JP2005272615A - Polymer and optical film composed of polyester or polyurethane - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer suited to an application for optical parts and excellent in heat resistance, optical properties and mechanical properties, and to provide an optical film using the polymer and excellent in heat resistance, optical properties and mechanical properties, and an image display device using the optical film and excellent in the display quality. <P>SOLUTION: It comprises using a polymer composed of a polyester or a polyurethane having a cross-linking reactive group, preferably an alkenyl group or an alkynyl group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel polymer excellent in heat resistance, optical properties and mechanical properties, an optical film formed using the polymer, and an image display device excellent in display quality using the optical film.

  In recent years, in the field of flat panel displays such as liquid crystal display elements and organic electroluminescence elements (hereinafter referred to as “organic EL elements”), the substrate is replaced from glass to plastic in order to improve breakage resistance, reduce weight, and reduce thickness. Is being considered. In particular, there is a strong demand for a plastic substrate in a display device for mobile information communication equipment such as a portable information terminal such as a mobile phone, an electronic notebook, or a laptop personal computer.

  The plastic substrate needs to have conductivity. Therefore, in recent years, on a plastic film, a semiconductor film such as an oxide of indium oxide, tin oxide, or a tin-indium alloy, a metal film such as an oxide film of gold, silver, or a palladium alloy, the semiconductor film and the metal film It has been studied to use a transparent conductive substrate provided with a film formed by combining as a transparent conductive layer as an electrode substrate of a display element.

  As the transparent conductive substrate used for this purpose, a heat-resistant amorphous polymer such as a modified polycarbonate (modified PC) (for example, see Patent Document 1), polyethersulfone (PES) (for example, see Patent Document 2). A laminate in which a transparent conductive layer and a gas barrier layer are laminated on a substrate made of a cycloolefin copolymer (see, for example, Patent Document 3) is known.

  However, even if the above heat-resistant plastic is used, a plastic substrate having sufficient heat resistance cannot be obtained. That is, if a gas barrier layer and a conductive layer are formed on a plastic substrate using these heat-resistant plastics and then exposed to a temperature of 150 ° C. or higher for providing an alignment film, the conductivity and gas barrier properties are greatly reduced. There was a problem.

Further, in recent years, a higher level of heat resistance is required for a base film in the case where a TFT for manufacturing an active matrix image element is installed. For example, Patent Document 4 describes a method of forming a polycrystalline silicon film at a temperature of 300 ° C. or lower by plasma decomposition of a gas containing SiH ₄ . Patent Document 5 describes a method for forming a semiconductor layer in which amorphous silicon and polycrystalline silicon are mixed on a polymer substrate by irradiation with an energy beam. Patent Document 6 describes a method of providing a thermal buffer layer and irradiating a pulsed laser beam to form a polycrystalline silicon semiconductor layer on a plastic substrate.

  As shown in Patent Documents 4 to 6, various methods for forming a polycrystalline silicon film for TFT at 300 ° C. or lower have been proposed. However, the structure and apparatus are complicated, resulting in high costs, and 300 to 350 ° C. The above heat resistance is required for the plastic substrate.

  In view of these needs, several plastic substrates made of heat-resistant polymers have been developed so far. For example, Patent Document 7 describes a thin film transistor substrate using polyimide derived from an aliphatic tetracarboxylic acid anhydride. The polyimide film described in the Examples of Patent Document 7 is excellent in heat resistance and transparency with a glass transition temperature (hereinafter referred to as “Tg”) of 315 ° C. and a total light transmittance of 85%. However, the aliphatic tetracarboxylic acid anhydride used as a raw material is expensive, and further, film formation at a high temperature using a high-boiling solvent is necessary.

  Patent Documents 8 and 9 also describe a polyester film derived from 9,9-bis (4-hydroxyphenyl) fluorene (hereinafter also referred to as “bisphenolfluorene”), isophthalic acid and terephthalic acid. Patent Document 10 describes a polyester film derived from alkyl-substituted bisphenolfluorene, isophthalic acid and terephthalic acid. Polyesters derived from these alkyl-substituted or unsubstituted bisphenolfluorenes, isophthalic acid and terephthalic acid can be synthesized from inexpensive raw materials and have a Tg of around 300 ° C. Further, Patent Document 10 describes a flexible film excellent in transparency and elongation at break using a low boiling point solvent such as dichloromethane or cyclohexanone. However, these polymers do not necessarily have sufficient heat resistance for the TFT installation process in the production of an active matrix type image device, and meet the demands for mechanical properties required for plastic substrates. Further improvement was desired.

  Patent Document 11 describes a polyimide or polyimide oligomer end-capped with diarylacetylene. Since the polyimide has a low molecular weight, good solubility can be obtained, while heat resistance and mechanical properties can be improved by a cross-linking reaction of alkynyl groups by heating after film formation. However, there is a drawback that the coloring of the polymer is not preferable for use as an optical film.

  As described above, there has been a strong demand for the development of a polymer that satisfies all the characteristics of transparency, heat resistance, and mechanical properties, and an optical film formed of the polymer.

JP 2000-227603 A (Claim 7, [0009] to [0019]) JP 2000-284717 A ([0010], [0021] to [0027]) JP 2001-150584 A ([0027] to [0039]) JP-A-7-81919 (Claim 3, [0016] to [0020]) JP 10-512104 A (pages 14-22, FIGS. 1 and 7) JP-A-11-102867 (Claims 1 to 10, [0036]) JP 2003-168800 A (Claims) JP-A-57-192432 (Claims) JP-A-3-28222 (Claims) WO 99/18141 (claim part) US Pat. No. 5,138,028 (claim part)

  The present invention has been made in view of the above-mentioned problems, and a first object of the present invention is to provide a polymer suitable for optical component applications having both excellent transparency, heat resistance and mechanical properties. . The second object of the present invention is to provide an optical film which is formed using the polymer and has both excellent transparency, heat resistance and mechanical properties. A third object of the present invention is to provide an image display device having excellent display quality using the optical film.

  As a result of various studies on the structure of the polymer in order to achieve the above object, the present inventor has found that a polymer having a predetermined structure satisfies all of transparency, heat resistance and mechanical properties. Furthermore, it was confirmed that an optical film formed of this polymer and an image display element using the optical film exhibit excellent transparency, heat resistance and mechanical properties, and the present invention has been completed.

That is, the above object of the present invention is achieved by the following means.
(1) A polymer comprising a polyester or polyurethane having a crosslinking reactive group.
(2) The polymer according to (1), wherein the crosslinking reactive group is an alkenyl group or an alkynyl group.
(3) The polymer as described in (1) or 2 containing the chemical structure shown by the following general formula (1) or general formula (2).

  In general formula (1), ring α represents a monocyclic or polycyclic ring, and the two rings are connected by a spiro bond.

In general formula (2), ring β and ring γ represent a monocyclic or polycyclic ring, and two rings γ may be the same or different, and one quaternary ring on ring β. Linked to carbon.
(4) An optical film formed of the polymer according to any one of (1) to (3).
(5) The optical film as described in (4) whose total light transmittance is 80% or more.
(6) The optical film according to (4) or (5), wherein a gas barrier layer is laminated on at least one surface.
(7) The optical film according to any one of (4) to (6), wherein a transparent conductive layer is laminated on at least one surface.
(8) An image display device using the optical film according to any one of (4) to (7).

  The polymer of the present invention comprises a polyester or polyurethane having a predetermined crosslinking reactive group. Thereby, according to this invention, the polymer which has the outstanding heat resistance, an optical characteristic, and a dynamic characteristic can be provided. The optical film of the present invention is a film made of the polymer. Thereby, according to this invention, the optical film which has the outstanding heat resistance, the optical characteristic, and the dynamic characteristic which can laminate | stack a gas barrier layer and a transparent conductive layer can be provided. Furthermore, the optical film is used for the image display element of the present invention. Thereby, according to this invention, the image display apparatus excellent in the display quality can be provided.

Hereinafter, the polymer, the optical film and the image display element of the present invention will be described in detail.
In the present specification, “to” is used as a meaning including numerical values described before and after the lower limit value and the upper limit value.

[Polymer of the present invention]
The polymer of the present invention is composed of a polyester or polyurethane having a crosslinking reactive group.
In the present invention, the “crosslinking reactive group” is not particularly limited as long as it can form a three-dimensional network structure by connecting polymer chains by chemical bonds. Examples of crosslinking reactive groups include alkynyl groups (eg, ethynyl group, phenylethynyl group, etc.), alkenyl groups (eg, maleimide group, cinnamoyl group, (meth) acryloyl group, vinyl group, vinyloxy group, allyl group) , Ring-opening polymerizable groups (for example, epoxy groups, oxetanyl groups, oxazolyl groups, etc.) and reactive silyl groups (for example, alkoxysilyl groups, acetoxysilyl groups, hydroxysilyl groups, etc.), preferably alkynyl groups or An alkenyl group, particularly preferably an alkynyl group.

  The cross-linking reactive group may be substituted on the polyester side chain or polyurethane side chain, or may be substituted on the terminal, and may be further substituted in plural. When a plurality of crosslinking reactive groups present in the polyester chain or the polyurethane chain are substituted, these crosslinking reactive groups may be the same as or different from each other. In the present invention, a form in which at least a crosslinking reactive group is substituted at the terminal of the polyester chain or the polyurethane chain is particularly preferable.

  Polyester or polyurethane having a crosslinking reactive group in the side chain is synthesized by performing polycondensation using a crosslinking reactive group-containing monomer (for example, alkynyl group-containing diol, alkynyl group-containing dicarboxylic acid, alkynyl group-containing diamine, etc.). it can. Further, the polyester or polyurethane having a crosslinking reactive group at the terminal is used in the presence of a crosslinking reactive group-containing end-capping agent (for example, alkynyl group-containing monoalcohol, alkynyl group-containing monocarboxylic acid, alkynyl group-containing monoamine, etc.). It can be synthesized by polymerization.

By increasing the introduction amount of the crosslinking reactive group, the heat resistance and mechanical properties of the polyester or polyurethane can be improved. On the other hand, if the introduction amount of the crosslinking reactive group is too large, curing shrinkage may become a problem. is there. The optimum introduction amount of the crosslinking reactive group varies depending on the structure of the polyester or polyurethane. Generally, the amount of the crosslinking reactive group introduced into the polyester or polyurethane is 1 × 10 ^{−4 to} 10 mmol. / G is preferable, 1 × 10 ^{−3 to 2} mmol / g is more preferable, and 1 × 10 ^{−2 to} 1 mmol / g is particularly preferable.

  The polymer of the present invention preferably has a spiro structure represented by the following general formula (1) or a cardo structure represented by the general formula (2). With these structures, organic EL elements, etc. that exhibit high heat resistance, high elastic modulus, and high tensile fracture stress, require various heating operations in the manufacturing process, and are resistant to breaking even when bent It is suitable as a substrate material.

  In general formula (1), ring α represents a monocyclic or polycyclic ring, and the two rings are connected by a spiro bond.

  In general formula (2), ring β and ring γ represent a monocyclic or polycyclic ring, and two rings γ may be the same or different, and one quaternary ring on ring β. Linked to carbon.

Preferred examples of the polymer having a spiro structure represented by the general formula (1) include a polymer containing a spirobiindane structure represented by the following general formula (3) in a repeating unit, and a spiro represented by the following general formula (4). Examples thereof include a polymer containing a bichroman structure in the repeating unit and a polymer containing a spirobibenzofuran structure represented by the following general formula (5) in the repeating unit.
Moreover, the polymer which contains the fluorene structure represented by following General formula (6) in a repeating unit as a preferable example of resin which has a cardo structure represented by General formula (2) is mentioned.

In General Formula (3), R ³¹ , R ³² , and R ³³ each independently represent a hydrogen atom or a substituent, and each may be linked to form a ring. Moreover, m and n represent the integer of 1-3. Examples of preferred substituents are a halogen atom, an alkyl group or an aryl group. More preferred examples of R ³¹ and R ³² are hydrogen atom, methyl group or phenyl group, and more preferred examples of R ³³ are hydrogen atom, chlorine atom, bromine atom, methyl group, isopropyl group, tert-butyl group or It is a phenyl group.

In the general formula (4), R ⁴¹ and R ⁴² each independently represent a hydrogen atom or a substituent, and each may be linked to form a ring. Moreover, m and n represent the integer of 1-3. Examples of preferred substituents are a halogen atom, an alkyl group or an aryl group. More preferred examples of R ⁴¹ are hydrogen atom, methyl group or phenyl group, and more preferred examples of R ⁴² are hydrogen atom, chlorine atom, bromine atom, methyl group, isopropyl group, tert-butyl group or phenyl group. .

一般式（５）中、Ｒ⁵¹、Ｒ⁵²は、それぞれ独立に水素原子または置換基を表し、それぞれが連結して環を形成してもよい。また、ｍおよびｎは１〜３の整数を表す。好ましい置換基の例は、ハロゲン原子、アルキル基、アリール基である。Ｒ⁵¹のより好ましい例は水素原子、メチル基またはフェニル基であり、Ｒ⁵²のより好ましい例は水素原子、塩素原子、臭素原子、メチル基、イソプロピル基、tert−ブチル基またはフェニル基である。

In the general formula (5), R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a substituent, and each may be linked to form a ring. Moreover, m and n represent the integer of 1-3. Examples of preferred substituents are a halogen atom, an alkyl group, and an aryl group. More preferred examples of R ⁵¹ are hydrogen atom, methyl group or phenyl group, and more preferred examples of R ⁵² are hydrogen atom, chlorine atom, bromine atom, methyl group, isopropyl group, tert-butyl group or phenyl group.

In the general formula (6), R ⁶¹ and R ⁶² each independently represent a hydrogen atom or a substituent, and each may be linked to form a ring. Moreover, j and k represent the integer of 1-4. Examples of preferred substituents are a halogen atom, an alkyl group or an aryl group. More preferred examples of R ⁶¹ and R ⁶² are a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, an isopropyl group, a tert-butyl group, or a phenyl group.

  The polyester or polyurethane containing the chemical structure represented by the general formula (1) or (2) in the repeating unit is derived from a bisphenol compound having the chemical structure represented by the general formula (1) or (2). It is preferably a polyester or polyurethane.

  Although the preferable specific example of a crosslinkable reactive group containing polymer useful for this invention is given to the following, this invention is not limited to this.

  The crosslinkable group-containing polyester or polyurethane used in the present invention may be used singly or as a mixture of plural kinds. Moreover, a homopolymer may be sufficient and the copolymer which combined multiple types of structure may be sufficient. Even in a polyester or polyurethane having a chemical structure represented by the general formula (1) or (2) as a repeating unit, a known monomer that does not contain these chemical structures is used as a comonomer, so that solubility and transparency can be achieved. In many cases, improvement is preferred from the viewpoint.

  The preferred molecular weight of the polymer of the present invention is 1,000 to 500,000 in terms of weight average molecular weight, more preferably 5,000 to 300,000, and particularly preferably 10,000 to 200,000. If the molecular weight is 1,000 or more, it is preferable because film formation is not difficult and mechanical properties are not deteriorated. A molecular weight of 500,000 or less is preferable because the molecular weight can be controlled in the synthesis, and a solution having an appropriate viscosity can be obtained and handled easily. The molecular weight can be based on the corresponding viscosity.

  When the polymer of the present invention comprises the above polyester, the polyester can be obtained by polycondensation of a bisphenol compound and a dicarboxylic acid or a derivative thereof. At this time, bisphenol or dicarboxylic acid having a crosslinking reactive group or a derivative thereof is used, or the polycondensation reaction is performed in the presence of the aforementioned crosslinking reactive group-containing end-capping agent.

  The polycondensation method includes a melt polycondensation method in which bisphenol diacetate and dicarboxylic acid are reacted to remove acetic acid, a melt polycondensation method in which bisphenol and dicarboxylic acid dibenzoate are reacted to remove phenol, and dicarboxylic acid chloride and bisphenol are organic bases. Dehydrochlorination homogeneous polymerization method in which the polymer is reacted in an organic solvent system in which the polymer is soluble, and interfacial polycondensation method in which dicarboxylic acid chloride and bisphenol are reacted in a two-phase system of an aqueous alkali solution and a water-immiscible organic solvent. A known method can be used. When the polyester has a Tg of 300 ° C. or higher, melt polycondensation becomes difficult. However, as described in JP-A-7-188405, polymerization at a reaction temperature of about 300 ° C. is performed by using a high-boiling plasticizer together. There are also known ways to enable this.

  The polyester can be synthesized by any of the synthesis methods described above, but the interfacial polycondensation method is particularly convenient and preferable. In the interfacial polycondensation reaction, a method in which a bisphenol compound dissolved in an aqueous alkali solution and a dicarboxylic acid chloride dissolved in a water-immiscible organic solvent (typically dichloromethane or the like) are mixed in a short time is common. In some cases, the solubility of the bisphenol compound in an alkaline aqueous solution is low. In addition, in the case of a dicarboxylic chloride having low solubility in a water-immiscible organic solvent, such as 2,6-naphthalenedicarboxylic acid chloride, the polyester may not be synthesized by a known method. In such a case, it is effective to increase the molecular weight by preliminarily mixing and stirring water, a water-immiscible organic solvent, a bisphenol compound, and a dicarboxylic acid chloride in a slurry state and gradually adding a high concentration alkaline aqueous solution. is there.

  The method for adjusting the molecular weight of the polyester can be carried out by adding a monofunctional substance at the time of polymerization, regardless of the production method described above. Monofunctional substances used as molecular weight regulators include monohydric phenols such as phenol, cresol, p-tert-butylphenol, monovalent acid chlorides such as benzoic acid chloride, methanesulfonyl chloride, and phenylchloroformate, methanol, Monovalent alcohols such as ethanol, n-propanol, isopropanol, n-butanol, pentanol, hexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol, phenethyl alcohol, acetic acid, propionic acid, octanoic acid, cyclohexanecarboxylic acid, benzoic acid Monovalent carboxylic acid such as toluic acid, phenyl acid, p-tert-butylbenzoic acid, p-methoxyphenylacetic acid, etc. can be used. It is preferable to use a sealant.

  The carboxyl value of the polyester is preferably 300 μmol / g or less, more preferably 30 μmol / g or less, and particularly preferably 10 μmol / g or less. If the carboxyl value is 300 μmol / g or less, without affecting the electrical characteristics such as arc discharge resistance and dielectric constant, without affecting the storage stability of the polymer solution prepared by dissolving in a solvent, This is preferable because it hardly affects the surface properties of the cast film obtained by the solution casting method. The carboxyl value of the resin can be measured by a known method such as neutralization titration using a potentiometric titrator.

When the polymer of the present invention is made of polyurethane, it can be synthesized according to a known production method, as in the case of the polyester, and includes a polyaddition method of bisphenol compound and diisocyanate compound, and a polycondensation method of bisphenol compound and dicarbamic acid chloride. preferable. The polyurethane can be synthesized by reacting dicarbamic acid chloride with phosgene acting on a diamine compound, and the diisocyanate compound can be synthesized by dehydrochlorination of dicarbamic acid chloride.
In the present invention, it is preferable to use a bisphenol, diisocyanate or dicarbamic acid chloride having a crosslinking reactive group, or to carry out the polymerization reaction in the presence of the aforementioned crosslinking reactive group-containing end-capping agent.

  The amount of residual alkali metal and halogen in the polymer of the present invention is preferably 50 ppm or less, particularly preferably 10 ppm or less. If the residual alkali metal content and halogen content are 50 ppm or less, the above-mentioned electrical characteristics will not be deteriorated, and the surface characteristics of the film will be adversely affected, and a functional film provided with a conductive film, a semiconductor film, etc. This is preferable because it does not cause a decrease in performance. The amount of residual alkali metal and halogen in the polymer can be quantified using known methods such as ion chromatography analysis, atomic absorption spectrometry, and plasma emission spectroscopy.

  Further, the amount of the catalyst such as quaternary ammonium salt and quaternary phosphonium salt remaining in the polymer of the present invention is preferably less than 200 ppm, more preferably less than 100 ppm. If the amount of the remaining catalyst is less than 200 ppm, the above-described electrical characteristics do not deteriorate, and the surface characteristics of the film are not adversely affected, and the functional film provided with a conductive film, a semiconductor film, etc. This is preferable because the performance does not deteriorate. Catalysts such as quaternary ammonium salts and quaternary phosphonium salts remaining in the polymer can be quantified using HPLC, gas chromatography, or the like.

  Further, the amount of residual components derived from monomers such as phenol monomer, dicarboxylic acid, dicarboxylic chloride, diamine and diisocyanate remaining in the polymer of the present invention is preferably 3000 ppm or less, more preferably 500 ppm or less, and still more preferably 100 ppm. It is as follows. If the amount of the remaining monomer component is 3000 ppm or less, the above-described electrical characteristics will not be deteriorated, and the surface characteristics of the film will be adversely affected, or a functional film provided with a conductive film, a semiconductor film, etc. This is preferable because it does not cause a decrease in performance. For example, if the residual monomer component is within the above range, when a transparent conductive film is formed on the film, a gas derived from the residual monomer component is generated due to the influence of heating or plasma during film formation, thermal decomposition, etc. It is preferable that no crystal grains are formed in the transparent conductive film, or an uncoated part called “missing” is generated, and the low resistance of the transparent conductive film is not hindered. The amount of monomer remaining in the polymer and its film can be analyzed by a known method such as HPLC or nuclear magnetic resonance.

[Optical Film of the Present Invention]
The optical film of the present invention is formed of the polymer of the present invention. As a method for forming the polymer of the present invention into a film or sheet shape, a known method can be adopted, and a solution casting method is preferable.
Regarding the casting and drying methods in the solution casting method, US Pat. No. 2,336,310, US Pat. No. 2,367,603, US Pat. No. 2,429,078, US Pat. No. 2,429,297, US Pat. No. 2,492,978, US Pat. No. 2739070, British Patent No. 640731, British Patent No. 736892, Japanese Examined Patent Publication No. 45-4554, Japanese Examined Patent Publication No. 49-5614, Japanese Unexamined Patent Publication No. 60-176634, Japanese Unexamined Patent Publication No. 60-203430, Japanese Unexamined Patent Publication No. There is description in each gazette of 62-1115035. Examples of the production apparatus produced by the solution casting method include the production apparatuses described in paragraphs [0061] to [0068] of JP-A No. 2002-189126, FIG. 1 and FIG. The present invention is not limited to these.

  In the solution casting method, the polymer is dissolved in a solvent. Any solvent can be used as long as it dissolves the polymer, but a solvent that can dissolve a solid concentration of 10% by mass or more at 25 ° C. is particularly preferable. The solvent used preferably has a boiling point of 200 ° C. or lower, more preferably 150 ° C. or lower. When the boiling point is high, the solvent may be insufficiently dried and may remain in the film. Moreover, it is also possible to mix a poor solvent in the range which does not impair the solubility of the polymer used for this invention, In this case, it may become advantageous in terms of stripping after solution casting and a drying rate.

  Solvents used in the present invention include methylene chloride, chloroform, tetrahydrofuran, 1,4-dioxane, benzene, cyclohexane, toluene, xylene, anisole, γ-butyrolactone, benzyl alcohol, isophorone, cyclohexanone, cyclopentanone, 1,2 -Dichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, acetone, chlorobenzene, dichlorobenzene, dimethylformamide, methanol, ethanol and the like are exemplified, but the present invention is not limited thereto. In addition, two or more solvents may be used as a mixture, and a mixed solvent is preferable from the viewpoint of achieving both dryness and solubility. Moreover, by using a mixed solvent, the transparency of the optical film of the present invention may be improved, which is preferable.

  The polymer concentration in the solution used for solution casting is 5 to 60% by mass, preferably 10 to 40% by mass, and more preferably 10 to 30% by mass. When the polymer concentration is 5 to 60% by mass, an appropriate viscosity is obtained, the thickness can be easily adjusted, and the film forming property is good, so that the unevenness is small. Moreover, the transmittance | permeability of the optical film of this invention and the impurity in a film can be reduced by filtering as needed before solution casting.

  The method for casting the solution is not particularly limited, but it can be cast on a flat plate or a roll using a bar coater, a T die, a T die with a bar, a doctor blade, a roll coat, a die coat or the like.

The temperature at which the solvent is dried varies depending on the boiling point of the solvent used, but it is preferable to dry the solvent in two stages. Thereby, a polymer film having optical isotropy can be obtained. As a first step, drying is performed at 30 to 100 ° C. until the concentration of the solvent is 10% by mass or less, preferably 5% by mass or less. Next, as a second step, the film is peeled off from the flat plate or roll and dried in the range from 60 ° C. or higher to the Tg of the polymer.
When peeling a film from a flat plate or a roll, you may peel immediately after completion | finish of drying of a 1st step, or you may peel after cooling once.

  If the optical film of the present invention is insufficiently dried by heating, the amount of residual solvent is large, and if it is excessively heated, it causes thermal decomposition of the polymer and the amount of residual monomer increases. Furthermore, rapid drying by heating causes rapid vaporization of the contained solvent, and causes defects such as bubbles in the film. The amount of the solvent remaining in the optical film of the present invention is preferably 2000 ppm or less, more preferably 1000 ppm or less, and particularly preferably 100 ppm or less. If the amount of residual solvent is 2000 ppm or less, the surface properties of the film will not be deteriorated, the surface treatment will be adversely affected, or the performance of the functional film provided with a conductive film, semiconductor film, etc. may be reduced. It is preferable because there is no. The amount of the solvent remaining in the polymer film of the present invention can be quantified using a known method such as gas chromatography.

  The optical film of the present invention is preferably a method in which a solution is cast on a rotating drum or a band, peeled off, and dried continuously to be wound into a roll. Thus, when the optical film of this invention is conveyed mechanically, it is preferable that the mechanical strength of a film is high. Although the preferable mechanical strength depends on the conveying device, it cannot be generally specified, but as a guide, the breaking stress and the breaking elongation obtained from the film tensile test can be used. A preferable breaking stress is 50 MPa or more, more preferably 80 MPa or more, and further preferably 100 MPa or more. The elongation at break may vary depending on the sample preparation conditions and the like, but is preferably 5% or more, more preferably 10% or more, and further preferably 15% or more.

  The optical film of the present invention may be stretched. By stretching, mechanical strength such as folding strength is improved, and there is an advantage that handling property is improved. In particular, those having an orientation release stress (ASTMD1504, hereinafter abbreviated as ORS) in the stretching direction of 0.3 to 3 GPa are preferred because the mechanical strength is improved. ORS is an internal stress generated by stretching inherent in a stretched film or sheet.

  For the stretching, a known method can be used. However, when the polymer of the present invention has a Tg of 300 ° C. or higher, it is difficult to stretch only by heating, and therefore stretching in a state containing a solvent is preferable. In this case, it is preferable to perform stretching in the course of drying, for example, a roll uniaxial stretching method, a tenter uniaxial stretching method, at a temperature between 10 ° C. and 50 ° C. higher than the Tg containing the solvent, The film can be stretched by a simultaneous biaxial stretching method, a sequential biaxial stretching method, or an inflation method. The draw ratio is 1.1 to 3.5 times, preferably 1.1 to 2.0 times.

  The polymer of the present invention that forms the optical film of the present invention may be only one kind or two or more kinds may be mixed. Moreover, the polymer other than the said polyester and polyurethane may be included in the range which does not impair the effect of this invention. Moreover, you may add crosslinked resin from viewpoints, such as solvent resistance, heat resistance, and mechanical strength. As the kind of the cross-linked resin, various known ones can be used without any particular limitation as the thermosetting resin and the radiation curable resin.

  Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, silicone resin, diallyl phthalate resin, furan resin, bismaleimide resin, cyanate resin and the like. In addition, the crosslinking method can be used without particular limitation as long as it is a reaction that forms a covalent bond, and there is a system in which the reaction proceeds at room temperature using a polyalcohol compound and a polyisocyanate compound to form a urethane bond. Can be used without any particular restrictions. However, such a system often has a problem of pot life before film formation, and is usually used as a two-component mixed type in which a polyisocyanate compound is added immediately before film formation.

  On the other hand, when used as a one-component type, it is effective to protect the functional group involved in the crosslinking reaction, and it is also commercially available as a block type curing agent. As commercially available block type curing agents, B-882N manufactured by Mitsui Takeda Chemical Co., Ltd., Coronate 2513 manufactured by Nippon Polyurethane Industry Co., Ltd. (above block polyisocyanate), Cymel 303 manufactured by Mitsui Cytec Co., Ltd. (methylated melamine resin) ) Etc. are known. Further, a blocked carboxylic acid such as the following B-1 that protects a polycarboxylic acid that can be used as a curing agent for an epoxy resin is also known.

  Radiation curable resins are roughly classified into radical curable resins and cationic curable resins. As the curable component of the radical curable resin, a compound having a plurality of radical polymerizable groups in the molecule is used. As a typical example, a polyfunctional acrylate having 2 to 6 acrylate groups in the molecule A compound called a monomer or a compound having a plurality of acrylate groups in a molecule called urethane acrylate, polyester acrylate, or epoxy acrylate is used. As a typical curing method of the radical curable resin, there are a method of irradiating an electron beam and a method of irradiating ultraviolet rays. Usually, in the method of irradiating with ultraviolet rays, a polymerization initiator that generates radicals upon irradiation with ultraviolet rays is added. In addition, if the polymerization initiator which generate | occur | produces a radical by heating is added, it can also be used as a thermosetting resin.

  As the curable component of the cationic curable resin, a compound having a plurality of cationic polymerizable groups in the molecule is used. As a typical curing method, a photoacid generator that generates an acid upon irradiation with ultraviolet rays is added, and ultraviolet rays are added. And a method of curing by irradiation. Examples of the cationically polymerizable compound include a compound containing a ring-opening polymerizable group such as an epoxy group and a compound containing a vinyl ether group.

  In the optical film of the present invention, a plurality of the thermosetting resins and radiation curable resins mentioned above may be mixed and used, or a thermosetting resin and a radiation curable resin may be used in combination. Moreover, you may mix and use a crosslinkable resin and the polymer which does not have a crosslinkable group.

  The optical film of the present invention can contain a metal oxide and / or a metal complex oxide and a metal oxide obtained by a sol-gel reaction. In this case, heat resistance and solvent resistance can be imparted in the same manner as the above-mentioned crosslinked resins. Furthermore, resin modifiers such as plasticizers, dyes / pigments, antistatic agents, ultraviolet absorbers, antioxidants, inorganic fine particles, peeling accelerators, leveling agents, and lubricants as long as the effects of the present invention are not impaired as necessary. May be added.

  The thickness of the optical film of the present invention is not particularly limited, but is preferably 30 to 700 μm, more preferably 40 to 200 μm, and further preferably 50 to 150 μm. Moreover, it is preferable that the haze of the optical film of this invention is 3% or less, More preferably, it is 2% or less, More preferably, it is 1% or less. Moreover, it is preferable that the total light transmittance of the optical film of this invention is 70% or more, More preferably, it is 80% or more, More preferably, it is 85% or more.

  The heat resistant temperature of the optical film of the present invention is preferably higher, and Tg by DSC measurement can be used as a guide. In this case, a preferable Tg is 250 ° C. or higher, more preferably 300 ° C. or higher, and particularly preferably 330 ° C. or higher. When the optical film of the present invention is produced by the solution casting method using only the polymer of the present invention, if the drying is sufficient, there is almost no difference between the Tg of the polymer used and the glass transition temperature of the optical film, Within measurement error range.

  The surface of the optical film of the present invention is subjected to saponification, corona treatment, flame treatment, glow discharge treatment, etc. on the surface of the film substrate in order to enhance the adhesion with other layers or components depending on the application. Can do. Furthermore, an adhesive layer and an anchor layer may be provided on the film surface. Depending on the purpose, smoothing layer for surface smoothing, hard coat layer for imparting scratch resistance, ultraviolet absorbing layer for enhancing light resistance, surface roughening layer for improving film transportability, etc. Various known functional layers can be provided.

  The optical film of the present invention can form a transparent conductive layer. As the transparent conductive layer, a known metal film, metal oxide film, or the like can be applied. Among these, a metal oxide film is preferable from the viewpoint of transparency, conductivity, and mechanical properties. For example, metal oxide films such as indium oxide, cadmium oxide and tin oxide to which tin, tellurium, cadmium, molybdenum, tungsten, fluorine, zinc, germanium, etc. are added as impurities, zinc oxide, titanium oxide, etc. to which aluminum is added as impurities, Can be mentioned. Among them, an indium oxide thin film mainly composed of tin oxide and containing 2 to 15% by mass of zinc oxide is excellent in transparency and conductivity, and is preferably used.

  The transparent conductive layer can be formed by any method as long as the target thin film can be formed. For example, the material can be formed from the gas phase such as sputtering, vacuum deposition, ion plating, and plasma CVD. A vapor phase deposition method in which a film is deposited to form a film is suitable, and a film can be formed using the methods described in Japanese Patent No. 3434344, Japanese Patent Application Laid-Open No. 2002-322561, and Japanese Patent Application Laid-Open No. 2002-361774. Especially, it is preferable to form a transparent conductive layer by sputtering method from a viewpoint that the outstanding electroconductivity and transparency are acquired.

  A preferable vacuum degree of the sputtering method, the vacuum deposition method, the ion plating method, and the plasma CVD method is 0.133 mPa to 6.65 Pa, more preferably 0.665 mPa to 1.33 Pa. Before providing such a transparent conductive layer, it is preferable to subject the base film to a surface treatment such as plasma treatment (reverse sputtering) or corona treatment. Moreover, you may heat up to 50-200 degreeC during providing the transparent conductive layer.

  The film thickness of the transparent conductive layer is preferably 20 to 500 nm, more preferably 50 to 300 nm.

  The surface electrical resistance measured at 25 ° C. and 60% RH (relative humidity) of the transparent conductive layer is preferably 0.1 to 200Ω / □, more preferably 0.1 to 100Ω / □, and still more preferably. 0.5 to 60Ω / □ or less. Moreover, it is preferable that the light transmittance of a transparent conductive layer is 80% or more, More preferably, it is 83% or more, More preferably, it is 85% or more.

  The optical film of the present invention is preferably provided with a gas barrier layer in order to suppress gas permeability. Preferred gas barrier layers include, for example, metal oxides composed mainly of one or more metals selected from the group consisting of silicon, aluminum, magnesium, zinc, zirconium, titanium, yttrium, and tantalum, silicon, aluminum, boron Metal nitrides or mixtures thereof. Among these, the main component is silicon oxide having a ratio of the number of oxygen atoms to the number of silicon atoms of 1.5 to 2.0 in terms of gas barrier properties, transparency, surface smoothness, flexibility, film stress, cost, and the like. Metal oxide is good. These inorganic gas barrier layers can be produced by a vapor deposition method in which a film is formed by depositing a material in a vapor phase, such as a sputtering method, a vacuum deposition method, an ion plating method, or a plasma CVD method. Among these, the sputtering method is preferable from the viewpoint that particularly excellent gas barrier properties can be obtained. Further, the temperature may be raised to 50 to 200 ° C. while the gas barrier layer is provided.

  The film thickness of the gas barrier layer is preferably 10 to 300 nm, more preferably 30 to 200 nm.

  The gas barrier layer may be formed on the same side or the opposite side as the transparent conductive layer, but is preferably formed on the opposite side.

The gas barrier property of the optical film of the present invention in which a gas barrier layer is formed has a water vapor permeability measured at 40 ° C. and 90% RH of preferably 5 g / m ² · day or less, and preferably 1 g / m ² · day or less. Is more preferably 0.5 g / m ² · day or less. The oxygen permeability was measured at 40 ° C. 90% RH is preferably from ^{1ml / m 2 · day · atm} , more preferably not more than ^{0.7ml / m 2 · day · atm} , 0. More preferably, it is 5 ml / m ² · day · atm or less.

  In order to improve the gas barrier property, it is particularly desirable to provide a defect compensation layer adjacent to the gas barrier layer. As the defect compensation layer, (1) a method using an inorganic oxide layer produced by using a sol-gel method as described in US Pat. No. 6,171,663 and JP-A-2003-94572, (2) US Pat. Examples thereof include a method using an organic layer as described in US Pat. Nos. 6413645 and 64163645. The organic layer is formed by depositing an organic monomer under vacuum as described in the above specification and curing it with ultraviolet rays or an electron beam, or after applying an organic monomer, it is cured with heating, electron beam, ultraviolet rays or the like. It can be produced by a method. When the coating method is used, various conventionally used coating methods such as spray coating, spin coating, and bar coating can be used.

[Image display element]
The optical film of the present invention can be used as a substrate for a thin film transistor (TFT) display element. Examples of the method for producing the TFT array include the method described in JP-T-10-512104. Further, these substrates may have a color filter for color display. The color filter may be produced by any method, but is preferably produced by a photolithography technique.

  The optical film of the present invention can be used in an image display device after providing various functional layers as necessary. Here, the image display device is not particularly limited, and a conventionally known one can be used. Moreover, the flat panel display excellent in display quality can be produced using the optical film of this invention. Flat panel displays include liquid crystal displays, plasma displays, electroluminescence (EL), fluorescent display tubes, light emitting diodes, etc. In addition to these, as a substrate that replaces the glass substrate of the display system in which a conventional glass substrate has been used. Can be used. Furthermore, the optical film of the present invention can also be used for applications such as solar cells and touch panels. The touch panel can be applied to those described in JP-A-5-127822, JP-A-2002-48913, and the like.

  When the optical film of the present invention is used for liquid crystal display applications, it is preferably an amorphous polymer in order to achieve optical uniformity. Further, it is preferable that the birefringence is small, and in particular, the in-plane retardation (Re) is preferably 50 nm or less, more preferably 30 nm or less, and further preferably 15 nm or less. In order to obtain an optical film having a small birefringence by using only the polymer of the present invention, it is possible to appropriately adjust the solvent and the drying conditions during solution casting. Moreover, it can also extend | stretch and adjust as needed. Furthermore, for the purpose of controlling retardation (Re) and its wavelength dispersion, resins having different signs of intrinsic birefringence can be combined, or resins having large (or small) wavelength dispersion can be combined. In addition, the optical film of the present invention can be suitably used for the purpose of controlling retardation (Re) and improving gas permeability and mechanical properties, and the like. Further, phase difference compensation can be performed by using a known retardation plate in combination.

  The reflective liquid crystal display device includes, in order from the bottom, a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film. Among these, the optical film of the present invention may be used as a λ / 4 plate or a protective film for a polarizing film by adjusting optical properties, but is preferably used as a substrate from the viewpoint of heat resistance, and further from the viewpoint of transparency. It is preferable to use as a transparent electrode and an upper substrate with an alignment film. Moreover, a gas barrier layer, TFT, etc. can also be provided as needed. In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.

  The transmissive liquid crystal display device includes, in order from the bottom, a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a λ / 4 plate, and a polarization It consists of a membrane. Of these, the optical film of the present invention may be used as a λ / 4 plate or a polarizing film protective film by adjusting the optical properties, but is preferably used as a substrate from the viewpoint of its heat resistance, and has a transparent electrode and an alignment film attached. It is preferable to use it as a substrate. Moreover, a gas barrier layer, TFT, etc. can also be provided as needed. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.

  The liquid crystal cell is not particularly limited, but TN (Twisted Nematic), IPS (In-P1ane Switching), FLC (Ferroelectric Liquid Crysta1), AFLC (Anti-ferroelectric Liquid Crystal), OCB (Optica1ly Compensatory Bend), STN (Supper Twisted Nematic) ), VA (Vertically Aligned) and HAN (Hybrid Aligned Nematic) have been proposed. In addition, a display mode in which the above display mode is oriented and divided has been proposed. The polarizing optical film of the present invention is effective in any display mode liquid crystal display device. Further, it is effective in any of a transmissive, reflective, and transflective liquid crystal display device.

The liquid crystal cell is disclosed in JP-A-2-176625, JP-B-7-69536, MVA (SID97, Digest of tech. Papers (Preliminary Collection) 28 (1997) 845), SID99, Digest of tech. Papers (Preliminary Collection). ) 30 (1999) 206, JP-a-11-258605 discloses, a SURVIVAL (monthly display, Vol. 6, No. 3 (1999) 14), PVA ( Asia display 98, Proc. of the 18 th Inter. display res. Conf. (Proceedings) (1998) 383), Para-A (LCD / PDP International`99), DDVA (SID98, Digest of tech. Papers (Proceedings) 29 (1998) 838), EOC (SID98, Digest of tech. Papers (Preliminary Collection) 29 (1998) 319), PSHA (SID98, Digest of tech. Papers (Preliminary Collection) 29 (1998) 1081), RFFMH (Asia Display 98, Proc. of the 18th Inter. Display res. Conf. (Preliminary Collection) (1998) 375), HMD (SID98, Digest of tech. Papers (Preliminary Collection) 29 (1998) 702), JP-A-10-123478, International Publication W098 / 48320, Patent No. 30 2477 JP, and are described in International Publication WO00 / sixty-five thousand three hundred and eighty-four No. or the like.

The optical film of the present invention is provided with a gas barrier layer and TFT as necessary, and can be used as a substrate with a transparent electrode for organic EL display applications.
As a specific layer structure as the organic EL display element, anode / light emitting layer / transparent cathode, anode / light emitting layer / electron transport layer / transparent cathode, anode / hole transport layer / light emitting layer / electron transport layer / transparent cathode , Anode / hole transport layer / light emitting layer / transparent cathode, anode / light emitting layer / electron transport layer / electron injection layer / transparent cathode, anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron Examples include injection layer / transparent cathode.

  The organic EL element in which the optical film of the present invention can be used applies a direct current (which may include an alternating current component as necessary) voltage (usually 2 to 40 volts) or a direct current between the anode and the cathode. Thus, light emission can be obtained.

  The driving of these light emitting elements is described in JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7-134558, JP-A-8-234658, and JP-A-8-241047. The methods described in each publication, US Pat. Nos. 5,828,429 and 6023308, Japanese Patent No. 2784615, and the like can be used.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these.

Example 1 Synthesis of Exemplified Compound (Synthesis Example 1) Synthesis of Exemplified Compound P-1 BPFL (trade name) manufactured by JFE Chemical Co., Ltd. was recrystallized twice with acetonitrile and heated at 70 ° C. for 3 hours under vacuum. After drying, it was used as the following raw material. Impurities were not observed in the HPLC analysis except that the obtained BPFL contained 9.4% by mass of acetonitrile.
7.43 g (19.2 mmol) of BPFL containing acetonitrile obtained above, 304.11 mg (1.6 mmol) of 4-phenylethynylphenol, 278 mg (1.0 mmol) of tetrabutylammonium chloride, 0.06 g of sodium hydrosulfite, Dichloromethane (37.5 ml), 2M (2N) aqueous sodium hydroxide solution (21.0 ml (42 mmol)) and water (79 ml) were charged into a reaction vessel equipped with a stirrer, and stirred in a water bath at 300 rpm in a nitrogen stream. After 30 minutes, 2.03 g (10 mmol) of terephthalic acid and 2.03 g (10 mmol) of isophthalic acid were charged as powders, and washed with 57.5 ml of dichloromethane. Thereafter, stirring was continued for 6 hours, 100 ml of dichloromethane was added, and the organic phase was separated. Further, 100 ml of 0.1M (0.1N) hydrochloric acid aqueous solution was added to wash the organic phase. After further washing with 100 ml of water three times, the separated organic phase was put into 2 L of methanol that was vigorously stirred over about 15 minutes. The resulting white precipitate was collected by filtration, dried by heating at 40 ° C. for 12 hours, and then dried at 70 ° C. for 3 hours under reduced pressure to obtain 8.94 g of Exemplified Compound P-1.
As a result of measuring the molecular weight of the obtained P-1 by GPC (THF solvent), the weight average molecular weight was 14,000. Moreover, Tg measured by DSC was 281 ° C.
According to FT-IR (V-550 manufactured by JASCO Corporation), 2221 cm ⁻¹ (alkynyl group),
1738 cm < ^-1 > (ester carbonyl group) and 2900-3100 cm < ^-1 > (aromatic ring) were confirmed.

(Synthesis Example 2) Synthesis of Exemplified Compound P-17 BPFL (trade name) manufactured by JFE Chemical Co., Ltd. (containing 9.4% by mass of acetonitrile) purified according to Synthesis Example 1 7.74 g (20.0 mmol), tetrabutylammonium 278 mg (1.0 mmol) of chloride, 0.06 g of sodium hydrosulfite, 37.5 ml of dichloromethane, 21.0 ml (42 mmol) of 2M (2N) sodium hydroxide aqueous solution and 79 ml of water were put into a reaction vessel equipped with a stirrer. The mixture was stirred at 300 rpm in a water bath under a nitrogen stream. After 30 minutes, 6.06 g (20.0 mmol) of 5- (2-phenylethynyl) isophthalic acid dichloride synthesized according to the method described in Example 2 of JP-A-2002-201158 was charged as powder. And washed with 86.3 ml of dichloromethane. Thereafter, stirring was continued for 6 hours, 100 ml of dichloromethane was added, and the organic phase was separated. Further, 100 ml of 0.1M (0.1N) hydrochloric acid aqueous solution was added to wash the organic phase. After further washing with 100 ml of water three times, the separated organic phase was put into 2 L of methanol that was vigorously stirred over about 15 minutes. The obtained white precipitate was collected by filtration, dried by heating at 40 ° C. for 12 hours, and then dried at 70 ° C. under reduced pressure for 3 hours to obtain 9.50 g of Exemplified Compound P-17.
As a result of measuring the molecular weight of the obtained P-17 with GPC (THF solvent), the weight average molecular weight was 20000. The Tg measured by DSC was 295 ° C.
2220 cm ⁻¹ (alkynyl group), 1738 cm ⁻¹ (ester carbonyl group), and 2900 to 3100 cm ⁻¹ (aromatic ring) were confirmed by FT-IR (V-550 manufactured by JASCO Corporation).

(Synthesis Example 3) Synthesis of Exemplified Compound P-22 In place of BPFL of Synthesis Example 1, an equimolar amount of the following spirobiindane M-1 (synthesized by the method described in Example 1 of Kokai 62-10030) was used. P-22 was synthesized by synthesizing in the same manner as in Synthesis Example 1 except that an equimolar amount of 4-ethynylphenol was used instead of 4-phenylethynylphenol.
As a result of measuring the molecular weight of the obtained P-22 with GPC (THF solvent), the weight average molecular weight was 12,000. Moreover, Tg measured by DSC was 269 ° C.

(Synthesis Example 4) Synthesis of Exemplified Compound P-23 Instead of BPFL of Synthesis Example 1, an equimolar amount of the following Spirobichroman M-2 (Journal of Chemical Society, Vol. 111, page 4953 (1989)) P-23 was synthesized by synthesizing in the same manner as in Synthesis Example 1, except that an equimolar amount of allyl alcohol was used instead of 4-phenylethynylphenol.
As a result of measuring the molecular weight of the obtained P-23 by GPC (THF solvent), the weight average molecular weight was 14,000. Moreover, Tg measured by DSC was 262 degreeC.

Synthesis Example 5 Synthesis of Exemplified Compound P-35 Piperazine 5.69 g, 4-ethynylphenol 1.05 g, tetrabutylammonium chloride 0.92 g, dichloromethane 223 ml, and water 248 ml were charged into a reaction vessel equipped with a stirrer. The mixture was stirred at 300 rpm in a water bath under a nitrogen stream. After 30 minutes, a solution of 28.6 g of bischloroformate (hereinafter also referred to as INBC) synthesized from tetramethylspirobiindanediol (M-1 above) using triphosgene dissolved in 74 ml of dichloromethane, and 2M (2N) A solution obtained by diluting 69 ml of an aqueous sodium hydroxide solution with 13 ml of water was added dropwise simultaneously over 1 hour using separate dropping devices, and after completion of the dropping, each was washed with 16.5 ml of water and dichloromethane. Thereafter, stirring was continued for 3 hours, 100 ml of dichloromethane was added, and the organic phase was separated. Further, a solution obtained by diluting 0.66 ml of 12M (12N) hydrochloric acid with 250 ml of water was added to wash the organic phase. Further, after washing twice with 250 ml of water, 100 ml of dichloromethane was added to the separated organic phase, diluted, and then poured into 2.5 L of methanol that was vigorously stirred over 1 hour. The resulting white precipitate in methanol was collected by filtration, dried by heating at 40 ° C. for 12 hours, and then dried at 70 ° C. under reduced pressure for 3 hours to obtain 24.5 g of P-35.
As a result of measuring the molecular weight of the obtained P-35 by GPC (chloroform solvent), the weight average molecular weight was 15000. Moreover, Tg measured by DSC was 268 degreeC.
The FT-IR (manufactured by JASCO Corporation V-550), 2120 cm ^-1 (alkynyl), 1680 cm ^-1 (urethane carbonyl group) was confirmed 2900～3100Cm ^-1 a (aromatic ring).

(Synthesis Example 6) Synthesis of Exemplified Compound P-15 Exemplified Compound P-15 was obtained in the same manner as in Synthetic Example 1 except that 3,4-epoxycyclohexylmethanol was used instead of 4-phenylethynylphenol.
As a result of measuring the molecular weight of the obtained P-35 with GPC (chloroform solvent), the weight average molecular weight was 16000. Moreover, Tg measured by DSC was 285 degreeC.

(Synthesis Example 7) Synthesis of Exemplified Compound P-40 Bisphenol A (manufactured by Aldrich) was used in place of BPFL in Synthesis Example 1, and an equimolar amount of 2-hydroxyethyl methacrylate was used instead of 4-phenylethynylphenol. P-40 was synthesized by synthesizing in the same manner as in Synthesis Example 1 except that.
As a result of measuring the molecular weight of the obtained P-40 with GPC (THF solvent), the weight average molecular weight was 15000. The Tg measured by DSC was 215 ° C.
Other compounds of the present invention can be synthesized in the same manner as described above.

(Synthesis of Comparative Compound X-1)
A comparative compound X-1 having the following structure was synthesized according to the synthesis method described in Example 1 of JP-A-57-192432.
As a result of measuring the molecular weight and Tg of the obtained X-1, the weight average molecular weight was 30000 and Tg was 293 ° C.

(Synthesis of Comparative Compound X-2)
Comparative compound X-2 having the following structure was synthesized in the same manner as in Synthesis example 1 except that tert-butylphenol was used instead of 4-phenylethynylphenol in Synthesis example 1.
As a result of measuring the molecular weight and Tg of the obtained X-2, the weight average molecular weight was 14000, and Tg was 288 ° C.

(Synthesis of Comparative Compound X-3)
Comparative compound X-3 having the following structure was synthesized in the same manner as comparative compound X-1, except that bisphenol A was used instead of BPFL.
As a result of measuring the molecular weight and Tg of the obtained X-3, the weight average molecular weight was 14000, and Tg was 215 ° C.

[Measurement method of characteristic values]
The characteristic value of the polymer synthesized in each of the above synthesis examples was measured by the following measuring method.
<Weight average molecular weight>
It was obtained by comparison with a polystyrene molecular weight standard product by polystyrene conversion GPC measurement using tetrahydrofuran as a solvent (HLC-8120GPC, manufactured by Tosoh Corporation).
<Glass transition temperature (Tg)>
Measured by DSC (in nitrogen, temperature rising temperature 10 ° C./min) (Seiko Co., Ltd., DSC6200).
<Thickness of film>
It was measured with a dial-type thickness gauge (manufactured by Anritsu Co., Ltd., K402B).
<Total light transmittance of film>
It measured with the JASCO-made haze meter.
<Mechanical properties of film>
A film sample (1.0 cm × 5.0 cm piece) was prepared and measured with Tensilon (manufactured by Toyo Baldwin Co., Ltd., Tensilon RTM-25) under the condition of a tensile speed of 3 mm / min. Three samples were measured, and the average value was obtained (the sample was used after standing overnight at 25 ° C. and RH 60%. Distance between chucks: 3 cm).

Example 2 Production and Evaluation of Optical Film Samples (Samples 101 to 107) The polymer of the present invention and the comparative polymer were dissolved so that the solution viscosity after dissolving in dichloromethane was a concentration in the range of 500 to 1500 mPa · s. The solution was filtered through a 5 μm filter and cast on a glass substrate using a doctor blade. After casting, the film was dried for 2 hours at room temperature, 2 hours at 80 ° C., 4 hours at 100 ° C., and further heated for 2 hours at each temperature described in the table under a nitrogen atmosphere. A film sample was obtained.
Tg, film thickness, total light transmittance, breaking stress, and breaking elongation of the obtained optical film sample were measured. The results are shown in Table 1 together with the Tg of the polymer used.

  From Table 1, it can be seen that the optical film of the present invention has a high Tg after heat treatment and excellent heat resistance compared to the film of the comparative example. Further, it can be seen that the optical film of the present invention has a large breaking stress and excellent mechanical properties as compared with the film of the comparative example.

[Example 3] Preparation of organic EL element sample Formation of Gas Barrier Layer On both surfaces of the optical film samples 101 to 107 of the present invention prepared in Example 2 and the optical film samples 108 to 110 of the comparative example, a DC magnetron sputtering method was used, with ArO ₂ as a target and a vacuum of 500 Pa. Sputtering was performed at an output of 5 kW in an atmosphere. The film thickness of the obtained gas barrier layer was 60 nm.

2. Formation of transparent conductive layer While heating an optical film sample provided with a gas barrier layer to 100 ° C., ITO (In ₂ O ₃ 95% by mass, SnO ₂ 5% by mass) as a target and 0.665 Pa by DC magnetron sputtering method. A transparent conductive layer made of an ITO film having an output of 5 kW and a thickness of 140 nm was provided on one side under an Ar atmosphere.

3. Heat Treatment of Optical Film with Transparent Conductive Layer The optical film sample on which the transparent conductive layer obtained above was formed was subjected to a heat treatment at 300 ° C. for 1 hour assuming TFT installation.

4). Preparation of Organic EL Element Aluminum lead wires were connected from the transparent electrode layer of the optical film sample provided with the transparent conductive layer subjected to the heat treatment to form a laminated structure. The optical film sample formed with the transparent conductive layer obtained from the optical film samples 101 to 107 of the present invention was not deformed, whereas the transparent conductive layer obtained from the optical film sample 110 of the comparative example was formed. The optical film sample was severely deformed, and no organic EL device was produced. The optical film sample on which the transparent conductive layer obtained from the optical film samples 108 and 109 of the comparative example was formed was also slightly deformed, but it was not remarkable, and thus an organic EL device was produced.
The surface of the transparent electrode was spin-coated with an aqueous dispersion of polyethylene dioxythiophene / polystyrene sulfonic acid (BAYER, Baytron P: solid content 1.3% by mass), and then vacuum-dried at 150 ° C. for 2 hours to obtain a thickness of 100 nm. A hole-transporting organic thin film layer was formed. This was designated as substrate X.
On the other hand, a coating solution for a light-emitting organic thin film layer having the following composition was formed on one surface of a temporary support made of 188 μm thick polyethersulfone (Sumilite FS-1300 manufactured by Sumitomo Bakelite Co., Ltd.) using a spin coater. The luminescent organic thin film layer having a thickness of 13 nm was formed on the temporary support by applying and drying at room temperature. This was designated as transfer material Y.

Polyvinylcarbazole (Mw = 63000, manufactured by Aldrich): 40 parts by mass Tris (2-phenylpyridine) iridium complex (orthometalated complex): 1 part by mass Dichloroethane: 3200 parts by mass

  The luminescent organic thin film layer side of the transfer material Y is superimposed on the upper surface of the organic thin film layer of the substrate X, heated and pressurized at 160 ° C., 0.3 MPa, 0.05 m / min using a pair of heat rollers, By peeling off, a light-emitting organic thin film layer was formed on the upper surface of the substrate X. This was designated as substrate XY.

In addition, a patterned evaporation mask (a mask with a light emitting area of 5 mm × 5 mm) is placed on one side of a polyimide film (UPILEX-50S, manufactured by Ube Industries) with a thickness of 50 μm cut into 25 mm square, and about 0. Al was evaporated in a reduced pressure atmosphere of 1 mPa to form an electrode having a film thickness of 0.3 μm. Using an Al ₂ O ₃ target by DC magnetron sputtering, the Al ₂ O ₃ was deposited in the same pattern as the Al layer and the thickness of 3 nm. Aluminum lead wires were connected from the Al electrode to form a laminated structure. A coating solution for an electron transporting organic thin film layer having the following composition is coated on the obtained laminated structure using a spin coater coating machine, and vacuum dried at 80 ° C. for 2 hours, thereby transporting an electron having a thickness of 15 nm. An organic thin film layer was formed on LiF. This was designated as substrate Z.

Polyvinyl butyral 2000L (Mw = 2000, manufactured by Denki Kagaku Kogyo Co., Ltd.): 10 parts by mass 1-butanol: 3500 parts by mass Electron transporting compound having the following structure: 20 parts by mass

  Using the substrates XY and Z, the electrodes are stacked so that the electrodes face each other with the light-emitting organic thin film layer interposed therebetween, and heated and pressurized at 160 ° C., 0.3 MPa, 0.05 m / min using a pair of heat rollers, The organic EL element samples 201 to 209 were obtained by bonding.

  The obtained organic EL element samples 201 to 209 were applied with a direct voltage to the organic EL element using a source measure unit type 2400 (manufactured by Toyo Technica Co., Ltd.). The comparative samples 208 and 209, which were slightly deformed, could not be confirmed to emit light, but the samples 201 to 207 of the present invention were confirmed to emit light.

  From the above examples, the optical film of the present invention is excellent in heat resistance, transparency and mechanical properties, and can be laminated with a gas barrier layer and a transparent conductive layer. It became clear to function as.

  Since the polymer of the present invention has excellent heat resistance, optical properties and mechanical properties, optical films having heat resistance, optical properties and mechanical properties, in particular, liquid crystals, plasma displays, electroluminescence (EL), fluorescent display tubes, As a substrate for flat panel displays such as light emitting diodes, it can be used for applications such as solar cells and touch panels.

Claims (8)

A polymer comprising a polyester or polyurethane having a crosslinking reactive group. The polymer according to claim 1, wherein the crosslinking reactive group is an alkenyl group or an alkynyl group. The polymer of Claim 1 or 2 containing the chemical structure shown by the following general formula (1) or general formula (2).

In general formula (1), ring α represents a monocyclic or polycyclic ring, and the two rings are connected by a spiro bond.

In general formula (2), ring β and ring γ represent a monocyclic or polycyclic ring, and two rings γ may be the same or different, and one quaternary ring on ring β. Linked to carbon. The optical film formed with the polymer as described in any one of Claims 1-3. The optical film according to claim 4, wherein the total light transmittance is 80% or more. The optical film according to claim 4 or 5, wherein a gas barrier layer is laminated on at least one side. The optical film according to any one of claims 4 to 6, wherein a transparent conductive layer is laminated on at least one side. The image display apparatus using the optical film as described in any one of Claims 4-7.