Stretched films, optical films, and display devices

Abstract

To provide a cellulose ester resin drawn film having an in-plane phase difference Re of a fixed value or more while having a reduced out-of-plane phase difference Rth.SOLUTION: A drawn film is formed from a composition comprising a cellulose ester resin and a polyester represented by the general formula (I). When the plane orientation coefficient of the drawn film comprising the cellulose ester resin is ΔP0 and the plane orientation coefficient of the drawn film comprising the cellulose ester resin and the polyester is ΔP1, ΔP0>ΔP1 holds. When the in-plane refractive index of the drawn film comprising the cellulose ester resin is ΔN0 and the in-plane refractive index of the drawn film comprising the cellulose ester resin and the polyester is ΔN1, ΔN0×0.90<ΔN1 holds.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to stretched films, optical films, and display devices. [Background technology]

[0002] In recent years, as the demand for power saving has increased, the requirements for viewing angle and display performance have also risen. As a result, organic electroluminescent (hereinafter abbreviated as organic EL) displays, or organic EL displays, are attracting attention as a new type of display device to replace liquid crystal displays.

[0003] In organic EL displays, to efficiently extract light from the light-emitting layer to the viewing side, it is common practice to use a highly light-reflective metal material for the cathode, or to provide a separate metal plate as a light-reflecting member, thereby placing the light-reflecting member on the side opposite to the light extraction surface. However, unlike liquid crystal displays, organic EL displays do not have polarizing plates, so ambient light is reflected off the light-reflecting member used for light extraction, causing reflections and a significant decrease in contrast in brightly lit environments.

[0004] To solve the above reflection problem, one method is to use a circular polarizer that is constructed by laminating λ / 4 phase difference plates, λ / 2 phase difference plates, etc. In organic EL displays for smartphones, a λ / 4 phase difference plate is required from the standpoint of preventing external light reflection, and cycloolefin (COP) resin film or polycarbonate (PC) resin film, which have excellent phase difference expression properties, are used as such phase difference plates.

[0005] While COP resin films and PC resin films exhibit excellent phase difference characteristics, they suffer from flexibility issues. Cellulose ester resin films, widely used as polarizer protective films for liquid crystal displays, are highly flexible and have been considered for use in phase difference plates. However, obtaining the necessary phase difference for λ / 4 phase difference plates has proven difficult with cellulose ester resin films.

[0006] In order to impart retardation expressivity to a cellulose ester resin film, there is a method of adding a retardation adjusting agent to the cellulose ester resin, and various retardation adjusting agents have been proposed (Patent Documents 1-2).

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0008] The retardation adjusting agents of Patent Documents 1 and 2 both serve as "retardation increasing agents" in which both the retardation in the plane direction (in-plane retardation) Re of the film and the retardation in the thickness direction (out-of-plane retardation) Rth of the film increase. On the other hand, when a cellulose ester resin stretched film is used for a λ / 4 retardation plate of an organic EL display or the like, a retardation adjusting agent that makes the in-plane retardation Re a certain value or more and reduces the out-of-plane retardation Rth is required, but there was no such retardation control agent.

[0009] The problem to be solved by the present invention is to provide a cellulose ester resin stretched film in which the in-plane retardation Re is a certain value or more and the out-of-plane retardation Rth is reduced.

Means for Solving the Problems

[0010] As a result of intensive studies to solve the above problems, the present inventors have found that by adding a polyester having a specific structure to a cellulose ester resin, a cellulose ester resin stretched film in which the in-plane retardation Re is a certain value or more and the out-of-plane retardation Rth is reduced can be obtained, and the present invention has been completed.

[0011] That is, the present invention relates to a stretched film formed from a composition containing a cellulose ester resin and a polyester represented by the following general formula (I), wherein the in-plane orientation coefficient of the stretched film made of the cellulose ester resin is ΔP0, and the in-plane orientation coefficient of the stretched film made of the cellulose ester resin and the polyester is ΔP1. When ΔP0>ΔP1 is satisfied, and the in-plane refractive index of the stretched film made of the cellulose ester resin is ΔN0, and the in-plane refractive index of the stretched film made of the cellulose ester resin and the polyester is ΔN1, the stretched film satisfies ΔN0×0.90<ΔN1.

[0012]

Chemical formula

Advantages of the Invention

[0013] According to the present invention, a cellulose ester resin stretched film with an in-plane retardation Re of a certain level or more and a reduced out-of-plane retardation Rth can be provided.

Brief Description of the Drawings

[0014] [Figure 1] It is a diagram showing the correlation between the in-plane refractive index and the in-plane orientation coefficient of the stretched films of the examples and the comparative examples.

Embodiments for Carrying Out the Invention

[0015] The following describes one embodiment of the present invention. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications without impairing the effects of the present invention.

[0016] [Stretched film] The stretched film of the present invention is a stretched film formed from a composition containing a cellulose ester resin and a polyester represented by the following general formula (I).

[0017] [ka] (In the above formula (I), G 1 These are alkylene glycol residues, oxyalkylene glycol residues, or aryl glycol residues. A is a dicarboxylic acid residue, and at least 20 mol% of the total moles of A are isophthalic acid residues. B 1 and B 2 Each of these is independently a hydrogen atom or a monocarboxylic acid residue. n is the number of repetitions. However, G 1 (These elements may be identical or different from each other, and A may be identical or different from each other in each repetition.)

[0018] In the stretched film of the present invention, when the surface orientation coefficient of the stretched film made of cellulose ester resin is ΔP0, and the surface orientation coefficient of the stretched film made of cellulose ester resin and polyester represented by the general formula (I) is ΔP1, then ΔP0 > ΔP1 is satisfied. Furthermore, in the stretched film of the present invention, when the in-plane refractive index of the stretched film made of cellulose ester resin is ΔN0, and the in-plane refractive index of the stretched film made of cellulose ester resin and polyester represented by the general formula (I) is ΔN1, the condition ΔN0 × 0.90 < ΔN1 is satisfied, and preferably ΔN0 < ΔN1 is satisfied. Furthermore, the plane orientation coefficient ΔP is obtained by dividing the out-of-plane phase difference Rth of the stretched film by the thickness of the stretched film, and the in-plane refractive index ΔN is obtained by dividing the in-plane phase difference Re of the stretched film by the thickness of the stretched film.

[0019] The polyester represented by the general formula (I) is thought to simultaneously orient itself in the main chain orientation of the cellulose ester resin in the stretched film, thereby enabling the in-plane refractive index to be above a certain level. Furthermore, the polyester of the present invention is thought to act as a plasticizer for the cellulose ester resin, and this plasticizing effect is thought to reduce the plane orientation coefficient.

[0020] The above-mentioned "stretched film made of cellulose ester resin" means a stretched film obtained using a composition in which the resin component is solely cellulose ester resin, and the above-mentioned "stretched film made of cellulose ester resin and polyester" means a stretched film obtained using a composition in which the resin components are solely cellulose ester resin and polyester.

[0021] The in-plane refractive index ΔN, in-plane phase difference Re, plane orientation coefficient ΔP, and out-of-plane phase difference Rth of the stretched film are defined by the following formulas and are measured by the method described in the examples. The wavelength of the measurement light should preferably be in the visible light range of 380 nm to 780 nm. ΔN = nx - ny Re = (nx-ny) × d = ΔN × d ΔP = (nx + ny) / 2 - nz Rth = ((nx + ny) / 2) - nz) × d = ΔP × d (In the formula, nx is the principal refractive index in the x-direction, where x is the direction in which the refractive index is maximum within the plane of the stretched film.) ny is the principal refractive index in the y-direction, where y is defined as the direction perpendicular to the x-direction within the plane of the stretched film. NZ is the principal refractive index in the thickness direction of the stretched film. d is the thickness of the stretched film (nm).

[0022] The following describes each component contained in the stretched film of the present invention.

[0023] (Cellulose ester resin) Examples of cellulose ester resins include cellulose acetate (CA), cellulose diacetate (DAC), cellulose triacetate (TAC), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose acetate phthalate, and polycaprolactone-grafted cellulose acetate. Among these, acetylated cellulose such as cellulose acetate, cellulose diacetate, and cellulose triacetate is preferred because of its good mechanical properties (tensile strength, flexural strength, flexural elasticity, etc.). Cellulose ester resins can be used individually or in combination of two or more types.

[0024] When the cellulose ester resin is acetylated cellulose, its degree of polymerization is preferably in the range of 250 to 400. Furthermore, when the cellulose ester resin is acetylated cellulose, its degree of acetation is preferably in the range of 54.0 to 62.5% by mass, and more preferably in the range of 58.0 to 62.5% by mass. If the degree of polymerization and degree of acetic acid of the cellulose acetate are within the above range, a film with excellent mechanical properties can be obtained. In the present invention, it is more preferable to use so-called cellulose triacetate. In this invention, the degree of acetic acid refers to the mass ratio of acetic acid produced by saponification of the cellulose acetate to the total amount of cellulose acetate.

[0025] The "average degree of polymerization" can be measured in accordance with the limiting viscosity method of Uda et al. (Kazuo Uda, Hideo Saito, "Journal of the Fiber Society", Vol. 18, No. 1, pp. 105-120, 1962). Specifically, 0.2 g of absolutely dry cellulose ester is precisely weighed and dissolved in 100 ml of a mixed solvent of methylene chloride:ethanol = 9:1 (mass ratio). The dropping time of this solution is measured at a constant water bath temperature of 25°C using an Ostwald viscometer, and the average degree of polymerization is calculated by the following [Formula 1]. Average degree of polymerization = [η] / K m ··· [Formula 1] [η] = (lnη rel ) / C η rel = T / T0 K m = 6×10 -4 T: Dropping time of the measurement sample (seconds) T0: Dropping time of the solvent (seconds) C: Concentration of the sample (g / l)

[0026] The number average molecular weight of the cellulose ester resin is preferably in the range of 50,000 to 300,000, and more preferably in the range of 60,000 to 200,000.

[0027] The cellulose ester resin may be a commercially available product, such as, for example, cellulose diacetates such as "L-20" (average acetyl substitution degree 2.41, average degree of polymerization 145), "L-30" (average acetyl substitution degree 2.41, average degree of polymerization 160), "L-50" (average acetyl substitution degree 2.41, average degree of polymerization 180), and "L-70" (average acetyl substitution degree 2.41, average degree of polymerization 190) manufactured by Daicel Corporation; and "LT-35" (average acetyl substitution degree 2.87, average degree of polymerization 270), "L Examples include cellulose triacetates such as "T-105" (average acetyl substitution degree 2.87, average degree of polymerization 350); cellulose acetate propionates such as "CAP-482-20" (average acetyl content 2.5%, average propionyl content 46.0%, number average molecular weight 75,000) manufactured by Eastman Chemical Co., Ltd.; and cellulose acetate butyrates such as "CAB-381-20" (average acetyl content 13.5%, average butyryl content 37.0%, number average molecular weight 70,000) manufactured by Eastman Chemical Co., Ltd.

[0028] In addition to using commercially available cellulose ester resins, synthesized cellulose ester resins can also be used. The method of synthesizing the cellulose ester resin is not particularly limited and can be done by known methods.

[0029] Cellulose ester resins can be synthesized, for example, by esterifying all or some of the hydroxyl groups at positions 2, 3, and 6 of glucose residues within cellulose molecules in wood pulp (e.g., softwood pulp, hardwood pulp, etc.) and cotton linters.

[0030] When obtaining acetylated cellulose as a cellulose ester resin, it can be produced by known esterification, which involves reacting cellulose with a predetermined amount of acetylating agent. If necessary, it can be synthesized through processes such as maturation, precipitation, purification, and drying.

[0031] For example, it can be synthesized by a series of steps including (1) an esterification step in which pulp (cellulose) is crushed, pre-treated and activated by spraying and mixing a monocarboxylic acid mainly composed of acetic acid, and then an esterification step in which the monocarboxylic anhydride mainly composed of acetic anhydride is prepared using an esterification catalyst such as sulfuric acid; (2) a maturation step in which the obtained cellulose triacetate is adjusted to the desired degree of acyl substitution by hydrolysis; and (3) a post-treatment step in which the obtained cellulose acetylated product is filtered, precipitated and separated, washed with water, dehydrated, and dried.

[0032] The type, amount, reaction temperature, and other conditions of the esterification catalyst are not particularly limited. Furthermore, if an acid such as sulfuric acid is used as the esterification catalyst, the product may be treated with a base such as a metal monocarboxylate salt to neutralize the residual acid, and the type of base used for neutralization is not particularly limited.

[0033] (polyester) The polyester contained in the stretched film of the present invention (hereinafter sometimes referred to as "the polyester of the present invention") is a polyester represented by the following general formula (I).

[0034] [ka] (In the above formula (I), G 1 These are alkylene glycol residues, oxyalkylene glycol residues, or aryl glycol residues. A is a dicarboxylic acid residue, and at least 20 mol% of the total moles of A are isophthalic acid residues. B 1 and B 2 Each of these is independently a hydrogen atom or a monocarboxylic acid residue. n is the number of repetitions. However, G 1 (These two elements may be the same or different from each other, and A may be the same or different from each other in each repetition.)

[0035] In this invention, "carboxylic acid residue" refers to the remaining organic group after removing the hydroxyl group from a carboxylic acid. In this invention, "alcohol residue" refers to the remaining organic group after removing a hydrogen atom from an alcohol. In this invention, "glycol residue" refers to the organic group remaining after removing a hydrogen atom from a glycol.

[0036] G 1 From the viewpoint of more easily expressing the effects of the present invention, the alkylene glycol residue is preferably an alkylene glycol residue having 2 to 12 carbon atoms, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2- Examples of residues include diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol.

[0037] G 1 The alkylene glycol residue having 2 to 12 carbon atoms may include an alicyclic structure. Examples of aliphatic diol residues having 2 to 12 carbon atoms that include such an alicyclic structure include 1,3-cyclopentanediol residue, 1,2-cyclohexanediol residue, 1,3-cyclohexanediol residue, 1,4-cyclohexanediol residue, 1,2-cyclohexanedimethanol residue, and 1,4-cyclohexanedimethanol residue.

[0038] G 1From the viewpoint of providing an ester resin with superior compatibility when mixed with cellulose ester resins, the alkylene glycol residue is preferably an alkylene glycol residue with 3 or fewer carbon atoms that does not have branching between OH groups. In particular, it is preferably a residue of ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, or 2,2-dimethyl-1,3-propanediol (neopentyl glycol), more preferably a residue of ethylene glycol or 1,2-propylene glycol, and most preferably a residue of 1,2-propylene glycol.

[0039] G 1 Oxyalkylene glycol residues having 4 to 12 carbon atoms are groups in which an ether bond (-O-) is inserted between any one carbon-carbon bond of an alkylene glycol residue. Examples include diethylene glycol residues, triethylene glycol residues, tetraethylene glycol residues, dipropylene glycol residues, and tripropylene glycol residues.

[0040] G 1 From the viewpoint of more easily expressing the effects of the present invention, the aryl glycol residue is preferably an aryl glycol residue having 6 to 18 carbon atoms. Examples include residues of alkylene oxide adducts such as hydroquinone, resorcinol, bisphenol A, and bisphenol A; alkylene oxide adducts such as bisphenol F, and bisphenol F; and alkylene oxide adducts such as biphenol, and biphenol.

[0041] Examples of dicarboxylic acid residues in A include alkylenedicarboxylic acid residues (A1) and aryldicarboxylic acid residues (A2), and the number of moles of isophthalic acid residues in the total number of moles of A is 20 mol% or more.

[0042] The isophthalic acid residue in the dicarboxylic acid residue is 20 mol% or more, preferably in the range of 20 to 100 mol%, and more preferably in the range of 25 to 100 mol%.

[0043] As for the alkylenedicarboxylic acid residue (A1) of A, it is preferable that it be an alkylenedicarboxylic acid residue having 2 to 12 carbon atoms, from the viewpoint of more easily exhibiting the effects of the present invention. Examples of residues include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, decandioic acid, maleic acid, fumaric acid, 1,2-dicarboxycyclohexane, 1,4-dicarboxycyclohexane, and 1,2-dicarboxycyclohexene. Among these, succinic acid, adipic acid, and 1,2-dicarboxycyclohexane residues are preferred, and adipic acid residues are more preferred, as they yield optical films with superior transparency.

[0044] Examples of aryldicarboxylic acid residues other than isophthalic acid residues in A (A2) include phthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,8-naphthalenedicarboxylic acid. Among these, phthalic acid and terephthalic acid residues are preferred, and phthalic acid residues are more preferred, as they yield optical films with higher strength.

[0045] B 1 and B 2 Examples of monocarboxylic acid residues include aryl monocarboxylic acid residues and aliphatic monocarboxylic acid residues.

[0046] B 1 and B 2 Preferably, the aryl monocarboxylic acid residue is an aryl monocarboxylic acid residue having 6 to 12 carbon atoms, and examples include residues of benzoic acid, dimethylbenzoic acid, trimethylbenzoic acid, tetramethylbenzoic acid, ethylbenzoic acid, propylbenzoic acid, butylbenzoic acid, cumic acid, para-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, paratoluic acid, ethoxybenzoic acid, propoxybenzoic acid, naphthoic acid, and anisic acid.

[0047] B1 and B 2 The aliphatic monocarboxylic acid residue is preferably an aliphatic monocarboxylic acid residue having 1 to 6 carbon atoms, such as residues of acetic acid, propionic acid, butanoic acid, hexanoic acid, and cyclohexanecarboxylic acid.

[0048] B 1 and B 2 As the monocarboxylic acid residue, aryl monocarboxylic acid residues having 6 to 10 carbon atoms or aliphatic monocarboxylic acid residues having 2 to 6 carbon atoms are preferred because they yield an optical film with excellent moisture resistance, and one or more monocarboxylic acid residues selected from the group consisting of benzoic acid, p-toluic acid, and cyclohexanecarboxylic acid are more preferred.

[0049] From the viewpoint of further enhancing the effects of the present invention, in general formula (I), G 1 Preferably, A1 is a residue of ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, or 2-methyl-1,3-propanediol, A1 is a residue of succinic acid, adipic acid, or 1,2-dicarboxycyclohexane, and A2 is a residue of isophthalic acid, phthalic acid, or terephthalic acid, and in particular, G 1 It is most preferable that A1 is an ethylene glycol or 1,2-propylene glycol residue, A1 is an adipic acid residue, and A2 is an isophthalic acid or phthalic acid residue.

[0050] The number of repetitions of n is, for example, an integer in the range of 0 to 20. The average value of the number of repetitions of n is preferably in the range of 1.0 to 10.0, more preferably in the range of 1.0 to 8.0, and more preferably in the range of 1.5 to 7.0. The average number of repeats of n can be calculated from the number-average molecular weight of the polyester of the present invention.

[0051] The number-average molecular weight (Mn) of the polyester of the present invention is, for example, 100 to 5,000, preferably 300 to 2,000, and more preferably 350 to 1,500. The above number-average molecular weight (Mn) is a value converted to polystyrene based on gel permeation chromatography (GPC) measurement, and is measured by the method described in the examples.

[0052] The acid value of the polyester of the present invention is, for example, 10 mg KOH / g or less, preferably 5 mg KOH / g or less, more preferably 3 mg KOH / g or less, and even more preferably 1 mg KOH / g or less. The lower limit of the acid value of the polyester of the present invention is not particularly limited, but for example, it is 0 mgKOH / g. The acid value of the above polyester is confirmed by the method described in the examples.

[0053] The properties of the polyester of the present invention vary depending on the number-average molecular weight and composition, but are typically liquid, solid, or paste-like at room temperature.

[0054] The polyester included in the stretched film of the present invention may be any polyester that satisfies the above general formula (1), and may be, for example, two or more polyesters with different structures.

[0055] The polyester content in the stretched film of the present invention is, for example, 0.1 to 50 parts by mass, preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass, per 100 parts by mass of cellulose ester resin. A sufficient phase difference adjustment effect can be obtained if the polyester content is 0.1 parts by mass or more per 100 parts by mass of cellulose ester resin.

[0056] The polyester of the present invention is obtained, for example, by using glycols, dicarboxylic acids, and any monocarboxylic acids constituting each residue as reaction raw materials, and by ensuring that the amount of isophthalic acid in the dicarboxylic acid is 20 mol% or more. Here, "reaction raw materials" means the raw materials that constitute the polyester, and does not include solvents or catalysts that do not constitute the polyester.

[0057] The method for producing polyester according to the present invention is not particularly limited and can be produced by known methods, or by the production method described later.

[0058] The dicarboxylic acid used in the production of the polyester of the present invention is a dicarboxylic acid corresponding to the dicarboxylic acid residue of A, and the dicarboxylic acid used may be one type alone or two or more types may be used in combination. The glycol used in the production of the polyester of the present invention is G 1 The glycol corresponds to the glycol residue, and the glycol used may be a single type or two or more types may be used in combination. The monocarboxylic acid used in the production of the polyester of the present invention is B 1 and B 2 The monocarboxylic acid corresponds to the monocarboxylic acid residue of the compound, and the monocarboxylic acid used may be used alone or in combination of two or more types.

[0059] In the production of the polyester of the present invention, dicarboxylic acids, glycols, and monocarboxylic acids can all be used in the form of their derivatives. Examples of such derivatives include esterified compounds, acid chlorides, and cyclic esters.

[0060] Specific examples of the polyester manufacturing method of the present invention include the following methods 1 and 2. Method 1: A method in which the dicarboxylic acid, glycol, and any monocarboxylic acid constituting each residue of the polyester are charged together and reacted. Method 2: A method in which the dicarboxylic acid and glycol constituting each residue of a polyester are reacted under conditions in which the equivalent amount of hydroxyl groups is greater than the equivalent amount of carboxyl groups to obtain a polyester having hydroxyl groups at the ends of the main chain, and then optionally react the obtained polyester resin with the monocarboxylic acid constituting the monocarboxylic acid residue.

[0061] In the production of polyester according to the present invention, the reaction of the reaction raw materials may be carried out in the presence of an esterification catalyst as needed, for example, in a temperature range of 170 to 250°C for 10 to 25 hours. Furthermore, the temperature, time, and other conditions for the esterification reaction are not particularly limited and may be set as appropriate.

[0062] Examples of the esterification catalysts include titanium-based catalysts such as tetraisopropyl titanate and tetrabutyl titanate; zinc-based catalysts such as zinc acetate; tin-based catalysts such as tin octoate and dibutyltin oxide; and organic sulfonic acid-based catalysts such as p-toluenesulfonic acid.

[0063] The amount of esterification catalyst used can be set as appropriate, but it is usually used in the range of 0.0001 to 0.1 parts by mass per 100 parts by mass of the total amount of reaction raw materials.

[0064] (Diester) The stretched film of the present invention may further contain a diester represented by the following general formula (II) (hereinafter sometimes referred to as "the diester of the present invention"). [ka] (In the above formula (II), G 2 These are alkylene glycol residues, oxyalkylene glycol residues, or aryl glycol residues. B 3 and B 4 (Each of these is independently a monocarboxylic acid residue.)

[0065] G in the above general formula (II) 2 The glycol residue is the G of the general formula (I) above. 1 Examples include the same glycol residues as in the above general formula (II) B. 3 and B 4 The monocarboxylic acid residue is B of the general formula (I) above. 1 and B 2 Examples include the same monocarbone residues as in [the given example].

[0066] The diester included in the stretched film of the present invention may be any diester compound that satisfies the above general formula (2), and may be, for example, two or more diester compounds with different structures from each other.

[0067] The method for producing the diester of the present invention is not particularly limited and can be produced by known methods, or a commercially available product may be used.

[0068] When the stretched film of the present invention contains the diester of the present invention, the content of the diester should be such that the mass ratio of the polyester of the present invention to the diester of the present invention (polyester / diester) is between 100 / 0 and 80 / 20.

[0069] (Other additives) The stretched film of the present invention may contain other additives as long as they do not impair the effects of the present invention. Examples of the aforementioned other additives include modifiers other than the polyesters and diesters of the present invention, thermoplastic resins, ultraviolet absorbers, matting agents, stabilizers, degradation inhibitors (e.g., antioxidants, peroxide decomposing agents, radical inhibitors, metal deactivators, acid scavenging agents, etc.), and dyes.

[0070] Other modifiers include ester compounds other than polyesters and diesters of the present invention, phosphate esters such as triphenyl phosphate (TPP), tricresyl phosphate, and cresyl diphenyl phosphate, phthalate esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, and di-2-ethylhexyl phthalate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, trimethylolpropane tribenzoate, pentaerythritol tetraacetate, and tributyl acetylcitrate.

[0071] Examples of the thermoplastic resin include polyester resins other than the ester resin of the present invention, polyester ether resins, polyurethane resins, acrylic resins, epoxy resins, toluenesulfonamide resins, and the like.

[0072] Examples of the aforementioned ultraviolet absorbers include oxybenzophenone compounds, benzotriazole compounds, salicylate ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex salt compounds, and the like. The ultraviolet absorber is preferably used in an amount of 0.01 to 2 parts by mass per 100 parts by mass of the cellulose ester resin.

[0073] Examples of the matting agent include silicon dioxide, titanium dioxide, aluminum oxide, calcium carbonate, calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, kaolin, and talc. The matting agent is preferably used in an amount of 0.1 to 0.3 parts by mass per 100 parts by mass of the cellulose ester resin.

[0074] Examples of the aforementioned stabilizers include calcium hydroxide, calcium carbonate, and fatty acid metal salts. The stabilizer is preferably used in an amount of 50 to 5000 ppm per 100 parts by mass of the cellulose ester resin.

[0075] The dyes mentioned above are not particularly limited in type or quantity, as long as they do not impair the effects of the present invention.

[0076] The stretched film of the present invention may preferably consist of, for example, 70% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, 99% or more by mass, or 99.9% or more by mass of cellulose ester resin and the polyester of the present invention. The optical film of the present invention may essentially consist of a cellulose ester resin and the polyester of the present invention. In this case, it may contain unavoidable impurities. Furthermore, the optical film of the present invention may consist only of a cellulose ester resin and the polyester of the present invention.

[0077] (Method of manufacturing stretched film) The stretched film of the present invention is obtained, for example, by producing an unstretched film using a composition containing a cellulose ester resin and the polyester of the present invention by methods such as extrusion molding or casting molding, and then stretching the unstretched film.

[0078] One method for manufacturing unstretched films is the solution casting method, which is a type of casting. The solution casting method will be described in detail below. Unstretched films obtained by solution casting exhibit substantially optical isotropy. These optically isotropic films can be used as optical materials, such as liquid crystal displays, and are particularly useful as protective films for polarizing plates. Furthermore, films obtained by this method are less prone to surface irregularities and have excellent surface smoothness.

[0079] The solution casting method described above comprises, for example, a first step of dissolving a cellulose ester resin and the polyester of the present invention in a solvent and casting the resulting resin solution onto a metal support; a second step of distilling off the organic solvent contained in the cast resin solution and drying it to form a film; and a third step of peeling the film formed on the metal support from the metal support and heating and drying it.

[0080] The organic solvent that can be used to dissolve the cellulose ester resin and the polyester of the present invention is not particularly limited as long as it is capable of dissolving them, but it is preferable to use, for example, organic halogen compounds such as chloroform, methylene dichloride, methylene chloride, or dioxolanes as good solvents.

[0081] In addition to the good solvent, a poor solvent such as methanol, ethanol, 2-propanol, n-butanol, cyclohexane, or cyclohexanone may be used in combination. The mixing ratio of the good solvent to the poor solvent is preferably in the range of good solvent / poor solvent = 75 / 25 to 95 / 5 by mass.

[0082] The concentration of cellulose ester resin in the resin solution is preferably 10 to 50% by mass, and more preferably 10 to 35% by mass.

[0083] Examples of metal supports used in the first step include endless belt-shaped or drum-shaped metal supports, and for example, stainless steel supports with a mirror-finished surface can be used.

[0084] When casting the resin solution onto the metal support, it is preferable to use a filtered resin solution to prevent foreign matter from being mixed into the resulting film.

[0085] The drying method for the second step is not particularly limited, but one example is to apply air at a temperature range of 30 to 50°C to the upper and / or lower surfaces of the metal support to evaporate 50 to 80% by mass of the organic solvent contained in the cast resin solution, thereby forming a film on the metal support.

[0086] Next, the third step is to peel the film formed in the second step from the metal support and heat-dry it under a higher temperature than that of the second step. As for the heat-drying method, a method of gradually increasing the temperature at a temperature of 100 to 160°C is preferred because it allows for good dimensional stability to be obtained. By heat-drying at the above temperature conditions, the organic solvent remaining in the film after the second step can be removed almost completely.

[0087] Furthermore, the solvent can be recovered and reused in the first to third steps described above.

[0088] The stretched film of the present invention is obtained by stretching the obtained unstretched film. The stretching method is not particularly limited, and the stretched film of the present invention can be obtained by longitudinal uniaxial stretching in the direction of mechanical flow, or transverse uniaxial stretching in a direction perpendicular to the direction of mechanical flow. The stretched film of the present invention can also be obtained by free-end uniaxial stretching. Free-end uniaxial stretching means that there are no members such as conveying rollers, support plates, or support belts between the pair of stretching rollers that support or contact the film, and the film is stretched longitudinally in a state in which it can freely contract and expand in the width direction. Furthermore, the stretched film of the present invention can also be obtained by biaxially stretching the obtained unstretched film using methods such as sequential biaxial stretching with roll stretching and tenter stretching, simultaneous biaxial stretching with tenter stretching, or biaxial stretching with tubular stretching.

[0089] The stretching ratio is not particularly limited, but it is preferable to have a stretching ratio of 1% to 1000% in at least one direction. Preferably, the stretching ratio is 3% to 600%, more preferably 5% to 300%, and even more preferably 10% to 300% in at least one direction. By setting the stretching ratio within this range, a stretched film with desirable birefringence, heat resistance, and strength can be obtained.

[0090] The film thickness of the stretched film of the present invention is preferably in the range of 20 to 200 μm, more preferably in the range of 25 to 150 μm, and particularly preferably in the range of 25 to 120 μm.

[0091] The stretched film of the present invention can be suitably used as an optical material in polarizing lens and sunglasses polarizing plate protective films, polarizing plate protective films used in displays such as liquid crystal display devices, plasma displays, organic EL displays, field emission displays, and rear projection televisions, as well as phase difference films such as quarter-wave plates, half-wave plates, viewing angle control films, and liquid crystal optical compensation films, and display front panels.

[0092] Of the above applications, when the stretched film of the present invention is used in a quarter-wave plate, the in-plane phase difference Re of the stretched film is preferably in the range of 100 to 200 nm. Furthermore, when the stretched film of the present invention is used in a half-wave plate, the in-plane phase difference Re of the stretched film is preferably in the range of 200 to 400 nm. When the stretched film of the present invention is used in a VA (Vertical Alignment) type viewing angle control film, the in-plane phase difference Re per stretched film is preferably in the range of 30 to 70 nm. [Examples]

[0093] The present invention will be specifically described below with reference to examples and comparative examples. Furthermore, the present invention is not limited to the following embodiments.

[0094] In the embodiments of this invention, the acid value and hydroxyl value are values ​​evaluated by the following method. [Method for measuring acid value] Measurements were taken according to the method specified in JIS K0070-1992. [Method for measuring hydroxyl value] Measurements were taken according to the method specified in JIS K0070-1992.

[0095] In the embodiments of this invention, the number-average molecular weight of polyester is a value converted to polystyrene based on GPC measurement, and the measurement conditions are as follows. [GPC measurement conditions] Measurement device: Tosoh Corporation high-speed GPC system "HLC-8320GPC" Columns: Tosoh Corporation's "TSK GURDCOLUMN SuperHZ-L" + Tosoh Corporation's "TSK gel SuperHZM-M" + Tosoh Corporation's "TSK gel SuperHZM-M" + Tosoh Corporation's "TSK gel SuperHZ-2000" + Tosoh Corporation's "TSK gel SuperHZ-2000" Detector: RI (Differential Refractometer) Data processing: EcoSEC Data Analysis version 1.07 manufactured by Tosoh Corporation. Column temperature: 40℃ Developing solvent: tetrahydrofuran Flow rate: 0.35mL / min Measurement sample: 7.5 mg of the sample was dissolved in 10 ml of tetrahydrofuran, and the resulting solution was filtered through a microfilter to be used as the measurement sample. Sample injection volume: 20 μl Standard sample: In accordance with the measurement manual for "HLC-8320GPC" mentioned above, the following monodisperse polystyrenes with known molecular weights were used.

[0096] (Monodisperse polystyrene) "A-300" manufactured by Tosoh Corporation "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation Tosoh Corporation's "F-10" F-20 manufactured by Tosoh Corporation Tosoh Corporation's "F-40" Tosoh Corporation's "F-80" Tosoh Corporation's "F-128" Tosoh Corporation's "F-288"

[0097] (Synthesis Example 1: Production of Polyester (1)) In a 0.5-liter four-necked flask, 171 g of 1,2-propylene glycol (hereinafter abbreviated as "PG") as the glycol component, 62 g of isophthalic acid (hereinafter abbreviated as "IPA") and 164 g of adipic acid (hereinafter abbreviated as "AA") as the dicarboxylic acid components, and 0.02 g of tetraisopropyl titanate (hereinafter abbreviated as "TIPT") as the catalyst were charged, and the temperature was gradually raised to 220°C under a nitrogen stream via a nitrogen inlet tube. The condensation reaction was carried out at 220°C for 10 hours, and it was confirmed that the acid value was 1.0 or less. Under reduced pressure, the excess glycol was removed at 150°C to obtain the polyester (1) of the present invention. The obtained polyester (1) was a pale yellow liquid at room temperature, with an acid value of 0.2, a hydroxyl value of 143, and a number-average molecular weight of 860.

[0098] (Synthesis Example 2: Production of Polyester (2)) Polyester (2) was obtained in the same manner as in Synthesis Example 1, except that 172g of PG was used as the glycol component, 125g of IPA and 110g of AA were used as the dicarboxylic acid components, and 0.02g of TIPT was used as the catalyst. The obtained polyester (2) was a pale yellow liquid at room temperature, with an acid value of 0.3, a hydroxyl value of 149, and a number-average molecular weight of 840.

[0099] (Synthesis Example 3: Production of Polyester (3)) Polyester (3) was obtained in the same manner as in Synthesis Example 1, except that 174 g of PG was used as the glycol component, 187 g of IPA and 55 g of AA were used as the dicarboxylic acid components, and 0.02 g of TIPT was used as the catalyst. The obtained polyester (3) was a pale yellow solid at room temperature, with an acid value of 0.3, a hydroxyl value of 149, and a number-average molecular weight of 850.

[0100] (Synthesis Example 4: Production of Polyester (4)) In a 2-liter four-necked flask, 416 g of PG as the glycol component, 224 g of IPA and 66 g of AA as the dicarboxylic acid components, 732 g of benzoic acid (hereinafter abbreviated as "BzA") as the monocarboxylic acid component, and 0.08 g of TIPT as the catalyst were charged. The mixture was then heated stepwise to 230°C under a nitrogen stream via a nitrogen inlet tube. The condensation reaction was carried out at 230°C for 8 hours, and it was confirmed that the acid value was 1.0 or less. Under reduced pressure, excess glycol and low molecular weight components were removed at 195°C to obtain polyester (4). The obtained polyester (4) was a pale yellow liquid at room temperature, with an acid value of 0.1, a hydroxyl value of 2.0, and a number-average molecular weight of 440.

[0101] (Synthesis Example 5: Production of Polyester (5)) Polyester (5) was obtained in the same manner as in Synthesis Example 1, except that 175 g of PG was used as the glycol component, 249 g of IPA as the dicarboxylic acid component, and 0.03 g of TIPT as the catalyst. The obtained polyester (5) was a pale yellow solid at room temperature, with an acid value of 0.5, a hydroxyl value of 142, and a number-average molecular weight of 850.

[0102] (Synthesis Example 6: Production of Diester (A)) Diester (A) was obtained in the same manner as in Synthesis Example 1, except that 294 g of PG and 50 g of dipropylene glycol were used as glycol components, and 900 g of BzA and 0.62 g of TIPT as monocarboxylic acid components. The obtained diester (A) was a short yellow liquid at room temperature, with an acid value of 0.2 and a hydroxyl value of 5.

[0103] (Synthesis Example 7: Production of Polyester (6)) Polyester (6) was obtained in the same manner as in Synthesis Example 1, except that 197 g of 2-methyl-1,3-propanediol was used as the glycol component, 174 g of IPA and 51 g of AA were used as the dicarboxylic acid components, and 0.03 g of TIPT was used as the catalyst. The obtained polyester (6) was a pale yellow solid at room temperature, with an acid value of 0.1, a hydroxyl value of 143, and a number-average molecular weight of 950.

[0104] (Synthesis Example 8: Production of Polyester (7)) Polyester (7) was obtained in the same manner as in Synthesis Example 1, except that 172 g of PG was used as the glycol component, 187 g of IPA and 44 g of succinic acid were used as the dicarboxylic acid component, and 0.01 g of TIPT was used as the catalyst. The obtained polyester (7) was a pale yellow solid at room temperature, with an acid value of 0.2, a hydroxyl value of 151, and a number-average molecular weight of 830.

[0105] (Synthesis Example 9: Production of Polyester (8)) Polyester (8) was obtained in the same manner as in Synthesis Example 1, except that 159 g of PG was used as the glycol component, 168 g of IPA and 68 g of sebacic acid were used as the dicarboxylic acid components, and 0.01 g of TIPT was used as the catalyst. The obtained polyester (8) was a pale yellow solid at room temperature, with an acid value of 0.1, a hydroxyl value of 144, and a number-average molecular weight of 850.

[0106] (Synthesis Comparison Example 1: Manufacturing of Polyester (1')) Polyester (1') was obtained in the same manner as in Synthesis Example 1, except that 174 g of PG was used as the glycol component, 187 g of phthalic anhydride (hereinafter abbreviated as "PA") and 55 g of AA were used as the dicarboxylic acid components, and 0.02 g of TIPT was used as the catalyst. The obtained polyester (1') was a pale yellow liquid at room temperature, with an acid value of 0.3, a hydroxyl value of 153, and a number-average molecular weight of 820.

[0107] (Synthesis Comparison Example 2: Production of Polyester (2')) Polyester (2') was obtained in the same manner as in Synthesis Example 1, except that 174 g of PG was used as the glycol component, 187 g of terephthalic acid (hereinafter abbreviated as "TPA") and 55 g of AA were used as the dicarboxylic acid components, and 0.02 g of TIPT was used as the catalyst. The obtained polyester (2') was a pale yellow solid at room temperature, with an acid value of 0.3, a hydroxyl value of 144, and a number-average molecular weight of 930.

[0108] (Examples 1-12 and Comparative Examples 1-4: Preparation and Evaluation of Resin Compositions for Optical Materials) The commercially available cellulose ester resin A (cellulose diacetate, "L-50" manufactured by Daicel Corporation) in the amounts shown in Table 1, along with the polyester, methylene chloride (810 parts by mass), and methanol (90 parts by mass) in the amounts shown in Table 1, were dissolved to obtain a dope solution. The obtained doping solution was cast onto a glass plate, and the solvent was removed by distillation (drying) to obtain a film with a thickness of approximately 60 μm. The transparency of the obtained unstretched film was evaluated according to the method described below. The results are shown in Table 1.

[0109] (Transparency of unstretched film) The obtained film was punched out using a die-cutting machine to form 40mm square test pieces, and the HAZE value of these test pieces was measured using a HAZE meter NDH-5000 (manufactured by Nippon Denshoku Industries). Furthermore, a lower HAZE value indicates superior transparency.

[0110] Unstretched films were uniaxially stretched at the free end using the method and conditions described below to obtain stretched films. The optical properties of the obtained stretched films were evaluated using the method described below. The results are shown in Table 1.

[0111] (Thermal stretching method and conditions 1; Uniaxial stretching of the free end) Unstretched film was punched out using a die-cutting machine to produce test pieces with a width of 20 mm and a length of 25 mm. Evaluation test pieces were then manufactured by performing uniaxial stretching of the free end using a heat stretcher (manufactured by UniOpt Co., Ltd.) under the following conditions. Temperature: 190℃ Magnification: 1.5x Speed: 100% / min

[0112] (Method for measuring the optical properties of stretched film) The manufactured evaluation test specimens were left to stand at 23°C and 55% relative humidity for at least one hour, and the in-plane refractive index (ΔN value) and plane orientation coefficient (ΔP value) at a measurement wavelength of 589 nm were measured using a birefringence measuring device (KOBRA-WR, manufactured by Oji Keisokuki Co., Ltd.).

[0113] [Table 1]

[0114] In Table 1, the numbers in parentheses for the dicarboxylic acids IPA, PA, TPA, and AA indicate their proportion to the total number of moles of dicarboxylic acid.

[0115] Figure 1 shows a balance diagram with the in-plane refractive index on the horizontal axis and the plane orientation coefficient on the vertical axis, based on the results in Table 1. From Figure 1, it can be seen that the stretched film of the present invention maintains a constant level of in-plane refractive index while reducing the plane orientation coefficient.

[0116] (Examples 13-18 and Comparative Examples 5-7: Preparation and Evaluation of Resin Compositions for Optical Materials) The amounts of commercially available cellulose ester resin B (cellulose acetate pyropionate, "CAP-482-20" manufactured by Eastman Chemical Co., Ltd.) shown in Table 2, along with 670 parts by mass of polyester and methylene chloride shown in Table 2, were added and dissolved to obtain a dope solution. The obtained doping solution was cast onto a glass plate, and the solvent was removed by distillation (drying) to obtain a film with a thickness of approximately 60 μm. The transparency of the obtained unstretched film was evaluated using the same method as in Example 1. The results are shown in Table 2.

[0117] An unstretched film was uniaxially stretched at its free end using the method and conditions described below to obtain a stretched film. The optical properties of the obtained stretched film were evaluated using the same method as in Example 1. The results are shown in Table 2.

[0118] (Thermal stretching method and conditions 2; Uniaxial stretching of the free end) Unstretched film was punched out using a die-cutting machine to produce test pieces with a width of 20 mm and a length of 25 mm. Evaluation test pieces were then manufactured by performing uniaxial stretching of the free end using a heat stretcher (manufactured by UniOpt Co., Ltd.) under the following conditions. Temperature: 140℃ Magnification: 1.5x Speed: 100% / min

[0119] [Table 2]

[0120] The results in Table 2 show that while the in-plane refractive index is maintained at a constant level even when the type of cellulose ester resin is changed, the surface orientation coefficient is reduced.

Claims

1. A stretched film formed from a composition containing a cellulose ester resin and a polyester represented by the following general formula (I), The surface orientation coefficient of the stretched film made of the cellulose ester resin is ΔP ０ The planar orientation coefficient of the stretched film made of the cellulose ester resin and the polyester is set to ΔP １ When this is the case, ΔP ０ >ΔP １ Satisfying the conditions, The in-plane refractive index of the stretched film made of the cellulose ester resin is ΔN ０ The in-plane refractive index of the stretched film made of the cellulose ester resin and the polyester is set to ΔN １ When this is the case, ΔN ０ ×0.90 < ΔN １ A stretched film that satisfies the requirements. 【Chemistry 1】 (In the above formula (I), G １ is an alkylene glycol residue, an oxyalkylene glycol residue or an aryl glycol residue, A is a dicarboxylic acid residue, and at least 20 mol% of the total moles of A are isophthalic acid residues. B １ and B ２ Each of these is independently a hydrogen atom or a monocarboxylic acid residue. n is the number of repetitions, and the average value of n is between 1.0 and 10.

0. However, G １ (These two elements may be the same or different from each other, and A may be the same or different from each other in each repetition.)

2. In the above general formula (I), G １ The stretched film according to claim 1, wherein is an alkylene glycol residue having 2 to 12 carbon atoms, an oxyalkylene glycol residue having 4 to 12 carbon atoms, or an aryl glycol residue having 6 to 18 carbon atoms.

3. In the above general formula (I), G １ The stretched film according to claim 1, wherein is one or more glycol residues selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, and 2-methyl-1,3-propanediol, and 2,2-dimethyl-1,3-propanediol, and A is one or more dicarboxylic acid residues selected from the group consisting of succinic acid, adipic acid, dicarboxycyclohexane, phthalic acid, terephthalic acid, and isophthalic acid.

4. The stretched film according to claim 1, wherein 25 to 100 mol% of the total number of moles of A in the general formula (I) is isophthalic acid residues.

5. The stretched film according to claim 1, wherein the number-average molecular weight of the polyester is 350 to 2,000.

6. The stretched film according to claim 1, wherein the polyester is contained in 1 to 30 parts by mass per 100 parts by mass of the cellulose ester resin.

7. The stretched film according to claim 1, wherein the in-plane phase difference Re is in the range of 100 to 200 nm.

8. An optical film which is a stretched film according to any one of claims 1 to 7.

9. The optical film according to claim 8, for protecting polarizing plates.

10. A display device characterized by having the optical film of claim 8.

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