryloyloxyphenyl isocyanate and the like can be mentioned, and as polyalcohols, ethylene glycol, propylene glycol, 1,4-butanediol, glycerin, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like can be mentioned. Further, examples of acrylates having a hydroxyl group include hydroxyethyl acrylate, polyethylene glycol acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and the like, and as polyisocyanates, 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 is, for example, the reaction product of hydroxyethyl acrylate and hexamethylene diisocyanate, the 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 Reaction product of propane with bis (4-isocyanatocyclohexyl) methane, reaction product of polyethylene glycol acrylate with isophorone diisocyanate, pentaerythritol The reaction product of lithium acrylate and hexamethylene diisocyanate, the reaction product of pentaerythritol triacrylate and isophorone diisocyanate, the reaction product of dipentaerythritol pentaacrylate and hexamethylene diisocyanate trimer, etc. These may be contained alone or in combination of two or more.

  Moreover, the polyfunctional acrylate having the urethane bond is, for example, (trade name) U-2PPA (manufactured by Shin-Nakamura Chemical Co., Ltd.), (trade name) U-6HA (manufactured by Shin-Nakamura Chemical Co., Ltd. Ltd.), (trade name) UA-32P (made by Shin-Nakamura Chemical Co., Ltd.), (trade name) UA-NDP (made by Shin-Nakamura Chemical Co., Ltd.), (trade name) U-108A (newly made) Nakamura Chemical Industry Co., Ltd., (trade name) UA-511 (Shin Nakamura Chemical Co., Ltd.), (trade name) UA-4200 (Shin Nakamura Chemical Co., Ltd.), (trade name) UA -340P (made by Shin-Nakamura Chemical Co., Ltd.), (trade name) UA-6200 (made by Shin-Nakamura Chemical Co., Ltd.), (trade name) U-108 (made by Shin-Nakamura Chemical Co., Ltd.), Trade name) UA-512 (Shin-Nakamura Chemical Co., Ltd.), (trade name) UA-7000 (Shin-Nakamura Chemical Co., Ltd.) (Trade name) UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), (trade name) M-1200 (manufactured by Toagosei Co., Ltd.), (trade name) M- 1600 (Toagosei (trade name) (Trade name) M-1960 (manufactured by Toagosei Co., Ltd.) and the like are available.

  The alkoxycinnamic acid ester-acrylate copolymer may contain other monomer residue units as long as the scope of the present invention is not exceeded. A styrene residue unit such as a styrene residue unit or an α-methylstyrene residue unit; (meth) acrylic acid residue unit; methyl (meth) acrylate residue unit, ethyl (meth) acrylate residue unit, (Meth) acrylic acid ester residue units such as butyl (meth) acrylate residue unit; vinyl ester residue units such as vinyl acetate residue unit and vinyl propionate residue unit; acrylonitrile residue unit; 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-methyl maleimide residue -Substituted maleimides residue units such as N-, N-cyclohexyl maleimide residue units, N-phenyl maleimide residue units, etc .; olefins residue units such as ethylene residue units, propylene residue units; fumaric acid di-n- 1 type, or 2 or more types selected from fumaric-acid diesters residual units, such as a butyl residue unit, a fumaric-acid diisopropyl residue unit, a fumaric-acid bis (2-ethylhexyl) residual unit, can be mentioned.

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

  The alkoxycinnamic acid ester-acrylate copolymer of the present invention is excellent in mechanical properties and strength at the time of forming a film, so from the elution curve measured by gel permeation chromatography (GPC) The weight average molecular weight in terms of standard polystyrene obtained is preferably 120,000 to 1,000,000, more preferably 140,000 to 700,000, and 150,000 to 500,000. Particularly preferred.

  The alkoxycinnamic acid ester-acrylate copolymer of the present invention may be produced by any method as long as an alkoxycinnamic acid ester-acrylate copolymer can be obtained, for example, alkoxycinnamic acid ester And the radical polymerization of a polyfunctional acrylate having a urethane bond. Here, as a polyfunctional acrylate which has a urethane bond, the compound etc. which derive the residue unit of the above-mentioned polyfunctional acrylate which has a urethane bond can be mentioned.

  The radical polymerization may be any of known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, precipitation polymerization and emulsion polymerization.

  As a polymerization initiator at the time of radical polymerization, for example, benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, 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 Examples include azo initiators such as (cyclohexane-1-carbonitrile) and the like.

  And there is no restriction 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 etc; methanol, ethanol, propanol, butanol etc Cyclohexane, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, dimethylformamide, isopropyl acetate, water and the like, and a mixed solvent thereof is also mentioned.

  In addition, the polymerization temperature at the time of radical polymerization can be appropriately set according to the decomposition temperature of the polymerization initiator, and control of the reaction is easy, so it is generally performed in the range of 30 to 150 ° C. Is preferred.

  Furthermore, when producing the alkoxycinnamic acid ester-acrylate copolymer of the present invention, it becomes possible to produce an alkoxycinnamic acid ester-acrylate copolymer of higher molecular weight more efficiently, 100 mol of total monomers containing 50 to 99 mol% of alkoxycinnamic acid ester, 0.01 to 1 mol% of polyfunctional acrylate having urethane bond, and 0 to 49.99 mol% of other monomers It is preferable to perform a radical polymerization reaction in the presence of 0.001 to 5 mol% of a radical polymerization initiator as%.

  When an optical film using the alkoxycinnamic acid ester-acrylate copolymer of the present invention is obtained, it is possible to use a retardation film because it has high out-of-plane retardation even in a thin film and is excellent in optical characteristics. 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 orthogonal thereto is ny, and the refractive index in the film thickness direction is nz. The retardation film is characterized in that the relationship is nx ≦ ny <nz, and the viewing angle of STN-LCD, IPS-LCD, reflective LCD, transflective LCD etc. by satisfying the above nx ≦ ny <nz It becomes a retardation film excellent in compensation performance. In general, the control of the three-dimensional refractive index of the film is carried out by stretching the film, etc., but the control of the production process and quality becomes complicated, but the retardation film of the present invention is unstretched and the refractive index in the film thickness direction Is found to exhibit a unique behavior that is high.

Further, since the retardation film of the present invention becomes a retardation film having more excellent optical properties, the out-of-plane retardation (Rth) measured at a wavelength of 550 nm represented by the following formula (a) is -100 to- The wavelength 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 represents 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 relationship between the film thickness and the out-of-plane retardation is preferably 5.5 nm / film thickness (μm) or more in absolute value, 6 nm / The film thickness (μm) or more is more preferable, and 8 nm / film thickness (μm) or more is particularly preferable.

  The retardation film of the present invention preferably has a light transmittance of 85% or more, and more preferably 90% or more, because the characteristics of the image quality are excellent when used in a liquid crystal display device. . The haze 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 retardation film of this invention, For example, methods, such as a solution cast method and a melt casting method, are mentioned.

  In the solution casting method, a solution in which an alkoxycinnamic acid ester-acrylate copolymer is dissolved in a solvent (hereinafter referred to as a dope) is cast on a supporting substrate, and then the solvent is removed by heating or the like to obtain a film. It is a method. At that time, as a method of 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, the method of continuously extruding the dope from the die onto a belt-like or drum-like support substrate is the most common. Examples of the support substrate to be used include a glass substrate, a metal substrate such as stainless steel or ferro type, and a film such as polyethylene terephthalate. When forming a film having high transparency and excellent thickness accuracy and surface smoothness in the solution casting method, the solution viscosity of the dope is a very important factor, and 10 to 20000 cPs is preferable, 100 It is further more preferable that it is-10000 cPs.

  In this case, the coating thickness of the alkoxycinnamic acid ester-acrylate copolymer is preferably 1 to 200 μm after drying, more preferably 5 to 100 μm, and particularly preferably 10 to 50 μm, because handling of the film is easy. is there.

  The melt casting method is a molding method in which an alkoxycinnamic acid ester-acrylate copolymer is melted in an extruder, extruded from a slit of a T-die into a film, and then cooled while being cooled by a roll, air or the like.

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

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

  The retardation film of the present invention is preferably blended with an antioxidant in order to enhance the thermal stability of the film formation or the retardation film itself. Examples of the antioxidant include hindered phenol-based antioxidants, phosphorus-based antioxidants, and other antioxidants. These antioxidants may be used alone or in combination. And, it is preferable to use a combination of a hindered antioxidant and a phosphorus-based antioxidant because the antioxidant effect is synergistically improved, and in that case, for example, with respect to 100 parts by weight of the hindered antioxidant, It is further preferable to mix and use a phosphorus-based antioxidant in an amount of 100 to 500 parts by weight. In addition, the addition amount of the antioxidant is 0.01 to 10 weight because it is excellent in the antioxidant action with respect to 100 parts by weight of the alkoxycinnamic acid ester-acrylate copolymer constituting the retardation film of the present invention. Part is preferred, and 0.5 to 1 part by weight is more preferred.

  Furthermore, as an ultraviolet absorber, for example, an ultraviolet absorber such as benzotriazole, benzophenone, triazine, benzoate and the like may be blended as needed.

  The retardation film of the present invention contains other polymers, surfactants, polymer electrolytes, conductive complexes, inorganic fillers, pigments, antistatic agents, antiblocking agents, lubricants and the like within the range not exceeding the scope of the invention. You may

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

  The present invention provides a novel alkoxycinnamic acid ester-acrylate copolymer which is excellent in the properties of a film or the like due to its high molecular weight, and a method for efficiently producing the alkoxycinnamic acid ester-acrylate copolymer. It is provided.

  Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples.

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

<Composition of Alkoxycinnamic Acid Ester-Acrylate Copolymer>
It calculated | required from proton nuclear magnetic resonance spectroscopy (< ¹ > H-NMR) spectrum analysis using the nuclear magnetic resonance measuring apparatus (made by JEOL, product name JNM-GX270).

<Measurement of weight average molecular weight>
Measured at 40 ° C using tetrahydrofuran as a solvent using a gel permeation chromatography (GPC) apparatus (made by Tosoh Corporation, trade name C0-8011 (column GMH _HR -H)), and converted to standard polystyrene I asked.

<Method of evaluating transparency>
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>
It measured based on JISK7142 (1981 version) using the Abbe refractometer (made by Atago).

<Measurement of retardation and three-dimensional refractive index of film>
It measured using the fully automatic birefringence meter (Oji Scientific Instruments make, brand name KOBRA-WR).

Example 1 Synthesis of Alkoxycinnamic Acid Ester-Acrylate Copolymer (Ethyl 4-Methoxycinnamate / 4-Ethylhexyl 4-Methoxycinnamic Acid / Acrylate Copolymer) 1)
50 g (0.26 mol) of ethyl 4-methoxycinnamate, 15.2 g (0.065 mol) of 2-ethylhexyl 4-methoxycinnamate, urethane as a multifunctional acrylate having a urethane bond in a 75 mL glass ampoule 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 as a polymerization initiator 0.38 g (0.0022 mol) of pivalate was added, nitrogen substitution and depressurization were repeated, and then sealing was performed under reduced pressure. The ampoule was placed in a thermostat at 50 ° C. and radical polymerization was performed by holding for 48 hours. After completion of the polymerization reaction, the polymer was taken out of the ampoule and dissolved in 400 g of tetrahydrofuran. The polymer solution was dropped into 3 L of methanol for precipitation, and then vacuum dried at 80 ° C. for 10 hours to obtain 17 g of an alkoxycinnamic acid ester-acrylate copolymer (yield: 26%).

  The weight average molecular weight of the obtained alkoxycinnamic acid ester-acrylate copolymer was 153,000.

In addition, according to ¹ H-NMR measurement, the copolymer composition is ethyl 4-methoxycinnamate residue unit / 4-methoxycinnamic acid 2-ethylhexyl residue unit / acrylate residue unit = 83.96 / 15.99 It was confirmed to be /0.05 (mol%).

  Alkoxycinnamic acid ester-acrylate copolymer is dissolved in methyl isobutyl ketone to make a 15 wt% resin solution, cast by a coater on a 10 cm × 10 cm polyethylene terephthalate film, and dried at 130 ° C. for 10 minutes A transparent film using an alkoxycinnamic acid ester-acrylate copolymer having a thickness of 30 μm was obtained. The retardation of the obtained film was measured. The out-of-plane retardation Rth was as large 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 the bending test which makes edge parts contact was implemented, generation | occurrence | production of a crack etc. was not seen in the alkoxy cinnamate ester-acrylate copolymer layer, but it was excellent in toughness.

Example 2 Synthesis of Alkoxycinnamic Acid Ester-Acrylate Copolymer (Ethyl 4-Methoxycinnamate / Diisopropyl Fumarate / Acrylate Copolymer) 2
50 g (0.24 mol) of ethyl 4-methoxycinnamate, 20.8 g (0.10 mol) of diisopropyl fumarate in a 75 mL glass ampoule, urethane acrylate compound as a polyfunctional acrylate having a urethane bond (trade name) 0.54 g (4.2 × 10 ^-4 mol (0.120 mol%)) of UA-4200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 0.40 g of tert-butyl peroxypivalate as a polymerization initiator ( 0.0023 mol) was added, nitrogen substitution and depressurization were repeated, and then sealing was performed under reduced pressure. The ampoule was placed in a thermostat at 50 ° C. and radical polymerization was performed by holding for 48 hours. After completion of the polymerization reaction, the polymer was taken out of the ampoule and dissolved in 400 g of tetrahydrofuran. The polymer solution was dropped into 3 L of methanol for precipitation, 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 acid ester-acrylate copolymer was 184,000.

Further, according to ¹ H-NMR measurement, the copolymer composition is ethyl 4-methoxycinnamate residue unit / diisopropyl fumarate residue unit / acrylate residue unit = 54.81 / 45.07 / 0.12 (mole %) Was confirmed.

  The obtained alkoxycinnamic acid ester-acrylate copolymer was formed into a film by the same method as in Example 1 and retardation was measured. The out-of-plane retardation Rth was as large as −258 nm, and the film thickness and the surface The absolute value of the external retardation was 8.6 nm / film thickness (μm). Furthermore, when the bending test of this film was implemented, the crack generation etc. were not seen in the obtained transparent film, but it was excellent in toughness.

Example 3 Synthesis of Alkoxycinnamic Acid Ester-Acrylate Polymer (Isopropyl 4-Methoxycinnamate / Diethyl Fumarate / Acrylate Copolymer) 3
50 g (0.21 mol) of isopropyl 4-methoxycinnamate, 4.1 g (0.024 mol) of diethyl fumarate in a 75 mL glass ampoule, urethane acrylate compound as a polyfunctional acrylate having a urethane bond (trade name) 0.52 g (4.3 × 10 ⁻⁴ mol (0.182 mol%)) of U-6 HA (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 0.28 g of tert-butyl peroxypivalate as a polymerization initiator (0.0016 mol) was added, nitrogen substitution and depressurization were repeated, and then sealing was performed under reduced pressure. The ampoule was placed in a thermostat at 50 ° C. and radical polymerization was performed by holding for 48 hours. After completion of the polymerization reaction, the polymer was taken out of the ampoule and dissolved in 400 g of tetrahydrofuran. The polymer solution was dropped into 3 L of methanol for precipitation, and then vacuum dried at 80 ° C. for 10 hours to obtain 17 g of an alkoxycinnamic acid ester-acrylate copolymer (yield: 31%).

  The weight average molecular weight of the obtained alkoxycinnamic acid ester-acrylate copolymer was 195,000.

In addition, according to ¹ H-NMR measurement, the copolymer composition is 4-methoxycinnamic acid isopropyl residue unit / diethyl fumarate residue unit / acrylate residue unit = 89.86 / 9.96 / 0.18 (mole %) Was confirmed.

  The obtained alkoxycinnamic acid ester-acrylate copolymer was formed into a film by the same method as in Example 1 and retardation was measured. The out-of-plane retardation Rth was as large as −261 nm, and the film thickness and the surface The absolute value of the external retardation was 8.7 nm / film thickness (μm). Furthermore, when the bending test of this film was implemented, the crack generation etc. were not seen in the obtained transparent film, but it was excellent in toughness.

Example 4 Synthesis of alkoxycinnamic acid ester-acrylate copolymer (ethyl 3,4-dimethoxycinnamate copolymer / N-phenylmaleimide / acrylate copolymer) 4)
50 g (0.23 mol) of ethyl 3,4-dimethoxycinnamate, 4.4 g (0.025 mol) of N-phenylmaleimide in a 75 mL glass ampoule, a urethane acrylate compound as a 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 as a polymerization initiator After adding .29 g (0.0017 mol), repeating nitrogen substitution and depressurization, sealing was performed under reduced pressure. The ampoule was placed in a thermostat at 50 ° C. and radical polymerization was performed by holding for 24 hours. After completion of the polymerization reaction, the polymer was taken out of the ampoule and dissolved in 400 g of tetrahydrofuran. The polymer solution was dropped into 3 L of methanol for precipitation, and then vacuum dried at 80 ° C. for 10 hours to obtain 16 g of an alkoxycinnamic acid ester-acrylate copolymer (yield: 30%).

  The weight average molecular weight of the obtained alkoxycinnamic acid ester-acrylate copolymer was 195,000.

Further, according to ¹ H-NMR measurement, the copolymer composition is ethyl 3,4-dimethoxycinnamate residue unit / N-phenylmaleimide residue unit / acrylate residue unit = 81.95 / 17.98 / 0. It was confirmed to be 07 (mol%).

  The obtained alkoxycinnamic acid ester-acrylate copolymer was formed into a film by the same method as in Example 1 and retardation was measured. The out-of-plane retardation Rth was as large as −254 nm, and the film thickness and the surface The absolute value of the external retardation was 8.5 nm / film thickness (μm). Furthermore, when the bending test of this film was implemented, the crack generation etc. were not seen in the obtained transparent film, but it was excellent in toughness.

Example 5 Synthesis of Alkoxycinnamic Acid Ester-Acrylate Copolymer (Ethyl 4-Ethoxycinnamate / Ethyl Acrylate / Acrylate Copolymer) 5
50 g (0.24 mol) of ethyl 4-ethoxycinnamate, 1.3 g (0.013 mol) of ethyl acrylate in a 75 mL glass ampoule, urethane acrylate compound (trade name) UA as a polyfunctional acrylate having a urethane bond -4200 (Shin-Nakamura chemical Co., Ltd.) 0.40 g (3.1 × ^{10 -4} mol (0.120 mol%)) and a polymerization initiator tert- butyl peroxypivalate 0.30 g (0 .0017 mol) was added, nitrogen substitution and depressurization were repeated, and then sealing was performed under reduced pressure. The ampoule was placed in a thermostat at 50 ° C. and radical polymerization was performed by holding for 36 hours. After completion of the polymerization reaction, the polymer was taken out of the ampoule and dissolved in 400 g of tetrahydrofuran. The 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 weight average molecular weight of the obtained alkoxycinnamic acid ester-acrylate copolymer was 194,000.

Further, according to ¹ H-NMR measurement, the copolymer composition is ethyl 4-ethoxycinnamate residue unit / ethyl acrylate residue unit / acrylate residue unit = 88.93 / 10.95 / 0.12 (mol% It confirmed that it was).

  The obtained alkoxycinnamic acid ester-acrylate copolymer was formed into a film by the same method as in Example 1, and retardation was measured. The out-of-plane retardation Rth was as large as −257 nm, and the film thickness and the surface were large. The absolute value of the external retardation was 8.6 nm / film thickness (μm). Furthermore, when the bending test of this film was implemented, the crack generation etc. were not seen in the obtained transparent film, but it was excellent in toughness.

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

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

  The obtained alkoxycinnamic acid ester copolymer was formed into a film by the same method as in Example 1, and a bending test of this film was carried out. Crack occurred on the

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

The weight average molecular weight of the obtained ethyl 4-methoxycinnamic acid-diisopropyl fumaric acid 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 acid ester copolymer was formed into a film by the same method as in Example 1, and a bending test of this film was carried out. Crack occurred on the

Comparative example 3
9 g of isopropyl 4-methoxycinnamic acid-diethyl 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 weight average molecular weight of the obtained 4-methoxycinnamic acid isopropyl-fumaric acid copolymer was as low as 60000. ^The copolymer composition obtained by ¹ H-NMR measurement was 4-methoxycinnamic acid isopropyl residue unit / diethyl fumarate residue unit = 90/10 (mol%).

  The obtained alkoxycinnamic acid ester copolymer was formed into a film by the same method as in Example 1, and a bending test of this film was carried out. Crack occurred on the

Comparative example 4
9 g of ethyl 3,4-dimethoxycinnamate-N-phenylmaleimide copolymer was obtained by the same method 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 ethyl 3,4-dimethoxycinnamate-N-phenylmaleimide copolymer was as low as 94000. 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 acid ester copolymer was formed into a film by the same method as in Example 1, and a bending test of this film was carried out. Crack occurred on the

Comparative example 5
According to the same method as in Example 5 except that the polyfunctional acrylate having a urethane bond was not used, 5 g of ethyl 4-ethoxycinnamate-ethyl acrylate copolymer was obtained (yield: 10%).

The weight average molecular weight of the obtained 4-ethoxy cinnamate-ethyl acrylate copolymer was as low as 78,000. Moreover, the copolymer composition obtained by ¹ H-NMR measurement was ethyl 4-ethoxycinnamate residue unit / ethyl acrylate residue unit = 89/11 (mol%).

  The obtained alkoxycinnamic acid ester copolymer was formed into a film by the same method as in Example 1, and a bending test of this film was carried out. Crack occurred on the

Claims (12)

An alkoxy cinnamate-acrylate copolymer comprising at least an alkoxy cinnamic acid ester residue unit represented by the general formula (1) and a residual unit of a polyfunctional acrylate having a urethane bond.

(Wherein, 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 -6 cyclic alkyl group is shown, n is an integer of 1-5.) 50 to 99.99 mol% of alkoxycinnamic acid 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 alkoxycinnamic acid ester-acrylate copolymer according to claim 1, characterized in that The weight average molecular weight of standard polystyrene conversion is 120,000-1,000,000, The alkoxy cinnamate ester-acrylate copolymer of Claim 1 or Claim 2 characterized by the above-mentioned. 4. The alkoxycinnamate residue unit is one or more residue units selected from methoxycinnamic acid ester residue units and ethoxycinnamic acid ester residue units. The alkoxy cinnamate ester-acrylate copolymer in any one. The alkoxycinnamic acid ester-acrylate copolymer according to any one of claims 1 to 4, wherein the alkoxycinnamic acid ester residue unit is a 4-methoxycinnamic acid ester residue unit. Alkoxycinnamic acid ester residue unit is 4-methoxycinnamic acid methyl residue unit, 4-methoxycinnamic acid ethyl residue unit, 4-methoxycinnamic acid n-propyl residue unit, 4-methoxycinnamic acid 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 and 4-methoxycinnamic acid The alkoxycinnamic acid ester-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 alkoxy cinnamate ester-acrylate copolymer according to any one of claims 1 to 6, wherein the polyfunctional acrylate having a urethane bond is a difunctional acrylate. The alkoxy cinnamate ester-acrylate copolymer according to any one of claims 1 to 7, wherein the polyfunctional acrylate having a urethane bond contains a polyester skeleton and / or a polyether skeleton. A total monomer containing 50 to 99.99 mol% of alkoxycinnamic acid ester, 0.01 to 1 mol% of polyfunctional acrylate having a urethane bond, and 0 to 49.99 mol% of other monomers A radical polymerization reaction is performed in the presence of 0.001 to 5 mol% of a radical polymerization initiator as 100 mol%, and a method for producing an alkoxycinnamic acid ester-acrylate copolymer. A film comprising the alkoxycinnamic acid ester-acrylate copolymer according to any one of claims 1 to 8. A retardation film comprising the film according to claim 10. In the case where 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 film thickness direction is nz, The retardation film according to claim 11, characterized in that