JP2012224763A - Polymer, film, resin composition, and method for manufacturing the film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer and a film which have excellent light permeability, heat resistance, low coloring property and optical isotropy in a well-balanced manner.SOLUTION: The polymer has a structural unit represented by formula (1), wherein Rand Reach independently represent 1C-12C monovalent organic group having aliphatic hydrocarbon group or alicyclic hydrocarbon group, R-Reach independently represent 1C-12C monovalent organic group, a and b each independently represent an integer of 0-3, and c and d each independently represent an integer of 0-4.

Description

  The present invention relates to a polymer, a film, a resin composition, and a film production method.

In recent years, with the increase in size of liquid crystal displays, it has become necessary to increase the size of optical films such as retardation films and films for deflecting plates.
However, when the optical film is increased in size, the bias of external force is likely to occur. Therefore, a film made of a material having a large absolute value such as a photoelastic coefficient and a stress optical coefficient is likely to have a birefringence distribution and the contrast is not uniform. Prone. Therefore, development of an optical film having a small absolute value such as a photoelastic coefficient and a stress optical coefficient is desired.

  Further, such an optical film is also required to be excellent in heat resistance, mechanical strength and transparency, and a polymer corresponding to the characteristics required for the film is used. A typical transparent resin is polymethyl methacrylate (PMMA). PMMA is excellent in light transmittance, optical isotropy, and moldability, and has been used for films and lenses. On the other hand, heat resistance is low, and there is a problem that the application to be used is limited.

  Polycarbonate (PC) etc. are mentioned as resin excellent in heat resistance from PMMA. However, the film made of PC has a problem that the optical isotropy is lowered due to the influence of the aromatic ring forming the main chain skeleton of PC.

  Although these PMMA and PC are excellent in transparency, their glass transition temperature is low and their heat resistance is insufficient, so that they are difficult to use for applications requiring high heat resistance. Moreover, since it contains a hydrolyzable polar group, there is a limitation during secondary processing of the product with acid, alkali, or the like.

  Reaction of 9,9-bis (4-hydroxyphenyl) fluorene with various bisphenols and / or 2,6-dihalogenated benzonitrile as a polymer with excellent heat resistance and mechanical strength and excellent transparency Aromatic polyethers (Patent Documents 1 and 2) obtained by the above are proposed.

JP 2007-246629 A Japanese Patent Laid-Open No. 2-45526

However, films containing these aromatic polyethers sometimes have large absolute values such as photoelastic coefficient and stress optical coefficient.
The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a polymer and a film which are excellent in light transmittance, heat resistance, low colorability and optical isotropy in a good balance.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be achieved by a polymer having a specific structural unit, and have completed the present invention.
That is, the present invention provides the following [1] to [12].

  [1] A polymer having a structural unit represented by the following formula (1).

（式（１）中、Ｒ¹およびＲ²は、それぞれ独立に脂肪族炭化水素基または脂環式炭化水素基を有する炭素数１〜１２の１価の有機基を示し、Ｒ³〜Ｒ⁶は、それぞれ独立に炭素数１〜１２の１価の有機基を示し、ａおよびｂは、それぞれ独立に０〜３の整数を示し、ｃおよびｄは、それぞれ独立に０〜４の整数を示す。）

(In the formula (1), R ¹ and R ² represents a monovalent organic group having 1 to 12 carbon atoms having independently an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, R ³ to R ⁶ Each independently represents a monovalent organic group having 1 to 12 carbon atoms, a and b each independently represent an integer of 0 to 3, and c and d each independently represents an integer of 0 to 4. .)

[2] The polymer according to [1], wherein in the formula (1), the bonding position of R ¹ and R ² is an ortho position of an ether bond that forms the main chain skeleton of the polymer.
[3] The polymer further comprises a structural unit represented by the following formula (1-1), a structural unit represented by the following formula (2), and a structural unit represented by the following formula (3). The polymer according to [1] or [2], which has at least one structural unit selected from the above.

（式（１−１）中、Ｒ¹〜Ｒ⁶およびａ〜ｄは、それぞれ独立に前記式（１）中のＲ¹〜Ｒ⁶およびａ〜ｄと同義であり、Ｒ⁷およびＲ⁸は、それぞれ独立にハロゲン原子、炭素数１〜１２の１価の有機基またはニトロ基を示し、ｊおよびｋは、それぞれ独立に０〜４の整数を示し、Ｙは単結合、−ＳＯ₂−または＞Ｃ＝Ｏを示し、ｍは０または１を示す。）

(In the formula (1-1), R ^{1 to} R ⁶ and a to d are independently the same as R ^{1 to} R ⁶ and a to d in the formula (1), and R ⁷ and R ⁸ are Each independently represents a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, j and k each independently represents an integer of 0 to 4, Y is a single bond, —SO ₂ — or > C = O, m represents 0 or 1)

（式（２）中、Ｒ⁷、Ｒ⁸、Ｙ、ｍ、ｊおよびｋは、それぞれ独立に前記式（１−１）中のＲ⁷、Ｒ⁸、Ｙ、ｍ、ｊおよびｋと同義であり、Ｒ⁹〜Ｒ¹²は、それぞれ独立に炭素数１〜１２の１価の有機基（ただし、脂肪族炭化水素基または脂環式炭化水素基を有する炭素数１〜１２の１価の有機基を除く。）を示し、ｅ〜ｈは、それぞれ独立に０〜４の整数を示す。）

(In the formula (2), R ⁷ , R ⁸ , Y, m, j and k are each independently synonymous with R ⁷ , R ⁸ , Y, m, j and k in the formula (1-1). R ^{9 to} R ¹² are each independently a monovalent organic group having 1 to 12 carbon atoms (however, a monovalent organic group having 1 to 12 carbon atoms having an aliphatic hydrocarbon group or an alicyclic hydrocarbon group) Group is excluded.), And e to h each independently represents an integer of 0 to 4.)

（式（３）中、Ｒ¹³およびＲ¹⁴は、それぞれ独立に炭素数１〜１２の１価の有機基を示し、Ｚは単結合、−Ｏ−、−Ｓ−、−ＳＯ₂−、＞Ｃ＝Ｏ、−ＣＯＮＨ−、−ＣＯＯ−または炭素数１〜１２の２価の有機基を示し、ｐおよびｑは、それぞれ独立に０〜４の整数を示し、ｎは０または１を示し、Ｒ⁷、Ｒ⁸、Ｙ、ｍ、ｊおよびｋは、それぞれ独立に前記式（１−１）中のＲ⁷、Ｒ⁸、Ｙ、ｍ、ｊおよびｋと同義である。）

(In the formula (3), R ¹³ and R ¹⁴ are each independently a monovalent organic group having 1 to 12 carbon atoms, Z is a single bond, -O -, - S -, - SO 2 -,> C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, p and q each independently represents an integer of 0 to 4, n represents 0 or 1, ^{R 7, R 8, Y,} m, j and k are, R ⁷ each independently the formula (1-1) in, R ^8, Y, m, is synonymous with j and k.)

[4] The weight according to any one of [1] to [3], wherein the glass transition temperature measured by differential scanning calorimetry (DSC, temperature rising rate: 20 ° C./min) of the polymer is 230 to 350 ° C. Coalescence.
[5] A film comprising the polymer according to any one of [1] to [4].
[6] The film according to [5], wherein the total light transmittance by a JIS K7105 transparency test method is 85% or more when the thickness of the film is 30 μm.
[7] The film according to [5] or [6], wherein the YI value (yellow index) is 3.0 or less at a thickness of 30 μm.

[8] The film according to any one of [5] to [7], wherein a retardation (Rth589) in the thickness direction of the film measured at a wavelength of 589 nm at a thickness of 30 μm is 60 nm or less.
[9] The film according to any one of [5] to [8], wherein the photoelastic coefficient (C _d ) of the film measured at a wavelength of 589 nm has an absolute value of 0 to 50 (× 10 ⁻¹² Pa ⁻¹ ). .
[10] The film according to any one of [5] to [9], wherein the absolute value of the stress optical coefficient (C _R ) of the film measured at a wavelength of 589 nm is ¹ to 1500 (× 10 ⁻¹² Pa ⁻¹ ). .

  [11] A resin composition comprising the polymer according to any one of [1] to [4] and an organic solvent.

  [12] A method for producing the film according to any one of [5] to [10], wherein the resin composition according to [11] is applied onto a support to form a coating film; Removing the organic solvent from the coating film by evaporation to obtain a film.

According to the present invention, it is possible to obtain a polymer and a film excellent in light transmittance, heat resistance, low colorability, low retardation, optical isotropy and the like in a good balance.
Moreover, the film of this invention can be used conveniently as films, such as a light-guide plate, a polarizing plate, a film for a display, a film for optical disks, a transparent conductive film, a film for touch panels, a waveguide board.

≪Polymer≫
The polymer of the present invention has a structural unit represented by the following formula (1) (hereinafter also referred to as “structural unit (1)”).
Since the polymer of the present invention has the structural unit (1), it is excellent in balance in light transmittance, heat resistance, low colorability, low retardation, optical isotropy, and the like. This is particularly true when the structural unit (1) is R ¹ and R ² (one having 1 to 12 carbon atoms having an aliphatic hydrocarbon group or an alicyclic hydrocarbon group on the benzene ring bonded to the 9-position of fluorene). This is considered to be due to having at least one valent organic group.
In addition, a structural unit (in the structural unit (1)) having no monovalent organic group having 1 to 12 carbon atoms having an aliphatic hydrocarbon group or an alicyclic hydrocarbon group on the benzene ring bonded to the 9-position of fluorene. A film comprising a polymer having a structural unit that does not have R ¹ and R ² ) tends to have a large photoelastic coefficient (C _d ) and stress optical coefficient (C _R ).

Formula (1), R ¹ and R ² each independently represents a monovalent organic group having 1 to 12 carbon atoms having an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, R ³ to R ⁶ Each independently represents a monovalent organic group having 1 to 12 carbon atoms, a and b each independently represent an integer of 0 to 3, and c and d each independently represents an integer of 0 to 4. . It is preferable that a to d are each independently 0.

The bonding position of R ¹ and R ² in the structural unit (1) is preferably the ortho position of the ether bond forming the main chain skeleton of the polymer. The “ether bond forming the main chain skeleton” means “—O—” which bonds a benzene ring bonded to the 9-position of fluorene and benzonitrile, and “forms the main chain skeleton”. The “ortho position of the ether bond” means, for example, as shown in the following formula (1 ′), when an ether bond is bonded to the 4-position of the benzene ring bonded to the 9-position of fluorene, R ¹ and R ² The bonding position means the 3rd position (5th position) of the benzene ring.
Since the bonding position of R ¹ and R ² in the structural unit (1) is in the position, the film containing the polymer having this structural unit has a smaller retardation and more photoelasticity. The absolute values of the coefficient and the stress optical coefficient are small, and the optical isotropy is excellent.

In the formula (1 ′), R ^{1 to} R ⁶ and a to d are independently the same as R ^{1 to} R ⁶ and a to d in the formula (1).

Examples of the monovalent organic group having 1 to 12 carbon atoms having an aliphatic hydrocarbon group or an alicyclic hydrocarbon group in R ¹ and R ² include an aliphatic hydrocarbon group or an alicyclic hydrocarbon group. The organic group containing the C1-C12 monovalent | monohydric oxygen atom which has a C1-C12 monovalent hydrocarbon group, an aliphatic hydrocarbon group, or an alicyclic hydrocarbon group which has can be mentioned.
The C1-C12 monovalent hydrocarbon group having an aliphatic hydrocarbon group or an alicyclic hydrocarbon group does not contain an aromatic group as a substituent from the viewpoint of improving the optical isotropy of the polymer. It is preferable.

Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms having an aliphatic hydrocarbon group or an alicyclic hydrocarbon group in R ¹ and R ² include linear or branched aliphatic carbonization having 1 to 12 carbon atoms. Examples thereof include a hydrogen group, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and an alicyclic hydrocarbon group having 4 to 12 carbon atoms having an aliphatic hydrocarbon group.

The linear or branched aliphatic hydrocarbon group having 1 to 12 carbon atoms in R ¹ and R ² is preferably a linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms. A linear or branched aliphatic hydrocarbon group of ˜5 is more preferred.

Preferable specific examples of the linear or branched aliphatic hydrocarbon group having 1 to 12 carbon atoms in R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. , Sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group and n-heptyl group.

As said C3-C12 alicyclic hydrocarbon group in R < ¹ > and R < ² >, a C3-C8 alicyclic hydrocarbon group is preferable, and a C3-C6 alicyclic hydrocarbon group is More preferred.

Preferable specific examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms in R ¹ and R ² include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; cyclobutenyl group, cyclo And cycloalkenyl groups such as a pentenyl group and a cyclohexenyl group. The bonding site of the alicyclic hydrocarbon group may be any carbon on the alicyclic ring.

The alicyclic hydrocarbon group having 4 to 12 carbon atoms having an aliphatic hydrocarbon group for R ¹ and R ^2, alicyclic hydrocarbon group having 4 to 9 carbon atoms and having an aliphatic hydrocarbon group is preferred.

Preferable specific examples of the alicyclic hydrocarbon group having 4 to 12 carbon atoms having the aliphatic hydrocarbon group in R ¹ and R ² include preferable specific examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms. Examples thereof include groups obtained by substituting any hydrogen atom of the groups listed as examples with the groups listed as preferred specific examples of the linear or branched aliphatic hydrocarbon group having 1 to 12 carbon atoms.

Examples of the organic group containing a monovalent oxygen atom having 1 to 12 carbon atoms having an aliphatic hydrocarbon group or an alicyclic hydrocarbon group in R ¹ and R ² include an aliphatic hydrocarbon group or an alicyclic hydrocarbon group And an organic group having 1 to 12 carbon atoms and having an ether bond.

Examples of the organic group having 1 to 12 carbon atoms having an aliphatic hydrocarbon group or an alicyclic hydrocarbon group in R ¹ and R ² and having an ether bond include an alkoxy group having 1 to 12 carbon atoms and 2 to 2 carbon atoms. Examples thereof include 12 alkenyloxy groups, alkynyloxy groups having 2 to 12 carbon atoms, cycloalkyloxy groups having 3 to 12 carbon atoms, and alkoxyalkyl groups having 1 to 12 carbon atoms. Specific examples include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a propenyloxy group, a cyclohexyloxy group, and a methoxymethyl group.

R ¹ and R ² in the formula (1) are preferably groups not containing an aromatic group from the viewpoint of optical isotropy, and are carbons having an aliphatic hydrocarbon group or an alicyclic hydrocarbon group. A monovalent hydrocarbon group having 1 to 12 carbon atoms is preferable, a linear or branched aliphatic hydrocarbon group having 1 to 12 carbon atoms is more preferable, and a methyl group, an ethyl group, or an isopropyl group is further preferable.

The monovalent organic group having 1 to 12 carbon atoms in R ^{3 to} R ⁶ is at least one atom selected from the group consisting of a monovalent hydrocarbon group having 1 to 12 carbon atoms and an oxygen atom and a nitrogen atom. And a monovalent organic group having 1 to 12 carbon atoms and the like.

Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms in R ^{3 to} R ⁶ include a linear or branched hydrocarbon group having 1 to 12 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms. Etc.

The linear or branched hydrocarbon group having 1 to 12 carbon atoms in R ^{3 to} R ⁶ is preferably a linear or branched hydrocarbon group having 1 to 8 carbon atoms, and a linear chain having 1 to 5 carbon atoms. A branched chain hydrocarbon group is more preferred.

Preferable specific examples of the linear or branched hydrocarbon group in R ^{3 to} R ⁶ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Group, n-pentyl group, n-hexyl group, n-heptyl group and the like.

The alicyclic hydrocarbon group having 3 to 12 carbon atoms in R ³ to R ^6, preferably an alicyclic hydrocarbon group having 3 to 8 carbon atoms, more alicyclic hydrocarbon group having 3 or 4 carbon atoms preferable.

Preferable specific examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms in R ^{3 to} R ⁶ include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; cyclobutenyl group, cyclo And cycloalkenyl groups such as a pentenyl group and a cyclohexenyl group. The bonding site of the alicyclic hydrocarbon group may be any carbon on the alicyclic ring.

From the viewpoint of optical isotropy, R ^{3 to} R ⁶ are preferably each independently a group not containing an aromatic group.

Examples of the organic group having 1 to 12 carbon atoms including an oxygen atom in R ^{3 to} R ⁶ include an organic group composed of a hydrogen atom, a carbon atom and an oxygen atom, and among them, an ether bond, a carbonyl group or an ester bond and a hydrocarbon. Preferred examples thereof include organic groups having 1 to 12 carbon atoms in total.

The organic group having 1 to 12 carbon atoms and having an ether bond in R ^{3 to} R ⁶ includes an alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, and an alkynyloxy group having 2 to 12 carbon atoms. And an alkoxyalkyl group having 1 to 12 carbon atoms. Specific examples include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a propenyloxy group, a cyclohexyloxy group, and a methoxymethyl group.

Moreover, as a C1-C12 organic group which has a carbonyl group in R < ³ > -R < ⁶ >, a C2-C12 acyl group etc. can be mentioned. Specific examples include an acetyl group, a propionyl group, and an isopropionyl group.

Examples of the organic group having 1 to 12 carbon atoms having an ester bond in R ^{3 to} R ⁶ include an acyloxy group having 2 to 12 carbon atoms. Specific examples include an acetyloxy group, a propionyloxy group, and an isopropionyloxy group.

The organic group having 1 to 12 carbon atoms containing R ³ to R ⁶ in a nitrogen atom, a hydrogen atom and an organic group composed of carbon atom, nitrogen atom, and specific examples thereof include cyano group.

Examples of the organic group having 1 to 12 carbon atoms including an oxygen atom and a nitrogen atom in R ^{3 to} R ⁶ include an organic group composed of a hydrogen atom, a carbon atom, an oxygen atom, and a nitrogen atom.

The polymer of the present invention further has a structural unit represented by the following formula (1-1) (hereinafter also referred to as “structural unit (1-1)”) and a structure represented by the following formula (2). At least one structural unit selected from the group consisting of a unit (hereinafter also referred to as “structural unit (2)”) and a structural unit represented by the following formula (3) (hereinafter also referred to as “structural unit (3)”) (Hereinafter also referred to as “structural unit (i)”). When the polymer of the present invention has such a structural unit, the film containing the polymer may have improved mechanical properties.
When the polymer of the present invention has the structural unit (i), the film containing the polymer tends to have a large photoelastic coefficient (C _d ) and stress optical coefficient (C _R ).

In the formula (1-1), R ^{1 to} R ⁶ and a to d are independently the same as R ^{1 to} R ⁶ and a to d in the formula (1), and R ⁷ and R ⁸ are Each independently represents a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, Y represents a single bond, —SO ₂ — or> C═O, and m represents 0 or 1. j and k each independently represent an integer of 0 to 4, preferably 0.

In the formula (1-1), the monovalent organic group having 1 to 12 carbon atoms in R ⁷ and R ⁸ includes a monovalent hydrocarbon group having 1 to 12 carbon atoms, an oxygen atom, and a nitrogen atom. Examples thereof include a monovalent organic group having 1 to 12 carbon atoms and containing at least one atom selected from the group.

Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms in R ⁷ and R ⁸ include a linear or branched hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and A C6-C12 aromatic hydrocarbon group etc. are mentioned.

The linear or branched hydrocarbon group having 1 to 12 carbon atoms in R ⁷ and R ⁸ is preferably a linear or branched hydrocarbon group having 1 to 8 carbon atoms, and a linear chain having 1 to 5 carbon atoms. A branched chain hydrocarbon group is more preferred.

Preferable specific examples of the linear or branched hydrocarbon group for R ⁷ and R ⁸ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Group, n-pentyl group, n-hexyl group, n-heptyl group and the like.

The alicyclic hydrocarbon group having 3 to 12 carbon atoms in R ⁷ and R ⁸ is preferably an alicyclic hydrocarbon group having 3 to 8 carbon atoms, more preferably an alicyclic hydrocarbon group having 3 or 4 carbon atoms. preferable.

Preferable specific examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms for R ⁷ and R ⁸ include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group; cyclobutenyl group, cyclo And cycloalkenyl groups such as a pentenyl group and a cyclohexenyl group. The bonding site of the alicyclic hydrocarbon group may be any carbon on the alicyclic ring.

Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms in R ⁷ and R ⁸ include a phenyl group, a biphenyl group, and a naphthyl group. The bonding site of the aromatic hydrocarbon group may be any carbon on the aromatic ring.

Examples of the organic group having 1 to 12 carbon atoms including an oxygen atom in R ⁷ and R ⁸ include an organic group composed of a hydrogen atom, a carbon atom and an oxygen atom, and among them, an ether bond, a carbonyl group or an ester bond and a hydrocarbon. Preferred examples thereof include organic groups having 1 to 12 carbon atoms in total.

The organic group having 1 to 12 carbon atoms having an ether bond in R ⁷ and R ⁸ includes an alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, and an alkynyloxy group having 2 to 12 carbon atoms. And an aryloxy group having 6 to 12 carbon atoms and an alkoxyalkyl group having 1 to 12 carbon atoms. Specific examples include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a phenoxy group, a propenyloxy group, a cyclohexyloxy group, and a methoxymethyl group.

As the total organic group having 1 to 12 carbon atoms having a carbonyl group in R ⁷ and R ^8, and the like can be given an acyl group having 2 to 12 carbon atoms. Specific examples include an acetyl group, a propionyl group, an isopropionyl group, and a benzoyl group.

Examples of the organic group having 1 to 12 carbon atoms having an ester bond in R ⁷ and R ⁸ include an acyloxy group having 2 to 12 carbon atoms. Specific examples include an acetyloxy group, a propionyloxy group, an isopropionyloxy group, and a benzoyloxy group.

Examples of the organic group having 1 to 12 carbon atoms including a nitrogen atom in R ⁷ and R ⁸ include an organic group composed of a hydrogen atom, a carbon atom and a nitrogen atom, and specifically includes a cyano group, an imidazole group, and a triazole group. Benzimidazole group and benztriazole group.

Examples of the organic group having 1 to 12 carbon atoms including an oxygen atom and a nitrogen atom in R ⁷ and R ⁸ include an organic group consisting of a hydrogen atom, a carbon atom, an oxygen atom and a nitrogen atom, and specifically, an oxazole group. Oxadiazole group, benzoxazole group, benzoxadiazole group and the like.

In the formula ^{(2), R 7, R} 8, Y, m, j and k are, R ^7, R ^8, Y each independently the formula (1-1) in, m, with j and k synonymous R ^{9 to} R ¹² are each independently a monovalent organic group having 1 to 12 carbon atoms (however, a monovalent organic group having 1 to 12 carbon atoms having an aliphatic hydrocarbon group or an alicyclic hydrocarbon group) And Y represents a single bond, —SO ₂ — or> C═O, and m represents 0 or 1. e to h each independently represent an integer of 0 to 4, preferably 0.

In the formula (2), the monovalent organic group having 1 to 12 carbon atoms in R ⁹ to R ^12, include an aromatic hydrocarbon group having 6 to 12 carbon atoms, specifically, a phenyl group , Biphenyl group and naphthyl group. The bonding site of the aromatic hydrocarbon group may be any carbon on the aromatic ring.

In the formula (2), R ^{9 to} R ¹² are not each an aliphatic hydrocarbon group or a monovalent organic group having 1 to 12 carbon atoms having an alicyclic hydrocarbon group, but the aliphatic hydrocarbon. the monovalent organic group having 1 to 12 carbon atoms having a group or an alicyclic hydrocarbon group, carbon atoms having an aliphatic hydrocarbon group or an alicyclic hydrocarbon group for R ¹ and R ² 1-12 And the same groups as the monovalent organic group.

In the formula (3), R ¹³ and R ¹⁴ each independently represent a monovalent organic group having 1 to 12 carbon atoms, Z represents a single bond, —O—, —S—, —SO ₂ —, > C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, and n represents 0 or 1. p and q each independently represent an integer of 0 to 4, preferably 0. R ^7, R ^8, Y, m, j and k are each R ⁷ in independent to the formula ^{(1-1), R 8, Y} , m, synonymous with j and k.

In the formula (3), the monovalent organic group having 1 to 12 carbon atoms in R ¹³ and R ¹⁴ is the same organic group as the monovalent organic group having 1 to 12 carbon atoms in R ⁷ and R ⁸ . Etc.

  In formula (3), the divalent organic group having 1 to 12 carbon atoms in Z is a divalent hydrocarbon group having 1 to 12 carbon atoms or a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms. , A C1-C12 divalent organic group containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom, and a carbon containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom Examples thereof include divalent halogenated organic groups of 1 to 12.

  Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms include a linear or branched divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and Examples thereof include a bivalent aromatic hydrocarbon group having 6 to 12 carbon atoms.

  Examples of the linear or branched divalent hydrocarbon group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a trimethylene group, an isopropylidene group, a pentamethylene group, a hexamethylene group, and a heptamethylene group.

  Examples of the divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms include cycloalkylene groups such as cyclopropylene group, cyclobutylene group, cyclopentylene group and cyclohexylene group; cyclobutenylene group, cyclopentenylene group and And cycloalkenylene groups such as a cyclohexenylene group.

  Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenylene group, a naphthylene group, and a biphenylene group.

  Examples of the divalent halogenated hydrocarbon group having 1 to 12 carbon atoms include a linear or branched divalent halogenated hydrocarbon group having 1 to 12 carbon atoms and a divalent halogenated fat having 3 to 12 carbon atoms. Examples thereof include a cyclic hydrocarbon group and a divalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms.

  Examples of the linear or branched divalent halogenated hydrocarbon group having 1 to 12 carbon atoms include a difluoromethylene group, a dichloromethylene group, a tetrafluoroethylene group, a tetrachloroethylene group, a hexafluorotrimethylene group, and a hexachlorotrimethylene group. Group, hexafluoroisopropylidene group, hexachloroisopropylidene group and the like.

  As the divalent halogenated alicyclic hydrocarbon group having 3 to 12 carbon atoms, at least a part of the hydrogen atoms exemplified in the divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms is a fluorine atom. , A group substituted with a chlorine atom, a bromine atom, or an iodine atom.

  As the divalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms, at least a part of the hydrogen atoms exemplified in the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms is a fluorine atom, chlorine And a group substituted with an atom, a bromine atom, or an iodine atom.

  The divalent organic group having 1 to 12 carbon atoms containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom is an organic group consisting of a hydrogen atom and a carbon atom and an oxygen atom and / or a nitrogen atom. And a divalent organic group having 1 to 12 carbon atoms and having an ether bond, a carbonyl group, an ester bond or an amide bond and a hydrocarbon group.

  The divalent halogenated organic group having 1 to 12 carbon atoms containing at least one atom selected from the group consisting of oxygen atom and nitrogen atom is specifically at least selected from the group consisting of oxygen atom and nitrogen atom Examples include a group in which at least a part of the hydrogen atoms exemplified in the divalent organic group having 1 to 12 carbon atoms containing one kind of atom is substituted with a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

  From the viewpoint of obtaining a polymer having excellent optical isotropy, the polymer of the present invention preferably contains 70 mol% or more of the structural unit (1) in all structural units, and 90 mol% or more of all structural units. Is more preferable. In addition, the content of the structural unit represented by the following (1 ″) in the polymer is preferably 50% by weight or more in all structural units, and more preferably 55% by weight or more in all structural units.

In the formula (1 ″), R ^{1 to} R ⁶ and a to d are independently the same as R ^{1 to} R ⁶ and a to d in the formula (1).

  The polymer of the present invention includes, for example, a component (hereinafter also referred to as “(A) component”) containing a compound represented by the following formula (A1) (hereinafter also referred to as “compound (A1)”) and the following formula. It can be obtained by reacting a component (hereinafter also referred to as “compound (B1)”) represented by (B1) with a component (hereinafter also referred to as “component (B)”).

  In the formula (A1), X independently represents a halogen atom, preferably a fluorine atom.

  Specific examples of the compound (A1) include 2,6-difluorobenzonitrile, 2,5-difluorobenzonitrile, 2,4-difluorobenzonitrile, 2,6-dichlorobenzonitrile, and 2,5-dichloro. Mention may be made of benzonitrile, 2,4-dichlorobenzonitrile and their reactive derivatives. In particular, 2,6-difluorobenzonitrile and 2,6-dichlorobenzonitrile are preferably used from the viewpoints of reactivity and economy. These compounds can be used in combination of two or more.

  Compound (A1) is preferably contained in an amount of 70 mol% to 100 mol%, more preferably 80 mol% to 100 mol% in 100 mol% of component (A), and 90 mol%. More preferably, it is contained in an amount of ˜100 mol%.

In the formula (B1), each R ^b independently represents a hydrogen atom, a methyl group, an ethyl group, an acetyl group, a methanesulfonyl group or a trifluoromethylsulfonyl group, and among these, a hydrogen atom is preferable.
In formula (B1), R ^{1 to} R ⁶ and a to d are independently the same as R ^{1 to} R ⁶ and a to d in the formula (1).

  The compound (B1) is preferably a compound represented by the following formula (B1 ′) (hereinafter also referred to as “compound (B1 ′)”).

In the formula (B1 ′), R ^{1 to} R ⁶ and a to d are independently the same as R ^{1 to} R ⁶ and a to d in the formula (1).

  Specific examples of the compound (B1 ′) include 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9-bis (3-ethyl-4-hydroxyphenyl) fluorene, 9-bis (3,5-dimethyl-4-hydroxyphenyl) fluorene, 9,9-bis (3,5-diethyl-4-hydroxyphenyl) fluorene, 9,9-bis (3-isopropyl-4-phenyl) Examples include fluorene, 9,9-bis (3-cyclohexyl-4-hydroxyphenyl) fluorene, and reactive derivatives thereof. Among the above-mentioned compounds, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9-bis (3-ethyl-4-hydroxyphenyl) fluorene and 9,9-bis (3-isopropyl- 4-hydroxyphenyl) fluorene is preferably used. These compounds can be used in combination of two or more.

The bonding position of R ¹ and R ² in the compounds (B1) and (B1 ′) is preferably the ortho position of the ether bond forming the main chain skeleton of the polymer.

  The compound (B1) is preferably contained in an amount of 80 mol% to 100 mol%, more preferably 90 mol% to 100 mol%, in 100 mol% of the component (B).

  The component (A) may include a compound represented by the following formula (A2) (hereinafter also referred to as “compound (A2)”) as necessary.

In the formula (A2), R ⁷ , R ⁸ , Y, m, j and k are each independently synonymous with R ⁷ , R ⁸ , Y, m, j and k in the formula (1-1). And each X is independently the same as X in the formula (A1).

  Specific examples of the compound (A2) include 4,4′-difluorobenzophenone, 4,4′-difluorodiphenylsulfone, 2,4′-difluorobenzophenone, 2,4′-difluorodiphenylsulfone, 2,2 '-Difluorobenzophenone, 2,2'-difluorodiphenylsulfone, 3,3'-dinitro-4,4'-difluorobenzophenone, 3,3'-dinitro-4,4'-difluorodiphenylsulfone, 4,4'- Dichlorobenzophenone, 4,4'-dichlorodiphenylsulfone, 2,4'-dichlorobenzophenone, 2,4'-dichlorodiphenylsulfone, 2,2'-dichlorobenzophenone, 2,2'-dichlorodiphenylsulfone, 3,3 ' -Dinitro-4,4'-dichlorobenzophenone and 3,3'-dinitro-4,4'-di Lolo diphenyl sulfone, and the like can be given. Among these, 4,4′-difluorobenzophenone is preferable. These compounds can be used in combination of two or more.

  The component (B) is a compound represented by the following formula (B2) (hereinafter also referred to as “compound (B2)”) and a compound represented by the following formula (B3) (hereinafter “compound (B3)” as necessary. ) ”)).

In the formula (B2), R ^{9 to} R ¹² and e to h are independently the same as R ^{9 to} R ¹² and e to h in the formula (2), and R ^b is independently the above. It is synonymous with ^Rb in Formula (B1).

  The compound (B2) is preferably a compound represented by the following formula (B2 ′) (hereinafter also referred to as “compound (B2 ′)”).

In the formula (B2 ′), R ^{9 to} R ¹² and e to h are independently the same as R ^{9 to} R ¹² and e to h in the formula (2).

  Examples of the compound (B2 ′) include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene, and 9,9-bis (3,5-diphenyl). -4-hydroxyphenyl) fluorene, and reactive derivatives thereof. These compounds can be used in combination of two or more.

In the formula (B3), R ^13, R ^14, Z, n, p and q are R ¹³ each independently to the formula (3) in, R ^14, Z, n, and p and q synonymous.

  Examples of the compound (B3) include hydroquinone, resorcinol, 2-phenylhydroquinone, 4,4′-biphenol, 3,3′-biphenol, 4,4′-dihydroxydiphenylsulfone, 3,3′-dihydroxydiphenylsulfone, 4 , 4′-dihydroxybenzophenone, 3,3′-dihydroxybenzophenone, 1,1′-bi-2-naphthol, 1,1′-bi-4-naphthol, 2,2-bis (4-hydroxyphenyl) propane, Examples include 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, and reactive derivatives thereof. It is done. Among these, 4,4′-biphenol and resorcinol are preferable, and 4,4′-biphenol is preferably used from the viewpoint of reactivity and mechanical properties. These compounds can be used in combination of two or more.

  In the present invention, the mechanical properties refer to properties such as the tensile strength, breaking elongation, and tensile modulus of the polymer.

More specifically, the polymer of the present invention can be synthesized by the following method.
The component (B) is reacted with an alkali metal compound in an organic solvent to obtain an alkali metal salt of the component (B) (compound (B1), compound (B2) and / or compound (B3), etc.). The obtained alkali metal salt is reacted with the component (A). In addition, the alkali metal salt of (B) component and (A) component can also be made to react by performing reaction with (B) component and an alkali metal compound in presence of (A) component.

  Examples of the alkali metal compound used in the reaction include alkali metals such as lithium, potassium and sodium; alkali hydrides such as lithium hydride, potassium hydride and sodium hydride; lithium hydroxide, potassium hydroxide and sodium hydroxide And alkali metal carbonates such as lithium carbonate, potassium carbonate and sodium carbonate; alkali metal hydrogen carbonates such as lithium hydrogen carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate. These can be used alone or in combination of two or more.

In the alkali metal compound, the amount of metal atoms in the alkali metal compound is usually 1 to 3 times equivalent, preferably 1.1 to 2 times equivalent to all —O—R ^b in the component (B). Preferably it is used in an amount of 1.2 to 1.5 times equivalent.

  Examples of the organic solvent used in the reaction include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ-butyllactone, Sulfolane, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropyl sulfone, diphenyl sulfone, diphenyl ether, benzophenone, dialkoxybenzene (1 to 4 carbon atoms of alkoxy group) and trialkoxybenzene (1 to 4 carbon atoms of alkoxy group) ) Etc. can be used. Among these solvents, polar organic solvents having a high dielectric constant such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, diphenylsulfone, and dimethylsulfoxide are particularly preferably used. These organic solvents can be used alone or in combination of two or more.

  Further, in the reaction, a solvent azeotropic with water such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole and phenetole can be further used.

  The proportion of component (A) and component (B) used is preferably 45 mol% or more and 55 mol% or less when component (A) is 100 mol% in total of component (A) and component (B). More preferably, it is 50 mol% or more and 52 mol% or less, more preferably more than 50 mol% and 52 mol% or less, and the component (B) is preferably 45 mol% or more and 55 mol% or less, more preferably 48 mol%. % Or more and 50 mol% or less, more preferably 48 mol% or more and less than 50 mol%.

  Moreover, reaction temperature becomes like this. Preferably it is 60 to 250 degreeC, More preferably, it is the range of 80 to 200 degreeC. The reaction time is preferably in the range of 15 minutes to 100 hours, more preferably 1 hour to 24 hours.

  The polymer of the present invention has a polystyrene-equivalent weight average molecular weight (Mw) measured by a TOSOH HLC-8220 GPC apparatus, preferably 5,000 to 500,000, more preferably 15,000 to 250,000. It is.

  The polymer of the present invention has a glass transition temperature (Tg) measured by using a differential scanning calorimeter (temperature increase rate 20 ° C./min) manufactured by Seiko Instruments Inc., preferably 230 to 350 ° C., more preferably It is 240-330 degreeC, More preferably, it is 250-300 degreeC. When the glass transition temperature of the polymer of the present invention is in the above range, the film containing the polymer exhibits a sufficient heat resistance. Therefore, the film containing the polymer is a light guide plate, a polarizing plate, a display film, an optical disk film, a transparent conductive film. It can be suitably used as a film for a film for a touch panel, a waveguide plate or the like.

≪Resin composition≫
The resin composition of the present invention contains the polymer of the present invention and an organic solvent.

  The mixture of the polymer and organic solvent obtained by the above method (the mixture after polymer synthesis) can be used as it is as the resin composition of the present invention. By using such a resin composition, a film can be produced easily and inexpensively.

  Further, after isolating (purifying) the polymer as a solid component from the mixture of the polymer and the organic solvent obtained by the above method, the resin composition of the present invention is prepared by re-dissolving in the organic solvent. You can also. By using such a resin composition, a film with less coloring and excellent light transmittance can be produced.

  The method of isolating (purifying) the polymer of the present invention as a solid content is, for example, reprecipitation of the polymer in a poor solvent of the polymer such as methanol, followed by filtration, and then drying the filtrate under reduced pressure. Can be performed.

  Examples of the organic solvent for dissolving the polymer include methylene chloride, ethylene glycol dimethyl ether, dioxane, anisole, propylene glycol monomethyl ether acetate, tetrahydrofuran, cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and γ-butyrolactone are preferably used, and methylene chloride, N, N-dimethylacetamide and N-methylpyrrolidone are more preferably used from the viewpoint of coating property and economy. These solvents can be used alone or in combination of two or more.

  In addition, the resin composition of the present invention can further contain an anti-aging agent, and the durability of the film obtained by containing the anti-aging agent can be further improved.

  Preferred examples of the antiaging agent include hindered phenol compounds.

  Examples of hindered phenol compounds that can be used in the present invention include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) proonate], 1,6-hexanediol- Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert- Butylanilino) -3,5-triazine, pentaerythritol tetrakis [3- (3,5-tert-butyl-4-hydroxyphenyl) propionate], 1,1,3-tris [2-methyl-4- [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -5-tert-butylphenyl] butane 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5- Di-tert-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate and 3,9-bis [2- [3- ( 3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [ .5] undecane, and the like. These anti-aging agents can be used alone or in combination of two or more.

  In this invention, it is preferable to use an anti-aging agent in the quantity of 0.01-10 weight part with respect to 100 weight part of polymers of the said invention.

  The polymer concentration in the resin composition of the present invention is usually 5 to 40% by mass, preferably 7 to 25% by mass, although it depends on the molecular weight of the polymer. When the concentration of the polymer in the composition is within the above range, it is possible to form a film that can be thickened, hardly causes pinholes, and has excellent surface smoothness.

  The viscosity of the resin composition of the present invention is usually 2,000 to 100,000 mPa · s, preferably 3,000 to 50,000 mPa · s, although it depends on the molecular weight and concentration of the polymer. When the viscosity of the composition is within the above range, the composition is easily retained during film formation, and the thickness can be easily adjusted, so that the film can be easily formed.

≪Film≫
The film of the present invention comprises the polymer of the present invention. The film of the present invention may contain an additive in addition to the polymer of the present invention, depending on the desired use, but it is preferably essentially composed of the polymer of the present invention.

Since the film of the present invention contains the polymer of the present invention, the film has excellent balance of light transmission, heat resistance, low colorability and optical isotropy, and is a light guide plate, polarizing plate, display film, optical disk. The film can be suitably used as a film such as a film, a transparent conductive film, a touch panel film, and a waveguide plate.
In particular, since the film of the present invention is excellent in optical isotropy, when the film is used for a touch panel or the like, it is preferable to suitably prevent display quality from being deteriorated due to coloring or interference fringes appearing on the display surface. it can.

  The method for producing the film of the present invention is not particularly limited, but the step of applying the resin composition on a support to form a coating film, and removing the organic solvent from the coating film by evaporation. A step of obtaining a film.

Examples of the method for forming the coating film by applying the resin composition on a support include a roll coating method, a gravure coating method, a spin coating method, and a method using a doctor blade.
Examples of the support include a polyethylene terephthalate (PET) film and a SUS plate.

  Although the thickness of a coating film is not specifically limited, For example, it is 1-250 micrometers, Preferably it is 2-150 micrometers, More preferably, it is 5-125 micrometers.

  Moreover, the process of removing an organic solvent by evaporating the said organic solvent from a coating film can be specifically performed by heating a coating film. By heating the coating film, the organic solvent in the coating film can be evaporated and removed. The heating conditions may be determined as long as the organic solvent evaporates, and may be appropriately determined according to the support or polymer. For example, the heating temperature is preferably 30 ° C to 300 ° C, and preferably 40 ° C to 250 ° C. It is more preferable that the temperature is 50 ° C to 230 ° C.

  Further, the heating time is preferably 10 minutes to 5 hours. Note that heating may be performed in two or more stages. Specifically, after drying at a temperature of 30 to 80 ° C. for 10 minutes to 2 hours, heating is further performed at 100 to 250 ° C. for 10 minutes to 2 hours. Further, if necessary, drying may be performed under a nitrogen atmosphere or under reduced pressure.

  The amount of residual solvent in the obtained film after the step of removing the organic solvent (thermogravimetric analysis method: TGA, under nitrogen atmosphere, heating rate 10 ° C./min) is preferably 0 with respect to 100% by weight of the film. It is -1.2 weight%, More preferably, it is 0-1 weight%. When the amount of the residual solvent is within this range, a film having excellent heat resistance and being less susceptible to deformation and mechanical strength reduction even at high temperatures can be obtained. Therefore, this film is suitably used as a film such as a light guide plate, a polarizing plate, a display film, an optical disk film, a transparent conductive film, a touch panel film, and a waveguide plate.

  The obtained film is preferably used after being peeled from the substrate, and can be used as it is without being peeled, although it depends on the type of the substrate used.

  The film of the present invention preferably has a glass transition temperature (Tg) of 230 to 350 ° C. measured using a differential scanning calorimeter (temperature increase rate 20 ° C./min) manufactured by Seiko Instruments Inc., and 240 to 330 More preferably, it is 250 degreeC, and it is more preferable that it is 250-300 degreeC. When the glass transition temperature is in such a range, it can be more suitably used as a film such as a light guide plate, a polarizing plate, a display film, an optical disc film, a transparent conductive film, a touch panel film, and a waveguide plate.

  The thickness of the film in this invention becomes like this. Preferably it is 1-250 micrometers, More preferably, it is 2-150 micrometers, More preferably, it is 10-125 micrometers.

  When the thickness of the film of the present invention is 30 μm, the total light transmittance in the JIS K7105 transparency test method is preferably 85% or more, and more preferably 88% or more. The total light transmittance can be measured using an SC-3H haze meter manufactured by Suga Test Instruments Co., Ltd.

  When the thickness of the film of the present invention is 30 μm, the light transmittance at a wavelength of 400 nm is preferably 70% or more, more preferably 75% or more, and further preferably 80% or more. The light transmittance at a wavelength of 400 nm can be measured using a JASCO V-570 UV / VIS / NIR spectrometer.

  The film of the present invention preferably has a tensile strength of 80 to 150 MPa, more preferably 85 to 130 MPa, and still more preferably 85 to 120 MPa. The tensile strength can be measured using a tensile tester 5543 (manufactured by INSTRON).

  The film of the present invention has an elongation at break of preferably 5 to 100%, more preferably 10 to 100%, and still more preferably 15 to 100%. The elongation at break can be measured using a tensile tester 5543 (manufactured by INSTRON).

  The film of the present invention preferably has a tensile modulus of 2.5 to 4.0 GPa, more preferably 2.7 to 3.7 GPa. The tensile elastic modulus can be measured using a tensile tester 5543 (manufactured by INSTRON).

  When the film of the present invention has a thickness of 30 μm, the thickness direction retardation (Rth589) measured using light having a wavelength of 589 nm is preferably 60 nm or less, and preferably 0.1 to 10 nm. More preferably, it is more preferably 0.2 to 5 nm. The phase difference can be measured using a RETS spectrometer (manufactured by Otsuka Electronics Co., Ltd.). When the retardation in the thickness direction of the film of the present invention is in the above range, the film is a film such as a light guide plate, a polarizing plate, a display film, an optical disc film, a transparent conductive film, a touch panel film, a waveguide plate, etc. Can be suitably used.

In the film of the present invention, the absolute value of the photoelastic coefficient (C _d ) measured using light having a wavelength of 589 nm is preferably 0 to 50 (× 10 ⁻¹² Pa ⁻¹ ), more preferably 0 to 40. (× 10 ⁻¹² Pa ⁻¹ ). If the absolute value of the C _d is in the range, is excellent in optical isotropy, hardly occurs distribution of birefringence, it is possible to contrast obtain a uniform film, light guide plate, a polarizing plate, a display film, It can be suitably used as a film for an optical disc film, a transparent conductive film, a touch panel film, a waveguide plate and the like. 1 × 10 ⁻¹² Pa ⁻¹ is 1 × 10 ⁻¹³ cm ² / dyn.

In the film of the present invention, the absolute value of the stress optical coefficient (C _R ) measured using light with a wavelength of 589 nm is preferably 1 to 1500 Br (Br = × 10 ⁻¹² Pa ⁻¹ ), more preferably 1 ˜1200Br, more preferably 1˜400Br, particularly preferably 1˜200Br. If the absolute value of C _R is in the range, is excellent in optical isotropy, hardly occurs distribution of birefringence, it is possible to contrast obtain a uniform film, light guide plate, a polarizing plate, a display film, It can be suitably used as a film for an optical disc film, a transparent conductive film, a touch panel film, a waveguide plate and the like.

Here, the photoelastic coefficient (C _d ) and the stress optical coefficient (C _R ) will be described. These coefficients are based on various documents (Polymer Journal: Vol.27, No. 9, pp 943-950 (1995), “Journal of Japanese Society of Rheology”: Vol. 19, No. 2, pp 93-97 (1991). , "Photoelastic experiment method": Nikkan Kogyo Shimbun, 7th edition of Showa 50), the meaning of the former is to provide phase difference to transmitted light due to stress in the glassy state of the polymer The latter indicates the degree of phase difference imparted to the transmitted light due to the stress in the flow state.

That is, when the photoelastic coefficient (C _d ) is large, the phase difference of transmitted light changes sensitively due to external stress or internal stress caused by strain accumulated during cooling when the polymer is used in a glass state. For example, when an optical film is bonded to a polarizing plate or glass plate, the residual stress at the time of bonding, or the minute stress generated by material shrinkage due to temperature change or humidity change, etc. This means that the phase difference of transmitted light is likely to change.

  When the thickness of the film of the present invention is 30 μm, the YI value (yellow index) is preferably 3.0 or less, more preferably 2.5 or less, and 2.0 or less. Is more preferable. The YI value can be measured using an SM-T color measuring device manufactured by Suga Test Instruments Co., Ltd. When the YI value is in such a range, it is possible to obtain a film that is difficult to be colored, so that the light guide plate, polarizing plate, display film, optical disk film, transparent conductive film, touch panel film, waveguide plate It can use suitably as films, such as.

  Moreover, when the film of this invention is 30 micrometers in thickness, it is preferable that YI value after heating for 1 hour at 230 degreeC in air | atmosphere with a hot air dryer is 3.0 or less. It is more preferably 5 or less, and further preferably 2.0 or less. When the YI value is in such a range, a substrate that is difficult to be colored even at high temperatures can be obtained, and a film having excellent optical properties can be obtained.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

(1) Structural analysis The structural analysis of the polymers obtained in the following Examples and Comparative Examples was performed by IR (ATR method, FT-IR, 6700, manufactured by NICOLET) and NMR (ADVANCE500 type, manufactured by BRUKAAR). .

(2) Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)
The weight average molecular weight (Mw), number average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the polymers obtained in the following Examples and Comparative Examples were measured by a TLCOH HLC-8220 GPC apparatus (column: TSKgelα-M). , Developing solvent: measured using tetrahydrofuran (THF).

(3) Glass transition temperature (Tg)
The glass transition temperatures of the polymers obtained in the following examples and comparative examples were measured using a differential scanning calorimeter (DSC) manufactured by Seiko Instruments Inc. under conditions of nitrogen atmosphere and heating rate: 20 ° C./min. .

(4) Optical characteristics About the film for evaluation obtained by the following Example and comparative example, total light transmittance and YI (yellow index) were measured according to the JISK7105 transparency test method. Specifically, the total light transmittance was measured using an SC-3H type haze meter manufactured by Suga Test Instruments Co., Ltd., and the YI value was measured using an SM-T color meter manufactured by Suga Test Instruments Co., Ltd. ( YI before heating). Furthermore, after the film for evaluation obtained in the following Examples and Comparative Examples was heated in the air at 230 ° C. for 1 hour with a hot air dryer, the YI value was measured using an SM-T type color measuring device manufactured by Suga Test Instruments Co., Ltd. And measured (YI after heating).

  Moreover, the retardation (Rth) of the film for evaluation obtained in the following Examples and Comparative Examples was measured using a RETS spectrometer manufactured by Otsuka Electronics Co., Ltd. In addition, the reference wavelength at the time of measurement was 589 nm, and the evaluation film thickness of the retardation was shown as a value normalized to 30 μm.

The photoelastic coefficient (C _d ) and the stress optical coefficient (C _R ) were determined by a known method (Polymer Journal, Vol. 27, No. 9, P. 943-950 (1995)). Specifically, the photoelastic coefficient (C _d ) was cut into strips from the evaluation films obtained in the following Examples and Comparative Examples, and several types of constants were obtained at room temperature (25 ° C.). A load was applied, the generated phase difference was measured, and the calculation was performed from the stress and phase difference applied to the film. The measurement wavelength was 589 nm, and a RETS spectrometer manufactured by Otsuka Electronics Co., Ltd. was used for measurement.

The stress optical coefficient (C _R ) is obtained by heating the films for evaluation obtained in the following Examples and Comparative Examples to Tg or more of the film and extending several percent by applying several constant loads at Tg or more. The phase difference generated after slowly cooling to room temperature was measured and calculated from the applied stress and the phase difference. The measurement wavelength was 589 nm, and KOBRA manufactured by Oji Scientific Instruments was used for the measurement.

(5) Mechanical properties The tensile strength, breaking elongation, and tensile modulus at room temperature of the films for evaluation obtained in the following examples and comparative examples were measured in accordance with JIS K7127 using a tensile tester 5543 (manufactured by INSTRON). Measured.

[Example 1]
In a 3 L four-necked flask, 70.59 g (0.5075 mol) of 2,6-difluorobenzonitrile, 189.23 g (0.5000 mol) of 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, potassium carbonate 82.93 g (0.6 mol), 983 g of N, N-dimethylacetamide (hereinafter also referred to as “DMAc”) and 496 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube and a cooling tube were attached to the four-necked flask.

Next, after the atmosphere in the flask was replaced with nitrogen, the obtained solution was reacted at 140 ° C. for 3 hours, and water produced was removed from the Dean-Stark tube as needed. When no more water was observed, the temperature was gradually raised to 160 ° C. and reacted at that temperature for 5 hours.
After cooling to room temperature (25 ° C.), the produced salt was removed with a filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum dried at 60 ° C. overnight to obtain a white powder (polymer) (yield 251 g, yield 97%).

Table 1 shows the physical properties of the obtained polymer. The obtained polymer was subjected to structural analysis and measurement of weight average molecular weight and number average molecular weight. The results show that the characteristic absorption of infrared absorption spectrum is 3035 (aromatic C—H stretching), 2935 (aliphatic C—H stretching), 2229 cm ⁻¹ (CN), 1574 cm ⁻¹ , 1499 cm ⁻¹ (aromatic ring skeleton). Absorption), 1240 cm ⁻¹ (—O—), a weight average molecular weight of 105,000, and a number average molecular weight of 28,000. The obtained polymer had the structural unit (1).

Next, the obtained polymer was redissolved in DMAc to obtain a resin composition having a polymer concentration of 20% by mass. The resin composition is applied onto a substrate made of polyethylene terephthalate (PET) using a doctor blade, dried at 80 ° C. for 30 minutes, and then dried at 150 ° C. for 60 minutes to form a film. It peeled. Thereafter, the film was fixed to a metal frame and further dried at 200 ° C. for 2 hours to obtain an evaluation film having a thickness of 30 μm.
Table 1 shows the physical properties of the obtained film for evaluation. The obtained film for evaluation had a retardation (Rth) of 1 [nm], a stress optical coefficient of 30 [× 10 ⁻¹² Pa ⁻¹ ], and a photoelastic coefficient of 20 [× 10 ⁻¹² Pa ⁻¹ ]. .

[Example 2]
Except for using 217.29 g (0.5000 mol) of 9,9-bis (3-isopropyl-4-hydroxyphenyl) fluorene instead of 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene The same operation as in Example 1 was performed. Table 1 shows the physical properties of the obtained polymer and the film for evaluation. Moreover, as a result of measuring about the optical characteristic of the obtained film for evaluation, it confirmed that the optical isotropy was improving compared with the comparative example 1. FIG.

[Example 3]
Aside from using 203.26 g (0.5000 mol) of 9,9-bis (3-ethyl-4-hydroxyphenyl) fluorene instead of 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene. The same operation as in Example 1 was performed. Table 1 shows the physical properties of the obtained polymer and the film for evaluation. Moreover, as a result of measuring about the optical characteristic of the obtained film for evaluation, it confirmed that the optical isotropy was improving compared with the comparative example 1. FIG.

[Example 4]
Instead of 189.23 g of 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 151.38 g (0.4000 mol) of 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene and 1, The same procedure as in Example 1 was carried out except that 11.01 g (0.1000 mol) of 3-dihydroxybenzene was used. Table 1 shows the physical properties of the obtained polymer and the film for evaluation. Moreover, as a result of measuring about the optical characteristic of the obtained film for evaluation, it confirmed that the optical isotropy was improving compared with the comparative example 1. FIG.

[Example 5]
Implemented except that 52.94 g (0.3806 mol) of 2,6-difluorobenzonitrile and 27.69 g (0.1269 mol) of 4,4′-difluorobenzophenone were used instead of 70.59 g of 2,6-difluorobenzonitrile. Performed as in Example 1. Table 1 shows the physical properties of the obtained polymer and the film for evaluation. Moreover, as a result of measuring about the optical characteristic of the obtained film for evaluation, it confirmed that the optical isotropy was improving compared with the comparative example 1. FIG.

[Comparative Example 1]
Instead of 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 251.30 g (0.5000 mol) of 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene was used. The same operation as in Example 1 was performed. Table 1 shows the physical properties of the obtained polymer and the film for evaluation. As a result of measuring the optical properties of the obtained film for evaluation, the phase difference (Rth) was 80 [nm], the stress optical coefficient was 215 [× 10 ⁻¹² Pa ⁻¹ ], and the photoelastic coefficient was 55 [× 10 ⁻¹² Pa. ^-1 ].

[Comparative Example 2]
The same procedure as in Example 1 was conducted except that 129.03 g (0.5075 mol) of 4,4′-difluorodiphenylsulfone was used instead of 2,6-difluorobenzonitrile. Table 1 shows the physical properties of the obtained polymer and the film for evaluation. As a result of measuring the optical properties of the obtained film for evaluation, the retardation (Rth) was 65 [nm], the stress optical coefficient was 1600 [× 10 ⁻¹² Pa ⁻¹ ], and the photoelastic coefficient was 50 [× 10 ^−12. Pa ^-1 ].

Claims (12)

The polymer which has a structural unit represented by following formula (1).

(In the formula (1), R ¹ and R ² represents a monovalent organic group having 1 to 12 carbon atoms having independently an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, R ³ to R ⁶ Each independently represents a monovalent organic group having 1 to 12 carbon atoms, a and b each independently represent an integer of 0 to 3, and c and d each independently represents an integer of 0 to 4. .) ^2. The polymer according to claim 1, wherein, in the formula (1), a bonding position of R ¹ and R ² is an ortho position of an ether bond forming a main chain skeleton of the polymer. The polymer is further selected from the group consisting of a structural unit represented by the following formula (1-1), a structural unit represented by the following formula (2), and a structural unit represented by the following formula (3). The polymer according to claim 1 or 2, which has at least one structural unit.

(In the formula (1-1), R ^{1 to} R ⁶ and a to d are independently the same as R ^{1 to} R ⁶ and a to d in the formula (1), and R ⁷ and R ⁸ are Each independently represents a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, j and k each independently represents an integer of 0 to 4, Y is a single bond, —SO ₂ — or > C = O, m represents 0 or 1)

(In the formula (2), R ⁷ , R ⁸ , Y, m, j and k are each independently synonymous with R ⁷ , R ⁸ , Y, m, j and k in the formula (1-1). R ^{9 to} R ¹² are each independently a monovalent organic group having 1 to 12 carbon atoms (however, a monovalent organic group having 1 to 12 carbon atoms having an aliphatic hydrocarbon group or an alicyclic hydrocarbon group) Group is excluded.), And e to h each independently represents an integer of 0 to 4.)

(In the formula (3), R ¹³ and R ¹⁴ are each independently a monovalent organic group having 1 to 12 carbon atoms, Z is a single bond, -O -, - S -, - SO 2 -,> C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, p and q each independently represents an integer of 0 to 4, n represents 0 or 1, ^{R 7, R 8, Y,} m, j and k are, R ⁷ each independently the formula (1-1) in, R ^8, Y, m, is synonymous with j and k.)   The polymer of any one of Claims 1-3 whose glass transition temperature measured by the differential scanning calorimetry (DSC, temperature rising rate of 20 degree-C / min) of the said polymer is 230-350 degreeC.   The film containing the polymer of any one of Claims 1-4.   The film according to claim 5, wherein the total light transmittance according to JIS K7105 transparency test method is 85% or more when the film has a thickness of 30 μm.   The film of Claim 5 or 6 whose YI value (yellow index) is 30 or less in thickness of 30 micrometers of the said film.   The film according to any one of claims 5 to 7, wherein a retardation (Rth589) in a thickness direction of the film measured at a wavelength of 589 nm at a thickness of 30 µm is 60 nm or less. The absolute value of the photoelastic coefficient of the film was measured at a wavelength of 589 nm (C _d) is ^{0~50 (× 10 -12 Pa -1)} , the film according to any one of claims 5-8. The film according to any one of claims 5 to 9, wherein the absolute value of the stress optical coefficient (C _R ) of the film measured at a wavelength of 589 nm is ¹ to 1500 (× 10 ⁻¹² Pa ⁻¹ ).   The resin composition containing the polymer and organic solvent of any one of Claims 1-4.   It is a method of manufacturing the film of any one of Claims 5-10, Comprising: The process of apply | coating the resin composition of Claim 11 on a support body, and forming a coating film, and this coating film And removing the organic solvent by evaporation to obtain a film.