WO2018173601A1 - Optical film, method for manufacturing same, and polarizing plate and display device provided with same - Google Patents

Abstract

The present invention addresses the problem of providing: an optical film containing a compound for absorbing light having a specific wavelength, bleed-out of the compound being suppressed in the optical film even when the optical film is placed in a high-temperature high-humidity environment, and the optical film being transparent and having minimal unevenness of color as well as excellent color reproduction properties (color shift) in an oblique direction; a method for manufacturing the optical film; and a polarizing plate and a display device provided with the optical film. This optical film is characterized by containing a resin, the solubility of which in dichloromethane at 23°C is in the range of 5-50% by mass, and a compound having a structure represented by general formula (A).

Description

Optical film, manufacturing method thereof, polarizing plate and display device provided with the same

The present invention relates to an optical film, a method for producing the same, a polarizing plate and a display device provided with the optical film, and more specifically, an optical film containing a compound that absorbs light of a specific wavelength, in a high-temperature and high-humidity environment. The present invention relates to an optical film or the like that suppresses the bleed-out of the compound even if it is placed, is transparent, has little color unevenness, and is excellent in oblique color reproducibility (color shift).

The market demand for high definition and high color gamut of displays is increasing, and broadband color reproducibility is a very big issue in next generation displays such as 4K / 8K.

In a liquid crystal display (LCD), a light emitting diode (LED) is used as a backlight light source, but the LED has an inherent wavelength dependency, and color purity depends on an unnecessary emission wavelength. As a result, color reproduction in a wide band was difficult.

Also, in organic electroluminescence (OLED: Organic Light Emitting Diode) displays, when emitting white light, there is unnecessary wavelength light that cannot be cut with a normal color filter, and color reproducibility in a wide band is difficult.

As a means for improving color purity, for example, in Patent Document 1, a color material (also referred to as a pigment or a dye) that absorbs a wavelength of an intermediate color is included in a binder resin as a substrate or a specific color material layer of an image sensor. Embodiments are disclosed.

However, the method described in Patent Document 1 has a problem in that the color material is thermally decomposed by reflow heating in the manufacturing process of the image sensor, and the absorption wavelength changes. In addition, there is a problem that the color material bleeds out when the humidity resistance is low and the temperature and humidity are high.

Further, Patent Document 2 discloses a configuration in which a transparent resin layer containing a colorant such as a cyanine dye is formed on a substrate. However, when a specific wavelength light is cut by 20% or more, the transparent resin layer is disclosed. It is necessary to add a sufficient amount of the coloring material. However, if a sufficient amount is added, bleeding out tends to occur. Particularly, in the case where the transparent resin layer is in contact with a fluid material such as an adhesive layer, the dye moves under a high temperature and high humidity environment. As a result, there is a problem that bleed-out is further promoted.

Even with a slight bleed out, high-quality displays such as 8K may cause color unevenness on the display and greatly affect visibility, and the color unevenness greatly affects the color reproducibility (color shift) in an oblique direction.

Further, when the color material is added to the hard coat layer or the like, there is a problem that the scratch resistance is deteriorated accompanying the bleed-out.

JP 2015-36796 A Japanese Patent No. 5331369

The present invention has been made in view of the above-described problems and situations, and a solution to the problem is an optical film containing a compound that absorbs light of a specific wavelength, even in a high-temperature and high-humidity environment. Provided are an optical film that suppresses bleeding out of the compound, is transparent, has small color unevenness, and is excellent in color reproducibility (color shift) in an oblique direction, a manufacturing method thereof, a polarizing plate and a display device including the optical film. That is.

In order to solve the above problems, the present inventor, in the process of examining the cause of the above problems, an optical film containing a resin having a specific solubility in dichloromethane and a compound having a specific structure has a high temperature. It has been found that even in a high humidity environment, bleeding of the compound is suppressed, an optical film that is transparent, has little color unevenness, and has excellent color reproducibility (color shift) in an oblique direction can be obtained.

That is, the above-mentioned problem according to the present invention is solved by the following means.

An optical film comprising a resin having a solubility in dichloromethane of 5 to 50% by mass at 1.23 ° C. and a compound having a structure represented by the following general formula (A).

(Wherein R ₁ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, or aryl group having 3 to 20 carbon atoms. R ₂ and R ₃ each independently represents a hydrogen atom or a halogen atom. Represents an atom, a substituted or unsubstituted alkyl group, or an alkoxycarbonyl group, Z is an atomic group necessary for forming a 5- or 6-membered ring with a nitrogen atom, and may have a substituent; Y may form a condensed ring, and Y is an atomic group necessary for forming a 5- or 6-membered ring together with a carbonyl group, may have a substituent, or may form a condensed ring. (N represents an integer of 1 to 2. m is an integer of 1 to 4 and is an integer of n or more.)

2. 2. The optical system according to item 1, wherein the compound having a structure represented by the general formula (A) is a compound having a structure represented by any one of the following general formulas (1) to (3): the film.

(Wherein R ₁ to R ₄ each independently represents a hydrogen atom or a halogen atom, a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, acyl group, aryl group, heterocyclic ring, alkoxycarbonyl group, carbamoyl group) A group, an alkoxy group, an amide group, an amino group, a cyano group, a nitro group, a hydroxy group, a carboxy group or a sulfonic acid group, R ₁ and R ₂ , R ₂ and R ₃ , or R ₃ and R ₄ are bonded to each other. The ring formed may have a substituent, and R ₅ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group or aryl group having 3 to 20 carbon atoms. It represents .R ₆ and R ₇ each independently represent a hydrogen atom or a halogen atom, .X to represent a substituted or unsubstituted, alkyl group or alkoxycarbonyl group, O, N _8, S, or _.R 8 _{~ R 10} representing a _CR 9 _{R 10} are independently a hydrogen atom, a substituted or unsubstituted, alkyl group, alkenyl group, .A ₁ alkynyl group or to an aryl group, (Selected from the following structural formulas (A1-1) to (A1-10))

(Wherein R ₁₁ to R ₁₆ have the same meanings as the groups represented by R ₁ to R ₄ in formula (1). X ₁ and X ₂ each independently represents an oxygen atom or a sulfur atom. (Connected to the general formula (1) at the wavy line)

(In the formula, R ₁ to R ₄ and R ₈ to R ₁₁ are synonymous with R ₁ to R ₄ in the general formula (1). R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R _{4, R 8} and _R 9, _{R 9} and _{R 10,} or _{R 10} and _{R 11} may be bonded to each other to form a ring, the formed ring may have a substituent .R ₅ and R ₁₂ is synonymous with R ₅ in general formula (1) R ₆ , R ₇ , R ₁₃ , and R ₁₄ are synonymous with R ₆ and R ₇ in general formula (1).

X represents O, NR ₁₅ , S, or CR ₁₆ R ₁₇ . R ₁₅ to R ₁₇ have the same meanings as R ₈ to R ₁₀ in the general formula (1).

B ₁ is selected from the following structural formulas (B1-1) to (B1-5). )

(In the formula, R ₁₈ and R ₁₉ are synonymous with the groups represented by R ₁ to R ₄ in the general formula (1). They are connected to the general formula (2) at the wavy line part.)

_(Wherein, R 1 ~ _{R 4} have the same meanings as in formula (1) _R 1 ~ _{R 4} in .R ₁ and _{R 2,} or _{R 3} and _{R 4} may combine with each other to form a ring well, the formed ring may have a substituent .R ₅ have the same meaning as _{R 5} in the general formula (1) .R ₆ and _{R 7,} the general formula (1) _{R 6} and in the same meaning as R ₇ .A ₁ has the same meaning as _{a 1} in formula (1).)

3. 3. The optical film as described in Item 1 or 2, wherein in General Formula (1) and General Formula (3), A ₁ has a structure represented by Formula (A1-6).

4). 3. The optical film according to item 1 or 2, wherein in the general formula (2), B ₁ has a structure represented by the formula (B1-4).

5). The optical system according to any one of items 1 to 3, wherein, in the general formula (1) and the general formula (3), R ₅ represents a branched alkyl group having 4 to 16 carbon atoms. the film.

6). In the general formula (2), R ₅ and R ₁₂ each represent a branched alkyl group having 4 to 16 carbon atoms, according to any one of the first, second, and fourth items, Optical film.

7. The compound having the structure represented by the general formula (1) to the general formula (3) has an absorption maximum peak in the wavelength range of 480 to 520 nm or in the wavelength range of 580 to 620 nm in the spectral absorption spectrum. The optical film as described in any one of 1st term | claim to 6th term | claim characterized by these.

8. Item 8. The optical film according to any one of Items 1 to 7, wherein the haze is in the range of 0.05 to 1.50%.

9. An optical film manufacturing method for manufacturing the optical film according to any one of items 1 to 8, wherein the optical film is manufactured by a solution casting film forming method. Manufacturing method.

10. A polarizing plate comprising the optical film according to any one of items 1 to 8 as a polarizing plate protective film.

11. A display device comprising the optical film according to any one of items 1 to 8.

By the above means of the present invention, an optical film containing a compound that absorbs light of a specific wavelength, the bleed-out of the compound is suppressed even in a high-temperature and high-humidity environment, and it is transparent and small in color unevenness. And the optical film which is excellent also in the color reproducibility (color shift) of a diagonal direction, its manufacturing method, a polarizing plate provided with the same, and a display apparatus can be provided.

The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

In the study of the present inventors, a resin having a solubility in dichloromethane at 23 ° C. in the range of 5 to 50% by mass (for example, cellulose ester resin, acrylic resin, cyclic olefin resin, polycarbonate resin, and polyimide resin); The optical film containing the compound having the structure represented by the general formula (A) according to the present invention has been found to have extremely suppressed bleeding out of the compound even in a high temperature and high humidity environment. This is presumed to be due to the structure in which the compound fits exactly in the gap between the network chains of the resin during dissolution of the solvent.

Further, in a solvent having a high polarity such as dichloromethane, in the resin containing the solvent, a compound having a structure in which the polar group of the resin faces the polar solvent side and the polar group is represented by the general formula (A) It is inferred that the interaction between the C═O bonding group and the compound is formed into a film as it is, so that the interaction between the resin and the compound is strong and bleed-out is difficult.

In addition, the bleed-out tends to be noticeable in a system that usually contains two kinds of compounds, but when two kinds of compounds having different absorption maximum peaks are contained as in the structure of the present invention, the general formula (A) By interposing the dimethine skeleton represented, it is speculated that the compatibility of another type of compound with the resin is greatly improved, and it becomes possible to produce a highly transparent film without bleeding out from each other. The

Further, by adding the compound to an optical film having a film thickness in the range of 20 to 250 μm, the optical path length becomes longer than when the compound is contained in a thin layer such as the transparent resin layer or the hard coat layer described above. Since the angle dependency of taste is relaxed, a display device (also referred to as a display) with favorable color reproducibility (color shift) in an oblique direction can be manufactured by providing the optical film. It is guessed.

Schematic diagram of an example of an apparatus used for the dope preparation step, casting step, drying step and stretching step of the preferred solution casting method for the present invention

The optical film of the present invention comprises a resin having a solubility in dichloromethane of 5 to 50% by mass at 23 ° C. and a compound having a structure represented by the general formula (A). To do. This feature is a technical feature common to or corresponding to the claimed invention.

It is specified that the compound having the structure represented by the general formula (A) is a compound having a structure represented by the general formula (1), the general formula (2), or the general formula (3). This is a preferred embodiment from the viewpoint of the light absorption ability of the wavelength and the suppression of bleed out.

When the compound having the structure represented by the general formula (A) has an absorption maximum peak in the wavelength range of 480 to 520 nm or in the wavelength range of 580 to 620 nm in the spectral absorption spectrum of the compound, display is performed. When used in an apparatus, it is an optical film that improves broadband color reproducibility, which is preferable.

As an embodiment of the present invention, from the viewpoint of expression of the effect of the present invention, the haze of the optical film is in the range of 0.05 to 1.50%, when used for a polarizing plate protective film and a display device, preferable.

The optical film of the present invention has a structure represented by the general formula (A) because it can be manufactured by a solution casting film forming method, and an optical film can be formed at a relatively low temperature. This is a preferable production method because the decomposition of the compound can be suppressed.

The optical film of the present invention is provided in a polarizing plate or a display device, thereby improving broadband color reproducibility and further improving oblique color reproducibility (color shift).

Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In the present application, “˜” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

<< Outline of Optical Film of the Present Invention >>
The optical film of the present invention comprises a resin having a solubility in dichloromethane at 23 ° C. in the range of 5 to 50% by mass and a compound having a structure represented by the following general formula (A): To do.

（式中、Ｒ_１は、置換若しくは無置換の、炭素数３～２０のアルキル基、アルケニル基、アルキニル基、又はアリール基を表す。Ｒ_２及びＲ_３はそれぞれ独立に、水素原子若しくはハロゲン原子、置換若しくは無置換の、アルキル基、又はアルコキシカルボニル基を表す。Ｚは、窒素原子と共に５又は６員環を形成するために必要な原子団であり、置換基を有していてもよく、縮環を形成してもよい。Ｙは、カルボニル基と共に５又は６員環を形成するために必要な原子団であり、置換基を有していてもよく、縮環を形成してもよい。ｎは１～２の整数を表す。ｍは１～４の整数であり、かつ、ｎ以上の整数である。）
　本発明に係る樹脂は、２３℃でのジクロロメタンに対する溶解度が５～５０質量％の範囲内であることを特徴とするものであるが、以下の方法によって溶解度を測定する。

(In the formula, R ₁ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, or aryl group having 3 to 20 carbon atoms. R ₂ and R ₃ each independently represents a hydrogen atom or a halogen atom. Represents a substituted or unsubstituted alkyl group or an alkoxycarbonyl group, Z is an atomic group necessary for forming a 5- or 6-membered ring with a nitrogen atom, and may have a substituent; Y may form a condensed ring, Y is an atomic group necessary for forming a 5- or 6-membered ring together with a carbonyl group, may have a substituent, and may form a condensed ring. N represents an integer of 1 to 2. m is an integer of 1 to 4 and is an integer of n or more.)
The resin according to the present invention is characterized in that the solubility in dichloromethane at 23 ° C. is in the range of 5 to 50% by mass, and the solubility is measured by the following method.

The resin is dissolved in 100 g of dichloromethane whose liquid temperature is adjusted to 23 ° C. while stirring the liquid, the upper limit amount (g) that can be dissolved is measured, and the solubility is obtained from the following equation.

Solubility (%) = {the upper limit amount (g) in which resin can be dissolved / 100 g of dichloromethane} × 100
As for the thickness of the optical film, it is preferable to select an appropriate thickness according to the application. The upper limit of the thickness is not particularly limited, but in the case of forming a film by a solution casting film forming method, the upper limit may be about 250 μm from the viewpoints of applicability, foaming, solvent drying and physical properties. preferable.

The haze of the optical film of the present invention is in the range of 0.05 to 1.5%, and can be used as a general-purpose optical film. Unnecessary light when used in a polarizing plate protective film or a display device. It is also preferable from the viewpoint of suppressing scattering.

The haze can be measured with a haze meter NDH-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K-7136. The light source of the haze meter is a halogen bulb of 5V9W, the light receiving part is a silicon photocell (with a relative visibility filter), and the measurement can be performed under conditions of 23 ° C. and 55% RH.

[1] Compound having structure represented by general formula (A) The optical film of the present invention contains a compound having a structure represented by the general formula (A).

Specific examples of R ₁ include alkyl groups such as propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, and isopentyl. Group, neopentyl group, tert-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group, octyl group, dodecyl group and the like. Examples of the alkenyl group include an allyl group, and an alkynyl group. As, for example, propynyl group and the like can be mentioned. Examples of the aryl group include a phenyl group. An alkyl group having 3 to 20 carbon atoms is preferable, and a branched alkyl group having 4 to 16 carbon atoms is more preferable. When the carbon number is in the above-described range, in addition to excellent solvent solubility, an effect of reducing haze is expected.

Specific examples of R ₂ and R ₃ include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n- Represents a pentyl group, sec-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group, octyl group, dodecyl group, etc. An atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, As an alkoxycarbonyl group, a methyloxycarbonyl group, an ethyloxycarbonyl group, a butyloxycarbonyl group etc. are mentioned, for example. Preferably, it is a hydrogen atom.

The molecular weight of the compound having the structure represented by the general formula (A) is preferably in the range of 100 to 1000 so that the compound fits in the gap between the network chains of the resin during dissolution of the solvent. More preferably, it is within the range of 300 to 800.

From the viewpoint of improving color reproducibility, the compound having the structure represented by the general formula (A) is preferably a compound having an absorption maximum peak in the light wavelength range of 480 to 520 nm or in the range of 580 to 620 nm. . The full width at half maximum of the absorption maximum peak is preferably 100 nm or less, more preferably 50 nm or less, more preferably 40 nm or less, and particularly preferably 30 nm or less.

The compound having the structure represented by the general formula (A) is a compound having an absorption maximum peak in the light wavelength range of 480 to 520 nm or in the range of 580 to 620 nm. And can be measured with a spectrophotometer by a conventional method. For example, Shimadzu spectrophotometer UVIDFC-610, Hitachi Ltd. 330 type self-recording spectrophotometer, U-3210 type self-recording spectrophotometer, U-3410 type self-recording spectrophotometer, U-4000 type self-recording spectrophotometer It can obtain | require by measuring using a photometer etc.

In the optical film of the present invention, the compound having the structure represented by the general formula (A) has an absorption maximum peak in the wavelength range of 480 to 520 nm or in the wavelength range of 580 to 620 nm in the spectral absorption spectrum of the compound. It is preferable that the optical absorptance at the absorption maximum peak wavelength at 23 ° C. is in the range of 20 to 99%.

The optical film of the present invention contains, in the spectral absorption spectrum, a compound having an absorption maximum peak in a wavelength range of 480 to 520 nm and a compound having an absorption maximum peak in a wavelength range of 580 to 620 nm. It is preferable that at least one of the compounds is a compound having a structure represented by the general formula (A), and the light absorption rate at the absorption maximum peak wavelength at 23 ° C. is in the range of 20 to 99%.

The light absorption rate (%) of the absorption maximum peak wavelength in the light wavelength range of 480 to 520 nm or in the range of 580 to 620 nm can be determined as follows.

Optical absorptance (%) of absorption maximum peak wavelength in light wavelength range of 480 to 520 nm or 580 to 620 nm
= 100 − {(Spectral transmittance of absorption maximum peak wavelength in light wavelength range of 480 to 520 nm or 580 to 620 nm) − (Spectrum of absorption maximum peak wavelength in range of light wavelength of 480 to 520 nm or 580 to 620 nm) Reflectance)}
Spectral transmittance and spectral reflectance can be measured using a spectrophotometer. In the present invention, the measurement is performed using an ultraviolet-visible near-infrared spectrophotometer V-670 manufactured by JASCO Corporation.

Specifically, the temperature inside the temperature-controlled room is set to 23 ° C. and 55% RH so that the temperature of the optical film as the measurement object is 23 ° C., and the optical film is left in the temperature-controlled room for 3 hours. The above measurement is performed after equilibration.

The means for setting the light absorption rate within the range of 20 to 99% can be controlled, for example, by adjusting the addition amount of the compound. The amount of addition varies depending on the absorption coefficient of the compound, but is approximately in the range of 0.01 to 1 part by mass, more preferably in the range of 0.1 to 1 part by mass with respect to 100 parts by mass of the resin. is there.

The larger the molar extinction coefficient of the compound, the more preferable the light absorptivity can be controlled within the above range even if the addition amount is small.

Furthermore, the compound having the structure represented by the general formula (A) is preferably a compound having a structure represented by the following general formula (1) to general formula (3).

(Wherein R ₁ to R ₄ each independently represents a hydrogen atom or a halogen atom, a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, acyl group, aryl group, heterocyclic ring, alkoxycarbonyl group, carbamoyl group) A group, an alkoxy group, an amide group, an amino group, a cyano group, a nitro group, a hydroxy group, a carboxy group or a sulfonic acid group, R ₁ and R ₂ , R ₂ and R ₃ , or R ₃ and R ₄ are bonded to each other. The ring formed may have a substituent, and R ₅ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group or aryl group having 3 to 20 carbon atoms. It represents .R ₆ and R ₇ each independently represent a hydrogen atom or a halogen atom, .X to represent a substituted or unsubstituted, alkyl group or alkoxycarbonyl group, O, N _8, S, or _.R 8 _{~ R 10} representing a _CR 9 _{R 10} represent each independently a hydrogen atom, a substituted or unsubstituted, alkyl group, alkenyl group, alkynyl group or an aryl group.)

Specific examples of R ₁ to R ₄ include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, Isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, sec-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group , 2-ethylhexyl group, octyl group, dodecyl group and the like. Examples of the alkenyl group include vinyl group and allyl group. Examples of the alkynyl group include ethynyl group and propynyl group. Acyl groups include, for example, acetyl, ethylcarbonyl, propylcarbonyl, pe Examples of the aryl group include a phenyl group, a tolyl group, and the like. Examples of the aryl group include a phenyl group, a tolyl group, and the like. , A mesityl group, a xylyl group, a naphthyl group, a biphenyl group, a terphenyl group, and the like. Examples include an oxazole ring, a quinoline ring, a benzothiazole ring, a benzoxazole ring, a thiophene ring, a furan ring, and a pyrrole ring. Examples include an oxy group, an octyloxy group, a dodecyloxy group, and the like. Examples of the alkoxycarbonyl group include a methyloxycarbonyl group, an ethyloxycarbonyl group, and a butyloxycarbonyl group. Examples of the carbamoyl group include an amino group. Examples include carbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, ethylaminocarbonyl group, diethylaminocarbonyl group and the like. Examples of the amide group include methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonyl group, and the like. Examples include amino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, and the like. Examples of the group include amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group and the like. It is done. Preferred are a hydrogen atom, a halogen atom, an alkyl group, an acyl group, an aryl group, and a cyano group, and more preferred are a hydrogen atom, an alkyl group, and an aryl group.

Specific examples of R ₅ include alkyl groups such as propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, and isopentyl. Group, neopentyl group, tert-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group, octyl group, dodecyl group and the like. Examples of the alkenyl group include an allyl group, and an alkynyl group. As, for example, propynyl group and the like can be mentioned. Examples of the aryl group include a phenyl group. An alkyl group having 3 to 20 carbon atoms is preferable, and a branched alkyl group having 4 to 16 carbon atoms is more preferable. When the carbon number is in the above-described range, in addition to excellent solvent solubility, an effect of reducing haze is expected.

X represents O, NR ₈ , S, or CR ₉ R ₁₀ . From the viewpoint of color reproducibility, NR ₈ , O, and S are preferable. More preferably, it is S. R ₈ to R ₁₀ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group.

Specific examples of R ₆ and R ₇ include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n- Represents a pentyl group, sec-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group, octyl group, dodecyl group, etc. An atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, As an alkoxycarbonyl group, a methyloxycarbonyl group, an ethyloxycarbonyl group, a butyloxycarbonyl group etc. are mentioned, for example. Preferably, it is a hydrogen atom.

Specific examples of R ₈ to R ₁₀ include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n- Examples include pentyl group, sec-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group, octyl group, dodecyl group, etc. Examples of the alkenyl group include Examples of the alkynyl group include an ethynyl group and a propynyl group. Examples of the aryl group include a phenyl group, a tolyl group, a mesityl group, a xylyl group, a naphthyl group, and a biphenyl group. Group, a terphenyl group, etc. are mentioned, Preferably it is an alkyl group.

A ₁ is selected from the following structural formulas (A1-1) to (A1-10).

(Wherein R ₁₁ to R ₁₆ have the same meanings as the groups represented by R ₁ to R ₄ in formula (1). X ₁ and X ₂ each independently represents an oxygen atom or a sulfur atom. (Connected to the general formula (1) at the wavy line)

(A1-1), (A1-2), (A1-3), (A1-4), (A1-5), and (A1-6) are preferable from the viewpoint of color reproducibility and bleed-out suppression. Particularly preferred is (A1-6).

In addition, the compound having the structure represented by the general formula (A) is preferably a compound having a structure represented by the following general formula (2).

(In the formula, R ₁ to R ₄ and R ₈ to R ₁₁ are synonymous with R ₁ to R ₄ in the general formula (1). R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R _{4, R 8} and _R 9, _{R 9} and _{R 10,} or _{R 10} and _{R 11} may be bonded to each other to form a ring, the formed ring may have a substituent .R ₅ and R ₁₂ is synonymous with R ₅ in general formula (1) R ₆ , R ₇ , R ₁₃ , and R ₁₄ are synonymous with R ₆ and R ₇ in general formula (1).
X represents O, NR ₁₅ , S, or CR ₁₆ R ₁₇ . R ₁₅ to R ₁₇ have the same meanings as R ₈ to R ₁₀ in the general formula (1). )
From the viewpoint of color reproducibility, NR ₈ , O, or S is preferable. More preferably, it is S.

B ₁ is selected from the following structural formulas (B1-1) to (B1-5). )

(In the formula, R ₁₈ and R ₁₉ are synonymous with the groups represented by R ₁ to R ₄ in the general formula (1). They are connected to the general formula (2) at the wavy line part.)
From the viewpoint of color reproducibility and suppression of bleed out, B ₁ is preferably (B1-4).

Moreover, it is preferable that the compound represented by the general formula (A) is a compound represented by the following general formula (3).

_(Wherein, R 1 ~ _{R 4} have the same meanings as in formula (1) _R 1 ~ _{R 4} in .R ₁ and _{R 2,} or _{R 3} and _{R 4} may combine with each other to form a ring well, the formed ring may have a substituent .R ₅ have the same meaning as _{R 5} in the general formula (1) .R ₆ and _{R 7,} the general formula (1) _{R 6} and in the same meaning as R ₇ .A ₁ has the same meaning as _{a 1} in formula (1).)
Specific examples of the substituent in the compounds having the structures represented by the general formula (A) and the general formulas (1) to (3) are as follows.

Examples of the substituent include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group (eg, methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group). N-octyl group, 2-ethylhexyl group, etc.), alkenyl group (for example, vinyl group, 2-propenyl group, 3-butenyl group, 1-methyl-3-propenyl group, 3-pentenyl group, 1-methyl-3 -Butenyl group, 4-hexenyl group, cyclohexenyl group, styryl group, etc.), cycloalkenyl group (eg, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl group, etc.), alkynyl group (eg, ethynyl group) , Propargyl group, etc.), acyl group (eg, acetyl group, pivaloyl group, benzoyl group, etc.), aryl group (eg, phenyl) Group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group, etc.), heterocyclic group (for example, 2-pyrrole group, 2-furyl group, 2-thienyl group, pyrrole group, imidazolyl group, oxazolyl group, thiazolyl group, benzoimidazolyl group, benzoxazolyl group, 2-benzothiazolyl group, pyrazolinone group, pyridyl group, pyridinone group 2-pyrimidinyl group, triazine group, pyrazole group, 1,2,3-triazole group, 1,2,4-triazole group, oxazole group, isoxazole group, 1,2,4-oxadiazole group, 1, 3,4-oxadiazole group, thiazole group, isothiazole group 1,2,4-thiodiazole group, 1,3,4-thiadiazole group, etc.), alkoxycarbonyl group (for example, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group) ), A carbamoyl group (for example, an aminocarbonyl group, a methylaminocarbonyl group, a dimethylaminocarbonyl group, a butylaminocarbonyl group, a cyclohexylaminocarbonyl group, a phenylaminocarbonyl group, etc.), and an alkoxy group (for example, a methoxy group, Preferred examples include ethoxy group, isopropoxy group, tert-butoxy group, n-octyloxy group, 2-methoxyethoxy group and the like.

<< Synthesis of Exemplary Compounds According to the Present Invention >>
The compound having the structure represented by the general formula (A) according to the present invention, the compound having the structure represented by the general formula (1), the general formula (2) and the general formula (3) is synthesized by the following method. It can be carried out.

<< Synthesis Example 1: Exemplary Compound 1 >>
<First step>
22.4 g of 2-methylbenzothiazole and 41.1 g of butyl p-toluenesulfonate were added and stirred at 150 ° C. for about 4 hours. After the reaction, the mixture was cooled to 110 ° C., toluene was added, and the mixture was slowly cooled to room temperature. The precipitated crude crystals were collected by filtration, and then added with ethyl acetate, and suspended and purified at 70 ° C. for about 30 minutes to obtain 36.9 g of intermediate (1-1).

<Second step>
Intermediate (1-1) (35.9 g), N, N′-diphenylformamidine (22.4 g) and acetic anhydride (11.6 g) were added, and the mixture was stirred for about 3 hours while heating under reflux. After the reaction, silica gel chromatography purification was performed using an ethyl acetate / methanol solution (v / v = 100/2). Ethyl acetate was added to the obtained solid, and suspension purification was performed at 70 ° C. for about 30 minutes to obtain 18.4 g of intermediate (1-2).

<Dyeing process>
4.2 g of intermediate (1-2), 2.4 g of 1-butyl-3- (2-ethylhexyl) barbituric acid and acetonitrile were added and stirred at 60 ° C. for about 30 minutes. Thereafter, a solution obtained by adding 0.81 g of acetic anhydride and 1.6 g of triethylamine to acetonitrile was slowly added dropwise to the reaction solution, followed by stirring at 75 ° C. for about 2 hours. After completion of the reaction, the solvent was distilled off and dissolved in ethyl acetate. After washing the organic phase with saturated brine, anhydrous magnesium sulfate was added, and the mixture was stirred at room temperature for about 10 minutes, and then anhydrous magnesium sulfate was removed by filtration. The filtrate was evaporated and 1.6 g of Exemplified Compound 1 was obtained by recrystallizing the precipitated solid with acetonitrile. The absorption maximum peak wavelength of the obtained compound in an acetone solution was 480 nm, and the half width was 30 nm.

≪Synthesis of other exemplified compounds≫
<Synthesis Example 2: Exemplary Compound 31>
The synthesis was performed in the same manner as in Synthesis 1 except that 1,2-diphenylpyrazolidine-3,5-dione was used in place of 1-butyl-3- (2-ethylhexyl) barbituric acid in Synthesis Example 1. This gave Example compound 31. The absorption maximum peak wavelength of the obtained compound in an acetone solution was 482 nm, and the half width was 35 nm.

<Synthesis Example 3: Exemplary Compound 37>
Synthesis was performed in the same manner as in Synthesis Example 1 except that 1,3-indandione was used in place of 1-butyl-3- (2-ethylhexyl) barbituric acid in Synthesis Example 1, and Exemplified Compound 37 was obtained. It was. The absorption maximum peak wavelength of the obtained compound in an acetone solution was 506 nm, and the half width was 29 nm.

<Synthesis Example 4: Exemplary Compound 39>
In Synthesis Example 1, 1,3-indandione was used in place of 1-butyl-3- (2-ethylhexyl) barbituric acid, and p-toluenesulfonic acid-2- Exemplified compound 39 was obtained in the same manner as in Synthesis Example 1 except that ethylhexyl was used. The absorption maximum peak wavelength of the obtained compound in an acetone solution was 506 nm, and the half width was 29 nm.

<Synthesis Example 5: Exemplary Compound 61>
Synthesis Example 1 except that 3-tert-butyl-1- (2-ethylhexanoyl) -5-pyrazolone was used in place of 1-butyl-3- (2-ethylhexyl) barbituric acid in Synthesis Example 1. Example 1 was obtained by synthesis in the same manner as in Example 1.

<Synthesis Example 6: Exemplary Compound 99>
Synthesis was performed in the same manner as in Synthesis Example 1 except that 4-methylpyridine was used in place of 2-methylbenzothiazole in Synthesis Example 1, and Example Compound 99 was obtained. The absorption maximum peak wavelength of the obtained compound in an acetone solution was 492 nm, and the half width was 41 nm.

<Synthesis Example 7: Exemplary Compound 129>
In Synthesis Example 1, except that 1,3-indandione was used instead of 1-butyl-3- (2-ethylhexyl) barbituric acid, and 4-methylquinoline was used instead of 2-methylbenzothiazole. Then, the synthesis was performed in the same manner as in Synthesis Example 1 to obtain Exemplary Compound 129. The absorption maximum of the obtained compound in an acetone solution was 589 nm, and the half width was 26 nm.
<Synthesis Example 8: Exemplary Compound 131>
In Synthesis Example 1, 1,3-indandione is used instead of 1-butyl-3- (2-ethylhexyl) barbituric acid, 4-methylquinoline is used instead of 2-methylbenzothiazole, p- Exemplified compound 131 was obtained in the same manner as in Synthesis Example 1 except that p-toluenesulfonic acid-2-ethylhexyl was used instead of butyltoluenesulfonate. The absorption maximum peak wavelength of the obtained compound in an acetone solution was 589 nm, and the half width was 26 nm.

Hereinafter, preferred compound examples of the compound having the structure represented by the general formula (A) according to the present invention, the compound having the structure represented by the general formula (1), the general formula (2), and the general formula (3). The present invention is not limited to this.

[2] Resin The resin according to the present invention is characterized in that the solubility in dichloromethane at 23 ° C. is in the range of 5 to 50% by mass.

When the solubility is less than 5% by mass, the compatibility with the compound having the structure represented by the general formula (A) according to the present invention is lowered, and bleed out is likely to occur. On the other hand, if it exceeds 50% by mass, the polymer chain as an optical film is likely to be thermally contracted, and the film properties are likely to be deteriorated.

In the present invention, any resin satisfying the solubility can be used without particular limitation. Among them, a resin selected from a cellulose ester resin, an acrylic resin, a cyclic olefin resin, a polycarbonate resin, and a polyimide resin, or a combination thereof. It is preferable that

[2.1] Cellulose ester resin The cellulose ester resin (also referred to as cellulose ester) that can be used in the present invention includes cellulose (di, tri) acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, It is preferably at least one selected from cellulose acetate butyrate, cellulose acetate phthalate, and cellulose phthalate.

Among these, particularly preferred cellulose esters include cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, and cellulose acetate butyrate.

As the substitution degree of the mixed fatty acid ester, when an acyl group having 2 to 4 carbon atoms is used as a substituent, the substitution degree of the acetyl group is X, and the substitution degree of the propionyl group or butyryl group is Y. A cellulose resin containing a cellulose ester that simultaneously satisfies the following formulas (I) and (II) is preferable.

Formula (I) 2.0 ≦ X + Y ≦ 3.0
Formula (II) 0 ≦ X ≦ 2.5
The total substitution degree of the acyl group of the cellulose ester can be about 1.0 to 3.0. The total substitution degree of the acyl group is preferably in the range of 2.0 to 2.95 from the viewpoint of reducing moisture permeability.

The substitution degree of the acyl group of the cellulose ester can be measured by a method prescribed in ASTM D817-96.

The number average molecular weight of the cellulose ester is preferably in the range of 6 × 10 ⁴ to 3 × 10 ⁵ in order to increase the mechanical strength of the obtained film. The molecular weight is in the range of 7 × 10 ⁴ to 2 × 10 ⁵ . It is more preferable that

Further, the cellulose ester used in the present invention preferably has a weight average molecular weight Mw / number average molecular weight Mn ratio of 1.5 to 5.5, particularly preferably 2.0 to 5.0, The cellulose ester resin is preferably 2.5 to 5.0, more preferably 3.0 to 5.0.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the cellulose ester are measured using gel permeation chromatography (GPC). The measurement conditions are as follows.

Solvent: dichloromethane;
Column: Three Shodex K806, K805, K803G (made by Showa Denko KK) are connected and used;
Column temperature: 25 ° C .; sample concentration: 0.1% by mass;
Detector: RI Model 504 (manufactured by GL Sciences);
Pump: L6000 (manufactured by Hitachi, Ltd.);
Flow rate: 1.0 ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) A calibration curve with 13 samples of Mw = 500 to 1000000 is used. Thirteen samples are used at approximately equal intervals.

The raw material cellulose of the cellulose ester resin used in the present invention may be wood pulp or cotton linter, and the wood pulp may be softwood or hardwood, but softwood is more preferable. A cotton linter is preferably used from the viewpoint of peelability during film formation. The cellulose ester made from these can be mixed suitably or can be used independently.

For example, the ratio of cellulose ester derived from cellulose linter: cellulose ester derived from wood pulp (coniferous): cellulose ester derived from wood pulp (hardwood) is 100: 0: 0, 90: 10: 0, 85: 15: 0, 50:50: 0, 20: 80: 0, 10: 90: 0, 0: 100: 0, 0: 0: 100, 80:10:10, 85: 0: 15, 40:30:30.

In the present invention, 1 g of cellulose ester resin is added to 20 mL of pure water (electric conductivity 0.1 μS / cm or less, pH 6.8), and the pH when stirred in a nitrogen atmosphere at 25 ° C. for 1 hr is 6 It is preferable that the electric conductivity is 1 to 100 μS / cm.

[2.2] Acrylic resin The acrylic resin that can be used in the present invention includes a methacrylic resin.

That is, the acrylic resin may be a homopolymer of (meth) acrylic acid ester or a copolymer of (meth) acrylic acid ester and other copolymerization monomers. The (meth) acrylic resin may be one type or a mixture of two or more types. The (meth) acrylic acid ester is preferably methyl methacrylate. The content ratio of the structural unit derived from methyl methacrylate in the copolymer is preferably 50% by mass or more, and more preferably 70% by mass or more.

Examples of the copolymerization monomer that forms a copolymer with methyl methacrylate include alkyl methacrylates having 2 to 18 carbon atoms in the alkyl portion; alkyl acrylates having 1 to 18 carbon atoms in the alkyl portion; Obtained alkyl (meth) acrylates having 1 to 18 carbon atoms in the alkyl moiety having a hydroxy group; α, β-unsaturated acids such as acrylic acid and methacrylic acid; unsaturated groups such as maleic acid, fumaric acid and itaconic acid Containing divalent carboxylic acids; aromatic vinyl compounds such as styrene and α-methylstyrene; α, β-unsaturated nitriles such as acrylonitrile and methacrylonitrile; maleic anhydride, maleimide, N-substituted maleimide, glutaric anhydride, Acrylamide derivatives such as acryloylmorpholine (ACMO); N-vinylpyrrolidone (VP), etc. Is included. These may be used alone or in combination of two or more.

Among them, alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, Alkyl (meth) acrylates having a hydroxy group such as methyl (hydroxymethyl) acrylate and ethyl 2- (hydroxymethyl) acrylate are preferred.

The weight average molecular weight Mw of the (meth) acrylic resin is preferably in the range of 2.0 × 10 ⁴ to 5.0 × 10 ⁵ , more preferably 5.0 × 10 ⁴ to 4.5 × 10 ⁵ . Within the range, more preferably within the range of 1.0 × 10 ⁵ to 4.0 × 10 ⁵ . If the weight average molecular weight Mw of the (meth) acrylic resin is 8.0 × 10 ⁴ or more, the brittleness resistance of the film is easily improved, and if it is 5.0 × 10 ⁵ or less, the haze of the film tends to be low.

The weight average molecular weight Mw of the (meth) acrylic resin can be measured by gel permeation chromatography in the same manner as the method for measuring the weight average molecular weight Mw of the cellulose ester.

As a method for producing an acrylic resin that can be used in the present invention, any known method such as suspension polymerization, emulsion polymerization, bulk polymerization, or solution polymerization may be used. Here, as a polymerization initiator, a normal peroxide type and an azo type can be used, and a redox type can also be used.

The polymerization temperature may be 30 to 100 ° C. for suspension or emulsion polymerization, and 80 to 160 ° C. for bulk or solution polymerization. In order to control the reduced viscosity of the obtained copolymer, polymerization can be carried out using alkyl mercaptan or the like as a chain transfer agent.

In addition to the above acrylic resins, known acrylic resins can be used. For example, an acrylic resin having a lactone ring unit as described in JP-A-2008-9378 has high heat resistance and is preferably used.

Commercially available acrylic resins can also be used. For example, Delpet 60N, 80N (Asahi Kasei Chemicals Co., Ltd.), Dianal BR52, BR80, BR83, BR85, BR88 (Mitsubishi Rayon Co., Ltd.), KT75 (Denki Kagaku Kogyo Co., Ltd.) and the like can be mentioned. .

[2.3] Cyclic Olefin Resin In the present invention, it is also preferable to use a cyclic olefin resin. Examples of the cyclic olefin resin include norbornene resins, monocyclic olefin resins, cyclic conjugated diene resins, vinyl alicyclic hydrocarbon resins, and hydrides thereof. Among these, norbornene-based resins can be suitably used because of their good transparency and moldability.

Examples of the norbornene-based resin include a ring-opening polymer of a monomer having a norbornene structure, a ring-opening copolymer of a monomer having a norbornene structure and another monomer, a hydride thereof, and a norbornene structure. An addition polymer of a monomer having a monomer, an addition copolymer of a monomer having a norbornene structure and another monomer, or a hydride thereof.

Among these, a ring-opening (co) polymer hydride of a monomer having a norbornene structure is particularly suitable from the viewpoints of transparency, moldability, heat resistance, low hygroscopicity, dimensional stability, lightness, and the like. Can be used.

Examples of the monomer having a norbornene structure include bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene. (Common name: dicyclopentadiene), 7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene (common name: methanotetrahydrofluorene), tetracyclo [4.4.0. 1 ^2,5 . 1 ^7,10 ] dodec-3-ene (common name: tetracyclododecene) and derivatives of these compounds (for example, those having a substituent in the ring). Here, examples of the substituent include an alkyl group, an alkylene group, and a polar group. In particular, a polar group is preferable from the viewpoint of solubility. In addition, these substituents may be the same or different and a plurality may be bonded to the ring. The monomer which has a norbornene structure can be used individually by 1 type or in combination of 2 or more types.

Examples of the polar group include a hetero atom or an atomic group having a hetero atom. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a halogen atom. Specific examples of the polar group include carboxy group, carbonyloxycarbonyl group, epoxy group, hydroxy group, oxy group, ester group, silanol group, silyl group, amino group, nitrile group, and sulfone group. Among them, a monomer that is a polar group represented by the formula — (CH ₂ ) nCOOR is such that the resulting cycloolefin resin has a high glass transition temperature, a low hygroscopic property, and excellent adhesion to various materials. This is preferable.

Other monomers capable of ring-opening copolymerization with monomers having a norbornene structure include monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene and derivatives thereof, cyclic conjugated dienes such as cyclohexadiene, cycloheptadiene, and the like. And derivatives thereof.

A ring-opening polymer of a monomer having a norbornene structure and a ring-opening copolymer of a monomer having a norbornene structure and another monomer copolymerizable with the monomer have a known ring-opening polymerization catalyst. It can be obtained by (co) polymerization in the presence.

Examples of other monomers that can be addition-copolymerized with a monomer having a norbornene structure include, for example, α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, and 1-butene, and derivatives thereof; cyclobutene, cyclopentene, Examples include cycloolefins such as cyclohexene and derivatives thereof; non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, and 5-methyl-1,4-hexadiene. These monomers can be used alone or in combination of two or more. Among these, α-olefin is preferable, and ethylene is more preferable.

An addition polymer of a monomer having a norbornene structure and an addition copolymer of another monomer copolymerizable with a monomer having a norbornene structure can be used in the presence of a known addition polymerization catalyst. It can be obtained by polymerization.

A hydrogenated product of a ring-opening polymer of a monomer having a norbornene structure, a hydrogenated product of a ring-opening copolymer of a monomer having a norbornene structure and another monomer capable of ring-opening copolymerization thereof, Hydrogenated products of addition polymers of monomers having a norbornene structure, and hydrogenated products of addition copolymers of monomers having a norbornene structure and other monomers capable of addition copolymerization with these A known hydrogenation catalyst containing a transition metal such as nickel or palladium is added to the polymer solution, and the carbon-carbon unsaturated bond is preferably hydrogenated by 90% or more.

Among norbornene-based resins, X: bicyclo [3.3.0] octane-2,4-diyl-ethylene structure and Y: tricyclo [4.3.0.1 ^2,5 ] decane-7 are used as repeating units. , 9-diyl-ethylene structure, the content of these repeating units is 90% by mass or more based on the entire repeating units of the norbornene resin, and the X content ratio and the Y content ratio are The ratio of X: Y is preferably 100: 0 to 40:60. By using such a resin, it is possible to obtain an optical film that has no dimensional change in the long term and is excellent in stability of optical characteristics.

The molecular weight of the cyclic olefin resin used in the present invention is appropriately selected according to the purpose of use. The polyisoprene or polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography using cyclohexane (toluene if the polymer resin does not dissolve) as a solvent is usually 20000 to 150,000. It is preferably 25,000 to 100,000, more preferably 30,000 to 80,000. When the weight average molecular weight is in such a range, the mechanical strength and molding processability of the film are highly balanced and suitable.

The glass transition temperature of the cyclic olefin resin may be appropriately selected according to the purpose of use. From the viewpoint of durability and stretchability, it is preferably in the range of 130 to 160 ° C, more preferably 135 to 150 ° C.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the cyclic olefin resin is 1.2 to 3.5, preferably 1.5 to 3.0, from the viewpoint of relaxation time, productivity and the like. More preferably, it is 1.8 to 2.7.

Commercially available products can be preferably used as the cyclic olefin resin described above. Examples of commercially available products are commercially available from JSR Corporation under the trade names Arton G, Arton F, Arton R, and Arton RX. ing.

[2.4] Polycarbonate Resin Various known polycarbonate resins can be used in the present invention. In the present invention, it is particularly preferable to use an aromatic polycarbonate. There is no restriction | limiting in particular about the said aromatic polycarbonate, and there will be no restriction | limiting in particular if it is an aromatic polycarbonate from which the various characteristics of a desired film are acquired.

In general, a polymer material collectively referred to as polycarbonate is a generic term for a polymer material in which a polycondensation reaction is used in its synthesis method and the main chain is linked by a carbonic acid bond. , Phosgene, diphenyl carbonate and the like obtained by polycondensation. Usually, an aromatic polycarbonate represented by a repeating unit having 2,2-bis (4-hydroxyphenyl) propane called bisphenol-A as a bisphenol component is preferably selected. Various bisphenol derivatives should be selected as appropriate. Thus, an aromatic polycarbonate copolymer can be constituted.

In addition to this bisphenol-A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 1,1 -Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) -2-phenyl Ethane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) sulfide, bis ( 4-hydroxyphenyl) sulfone and 1,1-bis (4-hydroxyphenyl) -3,3,5 It can be mentioned trimethyl cyclohexane.

It is also possible to use an aromatic polyester carbonate partially containing terephthalic acid and / or isophthalic acid components. By using such a structural unit as a part of the structural component of the aromatic polycarbonate composed of bisphenol-A, the properties of the aromatic polycarbonate, such as heat resistance and solubility, can be improved. The present invention is also effective for coalescence.

The aromatic polycarbonate used here preferably has a viscosity average molecular weight of 1 × 10 ⁴ or more and 4 × 10 ⁵ or less. A viscosity average molecular weight of 2 × 10 ⁴ to 1.2 × 10 ⁵ is particularly preferable. If a resin having a viscosity average molecular weight lower than 1 × 10 ⁴ is used, the mechanical strength of the obtained film may be insufficient, and if it has a high molecular weight of 4 × 10 ⁵ or more, the viscosity of the dope becomes too high, causing problems in handling. Since it occurs, it is not preferable. The viscosity average molecular weight can be measured by commercially available high performance liquid chromatography.

The glass transition temperature of the aromatic polycarbonate used in the present invention is preferably 200 ° C. or higher for obtaining a highly heat-resistant film, and more preferably 230 ° C. or higher. These can be obtained by appropriately selecting the copolymerization component. The glass transition temperature can be measured with a DSC apparatus (differential scanning calorimetry apparatus). For example, the Seiko Instruments Inc. product: RDC220 calculates the temperature at 10 ° C./min. It is the temperature that begins to do.

[2.5] Polyimide resin The polyimide resin used in the present invention is a resin having an imide structure, and a resin containing an imide bond in a repeating unit. The polyimide is preferably formed from diamine or a derivative thereof and an acid anhydride or a derivative thereof.

Preferred polyimide resins for the present invention from the viewpoint of solubility include polyimides, polyamideimides, polyetherimides, and polyesterimides having a structure represented by the following formula (1.1). It is preferable to use a polyimide having a structure represented by the formula (1.1).

[2.5.1] Polyimide having a structure represented by the formula (1.1) As a polyimide that can be used in the present invention, in particular, a polyimide having a repeating unit represented by the following formula (1.1) (Hereinafter referred to as polyimide (A)) is preferable.

In the formula (1.1), R represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, or a tetravalent aliphatic hydrocarbon group or alicyclic hydrocarbon group having 4 to 39 carbon atoms. A represents a group consisting of a divalent aliphatic hydrocarbon group having 2 to 39 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof, and as a bonding group, —O—, — At least one selected from the group consisting of SO ₂ —, —CO—, —CH ₂ —, —C (CH ₃ ) ₂ —, —OSi (CH ₃ ) ₂ —, —C ₂ H ₄ O—, and —S—. One group may be contained.

Examples of the aromatic hydrocarbon ring represented by R include fluorene ring, benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, o- Terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, pyrene ring, pyranthrene ring, and anthra An anthrene ring etc. are mentioned.

Similarly, examples of the aromatic heterocycle represented by R include a silole ring, a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, and an oxadiene ring. Azole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzthiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, thienothiophene ring, carbazole ring, azacarbazole ring ( Any one of the carbon atoms constituting the dicarbosyl ring, dibenzofuran ring, dibenzothiophene ring, benzothiophene ring or dibenzofuran ring. More than one nitrogen Ring substituted with a child, benzodifuran ring, benzodithiophene ring, acridine ring, benzoquinoline ring, phenazine ring, phenanthridine ring, phenanthroline ring, cyclazine ring, quindrine ring, tepenidine ring, quinindrine ring, triphenodithiazine ring, Triphenodioxazine ring, phenanthrazine ring, anthrazine ring, perimidine ring, naphthofuran ring, naphthothiophene ring, naphthodifuran ring, naphthodithiophene ring, anthrafuran ring, anthradifuran ring, anthrathiophene ring, anthradithiophene ring, thianthrene A ring, a phenoxathiin ring, a dibenzocarbazole ring, an indolocarbazole ring, a dithienobenzene ring, and the like.

Examples of the tetravalent aliphatic hydrocarbon group having 4 to 39 carbon atoms represented by R include a butane-1,1,4,4-tetrayl group, an octane-1,1,8,8-tetrayl group, And groups such as decane-1,1,10,10-tetrayl group.

Examples of the tetravalent alicyclic hydrocarbon group having 4 to 39 carbon atoms represented by R include cyclobutane-1,2,3,4-tetrayl group, cyclopentane-1,2,4,5. -Tetrayl group, cyclohexane-1,2,4,5-tetrayl group, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetrayl group, bicyclo [2.2.2] Octane-2,3,5,6-tetrayl group, 3,3 ′, 4,4′-dicyclohexyltetrayl group, 3,6-dimethylcyclohexane-1,2,4,5-tetrayl group, and 3,6 And groups such as -diphenylcyclohexane-1,2,4,5-tetrayl group.

The group represented by A is preferably a divalent aromatic hydrocarbon group having 2 to 39 carbon atoms having a linking group, or a combination of the aromatic hydrocarbon group and an aliphatic hydrocarbon group. A group represented by the following structural formula is preferred.

The polyimide of formula (1.1) is prepared by reacting an aromatic, aliphatic or alicyclic tetracarboxylic acid or derivative thereof with a diamine or derivative thereof to prepare a polyamic acid, and imidizing the polyamic acid. Is obtained.

Examples of the aliphatic or alicyclic tetracarboxylic acid derivatives include aliphatic or alicyclic tetracarboxylic acid esters, aliphatic or alicyclic tetracarboxylic dianhydrides, and the like. Of the aliphatic or alicyclic tetracarboxylic acids or derivatives thereof, alicyclic tetracarboxylic dianhydrides are preferred.

Examples of the aliphatic tetracarboxylic acid include 1,2,3,4-butanetetracarboxylic acid.

Examples of the aliphatic tetracarboxylic acid esters include monoalkyl esters, dialkyl esters, trialkyl esters, and tetraalkyl esters of the above aliphatic tetracarboxylic acids.

Examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride.

Examples of the aromatic tetracarboxylic acid include 4,4′-biphthalic anhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, and 2,3,3 ′, 4′-biphenyltetracarboxylic acid. And dianhydrides, 4,4'-oxydiphthalic anhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, and the like.

In the present invention, it is also preferable to use an acid anhydride having a fluorene structure, and 9,9-bis (3,4-dicarboxyphenyl) fluorenic dianhydride, and 9,9-bis [4- (3,4) -Dicarboxyphenoxy) phenyl] fluorenic dianhydride is preferably used from the viewpoint of heat resistance and transparency.

On the other hand, as the diamine or a derivative thereof, for example, an aromatic diamine or an isocyanate is preferable, and an aromatic diamine is preferable.

In the present invention, the term “aromatic diamine” refers to a diamine in which an amino group is directly bonded to an aromatic ring, and an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or any other part of its structure. A substituent (for example, a halogen atom, a sulfonyl group, a carbonyl group, an oxygen atom, etc.) may be contained. The term “aliphatic diamine” refers to a diamine in which an amino group is directly bonded to an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, and an aromatic hydrocarbon group or other substituent ( For example, a halogen atom, a sulfonyl group, a carbonyl group, an oxygen atom, etc.) may be included.

Examples of aromatic diamines include, for example, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, benzidine, o-tolidine, m-tolidine, bis (trifluoromethyl) Benzidine, octafluorobenzidine, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl 3,3′-difluoro-4,4′-diaminobiphenyl, 2,6-diaminonaphthalene and the like.

The diamine used in the present invention is 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-amino3-methylphenyl) fluorene, or 9,9-bis (3-fluoro- 4-aminophenyl) fluorene is preferable, and the acid anhydride is 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride or 9,9-bis [4- (3 , 4-Dicarboxyphenoxy) phenyl] fluorenic dianhydride is preferable from the viewpoint of improving non-coloring property, whitening and bending resistance.

In addition, it is preferable that the polyimide used in the present invention contains a fluorinated polyimide from the viewpoint of excellent transparency of the polyimide film and easy thermal correction by thermal shrinkage. The fluorine content is more preferably in the range of 1 to 40% by mass in the film because the effect of the present invention is great.

(2.5.2) Synthesis method and imidization of polyamic acid <Synthesis of polyamic acid>
The polyamic acid can be obtained by polymerizing at least one of the tetracarboxylic acids and at least one of the diamines in a suitable solvent.

<Imidization method>
Here, polyimide is a method in which a polyamic acid solution is heated to imidize the polyamic acid (thermal imidization method), or a method in which a polycyclic acid (imidation catalyst) is added to the polyamic acid solution to imidize the polyamic acid. (Chemical imidization method).

In the thermal imidization method, the polyamic acid in the polymerization solvent is heated for 0.1 to 200 hours in a temperature range of, for example, 80 to 300 ° C. to advance imidization. Further, the temperature range is preferably 150 to 200 ° C., and by setting the temperature range to 150 ° C. or higher, imidization can be reliably progressed and completed. It is possible to prevent an increase in the resin concentration due to oxidation of unreacted raw materials and volatilization of the solvent.

On the other hand, in the chemical imidization method, a known ring closure catalyst is added to the polyamic acid in the polymerization solvent to advance imidization. Specific examples of the ring-closing catalyst include aliphatic tertiary amines such as trimethylamine and triethylenediamine, and heterocyclic tertiary amines such as isoquinoline, pyridine and picoline.

[3] Other additives The optical film of the present invention may further contain various additives as described below, if necessary.

<Sugar ester>
The optical film of the present invention can contain a sugar ester other than the cellulose ester resin described above from the viewpoint of improving the plasticity of the optical film.

The sugar ester that can be used in the present invention refers to a compound having 1 to 12 furanose structures or pyranose structures in which all or part of the hydroxy groups in the compound are esterified.

Preferred examples of such sugar esters include sucrose esters represented by the following general formula (FA).

R ₁ to R _{8 in} formula (FA) each independently represent a hydrogen atom, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group. R ₁ to R ₈ may be the same as or different from each other.

The substituted or unsubstituted alkylcarbonyl group is preferably a substituted or unsubstituted alkylcarbonyl group having 2 or more carbon atoms. Examples of the substituted or unsubstituted alkylcarbonyl group include a methylcarbonyl group (acetyl group). Examples of the substituent that the alkyl group has include an aromatic hydrocarbon ring group such as a phenyl group.

The substituted or unsubstituted arylcarbonyl group is preferably a substituted or unsubstituted arylcarbonyl group having 7 or more carbon atoms. Examples of the arylcarbonyl group include a phenylcarbonyl group. Examples of the substituent that the aromatic hydrocarbon ring group has include an alkyl group such as a methyl group, an alkoxyl group such as a methoxy group, and the like.

The average substitution degree of the acyl group of the sucrose ester is preferably in the range of 3.0 to 7.5. When the average substitution degree of the acyl group is within this range, for example, sufficient compatibility with the cellulose ester is easily obtained.

The content of the sugar ester is preferably in the range of 0.5 to 35.0% by mass, more preferably in the range of 5.0 to 30.0% by mass with respect to the cellulose ester.

<Plasticizer>
The optical film of the present invention may contain a plasticizer in order to improve the fluidity of the composition during film production and the flexibility of the film as long as the effects of the present invention are not impaired. Examples of plasticizers include polyester plasticizers, polyhydric alcohol ester plasticizers, polycarboxylic acid ester plasticizers (including phthalate ester plasticizers), glycolate plasticizers, ester plasticizers ( Citrate ester plasticizers, fatty acid ester plasticizers, phosphate ester plasticizers, trimellitic ester plasticizers, and the like). These may be used alone or in combination of two or more.

The polyester plasticizer is a compound obtained by reacting a monovalent to tetravalent carboxylic acid and a monovalent to hexavalent alcohol, and preferably a compound obtained by reacting a divalent carboxylic acid and a glycol. It is.

Examples of the divalent carboxylic acid include succinic acid, glutaric acid, itaconic acid, adipic acid, phthalic acid, azelaic acid, sebacic acid and the like. In particular, a compound using succinic acid, adipic acid, phthalic acid or the like as the divalent carboxylic acid can impart good plasticity.

Examples of glycols include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, neopentylene glycol, diethylene glycol, triethylene glycol, and dipropylene glycol Is included. Each of the divalent carboxylic acid and glycol may be one kind, or two or more kinds may be used in combination.

The polyester plasticizer may be any of ester, oligoester, and polyester. The molecular weight of the polyester plasticizer is preferably in the range of 100 to 10,000, and more preferably in the range of 600 to 3,000 because the effect of imparting plasticity is great.

The viscosity of the polyester plasticizer depends on the molecular structure and molecular weight. However, in the case of an adipic acid plasticizer, the compatibility with the cellulose ester is high and the effect of imparting plasticity is high. It is preferably in the range of s (25 ° C.). The polyester plasticizer may be used alone or in combination of two or more.

The polyhydric alcohol ester plasticizer is an ester compound (alcohol ester) of a dihydric or higher aliphatic polyhydric alcohol and a monocarboxylic acid, preferably a divalent to 20-valent aliphatic polyhydric alcohol ester. The polyhydric alcohol ester compound preferably has an aromatic ring or a cycloalkyl ring in the molecule.

Examples of the aliphatic polyhydric alcohol include ethylene glycol, propylene glycol, trimethylolpropane, pentaerythritol and the like.

The monocarboxylic acid can be an aliphatic monocarboxylic acid, an alicyclic monocarboxylic acid, an aromatic monocarboxylic acid, or the like. One kind of monocarboxylic acid may be sufficient and a mixture of two or more kinds may be sufficient. Further, all of the OH groups contained in the aliphatic polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.

The aliphatic monocarboxylic acid is preferably a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms. The number of carbon atoms of the aliphatic monocarboxylic acid is more preferably 1-20, and still more preferably 1-10. Examples of such aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, and the like, and acetic acid may be preferable in order to enhance compatibility with the cellulose ester.

Examples of the alicyclic monocarboxylic acid include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid and the like.

Examples of aromatic monocarboxylic acids include benzoic acid; one having 1 to 3 alkyl groups or alkoxy groups (for example, methoxy group or ethoxy group) introduced into the benzene ring of benzoic acid (for example, toluic acid, etc.); benzene ring Aromatic monocarboxylic acids having two or more (for example, biphenyl carboxylic acid, naphthalene carboxylic acid, tetralin carboxylic acid, etc.) are included, and benzoic acid is preferred.

The molecular weight of the polyhydric alcohol ester plasticizer is not particularly limited, but is preferably in the range of 300 to 1500, and more preferably in the range of 350 to 750. In order to make it hard to volatilize, the one where molecular weight is larger is preferable. In order to improve moisture permeability and compatibility with the cellulose ester, a smaller molecular weight is preferable.

Specific examples of the polyhydric alcohol ester plasticizer include trimethylolpropane triacetate, pentaerythritol tetraacetate, and an ester compound (A) represented by the general formula (I) described in JP-A-2008-88292. included.

The polyvalent carboxylic acid ester plasticizer is an ester compound of a divalent or higher, preferably 2 to 20 valent polycarboxylic acid and an alcohol compound. The polyvalent carboxylic acid is preferably a 2-20 valent aliphatic polyvalent carboxylic acid, a 3-20 valent aromatic polyvalent carboxylic acid, or a 3-20 valent alicyclic polyvalent carboxylic acid.

Examples of polyvalent carboxylic acids include trivalent or higher aromatic polyvalent carboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid or derivatives thereof; succinic acid, adipic acid, azelaic acid, sebacic acid, oxalic acid Contains aliphatic polycarboxylic acids such as fumaric acid, maleic acid and tetrahydrophthalic acid; oxypolycarboxylic acids such as tartaric acid, tartronic acid, malic acid and citric acid, etc., and suppresses volatilization from the film. For this, oxypolycarboxylic acids are preferred.

Examples of the alcohol compound include an aliphatic saturated alcohol compound having a straight chain or a side chain, an aliphatic unsaturated alcohol compound having a straight chain or a side chain, an alicyclic alcohol compound, or an aromatic alcohol compound. The carbon number of the aliphatic saturated alcohol compound or the aliphatic unsaturated alcohol compound is preferably 1 to 32, more preferably 1 to 20, and further preferably 1 to 10. Examples of the alicyclic alcohol compound include cyclopentanol, cyclohexanol and the like. Examples of the aromatic alcohol compound include phenol, paracresol, dimethylphenol, benzyl alcohol, cinnamyl alcohol and the like. One kind of alcohol compound may be sufficient and a mixture of two or more kinds may be sufficient.

The molecular weight of the polyvalent carboxylic acid ester plasticizer is not particularly limited, but is preferably in the range of 300 to 1000, and more preferably in the range of 350 to 750. A larger molecular weight of the polyvalent carboxylic acid ester plasticizer is preferable from the viewpoint of suppressing bleeding out. From the viewpoint of moisture permeability and compatibility with cellulose ester, a smaller one is preferable.

The acid value of the polyvalent carboxylic acid ester plasticizer is preferably 1 mgKOH / g or less, more preferably 0.2 mgKOH / g or less. The acid value refers to the number of milligrams of potassium hydroxide necessary for neutralizing the acid (carboxy group present in the sample) contained in 1 g of the sample. The acid value is measured according to JIS K0070.

Examples of the polycarboxylic acid ester plasticizer include an ester compound (B) represented by the general formula (II) described in JP-A-2008-88292.

The polycarboxylic acid ester plasticizer may be a phthalate ester plasticizer. Examples of the phthalate ester plasticizer include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dicyclohexyl phthalate, and dicyclohexyl terephthalate.

Examples of glycolate plasticizers include alkylphthalyl alkyl glycolates. Examples of alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, and octyl phthalyl octyl glycolate It is.

The ester plasticizer includes a fatty acid ester plasticizer, a citrate ester plasticizer, a phosphate ester plasticizer, a trimellitic acid plasticizer, and the like.

Examples of the fatty acid ester plasticizer include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate and the like. Examples of the citrate plasticizer include acetyl trimethyl citrate, acetyl triethyl citrate, acetyl tributyl citrate and the like. Examples of the phosphate ester plasticizer include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate and the like. Examples of trimellitic acid plasticizers include octyl trimellitic acid, n-octyl trimellitic acid, isodecyl trimellitic acid, and isononyl trimellitic acid.

The plasticizer content is preferably in the range of 0.5 to 30.0% by mass with respect to the cellulose ester. If the content of the plasticizer is 30.0% by mass or less, the optical film hardly causes bleed out.

<Ultraviolet absorber>
The optical film of the present invention may further contain an ultraviolet absorber. The ultraviolet absorber may be benzotriazole, 2-hydroxybenzophenone, salicylic acid phenyl ester, or the like. Specifically, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- Triazoles such as (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole; 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2′-dihydroxy-4 -Benzophenones such as methoxybenzophenone.

Among them, an ultraviolet absorber having a molecular weight of 400 or more is difficult to volatilize at a high boiling point, and is difficult to scatter even at high temperature molding. Therefore, even if the addition amount is relatively small, weather resistance is imparted to the obtained film. Can do.

Examples of ultraviolet absorbers having a molecular weight of 400 or more include 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2-benzotriazole, 2,2-methylenebis [4- Benzotriazoles such as (1,1,3,3-tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol];
Hindered amines such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate;
2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy]- A hybrid system having both hindered phenol and hindered amine structures in the molecule such as 2,2,6,6-tetramethylpiperidine;
Preferably, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2-benzotriazole or 2,2-methylenebis [4- (1,1,3, 3-tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol]. These may be used alone or in combination of two or more.

<Fine particles>
The optical film of the present invention may contain fine particles composed of an inorganic compound or an organic compound for the purpose of imparting slipperiness and improving handleability.

Examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate , And calcium phosphate.

Examples of organic compounds include polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropyl methacrylate, polymethyl acrylate, polyethylene carbonate, acrylic styrene resin, silicone resin, polycarbonate resin, benzoguanamine resin, melamine Resin, polyolefin-based powder, polyester-based resin, polyamide-based resin, polyimide-based resin, pulverized classification of organic polymer compound (polyfluorinated ethylene-based resin, starch, etc.), polymer compound synthesized by suspension polymerization method, spray drying High molecular compounds made spherical by the method or dispersion method are included.

The fine particles can be composed of a compound containing silicon, preferably silicon dioxide, from the viewpoint that the haze of the obtained film can be kept low.

Examples of the silicon dioxide fine particles include Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, and TT600 (manufactured by Nippon Aerosil Co., Ltd.).

Among them, Aerosil 200V and Aerosil R972V are particularly preferable because they can increase the slipperiness of the film surface while keeping the haze of the optical film low.

Examples of the zirconium oxide fine particles include Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.).

Examples of the polymer compound include a silicone resin, a fluororesin, a (meth) acrylic resin, and the like, preferably a silicone resin, and more preferably a silicone resin having a three-dimensional network structure. Examples of such silicone resins include Tospearl 103, 105, 108, 120, 145, 3120, 240 (above, manufactured by Toshiba Silicone Co., Ltd.) and the like.

The average primary particle size of the fine particles is preferably in the range of 5 to 400 nm, more preferably in the range of 10 to 300 nm. The fine particles may form secondary aggregates mainly having a particle size in the range of 0.05 to 0.30 μm. If the average particle size of the fine particles is in the range of 100 to 400 nm, they can exist as primary particles without agglomeration.

It is preferable to contain fine particles so that the dynamic friction coefficient of at least one surface of the optical film is in the range of 0.2 to 1.0.

The content of the fine particles is preferably in the range of 0.01 to 1.00% by mass, more preferably in the range of 0.05 to 0.50% by mass with respect to the cellulose ester.

<Phase difference control agent>
In order to improve the display quality of an image display device such as a liquid crystal display device, a retardation control agent is added to the optical film or an alignment film is formed to provide a liquid crystal layer. By combining the phase difference, the optical compensation ability can be imparted to the optical film.

Examples of the retardation control agent include aromatic compounds having two or more aromatic rings as described in EP 911,656A2, and rod-like compounds described in JP-A-2006-2025. It is done. Two or more aromatic compounds may be used in combination. The aromatic ring of the aromatic compound is preferably an aromatic heterocyclic ring including an aromatic heterocyclic ring in addition to the aromatic hydrocarbon ring. The aromatic heterocycle is generally an unsaturated heterocycle. Of these, the 1,3,5-triazine ring described in JP-A-2006-2026 is preferable.

The addition amount of these retardation control agents is preferably in the range of 0.5 to 20% by mass, more preferably in the range of 1 to 10% by mass with respect to 100% by mass of the resin for film. preferable.

<Other additives>
The optical film of the present invention may further contain an antioxidant, an antistatic agent, a flame retardant and the like for preventing thermal decomposition during molding and coloring due to heat.

[4] Physical Properties of Optical Film The optical film of the present invention can be used as an optical film for image display devices such as organic EL display devices and liquid crystal display devices. The optical film of the present invention is preferably used for a polarizing plate protective film, a retardation film, and an optical compensation film. It is preferable that the retardation film or the optical compensation film also serves as a polarizing plate protective film.

The retardation value of the optical film of the present invention is not particularly limited and can be appropriately adjusted according to the use of the optical film.

When the optical film of the present invention is used as a general polarizing plate protective film or a retardation film for an IPS liquid crystal display device, the retardation value is preferably small, and the following conditions 1 and 2 are preferably satisfied.

Condition 1: An in-plane retardation value Ro (590) represented by the following formula (I) measured at a wavelength of 590 nm under an environment of a temperature of 23 ° C. and a relative humidity of 55% is in the range of 0 to 40 nm.

Formula (I): Ro = (n x -n y) × d
Condition 2: Retardation value Rt (590) in the thickness direction represented by the following formula (II) measured at a wavelength of 590 nm in an environment of a temperature of 23 ° C. and a relative humidity of 55% is within a range of −20 to 50 nm. It is.

Formula (II): Rt = {(n _x + _ny ) / 2−n _z } × d
(Here, the refractive index in the slow axis direction in the plane n _x of the film, the direction of the refractive index n _y perpendicular to the slow axis in the plane of the film, the refractive index in the thickness direction of the film n _z D represents the thickness (nm) of the film.)
In addition, when the optical film of the present invention is used as an optical compensation film for a vertical alignment type liquid crystal display device, it is preferable for the viewing angle expansion that the retardation value satisfies the following conditions 3 and 4.

Condition 3: An in-plane retardation value Ro (590) represented by the above formula (I) measured at a wavelength of 590 nm in an environment of a temperature of 23 ° C. and a relative humidity of 55% is in the range of 40 to 100 nm.

Condition 4: The retardation value Rt (590) in the thickness direction represented by the above formula (II) measured at a wavelength of 590 nm under an environment of a temperature of 23 ° C. and a relative humidity of 55% is within a range of 100 to 300 nm. is there.

Desired retardation can be adjusted by controlling the stretching ratio at the time of film production, the addition amount of the retardation increasing agent, the type and substitution degree of acyl groups, the film thickness of the film in the case of cellulose ester.

The above Ro and Rt can be measured using an automatic birefringence meter, for example, AxoScan manufactured by Axometric, and KOBRA-21ADH manufactured by Oji Scientific Instruments.

The film thickness of the optical film is preferably in the range of 10 to 250 μm from the viewpoint of thinning the display device and productivity. If the film thickness is 10 μm or more, a certain level of film strength and retardation can be expressed. If the film thickness is 250 μm or less, fluctuations in the phase difference due to heat and humidity can be suppressed. Preferably, it is in the range of 20 to 100 μm.

The visible light transmittance of the optical film of the present invention is preferably 90% or more, and more preferably 93% or more.

In the optical film of the present invention, the elongation at break in at least one direction measured according to JIS-K7127-1999 is preferably 10% or more, more preferably 20% or more, and further preferably 30. % Or more.

[5] Method for Producing Optical Film The optical film of the present invention can be produced by a solution casting method or a melt casting method.

In addition to the manifestation of the effects of the present invention, the solution casting method is preferred from the viewpoint of suppressing optical defects such as coloring of optical films, foreign matter defects, and die lines.

[5.1] Solution casting film forming method The method for producing an optical film by the solution casting film forming method is A1) a compound having at least a resin and a structure represented by the general formula (A) according to the present invention, and A step of preparing a dope by dissolving other additives in a solvent as necessary, A2) a step of casting a dope on an endless metal support, A3) a web by evaporating the solvent from the cast dope And A4) a step of peeling the web from the metal support, and A5) a step of drying the web and then stretching it to obtain a film, if necessary.

FIG. 1 is a diagram schematically showing an example of an apparatus used in a dope preparation step, a casting step, a drying step, and a stretching step of a solution casting film forming method preferable for the present invention.

As an example of an apparatus to be used, in FIG. 1, a melting pot 101, filters 103, 106, 112, 115, stock pots 104, 113, liquid feed pumps 102, 105, 111, 114, conduits 108, 116, additive charging pot 110 , Merge pipe 120, mixer 121, pressurizing die 130, metal belt 131, web 132, peeling position 133, first drying device 134, stretching device 135, second drying device 136, winding device 138, charging kettle 141, The stock pot 142, the pump 143, and the filter 144 can be mentioned, respectively. However, it is not limited to this.

A1) Dope preparation step In a dissolution vessel, a dope is prepared by dissolving a resin, a compound having a structure represented by the general formula (A) according to the present invention, and, if necessary, other additives in a solvent.

The solvent can be used without limitation as long as it dissolves the resin, the compound having the structure represented by the general formula (A) according to the present invention, and other additives. For example, as the chlorinated organic solvent, dichloromethane, as the non-chlorinated organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2 , 2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2 -Methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, etc. Preferably, dichloromethane, methyl acetate, ethyl acetate, acetone and the like can be used.

The dope preferably further contains 1 to 40% by mass of a linear or branched aliphatic alcohol having 1 to 4 carbon atoms. When the ratio of the alcohol in the dope is high, the web is gelled and peeling from the metal support becomes easy. On the other hand, when the ratio of alcohol in the dope is small, dissolution of cellulose acetate in a non-chlorine organic solvent system can be promoted.

Examples of linear or branched aliphatic alcohols having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol and the like. . Of these, ethanol is preferred because of high dope stability, relatively low boiling point, and high drying properties.

Among these, the dope preferably contains a solvent dichloromethane and a linear or branched aliphatic alcohol having 1 to 4 carbon atoms.

The resin concentration in the dope is preferably higher in order to reduce the drying load, but it is difficult to filter if the resin concentration is too high. Therefore, the concentration of the resin in the dope is preferably in the range of 10 to 35% by mass, more preferably in the range of 15 to 25% by mass.

The method of dissolving the resin in the solvent can be, for example, a method of dissolving under heating and pressure. A higher heating temperature is preferable from the viewpoint of increasing the solubility of the resin. If the temperature is too high, it is necessary to increase the pressure, and the productivity is lowered. Therefore, the heating temperature is preferably in the range of 45 to 120 ° C.

The additive may be added batchwise to the dope, or an additive solution may be separately prepared and added inline. In particular, it is preferable to add all or part of the fine particles in-line in order to reduce the load on the filter medium.

When adding an additive solution in-line, it is preferable to dissolve a small amount of resin in order to facilitate mixing with the dope. The content of the thermoplastic resin is preferably in the range of 1 to 10 parts by mass, more preferably in the range of 3 to 5 parts by mass with respect to 100 parts by mass of the solvent.

For in-line addition and mixing, for example, an in-line mixer such as a static mixer (manufactured by Toray Engineering) or SWJ (Toray static type in-pipe mixer Hi-Mixer) is preferably used.

The obtained dope may contain insoluble matters such as impurities contained in a resin as a raw material, for example. Such an insoluble matter can become a bright spot foreign material in the obtained film. In order to remove insoluble matter, it is preferable to further filter the obtained dope.

The dope filtration is preferably performed so that the number of bright spot foreign substances in the obtained film is a certain value or less. Specifically, the number of bright spot foreign matters having a diameter of 0.01 mm or more is 200 / cm ² or less, preferably 100 / cm ² or less, more preferably 50 / cm ² or less, and still more preferably 30 Filtration is performed so that the number of particles / cm ² or less, particularly preferably 10 / cm ² or less.

The bright spot foreign matter having a diameter of 0.01 mm or less is also preferably 200 pieces / cm ² or less, more preferably 100 pieces / cm ² or less, further preferably 50 pieces / cm ² or less, It is more preferably 30 pieces / cm ² or less, particularly preferably 10 pieces / cm ² or less, and most preferably none.

The number of bright spot foreign matter on the film can be measured by the following procedure.

1) Arrange two polarizing plates in a crossed Nicol state, and arrange the film obtained between them.

2) When the light is applied from the side of one polarizing plate and observed from the side of the other polarizing plate, the number where the light appears to leak is counted as a foreign object.

A2) Casting step The dope is cast on the endless metal support from the slit of the pressure die.

As the metal support, a stainless steel belt or a drum whose surface is plated with a casting is preferably used. The surface of the metal support is preferably mirror-finished.

The cast width can be in the range of 1-4m. The surface temperature of the metal support in the casting step is set to −50 ° C. or more and below the temperature at which the solvent boils and does not foam. A higher temperature is preferable because the web can be dried at a higher speed, but it is within a temperature range in which foaming of the web and deterioration of flatness can be prevented.

The surface temperature of the metal support is preferably in the range of 0 to 100 ° C., more preferably in the range of 5 to 30 ° C. Alternatively, the metal support may be cooled so that the web is gelled and can be peeled off from the drum in a state containing a large amount of residual solvent.

The method for adjusting the temperature of the metal support is not particularly limited, and there are a method of blowing hot air or cold air, and a method of bringing hot water into contact with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short.

When using warm air, considering the temperature drop of the web due to the latent heat of vaporization of the solvent, while using warm air above the boiling point of the solvent, there may be cases where wind at a temperature higher than the target temperature is used while preventing foaming. . In particular, it is preferable to efficiently dry by changing the temperature of the metal support and the temperature of the drying air during the period from casting to peeling.

A3) Solvent evaporation step The web (dope film obtained by casting the dope on the metal support) is heated on the metal support to evaporate the solvent. The drying method and drying conditions of the web can be the same as in the above-described A2) casting step.

A4) Peeling Step The web obtained by evaporating the solvent on the metal support is peeled off at the peeling position on the metal support.

The residual solvent amount of the web at the time of peeling at the peeling position on the metal support is preferably in the range of 10 to 150% by mass, and 20 to 40% by mass in order to improve the flatness of the obtained film. % Or in the range of 60 to 130% by mass, and more preferably in the range of 20 to 30% by mass or 70 to 120% by mass.

The amount of residual solvent in the web is defined by the following formula.

Residual solvent amount (%) = (mass before web heat treatment−mass after web heat treatment) / (mass after web heat treatment) × 100
Note that the heat treatment for measuring the residual solvent amount means a heat treatment at 115 ° C. for 1 hour.

A5) Drying and stretching step The web obtained by peeling from the metal support is dried as necessary and then stretched. The web may be dried while being conveyed by a large number of rollers arranged above and below, or may be dried while being conveyed while fixing both ends of the web with clips.

The method for drying the web may be a method of drying with hot air, infrared rays, a heating roller, microwaves, or the like, and a method of drying with hot air is preferable because it is simple.

The optical film having a desired retardation is obtained by stretching the web. The retardation of the optical compensation film can be controlled by adjusting the magnitude of tension on the web.

The web is stretched in one of the web width direction (TD direction), the transport direction (MD direction), and the diagonal direction.

When the optical film of the present invention is used as a λ / 4 retardation film for antireflection of an organic EL display device, it can be stretched at least in an oblique direction, specifically in a 45 ° direction with respect to the web conveyance direction. preferable.

A polarizing film unwound from the roll body by stretching in an oblique direction and having an absorption axis in the longitudinal direction, and an optical unwinding from the roll body and having a slow axis at an angle of 45 ° with respect to the longitudinal direction A circularly polarizing plate can be easily produced by simply laminating a film with a roll-to-roll so that the longitudinal directions overlap each other. The cut loss of the film can be reduced, which is advantageous in production.

The web may be stretched uniaxially or biaxially. Biaxial stretching may be sequential biaxial stretching or simultaneous biaxial stretching.

The draw ratio depends on the film thickness of the obtained optical film and the required retardation, but for example, the draw ratio in the biaxial direction perpendicular to each other is finally 0.8 to 1 in the casting direction. Within a range of 5 times, preferably within a range of 1.1 to 2.5 times in the width direction, within a range of 0.8 to 1.0 times in the casting direction, and 1.2 to 2 times in the width direction It is more preferable to be within the range of 2.0 times. The stretching ratio in the oblique direction is preferably in the range of 1.1 to 5.0 times, more preferably in the range of 1.2 to 2.5 times.

The draw ratio is represented by the ratio W / W0 of the film length in the drawing direction before and after stretching (W represents the length before stretching, and W0 represents the length after stretching). A draw ratio of 1.0 indicates that the film is not drawn.

The stretching temperature is preferably in the range of 120 to 230 ° C., more preferably in the range of 130 to 220 ° C., and even more preferably in the range of greater than 140 ° C. and 210 ° C. or less.

The stretching method of the web is not particularly limited, and a method of making a difference in circumferential speed between a plurality of rollers and stretching in the casting direction (conveying direction) using the circumferential speed difference (roller stretching method), both ends of the web Fix with clips and pins, widen the gap between clips and pins in the casting direction and stretch in the casting direction, spread in the width direction and stretch in the width direction, both in the casting direction and in the width direction It may be a method of expanding and stretching in both the casting direction and the width direction (tenter stretching method).

In order to extend in the oblique direction, a tenter that can independently control the web gripping length (distance from the start of gripping to the end of gripping) left and right by gripping means that grips the left and right in the width direction may be used. These stretching methods may be combined.

Examples of the stretching apparatus having a mechanism for stretching in an oblique direction include the stretching apparatus described in Example 1 of Japanese Patent Laid-Open No. 2003-340916, the stretching apparatus illustrated in FIG. The stretching apparatus described in 2007-30466 and the stretching apparatus used in Example 1 of Japanese Patent Laid-Open No. 2007-94007 are included.

The residual solvent of the web at the start of stretching is preferably 20% by mass or less, more preferably 15% by mass or less.

The film after stretching is dried as necessary and then wound. As described above, the film may be dried while being transported by a large number of rollers arranged on the top and bottom (roller method), or may be dried while being transported while fixing both ends of the web with clips. (Tenter method).

[5.2] Melt casting film forming method The optical film of the present invention can also be formed by a melt casting film forming method.

The method of producing the optical film of the present invention by the melt casting film forming method is as follows: B1) Step of producing molten pellet (pelletizing step), B2) Step of extruding after melting and kneading the molten pellet (melt extrusion step), B3) a step of cooling and solidifying the molten resin to obtain a web (cooling solidification step), and B4) a step of stretching the web (stretching step).

B1) Pelletizing step The resin composition containing the resin as the main component of the optical film and the compound having the structure represented by the general formula (A) according to the present invention is preferably kneaded and pelletized in advance. . Pelletization can be performed by a known method. For example, a resin composition containing the above-described resin and, if necessary, an additive such as a plasticizer, is melt-kneaded in an extruder, and then stranded from a die. Extrude into a shape. The molten resin extruded in a strand form can be cooled with water or air, and then cut to obtain pellets.

In order to prevent decomposition of the compound having a structure represented by the general formula (A) according to the present invention, it is preferable to dry the pellet raw material before supplying it to the extruder.

Moreover, when using an antioxidant, the mixture of the antioxidant and the resin may be mixed with each other, or the resin may be impregnated with an antioxidant dissolved in a solvent, You may spray and mix antioxidant in resin. The atmosphere around the feeder portion of the extruder and the outlet portion of the die is preferably an atmosphere of dehumidified air or nitrogen gas in order to prevent deterioration of the raw material of the pellet.

In the extruder, low shear force or low so as not to cause degradation of the resin (decrease in molecular weight, coloring, gel formation, etc.) or decomposition of the compound having the structure represented by the general formula (A) according to the present invention. It is preferable to knead at a temperature. For example, when kneading with a twin-screw extruder, it is preferable to use a deep groove type screw so that the rotational directions of the two screws are the same. In order to knead uniformly, it is preferable that two screw shapes mesh with each other.

The resin composition containing the resin and the compound having the structure represented by the general formula (A) according to the present invention is not pelletized, and is not melt-kneaded and represented by the general formula (A) according to the present invention. An optical film may be produced by using a compound having a structure as it is as a raw material and then melt-kneading with an extruder.

B2) Melt Extrusion Step The obtained molten pellets and other additives as necessary are supplied from the hopper to the extruder. The supply of pellets is preferably performed under vacuum, reduced pressure, or an inert gas atmosphere in order to prevent oxidative decomposition of the pellets. Then, in an extruder, melt pellets that are film materials and, if necessary, other additives are melt-kneaded.

Although the melting temperature of the film material in the extruder depends on the type of the film material, it is preferably in the range of Tg to (Tg + 100 ° C.), more preferably, when the glass transition temperature of the film is Tg (° C.). Is in the range of (Tg + 10 ° C.) to (Tg + 90 ° C.).

Furthermore, when additives such as plasticizers and fine particles are added in the middle of the extruder, a mixing device such as a static mixer is further arranged on the downstream side of the extruder to uniformly mix these components. May be.

The molten resin extruded from the extruder is filtered through a leaf disc filter or the like as necessary, and further mixed with a static mixer or the like, and extruded from a die into a film.

The extrusion flow rate is preferably stabilized using a gear pump. Moreover, it is preferable that the leaf disk filter used for removal of a foreign material is a stainless fiber sintered filter. The stainless steel fiber sintered filter is an integrated, intricately intertwined stainless steel fiber body that is compressed and sintered by integrating the contact points. The density is changed according to the thickness of the fiber and the amount of compression, and the filtration accuracy is adjusted. it can.

The melting temperature of the resin at the exit of the die can be in the range of about 200-300 ° C.

B3) Cooling and solidifying step The resin extruded from the die is nipped between the cooling roller and the elastic touch roller to make the film-like molten resin a predetermined thickness. Then, the film-like molten resin is cooled and solidified stepwise by a plurality of cooling rollers.

The surface temperature of the cooling roller can be Tg or less, where Tg is the glass transition temperature of the obtained film. The surface temperatures of the plurality of cooling rollers may be different.

The elastic touch roller is also called a pinching rotary body. A commercially available elastic touch roller can also be used. The film surface temperature on the elastic touch roller side can be in the range of Tg to (Tg + 110 ° C.) of the film.

The film-like molten resin solidified from the cooling roller is peeled off with a peeling roller or the like to obtain a web. When peeling the film-like molten resin, it is preferable to adjust the tension in order to prevent deformation of the obtained web.

B4) Stretching step The obtained web is stretched with a stretching machine to obtain a film. Stretching is performed in any of the web width direction, the conveyance direction, or the oblique direction.

When the optical film of the present invention is used as a λ / 4 retardation film for antireflection of an organic EL display device, it can be stretched at least in an oblique direction, specifically in a 45 ° direction with respect to the web conveyance direction. preferable.

The web stretching method, stretching ratio and stretching temperature are preferably the same as in the solution casting film forming method.

[6] Application example of optical film [6.1] Polarizing plate The optical film of the present invention is used for a liquid crystal display device or an organic EL display as a polarizing plate of the present invention and a display device of the present invention using the polarizing film. Can do. The optical film of the present invention can be used as a polarizing plate protective film or a retardation film. In the case of a retardation film, it is preferable that the film also serves as a polarizing plate protective film. In that case, it is not necessary to prepare an optical film having a retardation separately from the polarizing plate protective film. The thickness can be reduced and the manufacturing process can be simplified.

In the case of a polarizing plate protective film used on the surface side of a liquid crystal display device, it is preferable to have an antireflection layer, an antistatic layer, an antifouling layer, and a backcoat layer in addition to an antiglare layer or a clear hard coat layer.

A polarizer, which is a main component of a polarizing plate, is an element that allows only light of a plane of polarization in a certain direction to pass. A typical polarizer currently known is a polyvinyl alcohol-based polarizing film, which is polyvinyl alcohol. There are one in which iodine is dyed on a system film and one in which dichroic dye is dyed.

The polarizer is formed by forming a polyvinyl alcohol aqueous solution into a film and dyeing the film by uniaxial stretching or dyeing or uniaxially stretching, and then performing a durability treatment with a boron compound. The thickness of the polarizer is preferably in the range of 5 to 30 μm, particularly preferably in the range of 10 to 20 μm.

The polarizing plate according to the present invention can be produced by a general method. The optical film of the present invention is preferably bonded to at least one surface of a polarizer prepared by subjecting the polarizer side of the optical film to alkali saponification treatment and immersion drawing in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. .

Moreover, it is also preferable to bond the optical film of the present invention to the polarizer using an adhesive or a pressure-sensitive adhesive. In that case, curable adhesives such as active energy ray-curable adhesives, urethane adhesives, epoxy adhesives, aqueous polymer-isocyanate adhesives, thermosetting acrylic adhesives, moisture-curing urethane adhesives, An anaerobic adhesive such as polyether methacrylate type, ester methacrylate type, and oxidized polyether methacrylate, cyanoacrylate instantaneous adhesive, acrylate and peroxide type two-component instantaneous adhesive, and the like can be used. The pressure-sensitive adhesive may be a one-component type or a two-component type in which two or more components are mixed before use. The adhesive may be a solvent system using an organic solvent as a medium, or an aqueous system such as an emulsion type, a colloidal dispersion liquid type, or an aqueous solution type that is a medium containing water as a main component, or a solvent-free type. It may be a mold. The concentration of the adhesive solution may be appropriately determined depending on the film thickness after bonding, the coating method, the coating conditions, and the like, and is usually 0.1 to 50% by mass.

On the other side, the optical film of the present invention or other polarizing plate protective film can be bonded. When the optical film of the present invention is provided in a liquid crystal display device, the optical film is preferably disposed on the surface of the polarizer opposite to the liquid crystal cell. In this case, the film is bonded to the other surface of the polarizer. A conventional polarizing plate protective film or retardation film can be used.

For example, as a conventional polarizing plate protective film, a commercially available cellulose ester film (for example, Konica Minoltack KC8UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC6UY, KC4UY, KC4UE, KC8UE-HA, KC8UY-HA, HAC KC8UXW-RHA-C, KC8UXW-RHA-NC, KC4UXW-RHA-NC, manufactured by Konica Minolta Co., Ltd.) are preferably used.

[6.2] Liquid Crystal Display Device By using a polarizing plate using the optical film of the present invention for a liquid crystal display device, various display devices of the present invention having excellent visibility can be produced.

The optical film and polarizing plate of the present invention can be used in liquid crystal display devices of various drive systems such as STN, TN, OCB, HAN, VA (MVA, PVA), IPS, OCB.

In particular, it is preferably used for VA (MVA, PVA) type liquid crystal display devices and IPS type liquid crystal display devices.

In particular, even a large-screen liquid crystal display device having a 30-inch or larger screen can reduce coloration during black display due to light leakage and can provide a liquid crystal display device with excellent visibility such as front contrast.

As described above, the optical film of the present invention is a polarizing plate protective film on the LED backlight side or the surface side of the liquid crystal display device when the liquid crystal display device has two polarizing plates with the liquid crystal cell sandwiched therebetween. It is preferable to arrange as a polarizing plate protective film.

[6.3] Organic electroluminescence display device The optical film of the present invention can be suitably used for an organic electroluminescence (EL) display device.

The organic EL display device is a display device using an organic EL element. An organic EL element is an element including an organic light emitting material that emits light by current injection from a pair of electrodes. The energy when electrons injected from the cathode and holes injected from the anode are recombined in the organic light emitting material is taken out as light.

The organic EL display device has a sealing material, a light reflecting electrode, a light emitting layer, a transparent electrode layer, and a transparent substrate in this order, and the optical film of the present invention has a surface opposite to the light emitting layer of the transparent substrate. It is preferable to be used as the transparent substrate.

The sealing material has a function of protecting an organic layer such as a light emitting layer by blocking oxygen and moisture from the outside, and a material having extremely small oxygen permeability, moisture permeability, etc., such as aluminum foil is used. .

The light reflecting electrode is preferably made of a metal material having a high light reflectance. Examples of the metal material include Mg, MgAg, MgIn, Al, LiAl, and the like. The flatter surface of the light reflecting electrode is preferable because irregular reflection of light can be prevented.

The light reflecting electrode can be formed by a sputtering method. The light reflecting electrode may be patterned. Patterning is performed by etching.

The light emitting layer includes R (red), G (green) and B (blue) light emitting layers. Each light emitting layer contains a light emitting material. The light emitting material may be an inorganic compound or an organic compound, and is preferably an organic compound.

Each of the R, G, and B light emitting layers may further include a charge transport material and further have a function as a charge transport layer. Each of the R, G, and B light emitting layers further includes a hole transport material, and may further have a function as a hole transport layer. When each of the R, G, and B light emitting layers does not include a charge transport material or a hole transport material, the organic EL display device may further include a charge transport layer or a hole transport layer.

The light emitting layer can be formed by evaporating a light emitting material. Each of the R, G, and B light emitting layers is obtained by patterning. Patterning can be performed using a photomask or the like.

The transparent electrode layer can generally be an ITO (indium tin oxide) electrode. The transparent electrode layer 16 can be formed by a sputtering method or the like. The transparent electrode layer 16 may be patterned. Patterning can be performed by etching. The light emitted from the organic EL is extracted from this side.

The transparent substrate may be any material that can transmit light, and may be a glass substrate, a plastic film, or the like.

When the organic EL display device is energized between the light reflecting electrode and the transparent electrode layer, the light emitting layer emits light and can display an image. In addition, since each of the R, G, and B light-emitting layers is configured to be energized, a full-color image can be displayed.

The optical film of the present invention includes not only the organic EL display device having the above-described configuration, but also the organic EL display device described in International Patent Application Nos. 96/34514, JP-A Nos. 9-127585 and 11-45058. It can also be applied to.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented.

[1] Production of optical film [Production of optical film 101]
The following components were stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin to prepare a fine particle dispersion.

(Fine particle dispersion)
Fine particles (Aerosil R972V manufactured by Nippon Aerosil Co., Ltd.):
11 parts by mass Ethanol: 89 parts by mass Of the components of the following fine particle addition liquid, dichloromethane was charged into the dissolution tank, and the prepared fine particle dispersion was slowly added in the following addition amount with sufficient stirring. Subsequently, after being dispersed with an attritor so that the particle size of the secondary particles of the fine particles becomes a predetermined size, the fine particles are filtered through Finemet NF (manufactured by Nippon Seisen Co., Ltd.) to obtain a fine particle additive solution. .

(Particulate additive solution)
Dichloromethane: 99 parts by mass Fine particle dispersion: 5 parts by mass Of the following dope components, dichloromethane and ethanol were charged into a pressurized dissolution tank. Next, the following cellulose ester, Exemplified Compound 1 having the structure represented by the general formula (1), sugar ester S and the prepared fine particle additive solution were added with stirring, and heated and stirred to completely dissolve. The obtained solution was used as Azumi filter paper No. manufactured by Azumi Filter Paper Co., Ltd. Using 244, the dope 1 was prepared by filtration.

(Preparation of dope 1)
Dichloromethane: 520 parts by mass Ethanol: 45 parts by mass Cellulose ester (cellulose acetate (TAC): degree of acetyl group substitution 2.80, weight average molecular weight 200,000) 100 parts by mass Exemplary compound 1: 0.1 part by mass Sugar ester S: 5 Part by mass Particulate additive solution: 1 part by mass The structure of sugar ester S added as a plasticizer is shown below.

得られたドープを、無端ベルト流延装置を用いて、ステンレスベルト支持体上に均一に流延させた。ステンレスベルト支持体上で、流延（キャスト）したドープ膜中の溶媒を、残留溶媒量が７５質量％になるまで蒸発させ、得られたウェブをステンレスベルト支持体上から剥離した。剥離したウェブを、テンター延伸装置のクリップで把持しながら搬送した。次いで、得られたフィルムを、乾燥ゾーン内で、多数のローラーで搬送させながら乾燥させた。テンタークリップで把持していたフィルムの幅方向端部をレーザーカッターでスリット除去した後、巻き取って原反フィルムを得た。

The obtained dope was uniformly cast on a stainless belt support using an endless belt casting apparatus. On the stainless steel belt support, the solvent in the dope film cast (cast) was evaporated until the residual solvent amount became 75% by mass, and the obtained web was peeled from the stainless steel belt support. The peeled web was conveyed while being gripped by a clip of a tenter stretching apparatus. Next, the obtained film was dried while being conveyed by a number of rollers in a drying zone. The width direction end of the film held by the tenter clip was slit-removed with a laser cutter, and then wound up to obtain an original film.

The obtained raw film was unwound and stretched in the width direction of the film at a stretching temperature of glass transition temperature Tg + 20 ° C. and a stretching ratio of 1.10 times to obtain an optical film 101. The film thickness of the optical film 101 was 50 μm.

[Production of optical films 102 to 108]
Optical films 102 to 108 were produced in the same manner as in the production of the optical film 101 except that Exemplified Compound 1 was replaced with the compounds described in Table I.
[Production of optical film 109]
An optical film 109 was produced using the dope 2 in the same manner except that the preparation of the dope 1 was changed as follows.

(Preparation of dope 3)
Dichloromethane: 520 parts by mass Ethanol: 45 parts by mass Cellulose ester (cellulose acetate: acetyl group substitution degree 2.80)
, Weight average molecular weight 200,000) 100 parts by weight Sugar ester S: 5 parts by weight Exemplary compound 39: 0.1 part by weight Exemplary compound 129: 0.1 part by weight Particulate additive solution: 1 part by weight [Preparation of optical films 110 and 111 ]
Optical films 110 and 111 were prepared in the same manner as in the production of the optical film 101 except that the exemplified compound 1 was replaced with the following comparative compound 1 or 2.

[Preparation of optical film 112]
In the production of the optical film 109, the optical film 112 was produced in the same manner except that the exemplified compound 39 and the exemplified compound 129 were replaced with the following comparative compound 1 and comparative compound 2 (described in JP-A-2015-36796). .

〔光学フィルム１１３の作製〕
　〈アクリル共重合体の合成〉
　攪拌機を備えた内容積４０リットルのＳＵＳ製重合反応装置に、脱イオン水２４リットルを入れ、分散安定剤としてアニオン系高分子化合物水溶液３０ｇ、分散安定助剤として硫酸ナトリウム３６ｇを加え攪拌・溶解させた。また、別の攪拌機を備えた容器に、メタクリル酸メチル９６００ｇ、メタクリル酸イソボルニル２４００ｇの単量体混合物に、重合開始剤として２，２′－アゾビスイソブチロニトリル１２ｇ、連鎖移動剤としてｎ－オクチルメルカプタン２４ｇ、離型剤としてステアリルアルコール２４ｇを加え攪拌・溶解させた。このようにして得られた重合開始剤、連鎖移動剤及び離形剤を溶解した単量体混合物を、上述した攪拌機を備えた内容積４０リットルのＳＵＳ製重合反応装置（脱イオン水、分散安定剤及び分散安定助剤を収容する）に投入し、窒素置換しながら１７５ｒｐｍで１５分間攪拌した。その後、８０℃に加温して重合を開始させ、重合発熱ピーク終了後、１１５℃で１０分間の熱処理を行い、重合を完結させた。得られたビーズ状重合体を濾過、水洗し、８０℃で２４ｈｒ乾燥し、メタクリル酸メチルとメタクリル酸イソボルニルのアクリル共重合体（重量平均分子量１５万）を得た。

[Preparation of optical film 113]
<Synthesis of acrylic copolymer>
In a 40-liter SUS polymerization reactor equipped with a stirrer, 24 liters of deionized water was added, and 30 g of an anionic polymer compound aqueous solution as a dispersion stabilizer and 36 g of sodium sulfate as a dispersion stabilizer were added and stirred and dissolved. It was. Further, in a container equipped with another stirrer, a monomer mixture of 9600 g of methyl methacrylate and 2400 g of isobornyl methacrylate, 12 g of 2,2′-azobisisobutyronitrile as a polymerization initiator, and n-as a chain transfer agent. 24 g of octyl mercaptan and 24 g of stearyl alcohol as a release agent were added and stirred and dissolved. The monomer mixture in which the polymerization initiator, the chain transfer agent and the release agent thus obtained were dissolved was converted into a 40-liter SUS polymerization reaction apparatus (deionized water, dispersion-stabilized) equipped with the stirrer described above. Containing the agent and the dispersion stabilizing aid) and stirred at 175 rpm for 15 minutes while purging with nitrogen. Thereafter, the polymerization was started by heating to 80 ° C., and after completion of the polymerization exothermic peak, a heat treatment was performed at 115 ° C. for 10 minutes to complete the polymerization. The obtained bead polymer was filtered, washed with water, and dried at 80 ° C. for 24 hours to obtain an acrylic copolymer of methyl methacrylate and isobornyl methacrylate (weight average molecular weight 150,000).

(Preparation of dope 4)
Acrylic copolymer (MMA 80% by mass and isobornyl methacrylate 20
100% by weight Copolymer) 100 parts by weight Exemplary compound 37: 0.1 part by weight Matting agent: R972V (manufactured by Nippon Aerosil Co., Ltd., silica particles, average particle size = 16 nm) 0.3 part by weight Peeling aid: ELECUT S412 (manufactured by Takemoto Yushi Co., Ltd.) 0.5 parts by mass Dichloromethane 300 parts by mass Ethanol 40 parts by mass Using the belt casting apparatus, uniformly cast the dope 4 on a stainless steel band support at a temperature of 22 ° C. and a width of 2 m. did. With the stainless steel band support, the solvent was evaporated until the residual solvent amount reached 100%, and the web was peeled off from the stainless steel band support with a peeling tension of 162 N / m.

Next, the peeled web was evaporated at 35 ° C., and the solvent was slit to 1 m width, then 1.1 times in the transport direction (MD direction) by zone stretching, and 1. in the width direction (TD direction) by tenter stretching. It was made to dry at 135 degreeC drying temperature, extending | stretching 1 time. At this time, the residual solvent amount when starting stretching with the tenter was 8 mass%.

After stretching with a tenter, relaxation treatment is performed at 130 ° C. for 5 minutes, and then drying is completed while transporting a drying zone at 120 ° C. and 140 ° C. with a large number of rollers. did. The film thickness was 40 μm.

[Production of optical films 114 and 115]
Optical films 114 and 115 were produced in the same manner as in the production of the optical film 113 except that the exemplified compound 37 was replaced with the compounds described in Table I.

[Preparation of optical film 116]
(Preparation of fine particle dispersion and additive liquid)
11.3 parts by mass of fine particles (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd.) and 84 parts by mass of ethanol were stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin.

5 parts by mass of the fine particle dispersion was slowly added to dichloromethane (100 parts by mass) that was sufficiently stirred in the dissolution tank. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered with Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution.

(Preparation of dope 5)
A dope 5 having the following composition was prepared. First, dichloromethane and ethanol were added to the pressure dissolution tank. A cycloolefin resin, an additive, and a fine particle additive solution were added to a pressure dissolution tank containing dichloromethane with stirring. This was heated and completely dissolved with stirring, and this was dissolved in Azumi filter paper No. 1 manufactured by Azumi Filter Paper Co., Ltd. The dope 5 was prepared by filtration using 244.

(Preparation of dope 5)
Cycloolefin resin (ARTON G7810, manufactured by JSR Corporation: Table I)
100 parts by mass Dichloromethane 200 parts by mass Ethanol 10 parts by mass Exemplified compound 37: 0.1 part by mass Particulate additive solution 3 parts by mass Next, using an endless belt casting apparatus, the dope is made at a temperature of 31 ° C. and a width of 1800 mm. It was cast uniformly on a stainless belt support. The temperature of the stainless steel belt was controlled at 28 ° C. The conveyance speed of the stainless steel belt was 20 m / min.

The solvent was evaporated on the stainless steel belt support until the amount of residual solvent in the cast film was 30% by mass. Subsequently, it peeled from the stainless steel belt support body with the peeling tension of 128 N / m. The peeled film was stretched 1.1 times in the width direction at 160 ° C. The residual solvent at the start of stretching was 5% by mass. Next, drying was completed while transporting the drying zone with a large number of rollers, and the end sandwiched between tenter clips was slit with a laser cutter, and then wound up to obtain an optical film 116 with a film thickness of 40 μm.

[Preparation of optical films 117 and 118]
Optical films 117 and 118 were produced in the same manner as in the production of the optical film 116 except that the exemplified compound 37 was replaced with the compounds described in Table I.

[Production of Optical Film 119]
<Synthesis of polycarbonate>
Polycarbonate PC-1 was produced by the interfacial polymerization method at the following monomer ratio.

(Synthesis of polycarbonate PC-1)
A polycarbonate having a bisphenol component consisting only of 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as BisA) was synthesized by interfacial polymerization.

The obtained polycarbonate was heated at 25 ° C. to 350 ° C. under a nitrogen stream (20 ml / min) at a rate of temperature increase of 10 ° C./min using DSC220, and then immediately cooled immediately to obtain a sample. The glass transition temperature was measured according to JIS K 7121 at the same rate of temperature increase. As a result, the glass transition temperature of this polycarbonate was 154 ° C.

Moreover, as a result of measuring the weight average molecular weight of the polycarbonate according to the following measurement method, it was 60000, and the content of components having a weight average molecular weight of 1000 or less was 4% by mass from the profile.

An optical film 119 was produced in the same manner as in the production of the optical film 116, except that the same amount of the obtained polycarbonate (PC-1) was used instead of the cycloolefin resin.
[Production of optical films 120 and 121]
Optical films 120 and 121 were produced in the same manner as in the production of the optical film 119 except that the exemplified compound 37 was replaced with the compounds described in Table I.
[Preparation of optical film 122]
<Preparation of polyimide solution A>
To a 4-neck flask equipped with a dry nitrogen gas inlet tube, a condenser, a Dean-Stark agglomerator filled with toluene, and a stirrer, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1, 25,59 g (57.6 mmol) of 3,3,3-hexafluoropropane dianhydride (acid anhydride: manufactured by Daikin Industries, Ltd.) was added to N, N-dimethylacetamide (134 g) at room temperature under a nitrogen stream. Stir.

Then, 19.2 g (60 mmol) of 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl (diamine: manufactured by Daikin Industries, Ltd.) was added, and the mixture was heated and stirred at 80 ° C. for 6 hours. Thereafter, the external temperature was heated to 190 ° C., and water generated along with imidization was distilled off azeotropically with toluene. When heating, refluxing, and stirring were continued for 6 hours, generation of water was not observed. Subsequently, the mixture was heated for 7 hours while distilling off toluene, and after methanol was distilled off, methanol was added for reprecipitation, and the solid content was dried and converted into an 8% by mass dichloromethane solution to prepare polyimide solution A containing polyimide resin A. did.

(Preparation of dope 6)
A dope 6 having the following composition was prepared. First, dichloromethane (boiling point 40 ° C.) was added to the pressure dissolution tank. The prepared polyimide solution A and the remaining components were charged into a pressure dissolution tank containing a solvent while stirring. While this was heated and stirred, it was completely dissolved, and this was dissolved in Azumi Filter Paper No. The dope 6 was prepared by filtering using 244.

(Preparation of dope 6)
Dichloromethane 350 parts by weight Polyimide solution A 100 parts by weight as solid content Exemplary compound 37: 0.1 part by weight Matting agent (Aerosil R812, manufactured by Nippon Aerosil Co., Ltd.)
0.5 parts by mass Next, an endless belt casting apparatus was used to uniformly cast the dope on a stainless steel belt support at a temperature of 30 ° C. and a width of 1500 mm. The temperature of the stainless steel belt was controlled at 30 ° C.

On the stainless steel belt support, the solvent was evaporated until the amount of residual solvent in the cast film cast was 75%, and then peeled off from the stainless steel belt support with a peeling tension of 180 N / m. .

In the first drying step, the peeled cast film was dried at a first drying temperature of 200 ° C. so that the amount of residual solvent at the start of stretching became a desired value to obtain a film.

Next, the dried film was heated at 120 ° C. and stretched 1.1 times in the width direction using a clip type tenter. The residual solvent amount at the start of stretching was 10% by mass.

The stretched film was dried at a second drying temperature of 120 ° C. until the residual solvent amount was less than 0.5% by mass with a transport tension of 100 N / m and a drying time of 15 minutes, to obtain a polyimide film having a dry film thickness of 62 μm. . The obtained polyimide film was wound up to obtain an optical film 122.

[Production of optical films 123 and 124]
Optical films 123 and 124 were produced in the same manner as in the production of the optical film 122 except that the exemplified compound 37 was replaced with the compounds described in Table I.

[2] Production of polarizing plate [2.1] Production of polarizing plate with water glue (Production of polarizer)
A 70 μm thick polyvinyl alcohol film was swollen with water at 35 ° C. The obtained film was immersed in an aqueous solution consisting of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and further immersed in an aqueous solution at 45 ° C. consisting of 3 g of potassium iodide, 7.5 g of boric acid and 100 g of water. . The obtained film was uniaxially stretched under conditions of a stretching temperature of 55 ° C. and a stretching ratio of 5 times. The uniaxially stretched film was washed with water and dried to obtain a polarizer having a thickness of 20 μm.

(Preparation of polarizing plate)
The produced optical films 101 to 112 were prepared, and the surface thereof was subjected to corona discharge treatment. The corona discharge treatment was performed at a corona output intensity of 2.0 kW and a line speed of 18 m / min. Next, a 3% aqueous solution of polyvinyl alcohol (PVA-117H manufactured by Kuraray) is used as an adhesive on the corona discharge-treated surface of the film, and the adhesive layer is coated with a bar coater so that the film thickness after curing is about 3 μm. Formed. The polyvinyl alcohol-iodine polarizer was bonded to the obtained adhesive layer. On the other surface of the polarizer, Konica Minolta KC4UE manufactured by Konica Minolta Co., Ltd. was bonded to produce a polarizing plate.

[2.2] Preparation of polarizing plate with UV curable adhesive (Preparation of UV curable adhesive liquid)
Each of the following components was mixed and then defoamed to prepare an ultraviolet curable adhesive solution. Triarylsulfonium hexafluorophosphate was blended as a 50% propylene carbonate solution, and the solid content of triarylsulfonium hexafluorophosphate was shown below.

3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 45 parts by mass Epolide GT-301 (Daicel's alicyclic epoxy resin)
40 parts by mass 1,4-butanediol diglycidyl ether 15 parts by mass Triarylsulfonium hexafluorophosphate 2.3 parts by mass 9,10-dibutoxyanthracene 0.1 parts by mass 1,4-diethoxynaphthalene 2.0 parts by mass The produced optical films 113 to 124 were prepared, and the surface thereof was subjected to corona discharge treatment. The corona discharge treatment was performed at a corona output intensity of 2.0 kW and a line speed of 18 m / min. Next, an adhesive layer was formed on the corona discharge-treated surface of the film by coating with a bar coater so that the film thickness after curing was about 3 μm as the ultraviolet curable adhesive. The polyvinyl alcohol-iodine polarizer was bonded to the obtained adhesive layer. Similarly, Konica Minolta Konica Minolta KC4UE manufactured by Konica Minolta Co., Ltd. was bonded to the other surface of the polarizer to produce a polarizing plate.

Next, UV light is irradiated from both sides of the bonded laminate using an ultraviolet irradiation device with a belt conveyor (the lamp uses a D bulb manufactured by Fusion UV Systems) so that the integrated light quantity becomes 750 mJ / cm 2. Then, the ultraviolet curable adhesive layer was cured.

[3] Production of liquid crystal display device In order to evaluate the characteristics of the produced polarizing plate, the front and back surfaces of the liquid crystal panel of Hitachi Ltd. liquid crystal television (Woooo W32-L7000) in the IPS mode are arranged on the viewer side. The polarizing plate and the retardation film are peeled off, and the transmission axis of the polarizing plate originally bonded to the light source side (rear side) and the viewing side (front side) is respectively attached to the peeled portion. In the same manner as above, an acrylic transparent adhesive was used for bonding. At that time, the optical films 101 to 124 were arranged so that the front side polarizing plate was on the viewer side and the light source side polarizing plate was on the light source side.

From the above, the liquid crystal display devices 101 to 124 corresponding to the optical films 101 to 124 were produced, and the following evaluations were performed.
≪Evaluation≫
<Haze>
About each optical film immediately after preparation, haze value (%) was measured using the haze meter (NDH2000, Nippon Denshoku Industries Co., Ltd.), and the following references | standards evaluated.

A: 0.5 or less O: More than 0.5 and 1.5 or less ×: Greater than 1.5 If it is more than 1.5, there is no practical problem.

<Light Absorption Rate at Absorption Maximum Peak Wavelength>
For each optical film immediately after production, the light absorption rate (%) at the absorption maximum peak wavelength in the light wavelength range of 480 to 520 nm or in the range of 580 to 620 nm was determined as follows.

Optical absorptance (%) of absorption maximum peak wavelength in light wavelength range of 480 to 520 nm or 580 to 620 nm
= 100 − {(Spectral transmittance of absorption maximum peak wavelength in light wavelength range of 480 to 520 nm or 580 to 620 nm) − (Spectrum of absorption maximum peak wavelength in range of light wavelength of 480 to 520 nm or 580 to 620 nm) Reflectance)}
Spectral transmittance and spectral reflectance were measured using an ultraviolet-visible near-infrared spectrophotometer V-670 manufactured by JASCO Corporation and evaluated according to the following criteria.

A: 80% or more B: 20% or more and 80% or less B: Less than 20% B

After setting the temperature inside the temperature-controlled room to be 23 ° C. and 55% RH so that the temperature of the optical film as the measurement object is 23 ° C., the optical film is left in the temperature-controlled room for 3 hours to be in an equilibrium state, The above measurements were made.

<Durability visibility (bleed out)>
For each of the manufactured liquid crystal display devices, the liquid crystal display device after storage for 500 hours before storage (temperature 23 ° C., humidity 55% RH) and in a high temperature and high humidity environment (temperature 60 ° C., humidity 90% RH) is 2 The chromaticity in the CIE1931 color system when white is displayed at a viewing angle of 1000 cd / m2 is measured using a spectral radiance meter CS-1000 (manufactured by Konica Minolta Co., Ltd.), before and after storage. The chromaticity change amounts Δx and Δy in the chromaticity space were obtained and evaluated according to the following criteria.

◎: Δx and Δy are 0.03 or less ○: Δx and Δy are more than 0.03 and 0.05 or less ×: Δx and Δy are larger than 0.05 ○ If it is more than ○, there is no practical problem. .

<Visibility from oblique direction: Color shift>
The liquid crystal display device before the storage is similarly displayed in white, the chromaticity in the CIE1931 color system is measured from the front direction and the oblique 45 degree direction, and the chromaticity change amounts Δx and Δy in the XY chromaticity space are measured. Evaluation was made according to the following criteria.

◎: Δx and Δy are 0.03 or less ○: Δx and Δy are more than 0.03 and 0.05 or less ×: Δx and Δy are larger than 0.05 ○ If it is more than ○, there is no practical problem. .

The structure and evaluation results of the optical film are shown in Table I below.

From Table I, an optical film using the resin according to the present invention and a compound having a structure represented by general formula (A) or general formula (1) to general formula (3) is an optical film using a comparative compound. On the other hand, it can be seen that bleed-out is suppressed, the color is not transparent, the color unevenness is small, and the color reproducibility (color shift) in the oblique direction is excellent.

The optical film of the present invention is an optical film containing a compound that absorbs light of a specific wavelength, and even when placed in a high-temperature and high-humidity environment, the bleed-out of the compound is suppressed, and it is transparent and small in color unevenness. And since it is excellent also in the color reproducibility (color shift) of an oblique direction, it is utilized suitably for a polarizing plate and a display apparatus.

101 Melting pot 103, 106, 112, 115 Filter 104, 113 Stock pot 102, 105, 111, 114 Liquid feed pump 108, 116 Conduit 110 Additive charging pot 120 Merge pipe 121 Mixer 130 Pressure die 131 Metal belt 132 Web 133 Peeling position 134 First drying device 135 Stretching device 136 Second drying device 138 Winding device 141 Charging pot 142 Stock kettle 143 Pump 144 Filter

Claims (11)

An optical film comprising a resin having a solubility in dichloromethane at 23 ° C. in the range of 5 to 50% by mass and a compound having a structure represented by the following general formula (A).

(Wherein R ₁ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, or aryl group having 3 to 20 carbon atoms. R ₂ and R ₃ each independently represents a hydrogen atom or a halogen atom. Represents an atom, a substituted or unsubstituted alkyl group, or an alkoxycarbonyl group, Z is an atomic group necessary for forming a 5- or 6-membered ring with a nitrogen atom, and may have a substituent; Y may form a condensed ring, and Y is an atomic group necessary for forming a 5- or 6-membered ring together with a carbonyl group, may have a substituent, or may form a condensed ring. (N represents an integer of 1 to 2. m is an integer of 1 to 4 and is an integer of n or more.) 2. The optical system according to claim 1, wherein the compound having a structure represented by the general formula (A) is a compound having a structure represented by any of the following general formulas (1) to (3). the film.

(Wherein R ₁ to R ₄ each independently represents a hydrogen atom or a halogen atom, a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, acyl group, aryl group, heterocyclic ring, alkoxycarbonyl group, carbamoyl group) A group, an alkoxy group, an amide group, an amino group, a cyano group, a nitro group, a hydroxy group, a carboxy group or a sulfonic acid group, R ₁ and R ₂ , R ₂ and R ₃ , or R ₃ and R ₄ are bonded to each other. The ring formed may have a substituent, and R ₅ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group or aryl group having 3 to 20 carbon atoms. It represents .R ₆ and R ₇ each independently represent a hydrogen atom or a halogen atom, .X to represent a substituted or unsubstituted, alkyl group or alkoxycarbonyl group, O, N _8, S, or _.R 8 _{~ R 10} representing a _CR 9 _{R 10} represent each independently a hydrogen atom, a substituted or unsubstituted, alkyl group, alkenyl group, alkynyl group or an aryl group.
A ₁ is selected from the following structural formulas (A1-1) to (A1-10). )

(Wherein R ₁₁ to R ₁₆ have the same meanings as the groups represented by R ₁ to R ₄ in formula (1). X ₁ and X ₂ each independently represents an oxygen atom or a sulfur atom. (Connected to the general formula (1) at the wavy line)

(In the formula, R ₁ to R ₄ and R ₈ to R ₁₁ are synonymous with R ₁ to R ₄ in the general formula (1). R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R _{4, R 8} and _R 9, _{R 9} and _{R 10,} or _{R 10} and _{R 11} may be bonded to each other to form a ring, the formed ring may have a substituent .R ₅ and R ₁₂ is synonymous with R ₅ in general formula (1) R ₆ , R ₇ , R ₁₃ , and R ₁₄ are synonymous with R ₆ and R ₇ in general formula (1).
X represents O, NR ₁₅ , S, or CR ₁₆ R ₁₇ . R ₁₅ to R ₁₇ have the same meanings as R ₈ to R ₁₀ in the general formula (1).
B ₁ is selected from the following structural formulas (B1-1) to (B1-5). )

(In the formula, R ₁₈ and R ₁₉ are synonymous with the groups represented by R ₁ to R ₄ in the general formula (1). They are connected to the general formula (2) at the wavy line part.)

_(Wherein, R 1 ~ _{R 4} have the same meanings as in formula (1) _R 1 ~ _{R 4} in .R ₁ and _{R 2,} or _{R 3} and _{R 4} may combine with each other to form a ring well, the formed ring may have a substituent .R ₅ have the same meaning as _{R 5} in the general formula (1) .R ₆ and _{R 7,} the general formula (1) _{R 6} and in the same meaning as R ₇ .A ₁ has the same meaning as _{a 1} in formula (1).) The optical film according to claim 1 or 2, wherein in the general formula (1) and the general formula (3), A ₁ has a structure represented by the formula (A1-6). In Formula (2) The optical film according to claim 1 or 2 B ₁ is characterized by having a structure represented by the formula (B1-4). The optical system according to any one of claims 1 to 3, wherein, in the general formula (1) and the general formula (3), R ₅ represents a branched alkyl group having 4 to 16 carbon atoms. the film. 5. The general formula (2), wherein R ₅ and R ₁₂ represent a branched alkyl group having 4 to 16 carbon atoms, according to any one of claims 1, 2, and 4. Optical film. The compound having the structure represented by the general formula (1) to the general formula (3) has an absorption maximum peak in the wavelength range of 480 to 520 nm or in the wavelength range of 580 to 620 nm in the spectral absorption spectrum. The optical film according to any one of claims 1 to 6, wherein The optical film according to any one of claims 1 to 7, wherein the haze is in a range of 0.05 to 1.50%. An optical film manufacturing method for manufacturing the optical film according to any one of claims 1 to 8, wherein the optical film is manufactured by a solution casting film forming method. Manufacturing method. A polarizing plate comprising the optical film according to any one of claims 1 to 8 as a polarizing plate protective film. A display device comprising the optical film according to any one of claims 1 to 8.

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