TWI274765B - Transparent film - Google Patents

Abstract

A film is provided which comprises a thermoplastic resin A having a substituted or non-substituted imide group at a side chain of the resin A, and a thermoplastic resin B having a substituted or non-substituted phenyl group and a nitrile group at a side chain of the resin B. The film has a retardation value of 0 to 1000 nm, a light transmission of 85% or more, and a haze of 2% or less.

Description

1274765 V. INSTRUCTIONS (Technical Field) The present invention relates to a transparent optical film. In particular, the present invention relates to a film having excellent optical properties and having various optical uses. In particular, one aspect of the present invention relates to A retardation film. Another aspect of the invention relates to a film which does not substantially have a phase difference effect. A film which does not substantially have a phase difference effect is useful as a polarizing element protective film or the like. Recently, electronic devices have become smaller and smaller. In such electronic devices represented by notebook computers, paper-handling devices, mobile phones, and personal digital assistants, liquid crystal displays that are advantageous in terms of lightness and shortness are generally used. In such liquid crystal display devices, various films (for example, polarized films) are used to ensure display quality. In applications such as personal digital assistants or mobile phones, plastic liquid crystal display devices using a resin film instead of a glass substrate are actually used. A device used for polarized light, such as a resin in a liquid crystal display device The film not only needs to be optically transparent, but also needs to be optically uniform. In the case of a film substrate used in a plastic liquid crystal display device, the phase difference effect represented by the product of the film substrate (birefringence and thickness) is not only required It is small and needs to be changed even when external stress is applied. In the case of a resin film, it has been found that the polarization and alignment of the resin molecules in the film involve a phase difference effect. To obtain a film having a small phase difference effect A resin having a small polarization is used. In addition, the conditions for producing the film are adjusted in such a manner as to suppress the alignment of the molecules as much as possible. -4- The paper size is suitable for the product® S tm^(CNS) A4^(2i^297 ^)' 1274765

In general, engineering plastic resins such as polycarbonate, polyacrylic acid, polyfluorene, and polyether iron, and cellulose such as triethyl cellulose are known as a film resin. When such a resin is used to produce a film, various stresses are applied to the formed film. These stresses are caused by the following factors: back pressure for flowing the molten resin; shrinkage of the resin when the solvent is dried or heat shrinkage of the resin; tension when the film is conveyed, and the like. The stress causes the molecules in the film to align, so it is quite possible to have a phase difference effect in the film. In order to solve the aforementioned problems, attempts have been made to use a resin having a small polarization to produce a film. For example, attempts have been made to produce films using olefin resins, such as, for example, cyclic olefin resins. The application range of retardation films has become wider and wider. As films are increasingly used, there is a high demand for the performance of retardation films. The wavelength dependence of the phase difference effect is noticed as a particularly important feature. The wavelength dependence of the phase difference effect is generally defined as Re(400)/Re(550), where Re(400) represents the phase difference effect of the film measured using monochromatic light of 400 nm wavelength, and Re(550) Represents the phase difference effect of a film measured using monochromatic light at a wavelength of 550 nm. Unless otherwise specified, the value defined by Re(400)/Re(550) is referred to herein as wavelength dependence. For example, in an STN liquid crystal display device, a retardation film requires an appropriate wavelength dependency for use in color compensation. On the other hand, a film used for a quarter-wave plate or a half-wave plate needs to have a phase difference effect equivalent to a wavelength of 1 / 4 or 1 / 2 with respect to all wavelengths of visible light. However, the conventional phase difference film of polycarbonate has a wavelength dependence of 1 · 16 and an alignment retardation of 1400 ( -5 - the paper size is applicable to the Chinese National Standard (CNS) A4 specification. (210X297 public) 1274765 A7 ___B7 V. Description of invention (3) Description). In other words, the magnitude of the polarization varies depending on the wavelength. Assuming that this phase difference film having a large wavelength dependency is used in a reflective tft liquid crystal display device, the contrast will be remarkably deteriorated when black display is performed in the liquid crystal display device. Problems to be Solved by the Invention The engineering plastic resin, such as the above-mentioned film of poly-decomposition acid, has a phase difference effect. Therefore, it is necessary to reduce the residual phase difference effect by providing a special method such as heating and annealing the film. Even when a film having a function of lowering the phase difference is produced in this manner, the phase difference effect is again exhibited due to the subsequent operation of the film, resulting in alignment of molecules. For example, when the film and the polarizing plate are laminated to each other, the polarizing plate is usually deformed. If the polarizing plate is deformed, stress will be generated. Stress causes the alignment of the molecules, which leads to the appearance of phase differences. Therefore, the aforementioned film needs to be handled with care. Despite careful handling, the yield (i.e., the probability of producing an end product having a small phase difference effect) is still disadvantageously low. In particular, it is known that when the aforementioned film is used as a protective film for a polarizing element, the stress when the polarizing element is contracted may cause an undesired phase difference effect of the film. This phase difference effect adversely affects the polarization performance of the polarized film. The aforementioned film is produced by various manufacturing methods. One of the methods is a solvent casting method. The film produced by the solvent casting method has a relatively small phase difference effect in the plane of the film. However, the film produced by the solvent casting method has a large phase difference in the thickness direction of the film due to the birefringence caused by the alignment of the molecules, so that the viewing angle characteristics of the film may not be -6 - the paper size Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1274765 A7

Reduced interest. Alternatively, a retardation film can be produced by stretching. When a retardation film is produced by stretching, the phase difference effect changes due to a small change in the tension generated by the stretching device. Further, when the phase acoustic film produced by stretching is laminated to a polarizing element or the like, the phase difference effect may be changed due to the tension generated by the combination. It is unlikely to maintain the expected value due to & Further, the stress may be generated due to, for example, shrinkage of the polarizing plate after lamination, so that the phase difference may be adversely changed. In addition, the wavelength dependence of the phase difference effect is only dependent on the material of the phase difference film. The required wavelength dependence varies from application to application. Different materials were chosen to get different wavelengths related to 9%. Therefore, there is a need to find new materials for applications that require different wavelength correlations. Furthermore, the aforementioned film is usually laminated to glass or another film. However, in the case of a resin having a small polarization, such as a film made of a hydrocarbon-based resin, the film has poor adhesion to a glue or an adhesive. Therefore, a film usually requires a special adhesive. In addition, films usually require surface treatment. Disclosure of the Invention Mode for Solving the Problems The inventors have eagerly studied to solve the aforementioned problems. As a result, the inventors have found that the aforementioned problems can be solved by using a polymer white having a specific structure and composition and having a mouth. It is shown that a phase difference effect is unlikely to occur in the film of this polymer, and the phase difference ❹ and wavelength dependence of the film produced (4) are controlled by the composition ratio of the entangled polymer. The present invention has thus been completed.

1274765 V. Description of the Invention (In addition, according to the present invention, there is provided a transparent film comprising: (A) a thermoplastic resin having a substituted or unsubstituted quinone imine group in a side chain of a resin; and (B) A thermoplastic resin having at least a substituted or unsubstituted phenyl and nitrile group in the side chain of the resin. Note that a thermoplastic resin having a substituted or unsubstituted quinone imine group in its side chain is referred to herein as "thermoplastic". Resin A", while a thermoplastic resin having a substituted or unsubstituted phenyl group and a nitrile group in its side chain is referred to herein as "thermoplastic resin B". In the film of the present invention, the phase difference of the film is self-producing The film has a light transmittance of 85% or more and a haze of the film of 2% or less to 1 nm. In a preferred embodiment, the transparent film of the present invention has a film of 3 μm or less. Further, the transparent film of the present invention has a folding resistance of 30% or more. Further, the transparent film of the present invention has a tear propagation strength of more than gram/mm. The film has 3 at the same time The folding endurance of 0 or more and the tear propagation strength of 150 g/mm or more are more preferable. In a specific example, the thermoplastic resin A is a repeating unit represented by the following chemical formula (1) and is as follows The chemical formula (2) represents a copolymer composed of another repeating unit: R2 • CH Branch (1) J R3 -8 This paper is suitable for the Chinese National Standard (CNS) A4 specification (210X297 mm) (2) 1274765 A7 B7 V. Inventive Note (6) (In the chemical formula (1), R1, R2 and R3 respectively indicate a hydrogen atom or 1 to 8 broken atoms and a base group) (In the chemical formula (2), R indicates 1 to 18 The alkyl group of one carbon atom or the cycloalkyl group of 3 to 12 carbon atoms), and the content of the thermoplastic resin A, the weight of the royal resin in the film is from 60 to 90% by weight. In the present invention, 'thermoplastic Resin B is a substituted or unsubstituted substituted or unsubstituted phenylacetone repeating unit containing 20 to 50% by weight of a substituted or unsubstituted propylene acetonitrile repeating unit and 50 to 80% by weight of a substituted or unsubstituted phenethyl fluorene repeating unit. Copolymers of acetaminophen and substituted or unsubstituted phenethyl hydrazine are preferred. It is preferable to dissolve the resin composition of the present invention in an organic falling agent, and then to flow the solution onto the support, and to dry the solution. More specifically, the transparent film of the present invention comprises: A) a thermoplastic resin having a substituted or unsubstituted quinone imine group in a side chain of the resin; and (a) a thermoplastic tree having a substituted or unsubstituted phenyl and nitrile group in the side chain of the resin Wherein the phase difference of the film is from 0 to 1000 nm, the transmittance of the film is more than 85%, and the haze of the film is less than 2%. In one embodiment, the thermoplastic resin is composed of a repeating unit of a hydrocarbon. And a repeating unit having a substituted or unsubstituted quinone imine group in a side chain of the resin. In one embodiment, the phase difference of the film is less than 20 nanometers. In one embodiment, the phase difference of the film is 20 nanometers or more. In one embodiment, the alignment phase difference of the film is 300 nm or less. 一 In one embodiment, the film is a stretched film. -9- This paper scale applies to Chinese National Standard (CNS) A4 specification (21〇X297 mm) 1274765 A7 B7

In a specific example, the folding resistance of the film is at least 30 times in the plane of the film. In one embodiment, the tear propagation strength of the film is at least 150 grams force per millimeter in at least one direction in the plane of the film. In one embodiment, the surface energy of at least one surface of the film is 5 dyne/cm or more. In one embodiment, the phase difference of the film in the thickness direction of the film is 50 nm or less. In a specific example, the thermoplastic resin A includes a repeating unit represented by the following chemical formula (1), and another repeating unit represented by the following chemical formula (2)

(wherein R1, R2 and R3 each represent a hydrogen atom or an alkyl group of 1 to 8 carbon atoms, and R represents an alkyl group of 1 to 18 carbon atoms or a cycloalkyl group of 3 to 12 carbon atoms)] The content of the thermoplastic resin A is 50 to 90% by weight based on the total weight of the resin in the film. In one embodiment, the thermoplastic resin B has a substituted or unsubstituted propononitrile repeating unit and a substituted or unsubstituted styrene repeating unit, wherein the substituted or unsubstituted acrylonitrile repeating unit is thermoplastic 20 to 50% by weight of Resin B, and substituted or unsubstituted styrene-repeated single-sheet size applicable to China National Standard (CNS) A4 specification (210X 297 mm) 1274765 A7 _— _ B7_ _ The invention (8) is 50 to 80% by weight of the thermoplastic resin B. According to another aspect of the present invention, a method of making the aforementioned film is provided. The method comprises the steps of: expanding a falling liquid containing the thermoplastic resin A and the thermoplastic resin B onto the support; and drying the solution. According to still another aspect of the present invention, an elliptically polarizing plate comprising the foregoing retardation film and a polarizing plate, wherein the film and the polarizing plate are laminated σ, according to still another aspect of the present invention, provides a phase difference comprising the foregoing A circular polarizing plate of a film and a polarizing plate, wherein the film is laminated with a polarizing plate. According to still another aspect of the present invention, there is provided a polarizing plate comprising a polarizing element and a protective film for protecting at least one side of the biasing element, wherein the protective film is the aforementioned film " The film of the invention is made of a resin composition comprising the following components: (Α) a thermoplastic resin A having a substituted or unsubstituted quinone imine group in the side chain of the resin oxime; and (B) on the side of the resin B The chain has at least one substituted or substituted phenyl and nitrile group thermoplastic resin B. The film of the present invention is preferably made only of thermoplastic resins A and 3. However, a third resin may be used in addition to the thermoplastic resins A and B as needed. Note that when the thermoplastic resin A is a copolymer resin, the copolymer resin is also referred to herein as "thermoplastic copolymer A", and when the thermoplastic resin b is a two-material resin, the copolymer resin is also referred to herein as " Thermoplastic copolymerization_j 0 (thermoplastic resin A) -11- 1274765 A7 B7 V. INSTRUCTION DESCRIPTION (9) The thermoplastic resin A used in the present invention has a substituted or unsubstituted quinone imine group in its side chain. The main chain of A may be any thermoplastic resin main chain. For example, the main chain may be composed only of carbon atoms, or in this main chain, an atom other than carbon may be interposed between carbon atoms. Alternatively, the backbone may be composed of atoms other than carbon atoms. The backbone may preferably consist of only carbon atoms. For example, the backbone may be a hydrocarbon or a substituted product thereof. Addition polymerization is carried out. Specifically, the main chain is a polyolefin or a polyethylidene group. The main chain can be produced by condensation polymerization. For example, the main chain can be produced by an ester bond, a guanamine bond or the like. The main chain has a substituted ethylenic monomer via polymerization The polyvinyl backbone is preferably used. The substituted or unsubstituted quinone imine group can be introduced into the thermoplastic resin A by any conventional method. For example, the polymerizable group has a substituted or unsubstituted brewed imine group. a monomer having a substituted or unsubstituted quinone imine group, or, for example, a polymerizable monomer to form a backbone 'subsequently substituted or unsubstituted quinone a group is introduced into the side bond. For example, a compound having a substituted or unsubstituted brewed imine group can be graft-copolymerized into the side chain. When the quinone imine group is substituted with a substituent, the substitution The base may be a conventional substituent which may replace the hydrogen of the quinone imine group. Specifically, for example, the substituent is an alkyl group, etc. The thermoplastic resin A is a repeating unit including at least one olefin (埽) and has At least one type of substituted or unsubstituted cis-butyl quinone imine structure-12 - This paper scale applies to Chinese National Standard (CNS) A4 Regulation 297 public) 1274765 A7 B7 V. Invention Description (1Q) a repeating unit of copolymer (two or The copolymer of the component (multi-component polymer) is preferred. The above-mentioned dilute hydrocarbon-cis-butanediamine copolymer can be synthesized by a known method. For example, as described in Japanese Laid-Open Publication No. 5- 59193, Japanese Laid-Open Patent Publication No. 5-195-801, Japanese Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. a method of polymerizing two types of monomers; a method of polymerizing one type of monomer, and a method of graft-copolymerizing another type of monomer with the produced polymer; and introducing a quinone bond to the polymer based reaction The method of the precursor polymer (described later), etc. The thermoplastic resin A includes a repeating unit derived from at least one olefin (晞) and represented by the following chemical formula (1), and having at least one type of substituted or unsubstituted The cis-butanthrene diamine structure is substituted, and another repeating unit represented by the following chemical formula (2) is more preferable.

(In the chemical formula (1), R2 and inverse 3 respectively indicate a hydrogen atom or a burnt group of 1 to 8 gorgon atoms. The number of carbon atoms in the burnt group is preferably 1 to 4, more preferably 1 to 2, and 1 further More preferably.) (In the chemical formula (2), R represents a hydrogen atom, i to 丨 8 carbon atoms of a foot alkyl group, or a cycloalkyl group of 3 to 12 carbon atoms. The number of carbon atoms in the alkyl group is i to 4 is preferable, 1 to 2 is better, and 1 is more preferably. The carbon number in the ring-burning base is 3 to 9, which is better than the paper size. The national standard (CNS) A4 specification 1274765 5, the invention description (11) And 4 to 7 is more preferable.) Here, the formula (1) (the content of the repeating unit is preferably 20 to 70 mol% based on the entire repeating unit of the thermoplastic resin A, and preferably 4 to 6 mol%. And the percentage of 45 to 55 moles is more preferably. The content of the repeating unit of the tempering formula (2) is preferably from 30 to 80 mol%, based on the total repeating unit of the thermoplastic resin a, from 4 to (9) mole. The percentage is better' and the percentage of 45 to 55 moles is even better. When the content of the repeating unit of the chemical formula (7) is too small or too large, the obtained film may have reduced heat resistance and mechanical strength. The thermoplastic resin A includes repeating units of the chemical formulas (1) and (7) as a main component. In the specific example, the repeating unit of the entire chemical formulas (1) and (7) is more than 50% by mole of the thermoplastic resin A, and more than 7% by mole. Preferably, the percentage of 80 moles or more is more preferably, and the percentage of 9 moles or more is more. In a preferred embodiment, the repeating unit of the entire formula (1) and (2) is 100 mole percent. A third repeating unit to be described later may be used as needed. When the third repeating unit is used, the content of the third repeating unit is preferably 3 〇 mol% or less based on the entire repeating unit of the thermoplastic copolymer resin A. 2 The molar percentage is preferably less than 15%, more preferably 15% or less, and 10% or less. When the content of the third repeating unit is too large, it is expressed by the chemical formulas (1) and (2). The performance of the repeating unit may be insufficient. Further, when the third repeating unit is used, the content of the third repeating unit is 1 mole percent of the total repeating unit of the thermoplastic copolymer resin A to 14- This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1274765

Fifth, the invention description (12 is better, 2 mole percentage 0 L &, another s a better, more than 3 mole percentage is better = more than 5 ears above the percentage is particularly good. When the third repetition ^ When the performance of the three repeating units of the three parts of the composition of the composition may be ^ / the main use of the third replay set > 〗 〖When the stalks are set to go early, the ratio of repeating units (1) to (2) The same is preferred when the repeating unit is absent. (Repeating unit of the formula (1)) ^ The repeating unit of the formula (1) (ie, the hydrocarbon unit w is obtained from an olefin represented by the following (3): ^

2 3 RICIR ΗΗ 1 CIR (wherein R1, R2 and R3 are the same as chemical formula (1)). Examples of preferred anthracene hydrocarbon type monomers include isobutylene, 2-fluorenyl 2, methyl pentane, 2-methyl hexamethylene, 2 methyl dimethyl heptene, 2-methyl-1-ene broom,! - isooctene, 2. methyl octene, 2, ethyl pentylene, 2-ethyl-2-, 2. methyl. 2. pentane, and 2 _ methyl Wait. Isobutyl is the best. These hydrocarbons may be used singly or in combination of the above. (Repeating unit of the formula (2)) The repeating unit of the formula (2) may be derived from the related cis-butane bis(tetra)amine compound. This - cis-butane di-imine compound 15 paper size suitable for wealth S g family material (CNi) Μ specifications (21GX297 public) 1274765 A7 B7 five invention description (13) is represented by the following chemical formula (4) Η -C, ο

Η 〇 VUIC

NIR \/ 4 /1 (where R is the same as chemical formula (2)). Preferred examples of the maleimide compound include cis-butanediamine and N-substituted cis-butanediamine, such as N-methyl cis-imine, N. Ethyl cis-butane bis(tetra)amine, N. n-propyl cis-butane ruthenium, N-isopropyl cis-butanediamine, n-butyl cis-butanediamine, N-fluorenyldibutyl Dibutyl quinone imine, N_t-butyl cis-butane quinone imine, N-n-pentyl succinimide, N-n-hexyl succinimide, N-n-heptyl cis Dibutyl quinone imine, N_n-octyl cis-butane quinone imine, N· lauryl cis-butane diimine, N-stearyl cis-butane diimide, N·cyclopropyl cis Alkene (tetra)amine, cyclobutyl butyl sulfonium diimide, N_cyclopentyl succinimide, N-cyclohexyl cis-butane quinone imine, N-cycloheptyl cis-butane Imine, and Ν_cyclooctyl cis-butanedi-imine. Ν_Methyl cis-butane diimide is preferred. These cis-butadienimide compounds may be used singly or in combination of two or more thereof. Regarding the cis-butanthrene imine compound, hydrazine-substituted maleimide is preferred. Specifically, a compound which is very excellent in the chemical formula (4) has a size which is a base other than a hydrogen atom. An example of such a compound -16-1274765 A7 _ ____B7 1. Description (14) ~ - Includes N-methyl cis-butane diimine. Among the N•substituted cis-butanediamines, preferred examples of the N substituent include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and Tributyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, lauryl, stearyl, cyclopropyl, cyclobutyl, and cyclohexyl groups, and the like. (Third Repeating Unit) In addition to the aforementioned hydrocarbon and maleimide units, the thermoplastic copolymer A used in the present invention may comprise one or more types of copolymerizable monomers as the second repeat unit. For example, a vinyl type monomer can be included. Examples of such a copolymerizable monomer include: acrylic monomers such as methyl propionate and butyl propionate; methyl propionic acid monomers such as methyl methacrylate and methyl propyl acrylate Hexyl ester; a vinyl ester monomer such as vinyl acetate; an ethyl thiol monomer such as an ethyl ethoxylate monomer (for example, a vinylidene ether); an anhydride having an unsaturated double bond (for example, maleic anhydride) And substituted or unsubstituted phenethyl hydrazine monomers such as phenylethyl, methyl phenylethyl, and p-methoxy phenylene. These third repeating units may be used singly or in combination of two or more of them as the third repeating unit. When the third repeating unit is contained in the thermoplastic copolymer enthalpy to such an extent that the optical properties of the film are not lowered, the heat resistance or mechanical strength of the thermoplastic copolymer can be improved. (Polymerization Method of Thermoplastic Resin A) The thermoplastic resin A can be obtained, for example, by polymerizing the above-mentioned hydrocarbon and a maleimide compound using a known polymerization method. This known polymerization method includes graft polymerization. Alternatively, the aforementioned tobacco can be polymerized with cis-concanic acid or cis-butane dianhydride to form a precursor polymer by using a conventional method. According to the Chinese National Standard (CNS) A4 specification (210 X) 297 mm) 1274765

Further, it was reacted with an amine compound to prepare a thermoplastic resin A by making a cis-succinic anhydride knife of the precursor polymer into quinone. The precursor polymer may include a second repeat unit of (5) oxime as needed. Alternatively, the precursor polymer may comprise unsubstituted or substituted cis-butane diimine. In this case, examples of the amine compound to be used include an amine corresponding to the quinone imine moiety of the cis-butane diamine unit of the formula (7). More specifically, the amine compound represented by the chemical formula R_NH2 is the same as the chemical formula (2). Examples of such an amine compound which can be preferably used include: alkylamines such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, second butylamine, third butylamine, and cyclohexylamine, ammonia, One gall bladder, and two glands. In this case, a thermoplastic resin having repeating units of the chemical formulas (1) and (2) is also obtained. The thermoplastic copolymer A used in the present invention may be any random copolymer, embedded & copolymer, graft copolymer, and alternating copolymer. An alternating copolymer is preferred. More preferably, the thermoplastic copolymer A comprises at least one type of a cis-butanediamine unit selected from the group consisting of a methyl group, an ethyl group, an isopropyl group and a cyclohexyl group. An enediminoimine unit; and at least one type of olefin unit in which R1 in the chemical formula (1) is a hydrogen atom, and each of R2 and R3 is a methyl group is a hydrocarbon unit. These manufacturing methods are described in, for example, Japanese Laid-Open Patent Publication Nos. 5-59193, 5-1590001, 6-136,558, and 9-328523. When the term "unit" is used herein to refer to a monomer, the term "unit" refers to the residue of a monomer remaining after polymerization. Specifically, the term "cis-di-i-imine unit" means after polymerization. One of the residues of the squid and the second stalk. Similarly, the term "olefin unit" means the residue of a hydrocarbon-containing monomer after polymerization. -18 - This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 1274765

The thermoplastic copolymer A preferably contains an N-methylcis dianimide unit as the cis-butenediylene imide unit and the isobutylene unit as the indole hydrocarbon unit. The thermoplastic copolymer A is particularly preferred as an alternating copolymer of N-substituted cis-butyl quinone diimide and isobutylene. The thermoplastic resin A preferably has a weight average molecular weight of 丨X 103 or more, and more preferably 1 X 104 or more. The thermoplastic resin A is preferably a weight average molecular weight of 5 X 106 or less, and more preferably 5 X 1 〇 5 or less. In terms of heat resistance, the glass transition temperature of the thermoplastic copolymer A is 80 ° C or more, preferably more than 1 〇〇 C or more, and 13 Å. It’s better to be above. Alternatively, a thermoplastic resin of a pentylene diimine type may be preferably used as the thermoplastic resin A having a substituted or unsubstituted quinone imine group in its side chain. The pentane-imine type resin has a pentaneimine structural unit and a methyl acrylate or methyl propyl methacrylate structural unit, as described in Japanese Laid-Open Publication No. 2-153904, having the following chemical formula (5) The pentamethylene imine type resin of the repeating unit represented is preferably:

(wherein R is a hydrogen atom or a methyl group, and is a hydrogen atom, or has 1 to 8 -19 - This paper scale applies to Chinese national standards (1)^^) A4 size (21〇x 297 mm) 1274765

The alkyl group of a carbon atom 'cycloalkyl or aryl). In the thermoplastic resin A, for example, a glutaryleneimine type resin may be copolymerized with the third monomer as needed. Preferred examples of the third monomer include: a propylene group type monomer such as butyl acrylate; a styrene type monomer such as phenylethyl amide, substituted styrene, or α-methyl phenyl ethane; a monomer such as acrylonitrile or methacrylonitrile; and a maleimide-type monomer such as cis-butane diimide, hydrazine-methylbutyleneimine or n-stupyl Diterpenoid imine. These third monomers may be directly copolymerized with a glutarylene imine type resin or may be graft copolymerized with a glutarylene imine type resin. The preferred content of the oxime group (i.e., the rhythm of the repeating unit having a quinone imine group) is from 4 to 8 mole percent of the overall repeating unit in the thermoplastic resin oxime. Examples of the above-mentioned pentamethylene imine type resin are described, for example, in U.S. Patent No. 4,246,374 and the like. The film obtained by using the aforementioned thermoplastic resin A has a considerably poor flexibility and is therefore easily torn. In the aforementioned thermoplastic resin A, the film of the isobutylene-substituted cis-butyl quinone diimide type copolymer has remarkably poor flexibility and tends to be torn. However, when the thermoplastic resin A is blended with the thermoplastic resin B (for example, a acrylonitrile-styrene type copolymer), the mechanical properties of the film (thermoplastic resin B) can be improved for use in the thermoplastic resin B of the present invention. Its side chain has a substituted or unsubstituted phenyl and nitrile group. In this case, the main chain of the thermoplastic resin B may be a thermoplastic resin main chain. For example, the main chain may be composed only of carbon atoms, or in this main chain, an atom other than carbon may be inserted in the carbon atom -20-1274765

between. Alternatively, the king chain consists of atoms other than carbon atoms. The main chain can be composed only of helium atoms. For example, the backbone is a hydrocarbon or a substituted product thereof. Specifically, for example, the main chain can be produced by addition polymerization. It is clear that & the main chain is a polyolefin or a polyethylene group. Further, the main chain can be produced by condensation polymerization. For example, the backbone can be made from ester linkages, guanamine linkages, and the like. The king chain has a polyethylene backbone which is obtained by polymerizing a substituted ethylenic monomer. The substituted or unsubstituted phenyl group can be introduced into the thermoplastic resin B by any conventional method. For example, a monomer having a substituted or unsubstituted phenyl group can be polymerized to obtain a thermoplastic resin having a substituted or unsubstituted phenyl group. Alternatively, for example, various monomers are polymerized to form a backbone, followed by introduction of a substituted or unsubstituted phenyl group into their side chains. For example, a compound having a substituted or unsubstituted phenyl group can be graft-copolymerized into the side chain of the resin B. When the phenyl group is substituted with a substituent, the substituent which may be used may be a conventional substituent which may substitute a hydrogen of the phenyl group. Conventional substitution sites can be used. Specifically, for example, the substituent is an alkyl group or the like. The nitrile group can be introduced into the thermoplastic resin B by any conventional method. For example, a monomer having a nitrile group can be polymerized to obtain a thermoplastic resin having a nitrile group. Alternatively, for example, various monomers are polymerized to form a main chain, and then a nitrile group is introduced into the side chain of the resin B. For example, a compound having a nitrile group can be graft-copolymerized into the side chain of the resin B. The thermoplastic resin B series includes repeating units derived from unsaturated nitrile compounds ( -21 - This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1274765

Nitrile unit) and copolymer derived from phenylethylidene, one mouth and another heavy bismuth (styrene unit) are preferred (two or two 夕 次 一 or Yichengdao copolymer (multicomponent polymerization) ())). A propiononitrile/phenidene copolymer may preferably be used. (Nitrile compound) Any compound having an amino group and a reactive double bond can be used. Preferred examples of the unsaturated nitrile compound differ depending on the resins A and B to be used. Preferred examples of the unsaturated riding compound contained in the above preferred thermoplastic copolymer (IV) include: α. substituted (tetra) and nitrile such as propylene and methyl propyl suscept; and α, /3-disubstituted olefin unsaturated A nitrile compound such as fumaronitrile. (Styrene type compound) As the styrene type compound, any compound having a phenyl group and a reactive double bond can be used. Preferred examples of the styrene type compound vary depending on the thermoplastic resin used and the hydrazine. ^ Preferred examples of the phenethyl catechol compound contained in the above preferred thermoplastic copolymer B include: an unsubstituted or substituted phenethyl hydrazine type compound such as styrene, ethenyl toluene, methoxystyrene, or Gas styrene; and α-substituted phenethyl hydrazone type compound such as α-methyl phenyl hydrazine. In a particularly preferred embodiment, the thermoplastic resin oxime comprises an unsaturated nitrile unit represented by the following chemical formula (6) and a styrene-based unit represented by the following chemical formula (7).

-22- This paper scale is applicable to China National Standard (CNS) Α4 specification (210 X 297 mm) 1274765 A7 B7 V. Inventive Note (In Chemical Formula (4), each represents a gas atom or a pit of (1) carbon atoms. The number of carbon atoms in the alkyl group is preferably, (1) more (in the chemical formula (7), each represents an alkyl group of a hydrogen atom or a carbon atom, R represents a hydrogen atom, an alkyl group of 8 to 8 carbon atoms, a tooth Atom, light base, @oxy, or nitro. The carbon number in the job is preferably m, more preferably U 3 , and even more preferably 1 to 2. The carbon number in the alkoxy group is preferably 1 to 2 Å. More preferably, i to 8 and more preferably 1 to 4. Further preferred examples of the unsaturated nitrile compound contained in the above preferred thermoplastic copolymer B include an α-substituted unsaturated nitrile and have α, $ _ A nitrile compound having a disubstituted hydrocarbon unsaturated bond. Examples of the α-substituted unsaturated nitrile include acrylonitrile and methyl acrylonitrile. Examples of the nitrile compound having an α, a di- or di-substituted hydrocarbon unsaturated bond include an anti- Butadiene dinitrile. The unsaturated nitrile compound is more preferably acrylonitrile. The phenethyl amide compound contained in the aforementioned thermoplastic copolymer oxime Preferred examples include unsubstituted or substituted phenethyl compound and hydrazine; _ substituted styrene-type compound. Examples of unsubstituted or substituted phenethyl hydrazine type compounds include styrene, acetylated toluene, methoxy Examples of the compound of the benzophenone and the acetophenone. The α-substituted phenethyl compound includes α-methyl styrene, etc. The styrene compound is preferably styrene. The content of the repeating unit of the formula (6) Preferably, it is 10 to 70% by weight, more preferably 20 to 60% by weight, more preferably 20 to 50% by weight, still more preferably 20 to 40% by weight, and 20 to 3 by weight, based on the total repeating unit of the thermoplastic resin crucible. 0% by weight is the best. -23- This paper size is applicable to China A4 specification (210X297 mm) 1274765

The content of the repeating unit of the formula (7) is preferably from 30 to 70% by weight based on the total repeating unit of the thermoplastic resin b, more preferably from 40 to 80% by weight, still more preferably from 50 to 80% by weight, still more preferably from 60 to 8% by weight. Even better - and 70 to 80 weight percent is best. Very good results are obtained when the repeating unit of the formula (6) is 20 to 30% by weight and the repeating unit of the formula (7) is 70 to 80% by weight. When the content of the styrene-type repeating unit or the nitrile-type repeating unit is too large, the compatibility of the thermoplastic resin B with the thermoplastic resin A is deteriorated, so that the transparency of the resulting film may be lowered, and the degree of dreaming may be large. The thermoplastic copolymer B contains an unsaturated nitrile unit and a styrene unit as a main component. The overall unsaturated nitrile unit and the styrene-based unit are preferably 70% by weight or more of the thermoplastic copolymer B, more preferably 8% by weight or more, more preferably 90% by weight or more, and more preferably 5% by weight or more. good. Of course, the overall unsaturated nitrile unit and styrene unit can be i 重量 by weight. The thermoplastic copolymer β contains an unsaturated nitrile unit and a styrene-based unit as a main component. In a preferred embodiment, the unit of the formula (6) and (7) is 100 weight percent. The overall unsaturated nitrile unit and the styrene-based unit are more than 7% by weight of the thermoplastic resin 8, more preferably more than 100% by weight, more preferably 90% by weight or more, and particularly preferably 95% by weight or more. However, a third repeating unit to be described later may be used as needed. (The third type of repeating unit) -24 · This paper size applies to the Chinese National Standard (CNS) Α4 specification (210X297 public attack) 1274765

In addition to the illustrated nitrile unit and styrene unit, the thermoplastic copolymer β may include another copolymerizable monomer as the third repeating unit as needed. Preferred examples of the first repeating unit include a propylene-based monomer such as acrylonitrile and a hydrocarbon-type monomer such as ethylene and propylene. One or more of these third repeating units can be copolymerized, thereby improving the flexibility of the film. It is also possible to use hydrazine-substituted maleimide as the third repeating unit. When ν• is substituted with maleimide, especially phenyl cis-butane quinone imine, when used as a copolymerization component, the heat resistance of the resin can be improved. § When using a repeating unit, the content of the third repeating unit is preferably 3 〇 by weight or less based on the weight of the thermoplastic copolymer ,, more preferably 2 〇 by weight or less, more preferably 15 重量 %, and 1 0% by weight or less is particularly preferred. When the content of the second repeating unit is too large, the performance of the repeating unit represented by the chemical formula ((a) and (2) may be insufficient". Further, when the third repeating unit is used, the content of the third repeating unit is a thermoplastic resin. The weight is preferably 1% by weight or more, more preferably 2% by weight or more, more preferably 3% by weight or more, and more preferably 5% by weight or more. When the content of the third repeating unit is too small, the third type The performance of the repeating unit may be insufficient relative to the entire composition. Note that when the third repeating unit is used, the ratio of the repeating unit of the formula (6) to (7) is preferably the same as when the third repeating unit is absent. (Polymerization Method of Thermoplastic Resin) The thermoplastic resin hydrazine can be obtained by directly copolymerizing the above monomers. One of the polymer of the styrene-based compound and the polymer of the unsaturated nitrile compound can be connected to the other. Branch copolymerization. Alternatively, phenethyl amide compounds and -25-

This paper scale is applicable to China National Standard (CNS) Α4 specification (210 X 297 mm) 1274765 A7 ___ B7 V. Inventive Note (23) Unsaturated nitrile compound is graft polymerized with rubber-elastic propylene-based polymer. It makes it possible to make a better resin. A very preferred thermoplastic resin is a copolymer comprising propionitrile as an unsaturated nitrile compound and styrene as a styrene type compound. This copolymer is called As resin, AAS resin or the like. The thermoplastic resin B is preferably a weight average molecular weight of 1 X 1 〇 3 or more, and more preferably 1 X 104 or more. The thermoplastic resin B is preferably a weight average molecular weight of 5 X 1 〇 6 or less, and more preferably 5 X 1 〇 5 or less. The content of the unsaturated nitrile type repeating unit in the thermoplastic resin is preferably from 2 to 6 parts by weight, more preferably from 20 to 50% by weight. The content of the styrene-based repeating unit is preferably from 40 to 80% by weight, and more preferably from 5 to 8% by weight. In particular, very good results are obtained when the unsaturated nitrile type repeating unit is from 2 Torr to 3 Torr by weight and the styrene-type repeating unit is from 7 Torr to 8 Torr. When the content of the styrene-repeating repeating unit or the nitrile-type repeating unit is too large, the phase difference due to the molecular alignment in the film may be affected, and the wavelength dependence may become high. In addition, the compatibility of the thermoplastic resin B with the thermoplastic resin A may be lowered, and the haze of the obtained film may become large. Therefore, when the content of the styrene type repeating unit or the nitrile type repeating unit is too large, it is unlikely to be obtained. The actual transparent film. (Preparation of the composition) The resin composition used in the present invention can be obtained by any known method (method, as long as the thermoplastic resin A and the thermoplastic resin B are mixed to form a film-forming machine, that is, Yes. -26-

1274765 A7 B7 V. INSTRUCTION DESCRIPTION (24) Examples of the method include: a method of preparing a resin composition by simply mixing a thermoplastic resin A and a thermoplastic resin B; and heating the thermoplastic tree A and A A method of preparing a resin composition by melt kneading. (The ratio of thermoplastic resin Α to Β) The ratio of the thermoplastic resin A used in the film of the present invention to the thermoplastic resin b depends on the phase difference effect required to design the film. This tendency due to the effect of exhibiting the phase difference is significantly different depending on the ratio of the thermoplastic resin A to the thermoplastic resin β and the phase difference effect of the finally produced film will be remarkably changed. (Manufacture of film having no phase difference effect) A method of manufacturing a film having no phase difference effect will be described below. When the ratio of the mixture of the thermoplastic resin A to the thermoplastic resin B is appropriately determined, a film which does not substantially exhibit a phase difference effect even when the molecules in the film are aligned due to the stress applied to the film can be obtained. In other words, it is possible to produce a film exchange which does not exhibit a phase difference effect even if the film is stretched. Therefore, a stretched film having no phase difference effect on a lean state can be obtained. It is understood that a preferred mixture of this preferred property is based on the type of thermoplastic resin A and thermoplastic resin B. In general, the ratio of the molar number p of the phenyl group contained in the thermoplastic tree ϊΒ ϊΒ and A used to the molar number of the quinone imine group contained in the thermoplastic resins a and ^ (I/p) The ratio is preferably 13 or more, 14 or more is better, and 丨.5 or more is more preferable. Further, the ratio is preferably 2 or less, more preferably 2.6% or less, and even more preferably 2. 4 or less. In a specific example, the Ι/p ratio is preferably from 1. 7 to 2.9, more preferably from 1.8 to 2.6. It is more preferable in another specific example. 1 / Ρ is 1. 3 to 2 · 〇 better, and 1.5 to 1. 9 -27-

1274765 A7 ___- B7 V. Inventive Note (25) Regarding the mixture ratio of the thermoplastic resin A and the thermoplastic resin B, generally, the content of the thermoplastic resin A is preferably from 5 Å to 95% by weight based on the total amount of the resin contained in the film. More preferably, 6 to 95% by weight, and more preferably 65 to 90% by weight, and the content of the thermoplastic resin B is preferably 5 to 50% by weight, more preferably 5 to 40% by weight, based on the total resin contained in the film. 'And 10 to 35 weight percent is even better. It is more preferable to mix from 65 to 80% by weight of the thermoplastic resin A with 20 to 35 % by weight of the thermoplastic resin b. It is particularly preferable to mix from 65 to 75 weight percent of the thermoplastic resin A with from 25 to 35 weight percent of the thermoplastic resin. When the content of the thermoplastic resin A or B is too large, the phase difference in the stretched film may become large in the plane or thickness direction. When the thermoplastic resin A mainly contains a copolymer of isobutylene and N-methyl cis-butanediamine, and the thermoplastic resin B mainly contains a copolymer of propionitrile and styrene, the content of the cyanamide is 2 〇. Preferably, the weight percentage is from 5 to 5%, more preferably from 25 to 4 weight percent, and more preferably from 26 to 29 weight percent. Further, the content of the table is preferably from 5 to 80% by weight, preferably from 60 to 75 weight percent. More preferably, and 71 to 74 weight percent is even better. In particular, when the content of acrylonitrile is 26 to 29% by weight and the content of styrene is 71 to 74% by weight, the thermoplastic resin 〇 from 〇 to 8 重量% is satisfactorily compatible with the thermoplastic resin Α. Sex. In this mixture, the thermoplastic resin A and the thermoplastic resin B have satisfactory and broad compatibility with each other. Further, a stretched film having a small phase difference effect in both the planar direction and the thickness direction of the film can be obtained. The weight ratio of the thermoplastic resin a to the thermoplastic resin B is 50: 50 to 80: 2 0, preferably 60, · 4 0 -28-

1274765 A7 - —______ B7 V. Inventions (26) to 80: 20 is better, and 60: 40 to 7 5: 2 5 is even better. When such a preferred composition is appropriately selected, a stretched film which does not substantially exhibit a bifold shape can be obtained. Further, a ruthenium film having high total light transmittance and low haze can be obtained. This is because the phase difference effect due to the alignment of the molecules in the film can be made small, as the composition ratio of the thermoplastic resin octagonal plastic resin B is appropriately adjusted. In other words, the aforementioned composition can cause a decrease in the phase difference effect in the planar direction of the film. Specifically, for example, the phase difference in the planar direction of the film is preferably 1 G nm or less, and more preferably 5 nm or less. Further, the phase difference effect in the thickness direction of the film can be suppressed to be in the range of 5 Å * micron or less, and more preferably 2 Å or less. Further, it is preferable to suppress the alignment phase difference in the range of 100 nm or less, and more preferably 5 Å nm or less. Therefore, substantially no birefringence can be obtained, and the light transmittance thereof is 85% or more, more preferably 88% or more, and more preferably 9% by mass or more, and a haze of 2% or less, and 1 The preferred transparent film is below %. In a very preferred embodiment, the haze can be suppressed to a range of 5% or less. Note that when the phase difference in the plane direction of the film is 1 Å or less, and the phase difference in the thickness direction of the film is 5 Å or less, the film can generally be regarded as having substantially no birefringence. . If the film has a light transmittance of 85% or more and a haze of 2% or less, the film can be used as a high performance film in various optical applications. (Other Mixture Materials) The film according to the present invention may optionally include known additives such as a plasticizer, a heat stabilizer, a lubricant, an ultraviolet light absorber or a filler, or in addition to the foregoing -29-

1274765 V. INSTRUCTIONS (27) Resins other than thermoplastic resins A and B. Note that this resin other than the thermoplastic resins A and B is also referred to as "the third resin". In a preferred embodiment, the overall thermoplastic resins A and B are 1 weight percent. However, a third resin can be used as needed. A plasticizer for improving the mechanical properties of the flexible unstretched film and the polymer can be added to the resin composition for producing a film. 'When*, when using this material, the glass transition temperature of the film is lowered, so that the heat resistance or transparency of the film may be impaired. Therefore, when such a plasticizer or a flexible polymerization is used, the amount of addition should be set to an amount which does not detract from the performance of the film. The amount of addition is preferably 1% by weight or less of the resin composition, more preferably 5 parts by weight or less, and still more preferably 3% by weight or less. When the content of the imine of the thermoplastic resin A is high, for example, specifically, when the content of the cis-bonded diimide unit of the bismuth plastic resin A is 4 〇 mol%, the obtained film may be hard and easy. broken. In this case, if a small amount of plasticizer is added, it is useful because it can prevent stress whitening or tearing of the film. A conventional plasticizer can be used as the plasticizer. (Plasticizer) An example of a plasticizer which can be preferably used is described below. Examples of the tannic acid plasticizer include dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, di-n-octyl citrate, di-n-ethyl hexanoic acid, and diiso-octyl citrate. , bismuth citrate; ester, di-n-decyl phthalate, diisononyl phthalate, di-n-dodecyl phthalate bis-iso-tridecyl citrate, dicyclohexanoic citrate, hydrazine Acid butyl heart j--2-ethylhexyl ester, and diiso-hexyl phthalate. Examples of aliphatic dibasic acid plasticizers include adipic acid di-n-barium vinegar, adipic acid diiso-glycoside, hex-30- paper scale s s standard (CNS) Α 4 specifications (21GX297 public love) Γ 1274765 A7

Di-2-ethylhexyl dicarboxylate, di-2-ethylhexyl sebacate, dibutyl sulfonate 3, and Ge, a private di-2 _ethyl Cj S. Examples of the acid-transfer type plasticizer include tributyl phosphate, tris-2-ethylhexyl phosphate, 2-ethylhexyl phosphate, and tricresyl citrate. Examples of the epoxy type plasticizer include epoxidized soybean oil and epoxidized pine oil fatty acid 2-ethylhexyl group. Examples of the fatty acid ester type plasticizer include butyl stearate, butyl oleate, chlorinated paraffin, and vaporized methyl ester to prevent acid. Examples of the polymer type additive include polyethylene glycol dimethyl ether, polyethylene glycol benzoate, and a polymer compound containing an ester group (dibasic acid such as hexanoic acid, sebacic acid, or g-tanoic acid) A polycondensate with 1,2-propylene glycol, iota, 3-propylene glycol, etc.) Among these additives, the following plasticizers are preferred: dipyridyl adipic acid, adipic acid diisophoric acid Oxime ester, di-2-ethylhexyl adipate, di-2-ethylhexyl sebacate, dibutyl sebacate, di-2-ethylhexyl sebacate, dibutyl phosphate , tris-2-ethylhexyl citrate, 2-ethylhexyl phosphate, trimethyl citrate phosphate, epoxidized soybean oil, epoxidized pine oil fatty acid _ 2-ethylhexyl, butyl stearate, Butyl oleate, chlorite ant, chlorinated methyl fatty acid, polyethylene glycol dimethyl ether, which does not contain an aryl group; or a polymer compound containing an ester group (a dibasic acid such as adipic acid or sebacic acid) a polycondensate with propylene glycol, hydrazine-propanediol, and the like). These plasticizers do not absorb light in the short wavelength range of the visible light region, so the plasticizer does not adversely affect the wavelength dependence of the phase difference effect. Therefore, these plasticizers are particularly good additives. It is preferred to add 20 parts by weight or less of each plasticizer to 100 parts by weight of the above-mentioned film mixture material, preferably more than 1 part by weight of each plasticizer. When the amount of additive is too large, the additive may bleed out and contaminate the film of the reel -31 - This paper scale applies to China National Standard (CNS) A4 specification (21()X 297 mm) 1274765 A7 __- — B7 5. Description of the invention (29) Surface 'to make a roll film in a continuous manner. (Third Resin) The second resin means a resin other than the above thermoplastic resins A and B. The third resin may be a thermoplastic resin or a thermosetting resin. The third resin is preferably a thermoplastic resin. The third resin may be a single type of resin or a blend of a plurality of types of resins. The content of the third resin to be used is preferably 30% by weight or less, more preferably 2% by weight or less, based on the total amount of the resin used in the resin composition, that is, the total amount of the thermoplastic resins A and B and the third resin, and It is better to have ι〇 below the weight percentage. Further, the third resin is more preferably 1% by weight or more, more preferably 2% by weight or more, and still more preferably 3% by weight or more. When the content of the third resin is too large, the properties of the thermoplastic resins A and B are unlikely to be sufficiently exhibited. When the content of the resin having low compatibility with the thermoplastic resin A & b is too large, the optical properties of the resulting film may be lowered. When the content of the third resin is too small, the addition of the third resin is unlikely to exhibit an effect. Note that even when a third resin is used, the mixture ratio of the thermoplastic resin A to the thermoplastic tree 曰B is similar to that before the case where the third resin is not used. (Filler) A filler may be included in the film of the present invention as needed to improve the slip of the film or for other uses. It is possible to use a known filler which is used in a conventional film as a filler. The filler may be inorganic fine particles or organic fine particles. Examples of inorganic fine particles include: metal oxide fine particles such as 32. This paper scale is applicable to China National Standard (CNS) Α4 specification (210X297 mm) 1274765 A7 ~ ' ----- B7 _ V. Invented Titanium dioxide, aluminum oxide and zirconium oxide; fine particles of niobate are, for example, calcium sulphate, hydrated calcium citrate, aluminum citrate and magnesium citrate; calcium carbonate 'talc; clay; calcined kaolin; and calcium phosphate. Examples of the organic particles include resin particles such as polyfluorene type resin, fluorine type resin, propylene type resin, and crosslinked styrene type resin. (Ultraviolet Light Absorber) An ultraviolet light absorber may be contained in the film of the present invention as needed. The ultraviolet light absorber contained in the film can cause an improvement in the weather resistance of the film. Further, it can improve the durability of a liquid crystal display device using a film. Therefore, the external light absorption agent is preferred in practice. Any of the conventional ultraviolet light absorbers can be used for the film of the present invention. Examples of the ultraviolet light absorber include: a benzotriazole type ultraviolet light absorber such as 2-(2-indole-benzotriazol-2-yl)-p-Si? and 2-Winter di-salt-2-yl-4, 6-di-tertiary butyl; three-p well type ultraviolet light absorber such as 2-(4,6-diphenyl·1,3,5_three tillage-2 _yl)-5-[(hexyl) And benzophenone-type ultraviolet light absorbers such as 2-hydroxy-4-insyloxy-xanthene (octabenzon). Further, a light stabilizer other than the ultraviolet light absorber may be added to the film of the present invention as needed. Specifically, for example, a benzoate type light stabilizer such as 2,4-di-tert-butylphenyl-3,5-di-t-butyl-4-ylbenzoate may be used. Or a hindered amine type light stabilizer such as bis(2,2,6,6-tetramethyl-4 hexahydroacridinyl) sebacate. (Production of Film) The resin composition described above can be formed into a film form by any conventional method. Examples of the method include solution flow expansion method, melt forming method, etc. -33-

This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1274765

Temple. Any of these methods can be employed. Examples of the glazing forming method include a melt-squeezing method, an inflation film method, and the like. 1 In a preferred embodiment, the resin composition to be used is preliminarily dried before being formed into a film. Preliminary drying prevents flaws, such as bubbles in the film. Therefore, preliminary drying is very useful. The film can be formed by using a resin composition which is prepared purely by mixing a thermoplastic resin crucible and a thermoplastic resin crucible. The bondable thermoplastic resin Α and the thermoplastic resin B are melted and kneaded to form a material in the form of pellets or the like, and then the material of the pellet form or the like can be formed into a film form. (Solution Molding Method) The present invention (the film is characterized in that phase difference due to molecular alignment during processing can be suppressed. Therefore, a method of forming a film by a melt molding method is preferred. When the film is melted) The legal form "Japanese Temple" can adopt any known method. For example, a melt extrusion method such as a τ-die method or an inflation film method can be employed. Alternatively, a calendering method, a hot pressing method, and an injection molding method may be employed. The melt forming method using the τ-die method is preferable because it can easily produce a wide film having a satisfactory and accurate thickness. (Solution Flow Expansion Method) The solution flow expansion method is preferable because a film having an extremely accurate and uniform thickness can be obtained by this method. By the solution flow expansion method, a film which is free from defects such as die stripes can be obtained. Further, a film having a small film thickness variation can be easily produced. For example, a film having a thickness variation of 5% or less can be easily produced. In addition, it can be easily made with a small phase difference -34- This paper scale applies to the Chinese National Standard (CNS) Α4 specification (210 X 297 mm) 9 1274765 9 A7

Note that the solvent for the dynamic expansion method in which the flow expansion is referred to as "the optical isotropic film of the flow" is selected from known solvents. Before 唼: _ β tree ^ A and thermoplastic resin B are very soluble in halogenated hydrocarbon type, chlorine methyl k * and dichloroethane. In addition, this solvent has a low hysteresis point. It is preferred because of the halogenation/combination agent. Further, a non-halogen type solvent which is highly polar, such as dimethylformamide and dimethylacetamide, can be used. Further, aromatic solvents such as toluene, xylene, and sulphuric acid, cyclopental type solvents such as dioxin, dioxane, tetrahydroanthracene, and copper-type solvents such as methyl ethyl may be used. ketone. These solvents may be used singly or as a mixture of a plurality of solvents. Binding

Any amount of solvent may be used as long as it is sufficient to dissolve the thermoplastic resin for casting in a solvent. Note that the term "dissolved" as used herein means that the resin is present in the solvent in a state of sufficient uniformity for casting. The solute does not have to be completely dissolved in the solvent. Similarly, the term "solution" as used herein refers to a liquid in which a resin is present in a solvent in a state of sufficient uniformity for casting. Further, for example, an evaporation rate of a solvent is controlled by adding a non-solvent such as an alcohol. A preferred method of film having excellent surface properties. The non-solvent means a liquid which cannot dissolve the resin due to poor solubility of the resin when used alone. When the film is formed by the falling liquid flow expanding method, the thermoplastic resin A and the thermoplastic resin B are dissolved in the aforementioned solvent, and the thermoplastic resin A and the thermoplastic resin 3 to be used in the film of the present invention have the aforementioned appropriate composition - 35 1274765 A7 B7) 5. Inventive Note (33' and when dissolved in the aforementioned solvent, a substantially uniform falling liquid can be easily obtained. Note that thermoplasticity can be obtained by hot melt kneading before dissolving the resin in a solvent. The resin A and the thermoplastic resin B are formed into a form of pellets or the like. The concentration of the resin in the solution is preferably from 9 to 9% by weight, more preferably from 5 to 7 % by weight, and further preferably from 1 to 50% by weight. Thereafter, the solution thus obtained is flow-expanded on the support. Regarding the flow expansion method, any conventional method can be used. Preferred examples of the support for flow expansion may include a stainless steel endless belt, and a film such as Polyimide film or poly(p-phenylene terephthalate) film of ethylene glycol diacetate. Films such as A can be stretched. The film can be uniaxial or biaxially stretched film. A film is preferred. The obtained intermediate product is then dried to obtain a film. In a specific example, the intermediate product obtained by flow expansion can be dried on the support until the amount of residual solvent becomes 1 〇/0 or less. In another embodiment, the intermediate product may be removed from the support when the intermediate product is dried and supported. The film may be dried to obtain self-supporting capability and then stripped from the support. The obtained film may be dried as needed. Any drying method of any of the conventional methods may be used as the drying method. For example, the flaction method (flQat methGd) or the tenter transfer method may be used. The phase difference effect in the film having no phase difference effect), the phase difference of the film of the film having no phase difference effect on the quality is 9 〇 and α α t. _ ^ 友徂局 - υ先Micro is not below, i 〇 nanon and 5 nm or less is even better. Another 1 '-36 -

1274765 V. INSTRUCTIONS (34) = Medium = Conveniently, when the phase difference of the film is low (4), the position is: "There is no phase difference effect" or "substantially no work". The film has a phase difference of 20 nm or less, and the film has substantially no phase difference effect. The film is useful (the phase difference in the thickness direction) controls the phase difference effect in the thickness direction of the film and the in-plane phase difference. The role phase: the inside is to 'in particular, to reduce the phase dependence of the film phase difference effect. The phase difference effect of the film in the thickness direction is expressed by the following formula: I (nx+ny)/2-nz) | xd where nx represents the maximum refractive index in the plane of the film, and ^ represents perpendicular to nx < universal direction The refractive index, nz represents the refractive index 'in the thickness direction of the film' and d represents the thickness of the film. The foot film of the present invention tends not to exhibit a phase difference effect, so that the film can also have a small phase difference effect in the thickness direction. In the film of the present invention, the phase difference in the thickness direction is preferably less than 耄 micrometer, more preferably less than 1 nanometer, more preferably less than 5 nanometers, and more preferably 2 0 . Below the nanometer is especially good. (Alignment phase difference) The tendency to exhibit a phase difference effect due to molecular alignment can be evaluated by the phase difference effect (alignment phase difference) exhibited by stretching a film under certain conditions, which will be exhibited by stretching a film under certain conditions. This phase difference action is called the alignment phase difference. For example, the alignment phase difference is determined as follows. The two narrow sides of the film having a width of 5 cm and a length of 25 cm were fixed and left at the glass transition temperature for 1 minute. Apply the film to the Chinese National Standard (CNS) A4 size (210X 297 dong) in the length direction of 〇 2 m / -37 - This paper size 1274765 A7 ^__B7 V. Invention description (35) Minute speed uniaxial stretching , and a stretched film having a draw ratio of 7.5 was obtained. The resulting stretched film is allowed to cool. The phase difference effect was measured in the middle portion of the stretched film. Further, the thickness of the stretched film was measured. The phase difference effect in the case where the film thickness is 1 〇 〇 micrometer is calculated from the measured phase difference effect and thickness of the intermediate portion of the stretched film. The calculated phase difference effect is regarded as the alignment phase difference. The bisphenol A type polycarbonate which is typically used as an optical film exhibits a large alignment phase difference of 1000 Å or more. However, a film having a preferred composition as compared with a mixture of the thermoplastic resin A and the thermoplastic resin B may have a preferred alignment phase difference of 3 Å or less, more preferably 200 nm or less, and 100 nm or less. good. Further, the alignment phase difference can be controlled by changing the composition ' within these ranges. Surprisingly, a film having an alignment phase difference of 50 nm or less and which is less likely to exhibit a phase difference effect can be obtained by optimizing the composition. Therefore, when the specifications of the composition of the thermoplastic resin A and the thermoplastic resin B are as described above, an optically extremely transparent film having a high light transmittance and a small haze value can be obtained. The resulting film is characterized by being less likely to exhibit a phase difference effect due to molecular alignment caused by stress applied to the film or the like. In addition, when the film of the present invention having a large alignment phase difference is stretched to intentionally add a phase difference effect, the measurement wavelength dependence of the film phase difference effect is compared with other conventional films (for example, polycarbonate). In the case of a film), it is small. This is a feature of the film of the present invention. Further, the film of the present invention is characterized in that the alignment phase difference can be controlled by changing the composition of the thermoplastic resins A and B, and thus the film is very useful for a liquid crystal display device. -38 - I paper scale applies to China S standard (CNS) A4 specification (21〇X 297 public) — 1274765 A7

(Fold-resistant property) According to the present invention, a film having satisfactory folding endurance can be obtained. The folding endurance can be measured in accordance with JIS C5016. For example, a MIT type folding endurance, a tester D-type (manufactured by Toyo Seiki Seisaku_sh〇, Ltd.) or the like can be used as the measuring device. The folding resistance of the film is preferably 30 or more, more preferably 5 times or more, more preferably more than 100 times, and more preferably 15 times or more. Here, if the aforementioned folding endurance is obtained with respect to at least one of the planes of the film, the film is referred to as having the folding endurance. The above-mentioned satisfactory folding resistance (i.e., 30 or more, 50 or more, 1 or more, or 15 or more) is preferable in two directions perpendicular to each other in the plane of the film. Note that the folding resistance is measured when the film is 5 〇 micrometer thick unless otherwise specified. Alternatively, when the thickness of the film is not equal to 5 μm, the folding endurance of the film is converted into a folding resistance equivalent to a film having a thickness of 5 μm. For T's when the thickness of the film is not equal to 5 〇 microns, the folding resistance of another modified film having the same composition and stretched state and having a thickness of 50 μm was measured, and the obtained value was used as defined in the text. The folding resistance of the film. For example, when the thickness of the thin abdomen is 30 μm, another film having the same material composition, stretched state, and the like, except for changing the thickness to 50 μm, is used to evaluate a film having a thickness of 50 μm, and The result was regarded as the folding endurance of the film having a thickness of 3 μm. (Tear Resistance Spread Strength) According to the present invention, a film having a satisfactory tear propagation resistance can be obtained. The tear propagation strength can be measured in accordance with JIS K7128 (pants type method). An automatic recorder (manufactured by Shimadzu Corporation) can be used as the measuring device. -39· This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1274765 A7 B7 V. Description of invention (37) The tear propagation strength of the film is preferably 15 gram/mm or more. 18 gram / mm or more is better, and 200 gram force / mm or more is better. Here, the film is said to have the tear propagation strength as obtained by obtaining the aforementioned tear propagation strength in at least one of the planes of the film. The aforementioned satisfactory tear propagation strength (i.e., 150 gram force / mil or more, 18 gram force / mils or more, or 200 gram force / mm or more) is in two mutually perpendicular directions in the plane of the film. It is better. (Stretching) The unstretched film obtained from the thermoplastic resin A and the thermoplastic resin B typically has low mechanical strength. In particular, the folding endurance of this film (indicating durability for repeated bending) is typically 1 〇 or less. In addition, the tear propagation strength of the film is typically from about 100 to 120 grams force per millimeter. Therefore, the unstretched wide film is slightly disadvantageous in terms of industrial operation. As described above, the inventors have found that the mechanical strength of the film is greatly improved when the film is stretched. In the above composition, the phase difference effect in the film did not increase after the film was stretched to improve the tear propagation strength and the folding endurance. Therefore, stretching a film having a thermoplastic resin A and a thermoplastic resin B is very preferable for the present invention. The stretched film can be improved in the folding resistance to bending in the stretching direction. In addition, the stretched film can result in an improvement in the tear propagation strength in a direction perpendicular to the direction of stretching. Therefore, when the film in the form of a roll needs to have an improved tear propagation strength in the width direction of the film, the longitudinal stretching is generally preferred. In order to improve the tear propagation strength in the machine direction (lengthwise) of the film, stretching in the width direction is preferred. In order to achieve improved 'biaxial stretching' in both directions, it is preferred. Biaxial stretching can be continuous biaxial stretching or simultaneous double-40 - This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) !274765 ~Z --- ____B7 too, invention description (38) '~ -- Upper L stretch. At the same time, the stretching is particularly good, since the simultaneous stretching can improve the mechanical properties on the plane of the film. In biaxial stretching, when the "extension" in both directions is adjusted so that the phase difference effects due to stretching cancel each other out, the in-plane phase difference effect can be suppressed to a lower value. The stretching method can be any conventional stretching method. The hot stretching method is preferably: uniaxial or biaxial stretching can be used. The thermoplastic resin A and B film phase car X is less likely to be known as the polycarbonate. It exhibits a phase difference effect in stretching. Therefore, a larger film stretching ratio is used than in the conventionally stretched polycarbonate. Therefore, a uniaxial length of a large stretching ratio can be easily obtained. Stretching is preferred. Further, when the optical uniaxiality of the obtained retardation film is important, the free end longitudinal uniaxial stretching is an excellent method. Further, it can be disclosed in Japanese Laid-Open Patent Publication Ν〇 The special biaxial stretching in 5·15791丨 controls the refractive index in the three-dimensional of the film. When the film is provided with the phase difference of the plastic resin, it is impossible for the film to exhibit the phase difference due to the alignment. Thus the film has a reduced plane in which the film is made The advantage of the change of the phase difference effect in the film. The tear propagation strength of the obtained film can be used as a criterion, and the optimum value of the stretching temperature and the stretching ratio can be used. Generally, the stretching ratio is 1; 1 to 3 More preferably, it is preferably 1.3 to 2.5 times, and more preferably 1.5 to 2.3 times. If the thermoplastic resin A and the thermoplastic resin B fall within the above preferred composition range, the selection of appropriate stretching conditions may not be substantially The amount of luminescence and the haze are reduced to achieve the stretching of the film. In particular, when the film is stretched by a ratio of 13 or more, or at a magnification of 1.5 or more, the tear propagation strength and folding resistance of the film are improved. Significantly improved, so that it can be made to have a high -41 - paper scale for the China National Standard (CNS) A4 specification (210X297 mm) 1274765 A7

Degree of light transmittance (for example, 85% or more) and small haze value (for example, i% film; drawing member temperature is preferably selected from the range of (dg.3〇)t to (dg + 3〇rc) , wherein D is the glass transition temperature of the film measured by the DSC method. The particularly good stretching temperature is in the range of (Tg-2〇)t to (Tg + 2〇)t. When at the appropriate temperature When the film is stretched in the range, the whitening of the film during stretching can be reduced or prevented, and the phase difference effect in the obtained phase difference film can be reduced. When the stretching temperature is too high, the film is resistant. The tear propagation and folding resistance may be insufficient. In addition, the 'stretch ratio may be too large' makes it difficult to achieve the industrial applicability of the film. Conversely, when the film is stretched at too low a temperature, stretching The haze of the film may become large. At this extreme level, the film may be torn, etc., thus hindering the process. For the stretching method, a known stretching method may be used, including using a tenter width. Stretching 'longitudinal stretching using rolls, &amp; free end uniaxial stretching, and continuous combination of ^ such as continuous biaxial Stretching and stretching thereof are performed while the length and width are simultaneously performed, biaxial stretching, etc. The film obtained by the foregoing method and having substantially no phase difference effect has a lower than 2 in the plane direction of the film. 〇 nanometer phase difference effect. When a film having substantially no phase difference effect is used in a film substrate such as a plastic liquid crystal display device, such as a phase difference effect in a plane direction of the film exceeding 20 nm, The light leakage may occur due to the phase difference effect in the liquid crystal display device, which may cause insufficient contrast. The phase difference in the plane direction of the film is preferably 10 nm or less, and 5 nm or less. In addition, the film of the present invention has a size of 2 〇〇 -42 - in the thickness direction. It is applicable to the Chinese National Standard (CNS) A4 specification (210X297 public) 1274765 A7 B7 5. Invention Description (4〇) &quot &quot;-~~ The phase difference effect below micron is better, preferably 100 nm or less, more preferably 50 nm or less, and more preferably 25 nm or less. (Manufacture of retardation film) In one embodiment, the present invention relates to a retardation film. For convenience, a film having a phase difference of 20 nm or more is referred to as a "phase difference film" and has a thickness of less than 2 Å. The phase difference effect film is distinguished. Specifically, when the term "phase difference film of the present invention" is used, it means that the film of the present invention has a phase difference effect of 2 〇 nm or more. The method for producing a retardation film is described. When the film of the present invention is a retardation film, a material similar to the material of the film having no phase difference action can be basically used. Among the above materials, 'the material can be appropriately adjusted. The mixture ratio of thermoplastic resins A and B to control the measurement wavelength dependence of the phase difference effect. In general, the content of the thermoplastic resin A is preferably from 5 to 95% by weight, more preferably from 5 to 65 weight percent or from 75 to 95 weight percent, and from 5 to 60 weight percent or from 80 to 95 weight percent of the total resin in the film. The percentage is even better. The content of the thermoplastic resin B is preferably from 5 to 95 weight percent of the total resin in the film, more preferably from 5 to 25 weight percent or from 35 to 95 weight percent, and from 5 to 20 weight percent or from 4 to 95 weight percent. Better. Further, when the aforementioned stretching conditions are appropriately adjusted, a film having a desired phase difference effect can be easily produced. This is because the tendency to exhibit phase difference effects can be controlled by adjusting the mixture ratio of thermoplastic resin A and thermoplastic resin B. -43 - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1274765 A7

Those skilled in the art who need a film having a specific phase difference effect can easily adjust the mixture ratio of the thermoplastic resin A and the thermoplastic resin according to the description of the present specification, and adjust the stretching conditions to easily produce a desired phase. A film that works poorly. In other words, the tendency to exhibit the phase difference effect can be easily adjusted by appropriately adjusting the mixture ratio of the thermoplastic resin A and the thermoplastic resin B suitable for the film having no phase difference action described above. In addition, proper stretching can result in a desired retardation film. When a retardation film is produced, for example, a uniform phase difference effect can be provided on the unstretched film produced by the above method, and the film is subjected to at least uniaxial stretching by a known stretching method, thereby making the film Resin alignment. The retardation film produced by the stretched film by the above description has the advantage of measuring the wavelength dependence of the phase difference film of the conventional polycarbonate having a small phase difference effect. Further, with respect to the retardation film obtained by stretching the film by the above method, the mixture ratio of the thermoplastic resins A and B can be appropriately adjusted to control the measurement wavelength dependence of the phase difference effect. Regarding the stretching method, a stretching method similar to the foregoing film having no phase difference effect can be used. When the retardation film of the thermoplastic resins A and B is produced, the phase difference of the retardation film may be selected from the range of more than 2 〇 nm to 1 QQ Q nm depending on the use. The phase difference value can be set to a desired value by controlling the manufacturing conditions of the film such as the film thickness, the stretching temperature, and the stretching ratio. Regarding materials and manufacturing methods other than those described above, a retardation film can be produced by using a material and a manufacturing method of a film having no phase difference effect. -44- This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1274765

(Application of retardation film) When the retardation film of the present invention is used for color compensation in an STN liquid crystal display device, the phase difference value is typically selected from the range of nanometers to 2 centimeters. Further, when the retardation film of the present invention is used as a half-wave plate, the phase difference value is typically selected from the range of 200 Å to 400 nm. When the retardation film of the present invention is used as a quarter-wave plate, the phase difference value is typically selected from the range of 90 Å to 200 nm. For a quarter-wave plate, the phase difference is preferably selected from the range of 100 Å to 18 Å. The retardation film of the present invention can attain a measurement wavelength dependence of a low phase difference effect compared to the retardation film of the known polycarbonate. Therefore, the retardation film of the present invention can be suitably used in a reflective TFT liquid crystal display device or the like. Further, the retardation film of the present invention is characterized in that the phase difference value is less likely to be changed by stress. Therefore, when the retardation film is attached to the polarizing plate, the phase difference effect is less likely to change regardless of the stress generated by the deformation of the polarizing plate. In particular, the retardation film of the present invention is suitable for liquid crystal display having a large-sized screen. The common characteristics of the film and the retardation film which do not have a phase difference effect will be described below. (Thin film thickness) The film of the present invention preferably has a thickness of 20 to 300 μm, more preferably 30 to 200 μm, still more preferably 50 to 1 μm. (Light transmittance and haze) The light transmittance of the film is preferably 85% or more, more preferably 88% or more, and 90% -45 - The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). ) 1274765

The above is even better. The haze of the film is preferably 2% or less, and more preferably 1% or less. (Surface treatment method) The film having the thermoplastic resins A and B described above typically has a surface energy of 5 dynes/cm or less. The surface energy of the film can be measured by conventional methods. A clear description of the law is given in D. K. 0wens, Journal of Applied P〇lymer Science, Vol. 13, vol. 1741 (1969). When another film or glass layer is laminated to the surface surface with low surface energy by means of an adhesive or glue, it is difficult to obtain sufficient adhesive strength or glue strength, and the two may peel off each other. Even when the strength of the initial adhesive is sufficient, the strength of the adhesive or the strength of the glue may be lowered in long-term use, so that the two may peel off each other. The rate of decrease in the strength of the adhesive varies depending on the environmental conditions, but the strength of the adhesive is reduced in any environmental condition. Therefore, the obtained film can be subjected to surface treatment as needed. The surface treatment can be carried out at any time after the film formation. In the case of an unstretched film, the surface treatment is performed after the film is formed. In the case of a uniaxially stretched film, the surface treatment can be carried out before or after stretching. In the case of simultaneously biaxially stretching the film, the surface treatment can be carried out before or after stretching. In the case of a continuous biaxially stretched film, the surface treatment can be carried out before the first stretching, or after the first stretching and before the second stretching, or after the second stretching. In the case of stretching a film, in general, the surface treatment is preferably carried out after stretching. Regarding the surface treatment method, any of the conventional methods can be used. Examples of this method include: electrical treatment such as corona discharge treatment or spark discharge treatment; application of the Chinese National Standard &lt;CNS) A4 specification (21G X 297 mm) at -46 - ϋ 12 1274765 A7

==Electrical polymerization under pressure...with or without ozone bottom # it Ί,* treated with acid such as chromic acid; flame treatment; and factory treatment such as money-based primer treatment or enamel-type primer treatment and many more. The film surface activation treatment can be easily produced to more than 5°Dyne&quot;: the degree of sub-package discharge treatment can be controlled by the following formula (1)). The discharge content is controlled by H = p / (LSxM) ( II) represents the discharge content 'P stands for high frequency power (Watt), LS stands for film rate (not / min)' and river represents discharge width (Mib corona discharge treatment < condition 1 () to 5 (9) watts • minutes The price per square meter is considered to be considered. The upper limit of the discharge capacity is 3 watts per minute per square meter, preferably 1 watt hour per square meter. $ in: table processing, ambient gas It is preferred to use a single gas such as hydrogen, carbonic acid gas, helium, argon, neon or oxygen, or a mixed gas thereof. Plasma treatment at atmospheric pressure is preferred. In general, the atmospheric gas system is produced by mixing 1 to 20 volume percent. An active gas of the type or the like, such as oxygen, air, or carbonic acid gas, is preferably prepared with nitrogen or an inert gas such as helium or argon. Further, surprisingly, the film of the present invention is characterized in that it can be caused by a film storm. Improve the surface energy by going to an alkaline solution. Sodium, potassium hydroxide, tetramethylammonium hydroxide, etc. are used as an assay component of an assay solution. It is preferred to use water or an alcohol such as methanol, ethanol or isopropanol as an alkaline solution. The ingredients are dissolved in a single or mixed solvent to prepare the surface energy of the alkaline/liquid film by contacting the surface of the film with an alkaline solution. 47- This paper scale is suitable for National Standards (CNS) A4 (21GX297) Love) 1274765 A7

And react to mention South. The film thus produced having a high surface energy has a force against the adhesive or glue. Therefore, when the film is laminated with another film, glass or the like, the peeling strength is large. In particular, the film has the advantage of having a large peel strength even under high temperature and high humidity. The preferred value of the surface energy varies depending on the type of adhesive or glue used, but is preferably 5 dynes/cm or more, and W dynes ^^^^. When the surface is able to pass (4), it will not be able to get a satisfactory adhesion. Although there is no clear upper limit on the surface energy, the surface energy is preferably 80 dynes/cm or less, and 7 〇^/cm or less is preferable in terms of equipment and cost of surface treatment. The value of the surface energy can be adjusted by appropriately selecting a processing method or processing conditions. 'Typically, the surface energy thus modified is gradually reduced by storing the film at room temperature, and the effect of surface treatment is lowered. In particular, in the case of the cyclic hydrocarbon type resin, as shown in Comparative Example, the surface energy (54 dynes/cm) after storage for 3 days after the electropolymerization treatment was remarkably lowered after 2 days. 45 dyne / cm. This means that it is difficult to maintain optimal surface energy in a stable manner. In the case of T, there is a problem that the laminated film produced has a change in peel strength. The film of the thermoplastic resin A and the thermoplastic resin b is characterized in that the film is less likely to have a surface treatment effect with time passing, and it tends to maintain an optimum surface energy in a stable manner. (Coating) Further, a coating such as a hard coat layer may be provided on the surface of the transparent film of the present invention as needed. Further, in the film of the present invention, indium tin oxide or the like can be provided by sputtering or the like with or without a coating -48 « This paper size is applicable to the China National Standard (CNS) A4 specification ( 210 X 297 mm) 1274765

The film can be used as a base material for a plastic liquid crystal display device or a touch panel. The coating layer is preferably a thickness of 0.1 to 10 μm, more preferably 1 to 5 μm. Preferred examples of the coating include: a melamine resin type, a propylene base resin type, a urethane resin type, an alkyd resin type, or a fluorine-containing resin type organic type: a layer 'organic polyfluorene oxide compound, For example, it is prepared by mixing a partial hydrolyzate of an alkyltrialkoxide or a tetraalkoxysilane with a polyester polyol or an esterified methanol trihydrate. The coating may also be a partial hydrolyzate of a polyfluorene type material such as amino decane or % oxane, a partial hydrolyzate of a decane coupling agent and an alkyltrial alkane oxane or a tetraalkoxy oxane, and a colloidal cerium oxide and an alkyl group. The hydrolyzed product of the second oxyalkylene oxide is prepared. The coating material is coated on one or both sides of the transparent film of the present invention, and then thermally cured to obtain a film having a solvent-resistant film. In this case, if a low-temperature curing catalyst is used at the same time, the reaction can be carried out at a low temperature, thereby advantageously suppressing thermal denaturation of the film. Further, a monomer or oligomer via addition of a photosensitizer to a polyfunctional acrylate or the like can be used. Preferably, the cured layer obtained by curing the precursor or the emulsified polymer using ultraviolet light or a smear beam is preferred. Various fillers can be added to these coatings as needed. Examples of preferred fillers include organic fillers such as polymethyl acrylate type, polyacrylate type, polyalkylene type, polystyrene type, diethyl phenyl benzene type, benzoguanamine type, and organic polymerization. Shixi oxygen' or inorganic fillers such as cerium oxide, aluminum oxide, and titanium oxide. When a filler is applied to a film used in a display portion of a liquid crystal display device or the like, glare is sometimes recognized in a display image. In this case, the shape of the filler particles can be modified, the coating agent can be applied to the filler, and the coating conditions can be modified. -49- The paper size is applicable to the Chinese National Standard (CNS) Α4 specification (210 X 297 mm).

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Line 1274765 A7 B7 V. Inventive Note (47) etc. The performance of the improved coating is preferred. The film for the display portion is required to have a transmission image visibility of 8 〇 % or more as measured according to JIS K 7105 (6.6) using an optical comb (〇 125 Ai). (Application) The film of the present invention can be an end product used in various applications. Alternatively, the film can be subjected to various additional treatments and then used in a variety of applications. It is to be noted that the film is suitably used as an optically isotropic film, a retardation film, or a polarization protective film in an optical application, such as a peripheral device of a liquid crystal display device. The above-mentioned film which does not have a phase difference effect in the permeation is suitably used as an optically isotropic film, a polarizing element protective film, or the like. The foregoing film having a phase difference of 20 to 1 〇〇〇 nanometer is suitably used as a retardation film. A preferred application of the transparent film of the present invention is as an optically isotropic film. Another preferred application is as a retardation film. In addition, optically isotropic films are used in a variety of applications. One of the preferred applications is as an electrode substrate for use in a plastic liquid crystal display device or a resistive film touch panel. Another preferred application is as a polarizing element protective film. When the transparent film of the present invention is used as a protective film for a polarizing element, for example, a polarizing element can be obtained by adding a dye or a dye to a stretched film of polyethylene glycol. The polarizing element can be laminated to the film of the present invention using a squeezing adhesive, thereby producing a polarizing plate. ^ The polarizing element protective film is provided on one or both sides of the polarizing element. Typically, a polarizing element protective film is provided on both faces of the polarizing element. Eight soils not 50- This paper scale applies to China National Standard (CNS) Α4 specifications (X 297 gong | Ding 1274765 A7 B7 V. Invention description (48) In a specific example, the phase difference film is further included in the polarizing element a polarizing plate of a protective film. For example, if a polarizing element protective film is provided on both surfaces of a polarizing element, and a phase difference film is provided on the generated structure, a multilayer (four layers) structure is obtained. The sequence includes: (1) a polarizing element protective film; (2) a polarizing element; (3) a polarizing element protective film; and (4) a retardation film. Examples of the four-layer structure include a circular polarizing plate and an elliptically polarized light. Depending on the type of the adhesive, the surface-treated film of the present invention may have a viscosity of 50 kg/cm 2 or more for the polyglycol alcohol, preferably 100 kg/cm 2 or more, and 200. Kg/cm 2 or more is particularly preferable. In particular, since the film of the present invention has an appropriate vapor permeability, a water-based polyvinyl alcohol type adhesive can be suitably applied to the film. Further, another preferred application is recorded. Media branch A thin cover layer of the substrate or recording layer. Details of such applications are described in Nikkei Microdevice (issued by Nihon Keizai Shinbun, Inc.), page 155, July 17, 2000. (Embodiment) Examples and Comparative Example First, a method of measuring the physical property values shown in the examples and comparative examples will be described. <Glass Transfer Temperature> The glass transition temperature is based on JIS K7121, used by Seiko Instruments &amp; Electronics Ltd.) -51- This paper scale applies to China National Standard (CNS) A4 specification (210 x 297 mm)

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Line 1274765 A7 ___B7_ V. Description of the invention (49~) Differential Scanning Calorimeter (DSC) measurement. Specifically, a 10 gram sample was placed in a DSC apparatus, and the sample was heated from room temperature at a rate of i 〇 3 C/min, thereby measuring the glass transition temperature of the sample. &lt;Light transmittance&gt; Light transmittance was measured using a light of 550 nm according to the method described in JIS K7105-1981 (5. 5). &lt;Haze&gt; The haze was measured according to the method described in JIS K7105-1981 (6.4). <Phase Difference Effect> The phase difference effect is a polarization microscopic spectrophotometer (TFM-120AFT manufactured by ORC Manufacturing Co., Ltd.) using a wavelength of 514.5 nm. measuring. &lt;Phase difference action in the thickness direction&gt; Using a polarization microscopy spectrophotometer (TFM-120AFT manufactured by ORC Manufacturing Co., Ltd.), the angle dependence of the phase difference effect was measured using light having a wavelength of 514.5 nm, thereby obtaining η X, ny, and η ζ. Further, the thickness d of the film was measured. Based on the obtained measured values, the phase difference effect in the thickness direction is calculated using the following equation: Phase difference effect in the thickness direction = | (nx + ny)/2-nz) | xd. &lt;Alignment phase difference&gt; The two narrow sides of the film having a width of 5 cm and a length of 25 cm were fixed and left at the glass transition temperature for 1 minute. The film is uniaxially stretched at a speed of 0.2 m/min in the longitudinal direction to obtain a stretched film having a draw ratio of 7.5 - 52 - This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297) PCT) 1274765 A7

. The resulting stretched film is allowed to cool. The phase difference effect was measured in the middle portion of the stretched film. Further, the thickness of the stretched film was measured. The phase difference effect in the case where the film thickness is ι 〇〇 micrometer is calculated from the phase difference of the intermediate portion of the stretched film and the thickness ′. The calculated phase difference effect is regarded as the alignment phase difference. &lt;Measurement wavelength dependence of phase difference effect> The sample used for measuring the alignment phase difference is used in the following procedure to determine the measurement wavelength dependence of the phase difference effect: (1) Using a polarized microscopy spectrophotometer (TFM-120 AFT manufactured by 0RC Manufacturing Co., Ltd.), which measures phase difference values with respect to measurement wavelengths of 441·6 nm, 514.5 nm, 632.8 nm, and 780 nm according to the spin-turn analyzer method; 2) According to the measured value, the minimum variance method is used to determine the constants in the following experimental formula: R e = a + b / ( λ 2 - c) where λ represents the measurement wavelength and R e represents when the wavelength is used; The phase difference effect when the light is measured, and a, b, and c are constants; (3) using the experimental formula obtained, calculate the phase difference value (Re(400)) at 400 nm and at 550 nm. The phase difference value (Re(550)); and (4) calculates R = Re(400) / Re( 550) based on the calculated phase difference value, and regards this value as an indication of the measurement wavelength dependence. &lt;Photoelastic coefficient&gt; The birefringence of the film was measured using a polarization microscopic spectrophotometer (TFM-120AFT-PC manufactured by ORC Manufacturing Co., Ltd.). Apply the film in the optical axis direction -53- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Ϊ274765 A7 B7 Five invention instructions (51 cut into strips each having a width of 丨 cm. One end of the film is fixed ', and a load of 50 g, 1 g or 150 g is applied to the other end, so that the birefringence of the strip film is 1. According to the result, the birefringence change due to the unit stress is calculated. &lt;Tear Resistance Spread Strength&gt; The tear propagation strength was measured according to Jis K7128 (pants type method) using an automatic green counter (manufactured by Shimadzu Corporation). The pulling rate in the measurement was 200 mm/min. For the measurement, a film having an average thickness of 5 μm of 5 μm was used. &lt;Folding resistance&gt; The folding resistance was based on JIS C5016, using a MIT type folding resistance tester D-type (Toyo Seiki Seisaku-sho, Ltd. Measurements. Note that in the measurement, a sample having a width of 15 mm, a length of 200 mm, and an average thickness of 50 μm and 5 μm is used. The present invention will be described in more detail by way of the following illustrative examples (Example 1 a ) will be 100 parts weight Amount (90% by weight) of an alternating copolymer consisting of isobutyl hydrazine and N-methyl cis-butane diimide (containing 50 mole percent of N-methyl cis-butanediimide, glass transfer) a thermoplastic copolymer consisting of styrene and acrylonitrile at a temperature of 15 7 ° C) and a portion (1 重量% by weight) (containing 76 parts by weight of styrene and 24% by weight of acrylonitrile) Dissolved in dichloromethane' thus obtained a solution having a solid concentration of 15% by weight. The solution flow was spread on a biaxially stretched polyethylene terephthalate film laid on a glass plate. The sample is left at room temperature for 60 minutes. Thereafter -54- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm).

Line 1274475 A7 _____ _B7 Invention Description (52~) &quot;&quot;~&quot;, strip the sample from the polyethylene terephthalate film, fix the four sides of the sample, and dry the film for 10 minutes under the loot Then, it was dried again for 10 minutes. An unstretched film having a thickness of about 1 〇〇 micron was produced. This unstretched film has a phase difference of 83⁄4 μm, a transmittance of 92%, and a haze of 0.3%. (Example lb) A sample film of 3 〇 cm X 1 〇 cm was cut out from the unstretched film obtained in Example 1a. A sample was prepared using a tensile tester (X4HD-HT manufactured by Toyo Seiki Seisaku-sho, Ltd.) at a stretching rate of i〇 cm/min, a draw ratio of 1,500, and a stretching temperature of 1401. The film is in the length direction; the longitudinal end is uniaxially stretched. Thus, a retardation film having a phase difference of 143 nm (in which the measurement wavelength was 550 nm) was obtained. Re (400) / Re (550) was calculated to evaluate the wavelength dependence of the retardation film. As a result, Re(400)/Re(550) is 1·〇9. Further, the photo-elasticity of the retardation film was 6 χ 1 (Τ13 cm 2 / dyne. (Example 2) A film of the film prepared in Example 1 a was cut out to a film of 30 cm X 1 〇 cm. Example 1 b, the sample film was subjected to free end longitudinal uniaxial stretching in the longitudinal direction under a draw ratio of 1.9 and a tensile temperature of 140 C. Thus, a phase difference of 260 nm was obtained. A retardation film in which Re (400) / Re (550) was calculated at a measurement wavelength of 550 nm p was evaluated to evaluate the wavelength dependence of the retardation film. As a result, Re (400) / Re (550) was 1.09. 3a) 100 parts by weight (91% by weight) used in Example 1 a from Iso-55- This paper scale applies to Chinese National Standard (CNS) A4 specification (210 χ 297 gong) 1274765 A7

An alternating copolymer of olefin and dimethyl-maleimide, and a thermoplastic copolymer consisting of styrene and acrylonitrile (containing 27% by weight) (42 mole percent of acrylonitrile) was dissolved in dichloromethane, thus preparing a solution having a solid concentration of 15 weight percent. The solution was dynamically spread on a biaxially stretched polyethylene terephthalate film laid on a glass plate. The resulting sample was allowed to stand at room temperature for 6 minutes. Thereafter, the sample was peeled off from the polyethylene terephthalate film, and the four sides of the sample were fixed, and the film was dried at loot for ί ο, and then dried at 14 (rc for 10 minutes). An unstretched film having a thickness of 100 μm. The unstretched film has a phase difference of 5 nm, a light transmittance of 92%, and a haze of 〇·5 %. (Example 3b) and Example 1 b. In a similar manner, the sample film prepared in Example 3a was subjected to free end longitudinal uniaxial stretching in the longitudinal direction under a draw ratio of 1.5 and a stretching temperature of 150 ° C. A retardation film having a phase difference of 138 nm (in which the measurement wavelength was 550 nm) was obtained. Re (400) / Re (550) was calculated to evaluate the wavelength dependence of the retardation film. As a result, Re (400) ) / Re (550) is 1.07. Further, the photo-elasticity of the retardation film is 6X 1 (T 13 cm 2 / dyne. (Comparative Example 1 a) Using a polycarbonate resin (C-manufactured by Teijin Chemicals Ltd.) 1400, wherein the glass transition temperature is 149 ° C. The bisphenol component of the polycarbonate resin is bisphenol A. The ester resin is dissolved in methylene chloride, thus preparing a solution having a concentration of 15% by weight. The solution flow is spread on the glass-56-paper scale applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 PCT) 1274765 A7 _____B7 V. Inventive Note 54) &quot; ---- On the biaxially stretched polyethylene terephthalate film on the plate, the resulting sample is left at room temperature for 60 minutes. Thereafter, The sample was stripped from the polyethylene terephthalate film by polycondensation, and the four sides of the sample were fixed, and the film was dried under 1 Torr for 10 minutes, and then at 120 ° (: drying for 1 minute). An unstretched film having a thickness of about 80 μm. This unstretched film has a phase difference of a gate nanometer, a light transmittance of 9%, and a haze of 〇·3 % (Comparative Example 1 b) The unstretched film obtained in Comparative Example 1a was cut into a film of 3 〇 cm X ^ 〇 cm. The tensile test apparatus (X4HD-HT manufactured by Toyiki Seisaku_sho, Ltd.) was used at the stretching rate. For i〇 cm/min, the draw ratio is 1:1, and the stretching temperature is 165 t. The sample was stretched. Thus, a retardation film having a phase difference of 250 nm (in which the measurement wavelength was 550 nm) was obtained. Re (4 Å) / Re (55 Å) was calculated to evaluate the retardation film. Wavelength dependence. As a result, Re (4〇〇)/Re (550) was 1 · 16. (Example 4) 1 part by weight of isobutylene and N-methylbutyleneimine Alternating copolymer (containing 50% by mole of &gt; 1-methyl cis-butanthine, glass transition temperature of 1 57 ° C) and 33 (25 weight percent) of benzene A thermoplastic copolymer composed of propicononitrile (containing 74% by weight of styrene and 26% by weight of cyanamide) was dissolved in dichloromethane, thereby preparing a solution having a solid concentration of 15% by weight. The solution flow was spread over a biaxially stretched polyethylene terephthalate film laid on a glass plate. The resulting sample was allowed to stand at room temperature for 6 minutes. Thereafter, the sample was stripped from the polyethylene terephthalate film, and the four sides of the sample were fixed, and the thin-57-paper scale was applied to the China National Winter Standard (CNS) A4 specification (21〇X 297 public). Love) 1274765 A7 ____ B7 V. INSTRUCTIONS (55) The film was dried at 100 ° C for 10 minutes, then dried at 丨 4 〇 for 1 , and then dried at i60 s for 30 minutes. An unstretched film having a thickness of about 1 Å was obtained. The thickness of the unstretched film was changed by 2% with respect to the average thickness. The unstretched film had a phase difference of 3 nm, an alignment phase difference of 6 nm, a light transmittance of 92%, and a haze of 〇·3%. The film also has a tear propagation strength of 123 g/mm and a folding resistance of 7 times. Further, this film has a phase difference effect in the thickness direction of 33⁄4 μm. The glass transition temperature of the film was 1451. (Examples 5 to 12 and Comparative Examples 2 and 3) Films were produced in a manner similar to that of Example 1, except that the content of acrylonitrile ▲ and the content of the thermoplastic copolymer composed of hexamethylene and acrylonitrile were changed. Weight percentage. The properties of the resulting film are shown in Table 2. (Comparative Example 4) A film of an alternating copolymer composed of isobutyl hydrazine and N-methylbutyleneimine was obtained in a manner similar to that of Example 1 b except that styrene was not used. A thermoplastic copolymer composed of propionitrile. The properties of the resulting film are shown in Table 2. (Comparative Example 5) A polycarbonate resin (C-1400 manufactured by Teijin Chemicals Ltd., glass transition temperature: 149 ° C) was dissolved in dichloromethane, thereby preparing a solution having a solid concentration of 5% by weight. The solution flow was spread over a biaxially stretched polyethylene terephthalate film laid on a glass plate. The resulting sample was allowed to stand at room temperature for 60 minutes. Thereafter, the sample was stripped from the polyethylene terephthalate film and the four sides of the sample were fixed, and the film was applied to the Chinese National Standard (CNS) A4 specification (210 X 297) at 1 〇〇-58. 1274765 A7 B7 Description of the invention Drying for 10 minutes, followed by drying at 12 (TC for 10 minutes) to obtain an unstretched film having a thickness of about 80 μm. This unstretched film has a phase of 2 μm. The difference, 90% transmittance, and 雾.3% haze. The alignment phase difference of the film is about 1400 nm. The wavelength dependence of the film is i.丨6. This wavelength correlation is more implemented. The example is significantly larger. (Example 1 3 ) 75 parts by weight of an alternating copolymer consisting of isobutylidene and methyl cis-butane quinone imine (containing 50% of the total ν · A Base butyl quinone diimine, glass transition temperature of 1571) and 25 parts by weight of acrylonitrile-styrene copolymer (containing 28% by weight of acetonitrile) (I/P ratio = 2.46) Dissolved in di-methane, thus producing a solution having a solids concentration of 15 weight percent. The solution flow is spread over the glass. The biaxially stretched polyethylene terephthalate film on the plate, and the obtained sample was left at room temperature for 6 。 minutes. Thereafter, the sample was peeled off from the polyethylene terephthalate film, and The four sides of the sample were solidified and the film was placed at 1 Torr. (3 days drying for 1 minute, then drying at 14 Torr for 10 minutes, and drying at 16 ° for 3 minutes at rc. The film has a phase difference of 43⁄4 μm in the plane direction of the film, and a phase difference of * nanometer in the thickness direction of the film, a transmittance of 92%, and a haze of 0. 3 %. The temperature is 147 ° C. The film also has a folding resistance of 5 times in the MD direction (flow expansion direction) and a folding resistance of 6 times in the td direction (direction perpendicular to the direction in which the mud expands). It also has a tear propagation strength in the MD direction of 7 9 gram force / 3⁄4 meter, and a 柷 tear propagation strength in the TD direction of 76 gram force / mm. Note that the direction of flow expansion is referred to as "MD" Direction", and will be perpendicular to the direction of flow expansion 297 mm)

k -59- 1274765 A7 B7 V. Description of Invention (57) "TD direction". (Example 1 4) A film obtained in a manner similar to that of Example 13 was placed at 16 Å. (: in the MD direction The film is stretched at a magnification of 1 · 5. The film has a haze of 〇·4%. The film also has a phase difference of 5 nm in the plane direction of the film, and a phase of 7 nm in the thickness direction of the film. The film has a folding resistance of 5 times in the MD direction and 173 times in the TD direction. The tear propagation strength of the film is 62 gram force/mm in the MD direction and 177 gram force in the TD direction/ (Example 1 5 ) A film obtained in a manner similar to that of the operation and 13 was stretched at a magnification of 1.25 in the MD direction at 160 ° C, and then in the TD direction at 160 ° C. The film is stretched at a magnification of 1.5. The film has a haze of 〇·4%. The film also has a phase difference of 4 nm in the plane direction of the film, and a phase difference of 11 nm in the thickness direction of the film. The folding resistance of the film is 161 times in the MD direction and 133 times in the TD direction. The tear propagation strength of the film is in the MD direction. 151 gram force/mm, and 148 gram force/mm in the TD direction. (Examples 1 to 6 and Comparative Example 6) Films were produced in a manner similar to that of Example 14, except that the modification was made by the gambling And the weight fraction of the thermoplastic copolymer composed of styrene and the stretching conditions. The composition of the film and the stretching conditions are shown in Table 3. The properties of the resulting film are shown in Table 4 (Example 19) to Example 1 a similar manner, using 100 parts by weight (7 〇 weight percent - 60 - paper scale applicable to China National Standard &lt;CNS) A4 size (210 X 297 mm) 1274765 A7 ___B7 V. Description of invention ( 58) an alternating copolymer consisting of Isopresin and N-methyl cis-butanediamine (containing 50 mol% of N-methyl maleimide, the glass transition temperature is 147 ° C) and 43 parts by weight (30% by weight) of a thermoplastic copolymer of styrene and acrylonitrile (containing 73% by weight of styrene and 27% by weight of acrylonitrile) to prepare a film. Self-made film cut out a film of 30 cm X 1 〇 cm. Using a tensile test device (Toyo Seiki X4HD-HT manufactured by Seisaku-sho, Ltd.) The sample film was subjected to free end longitudinal uniaxial stretching, wherein the stretching rate was i 〇 cm/min, the stretching ratio was 1.5, and the stretching temperature was l5. (rc. The resulting uniaxially stretched film has a phase of 3 nm in the plane direction of the film] and a phase difference of 3 nm in the thickness direction of the film. The film has a transparency of 92%. Light rate and 〇·4% haze. The stretched film having a thickness of 45 μm has a tear propagation strength of 192 g/mm in a direction perpendicular to the direction of stretching and a folding endurance of 218 times in the direction of stretching (wherein the stretching direction is The length direction of the sample). (Example 20) A uniaxially stretched film was obtained in the same manner as in Example 19. Thereafter, the film was stretched in a direction perpendicular to the previous stretching direction, thereby producing a continuous biaxially stretched film having a thickness of 50 μm. The tear propagation strength of the film was 151 gram force/mm in the direction perpendicular to the second stretching direction. The film has a folding resistance of 121 times. The phase difference of the film was 3 nm in the direction of the film and 3 nm in the thickness direction of the film. (Example 2 1 to 2 4) A film was produced in a manner similar to that of Example 19 except that the acrylonitrile was changed to -61 - the paper size was applied to the Chinese National Standard (CNS) A4 specification Q1〇x 297 public) 1274765 A7 "-__ B7 V. Inventive Note (59) &quot;~ Content and content of thermoplastic copolymer composed of styrene and acrylonitrile. In a manner similar to Example 20, at the glass transition temperature of the film Each film was continuously biaxially stretched by a draw ratio of 1.5. The properties of the resulting film are shown in Table 5. The tear propagation strength in Table 5 indicates tear resistance in a direction perpendicular to the second direction of stretching. The value of the crack propagation strength. The folding endurance in Table 5 indicates the value of the folding endurance measured when the stretching direction is the longitudinal direction of the sample. (Example 2 5 ) By similar to Example 19 The uniaxial stretching ratio of 2 is obtained to obtain a stretched film, in addition to changing the content of acrylonitrile and the content of the thermoplastic copolymer 苯 of styrene and acrylonitrile. The stretched film has 5 5 μm. The thickness and phase difference function. The characteristics of the film are shown in Table 5. (Example 2 6) Make 1 00 parts by weight (70% by weight) of an alternating copolymer composed of Isopresin and N-methyl cis-butanediamine (containing 5 〇 mole percentage of n-methyl maleimide , glass transfer temperature of 157 art) and 43 parts (3 〇 weight percent) of thermoplastic copolymer composed of styrene and acrylonitrile (including 7 3 weight $: percentage + female and 27 weight percent C The phthalonitrile was melt-kneaded to produce pellets. The pellets were supplied to a melt extruder having a T-die to prepare a film having a thickness of 100 μm. The phase difference of the films was 8 nm. The phase difference is 38 nm. The film has a light transmittance of 92% and a haze of 0.7%. The film also has a tear propagation strength of 123 g/mm and a folding resistance of 7 times. The glass transition temperature of the film is丨37. (: Example 2 7 to 31 and Comparative Examples 7 to 9) A film was obtained in a manner similar to that of Example 26 except that the acrylonitrile-62-paper scale was applied to the Chinese country. Standard &lt;CNS) A4 specification (210 X 297 public attack*) 1274765

The content and the content of the thermoplastic resin composed of styrene and acrylonitrile. The properties of the resulting film are shown in Table 4. (Example 3 2 ) The film obtained in Example 27 was stretched by 15 in the MD direction (flow expansion direction) at rc6 (the ratio of the surface energy of the film was 46 dynes/cm) The film was subjected to corona treatment using a discharge rod having a length of 25 cm under the following conditions: 40 volts, 3 amps, and a line speed of glutinous rice/minute. The resulting film had a haze of 0.4%. The phase difference is 5 nm in the plane direction of the film and 7 nm in the thickness direction of the film. The folding resistance of the film is 5 times in the MD direction, and in the TD direction (perpendicular to the flow expansion direction &lt; The direction is 173 times. The tear propagation strength of the film is 62 gram force/mm in the 1^1:&gt; direction, and 77 gram force/mm in the TD direction. The photoelasticity of the film is 6 X 10 1. square centimeter/dyne. The film was stored for 3 days after corona treatment &lt; surface energy was 56 dynes/cm. The film was left at room temperature for a long time. The surface energy of the film after 10 days It is 54 dynes/cm. The surface energy of the film after 20 days is 54 dynes/cm. The surface energy of the film after 7 days. :&gt; 3 dynes/cm. Therefore, the surface energy of the film produced can be stabilized for a long time. (Example 3 3 ) An unstretched film obtained by a method similar to that of Example 32 was placed under 16 〇 Stretching a magnification of 1.5 in the MD direction, followed by a further 16 〇 [stretching a magnification of 1.5 in the direction of the strand. The surface energy of the film is 46 dynes/cm. Using 5 kHz - 150 The 咼 咼 frequency power supply uses a barometric pressure plasma of the same volume of atmospheric pressure plasma of argon and a mixture of krypton and 2% oxygen. The resulting film has a haze of 0.4%. The phase difference of the film acts on Thin-63 -

This paper scale applies to China S standard (CNS) A4 specification (210 X 297 mm) 1274765 A7 ____— _B7__ V. Description of invention (61) 4 nm in the plane direction of the film and 11 m in the thickness direction Micron. The folding resistance of the film was 161 times in the MD direction and 133 times in the TD direction. The tear propagation strength of the film was 151 gram force/mm in the MD direction and 148 gram force/mm in the TD direction. The surface energy of the film after storage of the film for 3 days was 5 9 dynes/cm. The film was allowed to stand at room temperature for a long time. The surface energy of the film after 10 days was 57 dynes/cm. The surface energy of the film after 20 days was 55 dynes/cm. The surface energy of the film after 70 days was 54 dynes/cm. Therefore, the surface energy of the obtained film can be stabilized for a long time. (Comparative Example 1 0) A cycloolefin type resin (Nippon Zeon Co., Ltd., a thinned ZEONOR 1420R) was dissolved in xylene to obtain a coating varnish having a resin concentration of 35 wt%. The obtained coating varnish was cast on a biaxially stretched polyethylene terephthalate film using a bar coater, and then stored at room temperature for 6 〇 minutes, and then dried at 80 ° C for 12 minutes. Thus, a film (Tg (glass transition temperature) = 127 eC) was obtained. The resulting film was stretched at a magnification of 1.5 in the MD direction at 150 °C. The resulting film had a haze of 0.4%. The phase difference of the film was 38 nm in the plane direction of the film and 66 nm in the thickness direction of the film. The folding resistance of the film was 216 times in the MD direction and 3 89 times in the TD direction. The tear propagation strength of the film was 138 g/m in the md direction and 210 g/mm in the TD direction. The photoelasticity of the film is 5 χ 10 13 cm 2 / dyne "the surface energy of the film is 42 dynes/cm. Similar to the examples, the film was subjected to a plasma treatment. The resulting film had a surface energy of 54 dynes/cm 3 days after the subsequent electroforming treatment. Make the film in the room -64 - This paper size applies to the Chinese national standard &lt;CNS) Α4 specification (210X297 public) Ϊ274765

Leave it for a long time. The surface energy of the film after 10 days was 47 dynes/cm. The surface energy of the film after 20 days was 45 dynes/cm. The film has a surface energy of 44 dynes/cm at 7 〇1彳. Therefore, the surface of the film produced can be = ground = low. (Example 3 4) A roll film having a width of 450 nm and a length of 2 mm was obtained according to Example 27. Using this roll film, a longitudinal stretching of 2 times magnification was carried out at 150 ° C using 6 rolls having a distance of 1 cm between each of the tweezers. The resulting film was further stretched by a factor of 2 at 150 C using a tenter. The surface 妒 of the film was 46 dynes/cm. A coextruded film of polyethylene enamel having a thickness of 5 Å and partially saponified vinyl acetate was attached to one side of the film as a protective film. Further, the attached film was subjected to an atmospheric pressure plasma of a mixture gas of an equal volume of argon and helium and 2% oxygen at a linear velocity of 1.8 m/min by using a high-frequency power source of a Shihe-4 watt tile. Thus, the film produced by surface treatment of one side of the film has a haze of 0.8%. The phase difference of the film is 〇 nanometer in the plane direction of the film and 〇 nanometer in the thickness direction of the film. The folding resistance of the film was in times in the MD direction and 145 times in the td direction. The tear propagation strength of the film was 252 gram force/mm in the MD* direction and 194 gram force/mm in the TD direction. The surface energy of the film after storage of the film for 3 days was 60 dynes/cm. The film was allowed to stand at room temperature for a long time. As a result, the surface energy of the film after 5 days was 5 5 dynes/cm. The surface energy of the film after 20 days was 54 dynes/cm. The surface of the film after 5 days is 5 4 dynes/cm. Therefore, the surface energy of the film can be stabilized for a long time -65- The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 1274765 A7

(Example 3 5) Surface energy of the film The surface energy of the film obtained in Example 18 was measured to be 46 dynes/cm. The surface of the film obtained in Example 18 was subjected to treatment according to Example 32. The resulting film had a haze of 〇.5%. The phase of the film = 4 nm in the plane direction of the film and 28 nm in the thickness of the film. The mechanical strength of the treated film was almost the same as before the treatment. The surface energy of the film after storage for 3 days was "Dyne/Benti". The film was left at room temperature for a long time. The surface of the film after 1 day was ^14 dynes/cm. After 20 days, the film was after 20 days. The surface energy of the film is dyadin/cm, and the surface energy of the film after 50 days is 52 dynes/cm. Therefore, the surface energy of the film can be stabilized for a long time. (Example 3 6) Example 1 b The retardation film prepared in the film was subjected to corona treatment under the conditions of Example 32. As a result, the surface energy of the corona-treated surface of the film was 56 dynes/cm. The polarization axis of the polarizing plate and the electricity were charged. The retardation film of the halo treatment is set to an angle of 45°. The polarizing plate is placed on the corona-treated surface, and the two are attached to each other using a propylene-based adhesive. A polarizing plate was placed, and the circular polarizing plate was left for 70 days in an environment of a temperature of 40 ° C and a humidity of 95 %. No peeling at the interface between the polarizing plate and the retardation film was observed. - The paper size is applicable to the Chinese National Standard (CNS) Α4 specification (210 X 297 mm) 1274765 A7 B7 V. Invention (64) Table 1 Nitrile content * Wt% Resin B content Wt% Stretching temperature °c Stretch ratio magnification Transmittance % Haze % Phase difference effect nm Wavelength light dependence R Photoelastic cm2/dyn Example la 24 10 92 0.3 8 Example lb 24 10 140 1.5 1.09 6 X10·13 Example 2 24 10 140 1.9 1.09 Example 3a 27 9 92 0.5 5 Example 3b 2Ί 9 150 1.5 138 1.07 6 ΧΙΟ·13 Comparative Example la - 0 - - 90 0.3 21 - - Comparative Example lb - 0 165 1.1 - - 250 1.16 - Note)* : Content of nitrile unit in thermoplastic resin B -67- This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1274765 A7 B7 V. Inventive Note (65) Table 2 Nitrile Content Wt% Resin B Content Wt% Transmittance?/〇Haze% Phase Difference Effect nm Phase Difference in Thickness Direction nm Orientation Phase Difference Nm wavelength light dependence R Example 4 26 25 92 0.3 3 3 6 Example 5 24 10 92 0.7 5 3 217 1.09 Comparative Example 2 24 15 87 3.0 Example 6 26 20 92 0.4 5 4 80 1.04 Example 7 26 30 92 0.4 4 1 18 Example 8 26 50 91 0.3 5 140 Example 9 26 70 90 0.3 6 Example 10 26 90 90 0.4 7 197 Example 11 28 20 92 0.4 5 1.04 Example 12 28 70 91 0.3 7 Comparative Example 3 28 85 85 4.1 Comparative Example 4 0 92 0.3 6 5 529 Comparative Example 5 • 90 0.3 21 1400 1.16 -68 - This paper size applies to Chinese National Standard (CNS) A4 size (210 X 297 mm) 1274765 A7 B7 V. Description of invention (66) Table 3. Resin A: B (weight ratio) Content (% by weight) of nitrile-containing monomer in Resin B Tensile conditions MD direction TD direction Example 13 75 : 25 28 Example 14 75 : 25 28 160 ° C - 1.5 times Example 15 75 : 25 28 160 ° C 160 ° C 1.5 times 1.5 times Example 16 70 : 30 26 150 ° C - 1.5 times Example 17 70 : 30 26 150 ° C 150 ° C 1.5 times 1. 5 times Example 18 70 : 30 26 150 °C 150 ° C 2.0 times 2.0 times Comparative Example 6 100 : 0 - 170. (:' - 1.5 times -69 * This paper size applies to China National Standard (CNS) A4 size (210 X 297 mm) 1274765 A7 B7 V. Invention description (67) Table 4 Film thickness (μηι) Transmittance (% Haze (%) Phase difference effect (nm) Phase difference effect in thickness direction (nm) Tear propagation strength (gf/mm) UO/TO Fold resistance (times) MD/TD Example 13 50 92 0.3 4 4 79/76 5/6 Example 14 47 92 0.4 5 7 62/177 5/173 Example 15 46 92 0.4 4 11 151/148 161/133 Example 16 52 92 0.4 4 9 90/169 12/215 Example 17 48 91 0.5 4 22 183/132 205/148 Example 18 49 91 0.5 4 32 172/163 199/205 Comparative Example 6 50 93 0.5 190 201 68/123 3/101 Table 5 Nitrile content Wt°/ Indole B content Wt% Transmittance % Haze % Phase difference effect nm Phase difference in thickness direction (nm) Fold resistance (times) Tear propagation strength gf/mni Wavelength light dependence R Example 19 27 30 92 0.4 3 3 218 192 Example 20 27 30 92 0.5 3 3 121 151 Example 21 24 20 92 0.3 6 151 108 179 Example 22 27 40 92 0.4 5 29 181 221 Example 23 27 45 92 0.4 4 95 215 16 9 Example 24 29 33 92 0.7 6 90 177 252 Example 25 27 30 92 0.5 90 46 252 292 1.04 _ -70- This paper ruler New Zealand® A4 Secret (^OX297 mm)---- I274765 A7

Table 6 ^—__ Nitrile Content Wt% Resin B Content Wt% Transmittance % Haze % Phase Difference Effect nm Alignment Phase Difference nm Wavelength Light Verticality R ί^(Η26 27 30 92 0.7 8 38 Examples 27 24 10 92 0.7 7 246 1.09 - a 24 20 88 3.5 Example 28 27 40 92 0.8 4 50 a • 1 __ an example 29 27 70 90 0.8 5 175 Example 30 27 90 90 0.4 7 197 • Example 31 28 30 92 0.6 5 -- --- 1.04 Example 8 29 40 85 4.0 7 .·«««—Example 9 28 85 85 5.3 ____———-- Table 7 Tensile conditions using film — ____—- Surface treatment MD TD f Example 32 Example 27 was given 1.5 times - - - _ Example 33 Example 32 160 〇 C 1.5 times 160 〇 C 1-5 times - Comparative Example 10 ZEONOR * 150t 1 · 5 times -. - - Example 34 Example 27 15 (TC2 times 150 〇 C2 times ^. «*·*------ Plasma Example 35 Example 18 150 ° C 2 times 150 ° C 2 times. Note) *: by the ring Film made of hydrocarbon resin (Zeonor 1420R manufactured by Nippon Ze〇n C〇., Ltd.) -71 - This paper scale applies to Chinese National Standard (CNS) A4 specification (21〇x 297 mm) 1274765 A7 B7 , invention description (69) table 8 - haze % in-plane phase difference effect nm phase difference in thickness direction effect nm folding resistance tear propagation strength photoelastic coefficient MD TD MD TD Example 32 0.4 5 7 5 173 62 177 6X10-13 Example 33 0.4 4 11 161 133 151 148 Xiaoming Comparative Example 10 0.4 38 66 216 389 178 210 5χισ13 Handle 34 0.8 0 0 112 145 252 194 Mine Example 35 0.5 4 28 Touchdown • Table 9 Surface energy (dyne/cm) 3 days after treatment, 10 days after 20 days, and after 70 days, Example 32 46 56 54 54 53 Example 33 46 59 57 55 54 Comparative Example 10 42 54 47 45 44 Example 34 46 60 55 54 54 Example 35 46 58 54 53 52 -72- This paper size is applicable to China National Standard (CNS) A4 specification &lt; '210X297 mm) 1274765 A7 B7 V. INSTRUCTIONS (70) Utility of industrial application invention. According to the present invention, via use A polymer having a specific structure and composition produces a transparent film having a small phase difference effect. The film of the present invention has an advantage that a phase difference due to molecular alignment is less likely to occur. According to the present invention, the phase difference effect can be adjusted to a desired value by appropriately adjusting the composition ratio of the resin used in the film. Further, the optical film according to the present invention has an advantage that the measurement wavelength dependency can be easily controlled. -73- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm)

Claims (1)

A8 B8 C8 D8 1 · A transparent film comprising: (A) a thermoplastic resin having a substituted or unsubstituted quinone imine group in a side chain of the resin; and (B) having a substituted or unsubstituted side chain of the resin The thermoplastic resin substituted with a phenyl group and a nitrile group, the content of the thermoplastic resin A is 5 to 95% by weight based on the total weight of the resin in the film, and the content of the thermoplastic resin 6 is 5 to 95% by weight. %; wherein the film phase difference is from 1 to 20 nm, the transmittance of the film is 85% to 92%, and the haze of the film is 0% to 2% or less; the folding resistance of the film is At least one direction in the plane of the film is 3 〜 to 2 52 times. 2. The film of claim 1, wherein the thermoplastic resin A is composed of a compound of a hydrocarbon hydrocarbon and a repeating unit having a substituted or unsubstituted quinone group in a side chain. 3 · The film according to claim 1, wherein the phase difference is 0 nm to less than 20 nm. 4. The film of claim 1, wherein the phase difference is from 20 μm to 1000 μm. 5. The film of claim 1, wherein the film has an alignment phase difference of 0 nm to 3 〇 〇 nm. 6. The film of claim 1, wherein the film is a stretch film. 7 · For the film of the scope of patent application No. 1, the film of 67576-940712.DOC &quot; ” This paper scale applies to the Chinese National Standard (CNS) A4 specification (21〇χ 2 towns) ----- --- A8 B8 C8 1274765 ^ The at least one direction of the tear propagation intensity in the plane of the film is Η. Cree / mm ~ 292 grams force / mm. 8. The film of claim 1, wherein the surface energy of at least one surface of the film is 50 dynes/cm to 80 dynes/cm. 9. The film of claim 3, wherein the film has a phase difference of from 〇 nanometers to 5 inches in the thickness direction of the film. 1) The film of the third aspect of the patent, wherein the thermoplastic resin comprises a repeating unit represented by the following chemical formula (1), and another repeating unit represented by the following chemical formula (2): R2R1 R3 (1) (wherein RR and R each represent a deuterium atom or a k group of 1 to 8 carbon atoms, and R means an alkyl group of 1 to 18 carbon atoms or a cycloalkyl group of 3 to 2 carbon atoms&gt;, And /, the content of the thermoplastic resin of the medium S is from 50 to 90% by weight based on the total weight of the entire resin in the film. 11. The film of the invention, wherein the thermoplastic resin b has a substituted or not a substituted acrylonitrile repeating unit and a substituted or unsubstituted phenylethylene repeating unit, 20 to 50% by weight of the thermoplastic resin in the substituted or unsubstituted acrylonitrile repeating unit film, and 1274765 A8 B8 C8 D8 Patent Application No. 50 to 80% by weight of the thermoplastic resin B in the substituted or unsubstituted phenylethylene repeating unit film. 12. A method of producing a film as claimed in claim 1, the method comprising the steps of: subjecting a thermoplastic resin A having a substituted or unsubstituted quinone imine group to a side chain of the resin and a resin The thermoplastic resin B having a substituted or unsubstituted phenyl group and a nitrile group, and the content of the thermoplastic resin A is 5 to 9.5 wt% based on the total weight of the resin in the film, and thus The solution of the plastic resin B having a content of 5 to 95% by weight is flow-expanded on the support; and the solution is dried. A film according to claim 4, which is for use in an elliptically polarizing plate, the polarizing plate comprising the film and a polarizing plate, wherein the film and the polarizing plate are laminated. 14. The film of claim 4, which is for use in a circular polarizing plate, the polarizing plate comprising the film and a polarizing plate, wherein the film and the polarizing plate are laminated. A film according to the ninth aspect of the invention, which is for use in a polarizing plate, the polarizing plate comprising a polarizing element and the film, the film protecting at least one side of the polarizing element. 67576-940712.DOC _ 2 This paper size applies to the Chinese National Standard (CNS) A4 specification (21〇 X 297 public --