JP2002248725A - Coating film for optics - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating film for optics, for which a polyester manufactured by using a new polyester polycondensation catalyst, wherein a conventional polycondensation catalyst such as an antimony compound, a germanium compound or a titanium compound is not made the major component, is made a main constituent component, and which is excellent in transparency and color tone, and does not have foreign matters due to antimony. SOLUTION: For this coating film for optics, a biaxially drawn polyester film is made the base material, and a coating layer mainly constituted of a polymeric resin and particles is provided at least on one surface of the base material. In this case, for the polyester film, a polyester, which is polymerized using the polycondensation catalyst containing aluminum and/or its compound and a phenol based compound, is made the major constituent component. Also, the haze of the film is 2.0% or lower.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical coating film using a film base mainly composed of a polyester polymerized by using a novel polyester polycondensation catalyst, and more particularly to a germanium coating film. The present invention relates to an optical coating film using a film base mainly composed of a polyester polymerized using a novel aluminum-based polycondensation catalyst without using an antimony compound or a titanium compound as a catalyst main component.

[0002]

2. Description of the Related Art Polyethylene terephthalate (PE)
T), polyesters represented by polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and the like are excellent in mechanical properties and chemical properties. Widely used in various fields of industrial applications.

In particular, a prism lens sheet, a hard coat film, an antireflection film, a diffusion plate, a shatterproof film for a CRT used for a liquid crystal display, a near-infrared absorbing filter used for a front panel of a plasma display, a touch panel and electroluminescence Stretched polyester film used as a base film for an optical member such as a transparent conductive film (hereinafter abbreviated as an optical film) is required to have excellent strength and dimensional stability. Is suitably used.

[0004] The base film used for such an optical film has excellent adhesiveness and excellent transparency to a coating layer laminated on the film at the time of post-processing such as a prism lens layer, a hard coat layer, and an antireflection layer. In addition to the above, it is desired that the number of minute foreign matters contained in the film is extremely small because it causes optical defects. Also,
It is required that the color tone of the film is not dark or yellowish.

However, polyester films generally have poor adhesion to other materials, such as a prism lens containing acrylate as a main component or a hard coat. In addition, in order to impart handling properties, it is common practice to include particles in the film to form irregularities on the film surface, but the refractive index of these particles usually differs from the refractive index of polyester. For this reason, transparency tends to be hindered.

Further, conventionally, as a polyester polymerization catalyst used at the time of polycondensation of polyester, antimony trioxide has been widely used. This antimony trioxide is an inexpensive catalyst having excellent catalytic activity.However, when this is used as a main component of the polycondensation catalyst, that is, in an amount added so as to exhibit a practical polymerization rate, During polycondensation, antimony trioxide is reduced, and metal antimony particles of 10 μm or less are produced. Then, metal antimony particles are aggregated in the melt extrusion step at the time of film production, and 20 to 5
As a foreign matter of 0 μm, it is present in the film.

[0007] Aggregates of the metal antimony particles are:
In the film stretching step, the orientation of the polyester film around the foreign matter is adversely affected, and optical distortion occurs.
Therefore, it is detected as a defect considerably larger than the actual size of the foreign matter, and the quality is significantly impaired. For example, a foreign substance having a size of 20 μm may be optically recognized as an optical defect having a size of 50 μm or more, and may be further recognized as an optical defect having a size of 100 μm or more.

[0008] Even if a filter is used at the time of melt extrusion to remove these aggregates of metal antimony particles, it is extremely difficult to completely remove the aggregates of metal antimony particles through the filter while deforming. there were.

Generally, optical films are required to have strict transparency, but the higher the transparency, the more the optical defects due to such fine metal antimony particles tend to be sharper. Further, the polyester produced using an antimony compound as a polycondensation catalyst has a dark color tone of the film, and further improvement is required. Therefore, a polyester containing no antimony compound as a main component of the catalyst is desired.

Further, when a germanium compound is used as a polycondensation catalyst in the production of a polyester which is a raw material of a base film for an optical coating film, it is expensive and not preferable for production on an industrial scale. When a compound is used, heat resistance is poor, so that the color tone of the film is yellowish, which is not preferable.

As a method for solving the above-mentioned problem, an attempt has been made to use antimony trioxide as a polycondensation catalyst and to suppress the occurrence of darkening or foreign matter in PET. For example, in Japanese Patent No. 2666502, generation of black foreign matter in PET is suppressed by using a compound of antimony trioxide, bismuth, and selenium as a polycondensation catalyst. JP-A-9-291141 describes that when antimony trioxide containing sodium and iron oxides is used as a polycondensation catalyst, the precipitation of antimony metal is suppressed. However, these polycondensation catalysts cannot ultimately achieve the purpose of reducing the content of antimony in the polyester.

Studies have been made on polycondensation catalysts which can replace antimony catalysts such as antimony trioxide, and titanium compounds and tin compounds represented by tetraalkoxy titanates have already been proposed. However, polyesters produced using these materials are susceptible to thermal degradation during melt molding, and have the problem that the polyester is significantly colored.

As an attempt to overcome such problems when a titanium compound is used as a polycondensation catalyst, for example, Japanese Patent Application Laid-Open No. 55-116722 discloses a method in which a tetraalkoxy titanate is used simultaneously with a cobalt salt and a calcium salt. Has been proposed. Also, Japanese Patent Application Laid-Open No. 8-735
No. 81 proposes a method in which a tetraalkoxy titanate is used simultaneously with a cobalt compound as a polycondensation catalyst and a fluorescent whitening agent is used. However, in these techniques, although the coloring of PET is reduced when tetraalkoxy titanate is used as a polycondensation catalyst, the P
Effective suppression of thermal decomposition of ET has not been achieved.

As another attempt to suppress the thermal degradation during melt molding of a polyester polymerized by using a titanium compound as a polycondensation catalyst, for example, JP-A-10-259296 discloses a method in which a polyester is polymerized using a titanium compound as a catalyst. A method of adding a phosphorus compound is disclosed. However, it is not only technically difficult to effectively mix the additive into the polymer after polymerization, but also increases the cost and is not practically used.

A technique is also known in which an alkali metal compound is added to an aluminum compound to obtain a polyester polycondensation catalyst having sufficient catalytic activity. Use of such a known polycondensation catalyst yields a polyester having excellent thermal stability.
In order to obtain a practical catalyst activity, a large amount of these additives is required. As a result, at least one of the following problems is caused due to the alkali metal compound in the obtained polyester polymer.

1) The amount of foreign matters increases, and when used for a film, the film-forming properties and the film properties deteriorate. 2) The hydrolysis resistance of the polyester polymer decreases, and the transparency decreases due to the generation of foreign substances. 3) Poor color tone of the polyester polymer, that is, a phenomenon in which the polymer is colored yellow occurs, which causes a problem that the color tone of a molded product is deteriorated when used for a film. 4) When producing for a long time, the pressure of the filter is increased due to clogging of foreign matters in the melt extrusion process, so that the frequency of replacing the filter is shortened and the productivity is reduced.

As a polycondensation catalyst for providing a polyester which has excellent catalytic activity other than the antimony compound and does not have the above-mentioned problems, a germanium compound has already been put to practical use, but this catalyst is very expensive. There is a problem and it is difficult to control the polymerization because the concentration of the catalyst in the reaction system changes because it is easy to distill out of the reaction system during the polymerization. is there.

Further, as a method for suppressing thermal deterioration during melt molding of polyester, there is a method of removing a catalyst from polyester. As a method for removing a catalyst from polyester, for example, JP-A-10-251394 discloses a method in which a polyester resin is contacted with an extractant which is a supercritical fluid in the presence of an acidic substance.
However, such a method using a supercritical fluid is not preferable because it is technically difficult and leads to an increase in product cost.

The antimony compound,
It contains metal components other than germanium compounds and titanium compounds as main components and has excellent catalytic activity and hardly causes thermal deterioration during melt molding. (A) Thermal stability, (b) Thermal oxidation stability, (c) Hydrolysis resistance Excellent in at least one of sex,
In addition, a polycondensation catalyst that can provide a polyester having a small amount of foreign matter and excellent color tone and transparency is desired.

[0020]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyester produced by using a novel polyester polycondensation catalyst which does not mainly comprise a conventional polycondensation catalyst such as an antimony compound, a germanium compound, or a titanium compound. An object of the present invention is to provide a coating film for optical use which has excellent transparency and color tone and is free from foreign matter due to antimony, which is a main constituent component.

[0021]

The technical gist of the present invention is as follows.
In order to improve the thermal stability of polyesters polymerized using conventional aluminum compounds as polycondensation catalysts, the effect of adding various antioxidants and stabilizers during polymerization was examined. Or, by combining a phosphorus compound having a phenol moiety in the same molecule, the thermal stability of the polyester is improved, and an aluminum compound originally having poor catalytic activity is found to have sufficient activity as a polycondensation catalyst, Using the polyester obtained using the polycondensation catalyst as a main component of the raw material polymer of the base film in the optical coating film, providing a coating layer on the base material, and optimizing the optical characteristics, the transparent Optical properties, excellent in properties and color tone, and free of foreign matter caused by antimony There is in the place where it was found that the covering film is obtained.

That is, the present invention relates to a coated film comprising a biaxially stretched polyester film as a base material, and a coating layer mainly composed of a polymer resin and particles provided on at least one surface of the base material. The optical film is characterized in that the main component of the film is a polyester polymerized using aluminum and / or a compound thereof and a polycondensation catalyst containing a phenolic compound, and the haze of the film is 2.0% or less. Coating film.

A coating film comprising a biaxially stretched polyester film as a substrate and a coating layer mainly composed of a polymer resin and particles provided on at least one surface of the substrate, wherein the polyester film is made of aluminum and And / or a compound thereof and a polyester polymerized using a polycondensation catalyst containing a phosphorus compound as a main component, and a haze of the film is 2.0% or less. .

A coating film comprising a biaxially stretched polyester film as a base material and a coating layer mainly composed of a polymer resin and particles provided on at least one surface of the base material, wherein the polyester film is a phosphorus compound. A polyester film polymerized using a polycondensation catalyst containing an aluminum salt of (1) as a main component, and the haze of the film is 2.0% or less.

Further, the present invention is a coating film comprising a biaxially stretched polyester film as a base material and a coating layer mainly composed of a polymer resin and particles provided on at least one surface of the base material. Polyester polymerized using a polycondensation catalyst containing at least one selected from compounds represented by formula (7) as a main component, and a film having a haze of 2.0
% Or less.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION The polycondensation catalyst used for polymerizing the polyester which is a main component of the optical coating film of the present invention is aluminum and / or a catalyst containing the compound and a phenol compound, aluminum and And / or a catalyst containing the compound and a phosphorus compound, a catalyst containing an aluminum salt of the phosphorus compound, or a catalyst containing at least one selected from the compounds represented by the general formula (7).

As aluminum and / or an aluminum compound, known aluminum compounds can be used without limitation in addition to metallic aluminum.

Specific examples of the aluminum compound include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, and aluminum trichloroacetate. , Aluminum lactate,
Carboxylates such as aluminum citrate and aluminum salicylate; inorganic acid salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate and aluminum phosphonate; aluminum methoxide, aluminum ethoxide, and aluminum n -Propoxide, aluminum is
aluminum chelate compounds such as o-propoxide, aluminum n-butoxide, aluminum alkoxide such as aluminum t-butoxide, aluminum acetylacetonate, aluminum acetyl acetate, aluminum ethyl acetoacetate, aluminum ethyl acetoacetate di-iso-propoxide, trimethyl aluminum, Organoaluminum compounds such as triethylaluminum and partial hydrolysates thereof,
Aluminum oxide and the like can be mentioned. Of these, carboxylate, inorganic acid salt and chelate compound are preferred,
Among these, aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred.

The amount of the aluminum and / or aluminum compound to be added is 0.001 to 0.05 mol per mol of all the constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the obtained polyester. %, More preferably 0.005 to 0.0%
2 mol%. If the addition amount is less than 0.001 mol%, the catalytic activity may not be sufficiently exhibited, and if the addition amount is 0.05 mol% or more, the thermal stability and thermooxidative stability decrease, and aluminum is caused. In some cases, the generation of foreign matter and the increase in coloring may become a problem. As described above, even when the addition amount of the aluminum component is small, the polymerization catalyst of the present invention is greatly characterized in that it exhibits a sufficient catalytic activity. As a result, thermal stability and thermal oxidation stability are excellent, and foreign substances and coloring due to aluminum can be reduced.

The phenolic compound constituting the polycondensation catalyst is not particularly limited as long as it has a phenol structure. For example, 2,6-di-tert-butyl-4
-Methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol,
2,6-diisopropyl-4-ethylphenol, 2,6-di-tert
-Amyl-4-methylphenol, 2,6-di-tert-octyl-4
-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-tert-
Butylphenol, 2-tert-butyl-2-ethyl-6-tert-octylphenol, 2-isobutyl-4-ethyl-6-tert-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, 1, 1,1-tris (4-hydroxyphenyl) ethane, 1,1,3-tris (2-methyl-4-hydroxy
-5-tert-butylphenyl) butane, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thiodiethylenebis [3-
(3,5-di-tert-butyl-4,4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-tert
-Butyl-4-hydroxy-hydrocinnamide), 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5- Di-tert-
Butyl-4-hydroxybenzyl) isocyanurate, 1,
3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate,
Tris (4-tert-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, tetrakis [methylene (3,5-
Di-tert-butyl-4-hydroxy) hydrocinnamate]
Methane, bis [(3,3-bis (3-tert-butyl-4-hydroxyphenyl) butyric acid) glycol ester, N, N'-bis [3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionyl] hydrazine, 2,2'-oxazamide bis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-
Methyl-6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 1,3,5-trimethyl
-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,9-bis [1,1-dimethyl2- {β- (3-t
ert-butyl-4-hydroxy-5-methylphenyl) propionyloxydiethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2-bis [4- (2- (3 , 5-di-tert-
Butyl-4-hydroxycinnamoyloxy)) ethoxyphenyl] propane, β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid alkyl ester, tetrakis- [methyl-3- (3 ′, 5 '-Di-tert-butyl-4-hydroxyphenyl) propionate] methane, octadecyl-3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-
Butylphenyl) butane, thiodiethylene-bis [3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate], ethylenebis (oxyethylene) bis [3- (5-tert-
Butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol-bis-[-3- (3 ′ -tert-butyl-4-hydroxy-5-methylphenyl)] propionate, 1,1,3-tris [2-methyl-4- [3- (3,
5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -5-tert-butylphenyl] butane.

These can be used in combination of two or more kinds at the same time. Of these, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis- [methyl-3- (3 ′, 5 ′) -Di-tert-butyl
4-Hydroxyphenyl) propionate] methane and thiodiethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] are preferred.

The addition of these phenolic compounds during the polymerization of the polyester improves the catalytic activity of the aluminum compound and also improves the thermal stability of the polymerized polyester.

The amount of the phenolic compound to be added is preferably 5 × 10 ^{−7 to} 0.01 mol based on the total number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the obtained polyester. More preferably 1
× 10 ^{-6 to} 0.005 mol. In the present invention, a phosphorus compound may be used together with the phenolic compound.

The phosphorus compound constituting the polycondensation catalyst is not particularly restricted but includes phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds, phosphine compounds. The use of one or more compounds selected from the group consisting of the above is preferred because the effect of improving the catalytic activity is large. Among these, the use of one or more phosphonic acid compounds is particularly preferable because the effect of improving the catalytic activity is particularly large.

The above phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds, and phosphine compounds are represented by the following formulas (8) to (13), respectively. Is a compound having the structure

[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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Examples of the phosphonic acid compounds include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate and the like. .

Examples of the above-mentioned phosphinic acid compounds include diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate, phenylphosphinic acid, methyl phenylphosphinate, phenyl phenylphosphinate and the like.

Examples of the phosphine oxide compounds include diphenylphosphine oxide, methyldiphenylphosphine oxide, and triphenylphosphine oxide.

Among the phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds and phosphine compounds, the phosphorus compounds are represented by the following formulas (14) to (19). Preferably, a compound is used.

[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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Of the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is more preferable because the effect of improving the catalytic activity is large.

As the phosphorus compound constituting the above-mentioned polycondensation catalyst, the use of compounds represented by the following general formulas (20) to (22) is particularly preferable since the effect of improving the catalytic activity is particularly large.

[0054]

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[0055]

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[0056]

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(In the formulas (20) to (22), R ¹ , R ⁴ , R
⁵ and R ⁶ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a halogen group, or a hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl group or an amino group. R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. However, the hydrocarbon group may contain an alicyclic structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

In the above formulas (20) to (22), the phosphorus compounds constituting the polycondensation catalyst include R ¹ , R ⁴ ,
Compounds in which R ⁵ and R ⁶ are groups having an aromatic ring structure are particularly preferred.

Examples of the phosphorus compound constituting the above-mentioned polycondensation catalyst include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, and diethyl benzylphosphonate. And diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate, phenylphosphinic acid, methyl phenylphosphinate, phenyl phenylphosphinate, diphenylphosphine oxide, methyldiphenylphosphine oxide, triphenylphosphine oxide and the like. Of these, dimethyl phenylphosphonate and diethyl benzylphosphonate are particularly preferred.

The amount of the phosphorus compound to be added is 5 to 5 moles of all constituent units of a carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the obtained polyester.
× 10 ^{- 7} to 0.01 mol are preferred, more preferably 1 × 10 ^-6
~ 0.005 mol.

The phosphorus compound having a phenol moiety in the same molecule that constitutes the polycondensation catalyst is not particularly limited as long as it is a phosphorus compound having a phenol structure. -Based compound, phosphinic acid-based compound, phosphine oxide-based compound, phosphonous acid-based compound, phosphinous acid-based compound, and the use of one or more compounds selected from the group consisting of phosphine-based compounds have an effect of improving the catalytic activity. Large and preferred. Among these, the use of a phosphonic acid-based compound having one or more phenol moieties in the same molecule is particularly preferable because the effect of improving the catalytic activity is particularly large.

Examples of the phosphorus compound having a phenol moiety constituting the polycondensation catalyst in the same molecule include compounds represented by the following general formulas (23) to (25). Among these, the use of the following formula is particularly preferable because the catalytic activity is improved.

[0063]

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[0064]

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[0065]

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(In the formulas (23) to (25), R ¹ contains a substituent such as a hydrocarbon group having 1 to 50 carbon atoms including a phenol moiety, a hydroxyl group, a halogen group, an alkoxyl group or an amino group, and a phenol moiety. Represents a hydrocarbon group having 1 to 50 carbon atoms, and R ⁴ , R ⁵ , and R ⁶ each independently represent hydrogen, a substituent group such as a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group. R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a carbon group having 1 to 50 carbon atoms including a substituent such as a hydroxyl group or an alkoxyl group. Wherein the hydrocarbon group may contain a branched structure, an alicyclic structure such as cyclohexyl, or an aromatic ring structure such as phenyl or naphthyl. The terminals of R ² and R ⁴ are bonded to each other. May )

Examples of the phosphorus compound having the phenol moiety in the same molecule include p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate, and p-hydroxyphenylphosphonate.
Diphenyl hydroxyphenylphosphonate, bis (p-
(Hydroxyphenyl) phosphinic acid, methyl bis (p-hydroxyphenyl) phosphinate, phenyl bis (p-hydroxyphenyl) phosphinate, p-hydroxyphenylphenylphosphinic acid, methyl p-hydroxyphenylphenylphosphinate, p-hydroxyphenylphenyl Phenyl phosphinate, p-hydroxyphenylphosphinic acid, methyl p-hydroxyphenylphosphinate, phenyl p-hydroxyphenylphosphinate, bis (p-hydroxyphenyl) phosphine oxide, tris (p-hydroxyphenyl) phosphine oxide, bis (p -Hydroxyphenyl) methylphosphine oxide, and compounds represented by the following formulas (26) to (29). Among these, a compound represented by the following formula (28) and dimethyl p-hydroxyphenylphosphonate are particularly preferred.

[0068]

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[0069]

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[0070]

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[0071]

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As the compound represented by the above formula (28), for example, SANKO-220 (manufactured by Sanko Co., Ltd.) can be used.

By adding a phosphorus compound having such a phenol moiety in the same molecule during the polymerization of the polyester, the catalytic activity of the aluminum compound is improved and the thermal stability of the polymerized polyester is also improved.

The amount of the phosphorus compound having the phenol moiety in the same molecule may be 5 × 10 5 moles per mole of all the constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the obtained polyester. ^{-7 to} 0.01 mol is preferred, and more preferably 1 × 10 ^{-6 to} 0.005 mol.

It is preferable to use a phosphorus metal salt compound as the phosphorus compound. The phosphorus metal salt compound is not particularly limited as long as it is a metal salt of a phosphorus compound, but when a metal salt of a phosphonic acid compound is used,
The effect of improving the catalyst activity is large and is preferable. Examples of the metal salt of a phosphorus compound include a monometal salt, a dimetal salt, and a trimetal salt.

In the above phosphorus compounds, the metal part of the metal salt is Li, Na, K, Be, Mg, Sr, B
It is preferable to use a material selected from a, Mn, Ni, Cu, and Zn because the effect of improving the catalytic activity is large. Of these, Li, Na, and Mg are particularly preferred.

The use of at least one selected from the compounds represented by the following general formula (30) as the phosphorus metal salt compound is preferred because the effect of improving the catalytic activity is large.

[0078]

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(In the formula (30), R ¹ is hydrogen and has 1 to 1 carbon atoms.
Represents a hydrocarbon group having 1 to 50 carbon atoms including 50 hydrocarbon groups, hydroxyl groups, halogen groups, alkoxyl groups, or amino groups. R ² represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group having 1 to 5 carbon atoms.
Represents a hydrocarbon group of 0. R ³ is hydrogen, carbon number 1-50
Represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group, a hydroxyl group, an alkoxyl group or a carbonyl. l represents an integer of 1 or more; m represents 0 or an integer of 1 or more;
+ M) is 4 or less. M represents a (l + m) -valent metal cation. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

As the above R ¹ , for example, phenyl,
Examples thereof include 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like. R above
^{As 2} , for example, hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, phenyl, naphthyl, substituted Phenyl and naphthyl groups,
And a group represented by —CH ₂ CH ₂ OH. R ³
Examples of O ^- include a hydroxide ion, an alcoholate ion, an acetate ion and an acetylacetone ion.

Among the compounds represented by the general formula (30), it is preferable to use at least one selected from the compounds represented by the following general formula (31).

[0082]

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(In the formula (31), R ¹ is hydrogen and has 1 to 1 carbon atoms.
Represents a hydrocarbon group having 1 to 50 carbon atoms including 50 hydrocarbon groups, hydroxyl groups, halogen groups, alkoxyl groups, or amino groups. R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl. l represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and (l + m) is 4 or less. M represents a (l + m) -valent metal cation. The hydrocarbon group may contain an alicyclic structure or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

As the above R ¹ , for example, phenyl,
Examples thereof include 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like. Examples of R ³ O ⁻ include a hydroxide ion, an alcoholate ion,
Examples include acetate ion and acetylacetone ion.

Of the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is preferred because the effect of improving the catalytic activity is large.

In the above formula (31), M is Li, N
a, K, Be, Mg, Sr, Ba, Mn, Ni, Cu,
It is preferable to use a material selected from Zn because the effect of improving the catalytic activity is large. Of these, Li, Na, and Mg are particularly preferred.

The metal salt compounds of phosphorus include lithium [ethyl (1-naphthyl) methylphosphonate], sodium [ethyl (1-naphthyl) methylphosphonate], magnesium bis [(1-naphthyl) methylphosphonate], Potassium [ethyl (2-naphthyl) methyl phosphonate], magnesium bis [(2-naphthyl) methyl phosphonate], lithium [ethyl benzyl phosphonate], sodium [ethyl benzyl phosphonate], magnesium bis [ethyl benzyl phosphonate], Beryllium bis [ethyl benzylphosphonate],
Strontium bis [ethyl benzylphosphonate], manganese bis [ethyl benzylphosphonate], sodium benzylphosphonate, magnesium bis [benzylphosphonic acid], sodium [ethyl (9-anthryl) methylphosphonate], magnesium bis [(9-anthryl) ) Ethyl methyl phosphonate], sodium [ethyl 4-hydroxybenzyl phosphonate], magnesium bis [ethyl 4-hydroxybenzyl phosphonate], sodium [phenyl chlorophenyl phosphonate], magnesium bis [4-chlorobenzyl phosphonate ethyl] ], Sodium [methyl 4-aminobenzylphosphonate], magnesium bis [methyl 4-aminobenzylphosphonate], sodium phenylphosphonate, magnesium bis [phenylphosphonate] Ethyl phosphate], zinc bis [phenylphosphonic acid ethyl] and the like.

Among these, lithium [ethyl (1-naphthyl) methylphosphonate], sodium [ethyl (1-naphthyl) methylphosphonate], magnesium bis [ethyl (1-naphthyl) methylphosphonate], lithium [benzyl-phosphonate] Ethyl], sodium [ethyl benzylphosphonate], magnesium bis [ethyl benzylphosphonate], sodium benzylphosphonate, and magnesium bis [benzylphosphonic acid] are particularly preferred.

The metal salt compound of phosphorus, which is another preferred phosphorus compound constituting the polycondensation catalyst, comprises at least one selected from compounds represented by the following general formula (32).

[0090]

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[0091] (In the formula ^{(32), R 1, R} 2 are each independently hydrogen, .R ³ representing a hydrocarbon group having 1 to 30 carbon atoms,
Represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group.
R ⁴ is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a carbon atom having 1 to 5 carbon atoms including carbonyl.
Represents 50 hydrocarbon groups. Examples of R ⁴ O ⁻ include a hydroxide ion, an alcoholate ion, an acetate ion and an acetylacetone ion. l is an integer of 1 or more, m is 0 or an integer of 1 or more, and (l + m)
Is 4 or less. M represents a (l + m) -valent metal cation. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Among these, it is preferable to use at least one selected from compounds represented by the following general formula (33).

[0093]

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(In the formula (33), M ^{n +} represents an n-valent metal cation, and n represents 1, 2, 3 or 4.)

In the above formula (32) or (33),
M is Li, Na, K, Be, Mg, Sr, Ba, M
It is preferable to use one selected from n, Ni, Cu, and Zn because the effect of improving the catalytic activity is large. Of these, L
i, Na and Mg are particularly preferred.

Examples of the specific metal salt compounds of phosphorus include lithium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-t-t
ethyl ert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], potassium [3,5-di-tert-butyl]
-Butyl-4-hydroxybenzylphosphonate], magnesium bis [3,5-di-tert-butyl-4-]
Ethyl hydroxybenzylphosphonate], magnesium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid], beryllium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate methyl], Strontium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl], barium bis [3,5-
Phenyl di-tert-butyl-4-hydroxybenzylphosphonate], manganese bis [3,5-di-tert-butyl-4
-Ethyl ethyl hydroxybenzylphosphonate], nickel bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], copper bis [3,5-di-tert-butyl-4]
-Ethyl ethyl hydroxybenzylphosphonate] and zinc bis [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate]. Among these, lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis [ Ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate] is particularly preferred.

Another embodiment of the present invention is a polyester polymerization catalyst comprising at least one selected from aluminum salts of phosphorus compounds. An aluminum salt of a phosphorus compound may be used in combination with another aluminum compound, a phosphorus compound, a phenol compound or the like.

The aluminum salt of a phosphorus compound, which is a preferred component of the polycondensation catalyst, is not particularly limited as long as it is a phosphorus compound having an aluminum moiety.
It is preferable to use an aluminum salt of a phosphonic acid compound because the effect of improving the catalytic activity is large. Examples of the aluminum salt of the phosphorus compound include a monoaluminum salt, a dialluminum salt, and a trialuminum salt.

Of the above-mentioned aluminum salts of phosphorus compounds, the use of a compound having an aromatic ring structure is preferred because the effect of improving the catalytic activity is large.

As the aluminum salt of the phosphorus compound constituting the above-mentioned polymerization catalyst, it is preferable to use at least one selected from the compounds represented by the following general formula (34) since the effect of improving the catalytic activity is large.

[0101]

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(In the formula (34), R ¹ is hydrogen and has 1 to 1 carbon atoms.
Represents a hydrocarbon group having 1 to 50 carbon atoms including 50 hydrocarbon groups, hydroxyl groups, halogen groups, alkoxyl groups, or amino groups. R ² represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group having 1 to 5 carbon atoms.
Represents a hydrocarbon group of 0. R ³ is hydrogen, carbon number 1-50
Represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group, a hydroxyl group, an alkoxyl group or a carbonyl. l represents an integer of 1 or more; m represents 0 or an integer of 1 or more;
+ M) is 3. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

As the above R ¹ , for example, phenyl,
Examples thereof include 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like. R above
^{As 2} , for example, hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, phenyl, naphthyl, substituted Phenyl and naphthyl groups,
And a group represented by —CH ₂ CH ₂ OH. Examples of R ³ O ⁻ include a hydroxide ion, an alcoholate ion, an ethylene glycolate ion, an acetate ion and an acetylacetone ion.

Examples of the aluminum salt of the phosphorus compound include an aluminum salt of ethyl (1-naphthyl) methylphosphonate, an aluminum salt of ethyl (1-naphthyl) methylphosphonate, an aluminum salt of ethyl (2-naphthyl) methylphosphonate, and benzylphosphonate. Aluminum salt of ethyl acid, aluminum salt of benzylphosphonic acid, (9-
Anthryl) aluminum salt of ethyl methylphosphonate, aluminum salt of ethyl 4-hydroxybenzylphosphonate, aluminum salt of ethyl 2-methylbenzylphosphonate, aluminum salt of phenyl 4-chlorobenzylphosphonate, methyl 4-aminobenzylphosphonate Aluminum salts, aluminum salts of ethyl 4-methoxybenzylphosphonate, aluminum salts of ethyl phenylphosphonate and the like can be mentioned.

Of these, aluminum salts of ethyl (1-naphthyl) methylphosphonate and aluminum salts of ethyl benzylphosphonate are particularly preferred.

In another embodiment, the following general formula (3)
It is a polyester polymerization catalyst comprising at least one selected from aluminum salts of phosphorus compounds represented by 5). The aluminum salt of the phosphorus compound may be used in combination with another aluminum compound, a phosphorus compound, a phenol compound, or the like.

[0107]

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[0108] (In the formula ^{(35), R 1, R} 2 are each independently hydrogen, .R ³ representing a hydrocarbon group having 1 to 30 carbon atoms,
Represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group.
R ⁴ is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a carbon atom having 1 to 5 carbon atoms including carbonyl.
Represents 50 hydrocarbon groups. l represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and (l + m) is 3. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Among these, it is preferable to use at least one selected from compounds represented by the following general formula (36).

[0110]

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(In the formula (36), R ³ is hydrogen, carbon number 1
Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrocarbon group of 50 to 50, a hydroxyl group or an alkoxyl group. R ⁴ is hydrogen,
It represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group or carbonyl. l represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and (l + m) is 3. The hydrocarbon group may contain an alicyclic structure or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

The above R^ThreeFor example, hydrogen, methyl
, Ethyl, propyl, isopropyl, n-butyl
Tyl group, sec-butyl group, tert-butyl group, long chain
Aliphatic, phenyl, naphthyl, substituted
Nyl group, naphthyl group, -CH _TwoCH_TwoGroup represented by OH
And so on. R above^FourO^-As, for example, hydroxyl
Chloride ion, alcoholate ion, ethylene glycoler
Toion, acetate ion and acetylacetone ion
And the like.

Examples of the aluminum salt of the phosphorus compound include an aluminum salt of ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and an aluminum salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonate. Aluminum salt of methyl, aluminum salt of isopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5
Aluminum salts of phenyl-di-tert-butyl-4-hydroxybenzylphosphonate, aluminum salts of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, and the like.

Among them, 3,5-di-tert-butyl-4
Particularly preferred are the aluminum salts of ethyl-hydroxybenzylphosphonate and the methyl salts of methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate.

It is preferable to use a phosphorus compound having at least one P—OH bond as the phosphorus compound. The phosphorus compound having at least one P-OH bond is not particularly limited as long as it is a phosphorus compound having at least one P-OH in the molecule. Among these phosphorus compounds, the use of a phosphonic acid-based compound having at least one P-OH bond is preferable because the effect of improving the catalytic activity is large.

Among the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the effect of improving the catalytic activity is large.

When at least one selected from compounds represented by the following general formula (37) is used as the phosphorus compound having at least one P-OH bond constituting the polycondensation catalyst, the catalytic activity is improved. Is preferred.

[0118]

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(In the formula (37), R ¹ is hydrogen and has 1 to 1 carbon atoms.
Represents a hydrocarbon group having 1 to 50 carbon atoms including 50 hydrocarbon groups, hydroxyl groups, halogen groups, alkoxyl groups, or amino groups. R ² represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group having 1 to 5 carbon atoms.
Represents a hydrocarbon group of 0. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

[0120] As R ¹ in the above example, phenyl,
Examples thereof include 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like. R above
^{As 2} , for example, hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, phenyl, naphthyl, substituted Phenyl and naphthyl groups,
And a group represented by —CH ₂ CH ₂ OH.

Among the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is preferred because the effect of improving the catalytic activity is large.

Examples of the phosphorus compound having at least one P-OH bond include ethyl (1-naphthyl) methylphosphonate, (1-naphthyl) methylphosphonic acid, ethyl (2-naphthyl) methylphosphonate, ethyl benzylphosphonate, and benzylphosphonate. Acid, ethyl (9-anthryl) methyl phosphonate, ethyl 4-hydroxybenzyl phosphonate, ethyl 2-methylbenzyl phosphonate, phenyl 4-chlorobenzyl phosphonate, methyl 4-aminobenzyl phosphonate, ethyl 4-methoxybenzyl phosphonate And the like. Among them, ethyl (1-naphthyl) methylphosphonate and ethyl benzylphosphonate are particularly preferred.

Preferred phosphorus compounds include P-
Specific phosphorus compounds having at least one OH bond are exemplified. The specific phosphorus compound having at least one P-OH bond, which is a preferable phosphorus compound constituting the polycondensation catalyst, means at least one compound selected from the compounds represented by the following general formula (38). I do.

[0124]

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[0125] (In the formula ^{(38), R 1, R} 2 are each independently hydrogen, .R ³ representing a hydrocarbon group having 1 to 30 carbon atoms,
Represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group.
n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Among these, it is preferable to use at least one selected from compounds represented by the following general formula (39).

[0127]

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(In the formula (39), R ³ represents hydrogen, carbon number 1
Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrocarbon group of 50 to 50, a hydroxyl group or an alkoxyl group. The hydrocarbon group may contain an alicyclic structure or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

The above R^ThreeFor example, hydrogen, methyl
, Ethyl, propyl, isopropyl, n-butyl
Tyl group, sec-butyl group, tert-butyl group, long chain
Aliphatic, phenyl, naphthyl, substituted
Nyl group, naphthyl group, -CH _TwoCH_TwoGroup represented by OH
And so on.

Examples of the specific phosphorus compound having at least one P-OH bond include ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and 3,5-di-
Methyl tert-butyl-4-hydroxybenzylphosphonate, isopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, phenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,3 5-di-tert
Octadecyl-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid and the like. Of these, ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.

A preferred phosphorus compound is represented by the following formula (4)
0).

[0132]

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[0133] (In the formula (40), R ¹ represents a hydrocarbon group having 1 to 49 carbon atoms containing a hydrocarbon group or a hydroxyl group or a halogen group, an alkoxyl group, or an amino group, of 1 to 49 carbon atoms, R ² , R ³ are each independently hydrogen, carbon number 1 to
Represents a hydrocarbon group having 1 to 50 carbon atoms including 50 hydrocarbon groups, hydroxyl groups or alkoxyl groups. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure. )

More preferably, the compound is a compound in which at least one of R ¹ , R ² and R ^{3 in} the chemical formula (40) contains an aromatic ring structure.

Specific examples of the phosphorus compound are shown below.

[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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The phosphorus compound having a large molecular weight is more preferable because it is difficult to be distilled off during polymerization.

Another phosphorus compound that is preferably used as a polycondensation catalyst is at least one phosphorus compound selected from compounds represented by the following general formula (47).

[0144]

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(In the formula (47), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.)
R ³ and R ⁴ are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, 1 to 1 carbon atoms including a hydroxyl group or an alkoxyl group.
Represents 50 hydrocarbon groups. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure or a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl. )

Of the above general formula (47), it is preferable to use at least one compound selected from the compounds represented by the following general formula (48) since the effect of improving the catalytic activity is high.

[0147]

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(In the above formula (48), R ³ and R ⁴ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl or a branched structure, or an aromatic ring structure such as phenyl or naphthyl.)

The above R ³ and R ⁴ are, for example, short-chain aliphatic groups such as hydrogen, methyl group and butyl group, long-chain aliphatic groups such as octadecyl, phenyl group, naphthyl group and substituted phenyl group. aromatic groups such as groups or naphthyl group, -CH ₂ CH ₂
And a group represented by OH.

As the specific phosphorus compound, 3,5-
Diisopropyl di-tert-butyl-4-hydroxybenzylphosphonate, di-n-butyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert
Dioctadecyl-butyl-4-hydroxybenzylphosphonate, diphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and the like.

Among them, 3,5-di-tert-butyl-4
-Dioctadecyl hydroxybenzylphosphonate, 3,5
Diphenyl di-tert-butyl-4-hydroxybenzylphosphonate is particularly preferred.

Another phosphorus compound preferably used as a polycondensation catalyst is at least one phosphorus compound selected from the compounds represented by the chemical formulas (49) and (50).

[0153]

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[0154]

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As the compound represented by the above formula (49), Irganox1222 (manufactured by Ciba Specialty Chemicals) is commercially available. Compounds represented by the chemical formula (50) include Irganox
1425 (manufactured by Ciba Specialty Chemicals) is commercially available.

Although phosphorus compounds are generally well known as antioxidants, even when these phosphorus compounds are used in combination with a conventional metal-containing polyester polymerization catalyst,
It is not known to greatly promote melt polymerization. In fact, when a polyester compound is melt-polymerized using a typical catalyst for polyester polymerization such as an antimony compound, a titanium compound, a tin compound or a germanium compound as a polymerization catalyst, even if a phosphorus compound is added, a substantially useful level is obtained. No accelerated polymerization is observed.

That is, by using the above phosphorus compound in combination, a sufficient catalytic activity can be exhibited even if the content of aluminum in the polyester polymerization catalyst is small.

The amount of the phosphorus compound to be added is preferably 0.0001 to 0.1 mol%, more preferably 0.005 to 0.1 mol%, based on the total number of moles of the constituent units of the dicarboxylic acid component constituting the polyester.
More preferably, it is 05 mol%. If the amount of the phosphorus compound is less than 0.0001 mol%, the effect of addition may not be exhibited. On the other hand, if it is added in excess of 0.1 mol%, the catalytic activity as a polyester polymerization catalyst may be reduced. Further, the tendency of the decrease varies depending on the amount of aluminum added and the like.

Without using a phosphorus compound, an aluminum compound was used as a main catalyst component, the amount of the aluminum compound added was reduced, and a cobalt compound was further added to reduce the thermal stability when the aluminum compound was used as a main catalyst. It is considered to prevent coloring by
If the cobalt compound is added to such an extent that it has a sufficient catalytic activity, the thermal stability also decreases. Therefore, it is difficult to achieve both using this technique.

The use of the phosphorus compound having the above-mentioned specific chemical structure does not cause problems such as a decrease in thermal stability and the generation of foreign matters, and a sufficient catalytic effect can be obtained even when the addition amount of the metal-containing component as aluminum is small. A polycondensation catalyst is obtained, and by using a polyester polymerized by the polycondensation catalyst, the thermal stability of the polyester film after melt molding is improved.

Further, even if a phosphoric acid ester such as phosphoric acid or trimethyl phosphoric acid is added instead of the phosphorus compound, the effect of the addition is not observed. Further, the phosphorus compound in the range of the preferred addition amount, a conventional antimony compound,
Even when used in combination with a metal-containing polyester polycondensation catalyst such as a titanium compound, a tin compound, and a germanium compound, the effect of promoting the melt polymerization reaction is not recognized.

On the other hand, in a preferred embodiment of the present invention, in addition to aluminum or a compound thereof, a small amount of at least one selected from alkali metals, alkaline earth metals and compounds thereof coexists as the second metal-containing component. The coexistence of such a second metal-containing component in the catalyst system increases the catalytic activity in addition to the effect of suppressing the production of diethylene glycol, and thus provides a catalyst component with a higher reaction rate, which is effective for improving productivity. .

It is known that a catalyst having sufficient catalytic activity can be obtained by adding an alkali metal compound or an alkaline earth metal compound to an aluminum compound. The use of such a known catalyst provides a polyester having excellent thermal stability. However, a known catalyst using an alkali metal compound or an alkaline earth metal compound in combination has a problem in that the amount of catalyst added is increased in order to obtain practical catalytic activity. Need to be more.

When an alkali metal compound is used in combination, the amount of foreign substances resulting therefrom increases, and the frequency of filter replacement in the melt extrusion step during film production tends to be short, and the film defect tends to increase.

Further, when an alkaline earth metal compound is used in combination, to obtain a practical activity, the thermal stability and the thermal oxidative stability of the obtained polyester are reduced, and coloring by heating is large. The amount of foreign matter generated also increases.

When an alkali metal, an alkaline earth metal, or a compound thereof is added, the addition amount M (mol%) is 1 × 10 ^{− based on the} number of moles of all the polycarboxylic acid units constituting the polyester. ⁶ or more 0.1 mol%
Is preferably less than 5 × 10
^{−6 to} 0.05 mol%, more preferably 1 × 1
0 ^- 5 to 0.03 the molar%, particularly preferably, 1 ×
It is 10 ^{-5 to} 0.01 mol%.

That is, since the addition amount of the alkali metal or the alkaline earth metal is small, the reaction rate can be increased without causing problems such as a decrease in thermal stability, generation of foreign matter, and coloring. Further, problems such as a decrease in hydrolysis resistance do not occur.

When the addition amount M of the alkali metal, alkaline earth metal, or a compound thereof is 0.1 mol% or more, the heat stability is reduced, the generation of foreign matters and coloration are increased, and the hydrolysis resistance is reduced. A problem may occur in processing. If M is less than 1 × 10 ⁻⁶ mol%, the effect is not clear even if added.

The alkali metal and alkaline earth metal constituting the second metal-containing component which is preferably used in addition to the aluminum or its compound include Li and N.
It is preferably at least one selected from a, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba, and more preferably an alkali metal or a compound thereof.

When an alkali metal or its compound is used, Li, Na and K are particularly preferred as the alkali metal. Examples of the alkali metal or alkaline earth metal compounds include, for example, saturated aliphatic carboxylate such as formic acid, acetic acid, propionic acid, butyric acid, and oxalic acid, and unsaturated aliphatic carboxylate such as acrylic acid and methacrylic acid. ,
Aromatic carboxylate such as benzoic acid, halogen-containing carboxylate such as trichloroacetic acid, hydroxycarboxylate such as lactic acid, citric acid, salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, phosphoric acid Hydrogen, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid,
Inorganic acid salts such as bromic acid, 1-propanesulfonic acid, 1-
Pentanesulfonic acid, organic sulfonates such as naphthalenesulfonic acid, organic sulfates such as lauryl sulfate, methoxy, ethoxy, n-propoxy, iso-propoxy,
Examples include alkoxides such as n-butoxy and tert-butoxy, chelate compounds with acetylacetonate and the like, hydrides, oxides and hydroxides.

When strong alkalis such as hydroxides are used among these alkali metals, alkaline earth metals or compounds thereof, they are less likely to be dissolved in organic solvents such as diols such as ethylene glycol or alcohols. Therefore, an aqueous solution must be added to the polymerization system, which may cause a problem in the polymerization step.

Further, when a highly alkaline substance such as a hydroxide is used, the polyester is liable to undergo side reactions such as hydrolysis during the polymerization, and the polymerized polyester tends to be easily colored. Also tends to decrease.

Accordingly, the above-mentioned alkali metal or a compound thereof, an alkaline earth metal or a compound thereof preferably include a saturated aliphatic carboxylate, an unsaturated aliphatic carboxylate and a fragrance of an alkali metal or an alkaline earth metal. Group carboxylate, halogen-containing carboxylate, hydroxycarboxylate, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, bromic acid Inorganic acid salts, organic sulfonates, organic sulfates, chelating compounds, and oxides of choice. Among these, from the viewpoints of ease of handling and availability, it is preferable to use an alkali metal or alkaline earth metal saturated aliphatic carboxylate, particularly an acetate.

The polyester which is a main component of the support of the optical coating film of the present invention preferably has a thermal stability parameter (TS) satisfying the following formula, more preferably 0.25 or less, and particularly preferably 0 or less. .20 or less. By using a polyester having a TS of less than 0.30, a polyester film having excellent heat stability in a melt extrusion step in producing a film and having little occurrence of coloring and foreign matters can be obtained. (1) TS <0.30

The TS is calculated by the following method. Polyester 1 having an intrinsic viscosity ([IV] _i ) of about 0.65 dl / g
g in a glass test tube and vacuum dried at 130 ° C. for 12 hours. Next, the sample is kept in a molten state at 300 ° C. for 2 hours under a non-circulating nitrogen atmosphere, and then the sample is taken out and freeze-ground. After drying it in a vacuum, the intrinsic viscosity ([IV] _f ) is measured. For example, when the polyester is polyethylene terephthalate, it can be calculated by the following equation. TS = 0.245 ｛[IV] _f ^-1.47- [IV] _i
^-1.47 ｝

The non-circulating nitrogen atmosphere means a non-circulating nitrogen atmosphere. For example, a glass test tube containing a resin chip is connected to a vacuum line, and the pressure becomes 100 Torr after the pressure reduction and nitrogen sealing are repeated 5 times or more. Is sealed with nitrogen.

Further, the polyester used in the present invention is:
The thermal oxidation stability parameter (TOS) preferably satisfies the following expression (2), more preferably 0.09 or less, and further preferably 0.08 or less. (2) TOS <0.10

The TOS is calculated by the following method. A polyester resin chip obtained by melt polymerization having an intrinsic viscosity ([IV] _i ) of about 0.65 dl / g is freeze-pulverized,
Make powder below mesh. The powder at 130 ° C. for 12
Dry under vacuum for an hour and place 0.3 g in a glass test tube. Next, after vacuum drying at 70 ° C. for 12 hours and further heating at 230 ° C. for 15 minutes under air dried with silica gel, the intrinsic viscosity ([IV] _f1 ) is measured. For example, when the polyester is polyethylene terephthalate, it can be calculated by the following equation. TOS = 0.245 ｛[IV] _f1 ^-1.47 − [IV] _i
^{-1.47 に お い} _{て In the} above formula, [IV] _i and [IV] _f1
Is the IV (dl / g) before and after the heating test, respectively.
Point to.

As a method for heating under air dried with silica gel, for example, a method in which a drying tube containing silica gel is connected to the upper part of a glass test tube and heated under dry air can be exemplified.

Further, the polyester used in the present invention is:
The hydrolysis resistance parameter (HS) preferably satisfies the following expression (3), more preferably 0.09 or less, and particularly preferably 0.085 or less. (3) HS <0.10

HS is calculated by the following method. Polyester chips obtained by melt polymerization having an intrinsic viscosity of about 0.65 dl / g (before the test: [IV] _i ) are freeze-pulverized to powder having a size of 20 mesh or less. After vacuum drying at 130 ° C. for 12 hours, 1 g thereof is put into a beaker together with 100 ml of pure water. After stirring in a closed system for 6 hours under the condition of heating and pressurizing at 130 ° C., the intrinsic viscosity ([IV] _f2 ) is measured. For example, when the polyester is polyethylene terephthalate, it can be calculated by the following equation. HS = 0.245 × ｛[IV] _f2 ^-1.47- [IV] _i
^-1.47 ｝

The beaker used for the measurement of HS does not elute any acid or alkali. Specifically, it is preferable to use a stainless beaker or a quartz beaker.

Further, the polyester used in the present invention is:
The solution haze value (SH) of the polyester preferably satisfies the following formula (4), more preferably 2.0 or less, and further preferably 1.0 or less. (4) SH <3.0 (%)

SH is calculated by the following method. A melt-polymerized polyester resin chip having an intrinsic viscosity of about 0.65 dl / g was dissolved in a 3/1 mixed solvent (weight ratio) of p-chlorophenol / 1,1,2,2-tetrachloroethane to give 8 g / 100 ml. Make a solution. A cell having a cell length of 1 cm is filled with the solution, and the haze value of the solution is measured using a haze meter.

The polyester resin chips used for measuring TS, TOS, HS, and SH are those produced by melt-polymerization and then quenched from the molten state. As the shape of the resin chip used for these measurements, for example, a cylindrical resin chip having a length of about 3 mm and a diameter of about 2 mm is used.

In the case of performing color measurement, a resin chip which is substantially amorphous and produced by quenching from a molten state after a melt polymerization step is used. As a method for obtaining a substantially amorphous resin chip, for example,
When taking out the polymer from the reaction system after melt polymerization, quenching with cold water immediately after discharging the polymer from the discharge port of the reaction system, then holding it in cold water for a sufficient time and then cutting it into chips Can be exemplified.

The resin chip thus obtained is
In appearance, whitening due to crystallization is not observed and a transparent product is obtained. The resin chip thus obtained is air-dried on a filter paper or the like at room temperature for about 24 hours, and then used for color measurement. Even after the above operation, the resin chip looks
No whitening due to crystallization was observed and the film remained transparent. It should be noted that no additive affecting the appearance such as titanium dioxide is used for the resin chip for color measurement. As the shape of the resin chip used for color measurement, for example, a cylindrical resin chip having a length of about 3 mm and a diameter of about 2 mm is used.

In a preferred embodiment, the polyester used in the present invention is further added with a cobalt compound as a cobalt atom in an amount of less than 10 ppm based on the polyester.

It is known that cobalt compounds themselves have a certain degree of polymerization activity. However,
When added to such an extent that a sufficient catalytic effect is exhibited as described above, the color tone and the thermal stability of the obtained polyester film decrease.

The polyester used in the present invention has good color tone and thermal stability. However, by adding the cobalt compound in the above-mentioned small amount and in an addition amount in which the catalytic effect of the addition is not clear, The coloring can be more effectively eliminated without lowering the color tone of the obtained polyester.

The purpose of adding the cobalt compound is to eliminate coloration, and the addition may be made at any stage of the polymerization step or after the end of the polymerization reaction.

The type of the cobalt compound is not particularly limited, and examples thereof include cobalt acetate, cobalt nitrate, cobalt chloride, cobalt acetylacetonate, cobalt naphthenate and hydrates thereof. Among them,
Particularly, cobalt acetate tetrahydrate is preferable.

It is preferable that the total amount of the aluminum compound and the cobalt atom is 50 ppm or less and the amount of the cobalt atom is less than 10 ppm with respect to the finally obtained polyester. More preferably, the total amount of aluminum atoms and cobalt atoms is 4
0 ppm or less, and the amount of cobalt atoms is 8 ppm or less, more preferably the total amount of aluminum atoms and cobalt atoms is 25 ppm or less, and the cobalt atoms
pm or less.

From the viewpoint of the thermal stability of the polyester, the total amount of aluminum atoms and cobalt atoms is preferably less than 50 ppm, and the amount of cobalt atoms is preferably 10 ppm or less. In order to have sufficient catalytic activity, the total amount of aluminum atoms and cobalt atoms must be 0.0
Preferably it is more than 1 ppm.

The polyester used in the present invention is the same as the polyester polymerization catalyst except that the above-mentioned specific catalyst is used.
It can be performed by a conventionally known manufacturing method. For example, PE
In the case of producing T, a method of subjecting terephthalic acid and ethylene glycol to an esterification reaction followed by polycondensation, or a polycondensation after performing an ester exchange reaction between an alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol And any of the above methods. Further, the polymerization apparatus may be a batch type or a continuous type.

The polyester catalyst used in the present invention has catalytic activity not only in polymerization but also in esterification and transesterification. For example, polymerization by transesterification of an alkyl ester of a dicarboxylic acid such as dimethyl terephthalate with a glycol such as ethylene glycol is usually carried out in the presence of a transesterification catalyst such as a titanium compound or a zinc compound. Alternatively or in combination with these catalysts, the catalysts described in the claims of the present invention can be used. Further, the catalyst has catalytic activity not only in melt polymerization but also in solid phase polymerization and solution polymerization, and it is possible to produce polyester which is a main component of the polyester film by any method. .

The polymerization catalyst for the polyester used in the present invention can be added to the reaction system at any stage of the polymerization reaction. For example, it can be added to the reaction system before or during the start of the esterification reaction or transesterification reaction, at any stage during the reaction, immediately before the start of the polycondensation reaction, or at any stage during the polycondensation reaction. In particular, it is preferable to add aluminum or its compound immediately before the start of the polycondensation reaction.

The method of adding the polyester polycondensation catalyst used in the present invention is not particularly limited, but may be a powder or neat addition, or a slurry or solution of a solvent such as ethylene glycol. It may be addition. Further, a mixture of aluminum metal or a compound thereof and another component, preferably a phenolic compound or a phosphorus compound of the present invention, may be added in advance, or they may be added separately. Further, the aluminum metal or its compound and another component, preferably a phenolic compound or a phosphorus compound, may be added to the polymerization system at the same time, or they may be added at different times.

The polyester polycondensation catalyst used in the present invention may be prepared by adding another polymerization catalyst such as an antimony compound, a titanium compound, a germanium compound, or a tin compound within a range that does not cause a problem in the product such as the properties, processability, and color of the polyester. In the above, it is advantageous to use an appropriate amount of coexistence, because it is advantageous when the productivity is improved by shortening the polymerization time.

More specifically, the amount of the antimony compound to be added is preferably 50 ppm or less, more preferably 30 ppm or less, in terms of antimony atoms, based on the polyester obtained by polymerization. Antimony atom equivalent of 5
If it exceeds 0 ppm, precipitation of antimony metal occurs, and the polyester becomes dark, which is not preferable in appearance. In addition, foreign matter due to metallic antimony increases, which is not preferable particularly in applications in which demand for defects is severe.

The amount of the titanium compound to be added is preferably 10 ppm or less, more preferably 5 ppm or less, still more preferably 2 ppm or less, in terms of titanium atoms based on the polyester obtained by polymerization. Titanium atom equivalent is 10
When the content exceeds ppm, the thermal stability of the obtained resin is significantly reduced.

The amount of the germanium compound added is preferably 20 ppm or less, more preferably 10 ppm, in terms of germanium atoms based on the polyester obtained by polymerization.
pm or less. It is not preferable that the amount of germanium atoms exceeds 20 ppm, because it is disadvantageous in terms of cost.

When polymerizing the polyester used in the present invention, one or more of an antimony compound, a germanium compound, a titanium compound and a tin compound can be used in addition to the catalyst described in the present invention.

The types of the antimony compound, titanium compound, germanium compound and tin compound are not particularly limited.

Specifically, as the antimony compound,
Examples include antimony trioxide, antimony pentoxide, antimony acetate, antimony glycooxide, and the like. Of these, antimony trioxide is preferable.

Further, as the titanium compound, tetra-n
-Propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetracyclohexyl titanate, tetraphenyl titanate, titanium oxalate and the like.
n-Butoxy titanate is preferred.

Further, examples of the germanium compound include germanium dioxide and germanium tetrachloride.
Of these, germanium dioxide is preferred.

Examples of the tin compound include dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, triethyltin hydroxide, monobutylhydroxytin oxide, triisobutyltin acetate, diphenyltin dilaurate, monobutyltin trichloride, Examples thereof include dibutyltin sulfide, dibutylhydroxytin oxide, methylstannoic acid and ethylstannoic acid, and the use of monobutylhydroxytin oxide is particularly preferred.

The polyester used as a film raw material in the present invention is a polyester selected from polyhydric carboxylic acids including dicarboxylic acids and one or more selected from ester-forming derivatives thereof and polyhydric alcohols including glycols. A compound consisting of two or more kinds, a compound consisting of hydroxycarboxylic acids and their ester-forming derivatives, or a compound consisting of cyclic esters.

Preferred polyesters are those wherein the main acid component is terephthalic acid or an ester-forming derivative thereof,
Alternatively, the polyester is naphthalenedicarboxylic acid or an ester-forming derivative thereof, and the main glycol component is an alkylene glycol.

The polyester in which the main acid component is terephthalic acid or an ester-forming derivative thereof or naphthalenedicarboxylic acid or an ester-forming derivative thereof is referred to as terephthalic acid or an ester-forming derivative thereof and naphthalenedicarboxylic acid or It is preferable that the polyester is a polyester containing at least 70 mol% of the ester-forming derivative in total, more preferably a polyester containing at least 80 mol%, more preferably
It is a polyester containing 90 mol% or more.

The polyester in which the main glycol component is an alkylene glycol is preferably a polyester containing alkylene glycol in a total amount of 70 mol% or more with respect to all glycol components, more preferably.
It is a polyester containing 80 mol% or more, and more preferably a polyester containing 90 mol% or more.

The dicarboxylic acids include oxalic acid, malonic acid,
Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,3-cyclo Pentanedicarboxylic acid,
Saturated aliphatic dicarboxylic acids exemplified by 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid and the like, and their ester-forming properties Derivatives, fumaric acid, maleic acid, unsaturated aliphatic dicarboxylic acids exemplified by such as itaconic acid or ester-forming derivatives thereof, orthophthalic acid,
Isophthalic acid, terephthalic acid, 5- (alkali metal) sulfoisophthalic acid, diphenic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,
5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4 ′
-Biphenyldicarboxylic acid, 4,4'-biphenylsulfonedicarboxylic acid, 4,4'-biphenyletherdicarboxylic acid, 1,2-bis (phenoxy) ethane-p,
Aromatic dicarboxylic acids exemplified by p'-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid and the like, and ester-forming derivatives thereof are exemplified.

Of these dicarboxylic acids, terephthalic acid, naphthalenedicarboxylic acid, or their ester-forming derivatives are preferred.

Examples of the naphthalenedicarboxylic acid or its ester-forming derivative include 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7 -Naphthalenedicarboxylic acid or ester-forming derivatives thereof.

Particularly preferably, terephthalic acid, 2,6-
Naphthalenedicarboxylic acids or their ester-forming derivatives. If necessary, another dicarboxylic acid may be used as a component.

Examples of polycarboxylic acids other than these dicarboxylic acids include ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ', 4'-biphenyltetracarboxylic acid. Examples include carboxylic acids and their ester-forming derivatives.

Examples of the glycol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, and 2,3-butylene glycol. , 1,4
-Butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol,
1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,
2-cyclohexane dimethanol, 1,3-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, 1,10-
Alkylene glycols such as decamethylene glycol and 1,12-dodecanediol, aliphatic glycols exemplified by polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, etc., hydroquinone, 4,4′-dihydroxybisphenol,
4-bis (β-hydroxyethoxy) benzene, 1,4
-Bis (β-hydroxyethoxyphenyl) sulfone,
Bis (p-hydroxyphenyl) ether, bis (p-
(Hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol C,
Aromatic glycols such as 2,5-naphthalene diol, glycols obtained by adding ethylene oxide to these glycols, and the like are exemplified.

Of these glycols, alkylene glycols are preferred, and ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol and 1,4-cyclohexanedimethanol are more preferred. The alkylene glycol may contain a substituent or an alicyclic structure in the molecular chain, and two or more kinds may be used at the same time.

Examples of polyhydric alcohols other than these glycols include trimethylolmethane, trimethylolethane,
Trimethylolpropane, pentaerythritol, glycerol, hexanetriol and the like.

Examples of hydroxycarboxylic acids include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, and 4-hydroxycyclohexanecarboxylic acid. Or ester-forming derivatives thereof.

Examples of the cyclic ester include ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycolide, lactide and the like.

Examples of the ester-forming derivatives of polycarboxylic acids or hydroxycarboxylic acids include these alkyl esters, acid chlorides and acid anhydrides.

Examples of the polyester used in the present invention include polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, poly (1,4-cyclohexane dimethylene terephthalate), polyethylene naphthalate, polybutylene naphthalate, polypropylene naphthalate and copolymers thereof. Coalescence is preferred, and polyethylene terephthalate and its copolymers are particularly preferred.

The polyester used in the present invention includes:
A known phosphorus compound can be included as a copolymer component. As the phosphorus compound, a bifunctional phosphorus compound is preferable. For example, (2-carboxyethyl) methylphosphinic acid, (2-carboxyethyl) phenylphosphinic acid, 9,10-dihydro-10-oxa- (2,3- (Carboxypropyl) -10-phosphaphenanthrene-
10-oxide and the like. By including these phosphorus compounds as copolymer components, it is possible to improve the flame retardancy and the like of the obtained polyester.

After the polyester is polymerized, the thermal stability of the polyester can be further enhanced by removing the catalyst from the obtained polyester or deactivating the catalyst by adding a phosphorus compound or the like.

In the polyester used in the present invention, depending on the purpose of use, inert particles such as inorganic particles, heat-resistant polymer particles, cross-linked polymer particles, fluorescent brighteners, ultraviolet inhibitors, infrared absorbing dyes. , Heat stabilizers, surfactants, antioxidants, and other various additives may be used alone or in combination of two or more. As antioxidants, aromatic amines,
A phenol-based antioxidant can be used, and as the stabilizer, a phosphorus-based stabilizer such as phosphoric acid or a phosphate ester, a sulfur-based stabilizer, or an amine-based stabilizer can be used.

However, in the present invention, it is preferable not to use an additive which lowers the transparency of the film as much as possible, and it is preferable that substantially no particles are contained in the base polyester film. Is a particularly preferred embodiment. The term "substantially free of particles" means that the elements due to particles were quantified using a calibration curve of a fluorescent X-ray analysis method previously created by quantitative analysis using another chemical analysis method such as an atomic absorption analysis method or an emission analysis method. In this case, it means that the content is below the detection limit.

However, for example, calcium acetate, calcium carbonate particles, calcium phosphate particles and the like used in the transesterification catalyst share calcium as an element, and it is sometimes difficult to determine whether the calcium element is a catalyst or a particle. is there. In such a case, the polyester resin or the polyester film is mixed with hexafluoroisopropanol / chloroform (= 2/3; volume ratio).
And then centrifuged to separate the particles, followed by decantation, and quantification of the amount of calcium element caused by the catalyst in the supernatant by atomic absorption analysis or emission analysis. Then, from the difference between the total calcium content in the polyester and the calcium element amount used for the catalyst, the calcium element amount due to the particles can be calculated.

Further, the intrinsic viscosity of the polyester resin is
A range of 0.45 to 0.80 dl / g is preferred. When the intrinsic viscosity is less than 0.45 dl / g, breakage tends to occur frequently during film production. On the other hand, the intrinsic viscosity is 0.80d
If it exceeds 1 / g, the increase in filtration pressure becomes large and high-precision filtration becomes difficult. Further, the heat shrinkage of the film is also deteriorated.

In the present invention, the coating liquid used for forming the coating layer mainly comprises a solvent, a polymer resin and particles. Either an aqueous solvent or an organic solvent can be used as the solvent, but an aqueous solvent is preferred from the viewpoint of working environment, environmental protection, productivity, and the like.

In the present invention, the polymer resin used for the coating layer of the base film may be an acrylate resin or a base resin commonly used for a prism lens layer, a hard coat layer, a light diffusion layer, an antireflection layer, etc. The material is not particularly limited as long as it is a polymer resin having good adhesiveness to both of the polyester films, and examples thereof include polyester resins, acrylic resins, polyurethane resins, and copolymers and mixtures thereof. Can be Further, it is preferable that the coating layer is composed of a polymer resin having a composition similar to the base polyester film in terms of the degree of segregation from the viewpoint of transparency. As such a polymer resin, for example, a resin composition mainly containing a copolymerized polyester resin (A) containing a branched glycol as a constituent component and a resin (B) containing a block type isocyanate group is used. No.

In the above-mentioned copolymerized polyester resin (A), the branched glycol component includes, for example, 2,2-dimethyl-1,3-propanediol, 2-methyl-2-
Ethyl-1,3-propanediol, 2-methyl-2-
Butyl-1,3-propanediol, 2-methyl-2-
Propyl-1,3-propanediol, 2-methyl-2
-Isopropyl-1,3-propanediol, 2-methyl-2-n-hexyl-1,3-propanediol,
2,2-diethyl-1,3-propanediol, 2-ethyl-2-n-butyl-1,3-propanediol,
-Ethyl-2-n-hexyl-1,3-propanediol, 2,2-di-n-butyl-1,3-propanediol, 2-n-butyl-2-propyl-1,3-propanediol, And 2,2-di-n-hexyl-1,3-propanediol.

The above-mentioned branched glycol component is contained in all the glycol components preferably in a proportion of 10 mol% or more, more preferably in a proportion of 20 mol% or more. As the glycol component other than the above compounds, ethylene glycol is most preferred. If it is a small amount, diethylene glycol, propylene glycol, butanediol,
Hexanediol or 1,4-cyclohexanedimethanol may be used.

The dicarboxylic acid component of the copolymerized polyester resin (A) is most preferably terephthalic acid or isophthalic acid. If it is a small amount, another dicarboxylic acid; an aromatic dicarboxylic acid of diphenylcarboxylic acid and 2,6-naphthalenedicarboxylic acid may be added and copolymerized.

In order to impart water dispersibility, 5-sulfoisophthalic acid is preferably used in an amount of 1 to 10 mol% in addition to the above dicarboxylic acid component. For example, sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfonaphthaleneisophthalic acid-2,7-dicarboxylic acid and 5-
(4-Sulfophenoxy) isophthalic acid and salts thereof can be mentioned.

Examples of the resin (B) containing a blocked isocyanate group include a heat-reactive water-soluble urethane in which a terminal isocyanate group is blocked with a hydrophilic group (hereinafter referred to as a block). Examples of the blocking agent for the isocyanate group include phenols containing bisulfites and sulfonic acid groups, alcohols, lactams,
Oximes and active methylene compounds.
The blocked isocyanate group renders the urethane prepolymer hydrophilic or water-soluble. When thermal energy is given to the resin during the drying or heat setting process during film production, the blocking agent separates from the isocyanate group, so that the resin fixes the water-dispersible copolymerized polyester resin mixed with the self-crosslinked stitches. And reacts with the terminal groups of the resin. The resin being adjusted for the coating liquid is poor in water resistance because it is hydrophilic, but when the coating, drying and heat setting and the thermal reaction are completed, the hydrophilic group of the urethane resin, that is, the blocking agent, comes off, so that the water resistance is good. A coating is obtained.

Among the above blocking agents, bisulfite cheek is most preferable as the one which is suitable for heat treatment temperature and heat treatment time and is widely used industrially.

The chemical composition of the urethane prepolymer used in the above resin is as follows: (1) an organic polyisocyanate having two or more active hydrogen atoms in a molecule;
Alternatively, a compound having a molecular weight of 200 to 20,000 having at least two active hydrogen atoms in the molecule, (2) an organic polyisocyanate having two or more isocyanate groups in the molecule, or (3) a compound in the molecule At least 2
A compound having a terminal isocyanate group, which is obtained by reacting a chain extender having an active hydrogen atom.

The compound (1) is generally known to contain two or more hydroxyl groups, carboxyl groups, amino groups or mercapto groups at the terminal or in the molecule. Particularly preferred compounds are Examples include polyether polyols and polyether ester polyols.

Examples of the polyether polyol include compounds obtained by polymerizing alkylene oxides such as ethylene oxide and propylene oxide, or compounds obtained by polymerizing styrene oxide and epichlorohydrin, or random polymerization, block polymerization or addition polymerization to polyhydric alcohol. There are compounds obtained. As the polyester polyol and the polyether ester polyol, mainly, linear or branched compounds can be mentioned. A polyvalent saturated or unsaturated carboxylic acid such as succinic acid, adipic acid, phthalic acid and maleic anhydride, or the carboxylic anhydride; and ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, Of polyhydric saturated and unsaturated alcohols such as 2,6-hexanediol and trimethylolpropane, polyalkylene ether glycols such as polyethylene glycol and polypropylene glycol of relatively low molecular weight, or a mixture of these alcohols. Can be obtained by

Further, polyesters obtained from lactone and hydroxy acid are used as polyester polyols, and polyether esters obtained by adding ethylene oxide or propylene oxide to polyesters produced in advance are used as polyether ester polyols. be able to.

As the organic polyisocyanate (2), isomers of toluylene diisocyanate, 4,4
Aromatic diisocyanates such as diphenylmethane diisocyanate, aromatic aliphatic diisocyanates such as xylylene diisocyanate, alicyclic diisocyanates such as isophorone diisocyanate and 4,4-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and 2,2,4 -Aliphatic diisocyanates such as trimethylhexamethylene diisocyanate, or polyisocyanates in which one or more of these compounds are previously added to trimethylolpropane or the like.

Examples of the chain extender having at least two active hydrogens of the above (3) include ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6
Glycols such as hexanediol, polyhydric alcohols such as glycerin, trimethylolpropane, and pentaerythritol; diamines such as ethylenediamine, hexamethylenediamine, and piperazine; aminoalcohols such as monoethanolamine and diethanolamine; Thiodiglycols such as diethylene glycol, or water.

In order to synthesize the urethane polymer of the above (3), usually at a temperature of 150 ° C. or less, preferably 70 to 120 ° C., by a one-stage or multi-stage isocyanate polyaddition method using the above chain extender. Let them react for a few minutes to a few hours. The ratio of isocyanate groups to active hydrogen atoms can be freely selected as long as it is 1 or more, but it is necessary that free isocyanate groups remain in the obtained urethane prepolymer.

Further, the content of free isocyanate groups may be 10% by weight or less, but is preferably 7% by weight or less in consideration of the stability of the aqueous urethane polymer solution after blocking.

The obtained urethane prepolymer is preferably blocked with bisulfite. The mixture is mixed with an aqueous bisulfite solution, and the reaction is allowed to proceed with good stirring for about 5 minutes to 1 hour. The reaction temperature is preferably set to 60 ° C. or lower. Thereafter, the mixture is diluted with water to an appropriate concentration to obtain a heat-reactive water-soluble urethane composition. When the composition is used, it is adjusted to an appropriate concentration and viscosity.
When heated to about 200 ° C., the bisulfite of the blocking agent is dissociated, and the active isocyanate group is regenerated. Thus, a polyurethane polymer is generated by a polyaddition reaction occurring within or between molecules of the prepolymer, or It has the property of causing addition to other functional groups.

As an example of the resin (B) containing a blocked isocyanate group, Elastron (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is typically exemplified. Elastron is obtained by blocking an isocyanate group with sodium bisulfite, and is water-soluble due to the presence of a carbamoyl sulfonate group having strong hydrophilicity at the molecular terminal.

When the coating polyester resin (A) containing the branched glycol component and the resin (B) containing a blocked isocyanate group are mixed to prepare a coating solution, the resin (A) and the resin (A) The weight ratio of B) is preferably (A) :( B) = 90: 10 to 10:90,
More preferably, (A) :( B) = 80: 20 to 20: 8
It is in the range of 0. When the weight ratio of the resin (A) to the weight of the solid content is less than 10%, the coatability on the base film is inappropriate, and the adhesion between the surface layer and the film tends to be insufficient. On the other hand, when the weight ratio of the resin (B) is less than 10%, it is difficult to obtain practical adhesiveness in a UV-curable hard coat.

A catalyst may be added to the aqueous coating solution used in the present invention in order to promote a thermal crosslinking reaction. Examples of the catalyst include inorganic substances, salts, organic substances, alkaline substances, acidic substances and metal-containing organic compounds. Various chemical substances are used. In order to adjust the pH of the aqueous solution, an alkaline substance or an acidic substance may be added.

When the aqueous coating solution is applied to the surface of a substrate film, a known anionic surfactant and nonionic surfactant are used in order to increase wettability to the film and uniformly coat the coating solution. Can be added and used in a required amount. The solvent used for the coating liquid is ethanol,
Alcohols such as isopropyl alcohol and benzyl alcohol may be mixed until the proportion of the total coating solution is less than 50% by weight. Further, when the content is less than 10% by weight, an organic solvent other than alcohols may be mixed in a range where it can be dissolved. However, the total of alcohols and other organic solvents in the coating liquid is less than 50% by weight.

When the addition amount of the organic solvent is less than 50% by weight, the drying property is improved at the time of coating and drying, and the appearance of the coating film is improved as compared with the case where only water is used. If it exceeds 50% by weight, the solvent evaporates at a high rate, the concentration of the coating solution changes during coating, the viscosity increases, and the coating property decreases, which may cause poor appearance of the coating film. In addition, there is a risk of fire.

Further, handling properties,
In order to impart other functions to the film, such as antistatic properties and antibacterial properties, inorganic and / or heat-resistant polymer particles, antistatic agents, ultraviolet absorbers, as long as the transparency and adhesiveness are not impaired. Additives such as organic lubricants, antibacterial agents, and photooxidation catalysts can be contained in appropriate amounts. Furthermore, since the coating solution is aqueous, within a range that does not impair transparency or adhesion,
In order to improve the performance, other water-soluble resins, water-dispersible resins, emulsions and the like may be added to the coating solution.

The optical coating film of the present invention preferably contains substantially no inert particles in the base polyester film from the viewpoint of transparency. Therefore, in order to improve the handleability and scratch resistance of the film. In addition, it is necessary that particles of an appropriate size are contained in the coating liquid in an appropriate amount in the coating layer to form irregularities on the surface of the coating layer.

Examples of such particles include (1) silica,
Glass filler, silica-alumina composite oxide particles, inorganic particles such as calcium carbonate, calcium phosphate, hydroxyapatite, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, etc. ) Cross-linked polymer particles such as cross-linked polystyrene, cross-linked polymethyl methacrylate, cross-linked acryl, (3) silicon resin particles,
Examples include heat-resistant polymer particles such as polyimide particles and fluorine-based resin particles, and (4) organic particles such as calcium oxalate. Among them, silica particles are most suitable because they have a refractive index relatively close to that of the polyester resin and can easily obtain a highly transparent film.

The average particle size of the particles added to the aqueous coating solution is preferably 0.001 to 1.0 μm, more preferably 0.005 to 0.5 μm, and particularly preferably 0.01 to 1.0 μm.
０．１0.1 μm. When the average particle diameter exceeds 1.0 μm, the film surface becomes rough, and the transparency of the film tends to decrease. On the other hand, if the thickness is less than 0.001 μm, the handleability becomes insufficient. Further, the content of the particles in the coating layer after drying is preferably 0.1 to 60% by weight, more preferably 0.5 to 50% by weight, and particularly preferably 1 to 50% by weight.
40% by weight. 60% by weight of the particle content in the coating layer
When the ratio exceeds, the transparency and adhesiveness of the film tend to be insufficient.

In the coating layer, two or more kinds of the above particles may be contained, or particles of the same kind but different in particle diameter may be contained. In any case, it is preferable that the average particle size of the whole particles and the total content satisfy the above range.
When applying the coating liquid, it is preferable to arrange a filter medium so that the coating liquid is subjected to microfiltration just before the application in order to remove coarse aggregates of particles in the coating liquid.

It is preferable that the filter medium for finely filtering the coating solution used for forming the coating layer of the film of the present invention has a filter particle size of 25 μm or less (initial filtration efficiency 95%). When the particle size is 25 μm or more, coarse aggregates cannot be sufficiently removed, and many large aggregates that cannot be removed are coated,
When monoaxially or biaxially stretched after drying, coarse aggregates of particles spread in the coating layer and are recognized as aggregates of 100 μm or more, and as a result, many optical defects are likely to occur.

Although the type of the filter medium is not particularly limited,
For example, there are a filament type, a felt type, and a mesh type. Also, the material of the filter medium is not particularly limited, and examples thereof include stainless steel, polyethylene, polypropylene, and nylon.

The biaxially stretched polyester film used as a support in the present invention preferably has a thickness of 100 to 250 μm from the viewpoint of workability and handleability in a post-processing step.

The optical coating film of the present invention needs to have a haze of not more than 2.0%, preferably 1.
It is at most 5%, particularly preferably at most 1.0%. If the haze value exceeds 2.0%, when the film is used as a lens film for LCD, an antireflection film for cathode ray tube, or the like, the sharpness of the screen deteriorates, which is not preferable.

Next, the method for producing the optical coating film of the present invention will be described with reference to polyethylene terephthalate (hereinafter referred to as PE).
T is abbreviated as an example, but is not limited to this.

Prepared using the above novel polymerization catalyst,
After substantially vacuum-drying PET pellets substantially containing no particles, the pellets are fed to a twin-screw extruder, melt-extruded into a sheet at 280 ° C., solidified by cooling, and then unstretched PE.
A T-sheet is formed. At this time, high-precision filtration is performed at an arbitrary place in the melt line where the molten resin is kept at 280 ° C.
The filter medium used for high-precision filtration of the molten resin is not particularly limited, but the filter medium of the stainless sintered body is made of Si, Ti, S
It is suitable because it has excellent performance of removing aggregates containing b, Ge, Cu, and the like as main components and high melting point organic substances.

Further, the filtration particle size (initial filtration efficiency: 95%) of the filter medium is 25 μm or less, more preferably 15 μm or less.
It is effective to set it to not more than μm in order to obtain an optical coating film with few optical defects. If it exceeds 25 μm, foreign substances cannot be sufficiently removed.

The obtained unstretched sheet is stretched 2.5 to 5.0 times in the longitudinal direction with a roll heated to 80 to 120 ° C. to obtain a uniaxially oriented PET film. Further, the end of the film is gripped with a clip and guided to a hot air zone heated to 80 to 180 ° C, and after drying, stretched 2.5 to 5.0 times in the width direction. Then, it is led to a heat treatment zone of 160 to 240 ° C. and heat treated for 1 to 60 seconds to complete the crystal orientation. During the heat treatment step and the cooling step, 1 to 12% relaxation treatment may be performed in the width direction or the longitudinal direction as necessary.

At any stage during this process, an aqueous solution of the water-soluble copolymerized polyester is applied to at least one surface of the polyester film. The aqueous coating solution can be applied by any known method. Examples include a reverse roll coating method, a gravure coating method, a kiss coating method, a roll brush method, a spray coating method, an air knife coating method, a wire barber coating method, a pipe doctor method, an impregnation / coating method and a curtain coating method. These methods can be performed alone or in combination.

The step of applying the aqueous coating liquid may be a usual coating step, that is, a step of coating a base film which has been biaxially stretched and heat-set, but is preferably applied during the production step of the film. More preferably, it is applied to the substrate film before the completion of the crystal orientation. The solid content concentration in the aqueous solution is usually 30% by weight or less, preferably 10% by weight or less.

The aqueous coating solution was applied to the running film 1
The coating is performed so that 0.04 to 5 g, preferably 0.2 to 4 g per m ² is adhered. The film to which the aqueous coating solution has been applied is guided to a tenter for stretching and heat setting, where it is heated to form a stable film by a thermal crosslinking reaction, and becomes a polyester-based laminated film. In order to obtain ink adhesion, the coating amount at this time is 0.01
g / m ² or more, and requires heat treatment at 100 ° C. for 1 minute or more.

The coated polyester film thus obtained has excellent transparency and adhesiveness, and contains substantially no agglomerates due to metal antimony particles.
It can be suitably used as a base film for a prism sheet, a base film for an antireflection film, a shatterproof film for a CRT, and the like.

[0270]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The evaluation method used in each of the examples and comparative examples will be described below.

[Evaluation Method] (1) Evaluation of Phosphorus Compound (a) ¹ H-NMR Measurement The compound was dissolved in CDCl ₃ or DMSO, and
Measured using GEMINI-200.

(B) Melting point measurement The compound was placed on a cover glass, and the sample was put on a Yanaco MICRO MELTING.
Measurement was performed at a heating rate of 1 ° C./min using POINT APPARATUS.

(C) Elemental Analysis The phosphorus was analyzed by molybdenum blue colorimetry after wet decomposition of a PET resin chip. Other metals are
After incineration / acid dissolution, the analysis was performed using high-frequency plasma emission analysis and atomic absorption analysis.

(2) Properties of Polyester (a) Intrinsic Viscosity (IV) Polyester was dissolved in a phenol / 1,1,2,2-tetrachloroethane 6/4 (weight ratio) mixed solvent, and the temperature was 30 ° C. Measured at ° C.

(B) Acid value 0.1 g of the polyester polymer was added to benzyl alcohol 10
After dissolving in methanol, 0.1N NaOH in methanol /
It was determined by titration using a solution of benzyl alcohol (= 1/9).

(C) Hue The color of the polyester polymer was determined by using a resin tip obtained by melt polymerization and using a color difference meter (MODEL TC-1500MC- manufactured by Tokyo Denshoku Co., Ltd.).
L value, a value, and b value were measured using 88).

(D) Differential Scanning Calorimetry (DSC) Measurement was performed using a DSC 2920 manufactured by TA Instruments. Put 10.0mg of polyester in an aluminum pan, 50 ℃
The temperature was raised to 280 ° C. at a heating rate of / min, and after reaching 280 ° C., the temperature was maintained for 1 minute, and immediately after that, quenched in liquid nitrogen. Thereafter, the temperature is increased from room temperature by 20 ° C./min.
℃, the crystallization temperature Tc1 and the melting point T
m was determined. After the temperature was maintained at 300 ° C. for 2 minutes, the temperature was lowered at a rate of 10 ° C./minute, and the crystallization temperature Tc2 at the time of temperature decrease was determined. Tc1, Tm, and Tc2 were the respective peak temperatures.

(E) Thermal Stability Parameter (TS) 1 g of PET resin chip ([IV] _i ) was immersed in an inner diameter of about 14 m.
After placing in a glass test tube of m and vacuum drying at 130 ° C. for 12 hours, it was set in a vacuum line and pressure reduction and nitrogen sealing were repeated 5 times or more. Then, 100 mmHg of nitrogen was sealed and sealed, immersed in a 300 ° C. salt bath, and maintained in a molten state for 2 hours. Thereafter, the sample was taken out, frozen, pulverized, and dried in a vacuum, and [IV] _f2 was measured, and determined by the following formula. The formula was quoted from a previous report (Kamiyama et al .: The Society of Rubber Industry, Japan, Vol. 63, No. 8, p. 497, 1990). TS = 0.245 ｛[IV] _f2 ^-1.47 − [IV] _i
^-1.47 ｝

(F) Thermal Oxidation Stability Parameter (TOS) PET resin chips ([IV] _i ) were frozen and pulverized to 20
The powder was smaller than the mesh. This powder is heated at 130 ° C for 12
After vacuum drying for 300 hours, 300 mg of the powder was placed in a glass test tube having an inner diameter of about 8 mm and a length of about 140 mm, and vacuum dried at 70 ° C. for 12 hours. Next, a drying tube containing silica gel was placed on the upper portion of the test tube, and the dried tube was immersed in a 230 ° C. salt bath under a dry air and heated for 15 minutes to measure [IV] _f1 .
TOS was determined as follows using the same formula as that for the above TS. Here, [IV] _i and [IV] _f1 indicate the IV (dl / g) before and after the heating test, respectively.
The freeze-pulverization is performed using a freezer mill (made by Spex, USA, 6
750). After putting about 2 g of resin chip and dedicated impactor in the dedicated cell, set the cell in the device, fill the device with liquid nitrogen and hold for about 10 minutes,
Then, crushing was performed for 5 minutes with RATE10 (the impactor is moved about 20 times per second). TOS = 0.245 ｛[IV] _f1 ^-1.47 − [IV] _i
^-1.47 ｝

(G) Hydrolysis resistance parameter (HS) A PET resin chip (before the test; [IV] _i ) was freeze-pulverized in the same manner as described above to obtain a powder of 20 mesh or less. The powder was vacuum dried at 130 ° C. for 12 hours. The hydrolysis test was performed using a mini color device (Texam Giken Co., Ltd., TypeMC12.EL).
B). 1 g of the above-mentioned powder was put into a special stainless beaker together with 100 ml of pure water, a special stirring blade was further put therein, and a closed system was set.
The mixture was stirred for 6 hours while heating and pressurizing to 30 ° C. The PET after the test was collected by filtration with a glass filter, dried under vacuum, and then measured for IV ([IV] _f2 ), and the hydrolysis resistance parameter (HS) was determined by the following equation. HS = 0.245 ｛[IV] _f2 ^-1.47- [IV] _i
^-1.47 ｝

(3) Film Characteristics (a) Thermal Stability of Film The appearance of the obtained cast film was visually observed and ranked according to the following criteria according to the degree of coloring of the film. A: No coloring. ：: Slightly colored. Δ: Colored. ×: markedly colored.

(B) Presence or absence of Sb particles in the film 40 g of the polyester film was mixed with a mixed solvent of parachlorophenol and tetrachloroethane (weight ratio of 75/25).
And filtered with a membrane filter made of hydrophilic polytetrafluoroethylene having an average pore size of 0.1 μm. After vacuum drying the residue on this membrane filter,
The particles trapped in the filter were observed with a scanning electron microscope, and the presence or absence of the Sb element was confirmed with an energy dispersive X-ray microanalyzer (EMAX 2770, manufactured by Horiba, Ltd.).

(C) Haze Measured using a haze meter (Model TC-H3DP, manufactured by Tokyo Denshoku Industries Co., Ltd.) according to JIS-K7105.

(D) Adhesiveness A hard coat agent having the following composition was applied to the surface of the coating layer of the polyester film using a # 8 wire bar.
After drying for one minute to remove the solvent, 80 w / c with a high pressure mercury lamp
m, an irradiation distance of 15 cm, and a 2 μm hard coat layer under the conditions of 5 m / min. JIS-
Adhesion was determined according to the test method described in 8.5.1. Specifically, 100 grid-shaped cuts that penetrate the coating layer and reach the base film are made using a cutter guide with a gap of 2 mm, and a cellophane adhesive tape (405 # 24 mm width, made by Nichiban) is grid-shaped. Was completely adhered to the cut surface by rubbing with an eraser, and then peeled off vertically, and the adhesion was visually determined by the following formula. In addition, the part which peeled partially in one square was counted as the square which peeled. Adhesiveness (%) = (1−number of peeled squares / 100) ×
100

Example 1 (1) Polymerization of Polyester A mixture of bis (2-hydroxyethyl) terephthalate and an oligomer prepared from a high-purity terephthalic acid and ethylene glycol according to a conventional method was mixed with 13 g of aluminum chloride as a polycondensation catalyst. / L of an ethylene glycol solution with respect to the acid component in the polyester as 0.015 mol% as aluminum atoms and Irganox 1425
10g / (Ciba Specialty Chemicals)
l Add ethylene glycol solution to Irgan
0.02 mol% as ox 1425 was added, and the mixture was stirred at 245 ° C. for 10 minutes under a nitrogen atmosphere at normal pressure. Then, the pressure of the reaction system was gradually lowered while raising the temperature to 275 ° C. over 50 minutes to 13.3 Pa (0.1 Torr), and the polycondensation reaction was further performed at 275 ° C. and 13.3 Pa. The intrinsic viscosity of polyethylene terephthalate is 0.65
The polymerization time (AP) required to reach dl / g was 7
5 minutes. Polyethylene terephthalate obtained by polycondensation was formed into chips according to a conventional method.

The properties of the obtained PET resin were as follows: intrinsic viscosity: 0.65 dl / g, acid value: 1.4 eq / ton, DE
G was 2.1 mol%. The thermal characteristics were as follows: the melting point (Tm) was 257.4 ° C., the rising crystallization temperature (Tc1) was 155.6 ° C., and the falling crystallization temperature (Tc2) was 181.5 ° C.
° C. The hue has an L value of 68.5, an a value of -2.7,
The b value was 5.3.

The thermal stability parameter (TS) of the above PET resin chip was 0.17, the thermal oxidation parameter (TOS) was less than 0.01, the hydrolysis resistance parameter (HS) was 0.05, and The size (SH) was 0.1%.

(2) Preparation of Coating Solution A coating solution for forming a coating layer was prepared according to the following method. A reaction vessel was charged with 95 parts by weight of dimethyl terephthalate, 95 parts by weight of dimethyl isophthalate, 35 parts by weight of ethylene glycol, 145 parts by weight of neopentyl glycol, 0.1 part by weight of zinc acetate and 0.1 part by weight of antimony trioxide. For 3 hours. Next, 6.0 parts by weight of 5-sodium isophthalic acid was added, and the esterification reaction was carried out at 240 ° C. for 1 hour, followed by 2 hours at 250 ° C. under reduced pressure (10 to 0.2 mmHg).
The polycondensation reaction was performed for a long time to obtain a polyester resin having a molecular weight of 19,500 and a softening point of 60 ° C.

6.7 parts by weight of a 30% aqueous dispersion of the obtained polyester resin and a 20% by weight aqueous solution of a self-crosslinking polyurethane resin containing an isocyanate group blocked with sodium bisulfite (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: 40 parts by weight of Elastron H-3), a catalyst for elastron (Cat
64), 47.8 parts by weight of water, and 5 parts by weight of isopropyl alcohol, respectively, and further, colloidal silica particles (Snowtex OL, manufactured by Nissan Chemical Industries, Ltd.) were added in an amount of 5 parts by weight based on the resin solid content. % By weight, and 1% by weight of the anionic surfactant based on the weight of the coating solution, to obtain a coating solution.

(3) Production of coated polyester film The polyethylene terephthalate chips obtained by the above method were dried under reduced pressure (1 Torr) at 135 ° C. for 6 hours, supplied to a twin screw extruder, and melted at about 280 ° C. into a sheet. Extrude,
It was quenched and solidified on a metal roll maintained at a surface temperature of 20 ° C. to obtain an unstretched sheet.

At this time, a stainless filter medium having a filtration particle size (initial filtration efficiency: 95%) of 15 μm was used as a filter medium for removing foreign matters from the molten resin. Next, the unstretched sheet is heated to 100 ° C. by a heated roll group and an infrared heater, and thereafter, 3.5 mm in a longitudinal direction by a roll group having a peripheral speed difference.
The film was stretched twice to obtain a uniaxially oriented PET film.

Thereafter, the coating solution was finely filtered through a felt-type polypropylene filter medium having a filtration particle size (initial filtration efficiency: 95%) of 25 μm, applied to one surface by a reverse roll method, and dried. After the application, the end of the film was subsequently gripped with a clip and led to a hot air zone heated to 130 ° C., and the coating solution was dried and stretched 4.0 times in the width direction.
Further, at 230 ° C. with the film width fixed.
And a 3% transverse relaxation treatment at 200 ° C. at the time of temperature decrease to obtain a 188 μm-thick coated polyester film having a coating layer having a coating amount of 0.01 g / m ² .

The obtained coated polyester film had a haze of 0.7% and an adhesiveness with the acrylate coat layer of 100%. Further, particles containing Sb as a main component were not detected in the polyester film. Further, similarly to Example 1, the darkening of the film was improved as compared with the case where a polyester produced using conventional antimony trioxide as a polycondensation catalyst was used as a film raw material.

(Example 2) (Synthesis example of phosphorus compound) Synthesis of phosphorus compound (phosphorus compound A) represented by the following formula (51)

[0295]

Embedded image

[0296] 1. Sodium (O-ethyl 3,5-di-tert-butyl-4
Synthesis of 50% aqueous sodium hydroxide solution 6.5 g (84 mmol) and methanol 6.1 ml in a mixed solution of diethyl (3,5-di-tert-butyl-4-h)
6.1 ml of a methanol solution of 5 g (14 mmol) of ydroxybenzyl) phosphonate was added, and the mixture was heated and refluxed for 24 hours under a nitrogen atmosphere. After the reaction, 7.33 g of concentrated hydrochloric acid (7
0 mmol), and the precipitate was collected by filtration, washed with isopropanol, and the filtrate was evaporated under reduced pressure. The obtained residue was dissolved in hot isopropanol, the insoluble matter was collected by filtration, and isopropanol was distilled off under reduced pressure.
dium (O-ethyl 3,5-di-tert-butyl-4-hydroxybenzylphos
phonate) 3.4g (69%). When a large amount was synthesized, the molar ratio of each of the above raw materials was adjusted.

Shape: white powder Melting point: 294-202 ° C. (decomposition) ¹ H-NMR (DMSO, δ): 1.078 (3H, t, J = 7 Hz), 1.354 (18H,
s), 2.711 (2H, d), 3.724 (2H, m, J = 7Hz), 6.626 (1H,
s), 6.9665 (2H, s) Elemental analysis (theoretical values in parentheses): Na 6.36% (6.56%), P
9.18% (8.84%)

[0298] 2. O-ethyl 3,5-di-tert-butyl-4-hydrox
Synthesis of ybenzylphosphonic acid (phosphorus compound A) Sodium (O-ethyl 3,5-di-tert-butyl-4-h
ydroxybenzylphosphonate) 1g (2.8mmol) aqueous solution 20ml
1.5 g of concentrated hydrochloric acid was added to the mixture, and the mixture was stirred for 1 hour. Water 1 to the reaction mixture
50 ml was added, and the precipitated crystals were collected by filtration, washed with water, and dried to remove O-et.
hyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonic ac
826 mg (88%) of the id were obtained. When a large amount is synthesized,
The molar ratio of each of the above raw materials was adjusted. Shape: plate-like crystal Melting point: 126-127 ° C. ¹ H-NMR (CDCl ₃ , δ): 1.207 (3H, t, J = 7 Hz), 1.436 (18H,
s), 3.013 (2H, d), 3.888 (2H, m, J = 7Hz.), 7.088 (2H,
s), 7.679-8.275 (1H, br)

(Polymerization of Polyester) A high-purity terephthalic acid and a 2-fold molar amount of ethylene glycol were charged into a polymerization reactor, and triethylamine was added in an amount of 0.3 m with respect to the acid component.
The esterification reaction was conducted for 120 minutes while distilling water out of the system at 245 ° C. under a pressure of 0.25 MPa, and bis (2-hydroxyethyl) terephthalate (BHET) and oligomer having an esterification rate of 95% were added. (Hereinafter, referred to as a BHET mixture). To this BHET mixture, a 2.5 g / l solution of aluminum trisacetylacetonate in ethylene glycol was added to the acid component in the polyester in an amount of 0.01 to 0.01 as aluminum atoms.
5 mol% was added, and 0.04 mol% of a 10 g / l ethylene glycol solution of the phosphorus compound A was added as a phosphorus compound A to the acid component in the polyester, followed by stirring at 245 ° C. for 10 minutes under a normal pressure under a nitrogen atmosphere. . Then 5
The temperature of the reaction system was gradually reduced to 0.1 Torr while raising the temperature to 275 ° C. in 0 minutes, and further increased to 275 ° C.
The polycondensation reaction was performed at 0.1 Torr. The polymerization time (AP) required for the intrinsic viscosity of polyethylene terephthalate to reach 0.65 dl / g was 103 minutes. Polyethylene terephthalate obtained by polycondensation was formed into chips according to a conventional method.

The properties of the obtained PET resin were such that the intrinsic viscosity was 0.65 dl / g, the acid value was 2.0 eq / ton,
G was 2.0 mol%. The thermal characteristics are as follows: the melting point (Tm) is 257.5 ° C., the rising crystallization temperature (Tc1) is 164.1 ° C., and the falling crystallization temperature (Tc2) is 185.4.
° C. The hue has an L value of 68.3, an a value of -1.1,
The b value was 1.9.

The thermal stability parameter (TS) of the above PET resin chip was 0.16, the thermal oxidation parameter (TOS) was less than 0.01, the hydrolysis resistance parameter (HS) was 0.04, and Is (SH) is 0.04%
Met.

A coated polyester film was obtained in the same manner as in Example 1 using the PET resin chips obtained by the above melt polymerization. The resulting coated polyester film is
The haze was 0.7%, and the adhesion to the acrylate coat layer was 100%. Further, particles containing Sb as a main component were not detected in the polyester film. Further, similarly to Example 1, the darkening of the film was improved as compared with the case where the polyester produced using conventional antimony trioxide as the polymerization catalyst was used as the film substrate.

Example 3 (Synthesis example of phosphorus compound) Synthesis of magnesium salt of phosphorus compound (phosphorus compound B) represented by the following formula (52)

[0304]

Embedded image

[0305] 1. Sodium (O-ethyl 3,5-di-tert-butyl-4
Synthesis of 50% aqueous sodium hydroxide solution (6.5 g, 84 mmol) and methanol (6.1 ml) in a mixed solution of diethyl (3,5-di-tert-butyl-4-h)
6.1 ml of a methanol solution of 5 g (14 mmol) of ydroxybenzyl) phosphonate was added, and the mixture was heated and refluxed for 24 hours under a nitrogen atmosphere. After the reaction, 7.33 g of concentrated hydrochloric acid (7
0 mmol), and the precipitate was collected by filtration, washed with isopropanol, and the filtrate was evaporated under reduced pressure. The obtained residue was dissolved in hot isopropanol, the insoluble matter was collected by filtration, and isopropanol was distilled off under reduced pressure.
dium (O-ethyl 3,5-di-tert-butyl-4-hydroxybenzylphos
phonate) 3.4g (69%). When a large amount was synthesized, the molar ratio of each of the above raw materials was adjusted.

Shape: white powder Melting point: 294-202 ° C. (decomposition) ¹ H-NMR (DMSO, δ): 1.078 (3H, t, J = 7 Hz), 1.354 (18H,
s), 2.711 (2H, d), 3.724 (2H, m, J = 7Hz), 6.626 (1H,
s), 6.9665 (2H, s) Elemental analysis (theoretical values in parentheses): Na 6.36% (6.56%), P
9.18% (8.84%)

[0307] 2. Magnesium bis (O-ethyl 3,5-di-tert-
butyl-4-hydroxybenzylphosphonate) (phosphorus compound B)
Synthesis of Sodium (O-ethyl 3,5-di-tert-butyl-4-
Hydroxybenzylphosphonate) 500mg (1.4mmol) aqueous solution
To 4 ml, 1 ml of an aqueous solution of 192 mg (0.75 mmol) of magnesium nitrate hexahydrate was added dropwise. After stirring for 1 hour, the precipitate was collected by filtration, washed with water, and dried to remove magnesium bis (O-ethyl 3,5-di-tert-buty).
359 mg (74%) of l-4-hydroxybenzylphosphonate) was obtained.
When a large amount was synthesized, the molar ratio of each of the above raw materials was adjusted.

Shape: white powder Melting point:> 300 ° C. ¹ H-NMR (DMSO, δ): 1.0820 (6H, t, J = 7 Hz), 1.3558 (36H,
s), 2.8338 (4H, d), 3.8102 (4H, m, J = 7Hz), 6.6328 (2
H, s), 6.9917 (4H, s)

(Polymerization of Polyester) A high-purity terephthalic acid and a 2-fold molar amount of ethylene glycol were charged into a polymerization reactor, and triethylamine was added in an amount of 0.3 m with respect to the acid component.
ol%, and an esterification reaction was carried out for 120 minutes while distilling water out of the system at 245 ° C. under a pressure of 0.25 MPa. (Hereinafter, referred to as a BHET mixture). This BHET
For the mixture, a 2.5 g / l solution of aluminum acetylacetonate in ethylene glycol was added to the acid component in the polyester in an amount of 0.015 as an aluminum atom.
mol%, and the above-mentioned phosphorus compound B was added at 0.02 mol% to the acid component, and 245 at normal pressure under a nitrogen atmosphere.
Stirred at C for 10 minutes. Then take 50 minutes to 27
While raising the temperature to 5 ° C., the pressure of the reaction system was gradually reduced to 0.1
The polycondensation reaction was further performed at 275 ° C. and 0.1 Torr as Torr. The polymerization time (AP) required for the intrinsic viscosity of polyethylene terephthalate to reach 0.65 dl / g was 39 minutes. Polyethylene terephthalate obtained by polycondensation was formed into chips according to a conventional method.

With respect to the characteristics of the obtained PET resin, the intrinsic viscosity was 0.65 dl / g and the acid value was 2.0 eq / to. The thermal characteristics were as follows: melting point (Tm): 256.5 ° C., rising temperature crystallization temperature (Tc1): 165.6 ° C., falling temperature crystallization temperature (Tc2): 185.1 ° C. Hue has L value of 6
6.6, the a value was -2.1, and the b value was 4.5.

The thermal stability parameter (TS) of the above-mentioned PET resin chip was 0.19, the thermal oxidation parameter (TOS) was less than 0.01, and the hydrolysis resistance parameter (HS) was 0.06. .

A coated polyester film was obtained in the same manner as in Example 1 using the PET resin chips obtained by the above melt polymerization. The resulting coated polyester film is
The haze was 0.7%, and the adhesion to the acrylate coat layer was 100%. Further, particles containing Sb as a main component were not detected in the polyester film. Further, similarly to Example 1, the blackening of the film was improved as compared with the case where a polyester produced using conventional antimony trioxide as a polymerization catalyst was used as a film raw material.

Example 4 (Synthesis Example of Aluminum Salt of Phosphorus Compound) O-ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphon
Synthesis of aluminum salt of ate (aluminum salt A)

[0314] 1. Sodium (O-ethyl 3,5-di-tert-butyl-4
Synthesis of 50% aqueous sodium hydroxide solution 6.5 g (84 mmol) and methanol 6.1 ml in a mixed solution of diethyl (3,5-di-tert-butyl-4-h)
6.1 ml of a methanol solution of 5 g (14 mmol) of ydroxybenzyl) phosphonate was added, and the mixture was heated and refluxed for 24 hours under a nitrogen atmosphere. After the reaction, 7.33 g of concentrated hydrochloric acid (7
0 mmol), and the precipitate was collected by filtration, washed with isopropanol, and the filtrate was evaporated under reduced pressure. The obtained residue was dissolved in hot isopropanol, the insoluble matter was collected by filtration, and isopropanol was distilled off under reduced pressure.
dium (O-ethyl 3,5-di-tert-butyl-4-hydroxybenzylphos
phonate) 3.4g (69%). When a large amount was synthesized, the molar ratio of each of the above raw materials was adjusted.

Shape: white powder Melting point: 294-202 ° C. (decomposition) ¹ H-NMR (DMSO, δ): 1.078 (3H, t, J = 7 Hz), 1.354 (18H,
s), 2.711 (2H, d), 3.724 (2H, m, J = 7Hz), 6.626 (1H,
s), 6.9665 (2H, s) Elemental analysis (theoretical values in parentheses): Na 6.36% (6.56%), P
9.18% (8.84%)

[0316] 2. O-ethyl 3,5-di-tert-butyl-4-hydro
Synthesis of aluminum salt of xybenzylphosphonate (aluminum salt A) Sodium (O-ethyl 3,5-di-tert-butyl-4-h
ydroxybenzylphosphonate) 1g (2.8mmol) aqueous solution 7.5m
5 ml of an aqueous solution of 364 mg (0.97 mmol) of aluminum nitrate nonahydrate was added dropwise to l. After stirring for 3 hours, the precipitate was collected by filtration, washed with water,
Dry to O-ethyl 3,5-di-tert-butyl-4-hydroxybenzylp
860 mg of aluminum salt A of hosphonate was obtained. When a large amount was synthesized, the molar ratio of each of the above raw materials was adjusted.

Shape: white powder Melting point: 183-192 ° C

(Polymerization of Polyester) A high-purity terephthalic acid and a 2-fold molar amount of ethylene glycol were charged into a polymerization reactor, and triethylamine was added in an amount of 0.3 m to the acid component.
The esterification reaction was carried out for 120 minutes while distilling water out of the system at 245 ° C. under a pressure of 0.25 MPa, and bis (2-hydroxyethyl) terephthalate (BHET) and oligomer having an esterification rate of 95% were added. (Hereinafter, referred to as a BHET mixture). This BHET
For the mixture, the above-mentioned aluminum salt A was added to the acid component in the polyester in an amount of 0.02 as an aluminum atom
mol% at 245 ° C under normal pressure under nitrogen atmosphere.
Stirred for minutes. Next, the temperature of the reaction system was gradually lowered while raising the temperature to 275 ° C. in 50 minutes, and the pressure was reduced to 0.1 Torr.
Further, a polycondensation reaction was performed at 275 ° C. and 0.1 Torr. Polymerization time required for the intrinsic viscosity of polyethylene terephthalate to reach 0.65 dl / g (A
P) was 98 minutes. Polyethylene terephthalate obtained by polycondensation was formed into chips according to a conventional method.

The properties of the obtained PET resin were such that the intrinsic viscosity was 0.65 dl / g and the acid value was 1.0 eq / ton or less. In addition, the thermal characteristics are such that the melting point (Tm) is 257.1.
° C, the rising temperature crystallization temperature (Tc1) was 160.7 ° C, and the falling temperature crystallization temperature (Tc2) was 185.1 ° C. Hue is L
The value was 64.3, the a value was -1.4, and the b value was 2.3.

The thermal stability parameter (TS) of the above PET resin chip was 0.14, the thermal oxidation parameter (TOS) was 0.01, and the hydrolysis resistance parameter (H
S) was 0.03, and the solution haze (SH) was 0.03%.

A coated polyester film was obtained in the same manner as in Example 1 using the PET resin chip obtained by the above melt polymerization. The resulting coated polyester film is
The haze was 0.7%, and the adhesion to the acrylate coat layer was 100%. Further, particles containing Sb as a main component were not detected in the polyester film. Further, similarly to Example 1, the darkening of the film was improved as compared with the case where a polyester produced using conventional antimony trioxide as a polymerization catalyst was used as a film raw material.

(Comparative Example 1) The procedure was carried out except that the polycondensation catalyst was changed to antimony trioxide, and the amount of antimony trioxide used was 0.05 mol% as antimony atom with respect to the acid component in PET. A coated polyester film was obtained in the same manner as in Example 1. The resulting coated polyester film had a haze of 0.7% and an adhesion to the acrylate coat layer of 100%. Further, particles containing Sb as a main component were detected in the polyester film. Further, darkening was observed in the film as compared with the film of the above example.

(Comparative Example 2) The polycondensation catalyst was changed to antimony trioxide, and the amount of antimony trioxide used was adjusted to 0.05 mol% as an antimony atom with respect to the acid component in PET. A coated polyester film was obtained in the same manner as in Example 1 except that silica particles having a particle size of 1.4 μm were added to a concentration of 300 ppm. The resulting coated polyester film had an adhesion to the acrylate coat layer of 100%, but had a haze of 2.8% and was inferior in transparency. Further, particles containing Sb as a main component were detected in the polyester film. Further, darkening was observed in the film as compared with the film of the above example.

(Comparative Example 3) A polyester film was obtained in the same manner as in Comparative Example 1 except that no coating layer was provided. The resulting polyester film has a haze of 0.5
%, But the adhesion to the acrylate coat layer was inferior to 6%. Further, particles containing Sb as a main component were detected in the polyester film. Further, darkening was observed in the film as compared with the film of the above example.

[0325]

The optical coating film of the present invention is a polyester having excellent heat stability, which comprises a component other than an antimony compound or a germanium compound as a main component and is produced using a novel catalyst having excellent catalytic activity. Is the main constituent of the film base, and the haze value of the film is in a specific range, so that the film has excellent effects of excellent transparency and color tone and no foreign matter due to antimony. Therefore, the optical coating film of the present invention can be used for, for example, a prism lens sheet used for a liquid crystal display, a hard coat film, an antireflection film, a diffusion plate, a shatterproof film for a CRT, and a front plate used for a plasma display. It can be used as a base film for an optical member such as an infrared absorption filter, a touch panel or a transparent conductive film for electroluminescence.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Shoichi Katamai, 2-1-1 Katata, Otsu-shi, Shiga Inside Toyobo Co., Ltd. Research Laboratory (72) Takahiro Nakajima 2-1-1 Katata, Otsu-shi, Shiga No. 1 F-term in Toyobo Co., Ltd. Research Laboratory (reference) 4F100 AA20 AK01B AK41A AK42 BA02 BA07 BA15 DE01B EJ38A JL08 JL08A JN01 JN01A YY00A 4J029 AA01 AA03 AB07 AE03 BA03 CB06A JB191 JCJ1J551

Claims (14)

[Claims] A coating film comprising a biaxially stretched polyester film as a base material and a coating layer mainly composed of a polymer resin and particles provided on at least one surface of the base material, wherein the polyester film is made of aluminum and And / or a polyester coated with a polycondensation catalyst containing the compound and a phenolic compound as a main component, and the haze of the film is 2.0% or less. 2. A coating film comprising a biaxially stretched polyester film as a base material and a coating layer mainly composed of a polymer resin and particles provided on at least one surface of the base material, wherein the polyester film is made of aluminum and And / or a polyester film polymerized using a polycondensation catalyst containing the compound and a phosphorus compound as a main component, and a haze of the film is 2.0% or less. 3. The coating film for optical use according to claim 1, wherein the polycondensation catalyst further contains a phosphorus compound. 4. The phosphorus compound is a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound,
4. A compound selected from the group consisting of a phosphonous acid compound, a phosphinic acid compound, and a phosphine compound.
The coated film for optics according to claim. 5. The phosphorus compound is one or two or more phosphonic acid compounds.
The optical coating film according to any one of the above. 6. The optical covering film according to claim 2, wherein the phosphorus compound is a compound having an aromatic ring structure. 7. The phosphorus compound represented by the following general formula (1)
The optical coating film according to any one of claims 2 to 6, wherein the coating film is one or more selected from the group consisting of compounds represented by (3). Embedded image Embedded image Embedded image (In the formulas (1) to (3), R ¹ , R ⁴ , R ⁵ , and R ⁶ each independently include hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group. Represents a hydrocarbon group having 1 to 50 carbon atoms, R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. However, the hydrocarbon group may contain an alicyclic structure or an aromatic ring structure.) 8. R ¹ , R ⁴ , R in the formulas (1) to (3)
^5, optical coating film according to claim 7, wherein the R ⁶ is a group having an aromatic ring structure. 9. The optical covering film according to claim 2, wherein the phosphorus compound has a phenol moiety in the same molecule. 10. The phosphorous compound having a phenol moiety in the same molecule is one or more selected from the group consisting of compounds represented by the following general formulas (4) to (6). The optical coating film according to claim 9. Embedded image Embedded image Embedded image (In the formulas (4) to (6), R ¹ is a hydrocarbon group having 1 to 50 carbon atoms including a phenol moiety, a hydroxyl group or a halogen group or an alkoxyl group or an amino group and a carbon atom having 1 to 50 carbon atoms including a phenol moiety. R ⁴ , R ⁵ and R ⁶ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a halogen group, or a hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl group or an amino group; R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group, provided that the hydrocarbon group has a branched structure. Or an alicyclic structure or an aromatic ring structure. The terminals of R ² and R ⁴ may be bonded to each other.) 11. A coating film comprising a biaxially stretched polyester film as a base material and a coating layer mainly composed of a polymer resin and particles provided on at least one surface of the base material, wherein the polyester film is a phosphorus compound An optically coated film comprising, as a main component, a polyester polymerized by using a polycondensation catalyst containing an aluminum salt, and having a haze of 2.0% or less. 12. A coating film comprising a biaxially stretched polyester film as a base material and a coating layer mainly composed of a polymer resin and particles provided on at least one surface of the base material. Polyester polymerized using a polycondensation catalyst containing at least one selected from compounds represented by formula (7) as a main component, and a film having a haze of 2.0
% Or less. Embedded image (In the formula (7), R ¹ and R ² each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R ³ represents hydrogen and 1 carbon atom.
Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrocarbon group of 50 to 50, a hydroxyl group or an alkoxyl group. R ⁴ is hydrogen,
It represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group or carbonyl. l represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and (l + m) is 3. n represents an integer of 1 or more. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure. ) 13. The optical covering film according to claim 1, wherein the base film does not substantially contain particles. 14. The optical coating film according to claim 1, wherein an adhesive property when a curable acrylic coating layer is provided on the coating layer is 85% or more.