JP2007063418A - Polymer, and optical film and image display device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer having excellent transparency, heat resistance and mechanical characteristics, and suitable for an optical part application; and to provide an optical film using the polymer, and an image display device using the optical film. <P>SOLUTION: The polymer has at least either one of an ester bond and a urethane bond obtained by using a diallylphenol having at least one substituted or nonsubstituted allyl group, and represented by a specific formula having a ring obtained by spiro-bonding two rings, a monocyclic ring or a polycyclic ring as a diol component. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

In recent years, in the field of flat panel displays such as liquid crystal display elements and organic EL elements, it has been studied to replace a substrate from glass to plastic in order to improve breakage resistance, reduce the weight, and reduce the thickness. In particular, there is a strong demand for plastic substrates in the field of mobile information communication device display devices such as mobile phones, electronic notebooks, laptop computers, and other portable information terminals.
Since this plastic substrate needs conductivity, a metal film such as a semiconductor film such as an oxide of indium oxide, tin oxide or tin-indium alloy, an oxide film of gold, silver or palladium alloy on the plastic film. The use of a transparent conductive substrate provided with a film formed by combining the semiconductor film and the metal film as a transparent conductive layer is used as an electrode substrate of a display element.
Plastics used for this purpose include heat-resistant amorphous polymers such as modified polycarbonate (modified PC) (for example, see Patent Document 1), polyethersulfone (PES) (for example, see Patent Document 2), cycloolefin. A copolymer obtained by laminating a transparent conductive layer and a gas barrier layer on a copolymer (for example, see Patent Document 3) is known.
However, even if such a heat-resistant plastic is used, sufficient heat resistance as a plastic substrate cannot be obtained. That is, when a conductive layer is 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, there is a problem that the conductivity and gas barrier properties are greatly reduced. . Further, when installing a TFT for manufacturing an active matrix image element, further heat resistance is required.

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. Further, Patent Document 6 describes a method of forming a polycrystalline silicon semiconductor layer on a plastic substrate by providing a thermal buffer layer and irradiating a pulse laser beam. Various methods for forming a polycrystalline silicon film for TFTs at 300 ° C. or lower like these have been proposed, but there is a problem that the configuration and the apparatus are complicated and the cost is high. For this reason, heat resistance of 300 ° C. to 350 ° C. or more is required for plastic substrates.

  Patent Document 7 discloses a thin film transistor substrate using polyimide derived from an aliphatic tetracarboxylic acid anhydride. The polyimide film described in Patent Document 7 has a glass transition temperature (Tg) of 315 ° C. and a total light transmittance of 85%, and is excellent in heat resistance and transparency. High cost. Further, it is not preferable in production that film formation at a high temperature using a high boiling point solvent is necessary.

Patent Documents 8 and 9 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 also describes a polyester film derived from alkyl-substituted bisphenolfluorene, isophthalic acid and terephthalic acid.
Polyesters derived from these alkyl-substituted or unsubstituted bisphenolfluorenes and isophthalic acid and terephthalic acid can be synthesized from inexpensive raw materials and have a glass transition temperature of around 300 ° C. Further, according to the above document, a flexible film excellent in transparency and breaking elongation is produced using a low boiling point solvent such as dichloromethane or cyclohexanone. However, it does not necessarily have sufficient heat resistance for the TFT installation process at the time of manufacturing an active matrix type image device, and further improvement is desired for the demand for mechanical properties required for plastic substrates. It was rare.

  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. On the other hand, heat resistance and mechanical properties are improved by a crosslinking reaction of alkynyl groups by heating after film formation. However, it was not preferable for optical film applications in terms of resin coloring.

  Patent Document 12 discloses a polycarbonate having an allyl group in the side chain. However, these compounds have a thermal deformation start temperature of about 200 ° C., which is an insufficient level for the heat-resistant substrate for display.

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

JP 2000-227603 A (all pages) JP 2000-284717 A (all pages) JP 2001-150584 A (all pages) JP-A-7-81919 (all pages) Japanese National Patent Publication No. 10-512104 (all pages) Japanese Patent Laid-Open No. 11-102867 (all pages) JP 2003-168800 A (all pages) JP-A-57-192432 (all pages) JP-A-3-28222 (all pages) WO99 / 18141 pamphlet (all pages) US Pat. No. 5,138,028 (all pages) JP-A-10-77338 (all pages)

  The first problem to be solved by the present invention is to provide a polymer that is excellent in transparency, heat resistance and mechanical properties, and is suitable for use in optical parts, and the second problem is formed using the polymer. Another object is to provide an optical film excellent in transparency, heat resistance and mechanical properties. A third problem is to provide an image display device using the optical film and having excellent display quality.

〔一般式（１）中、αは環構造を表し、２つの環はスピロ結合によって結合している。Ｒ¹〜Ｒ⁶は水素原子または置換基を表し、Ｒ¹〜Ｒ⁴の少なくとも１つが置換または無置換のアリル基を表す。Ｒ¹とＲ⁵、Ｒ⁴とＲ⁶とは互いに結合して環を形成していてもよい。〕 The above objects have been achieved by the present inventions 1) to 8) below.
1) A polymer comprising at least one repeating unit represented by the following general formula (1) or general formula (2), and having at least one of an ester bond and a urethane bond.

[In the general formula (1), α represents a ring structure, and the two rings are linked by a spiro bond. R ^{1 to} R ⁶ each represents a hydrogen atom or a substituent, and at least one of R ^{1 to} R ⁴ represents a substituted or unsubstituted allyl group. R ¹ and R ⁵ , R ⁴ and R ⁶ may be bonded to each other to form a ring. ]

〔一般式（２）中、環βは単環式または多環式の環を表す。Ｒ¹〜Ｒ⁸は水素原子または置換基を表し、Ｒ¹〜Ｒ⁴の少なくとも１つが置換または無置換のアリル基を表す。Ｒ¹とＲ⁵、Ｒ²とＲ⁶、Ｒ³とＲ⁷、Ｒ⁴とＲ⁸、Ｒ⁵とＲ⁷とは互いに結合して環を形成していてもよい。〕

[In general formula (2), ring β represents a monocyclic or polycyclic ring. R ^{1 to} R ⁸ represent a hydrogen atom or a substituent, and at least one of R ^{1 to} R ⁴ represents a substituted or unsubstituted allyl group. R ¹ and R ⁵ , R ² and R ⁶ , R ³ and R ⁷ , R ⁴ and R ⁸ , and R ⁵ and R ⁷ may be bonded to each other to form a ring. ]

2) An optical film formed of the polymer described in 1) above.
3) The optical film as described in 2) above, wherein allyl groups in the polymer as described in 1) above are crosslinked.
4) The optical film as described in 2) or 3) above, which has a total light transmittance of 80% or more.

5) The optical film as described in any one of 2) to 4) above, wherein a gas barrier layer is laminated on at least one surface.
6) The optical film as described in any one of 2) to 5) above, wherein a transparent conductive layer is laminated on at least one surface.
7) An image display device using the optical film according to any one of 2) to 6).

  According to the present invention, a polymer having heat resistance capable of forming various functional layers at a high temperature and having excellent optical properties such as transparency and mechanical properties capable of forming a film, and an optical film using the same In addition, an image display device excellent in display quality can be provided.

  The polymer, film and image display device of the present invention will be described in detail below.

(polymer)
The polymer of the present invention contains at least one spiro structure represented by the following general formula (1) or a cardo structure represented by the general formula (2) as a repeating unit, and includes an ester bond (—CO—O—) and a urethane bond. It has at least one of (-NH-COO-). That is, the polymer in the present invention is a crosslinkable polyester or polyurethane containing the following repeating unit (containing an allyl group).
These polymers are compounds with high heat resistance, high elastic modulus, and high tensile fracture stress, and various heating operations are required in the manufacturing process, and the organic EL elements are required to be resistant to fracture even when bent. It is suitable as a substrate material.

In general formula (1), α represents a ring structure, and the two rings are connected by a spiro bond. The ring structure is preferably a 5-membered or 6-membered ring. R ^{1 to} R ⁶ each represents a hydrogen atom or a substituent, and at least one of R ^{1 to} R ⁴ represents a substituted or unsubstituted allyl group. Examples of the substituent for the allyl group include a halogen atom (for example, fluorine, chlorine, bromine, etc.), an alkyl group (for example, methyl group, ethyl group, n-propyl group, etc.), an aryl group (for example, phenyl group, 4- Chlorophenyl group, naphthyl group, etc.) are preferred. These substituents may be substituted at any substitutable position, and may be substituted in plural. As the allyl group, an unsubstituted allyl group is particularly preferable.
Two or more of R ^{1 to} R ⁴ are preferably substituted or unsubstituted allyl groups, and at least R ¹ and R ³ are preferably substituted or unsubstituted allyl groups. When R ^{1 to} R ⁶ represent a substituent other than an allyl group, examples of the substituent include a halogen atom (eg, fluorine, chlorine, bromine), an alkyl group (eg, a methyl group, an ethyl group, a t-butyl group, Trifluoromethyl group, etc.), aryl groups (eg, phenyl group, 4-chlorophenyl group, 4-methoxyphenyl group, naphthyl group, etc.) and the like, and R ¹ and R ⁵ , R ⁴ and R ⁶ are bonded to each other. To form a ring. When R ^{1 to} R ⁶ represent a substituent other than an allyl group, it is particularly preferable to represent a hydrogen atom.

  Particularly preferred examples of the structure represented by the general formula (1) include structures represented by the general formulas (3) to (5).

In General Formula (3), R ^{1 to} R ⁶ represent the same meaning as in General Formula (1). R ^{7 to} R ¹⁴ each independently represents a hydrogen atom or a substituent. R ¹ and R ⁵ , R ⁴ and R ⁶ may be bonded to each other to form a ring. Preferable examples of R ^{7 to} R ¹⁴ are a hydrogen atom, a halogen atom, an alkyl group, and an aryl group, more preferably a hydrogen atom, a methyl group, and a phenyl group, and particularly preferably a hydrogen atom or a methyl group.

In general formula (4), R ^{1 to} R ⁶ represent the same meaning as in general formula (1). R ^{7 to} R ¹⁰ each independently represents a hydrogen atom or a substituent. R ¹ and R ⁵ , R ⁴ and R ⁶ may be bonded to each other to form a ring. Preferable examples of R ^{7 to} R ¹⁰ are a hydrogen atom, a halogen atom, an alkyl group, and an aryl group, more preferably a hydrogen atom, a methyl group, and a phenyl group, and particularly preferably a hydrogen atom or a methyl group.

In general formula (5), R < ¹ > -R < ⁶ > represents the same meaning as general formula (1). R ^{7 to} R ¹⁰ each independently represents a hydrogen atom or a substituent. R ¹ and R ⁵ , R ⁴ and R ⁶ may be bonded to each other to form a ring. Preferable examples of R ^{7 to} R ¹⁰ are a hydrogen atom, a halogen atom, an alkyl group, and an aryl group, more preferably a hydrogen atom, a methyl group, and a phenyl group, and particularly preferably a hydrogen atom or a methyl group.

  Next, general formula (2) will be described.

In general formula (2), ring β represents a monocyclic or polycyclic ring. R ^{1 to} R ⁸ represent a substituent. Each of these substituents may be the same or different. Further, at least one of R ^{1 to} R ⁴ represents a substituted or unsubstituted allyl group.

Examples of the substituent for the allyl group include a halogen atom (for example, fluorine, chlorine, bromine, etc.), an alkyl group (for example, methyl group, ethyl group, n-propyl group, etc.), an aryl group (for example, phenyl group, 4- Chlorophenyl group, naphthyl group, etc.) are preferred. These substituents may be substituted at any substitutable position, and may be substituted in plural. As the allyl group, an unsubstituted allyl group is particularly preferable. Two or more of R ^{1 to} R ⁴ are preferably substituted or unsubstituted allyl groups, and at least R ¹ and R ³ are preferably substituted or unsubstituted allyl groups. When R ^{1 to} R ⁸ represent a substituent other than an allyl group, examples of the substituent include a halogen atom (for example, fluorine, chlorine, bromine, etc.), an alkyl group (for example, a methyl group, an ethyl group, a t-butyl group, a tri group). A fluoromethyl group), an aryl group (for example, a phenyl group, a 4-chlorophenyl group, a 4-methoxyphenyl group, a naphthyl group, etc.), R ¹ and R ⁵ , R ² and R ⁶ , R ³ and R ⁷ , R ⁴ and R ⁸ , R ⁵ and R ⁷ may be bonded to each other to form a ring. When R ^{1 to} R ⁸ represent a substituent other than an allyl group, it is particularly preferable to represent a hydrogen atom.

  Of the structure represented by the general formula (2), a structure represented by the following general formula (6) is particularly preferable.

〔一般式（６）中、Ｒ¹〜Ｒ⁸は一般式（２）と同じ意味を表す。〕

[In General Formula (6), R ^{1 to} R ⁸ represent the same meaning as in General Formula (2). ]

  Preferred specific examples (exemplary compounds P-1 to P-39) of the allyl group-containing polyester and polyurethane useful as the polymer of the present invention are listed below, but the present invention is not limited thereto.

  The polymer of the present invention containing an allyl group may be used alone or as a mixture of two or more. Furthermore, an arbitrary monomer that does not include the repeating structure represented by the general formula (1) or (2) can be used as a comonomer from various viewpoints such as solubility, transparency, and mechanical properties.

  The polymer preferably used in the present invention has a weight average molecular weight of 1,000 to 500,000, more preferably 5,000 to 300,000, and particularly preferably 10,000 to 200,000. If the molecular weight is too low, film formation may be difficult and mechanical properties may be deteriorated. If the molecular weight is too high, it may be difficult to control the molecular weight in the synthesis, or the solution may be too viscous to be handled. The molecular weight can be based on the corresponding viscosity.

In the polymer of the present invention, by increasing the amount of allyl groups introduced, the heat resistance and mechanical properties of the resin can be improved. On the other hand, if the amount of crosslinking reactive groups introduced is too large, curing shrinkage becomes a problem. There is. Optimum introduction amount of crosslinkable groups and the structure of the resin, the amount of the crosslinking reactive group is generally introduced into the polymer is preferably 10 ^-4 ~10mmol / g, 10 ^- It is more preferably ^{3 to 2} mmol / g, and particularly preferably 10 ^{−2 to 1} mmol / g.

  According to the method described in JP-A-2004-137200, the polymer of the present invention, which is a bisphenol derivative containing an allyl group and having the structure of the general formula (1) or (2), is converted to the corresponding bisphenol derivative with allyl halide. Can be synthesized by heating to perform a Claisen rearrangement reaction.

When the polymer of the present invention is a polyester, the polymer of the present invention (the polyester of the present invention) is a bisphenol compound containing a structure of the general formula (1) or (2) containing an allyl group and optionally other bisphenols. It can be obtained by polycondensation of a compound and a dicarboxylic acid derivative.
The polycondensation method includes a dehydrochlorination homogeneous polymerization method in which dicarboxylic acid chloride and bisphenol are reacted in an organic solvent system in which the polymer is soluble in the presence of an organic base; A known method such as an interfacial polycondensation method for reacting in a two-phase system with a miscible organic solvent can be used.

  The polyester of the present invention can be synthesized by any of the synthesis methods described above, but the interfacial polycondensation method is particularly simple and preferred. In the interfacial polycondensation reaction, a method is generally used in which a bisphenol compound dissolved in an alkaline aqueous solution and a dicarboxylic acid chloride dissolved in a water-immiscible organic solvent (typically dichloromethane) are mixed in a short time. However, the solubility of the bisphenol compound in an alkaline aqueous solution may be low. In addition, in a dicarboxylic chloride having low solubility in a water-immiscible organic solvent such as 2,6-naphthalenedicarboxylic acid chloride, there are cases where a polyester cannot be synthesized by a known method. In this case, a method in which water, a water-immiscible organic solvent, a bisphenol compound, and a dicarboxylic acid chloride are mixed and stirred in a slurry state and a high-concentration alkaline aqueous solution is gradually added is effective for increasing the molecular weight.

  As a method for adjusting the molecular weight of the polymer of the present invention, a monofunctional substance can be added during polymerization. Examples of monofunctional substances used as molecular weight regulators here include monohydric phenols such as phenol, cresol, and p-tert-butylphenol; monohydric acid chlorides such as benzoic acid chloride, methanesulfonyl chloride, and phenyl chloroformate. Monohydric alcohols such as methanol, 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 And monovalent carboxylic acids such as acid, toluic acid, phenyl acid, p-tert-butylbenzoic acid, and p-methoxyphenylacetic acid.

  The carboxyl value of the polymer of the present invention 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 too high, it may affect electrical properties such as arc discharge resistance and dielectric constant, or may affect the storage stability of polymer solutions prepared by dissolving in a solvent, or a cast film obtained by the solution casting method. May affect the surface properties of the. The carboxyl value of the polymer of the present invention can be measured by a known method such as neutralization titration using a potentiometric titrator.

When the polymer of the present invention is a polyurethane, the polymer of the present invention (the polyurethane of the present invention) can also be synthesized according to a known production method. For example, a polyaddition method of a bisphenol compound and a diisocyanate compound, a bisphenol compound and a dicarbamic acid A polycondensation method with chloride is preferred. The diisocyanate compound can be synthesized by dehydrochlorination of dicarbamic acid chloride. The dicarbamic acid chloride can be synthesized by allowing phosgene to act on a diamine compound.
In the present invention, the polymerization reaction is preferably performed using the bisphenol having an allyl group.

  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 amount and the halogen amount are too high, the above-mentioned electrical characteristics tend to be reduced, and the surface characteristics of the film are also adversely affected, and the performance of the functional film provided with a conductive film, a semiconductor film, etc. Since it may cause a decrease, it is not preferable. The amount of residual alkali metal and halogen in the polymer can be quantified using a known method such as ion chromatography analysis, atomic absorption spectrometry, or plasma emission spectrometry.

  The amount of catalyst such as quaternary ammonium salt or quaternary phosphonium salt remaining in the polymer of the present invention is preferably less than 200 ppm, more preferably less than 100 ppm. When the amount of the remaining catalyst is too high, the above-mentioned electrical characteristics tend to be lowered, and further, the surface characteristics of the film are adversely affected, and the performance of the functional film provided with a conductive film, a semiconductor film, etc. is deteriorated. This is not preferable. Catalysts such as quaternary ammonium salts and quaternary phosphonium salts remaining in the polymer of the present invention can be quantified using HPLC, gas chromatography, or the like.

  Furthermore, the amount of residual components derived from monomers such as phenol monomer, dicarboxylic acid, dicarboxylic acid chloride, diamine, diisocyanate remaining in the polymer of the present invention is preferably 3000 ppm or less, more preferably 500 ppm or less, still more preferably Is 100 ppm or less. If the amount of the remaining monomer component is too large, the above-mentioned electrical characteristics tend to be lowered, and the surface characteristics of the film are also adversely affected, and the performance of the functional film provided with a conductive film, a semiconductor film, etc. is deteriorated. Since it may cause, it is not preferable. For example, when a transparent conductive film is formed on a film, a gas derived from the remaining monomer component is generated due to the influence of heating or plasma during film formation, or thermal decomposition occurs. This is not preferable because an agglomeration occurs, or an uncoated portion called “missing” is generated, which adversely affects the lowering of the resistance of the transparent conductive film. 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.

  The polyester and polyurethane of the present invention, that is, the allyl group introduced into the polymer of the present invention, can increase the solubility of the polymer in an organic solvent and improve the heat resistance by performing a crosslinking reaction after film formation. be able to. The crosslinking reaction can be performed by heating, ultraviolet rays, infrared rays, electron beams, microwave irradiation, or the like. At this time, it is not always necessary to add a polymerization initiator, but a polymerization initiator may be added for the purpose of carrying out a crosslinking reaction quickly and efficiently. Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator.

As the thermal polymerization initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Ammonium sulfate, potassium persulfate, etc., 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. as diazo compounds, diazoaminobenzene, p -Nitrobenzenediazonium etc. can be mentioned.

  Photopolymerization initiators that initiate (radical) polymerization by the action of light include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2, Examples include 3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, and aromatic sulfoniums. Examples of the acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of the benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of the phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Sensitizing dyes can also be preferably used in combination with these photopolymerization initiators.

  The addition amount of the polymerization initiator that initiates radical polymerization by the action of heat or light may be an amount that can initiate the polymerization of the carbon-carbon double bond, but is generally based on the total solid content of the polymer. 0.1-15 mass% is preferable, More preferably, it is 0.5-10 mass%, Especially preferably, it is the case of 2-5 mass%.

In the case of irradiation with ultraviolet light to the optical film of the present invention to crosslink the polymer of the present invention is usually performed with UV light energy density of 1 to 2,000 mJ / cm ^2, preferably 10~1000mJ / cm ^2, more preferably 50 Performed at ˜750 mJ / cm ² . When high-intensity ultraviolet rays are irradiated in a short time, the film may be deteriorated. In such a case, low-intensity ultraviolet rays can be irradiated for a long time. Here, the “optical film of the present invention” means a film formed using the polymer of the present invention.
Moreover, when irradiating the optical film of this invention with an electron beam, the intensity | strength of about 2-10 MeV is preferable.

The crosslinking reaction by the thermal polymerization is usually performed at a temperature of 50 to (Tg + 50 ° C.) or less, preferably 50 to 300 ° C., more preferably 70 to 250 ° C. The crosslinking reaction by irradiation with ultraviolet rays or the like is usually performed at 0 to 50 ° C, preferably 20 to 40 ° C.
In any crosslinking reaction, the reaction time is preferably 1 minute to 50 hours, more preferably 2 minutes to 25 hours, and particularly preferably 5 minutes to 10 hours.

The glass transition temperature of the polymer of the present invention is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and particularly preferably 200 ° C. or higher.
Furthermore, the glass transition temperature of the polymer after the crosslinking reaction is preferably 250 ° C. or higher, more preferably 300 ° C. or higher, and particularly preferably 350 ° C. or higher.
When the glass transition temperature after the crosslinking reaction of the polymer of the present invention is 250 ° C. or higher, it becomes possible to install an amorphous silicon semiconductor layer on the film.
Further, the upper limit of the glass transition temperature of the polymer of the present invention is not particularly limited. However, when the stretching operation is performed, it is difficult if the glass transition temperature is too high, and wet stretching in a form containing a solvent is assumed. Even so, the glass transition temperature of the polymer is preferably 400 ° C. or lower, more preferably 350 ° C. or lower.

[Optical film]
Next, the optical film of the present invention will be described.
The optical film of the present invention is an optical film comprising the above-described polymer of the present invention. The optical film used in the present invention means a film having a thickness in the range of 10 to 700 μm, a light transmittance at 420 nm of 40% or more, and a total light transmittance of 60% or more.

  The optical film of the present invention may contain a polymer other than the polymer of the present invention as long as the effects of the present invention are not impaired. In addition to the polymer of the present invention, a crosslinking reactive resin may be appropriately added. As the kind of the cross-linking reactive resin, various known ones can be used without particular limitation for both 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. Any other crosslinking method can be used without particular limitation as long as it is a reaction that forms a covalent bond, and a system in which the reaction proceeds at room temperature using a polyalcohol compound and a polyisocyanate compound to form a urethane bond, in particular. Can be used without limitation. 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. Commercially available block type curing agents include “B-882N” manufactured by Mitsui Takeda Chemical Co., Ltd., “Coronate 2513” (block polyisocyanate) manufactured by Nippon Polyurethane Industry Co., Ltd., and “Cymel manufactured by Mitsui Cytec Co., Ltd.” 303 "(methylated melamine resin) and the like 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.

The 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. Typical examples include compounds called polyfunctional acrylate monomers having 2 to 6 acrylate groups in the molecule, and a plurality of acrylics in the molecule called urethane acrylate, polyester acrylate, and epoxy acrylate. A compound having an acid ester group is used.
As the curable component of the cationic curable resin, a compound having a plurality of cationic polymerizable groups in the molecule is used, and as a typical curing method, a photoacid generator that generates an acid by irradiation with ultraviolet rays is added, A method of curing by irradiating with ultraviolet rays is mentioned. 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, in the production process, plural kinds of the thermosetting resin and the radiation curable resin mentioned above may be mixed and used, and the thermosetting resin and the radiation curable resin are used in combination. Also good. Further, a crosslinkable resin and a polymer having no crosslinkable group may be mixed and used.

  The optical film of the present invention may 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.

  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. The casting and drying methods in the solution casting method are described in 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. 2,429,978, US Japanese Patent No. 2607704, US Patent 2739069, US Patent 2739070, British Patent 640731, British Patent 736892, Japanese Examined Patent Publication No. 45-4554, Japanese Examined Patent Publication No. 49-5614, These are described in JP-A-60-176834, JP-A-60-203430, and JP-A-62-115035. Examples of the manufacturing apparatus manufactured by the solution casting method include the manufacturing apparatus described in paragraphs [0061] to [0068] of Japanese Patent Laid-Open No. 2002-189126, FIGS. 1 and 2, and the like. Is not limited to these.

  In the solution casting method, the polymer of the present invention and the polymer used in combination with the polymer are dissolved in a solvent. Any solvent may be used as long as it dissolves the polymer, but a solvent capable of dissolving the polymer at a solid content 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 be advantageous from the viewpoint of stripping after the casting of the solution and the drying speed.

  Examples of the solvent that can be used in the present invention include methylene chloride, chloroform, tetrahydrofuran, 1,4-dioxane, benzene, cyclohexane, toluene, xylene, anisole, γ-butyrolactone, benzyl alcohol, isophorone, cyclohexanone, and cyclopentanone. 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, acetone, chlorobenzene, dichlorobenzene, dimethylformamide, methanol, ethanol and the like. However, the present invention is not limited to these. Also, 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, the transparency of the optical film of the present invention may be improved by using a mixed solvent.

  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. If the concentration of the polymer is too low, the viscosity may be low and it may be difficult to adjust the thickness, and if it is too high, the film forming property may be poor and unevenness may be increased. 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. For example, the solution 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, an optical film having optical isotropy can be obtained. As a first step, drying is performed at 30 to 100 ° C. until the solvent has a mass concentration of 10% or less, more preferably 5% or less. Next, as a second step, the film is peeled off from the flat plate or roll and dried in the range of 60 ° C. or higher and the glass transition temperature of the resin or lower.
When peeling a film from a flat plate or a roll, it may be peeled off immediately after completion of drying in the first stage, or may be peeled off after being cooled.

  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, the polymer is thermally decomposed 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. For this reason, 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 the remaining solvent is too large, the characteristics of the film surface are deteriorated, which may adversely affect the surface treatment or the like, and may cause a decrease in performance of the functional film provided with a conductive film, a semiconductor film or the like. 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 band, peeled off, and dried continuously, and 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. The preferable mechanical strength cannot be generally specified for the conveying device, but the breaking stress and breaking elongation obtained from the tensile test of the film can be used as a guide. A preferable breaking stress is 50 MPa or more, more preferably 80 MPa or more, and further preferably 100 MPa or more. Since the elongation at break varies depending on the sample preparation conditions and the like, the reliability is low, 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 the film, 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 in the stretching direction (ASTMD1504, hereinafter abbreviated as “ORS”) of 0.3 to 3 GPa are preferred because the mechanical strength is improved. ORS is the internal stress caused by stretching that is frozen 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 glass transition temperature of 300 ° C. or higher, stretching by mere heating becomes difficult. Is possible. In this case, it is preferable to perform stretching in the course of drying. For example, the roll uniaxial stretching method and the tenter are performed at a temperature between 10 ° C. and 50 ° C. higher than the glass transition temperature (Tg) in the state containing the solvent. The film can be stretched by a uniaxial stretching method, a simultaneous biaxial stretching method, a sequential biaxial stretching method, or an inflation method. The draw ratio is preferably 1.1 to 3.5 times.

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

  The heat resistant temperature of the optical film of the present invention is preferably high, and the glass transition temperature (Tg) by DSC measurement or the thermal deformation start temperature by TMA can be used as a guide. In this case, the preferable glass transition temperature or thermal deformation start temperature 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 Tg of the optical film. Within the 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. Also, smoothing layer for surface smoothing, hard coat layer for imparting scratch resistance, anti-reflection layer for improving anti-reflection light transmittance, ultraviolet absorbing layer for enhancing light resistance, improved film transportability Various known functional layers can be provided depending on the purpose, such as a surface roughening layer.

  The optical film of the present invention can be provided with a transparent conductive layer. As the transparent conductive layer, known metal films, metal oxide films, and the like can be applied. Among these, metal oxide films are preferable from the viewpoint of transparency, conductivity, and mechanical properties. For example, indium oxide, cadmium oxide and tin oxide to which tin, tellurium, cadmium, molybdenum, tungsten, fluorine, zinc, germanium and the like are added as impurities; metal oxide films such as zinc oxide and titanium oxide 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 weight of zinc oxide is excellent in transparency and conductivity, and is preferably used.

The method for forming these transparent conductive layers may be any method as long as the target thin film can be formed. As the film forming method, for example, a vapor deposition method for forming a film by depositing a material from a gas phase such as a sputtering method, a vacuum evaporation method, an ion plating method, and a plasma CVD method is suitable. Films can be formed by the methods described in Japanese Patent No. 3400324, Japanese Patent Application Laid-Open No. 2002-322561, and Japanese Patent Application Laid-Open No. 2002-361774.
Among these, the sputtering method is preferable from the viewpoint that particularly excellent conductivity and transparency can be obtained.

  A preferable degree of vacuum of such a sputtering method, a vacuum deposition method, an ion plating method, and a 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 to 200 degreeC during providing the transparent conductive layer.

The thickness of the transparent conductive layer thus obtained is preferably 20 nm to 500 nm, more preferably 50 nm to 300 nm.
Further, the surface electrical resistance measured at 25 ° C. and 60% relative humidity of the transparent conductive layer thus obtained is preferably 0.1Ω / □ to 200Ω / □, more preferably 0.1Ω / □ to 100Ω / □. □, more preferably 0.5Ω / □ to 60Ω / □. Further, the light transmittance is 80% or more, more preferably 83% or more, and still more preferably 85% or more.

  In order to suppress gas permeability, the optical film of the present invention is preferably provided with a gas barrier layer. As the preferable gas barrier layer, for example, a metal oxide mainly composed 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 vapor deposition such as sputtering, vacuum deposition, ion plating, plasma CVD, etc., in which a material is deposited in the vapor phase to form a film. Of these, the sputtering method is preferred from the viewpoint that particularly excellent gas barrier properties can be obtained. Further, the temperature may be raised to 50 ° C. to 200 ° C. while the gas barrier layer is provided.

The film thickness of the gas barrier layer thus obtained is preferably 10 nm to 300 nm, more preferably 30 nm to 200 nm.
Such a gas barrier layer may be provided on the same side as the transparent conductive layer or on the opposite side, but it is more preferable to provide it on the opposite side.

Further, the barrier property of the film having the gas barrier layer thus obtained (gas barrier film) is preferably 5 g / m ² · day or less, more preferably water vapor permeability measured at 40 ° C. and 90% relative humidity. 1 g / m ² · day or less, more preferably 0.5 g / m ² · day or less. The oxygen permeability measured at 40 ° C. and 90% relative humidity is preferably 1 ml / m ² · day or less, more preferably 0.7 ml / m ² · day or less, and even more preferably 0.5 ml / m ² · day. It is as follows.

In the optical film of the present invention, it is particularly desirable to provide a defect compensation layer adjacent to the optical film for the purpose of improving barrier properties. 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 patent A method using an organic material layer as described in each specification of Nos. 6413645 and 64163645, and these defect compensation layers are hardened with ultraviolet rays or electron beams after being deposited under vacuum as described in the above publications. It can be produced by a method, or after being applied and cured by heating, electron beam, ultraviolet rays or the like.
When the coating method is used, various conventionally used coating methods such as spray coating, spin coating, and bar coating can be used.

  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 using any method, but a photolithography technique is preferable.

  The optical film of the present invention can be used in an image display device after providing various functional layers as necessary. Here, it does not specifically limit as an image display apparatus, Conventionally well-known things, such as flat panel displays, such as a liquid crystal display device, a plasma display, electroluminescence (EL), a fluorescent display tube, and a light emitting diode, 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 crystals, plasma displays, electroluminescence (EL), fluorescent display tubes, light emitting diodes, etc. In addition to these, they should be used as substrates instead of display-type glass substrates that have conventionally used glass substrates. Can do. 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 a liquid crystal display application or the like, the polymer of the present invention 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. Further, for the purpose of controlling retardation (Re) and its wavelength dispersion, resins having different intrinsic birefringence signs can be combined, or resins having a 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, etc. Further, phase difference compensation can be performed by using a known retardation plate in combination.
In addition, Re mentioned here is 25 ° C./relative humidity using an automatic birefringence meter (KOBRA-21ADH: manufactured by Oji Scientific Instruments) after conditioning the film for 24 hours at 25 ° C./60% relative humidity. It is a value measured at 60%. Re is measured by making light of wavelength λnm (normally λ = 590 ± 5 nm) incident in the normal direction of the film in KOBRA 21ADH (manufactured by Oji Scientific Instruments).

  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. Of 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 (upper and lower substrates) from the viewpoint of heat resistance. From the viewpoint of transparency, it is preferable to use it 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 It consists of a polarizing film. Of 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 (upper and lower substrates) from the viewpoint of heat resistance, and transparent electrodes It is preferable to use it as a 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 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. ), VA (Vertically Aligned) and HAN (Hybrid Aligned Nematic) have been proposed. There has also been proposed a display mode in which the display mode is orientation-divided. 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 type, a reflective type, and a transflective liquid crystal display device.

  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, SURVAIVAL (Monthly Display, Vol. 6, No. 3 (1999) 14), PVA (Asia Display 98, Proc. Of the-18th-Inter. Display res. Conf. (Preliminary Collection (1998) 383), Para-A (LCD / PDP Iternational`99), DDVA (SID98, Digest of tech. Papers (Preliminary Collection) 29 (1998) 838), EOC (SID98, Digest of tech Papers 29 (1998) 319), PSHA (SID98, Digest of tech. Papers 29 (1998) 1081), RFFMH (Asia Display 98, Proc. Of the-18th-Inter.Display res Conf. (Preliminary Proceedings) (1998) 375), HMD (SID98, Digest of tech. Papers (Preliminary Proceedings) 29 (1998) 702), JP-A-10-123478, International Publication No. W09848320, Patent No. 3022477 And International Publication No. 00/65384 Pamphlet It has been described in an equal.

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 contain an alternating current component as necessary) voltage (usually 2 to 40 volts) or a direct current between the anode and the cathode. By doing so, light emission can be obtained.
The driving of these light emitting elements is disclosed in JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7-134558, JP-A-8-234665, and JP-A-8-241047. U.S. Pat. Nos. 5,828,429, 6,023,308, and Japanese Patent No. 2,784,615 can be used.

  EXAMPLES Hereinafter, although a synthesis example and an Example are given and this invention is demonstrated further more concretely, this invention is not limited to these.

[Synthesis Example 1]
1. Synthesis of Exemplary Compound P-32 (1) Synthesis of 4,4 ′-(9-fluorenylidene) diallylphenol (III)

It was confirmed that 35 g of Compound (I) (trade name: BPFL, manufactured by JFE Chemical Co., Ltd.), 29 g of allyl bromide, 22 g of potassium carbonate and 300 ml of acetone were mixed, heated to reflux for 30 hours, and the reaction was almost complete by TLC. confirmed. After cooling to room temperature, the mixture was filtered and concentrated, and 400 ml of toluene was added to the residue and washed twice with 200 ml of water. Thereafter, the organic layer was dried over sodium sulfate and then concentrated to obtain 43 g of compound (II) crude crystals.
Next, 42 g of the crude crystal of compound (II) and 84 g of N, N-diethylaniline were mixed and heated and stirred at 200 ° C. for 18 hours under nitrogen. N, N-diethylaniline was distilled off under reduced pressure at 2.67 × 10 ⁻³ MPa, 50 ml of acetone was added, and the mixture was further heated to 60 ° C. and then cooled for recrystallization. The crystals were filtered and dried to obtain 36.45 g of the 4,4 ′-(9-fluorenylidene) diallylphenol (III). The product (4,4 ′-(9-fluorenylidene) diallylphenol (III) was identified by 400 MHz ¹ HNMR.
¹ HNMR (CDCl ₃ ), δ (ppm): 3.25 (d, 4H), 4.89 (s, 2H), 5.09 (dd, 4H), 5.85 to 6.00 (m, 2H) ), 6.61 (d, 2H), 6.89 (dd, 2H), 6.95 (d, 2H), 7.18-7.40 (m, 6H), 7.71 (d, 2H)

(2) Synthesis of Exemplified Compound P-32 In a 1 L three-necked flask, 21.1 g of 4,4 ′-(9-fluorenylidene) diallylphenol (III), 0.15 g of hydrosulfite sodium, tetrabutylammonium chloride 694 .8 mg, 163 ml of methylene chloride, and 188 ml of distilled water were added and stirred at room temperature under a nitrogen stream. Further, a solution prepared by dissolving 6.33 g of 2,6-naphthalenedicarboxylic acid chloride and 5.1 g of terephthalic acid chloride in 75 ml of methylene chloride was added. Next, an alkaline aqueous solution obtained by diluting 52.5 ml of a 2N aqueous sodium hydroxide solution with 22.5 ml of distilled water was dropped into the mixed solution at room temperature over 1 hour. After completion of the dropwise addition, stirring was continued for 2 hours, and then 0.9 g of acetic acid and 100 ml of methylene chloride were added. The organic layer was separated from the obtained solution, added to 2 L of methanol, and the precipitated polymer was separated by decantation. Furthermore, 26.3 g of exemplary compound P-32 was obtained by melt | dissolving the obtained polymer in 250 ml of methylene chloride, and reprecipitating in 1 L of methanol.
As a result of measuring the obtained exemplary compound P-32 with GPC (THF solvent), the weight average molecular weight was 21,600 and the number average molecular weight was 10100. Further, the thermal deformation start temperature measured with TMA8310 (Thermo Electric series, Thermo Plus series) was 214 ° C.

[Synthesis Example 2]
1. Synthesis of Exemplified Compound P-25 Piperazine (660 mmol), tetrabutylammonium chloride (33 mmol), dichloromethane (2227 ml) and water (2475 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, a solution obtained by dissolving 660 mmol of bischloroformate synthesized from the 4,4 ′-(9-fluorenylidene) diallylphenol (III) using triphosgene in 743 ml of dichloromethane and 693 ml of 2N aqueous sodium hydroxide solution The solution diluted with 132 ml of water was added dropwise using a separate dropping device simultaneously over 1 hour. After completion of the dropwise addition, each was washed with 165 ml of water and dichloromethane. Thereafter, stirring was continued for 3 hours, and then 1 L of dichloromethane was added to separate the organic layer. Further, a solution obtained by diluting 6.6 ml of 12N hydrochloric acid with 2.5 L of water was added to wash the organic layer. After further washing twice with 2.5 L of water, 1 L of dichloromethane was added to the separated organic layer, diluted, and then poured into 25 L of methanol that was vigorously stirred over 1 hour. The obtained white precipitate in methanol was collected by filtration and dried to obtain 240 g of the exemplified compound P-25.
As a result of measuring the molecular weight of the obtained exemplary compound P-25 with GPC (chloroform solvent), the weight average molecular weight was 150,000 and the number average molecular weight was 70000. Further, the thermal deformation start temperature measured with TMA8310 (Thermo Plus series, Thermo Plus series) was 190 ° C.
Other compounds of the present invention can be synthesized in the same manner as described above.

[Comparative Synthesis Example 1]
1. Synthesis of Comparative Compound X-1 The following comparative compound X-1 was synthesized according to the synthesis method described in Example 1 of JP-A-57-192432. The number average molecular weight was 30000, and the thermal deformation start temperature was 293 ° C.

[Comparative Synthesis Example 2]
2. Synthesis of Comparative Compound X-2 The following Comparative Compound X-2 was synthesized according to the synthesis method described in Example 1 of JP-A-10-77338. The number average molecular weight was 30000.

[Example 1]
<Measurement method of characteristic value>
In this example, the weight average molecular weight, film thickness, thermal deformation start temperature, total light transmittance of the film, and mechanical properties (breaking stress) of the film were measured as follows.

(Weight average molecular weight)
By GPC measurement in terms of polystyrene using tetrahydrofuran as a solvent, the weight average molecular weight was determined by using and comparing with a molecular weight standard product of polystyrene. In addition, GPC (manufactured by Tosoh Corporation, HLC-8120GPC) was used as a measuring apparatus.
(Film thickness)
It measured with the dial-type thickness gauge (Anritsu Co., Ltd. product, K402B).
(Thermal deformation start temperature)
Measured with TMA8310 (manufactured by Rigaku Corporation, Thermo Plus series) (in nitrogen, temperature rising temperature 10 ° C./min)

(Total light transmittance of film)
It measured using the haze meter (Suga Test Instruments Co., Ltd. product, HGM-2DP).
(Break stress 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 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 a relative humidity of 60%. The distance between chucks was 3 cm).

<Preparation of optical film samples (samples 101 to 109)>
The polymer of the present invention and the comparative polymer described in Table 1 below were dissolved in dichloromethane, and then dissolved at a concentration such that the solution viscosity was 500 to 1500 mPa · s or less. Further, 2-azo-bis-isobutyronitrile corresponding to 2% by mass of the total solid content was further added to the solution containing the polymer of the present invention or the comparative polymer X-2.
The obtained solution was filtered through a 5 μm filter and then cast on a glass substrate using a doctor blade. After casting, it was dried at room temperature for 2 hours and at 60 ° C. for 2 hours, and then heated at 150 ° C. for 4 hours in a nitrogen atmosphere. After heating, the film was peeled from the glass substrate to obtain optical film samples (samples 101 to 109).
The thermal deformation start temperature, film thickness, total light transmittance, and breaking stress of the obtained optical film sample were measured. Table 1 shows the results.

  From Table 1, it can be seen that the optical film of the present invention has a high thermal deformation start temperature and is excellent in heat resistance. It can also be seen that the stress at break is large and has excellent mechanical properties.

[Example 2]
<Preparation of organic EL element sample>
(Installation of gas barrier layer)
On both surfaces of the optical film samples 101 to 107 of the present invention prepared above and the optical film samples 108 and 109 of the comparative example, oxygen was introduced under an Ar atmosphere under a vacuum of 500 Pa using Si as a target by a DC magnetron sputtering method. The sputtering was performed at an output of 5 kW at a pressure of 0.1 Pa. The film thickness of the obtained gas barrier layer was 60 nm. The optical film sample on which the gas barrier layer is formed has a water vapor transmission rate of 0.1 g / m ² · day or less at 40 ° C. and a relative humidity of 90%, and an oxygen transmission rate of 0.1 ml / m ² at 40 ° C. and a relative humidity of 90%. m ² · day or less.

(Installation of transparent conductive layer)
While heating the optical film sample provided with the gas barrier layer to 100 ° C., ITO (In ₂ O ₃ 95% by mass, SnO ₂ 5% by mass) is used as a target and DC magnetron sputtering is performed under a vacuum of 0.665 Pa. 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 in an atmosphere. The surface electrical resistance at 25 ° C. and 60% relative humidity of the optical film sample provided with the transparent conductive layer was 30Ω / □.

(Heat treatment of optical film with transparent conductive layer)
The optical film sample provided with the transparent conductive layer obtained above was subjected to heat treatment at 300 ° C. for 1 h assuming TFT installation.

(Production of organic EL element)
The aluminum lead wire was connected from the transparent electrode layer of the optical film sample provided with the transparent conductive layer subjected to the heat treatment as described above to form a laminated structure. The optical film sample provided 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 109 of the comparative example was provided. The optical film sample was severely deformed, and no organic EL device was produced. In addition, although the optical film sample which installed the transparent conductive layer obtained from the optical film sample 108 of the comparative example also showed some deformation | transformation, since it was not remarkable, the organic EL element 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 mass%), and then vacuum-dried at 150 ° C. for 2 hours to obtain a thick A hole-transporting organic thin film layer having a thickness of 100 nm was formed. This was designated as substrate X.
On the other hand, using a spin coater, a coating solution for a light-emitting organic thin film layer having the following composition was formed on one side of a temporary support made of polyethersulfone having a thickness of 188 μm (Sumilite FS-1300, manufactured by Sumitomo Bakelite Co., Ltd.). By coating and drying at room temperature, a light-emitting organic thin film layer having a thickness of 13 nm was formed on the temporary support. This was designated as transfer material Y.

〔composition〕
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, and the temporary support is attached. 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 deposition mask (a mask with a light emission area of 5 mm and 5 mm) is placed on one side of a polyimide film (UPILEX-50S, manufactured by Ube Industries) having a thickness of 50 im that is cut into 25 mm square. Al was evaporated in a reduced pressure atmosphere of 1 mPa to form an electrode having a thickness of 0.3 im. 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. An aluminum lead wire was 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.

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

  Using substrate XY and substrate Z, the electrodes are stacked so that the electrodes face each other with the light-emitting organic thin film layer sandwiched between them, and heated and pressed at 160 ° C., 0.3 MPa, 0.05 m / min using a pair of heat rollers. Then, organic EL element samples 201 to 208 were obtained.

  A direct voltage was applied to the organic EL elements of the obtained organic EL element samples 201 to 208 using a source measure unit 2400 type (manufactured by Toyo Technica Co., Ltd.). The comparative sample 208, which was 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.

  As can be seen from the above, the polymer of the present invention and the optical film obtained therefrom are excellent in transparency, heat resistance and mechanical properties. Furthermore, the optical film of the present invention can be laminated with a gas barrier layer and a transparent conductive layer, and can provide an organic EL display excellent in display quality.

Claims (7)

A polymer comprising at least one repeating unit represented by the following general formula (1) or general formula (2) and having at least one of an ester bond and a urethane bond.

[In general formula (2), ring β represents a monocyclic or polycyclic ring. R ^{1 to} R ⁸ represent a hydrogen atom or a substituent, and at least one of R ^{1 to} R ⁴ represents a substituted or unsubstituted allyl group. R ¹ and R ⁵ , R ² and R ⁶ , R ³ and R ⁷ , R ⁴ and R ⁸ , and R ⁵ and R ⁷ may be bonded to each other to form a ring. ]   An optical film formed of the polymer according to claim 1.   The optical film according to claim 2, wherein allyl groups in the polymer according to claim 1 are crosslinked.   The optical film according to claim 2 or 3, wherein the total light transmittance is 80% or more.   The optical film according to any one of claims 2 to 4, wherein a gas barrier layer is laminated on at least one surface.   The optical film according to claim 2, 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 2-6.