JP2003268129A - Film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film excellent in homogeneity and surface smoothness and high in productivity. <P>SOLUTION: The film is one at least either surface of which has a center line average surface roughness of 5 nm or smaller and which is made from a polymer comprising structural units each being a phosphonic acid ressidue represented by structural formula (1) (wherein R<SP>1</SP>is an organic group; and X<SP>1</SP>is O, S, or Se) and structural units each of which is a dihydric phenol residue represented by structural formula (2) (wherein R<SP>2</SP>and R<SP>3</SP>are each H, NO<SB>2</SB>, a halogen atom, a 1-20C aliphatic group, or an aromatic group; p and q are integers with the proviso that 0≤p+q≤8; and Y<SP>1</SP>is O, S, an alkylene, an alkylidene, a cycloalkylene, a halo-substituted alkylene, a halo-substituted alkylidene, a phenylalkylidene, a carbonyl group, a sulfo group, an aliphatic phsphine oxide group, an aromatic phsphine oxide group, an alkylsilane group, a dialkylsilane group, or a fluorene group). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film having excellent surface smoothness and homogeneity and having high productivity, which is suitable for optical applications.

[0002]

2. Description of the Related Art As colorless transparent materials, various materials are applied according to their various uses such as optical lenses, functional optical films, disk substrates, etc., but with the rapid development of healthcare and electronics, The functions and performances required for themselves are becoming more precise and sophisticated.

Particularly, in the case of film, with the progress of IT, members for display such as a polarizing plate and a retardation plate, and polycarbonate as a disk protective film,
Cyclic polyolefins, cellulosic films, etc. have been used.

[0004]

As described above, colorless and transparent thermoplastic resins such as polycarbonate are widely used for electronic applications, and are used for optical films such as retardation films and disk substrates. Can be mentioned. In particular, the retardation film is one of the important constituent members that determine the contrast of the reflective color liquid crystal display. For example, currently used polycarbonates are disclosed in JP-A-4-204503 and JP-A-9-304619, but they cannot be said to have sufficient wavelength dispersion characteristics. To increase the contrast of reflective liquid crystal displays,
One of the technical issues is to improve the wavelength dispersion characteristic of a polymer film used as a retardation film.

Various polymers containing phosphorus functional groups are known, and a polymer containing a phosphonate ester group in its main chain is called polyphosphonate (KS Kim,
J. Appl. Polym. Sci., 28 , 1119 (1983); Y. Imai et
al, Makromol. Chem., Rapid Commun., 1 , 419 (198
0); USP3719727), active research is being conducted with the aim of improving the flame retardant function. Since there was no detailed knowledge about the physical properties such as optical properties and mechanical properties of these polyphosphonate-based polymers, the present inventors synthesized them and evaluated the physical properties. As a result, these polyphosphonate-based polymers have insufficient mechanical properties and optical properties due to their low molecular weight, and are difficult to form into a film, and even if they are formed into a film, it is difficult to obtain a homogeneous film.

The present invention solves the above-mentioned conventional problems,
It is an object of the present invention to provide a film that is colorless and transparent, has excellent homogeneity and surface smoothness, and has high productivity.

[0007]

According to the present invention for solving the above-mentioned problems, the center line average roughness of at least one surface is 5 nm.
A film containing a polymer which is as follows and which contains a phosphonic acid residue represented by the structural formula (1) and a dihydric phenol residue represented by the structural formula (2) in the molecule as constituent units: Characterize.

[0008]

[Chemical 3] R ¹ : organic group X ¹ : O, S or Se (however, two or more kinds of phosphonic acid residues having different R ¹ or X ¹ may be contained in the polymer.)

[0009]

[Chemical 4] ^{R 2, R 3: H,} NO 2, 1~ halogen atom or carbon atoms
20 aliphatic or aromatic groups p, q: integers and 0 ≦ p + q ≦ 8 Y ¹ : O, S, alkylene group, alkylidene group, cycloalkylene group, cycloalkylidene group, halo-substituted alkylene group, halo-substituted Alkylidene group, phenylalkylidene group, carbonyl group, sulfone group, aliphatic phosphine oxide group, aromatic phosphine oxide group, alkylsilane group, dialkylsilane group or fluorene group (wherein Y ¹ may be a single bond. Also,
Two or more dihydric phenol residues having different R ² , R ³ or Y ¹ may be contained in the polymer. )

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer contained in the film of the present invention has a structure having a pentavalent phosphorus atom, particularly a phosphonic acid structure represented by the structural formula (1) in the polymer main chain. It is a feature. In particular, when the polymer contains a carbonate residue, the molar fraction of the phosphonic acid residue is preferably 0.5 or more and less than 1.

[0011]

[Chemical 5] R ¹ : organic group X ¹ : O, S or Se (however, the polymer may contain two or more phosphonic acid residues having different R ¹ or X ¹ ). The ratio is calculated by the ratio of the number of moles of phosphonic acid residues to the total number of moles of phosphonic acid residues and carbonate residues present per unit, and is a value represented by the following formula.

Molar Fraction of Phosphonic Acid Residue = a / (a + b) a: Number of Molar Phosphonic Acid Residues Represented by Structural Formula (1) Present Per Unit b: Carbonate Residue Per Unit The number of moles can be said to represent the copolymerization fraction of the phosphonic acid residue, and if the reaction during polymer synthesis proceeds stoichiometrically, it can also be calculated by the raw material charging ratio. . Further, in the molded body, it can be measured by using NMR (nuclear magnetic resonance method).

When the molar fraction of the phosphonic acid residue represented by the structural formula (1) is less than 0.5, the high refractive index of the polymer is difficult to be exhibited, and the effect of the present invention tends to be difficult to be obtained. There is. This molar fraction is more preferably 0.75 or more and less than 1.

The substituent R ¹ on the phosphorus atom of the structural unit represented by the above structural formula (1) is an organic group, specifically, phenyl, halo-substituted phenyl, methoxyphenyl, ethoxyphenyl, ethyl, isopropyl. , Cyclohexyl,
Vinyl, allyl, benzyl, aminoalkyl, hydroxyalkyl, halo-substituted alkyl, alkylsulfide groups and the like can be used. Specific examples of the phosphonic acid forming the phosphonic acid residue having such a substituent include methylphosphonic acid, ethylphosphonic acid, and n.
-Propylphosphonic acid, isopropylphosphonic acid, n-
Butylphosphonic acid, isobutylphosphonic acid, t-butylphosphonic acid, n-pentylphosphonic acid, neopentylphosphonic acid, cyclohexylphosphonic acid, benzylphosphonic acid, chloromethylphosphonic acid, dichloromethylphosphonic acid, bromomethylphosphonic acid, dibromomethylphosphonic acid, 2 -Chloroethylphosphonic acid, 1,2-dichloroethylphosphonic acid, 2-bromoethylphosphonic acid, 1,
2-dibromoethylphosphonic acid, 3-chloropropylphosphonic acid, 2,3-dichloropropylphosphonic acid 3-bromopropylphosphonic acid, 2,3-dibromopropylphosphonic acid, 2-chloro-1-methylethylphosphonic acid,
1,2-dichloro-1-methylethylphosphonic acid, 2-
Bromo-1-methylethylphosphonic acid, 1,2-dibromo-1-methylethylphosphonic acid, 4-chlorobutylphosphonic acid, 3,4-dichlorobutylphosphonic acid, 4-bromobutylphosphonic acid, 3,4-dibromobutylphosphonic acid Acid, 3-chloro-1-methylpropylphosphonic acid,
2,3-dichloro-1-methylpropylphosphonic acid, 3
-Bromo-1methylpropylphosphonic acid, 2,3-dibromo-1-methylphosphonic acid, 1-chloromethylpropylphosphonic acid, 1-chloro-1-chloromethylpropylphosphonic acid, 1-bromomethylpropylphosphonic acid, 1
-Bromo-1-bromomethylpropylphosphonic acid, 5-
Chloropentylphosphonic acid, 4,5-dichloropentylphosphonic acid, 5-bromopentylphosphonic acid, 4,5-
Dibromopentylphosphonic acid, 1-hydroxymethylphosphonic acid, 2-hydroxyethylphosphonic acid, 3-hydroxypropylphosphonic acid, 4-hydroxybutylphosphonic acid, 5-hydroxypentylphosphonic acid, 1-aminomethylphosphonic acid, 2-aminoethylphosphonic acid Acid, 3
-Aminopropylphosphonic acid, 4-aminobutylphosphonic acid, 5-aminopentylphosphonic acid, methylthiomethylphosphonic acid, methylthioethylphosphonic acid, methylthiopropylphosphonic acid, methylthiobutylphosphonic acid,
Ethylthiomethylphosphonic acid, ethylthioethylphosphonic acid, ethylthiopropylphosphonic acid, propylthiomethylphosphonic acid, propylthioethylphosphonic acid, butylthiomethylphosphonic acid, phenylphosphonic acid, 4-chlorophenylphosphonic acid, 3,4-dichlorophenylphosphonic acid , 3,5-dichlorophenylphosphonic acid, 4-
Bromophenylphosphonic acid, 3,4-bromophenylphosphonic acid, 3,5-bromophenylphosphonic acid, 4-methoxyphenylphosphonic acid, 3,4-dimethoxyphenylphosphonic acid, 1-naphthylphosphonic acid, 2-naphthylphosphonic acid , 5,6,7,8-tetrahydro-2-naphthylphosphonic acid, 5,6,7,8-tetrahydro-1-
Naphthylphosphonic acid, benzylphosphonic acid, 4-bromophenylmethylphosphonic acid, 3,4-dibromophenylmethylphosphonic acid, 3,5-dibromophenylmethylphosphonic acid, 2-phenylethylphosphonic acid, 2- (4-
Bromophenyl) ethylphosphonic acid, 2- (3,4-dibromophenyl) ethylphosphonic acid, 2- (3,5-dibromophenyl) ethylphosphonic acid, 3-phenylpropylphosphonic acid, 3- (4-bromophenyl) Propylphosphonic acid, 3- (3,4-dibromophenyl) propylphosphonic acid, 3- (3,5-dibromophenyl) propylphosphonic acid, 4-phenylbutylphosphonic acid, 4-
(4-Bromophenyl) butylphosphonic acid, 4- (3,
4-dibromophenyl) butylphosphonic acid, 4- (3,
5-dibromophenyl) butylphosphonic acid, 2-pyridylphosphonic acid, 3-pyridylphosphonic acid, 4-pyridylphosphonic acid, 1-pyrrolidinomethylphosphonic acid, 1-pyrrolidinoethylphosphonic acid, 1-pyrrolidinopropylphosphonic acid, 1-pyrrolidinobutylphosphonic acid, pyrrole-1-phosphonic acid, pyrrole-2-phosphonic acid, pyrrole-3-phosphonic acid, thiophen-2-phosphonic acid, thiophen-3-phosphonic acid, dithian-2-phosphonic acid, Examples thereof include trithian-2-phosphonic acid, furan-2-phosphonic acid, furan-3-phosphonic acid, vinylphosphonic acid and allylphosphonic acid. Moreover, the thiophosphonic acid corresponding to X ¹ in which the oxygen atom (O) double-bonded to these phosphorus atoms is substituted with the sulfur atom (S) is also included. Furthermore, X ¹ is a selenium atom (S
e). These may be used alone or in combination of two or more. Further, these phosphonic acids may be phosphonic acid derivatives such as acid chlorides, esters and amides thereof.

When the polymer does not contain a carbonate residue, X ¹ is preferably S or Se.

Regarding these phosphonic acid residues,
Each may be partially replaced with a corresponding phosphonite residue which is a trivalent phosphorus functional group. Although the oxidation resistance of the polymer can be imparted by this, the substitution ratio is preferably 50% or less, more preferably 25% or less, still more preferably 10 in view of the characteristic stability such as optical characteristics.
% Or less. That is, it is preferable that the polymer contains a phosphonite residue, and the molar ratio of the phosphonite residue to the phosphonic acid residue and the phosphonite residue represented by the structural formula (1) is 0.5 or less, and more preferably. 0.
It is 25 or less, more preferably 0.1 or less.

Further, the polymer in the present invention contains a dihydric phenol residue represented by the following structural formula (2) as a constituent unit.

[0018]

[Chemical 6] ^{R 2, R 3: H,} NO 2, 1~ halogen atom or carbon atoms
20 aliphatic or aromatic groups p, q: integers and 0 ≦ p + q ≦ 8 Y ¹ : O, S, alkylene group, alkylidene group, cycloalkylene group, cycloalkylidene group, halo-substituted alkylene group, halo-substituted Alkylidene group, phenylalkylidene group, carbonyl group, sulfone group, aliphatic phosphine oxide group, aromatic phosphine oxide group, alkylsilane group, dialkylsilane group or fluorene group (wherein Y ¹ may be a single bond. Also,
Two or more dihydric phenol residues having different R ² , R ³ or Y ¹ may be contained in the polymer. ) Specific examples of this dihydric phenol residue in the form of dihydric phenol include 1,1-bis (4-hydroxyphenyl) methane and 1,1-bis (4-hydroxyphenyl).
Ethane, 1,1-bis (4-methyl-2-hydroxyphenyl) methane, 1,1-bis (3,5-dimethyl-4)
-Hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1
-Bis (4-hydroxyphenyl) cycloheptane,
1,1-bis (4-hydroxyphenyl) cyclooctane, 1,1-bis (4-hydroxyphenyl) cyclodecane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 2,2-bis (4-hydroxy) Phenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-
4-hydroxyphenyl) propane, 1,1-bis (4
-Hydroxyphenyl) -1-phenylethane, 1,1
-Bis (4-hydroxyphenyl) -2-ethylhexane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 1,1-bis (3-methyl-4-hydroxyphenyl) methane, 4, 4'-biphenol,
2,2-bis (4-hydroxyphenyl) butane, 1,
1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis (4-hydroxyphenyl) -1-
Phenylmethane, 2,2-bis (4-hydroxyphenyl) octane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-sec)
Butyl-4-hydroxyphenyl) propane, bisphenolfluorene, 1,1-bis (2-methyl-4-hydroxy-5-tert-butylphenyl) -2-methylpropane, 4,4 '-[1,4-phenylene -Bis (2-propylidene)]-bis (2-methylphenol), 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxyphenyl ether, 1,1-bis (2 -Hydroxyphenyl) methane, 2,4'-methylenebisphenol, 1,
1-bis (3-methyl-4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) propane, 1,1-bis (2-hydroxy-5-methylphenyl) ethane, 1,1-bis (4-hydroxyphenyl)
-3-methyl-butane, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-
Bis (3-methyl-4-hydroxyphenyl) cyclopentane, 3,3-bis (4-hydroxyphenyl) pentane, 3,3-bis (3-methyl-4-hydroxyphenyl) pentane, 3,3-bis ( 3,5-dimethyl-4
-Hydroxyphenyl) pentane, 2,2-bis (2-
Hydroxy-3,5-dimethylphenyl) propane,
2,2-bis (4-hydroxyphenyl) nonane, 1,
1-bis (3-methyl-4-hydroxyphenyl) -1
-Phenylethane, 1,1-bis (3,5-dimethyl-
4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (2
-Hydroxy-3-tert-butyl-5-methylphenyl) methane, 1,1-bis (4-hydroxyphenyl) diphenylmethane, terpene diphenol, 1,1
-Bis (3-tert-butyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (2-methyl-4-)
Hydroxy-5-tert-butylphenyl) -2-methylpropane, 2,2-bis (3-cyclohexyl-4)
-Hydroxyphenyl) propane, 1,1-bis (3,3
5-ditert-butyl-4-hydroxyphenyl) methane, 1,1-bis (3,5-disecbutyl-4-hydroxyphenyl) methane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) Cyclohexane,
1,1-bis (2-hydroxy-3,5-ditert-
Butylphenyl) ethane, 1,1-bis (3-nonyl-
4-hydroxyphenyl) methane, 2,2-bis (3,3
5-ditert-butyl-4-hydroxyphenyl) propane, 1,1-bis (2-hydroxy-3,5-dit)
ert-butyl-6-methylphenyl) methane, 1,1
-Bis (3-phenyl-4-hydroxyphenyl) -1
-Phenylethane, 4,4-bis (4-hydroxyphenyl) pentanoic acid, bis (4-hydroxyphenyl) acetic acid butyl ester, 1,1-bis (3-fluoro-4-)
Hydroxyphenyl) methane, 1,1-bis (2-hydroxy-5-fluorophenyl) methane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3
-Hexafluoropropane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 1,1-bis (3-fluoro-4-hydroxyphenyl) -1-phenylmethane, 1,1-bis (3 -Fluoro-4-hydroxyphenyl) -1- (p-fluorophenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-
(P-Fluorophenyl) methane, 2,2-bis (3-
Chloro-4-hydroxy-5-methylphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-)
Hydroxyphenyl) propane, 1,1-bis (3,5
-Dibromo-4-hydroxyphenyl) methane, 2,2
-Bis (3,5-dibromo-4-hydroxyphenyl)
Propane, 2,2-bis (3-nitro-4-hydroxyphenyl) propane, 3,3'-dimethyl-4,4'-
Biphenol, 3,3 ', 5,5'-tetramethyl-
4,4'-biphenol, 3,3 ', 5,5'-tetratert-butyl-4,4'-biphenol, bis (4
-Hydroxyphenyl) ketone, 3,3'-difluoro-4,4'-biphenol, 3,3 ', 5,5'-tetrafluoro-4,4'-biphenol, bis (4-hydroxyphenyl) dimethylsilane, Bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4)
-Hydroxyphenyl) sulfone, bis (3,5-dibromo-4-hydroxyphenyl) sulfone, bis (4-
Hydroxyphenyl) thioether, bis (3-methyl-4-hydroxyphenyl) ether, bis (3-methyl-4-hydroxyphenyl) thioether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,3 5-dimethyl-4-hydroxyphenyl) thioether, 1,1-bis (2,3,5-trimethyl-4-hydroxyphenyl) -1-phenylmethane, 2,2-bis (4-hydroxyphenyl) dodecane, 2 , 2-bis (3-methyl-4-hydroxyphenyl) dodecane, 2,2-bis (3,5-dimethyl-4-)
Hydroxyphenyl) dodecane, 1,1-bis (3-t
ert-butyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3,5-ditert-butyl-4-hydroxyphenyl) -1-phenylethane,
1,1-bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) -2-methylpropane, 1,1-
Bis (2-hydroxy-3,5-ditert-butylphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propanoic acid methyl ester, 2,2-bis (4-hydroxyphenyl) propanoic acid ethyl ester, Isatin bisphenol, isatin biscresol, 2,
2 ', 3,3', 5,5'-hexamethyl-4,4'-
Biphenol, bis (2-hydroxyphenyl) methane, 2,4'-methylenebisphenol, 1,2-bis (4-hydroxyphenyl) ethane, 2- (4-hydroxyphenyl) -2- (2-hydroxyphenyl) propane , Bis (2-hydroxy-3-allylphenyl) methane, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -2-methylpropane, 1,1-bis (2
-Hydroxy-5-tert-butylphenyl) ethane, bis (2-hydroxy-5-phenylphenyl) methane, 1,1-bis (2-methyl-4-hydroxy-5)
-Tert-butylphenyl) butane, bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) methane, 2,2-bis (4-hydroxyphenyl) pentadecane, 2,2-bis (3-methyl-4-) Hydroxyphenyl) pentadecane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) pentadecane, 1,2-
Bis (3,5-ditert-butyl-4-hydroxyphenyl) ethane, bis (2-hydroxy-3,5-dit
ert-butylphenyl) methane, 2,2-bis (3-
Styryl-4-hydroxyphenyl) propane, 1,1
-Bis (4-hydroxyphenyl) -1- (p-nitrophenyl) ethane, bis (3,5-difluoro-4-hydroxyphenyl) methane, bis (3,5-difluoro-4-hydroxyphenyl) -1- Phenylmethane, bis (3,5-difluoro-4-hydroxyphenyl) diphenylmethane, bis (3-fluoro-4-hydroxyphenyl) diphenylmethane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 3, 3 ',
5,5'-tetratert-butyl-2,2'-biphenol, 2,2'-diallyl-4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) -3,
3,5-Trimethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5,5-tetramethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,4 -Trimethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3
-Dimethyl-5-ethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl-cyclopentane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl)- 3,3,5-Trimethyl-cyclohexane, 1,1-bis (3,5-diphenyl-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis (3-methyl-4-) Hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis (3-phenyl-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis (3,5- Dichloro-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis ( , 5-Dimethyl-4-hydroxyphenyl) fluorene, 1,1-bis (3,5-dibromo-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, α, α-bis (4-hydroxyphenyl) ) -1,4-diisopropylbenzene and the like. These may be used alone or in combination of two or more. These dihydric phenols can be appropriately selected and used according to the performance of the obtained polymer.

If the carbon number of R ² exceeds 20, heat resistance and moldability may deteriorate.

Further, the same structure can be introduced into the polymer skeleton by using dihydroxybenzene within the range where the effect of the present invention is not impaired. Examples of these dihydroxybenzenes include resorcinol, hydroquinone, and 1,2-dihydroxybenzene. These may be used alone or in combination of two or more.

The polymer used in the present invention does not necessarily have to be linear, and a polyhydric phenol can be copolymerized depending on the performance of the obtained polymer. Specific examples of such polyphenols include tris (4-hydroxyphenyl) methane, 4,4 ′-[1- [4- [1
-(4-Hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 2,3,4
4'-tetrahydroxybenzophenone, 4- [bis (4-hydroxyphenyl) methyl] -2-methoxyphenol, tris (3-methyl-4-hydroxyphenyl) methane, 4- [bis (3-methyl-4-hydroxy) Phenyl) methyl] -2-methoxyphenol, 4-
[Bis (3,5-dimethyl-4-hydroxyphenyl)
Methyl] -2-methoxyphenol, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3-methyl-4-hydroxyphenyl) ethane,
1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, tris (3-methyl-4-hydroxyphenyl) methane, tris (3,5-dimethyl-4)
-Hydroxyphenyl) methane, 2,6-bis [(2-
Hydroxy-5-methylphenyl) methyl] -4-methylphenol, 4- [bis (3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2-dihydroxybenzene, 2- [bis (2-methyl- 4-hydroxy-5
-Cyclohexylphenyl) methyl] -phenol, 4
-[Bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) methyl] -1,2-dihydroxybenzene, 4-methylphenyl-1,2,3-trihydroxybenzene, 4-[(4-hydroxyphenyl ) Methyl] -1,2,3-trihydroxybenzene, 4- [1
-(4-hydroxyphenyl) -1-methyl-ethyl]
-1,3-dihydroxybenzene, 4-[(3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2,
3-trihydroxybenzene, 1,4-bis [1-bis (3,4-dihydroxyphenyl) -1-methyl-ethyl] benzene, 1,4-bis [1-bis (2,3,4-)
Trihydroxyphenyl) -1-methyl-ethyl] benzene, 2,4-bis [(4-hydroxyphenyl) methyl] -1,3-dihydroxybenzene, 2- [bis (3
-Methyl-4-hydroxyphenyl) methyl] phenol, 4- [bis (3-methyl-4-hydroxyphenyl) methyl] phenol, 2- [bis (2-methyl-4)
-Hydroxyphenyl) methyl] phenol, 4- [bis (3-methyl-4-hydroxyphenyl) methyl]-
1,2-dihydroxybenzene, 4- [bis (4-hydroxyphenyl) methyl] -2-ethoxyphenol,
2- [bis (2,3-dimethyl-4-hydroxyphenyl) methyl] phenol, 4- [bis (3,5-dimethyl-4-hydroxyphenyl) methyl] phenol, 3
-[Bis (3,5-dimethyl-4-hydroxyphenyl) methyl] phenol, 2- [bis (2-hydroxy-3,6-dimethylphenyl) methyl] phenol, 4
-[Bis (2-hydroxy-3,6-dimethylphenyl) methyl] phenol, 4- [bis (3,5-dimethyl-4-hydroxyphenyl) methyl] -2-methoxyphenol, 3,6- [bis ( 3,5-dimethyl-4-
Hydroxyphenyl) methyl] -1,2-dihydroxybenzene, 4,6- [bis (3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2,3-trihydroxybenzene, 2- [bis (2 , 3,6-Trimethyl-
4-hydroxyphenyl) methyl] phenol, 2-
[Bis (2,3,5-trimethyl-4-hydroxyphenyl) methyl] phenol, 3- [bis (2,3,5-
Trimethyl-4-hydroxyphenyl) methyl] phenol, 4- [bis (2,3,5-trimethyl-4-hydroxyphenyl) methyl] phenol, 4- [bis (2,3,5-trimethyl-4-hydroxyphenyl) )
Methyl] -1,2-dihydroxybenzene, 3- [bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) methyl] phenol, 4- [bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) Methyl] phenol, 4- [bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) methyl] -2-methoxyphenol, 2,4,6- [tris (4-hydroxyphenylmethyl) -1,3- Dihydroxybenzene, 1,1,2,2-tetra (3-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetra (3
5-dimethyl-4-hydroxyphenyl) ethane, 1,
4-[[bis (4-hydroxyphenyl) methyl]] benzene, 1,4-di [bis (3-methyl-4-hydroxyphenyl) methyl] benzene, 1,4-di [bis (3,5-dimethyl) -4-hydroxyphenyl) methyl] benzene, 4- [1,1-bis (4-hydroxyphenyl) ethyl] aniline, (2,4-dihydroxyphenyl) (4-hydroxyphenyl) ketone, 2- [bis (4 -Hydroxyphenyl) methyl] phenol,
1,3,3-tri (4-hydroxyphenyl) butane and the like are listed, and these may be used alone or in combination of two or more.

The film of the present invention has a center line average roughness of 5 nm or less on at least one side. Centerline average roughness is 5
When it exceeds nm, it becomes cloudy when light is transmitted through the film,
Image distortion may occur, and the film may not function as a high-performance optical film. The cloudiness and the image distortion are caused by the rough surface, the unevenness, and the like, and the light rays are likely to be irregularly reflected. Also, it may occur due to non-uniform internal structure during film formation, and even in such a case, the center line average roughness is 5
It is easy to exceed nm. Therefore, by controlling the center line average roughness of the film surface as an index, it becomes easy to obtain an optical film having a high function both on the surface and the internal structure. The center line average roughness is preferably 3 nm or less, more preferably 2 nm or less, still more preferably 1 nm or less. The lower limit of the center line average roughness is not particularly limited, but it is preferably 0.1 nm or more from the viewpoint of handleability during molding and processing. Further, it is more preferable that the center line average roughness satisfies the above-mentioned range on both sides of the film, because the haze of the film and the distortion of the image can be further reduced.

The number average molecular weight of the polymer contained in the film of the present invention is 20,000 or more and 500,000 or more.
When it is below, the toughness of the film is improved, and further the productivity in forming the film can be significantly improved. That is, when an optical film is molded, a solution film-forming method is generally used in which a polymer is dissolved in a solution and cast on a support, and the molecular weight of the polymer is 2
If it is less than 10,000, the film structure tends to have non-uniformity, and if it is attempted to avoid it, the step of removing the solvent will take an extremely long time, and the productivity will tend to be significantly reduced. A higher molecular weight is more effective from the above findings, but if it exceeds 500,000, it will be difficult to polymerize the polymer, the polymerization productivity will decrease, and the homogeneity of the polymer will decrease. Transparency may be impaired. The number average molecular weight is more preferably 30,000 or more and 450,000 or less, and further preferably 40,000 or more and 400,000 or less.

The thickness of the film of the present invention is 10 to 100 μm.
It is preferable that m is a thin film as an optical member and the weight can be reduced. Optical members having a thickness of more than 100 μm are currently used as optical members such as a polarizing plate and a retardation plate. However, in order to meet the growing demand for weight reduction and thinning, the thickness is 100 μm or less. , More preferably 80 μm or less, further preferably 60 μm or less. On the other hand, if the thickness is less than 10 μm, wrinkles may occur during processing, or adhesion with other members may become uneven.

When a film member is obtained by using the film of the present invention as a constituent material, particularly when the film of the present invention is used as a member of a half-wave retardation plate or a quarter-wave retardation plate, the birefringence of the film It is necessary to add a phase difference due to. The retardation to be given should be appropriately selected according to each purpose, but when used for a quarter wavelength retardation plate application, the retardation at a wavelength of 550 nm is 5
A thickness of 0 to 1,500 nm is preferable because a uniform retardation is likely to be exhibited. More preferably, 50 to 1,2
00 nm, and more preferably 100 to 500 nm. In addition, the phase difference is 400 to 400 which is a visible light wavelength range.
The above range at 700 nm is more preferable for use in optical applications.

Further, in the film of the present invention, it is a preferred embodiment when the retardation dispersion property, that is, the wavelength dependence of the retardation satisfies the following formula, when it is used for a quarter wavelength retardation plate.

R (450) / R (550) = 1.03 to 1.25 R (650) / R (550) = 0.80 to 0.95 Here, R is a phase difference (nm), The numbers in parentheses are
Represents a wavelength (nm).

The quarter-wave retarder is a visible light wavelength region,
It is required to make the phase difference ¼ of each wavelength. For that purpose, a method is generally used in which films having different retardation dispersion properties are laminated so that their principal axes are not parallel. A cyclic polyolefin-based film, a polycarbonate-based film, a triacetate acetic acid-based film, or an acrylic-based film is used for stacking, and a cyclic polyolefin is particularly preferably used.

When the retardation dispersibility of the film of the present invention is within the above range, when laminated with such a polymer film, it is 1/4 as compared with a conventionally used polycarbonate or acetic acid triacetate type film. As a wavelength retardation plate, it becomes possible to exhibit even better retardation dispersion.

The retardation dispersibility of the film of the present invention is more preferably R (450) / R (550) = 1.1-1.22 R (650) / R (550) = 0.82-0. .93.

The film of the present invention is JIS-C2318.
It is preferable that the tensile Young's modulus obtained by the measuring method according to the above is 3 GPa or more in at least one direction because the handling property when thinned is improved. More preferably, it is 4 GPa or more. In order to keep the Young's modulus within the above range, the polymer specified in the present invention is preferable because it is more rigid than conventionally used polycarbonate and the like. Further, in film forming, the Young's modulus can be adjusted to the above range by performing stretching, but if the stretching is too strong, the toughness may be lowered or the phase difference may exceed the practical range. Therefore, the upper limit of the Young's modulus is about 8 GPa. Further, it is preferable that the film of the present invention has a breaking elongation of at least 5% in at least one direction, more preferably 10% or more, because breakage during molding and processing is reduced. Although the upper limit of the breaking elongation is not particularly limited, it is practically about 250%.

When the film of the present invention has a thermal shrinkage of 10% or less in at least one direction when it is heat-treated at 100 ° C. for 30 minutes in a state in which substantially no tension is applied, dimensional change during processing, In addition, it is preferable because the change in the phase difference characteristics can be suppressed. It is more preferably 5% or less, still more preferably 2% or less. Here, the heat shrinkage rate is defined by the following equation.

Thermal contraction rate (%) = ((test length before heat treatment-test length after heat treatment and cooling) / test length before heat treatment) × 100 It is preferable that the heat contraction rate is low, but the lower limit is practically lower. Is 0.
It is about 1%.

The film of the present invention has a temperature of 25 ° C./75 RH%.
A moisture absorption rate of 3% or less, more preferably 2% or less, still more preferably 0.5% or less is preferable because the change in characteristics due to humidity change during use and processing is reduced. The moisture absorption rate here is measured by the following method. First, about 0.5 g of the film is dehumidified at 120 ° C for 3 days.
After heating for a period of time, the weight after cooling to 25 ° C. is accurately weighed to a unit of 0.1 mg so as not to absorb moisture (the weight at this time is defined as W0). Then 75 at 25 ℃
The sample is allowed to stand for 48 hours in an atmosphere of RH%, the weight is measured thereafter, and W1 is used to obtain the moisture absorption rate by the following formula.

Moisture absorption rate (%) = ((W1−W0) / W1) × 100 It is preferable that the moisture absorption rate is low, but in reality, the lower limit is 0.0.
It is about 3%.

The film of the present invention can be applied to any application in the field where transparency is required. In particular, a polarizing plate, a retardation plate, an antireflection plate, a display member such as a substrate, an optical disk substrate, When used as a film as a constituent material of various film members such as an optical recording member such as a protective film, the uniformity of the surface and the internal structure is high, which is preferable.

For these films, a substantially non-oriented film (optically isotropic) is used or an oriented film (having optical anisotropy) realized by stretching is used depending on the application. The film of the present invention can be preferably used in any case, but particularly when the polymer described in the present invention is used, since the polymer itself has a high polarizability, it is more preferably used as an oriented film. Specifically, the polarizing plate and the retardation plate, especially 1 /
When applied to a 4-wavelength phase difference plate application, the effect of the present invention can be best achieved.

As the method for producing the polymer described in the present invention, a solution polymerization method (A. Conix, Ind. Eng. Chem., 51 , 1) in which an acid halide and a divalent phenol are reacted in an organic solvent.
47 (1959), Japanese Examined Patent Publication No. 37-5599), a melt polymerization method of heating an acid halide and a divalent phenol in the presence of a catalyst such as magnesium chloride, a divalent acid and a divalent phenol in the presence of diallyl carbonate. Melt polymerization method of heating under temperature (Japanese Patent Publication No. 38-26299), interfacial weight of mixing divalent acid halide dissolved in an organic solvent incompatible with water and divalent phenol dissolved in an alkaline aqueous solution. Legal (WM Eareckson, J. Poly. Sci., XL 399 (195
9), Japanese Examined Patent Publication No. 40-1959) and the like.
In particular, the solution polymerization method is preferably adopted.

An example of the solution polymerization method will be described. A phosphonic acid derivative which is a precursor molecule of a phosphonic acid residue,
The polymer of the present invention can be obtained by mixing and reacting a dihydric phenol in the presence of a base such as triethylamine, followed by addition of a precursor molecule of a carbonate residue such as triphosgene and condensation polymerization. At this time, the phosphonic acid derivative and triphosgene can be simultaneously added and reacted, but more preferably, a higher molecular weight product can be obtained by adding triphosgene after the addition of the phosphonic acid derivative. As the phosphonic acid derivative or carbonate derivative, halides, acid anhydrides, esters and the like thereof are used, but are not particularly limited. The solvent is not particularly limited as long as it can dissolve the monomer and the polymer, and a plurality of solvents may be mixed and used, but a halogen-based solvent such as methylene chloride can be preferably used. However, in order to meet the purpose of the present invention, the water content of these solvents should be 20% or less.
It is preferably 0 ppm (weight basis) or less, and 15
0 ppm or less is more preferable, 100 ppm
Most preferably, This water content can be measured by a titration method such as using a Karl Fischer water content meter, a spectroscopic method, or the like.

Since the viscosity of the polymerization solution increases with the progress of polymerization, it is preferable to apply an efficient shearing force in order to control the molecular weight within a predetermined range. Examples of means for applying a shearing force include stirring, kneading, mixing and the like, and any of batch type and continuous type may be used, but batch type using stirring is more preferable. In the case of stirring, the shape and size of the blade are extremely important factors for controlling the molecular weight within a predetermined range.
As the shape of the wing, paddle type, anchor type, gate type,
Examples thereof include a double type such as a double motion paddle type, a helical ribbon, a double helical ribbon, a helical screw type, and the like, and the helical ribbon and the double helical ribbon are preferable for improving the uniformity of the reaction. The blade diameter is 90% or more and 100% of the inner diameter of the polymerization tank.
It is preferably less than 95%, more preferably 95% or more and 99% or less. Further, in order to effectively carry out stirring, it is important to control the stirring rotation speed. Generally, increasing the number of rotations improves the mixing efficiency, but on the other hand, the polymer may decompose due to the temperature rise and the efficiency may decrease due to co-rotation. It is necessary to select appropriate conditions. A specific preferred range is
For example, in the case of solution polymerization, 20 to 100 rpm is preferable, and 30 to 60 rpm is more preferable.

Further, for the purpose of preventing decomposition during film formation and further stabilizing the molecular weight, a monofunctional substance may be added at the time of polymerization to seal the molecular end. As the monofunctional substance here, phenol, cresol, p-
Examples include monohydric phenols such as tert-butylphenol, monohydric acid chlorides such as benzoic acid chloride, methanesulfonyl chloride, and phenylchloroformate.

To the polymer of the present invention, various hindered phenol-based, hindered amine-based, thioether-based, and phosphorus-based antioxidants can be added as long as the characteristics are not impaired.

Further, for the purpose of imparting plasticity to the polymer within a range not impairing the characteristics of the film of the present invention,
For the purpose of improving the releasability from the film-forming support, an inorganic material,
Softeners, dissimilar polymers, etc. may be added. Such substances include calcium chloride, lithium chloride, magnesium chloride, lithium nitrate, triethanolamine,
Examples thereof include triphenyl phosphate, polyethylene glycol, polysulfone, and polyether sulfone.

The polymer thus obtained is then filmed.

The polymer solution obtained above may be used as it is as a film-forming stock solution to form a film by solution film-forming, but after isolation by a method such as charging in a poor solvent, washing and drying are performed to obtain a powder. Alternatively, it may be formed into pellets, and may be directly melt-cast or dissolved in a solvent to form a film by solution casting. However, in order to improve the quality and homogeneity as an optical film, wash the polymer after isolation,
After drying, it is preferable to form a film by a solution film-forming method using a film-forming stock solution dissolved in a solvent.

The method of forming by the solution casting method will be described below.

The solvent used is not particularly limited as long as it dissolves the polymer. Such solvents include methylene chloride, chloroform, 1,1,2,2-
Tetrachloroethane, 1,2-dichloroethane, tetrahydrofuran, 1,4-dioxane, toluene, xylene, γ-butyrolactone, benzyl alcohol, isophorone, chlorobenzene, dichlorobenzene, hexafluoroisopropanol, dimethylacetamide, dimethylformamide, N-methyl-2. -Pyrrolidone (hereinafter
NMP) and the like. Further, it is preferable to filter the solution for the purpose of realizing the low defectivity required as an optical film. Filtration accuracy is 2,000
It is preferably 0 nm or less, more preferably 1,000 nm or less, still more preferably 600 nm or less. The filtration accuracy here means 90% when passing through a filter.
Is defined as the size of the filtrate that is captured on the filter with a probability of, for example, ANSI B93, 31-197.
It can be measured in accordance with the single pass F-2 test method based on 3.

The film-forming stock solution prepared as described above is formed into a film by a solution film-forming method such as a dry method, a dry-wet method, a wet method, and a semi-dry semi-wet method. In order to make the temperature uniform, a dry method or a dry-wet method is preferable, and the dry-wet method / dry method will be described below as an example.

The above stock solution is extruded from a die onto a support such as a drum or an endless belt to form a thin film, and then the solvent is scattered from the thin film layer to dry the thin film. In order to obtain the film of the present invention, after being cast on a support, it is kept for 0.1 to 5 seconds, preferably 0.2 to 1 second in a state where the solvent is not substantially evaporated, and then introduced into a drying oven. It is effective to do. Considering the productivity of the film, it is preferable to start the drying immediately after casting, but in that case, the cast spots and the die-shaped spots are fixed as they are, and the center line average roughness may exceed 5 nm. Regarding the conditions for holding the solvent in a state in which the solvent does not substantially evaporate, it is necessary to find the optimum conditions in consideration of the solvent used, the casting speed, etc. It is an effective means to cool the cast film by applying it for 0.1 to 5 seconds.

In the solvent drying, when NMP is used as the solvent, the drying temperature is preferably 70 to 180 ° C.,
100-150 degreeC is more preferable. If the drying temperature is too high, surface roughness and non-uniform structure tend to occur, and the center line average roughness may exceed the range of the present invention. On the other hand, if it is too low, productivity may be significantly reduced. The film from which most of the solvent has been removed in this way is self-supporting,
It is peeled off from the support. The polymer concentration when peeling the film from the support is preferably 30 to 90% by weight, and more preferably 60 to 80% by weight.
If the polymer concentration is less than 30% by weight, the self-supporting property of the film may be insufficient and the film may be easily broken. If it exceeds 90% by weight, peeling may be difficult.

The film is then introduced into a wet bath to remove residual solvent. As the wet bath, an aqueous bath is generally used, but for the purpose of increasing the solvent removal rate,
An organic solvent bath such as ethanol or methanol, or a mixed bath of these organic solvents and water may be used, or a bath containing an inorganic salt such as calcium chloride or lithium chloride may be used. In the case of the dry method, the residual solvent may be removed by heating in an oven or a tenter without using such a wet bath.

The film from which the residual solvent has been removed is introduced into a tenter and subjected to heat treatment. In the case of an oriented film, stretching is carried out in the tenter in the machine direction or the transverse direction. The heat treatment temperature is preferably 100 to 170 ° C., and 120 to 170 ° C. from the viewpoint of improving the dimensional stability of the film.
160 ° C. is more preferable. If the stretching temperature is out of the above range, the surface property may be deteriorated. Furthermore, when stretching is performed, it may be performed simultaneously with the heat treatment or after the heat treatment, depending on the purpose. The draw ratio should be appropriately set depending on the application, but is preferably 1.01 to 2 times, more preferably 1.0.
3 to 1.6 times.

The film of the present invention may be a laminated film. As a method of stacking, a normal method, for example, stacking in a die, stacking in a composite pipe, or a method of once forming one layer and then forming another layer thereon may be used.

In this way, the film of the present invention can be obtained, but the invention is not limited thereto.

[0055]

EXAMPLES The methods of measuring physical properties and the effects of the present invention were carried out according to the following methods.

(1) Centerline average roughness (Ra) Atomic force microscope Nano Scope II manufactured by Digital Instruments
Using I ver.3.20, 10 locations were measured under the following conditions, and an average value was obtained.

Cantilever: Silicon single crystal scanning mode: Tapping mode scanning range: 5 μm × 5 μm scanning speed: 1.0 Hz number of scanning lines: 256 measuring environment: 25 ° C., relative humidity 65% (2) number Dissolve average molecular weight film sample in solvent. Then, a gel permeation chromatograph (GPC) was incorporated with a low-angle laser light scattering photometer (LALLS) and a differential refractometer (RI), and the light scattering intensity and the refractive index difference of the molecular chain solution size-sorted by the GPC apparatus were incorporated. By measuring the elution time, the molecular weight of the solute and its content were sequentially calculated, and the molecular weight distribution was obtained. The measurement conditions are described below.

A. GPC device: Model 244 gel permeation chromatograph (WATERS
Column: TRC-GM (Toray Research Center) Shodex KD-802 (Showa Denko) Flow rate: 0.6 ml / min. LALLS device: CMX-100 type low-angle laser light scattering photometer (manufactured by Chromatix) Wavelength: 633 nm (4) Film thickness It was measured using a micro-thickness meter (manufactured by Anritsu).

(5) Phase difference It measured using the following measuring device.

Apparatus: Cell gap inspection apparatus RETS-1
100 (manufactured by Otsuka Electronics Co., Ltd.) Measurement diameter: φ5 mm Measurement wavelength: 400 to 800 nm In the above measurement, wavelengths of 450 nm, 550 nm, 650 nm
The phase difference at the time of is R (450), R (550),
It was set to R (650).

(6) Film uniformity The obtained film was visually observed under a white light source (D65 light source) and evaluated according to the following criteria.

◯: Haze of film, no image distortion Δ: Haze of film or partial image distortion ×: Haze of film or image distortion observed on the entire surface (7) Productivity The polymer concentration was set to 3 so that the thickness would be 80 μm without evaluation.
Cast 0 wt% NMP solution on SUS plate,
Let stand for 5 seconds under a stream of dry air at 0 ° C. Then, it is dried for 10 minutes with a dryer equipped with a hot air blowing nozzle. Then, the film is peeled from the SUS plate, washed with water, 180 ° C
The center line average roughness (Ra) of the non-support surface of the film after drying is measured. Drying temperature is 100 ℃, 140 ℃,
Experiments were performed with the temperature changed to 170 ° C and the center line average roughness was 5 nm.
The following evaluations are performed at a temperature above.

⊚: 170 ° C. drying, Ra ≦ 5 nm ○: 140 ° C. drying, Ra ≦ 5 nm, 170 ° C. R
a> 5 nm Δ: Ra ≦ 5 nm when dried at 100 ° C., R at 140 ° C.
a> 5 nm x: 100 ° C. drying, Ra> 5 nm The drying temperature is an important factor that governs productivity because it greatly affects the time for the film to peel from the support. That is, it can be said that the higher the drying temperature is, the higher the productivity is, as long as a uniform film can be obtained.

Specific embodiments of the present invention will be described below with reference to examples, but the present invention is not limited thereto. (Example 1) Blade diameter 27 cm and blade height 3 made of SUS316
Inner diameter 28c with 0 cm double helical ribbon blade
m SUS316 vertical polymerization tank (blade diameter / inner diameter = 0.9
6, clearance of 5 mm from the bottom of the tank to the lower surface of the blade was charged with 1,2-dichloroethane (15 L) under a nitrogen atmosphere. Next, 1,1-bis (4-hydroxyphenyl) cyclohexane (1,610 g) and triethylamine (1,335 g) were mixed, and the mixture was stirred under ice cooling. A 1,2-dichloroethane (6.75 L) solution of phenylphosphonic acid dichloride (873 g) was added dropwise to this solution over 60 minutes, and after the addition was completed, the mixture was stirred for 120 minutes. The stirring rotation speed at this time was 30 rpm. After that, the density of 0.
A solution of triphosgene in 1,2-dichloroethane (841 ml) of 571 mol / L was added dropwise over 30 minutes, and the mixture was stirred for 120 minutes after completion of the addition. During this time, the solution temperature is 20
The temperature was controlled to be -30 ° C.

The water content of the 1,2-dichloroethane used was 120 ppm.

The obtained reaction solution was poured into hexane for reprecipitation, and the polymer was collected by filtration, followed by (1) ethanol,
The polymer produced in the order of (2) water / ethanol = 1/1 mixed solution and (3) water was washed and dried to obtain a polymer.

The number average molecular weight of this polymer (hereinafter, M
n) was 35,000.

The polymer is then subjected to NMP at 30.degree.
And a filtration accuracy of 0.
5 μm filter (manufactured by Nippon Pole, MCY1001
Y005H4) was filtered to obtain a membrane-forming stock solution.

This film-forming stock solution was applied to SUS316 having a thickness of 1 mm.
It was cast on a plate, passed through a dry air flow at 30 ° C. for 1 second, and then dried with a dryer having a hot air blowing nozzle to 100
C., dried for 10 minutes. The dried film is peeled from the SUS plate, passed through a running water bath at 40 ° C, and then heat-treated at 180 ° C for 10 minutes under a fixed length to give a thickness of 80μ.
m film was obtained.

Ra of this film was 0.6 nm and 0.8 nm, respectively, for the support non-contact surface (hereinafter A surface) and the support contact surface (hereinafter B surface).
There was no distortion of the image.

The film was an optically isotropic film with R (550) = 2 nm, and the productivity evaluation was ◯. Example 2 Using the polymer of Example 1, a film having a thickness of 80 μm was obtained in the same manner as in Example 1, except that the film was dried at 140 ° C. for 7 minutes.

Ra of this film was 2.7 nm and 1.8 nm for the A and B sides, respectively, and image distortion was partially observed.

The film was an optically isotropic film with R (550) = 4 nm, and the productivity evaluation was ◯. (Example 3) A polymer was obtained in the same manner as in Example 1 except that the water content of 1,2-dichloroethane used was 70 ppm and the stirring rotation speed during polymerization was 60 rpm.

The Mn of this polymer was 45,000.

Further, film formation was carried out in the same manner as in Example 1 to obtain a film having a thickness of 80 μm.

Ra of this film was 0.6 nm and 0.7 nm for the A side and the B side, respectively, and no haze or image distortion was observed in the film.

The film was an optically isotropic film with R (550) = 2 nm, and the productivity evaluation was ⊚. Example 4 Using the polymer of Example 3, a film having a thickness of 80 μm was obtained in the same manner as in Example 1 except that the film was dried at 140 ° C. for 7 minutes.

Further, film formation was carried out in the same manner as in Example 1 to obtain a film having a thickness of 80 μm.

Ra of this film was 0.7 nm and 0.8 nm for the A side and the B side, respectively, and no clouding of the film or distortion of the image was observed at all.

The film was an optically isotropic film with R (550) = 2 nm, and the productivity evaluation was ⊚. (Example 5) A polymer was obtained in the same manner as in Example 1 except that the water content of 1,2-dichloroethane used was 180 ppm.

The Mn of this polymer was 22,000.

Further, film formation was carried out in the same manner as in Example 1 to obtain a film having a thickness of 80 μm.

Ra of this film was 3.5 nm and 2.3 nm for the A side and the B side, respectively, and image distortion was partially observed, and clouding occurred as compared with the film of Example 1.

The film was an optically isotropic film with R (550) = 4 nm, and the productivity evaluation was Δ. (Example 6) A polymer was obtained in the same manner as in Example 1 except that the blade diameter of the double helical ribbon blade used was 24 cm.

The Mn of this polymer was 18,000.

Example 1 except that the film-forming stock solution prepared in the same manner as in Example 1 was dried at a drying temperature of 80 ° C. for 30 minutes.
Film formation was performed in the same manner as in (1) to obtain a film having a thickness of 80 μm.

Ra of this film was 4.3 nm and 3.1 nm for the A side and the B side, respectively, and image distortion was observed in part, and clouding occurred as compared with the film of Example 1.

The film was an optically isotropic film with R (550) = 4 nm, and the productivity evaluation was x. (Example 7) The water content of 1,2-dichloroethane used was 30 ppm, and a 1,2-dichloroethane solution of triphosgene having a concentration of 0.571 mol / L was 893 m.
Polymerization was performed in the same manner as in Example 1 except that 1 l was dropped. However, as the degree of polymerization increased during the course of the reaction, the solution viscosity increased significantly, so the stirring speed was reduced to 15 rpm, and since heterogeneity was observed in the polymer solution, the stirring time after the addition of triphosgene was 540 minutes. Extended to. Then, reprecipitation, washing and drying were carried out in the same manner as in Example 1 to obtain a polymer.

The Mn of this polymer was 510,000.

Further, in the same manner as in Example 1, the thickness is 80 μm.
I got a film of.

Ra of this film was 3.1 nm and 3.1 nm for the A side and B side, respectively, and image distortion and clouding were observed in part.

Further, R (550) = 10 nm, and the productivity evaluation was Δ. Comparative Example 1 A film having a thickness of 80 μm was obtained in the same manner as in Example 1 except that the polymer of Example 1 and the stock solution for film formation were used and the drying temperature was 185 ° C.

Ra of this film was 5.6 nm and 5.1 nm for the A side and the B side, respectively, and image distortion and clouding were observed on the entire surface. Comparative Example 2 A film having a thickness of 80 μm was obtained in the same manner as in Example 1 except that the polymer of Example 5 and the stock solution for film formation were used and the drying temperature was 140 ° C.

Ra of this film was 6.2 nm and 5.3 nm for the A side and the B side, respectively, and image distortion and clouding were observed on the entire surface.

Table 1 shows the evaluation results of the above Examples and Comparative Examples.
2 shows. (Comparative Example 3) A 80 µm thick film was obtained in the same manner as in Example 2 except that the polymer of Example 1 was used in the drying step immediately after casting.

Ra of this film was 5.1 nm and 5.5 nm for the A side and the B side, respectively, and image distortion and clouding were observed on the entire surface.

[0097]

[Table 1]

[0098]

[Table 2] Examples 8 and 9 and Comparative Example 4 are examples of stretched films. Example 8 The film obtained in Example 3 was uniaxially stretched 1.4 times at 140 ° C. with the non-stretching direction being a constant length.

The thickness of the obtained film was 55 μm, Ra
Is better than the unstretched film, which is 1.2 nm and 1.3 nm on the A and B sides, respectively, which is excellent.
There was no distortion of the image and no cloudiness.

Further, R (550) is 520 nm and R (4
50) / R (550) and R (650) / R (550) were highly suitable as 1.12, 0.91 and 1/4 wavelength retardation plates, respectively. (Example 9) The film obtained in Example 3 was uniaxially stretched 1.4 times at 150 ° C with the non-stretching direction being a constant length.

The thickness of the obtained film was 55 μm, Ra
Is 0.7 nm and 0.8 nm respectively on the A side and the B side, which are excellent equivalent to those of the unstretched film, and no image distortion or clouding was observed.

Further, R (550) is 310 nm and R (4
50) / R (550) and R (650) / R (550) were highly suitable as 1.12, 0.91 and 1/4 wavelength retardation plates, respectively. Comparative Example 4 The film obtained in Example 6 was uniaxially stretched 1.4 times at 180 ° C. with the non-stretching direction being a constant length.

The thickness of the obtained film was 55 μm, Ra
Was worse than the unstretched film with 6.6 nm and 7.2 nm respectively on the A side and B side, and image distortion and clouding occurred on the entire surface.

Further, the phase difference was measured, but the unevenness was large and the measurement could not be performed accurately.

Table 3 shows the evaluation results of the above Examples and Comparative Examples.

[0106]

[Table 3]

[0107]

The film of the present invention is transparent, has excellent film homogeneity and surface smoothness, and has excellent productivity, and therefore exhibits excellent performance as an optical film. The film of the present invention can be suitably used as an optical film such as a display member such as a display and an optical recording member, but in particular, it exhibits excellent retardation properties by stretching, and therefore, the retardation plate, especially 1 / 4
It can be suitably used for wavelength retardation plate applications.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Keijiro Takanishi             1-1 1-1 Sonoyama, Otsu City, Shiga Prefecture Toray Co., Ltd.             Ceremony company Shiga business site F-term (reference) 4F071 AA50 AA51 AA68 AA81 AF27Y                       AF30 AF31 AH19 BA02 BB02                       BC01 BC08 BC16                 4J030 CA01 CB02 CB22 CB32 CB33                       CB34 CB35 CC25 CD11 CE02                       CE11 CG06

Claims (6)

[Claims] 1. The center line average roughness of at least one surface is 5 n.
A film containing a polymer having a molecular weight of m or less and containing a phosphonic acid residue represented by the structural formula (1) and a divalent phenol residue represented by the structural formula (2) as constituent units in the molecule. . [Chemical 1] R ¹ : organic group X ¹ : O, S or Se (however, two or more kinds of phosphonic acid residues having different R ¹ or X ¹ may be contained in the polymer) ^{R 2, R 3: H,} NO 2, 1~ halogen atom or carbon atoms
20 aliphatic groups or aromatic groups p, q: integers and 0 ≦ p + q ≦ 8 Y ¹ : O, S, alkylene group, alkylidene group, cycloalkylene group, cycloalkylidene group, halo-substituted alkylene group, halo-substituted Alkylidene group, phenylalkylidene group, carbonyl group, sulfone group, aliphatic phosphine oxide group, aromatic phosphine oxide group, alkylsilane group, dialkylsilane group or fluorene group (provided that Y ¹ may be a single bond. Also,
Two or more dihydric phenol residues having different R ² , R ³ or Y ¹ may be contained in the polymer. ) 2. The polymer according to claim 1, wherein the polymer contains a carbonate residue, and the molar ratio of the phosphonic acid residue to the total amount of the phosphonic acid residue and the carbonate residue is 0.5 or more and less than 1. the film. 3. The polymer contains a phosphonite residue, and the molar ratio of the phosphonite residue to the total amount of the phosphonic acid residue and the phosphonite residue is 0.5 or less.
Or the film according to 2. 4. The number average molecular weight of the polymer is 20,000.
The film according to claim 1, which is not less than 500,000 and not more than 500,000. 5. A thickness of 10 to 100 μm, and
Phase difference at a wavelength of 550 nm is 50 to 1,500 nm
The film according to any one of claims 1 to 4, which is 6. A film member comprising the film according to claim 1 as a constituent material.