JP2016186006A - Biaxially oriented polyester film and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a biaxially oriented polyester film excellent in light shielding properties, concealing properties, flame retardancy and continuous productivity and to provide a method for producing the same.SOLUTION: There is provided a biaxially oriented polyester film satisfying the following (1) to (5). (1) The film contains carbon black particles in a polyester resin composition constituting a film and the content of the carbon black particles is 0.01 to 10 wt.%. (2) The film substantially contains no dispersant in a polyester resin composition constituting a film. (3) The film contains a phosphorus element in a polyester resin composition constituting a film and the content of the phosphorus element is 0.01 to 5 wt.%. (4) The optical density unevenness is 0.10% or more and 50% or less. (5) The flame retardancy is one of VTM-0 and VTM-1.SELECTED DRAWING: None

Description

  The present invention relates to a biaxially oriented polyester film having excellent light shielding properties, concealing properties, and flame retardancy, and excellent continuous productivity, and a method for producing the same.

  Polyester (especially polyethylene terephthalate, polyethylene 2,6-naphthalene dicarboxylate, etc.) resins are excellent in mechanical properties, thermal properties, chemical resistance, electrical properties, and moldability, and are used in various applications. Polyester films made from polyester, especially biaxially oriented polyester films, are used for electrical insulation materials, building materials, and sensations used in optical devices, solar battery backsheets, and motors because of their mechanical and electrical properties. It is used as various industrial materials such as thermal transfer applications and process paper.

  Of these uses, the electrically insulating material is required to have flame retardancy. In addition, in optical devices, particularly for cellular phones, cameras, and video cameras, in addition to miniaturization and weight reduction of devices, flame retardant properties have been required for the members constituting them.

  Conventionally, metals have been used for light shielding members of optical devices such as shutters and diaphragms, but synthetic resin films have been increasingly used with the reduction in size and weight. As a method for imparting light-shielding properties to a synthetic resin film, it is common to add carbon black to a polyester film. For example, a polyester film composed of a polyester resin composition in which carbon black particles are added to a polyester resin having an intrinsic viscosity [η] of 0.5 to 0.85 dl / g has been devised (Patent Document 1).

  In addition, among the electrically insulating materials, for solar cell backsheet applications, in recent years, it has been desired that the wiring to the power generation element and the like cannot be seen from the outside from the viewpoint of design as well as flame retardancy. . Therefore, not only flame retardancy but also high concealability is required for the solar cell backsheet. In general, it is effective to blacken a polyester film in order to improve the concealability of the film, and it has been devised to use a polyester film to which a carbon black is added as a black pigment for a solar battery backsheet. (Patent Documents 2 and 3).

JP 2008-56771 A International Publication No. 2012/121076 Pamphlet JP2011-119651A

  However, although the polyester films described in Patent Documents 1 to 3 are excellent in light shielding properties and concealment properties, the flame retardancy of the polyester films is not sufficient.

  In order to increase the flame retardancy of the polyester film described in Patent Documents 1 to 3, the present inventors add a conventionally known flame retardant to the polyester resin composition constituting the film. A study was conducted. As a result, the polyester films described in Patent Documents 1 to 3 can obtain a certain effect of improving flame retardancy by adding and containing a flame retardant, but a large amount is necessary to obtain sufficient flame retardancy. It was found that there was a problem that the addition of a large amount of flame retardant, and when such a large amount of flame retardant was added, the film formability deteriorated and the continuous productivity deteriorated. .

  In addition, when a large amount of flame retardant or carbon black particles is added to the polyester resin composition constituting the film, a conventionally known dispersant may be added to prevent aggregation of the flame retardant or carbon black particles. Although necessary, it has been found that the addition of a dispersant has the problem that flame retardancy deteriorates.

  Therefore, the present invention aims to solve these problems, and to provide a biaxially oriented polyester film excellent in light shielding properties, concealing properties, flame retardancy, and excellent in continuous productivity and a method for producing the same. is there.

In order to solve the above problems, the present invention has the following configuration. That is,
[I] A biaxially oriented polyester film satisfying the following (1) to (5).
(1) Carbon black particles are contained in the polyester resin composition constituting the film, and the content thereof is 0.01 to 10% by weight.
(2) The polyester resin composition constituting the film does not substantially contain a dispersant.
(3) The phosphorus resin is contained in the polyester resin composition constituting the film, and the content thereof is 0.01 to 5% by weight.
(4) Optical density spots are 0.10% or more and 50% or less.
(5) The flame retardancy calculated | required by the following method must be either VTM-0 or VTM-1.
<Flame retardancy evaluation method>
(I) Sample preparation A measurement sample (biaxially oriented polyester film) is cut into 20 cm x 5 cm.
Sample A left at 23 ° C. and 50% RH for 48 hours is sample A, temperature 70 ° C., left for 168 hours, then cooled to 23 ° C. and 20% RH or less for 4 hours as sample B, and 5 samples each. Prepare as a set.

(Ii) Measuring method A line is drawn in a direction parallel to the short side at 125 mm from the short side of each sample, and wound around a rod having a diameter of 12.7 mm so that the short side is in the vertical direction. In the 75mm part above the 125mm mark, stick with pressure sensitive tape and pull out the stick. The top of the sample is closed during the test so that there is no chimney effect. Next, each sample is set vertically, and absorbent cotton is placed 300 mm below. Using a Bunsen burner with a diameter of 9.5 mm and a flame length of 20 mm as a heating source so that the burner tube is located 10 mm from the lower end of the sample, a blue flame is indirectly flamed at the center of the lower end of the sample for 3 seconds. Measure the combustion time (t1) after the flame release. Then, as soon as the flame has disappeared, the indirect flame is again emitted for 3 seconds, and the combustion time (t2) and the fire type time (t3) after the second flame-off are measured. In addition, at the time of the first and second flame contact, observation is also made as to whether there was combustion that burned up to the 125 mm mark, and whether there was a burning fallen object that would ignite absorbent cotton. For sample A and sample B, the above measurement is performed for each set (five pieces).

(Iii) Evaluation of flame retardancy Based on the following criteria, flame retardancy is evaluated as follows.
VTM-0: Satisfy any of the criteria (A), (I), (U), (E), (O).
VTM-1: Judgment criteria (A '), (I'), (U '), (E), (O) are all satisfied.
VTM-2: Satisfy any of the criteria (A '), (I'), (U '), (E).
No VTM: Does not correspond to any of VTM-0, VTM-1, and VTM-2.
Criteria (A): In all samples, the longer combustion time (t1) after the first flame release or the second combustion time (t2) after the second flame release is 10 seconds or less.
Judgment criteria (A '): In all samples, the longer combustion time after the first flame release (t1) or the second combustion time after the flame release (t2) is 30 seconds or less.
Judgment criteria (I): The total of the burning time after flame removal per set (the total of the burning time after flame removal of five samples (t1 + t2)) is 50 seconds or less for both sample A and sample B.
Criteria (I '): The total burning time after flame removal per set (the total burning time after flame removal (t1 + t2) of 5 samples) is less than 250 seconds for both sample A and sample B .
Judgment standard (U): In all samples, the sum of the combustion time (t2) and the ignition time (t3) after the second flame-off is 30 seconds or less.
Judgment criteria (U '): In all samples, the sum of the combustion time (t2) and the ignition time (t3) after the second flame-off is 60 seconds or less.
Judgment criteria (e): In all samples, combustion or fire type does not reach the 125 mm mark.
Judgment criteria (O): In all samples, absorbent cotton is not ignited by the fall of the burned sample.
[II] The biaxially oriented polyester film according to [I], wherein the polyester resin composition constituting the film contains an antimony element, and the content thereof is 0.005 to 0.1% by weight.
[III] The biaxially oriented polyester film according to [I] or [II] obtained by adding a phosphate ester.
[IV] The biaxially oriented polyester film according to any one of [I] to [III], wherein the film has a thickness of 10 μm to 300 μm.
[V] The biaxially oriented polyester film according to any one of [I] to [IV], wherein the degree of uneven distribution of the carbon black particles contained in the polyester resin composition constituting the film is 0.10% or more and 20% or less. .
[VI] The biaxially oriented polyester film according to any one of [I] to [V], which is used in any of a light shielding member of an optical device and a solar battery backsheet.
[VII] A method for producing a biaxially oriented polyester film comprising a step of melt-kneading a polyester resin composition and carbon black particles using a melt-kneading extruder, wherein the screw of the melt-kneading extruder in the melt-kneading step When the rotational speed is N ₁ (rpm), the screw rotational speed N ₁ is given a fluctuation of 0.01% or more and 10% or less, according to any one of [I] to [VI] A method for producing a biaxially oriented polyester film.
[VIII] The method for producing a biaxially oriented polyester film according to [VII], comprising the steps of satisfying the following (6) to (7).
(6) Carbon black-containing polyester resin composition master (b) obtained by melting and kneading a polyester resin composition (a) having an intrinsic viscosity [η] of 0.70 dl / g or more and 0.90 dl / g or less and carbon black particles ) And a polyester resin composition master containing a phosphate ester obtained by melting and kneading a polyester resin composition (a) having an intrinsic viscosity [η] of 0.70 dl / g to 0.90 dl / g and a phosphate ester ( c) including a step of melt kneading and extruding.
(7) The screw rotation speed of the melt-kneading extruder in the step of melt-kneading the carbon black-containing polyester resin composition master (b) and the phosphate ester-containing polyester resin composition master (c) was N ₂ (rpm). When giving the screw rotation speed N ₂ a fluctuation of 0.01% or more and 10% or less.
[IX] When producing the carbon black-containing polyester resin composition master (b), the intrinsic viscosity of the polyester resin of the polyester resin composition (a) before kneading and the resulting carbon black-containing polyester resin composition master ( The method for producing a biaxially oriented polyester film according to [VII] or [VIII], wherein the intrinsic viscosity of the polyester resin of b) satisfies the following formula (8-1):
(8-1) 0.75 ≦ [η] b / [η] a ≦ 0.90
[Η] a: Intrinsic viscosity (dl / g) of the polyester resin of the polyester resin composition (a) of 0.7 dl / g or more
[Η] b: Intrinsic viscosity (dl / g) of the polyester resin of the carbon black-containing polyester resin composition master (b)
[X] When producing the phosphoric ester-containing polyester resin composition master (c), the intrinsic viscosity of the polyester resin of the polyester resin composition (a) before kneading and the resulting phosphoric ester-containing polyester resin composition The method for producing a biaxially oriented polyester film according to [VIII], wherein the intrinsic viscosity of the polyester resin of the master (c) satisfies the following formula (9-1).
(9-1) 0.75 ≦ [η] c / [η] a ≦ 0.95
[Η] a: Intrinsic viscosity (dl / g) of the polyester resin of the polyester resin composition (a) of 0.7 dl / g or more
[Η] c: Intrinsic viscosity (dl / g) of polyester resin of phosphoric ester-containing polyester resin composition master (c)

  According to the present invention, it is possible to provide a biaxially oriented polyester film that satisfies high light-shielding properties, concealability, and flame retardancy, and is excellent in continuous productivity. Furthermore, by using such a film, it is possible to provide a light shielding member of an optical device or a solar battery back sheet that has high light shielding properties, concealment properties, and flame retardancy.

  The polyester resin composition constituting the biaxially oriented polyester film of the present invention contains carbon black particles in the polyester resin composition, and the content thereof is 0.01 to 10% by weight. It is preferable that the content rate of the polyester resin in the said polyester resin composition is 80 weight% or more with respect to the whole resin composition which comprises a film, More preferably, it is 85 weight% or more. By setting the content of the polyester resin in the above range, the mechanical properties of the film can be improved.

  The polyester constituting the polyester film in the present invention is a polymer obtained by reacting a dicarboxylic acid component and a diol component and having an ester bond as a main bond chain of the main chain.

  Examples of the dicarboxylic acid component constituting the polyester include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimer acid, eicosandioic acid, pimelic acid, azelaic acid, methylmalon. Aliphatic dicarboxylic acids such as acid, ethylmalonic acid and the like, adamantane dicarboxylic acid, norbornene dicarboxylic acid, isosorbide, cyclohexanedicarboxylic acid, decalin dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4 -Naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenylether dicarboxylic acid, 5-sodium Sulfoiso Examples include dicarboxylic acids such as taric acid, phenylendanedicarboxylic acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, aromatic dicarboxylic acid such as 9,9′-bis (4-carboxyphenyl) fluorenic acid, or ester derivatives thereof. It is not limited.

  Examples of the diol component constituting the polyester include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, and 1,3-butanediol. Aliphatic diols such as cyclohexanedimethanol, spiroglycol and isosorbide, bisphenol A, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 9,9′-bis (4 -Hydroxyphenyl) fluorene, diols such as aromatic diols, and a series of a plurality of the above-mentioned diols are listed as examples, but not limited thereto.

  Moreover, as a polyester used for this invention, a polyethylene terephthalate and a polyethylene naphthalate are preferable from a viewpoint of a mechanical characteristic, an electrical property, durability, and productivity.

  The biaxially oriented polyester film of the present invention needs to contain 0.01% by weight or more and 10% by weight or less of carbon black particles with respect to the entire polyester resin composition constituting the film. When the content of the carbon black particles is less than 0.01% by weight, the light shielding property is not sufficient. On the other hand, when the content of the carbon black particles exceeds 10% by weight, aggregates are generated due to deterioration of dispersibility of the carbon black particles, flame retardancy is deteriorated, and productivity is deteriorated. A more preferred lower limit is 0.5% by weight or more, and a still more preferred lower limit is 1.0% by weight. Moreover, as a more preferable upper limit, it is 5 weight% or less, More preferably, it is 3 weight% or less.

  The biaxially oriented polyester film of the present invention is required to have an optical density unevenness of 0.10% to 50%. The optical density spots are obtained by a measurement method described later. The optical density unevenness becomes large when the uneven distribution of the carbon black particles contained in the polyester resin composition constituting the film is large or when the crystallinity degree of the polyester resin constituting the film is large. When the optical density spot is in the above range, the flame retardancy is remarkably improved. On the other hand, when the optical density spot exceeds 50%, the appearance is deteriorated. The mechanism by which this effect is obtained is not limited to any theory, but the inventors presume as follows. Films with small optical density spots have uniform carbon black particles in the polyester resin composition constituting the film, and the degree of crystallinity is uniform, so that when the film burns, the combustion is uniform. As a result, the combustion time becomes longer. On the other hand, a film having an optical density unevenness in the above range has a problem that the polyester film combusts because the carbon black particles are unevenly distributed in the polyester resin composition constituting the film or the crystallinity of the film exists. It can be generated and stopped locally, and it is considered that it exhibits excellent flame retardancy. The optical density spots are more preferably 0.2% or more and 30% or less, and further preferably 0.3% or more and 25% or less.

  In the biaxially oriented polyester film of the present invention, the degree of uneven distribution of carbon black particles contained in the polyester resin composition constituting the film is preferably 0.10% or more and 20% or less. The uneven distribution of the carbon black particles is obtained by a measurement method described later. Rather than disperse | distributing the carbon black particle contained in the polyester resin composition which comprises a film uniformly, a flame retardance improves greatly by containing unevenly so that an uneven distribution degree may become said range. If the degree of uneven distribution of the carbon black particles is less than 0.10%, the flame retardancy improving effect may not be sufficiently obtained. On the other hand, when the uneven distribution degree of the carbon black particles exceeds 20%, not only the continuous productivity is deteriorated but also the flame retardancy may be lowered. The uneven distribution degree of the carbon black particles is more preferably 0.2% or more and 10% or less, and further preferably 0.3% or more and 8% or less. The method of setting the uneven distribution degree of the carbon black particles contained in the polyester resin composition constituting the film in the above range is not particularly limited. For example, (i) the carbon black particles and the polyester resin composition, A method of fluctuating the screw rotation speed of the melt kneader when carbon black is dispersed in the polyester resin composition by melt kneading using a melt kneader; (ii) carbon black particles and the polyester resin composition When the melt is kneaded using a melt kneader to disperse the carbon black in the polyester resin composition, the viscosity of the polyester resin composition used for melt kneading is exemplified to be in a specific range. The methods (i) and (ii) will be described in detail later.

  The polyester resin composition constituting the biaxially oriented polyester film of the present invention contains a phosphorus element in the polyester resin composition, and the content thereof is 0.01 to 5% by weight.

  In general, it is widely known to add a flame retardant in order to improve the flame retardancy of a resin typified by a polyester resin. There are various conventionally known flame retardants. For example, chlorine flame retardants, bromine flame retardants, inorganic flame retardants, nitrogen flame retardants, phosphorus flame retardants, silicone compounds, ammonium polyphosphate flame retardants, metal oxidation Things.

  As for the flame retardant, examples of the chlorinated flame retardant include chlorinated paraffin, chlorinated polyethylene, tetrachlorophthalic anhydride, and chlorendic acid. Brominated flame retardants include bromine-containing polyol, decabromodiphenyl oxide, ethylene glycose bis (pentabromophenyl), ethylene bispentabromophenol, tribromophenol, hexabromobenzene, tetradecabromodiphenoxybenzene, tetrabromobisphenol A (TBBA), TBBA / epoxy oligomer, TBBA / carbonate oligomer, tribromophenyl allyl ether, hexabromocyclododecane, ethylenebistetrabromophthalimide, brominated polystyrene, decabromophenyl oxide. Examples of the inorganic flame retardant include magnesium hydroxide, aluminum hydroxide, and antimony oxide. Examples of the antimony oxide include antimony trioxide and antimony pentoxide. Examples of nitrogen-based flame retardants include melamine compounds, guanidine compounds, and triazine compounds. Phosphorus flame retardants include phosphoric acid esters, ammonium polyphosphate, and the like, such as triphenyl phosphate, tricresyl phosphate, resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), resorcinol N bis (di-2). , 6-Xylyl) phosphate, phosphoric acid amide, red phosphorus, polyphosphate, phosphazene compound, ethylenediamine phosphate compound, triazine compound. Silicone compounds include high molecular weight silicone oils and silicone elastomers. Among the flame retardants, halogen-based flame retardants such as chlorine-based flame retardants and bromine-based flame retardants have a problem of environmental impact. Therefore, it is preferable to use a phosphorus flame retardant in the biaxially oriented polyester film of the present invention.

  The flame retardant as described above can improve the flame retardancy by adding it to the film composition. On the other hand, if a flame retardant is added and contained, the moldability of the resin and the mechanical strength decrease. There are problems such as an increase in surface defects due to bleed-out of additives. In particular, in a biaxially oriented polyester film including a step of biaxially orienting a film composed of a polyester resin composition containing carbon black particles at a high concentration, when a large amount of the above flame retardant is added, Film breakage during film formation is likely to occur, and mechanical strength is likely to decrease.

  In the present invention, by applying a method for producing a biaxially oriented polyester film, which will be described later, to exhibit the excellent flame retardancy with an addition amount that is extremely smaller than the addition amount of a conventional flame retardant. I found.

  The biaxially oriented polyester film of the present invention needs to contain 0.01% by weight or more and 5% by weight or less of phosphorus element with respect to the entire polyester resin composition constituting the film. If the phosphorus element content is less than 0.01% by weight, the flame retardancy is not sufficient. On the other hand, when the content of the phosphorus element exceeds 5% by weight, film breakage during film formation tends to occur, mechanical strength decreases easily, and formability and continuous productivity deteriorate. A more preferred lower limit is 0.5% by weight or more, and a still more preferred lower limit is 1.0% by weight. Moreover, as a more preferable upper limit, it is 4.0 weight% or less, More preferably, it is 3.0 weight% or less. As a method for setting the phosphorus element content within the above range, a phosphorus flame retardant may be added and contained. It is preferable to use a phosphoric ester as the phosphorus-based flame retardant because flame retardancy with at least a high content of phosphorus element can be imparted.

  The biaxially oriented polyester film of the present invention contains an antimony element in the polyester resin composition constituting the film, and the content is preferably 0.005 wt% or more and 0.1 wt% or less. . When the amount of the antimony element contained in the polyester resin composition constituting the film is within the above range, the effect of improving flame retardancy by adding and containing a phosphorus-based flame retardant can be dramatically improved. If the content of the antimony element is less than 0.005% by weight, the effect of improving the flame retardancy due to the use of the phosphorus flame retardant may not be sufficient. On the other hand, when the content of the antimony element exceeds 0.1% by weight, film breakage during film formation is likely to occur, mechanical strength is likely to be reduced, and moldability and continuous productivity may be deteriorated. The method of setting the content of the antimony element in the above range is not particularly limited. For example, a polyester resin composition obtained by melt-kneading an antimony trioxide that is an inorganic flame retardant and a polyester resin is used. And a method in which antimony trioxide or the like previously added at the time of polymerization of the polyester resin is used as a polyester resin composition constituting the film. It is a preferable embodiment in terms of productivity to use a polyester resin composition to which the antimony trioxide is added at the time of polymerization of the polyester resin as a polyester resin composition constituting the film.

  The biaxially oriented polyester film of the present invention needs to contain substantially no dispersant in the polyester resin composition constituting the film.

  In the present invention, “substantially does not contain” means that the content is less than 0.005% by weight. In the present invention, the content of the carbon black particles, the flame retardant, and the dispersant in the polyester resin composition constituting the polyester film is the amount added to the polyester resin composition constituting the polyester film. Further, in the present invention, the flame retardant represents a compound or resin having a function of improving the flame retardancy of the resin (increasing the limit oxygen index value (LOI value) of the resin) by being added to the resin.

  Dispersants that are generally added to improve the dispersibility of carbon black particles and flame retardants include metal soaps such as stearic acid, zinc stearate, magnesium stearate, aluminum stearate, calcium stearate, ethylene bis Examples thereof include hydrocarbon waxes such as amide, polyethylene wax and polypropylene wax, and derivatives thereof, and waxes composed of acid-modified products and hydroxyl-modified products. For example, metallocene polyolefin wax polymerized with a metallocene compound catalyst is used.

  The metallocene compound is a general term for compounds in which at least one ligand having a cyclopentadienyl skeleton is coordinated to a tetravalent transition metal such as titanium, zirconium, nickel, palladium, hafnium, niobium, platinum, and the like. As a ligand having a cyclopentadienyl skeleton, a cyclopentadienyl group; a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an n- or i-propylcyclopentadienyl group, n-, i-, sec -, Tert-butylcyclopentadienyl group, hexylcyclopentadienyl group, alkyl monosubstituted cyclopentadienyl group such as octylcyclopentadienyl group; dimethylcyclopentadienyl group, methylethylcyclopentadienyl group, Alkyl disubstituted cyclopentadienyl groups such as methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylhexylcyclopentadienyl group, ethylbutylcyclopentadienyl group, ethylhexylcyclopentadienyl group; trimethyl Cyclopentadie Alkyl group, tetramethylcyclopentadienyl group, alkyl polysubstituted cyclopentadienyl group such as pentamethylcyclopentadienyl group; cycloalkyl substituted cyclopentadienyl group such as methylcyclohexylcyclopentadienyl group; indenyl group, Examples include 4,5,6,7-tetrahydroindenyl group and fluorenyl group.

  Examples of ligands other than the ligand having a cyclopentadienyl skeleton include monovalent anion ligands such as base and bromine, divalent anion chelate ligands, hydrocarbon groups, alkoxides, amides, arylamides, aryloxides, phosphides, Examples include aryl phosphide, silyl group, and substituted silyl group. Examples of the hydrocarbon group include those having about 1 to 12 carbon atoms. For example, methyl group, ethyl group, propyl group, butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, hebutyl group, octyl group Alkyl groups such as nonyl group, decyl group, cecil group and 2-ethylhexyl group; cycloalkyl groups such as cyclohexyl group and cyclopentyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and neophyll group; Nonylphenyl group etc. are mentioned.

  Specific examples of metallocene compounds coordinated with a ligand having a cyclopentadienyl skeleton include cyclopentadienyl titanium tris (dimethylamide), methylcyclopentadienyl titanium tris (dimethylamide), and bis (cyclopentadiene). Enyl) titanium dichloride, dimethylsilyltetramethylcyclopentadienyl-tert-butylamidozirconium dichloride, dimethylsilyltetramethylcyclopentadienyl-pn-butylphenylamidozirconium dichloride, methylphenylsilyltetramethylcyclopentadienyl- tert-Butylamide Hafnium Dichloride, Dimethylsilyltetramethylcyclopentadienyl-tert-Butylamide Hafnium Dichloride, Indenyl Titanium Tris Dimethylamide), indenyl titanium tris (diethylamide), indenyl titanium bis (di -n- butylamide), indenyl titanium bis (di -n- propyl amide) and the like.

  The dispersant as described above can improve the dispersibility of the carbon black particles and the flame retardant contained in the resin composition, but greatly reduces the flame retardancy of the resin. Therefore, the polyester film which does not substantially contain the above dispersant in the polyester resin composition constituting the film is particularly excellent in flame retardancy. In addition, even if it adds and contains the compound illustrated as said dispersing agent in the polyester resin composition which comprises a film for the objectives other than improving a dispersibility, it becomes a factor which reduces the flame retardance of a film. . Therefore, it is preferable that the dispersant exemplified above is not substantially contained in the polyester resin composition constituting the film, even for purposes other than improving the dispersibility.

  The biaxially oriented polyester film of the present invention preferably has an optical density of 2.5 or more from the viewpoint of obtaining excellent light shielding properties and concealing properties. Preferably, it is 4 or more, more preferably 5 or more. The optical density can be adjusted by the thickness of the film and the content of carbon black particles in the polyester resin composition constituting the film. When the optical density is less than 2.0, the light shielding property and the concealing property may be insufficient, and the optical function may not be exhibited. The upper limit of the optical density is not particularly limited, but in order to obtain a film having an optical density of more than 6, it is necessary to increase the film thickness or to increase the content of carbon black particles, and the film forming property is deteriorated. There is. Therefore, the optical density is preferably 6 or less.

  The thickness of the biaxially oriented polyester film of the present invention is preferably in the range of 10 μm to 300 μm. A more preferable lower limit is 20 μm or more. Moreover, as a more preferable upper limit, it is 200 micrometers or less, More preferably, it is 150 micrometers or less. When the thickness of the polyester film is in the above-described range, it is preferable from the viewpoint that all of the light shielding property, concealing property, flame retardancy, and continuous productivity are improved.

  The biaxially oriented polyester film of the present invention is measured by the following method (according to the flame retardancy test (UL94VTM combustion test) of the American Insurer Safety Testing Laboratory (underwriters Laboratories Inc.)). It is necessary that the flame retardancy to be achieved is either VTM-0 or VTM-1. By having the above flame retardancy, it can be suitably used for a light shielding member of an optical device or a concealing member of a solar battery backsheet.

<Flame retardancy evaluation method>
(I) Sample preparation A measurement sample (biaxially oriented polyester film) is cut into 20 cm x 5 cm.
Sample A left at 23 ° C. and 50% RH for 48 hours is sample A, temperature 70 ° C., left for 168 hours, then cooled to 23 ° C. and 20% RH or less for 4 hours as sample B, and 5 samples each. Prepare as a set.

(Ii) Measuring method A line is drawn in a direction parallel to the short side at 125 mm from the short side of each sample, and wound around a rod having a diameter of 12.7 mm so that the short side is in the vertical direction. In the 75mm part above the 125mm mark, stick with pressure sensitive tape and pull out the stick. The top of the sample is closed during the test so that there is no chimney effect. Next, each sample is set vertically, and absorbent cotton is placed 300 mm below. Using a Bunsen burner with a diameter of 9.5 mm and a flame length of 20 mm as a heating source so that the burner tube is located 10 mm from the lower end of the sample, a blue flame is indirectly flamed at the center of the lower end of the sample for 3 seconds. Measure the combustion time (t1) after the flame release. Then, as soon as the flame has disappeared, the indirect flame is again emitted for 3 seconds, and the combustion time (t2) and the fire type time (t3) after the second flame-off are measured. In addition, at the time of the first and second flame contact, observation is also made as to whether there was combustion that burned up to the 125 mm mark, and whether there was a burning fallen object that would ignite absorbent cotton. For sample A and sample B, the above measurement is performed for each set (five pieces).

(Iii) Evaluation of flame retardancy Based on the following criteria, flame retardancy is evaluated as follows.
VTM-0: Satisfy any of the criteria (A), (I), (U), (E), (O).
VTM-1: Judgment criteria (A '), (I'), (U '), (E), (O) are all satisfied.
VTM-2: Satisfy any of the criteria (A '), (I'), (U '), (E).
No VTM: Does not correspond to any of VTM-0, VTM-1, and VTM-2.
Criteria (A): In all samples, the longer combustion time (t1) after the first flame release or the second combustion time (t2) after the second flame release is 10 seconds or less.
Judgment criteria (A '): In all samples, the longer combustion time after the first flame release (t1) or the second combustion time after the flame release (t2) is 30 seconds or less.
Judgment criteria (I): The total of the burning time after flame removal per set (the total of the burning time after flame removal of five samples (t1 + t2)) is 50 seconds or less for both sample A and sample B.
Criteria (I '): The total burning time after flame removal per set (the total burning time after flame removal (t1 + t2) of 5 samples) is less than 250 seconds for both sample A and sample B .
Judgment standard (U): In all samples, the sum of the combustion time (t2) and the ignition time (t3) after the second flame-off is 30 seconds or less.
Judgment criteria (U '): In all samples, the sum of the combustion time (t2) and the ignition time (t3) after the second flame-off is 60 seconds or less.
Judgment criteria (e): In all samples, combustion or fire type does not reach the 125 mm mark.
Judgment criteria (O): In all samples, absorbent cotton is not ignited by the fall of the burned sample.

The biaxially oriented polyester film of the present invention includes a step of melt-kneading the polyester resin composition and carbon black particles using a melt-kneading extruder, and the screw rotation speed of the melt-kneading extruder in the melt-kneading step is N _1. when the (rpm), the screw rotation speed N _1, to obtain a method for producing a polyester film to impart the variation of 10% or less than 0.01% carbon black particles in the polyester resin composition constituting the film Can be easily unevenly distributed, or spots can be generated in the crystallinity of the polyester resin constituting the film, and optical density spots can be imparted. As a result, a polyester film excellent in flame retardancy and continuous productivity can be obtained. Is preferable. Rather than melt-kneading while keeping the screw speed of the melt-kneading extruder constant, the screw speed of the melt-kneading extruder is increased or decreased in the range of 0.01% to 10%, screw rotation By varying the number, the flow rate of the polymer in the melt kneader is varied, resulting in uneven distribution of carbon black particles contained in the polyester resin composition constituting the film, and unevenness in crystallinity. It becomes possible to give. More preferably, it is 0.2% or more and 8% or less. Moreover, it is preferable that the generation frequency of the fluctuation | variation of screw rotation speed is 1 time / min-600 times / min.

Further, the biaxially oriented polyester film of the present invention is obtained by a method for producing a polyester film including the steps satisfying (6) to (7) below, whereby carbon black particles in the polyester resin composition constituting the film and Phosphoric esters can be easily unevenly distributed, spots can be generated in the degree of crystallinity, and a polyester film excellent in flame retardancy and continuous productivity can be obtained, which is preferable.
(6) Carbon black-containing polyester resin composition master (b) obtained by melting and kneading a polyester resin composition (a) having an intrinsic viscosity [η] of 0.70 dl / g or more and 0.90 dl / g or less and carbon black particles ) And a polyester resin composition (c) obtained by melt-kneading a polyester resin composition (a) having an intrinsic viscosity [η] of 0.70 dl / g to 0.90 dl / g and a phosphate ester (c) A step of melt kneading extrusion.
(7) When the screw speed of the melt-kneading extruder in the step of melt-kneading the carbon black-containing polyester resin composition master (b) and the phosphate ester-containing polyester resin composition (c) is N ₂ (rpm) , the screw rotation speed _{N 2} applying the variation of 10% or less than 0.01%.

  The carbon black-containing polyester resin composition master (b) of the present invention comprises a polyester resin composition (a) having an intrinsic viscosity [η] of a polyester resin of 0.70 g / dl to 0.90 dl / g and carbon black particles. By melt-kneading, it becomes easy to make the carbon black particles unevenly distributed in a suitable range or to give unevenness in the crystallinity. If the intrinsic viscosity [η] of the polyester resin exceeds 0.90 g / dl, the viscosity of the polyester resin is high, so that the uneven distribution of the carbon black particles and the unevenness of crystallinity may become too high. In addition, when the intrinsic viscosity [η] of the polyester resin is less than 0.70 g / dl, the viscosity of the polyester resin is low, and therefore it may be difficult to increase the uneven distribution of the carbon black particles and increase the degree of crystallinity. . The polyester resin composition (a) is more preferably 0.72 g / dl or more and 0.85 dl / g.

  The phosphoric ester-containing polyester resin composition master (c) of the present invention comprises a polyester resin composition (a) having a limiting viscosity [η] of the polyester resin of 0.70 g / dl to 0.90 dl / g and a phosphoric ester. By melt-kneading, it becomes easy to make the phosphate ester unevenly distributed in a suitable range or to give unevenness in the crystallinity. If the intrinsic viscosity [η] of the polyester resin exceeds 0.90 g / dl, the viscosity of the polyester resin is high, so that the phosphoric acid ester may be unevenly distributed and the crystallinity degree may become too high. In addition, when the intrinsic viscosity [η] of the polyester resin is less than 0.70 g / dl, the viscosity of the polyester resin is low, so that it may be difficult to increase the uneven distribution of phosphoric acid ester and the degree of crystallinity. . The polyester resin composition (a) is more preferably 0.72 g / dl or more and 0.85 dl / g.

Further, when the screw rotation speed of the melt-kneading extruder in the step of melt-kneading the carbon black-containing polyester resin composition master (b) and the phosphate ester-containing polyester resin composition (c) is N ₂ (rpm), the screw Carbon black contained in the polyester resin composition constituting the film as a result of variation in the flow rate of the polymer in the melt kneader by imparting a variation of 0.01% to 10% to the rotational speed N ₂ It is preferable because the particles and the phosphate ester can be easily unevenly distributed and the crystallinity can be uneven. More preferably, it is 0.2% or more and 8% or less. Moreover, it is preferable that the generation frequency of screw rotation speed is 1 time / min-600 times / min.

  The biaxially oriented polyester film of the present invention is preferably obtained by a method for producing a polyester film including a step that satisfies (8) below.

  (8) When preparing the carbon black-containing polyester resin composition master (b), the intrinsic viscosity of the polyester resin of the polyester resin composition (a) before kneading and the resulting carbon black-containing polyester resin composition master ( The intrinsic viscosity of the polyester resin of b) satisfies the following formula (8-1).

(8-1) 0.75 ≦ [η] b / [η] a ≦ 0.90
[Η] a: Intrinsic viscosity (dl / g) of the polyester resin of the polyester resin composition (a) of 0.7 dl / g or more
[Η] b: Intrinsic viscosity (dl / g) of the polyester resin of the carbon black-containing polyester resin composition master (b)
[Η] b / [η] a has a more preferable lower limit of 0.76 or more, and more preferably 0.78 or more. Moreover, a more preferable upper limit is 0.88 or less, More preferably, it is 0.85 or less. When [η] b / [η] a is less than 0.75, the intrinsic viscosity of the master raw material is greatly reduced, the mechanical properties of the film are deteriorated, and film formation may be broken. May be insufficiently distributed. If it exceeds 0.90, the shear in melt-kneading becomes insufficient, and the uneven distribution of carbon black particles may become too high, resulting in deterioration of light-shielding property and concealing property, and increase in filtration pressure during film formation. Productivity may deteriorate.

  In the present invention, from the viewpoint of excellent flame retardancy and continuous productivity, the polyester resin composition (a) is selected so that [η] b / [η] a is in a range satisfying the formula (8-1). ) And carbon black particles are melted and kneaded so that the carbon black particles are dispersed to the extent that they do not become foreign matter, and can be distributed unevenly, resulting in excellent flame retardancy, light shielding properties, concealment properties, and continuous productivity. It has been found that a polyester film can be obtained.

  [Η] b / [η] a satisfies the formula (8-1) by appropriately adjusting the temperature of the melt-kneading part, the melt-kneading time (polymer residence time), and the shearing force applied during melt-kneading. This can be achieved. The melt kneading apparatus may be a single screw extruder or a twin screw extruder, but a method using a high shear mixer with high shear stress such as a twin screw extruder is preferably exemplified. . In addition, from the viewpoint of reducing defective dispersion, it is preferable to equip a three- and two-screw type screw. When a twin screw extruder is used, the temperature range of 200 ° C. to 280 ° C. is preferable for the melt-kneading part. A more preferable temperature range is 210 ° C to 280 ° C, and a more preferable temperature range is 220 ° C to 280 ° C. The polymer residence time is preferably in the range of 1 to 5 minutes. Moreover, it is preferable to make biaxial screw rotation speed into 100-500 rotation / min, More preferably, it is the range of 200-300 rotation / min. By setting the screw rotation speed within a preferable range, high shear stress can be easily applied, the dispersibility of carbon black particles can be improved, and the decomposition reaction of polyester caused by excessive shear stress is suppressed. can do. Further, the ratio (L / D) of (screw shaft length / screw shaft diameter) of the twin screw extruder is preferably in the range of 20-60, more preferably in the range of 30-50.

  Further, in the screw configuration of the twin-screw extruder, it is preferable to provide a kneading part by a kneading paddle (kneading disk) or the like in order to increase the kneading force, and the kneading part is preferably two or more, more preferably three. It is preferable to use the screw configuration provided above. At this time, the mixing order of the polyester resin composition (a) and the carbon black particles is not particularly limited, and the polyester resin composition (a) in pellet form and the carbon black particles are mixed and melt-kneaded by the above method. Any method may be used, such as a method of mixing the carbon black particles using a side feeder during melt extrusion of the polyester resin composition (a) with a single or biaxial extruder.

  The content of carbon black particles in the carbon black-containing polyester resin composition master (b) is preferably 5% by weight or more and 30% by weight or less. A more preferred lower limit is 10% by weight or more. Moreover, a more preferable upper limit is 25 weight% or less. When the content of carbon black exceeds 30% by weight, it is difficult to control shearing heat generation and the dispersibility may be deteriorated. When the content of carbon black is less than 5% by weight, shear heat generation is not sufficient and dispersibility may deteriorate.

  Moreover, it is preferable to obtain the biaxially oriented polyester film of this invention with the manufacturing method of the polyester film including the process of satisfy | filling (9) below.

  (9) When preparing the phosphate ester-containing polyester resin composition master (c), the intrinsic viscosity of the polyester resin of the polyester resin composition (a) before kneading and the resulting phosphate ester-containing polyester resin composition The intrinsic viscosity of the polyester resin of the master (c) satisfies the following formula (9-1).

(9-1) 0.75 ≦ [η] c / [η] a ≦ 0.95
[Η] a: Intrinsic viscosity (dl / g) of the polyester resin of the polyester resin composition (a) of 0.7 dl / g or more
[Η] c: Intrinsic viscosity (dl / g) of polyester resin of phosphoric ester-containing polyester resin composition master (c)
[Η] c / [η] a has a more preferable lower limit of 0.76 or more, and more preferably 0.78 or more. Moreover, a more preferable upper limit is 0.93 or less, and further preferably 0.90 or less. When [η] c / [η] a is less than 0.75, the intrinsic viscosity of the master material is greatly reduced, the mechanical properties of the film are deteriorated, and film formation may be broken. May be insufficiently distributed. If it exceeds 0.95, shear in melt-kneading becomes insufficient, and the uneven distribution of phosphate ester may become too high, resulting in deterioration of light shielding property and concealing property, and increase in filtration pressure during film formation. Productivity may deteriorate.

  In the present invention, from the viewpoint of excellent flame retardancy and continuous productivity, the polyester resin composition (a) is selected so that [η] c / [η] a is in a range satisfying the formula (9-1). ) And phosphate ester are melt-kneaded to allow the phosphate ester to be appropriately distributed while being dispersed to the extent that it does not become a foreign substance, and is excellent in flame retardancy, light shielding properties, concealment properties, and continuous productivity. It has been found that a polyester film can be obtained.

  The method for [η] c / [η] a to satisfy Expression (9-1) is the same as the method for satisfying Expression (8-1) described above.

  The phosphate ester content in the phosphate ester-containing polyester resin composition master (c) is preferably 0.5% by weight or more and 30% by weight or less. A more preferred lower limit is 1.0% by weight or more. A more preferred upper limit is 20% by weight or less. If the phosphate ester content exceeds 30% by weight, it is difficult to control shearing heat generation, and the dispersibility may deteriorate. When the phosphate ester content is less than 0.5% by weight, shear heat generation is not sufficient, and dispersibility may deteriorate.

  The biaxially oriented polyester film of the present invention preferably uses as a raw material a mixture of the carbon black-containing polyester resin composition master (b) and the phosphate ester-containing polyester resin composition (c). In particular, when it is obtained by a production method including the steps satisfying the following (10) to (12), it is preferable from the viewpoint of expressing the effects of light shielding properties, hiding properties, flame retardancy, and continuous productivity.

  (10) The polyester raw material for producing the film contains the carbon black-containing polyester resin composition master (b) and the phosphate ester-containing polyester resin composition (c).

(11) The intrinsic viscosity of the polyester resin of the carbon black-containing polyester resin composition master (b) and the phosphate ester-containing polyester resin composition (c) satisfies the following formula (11-1).
(11-1) 0.75 ≦ [η] b / [η] c ≦ 1.10
[Η] b: Intrinsic viscosity (dl / g) of the polyester resin of the carbon black-containing polyester resin composition master (b)
[Η] c: Intrinsic viscosity (dl / g) of the polyester resin of the phosphoric ester-containing polyester resin composition (c)
(12) The content Wb (% by weight) of the carbon black-containing polyester resin composition master with respect to the entire polyester raw material for producing the film and the content Wc (% by weight) of the phosphate ester-containing polyester resin composition (c) The following formula (12-1) is satisfied.
(12-1) 0.03 ≦ Wb / Wc ≦ 0.5
Wb: Content (% by weight) of the carbon black-containing polyester resin composition master (b) with respect to the entire polyester raw material for producing the film
Wc: content (% by weight) of the phosphoric ester-containing polyester resin composition (c) with respect to the entire polyester raw material for producing the film
If [η] b / [η] c and Wb / Wc are out of the above preferred ranges, the light shielding property and flame retardancy are deteriorated and the continuous productivity is deteriorated (an increase in the filtration pressure during film formation occurs). There is a case. The cause of this is not clarified in detail at the present time. However, if [η] b / [η] c and Wb / Wc deviate from the above preferable ranges, the carbon black-containing polyester resin composition master (b ), Even if the carbon black particles are uniformly dispersed, the particles are aggregated during melt film formation, and the aggregates are estimated to cause deterioration of flame retardancy and continuous productivity. doing. [Η] b / [η] c is more preferably a lower limit of 0.85 or more, more preferably 0.90 or more, from the viewpoints of flame retardancy and continuous productivity. Moreover, a more preferable upper limit is 1.05 or less, More preferably, it is 0.95 or less. Moreover, a more preferable lower limit of Wb / Wc is 0.03 or more. A more preferred upper limit is 0.3 or less, and even more preferred is 0.15 or less.

  The biaxially oriented polyester film of the present invention is melt-extruded into a sheet form from a film forming die and formed, for example, under the following conditions. After being melt-extruded into a sheet form from a die of a film forming machine, it is closely cooled and solidified by static electricity on a drum cooled to a surface temperature of 10 ° C. or more and 60 ° C. or less to produce an unstretched sheet. The unstretched sheet thus obtained is biaxially stretched in the longitudinal and lateral directions to be formed into a sheet having a necessary and optimum thickness. For the stretching, a sequential biaxial stretching method or a simultaneous biaxial stretching method can be used. For example, in the case of sequential biaxial stretching, the unstretched sheet is led to a roll group heated to 70 to 120 ° C., and stretched 2 to 5 times in the longitudinal direction (longitudinal direction, that is, the traveling direction of the film). Cool with rolls. Subsequently, the film is guided to a tenter while holding both ends of the stretched film with clips in the longitudinal direction, and stretched 2 to 5 times in a direction (lateral direction) perpendicular to the longitudinal direction in an atmosphere heated to 90 to 150 ° C. The biaxially stretched film thus obtained is subjected to a heat treatment step at 150 to 240 ° C. for 1 to 30 seconds in order to complete crystal orientation and impart flatness and thermal dimensional stability. Then, after cooling uniformly, it cools to room temperature and winds up. In addition, you may perform a 3-12% relaxation process in a longitudinal direction and / or the width direction as needed during a heat treatment process.

  The biaxially oriented polyester film of the present invention has high light-shielding properties, concealability and flame retardancy, and excellent continuous productivity. Taking advantage of these features, optical devices such as mobile phones, cameras and video cameras, solar It can be used as an electrical insulating material used for battery backsheets or motors, various industrial materials such as building materials, thermal transfer applications, process paper, etc. Among them, optical devices that require flame retardancy, light shielding properties, and concealability It is suitably used as a light shielding member and a solar cell backsheet.

[Characteristic evaluation method]
(1) Melting point Using a differential scanning calorimeter DSC (RDC220) manufactured by Seiko Instruments Inc. according to JIS K7121-1987 and a disk station (SSC / 5200) manufactured by the company as a data analyzer, 5 mg of a sample is room temperature on an aluminum tray. The mixture was heated from 300 to 300 ° C. at a temperature rising rate of 20 ° C./min, melted and held at 300 ° C. for 5 minutes, rapidly solidified and held for 5 minutes, and then heated from room temperature at a temperature rising rate of 20 ° C./min. At that time, the peak temperature of the endothermic peak of melting observed was defined as the melting point.

(2) Intrinsic viscosity A measurement sample is dissolved in 100 ml of orthochlorophenol (solution concentration C = 1.2 g / dl), and the viscosity of the solution at 25 ° C. is measured using an Ostwald viscometer. Similarly, the viscosity of the solvent is measured. [Η] (dl / g) is calculated by the following formula (a) using the obtained solution viscosity and solvent viscosity, and the obtained value is used as the intrinsic viscosity.
(A) ηsp / C = [η] + K [η] ² · C
(Where ηsp = (solution viscosity (dl / g) / solvent viscosity (dl / g)) − 1, K is a Huggins constant (assuming 0.343)).

In addition, when there existed insoluble matters, such as inorganic particles, in the solution in which the measurement sample was dissolved, the measurement was performed using the following method.
i) A measurement sample is dissolved in 100 mL of orthochlorophenol to prepare a solution having a solution concentration higher than 1.2 mg / mL. Here, let the weight of the measurement sample used for orthochlorophenol be a measurement sample weight.
ii) Next, the solution containing the insoluble matter is filtered, and the weight of the insoluble matter and the volume of the filtrate after filtration are measured.
iii) Adding orthochlorophenol to the filtrate after filtration, (measurement sample weight (g) −insoluble matter weight (g)) / (volume of filtrate after filtration (mL) + volume of orthochlorophenol added) (ML)) is adjusted to 1.2 g / 100 mL.
(For example, when a concentrated solution having a measurement sample weight of 2.0 g / solution volume of 100 mL was prepared, the weight of insoluble matter when the solution was filtered was 0.2 g, and the filtrate volume after filtration was 99 mL Adjust to add 51 mL of orthochlorophenol ((2.0 g-0.2 g) / (99 mL + 51 mL) = 1.2 g / mL))
iv) Using the solution obtained in iii), the viscosity at 25 ° C. is measured using an Ostwald viscometer, and the obtained solution viscosity and solvent viscosity are used to calculate [η] according to the above formula (C). And the obtained value is taken as the intrinsic viscosity.

(3) Optical density, optical density spot 20 points of the polyester film to be measured are arbitrarily sampled, and the optical density in each sample is measured by the following method according to the old JIS K7605. The average value of the measured optical density values at 20 points was obtained as the optical density, and (difference between the maximum value and the minimum value) / (average value at 20 points) × 100 was obtained as the optical density spot.

<Optical density measurement method>
As the optical densitometer, XRite 361T (manufactured by Nippon Flat Plate Machinery Co., Ltd.) was used, and the sample was irradiated with a vertically transmitted light beam, and the ratio of the state with no sample expressed in log (logarithm) was defined as the optical density. The light flux width was circular with a diameter of 1 mm or wider.

S: Optical density is 5 or more A: Optical density is 4 or more and less than 5 B: Optical density is 3.5 or more and less than 4 C: Optical density is 2.5 or more and less than 3.5 D: Optical density is less than 2.5 S -B is good, and S is the best among them.

(4) Content of carbon black particles and degree of uneven distribution The polyester film to be measured is arbitrarily sampled at 20 points, and the content of carbon black particles in each sample is measured by the following method according to JIS K6813. The average value of the measured values of the obtained carbon black particles at 20 points is the carbon black particle content, and the difference between the maximum value and the minimum value / (average value of 20 points) × 100 is the uneven distribution degree. Asked.

<Measurement method of carbon black particle content>
The sample is weighed and weighed m1. The weighed sample is placed on a sample boat and heated in a cylindrical electric furnace preheated to 550 ° C. in a nitrogen atmosphere for 45 minutes. The sample boat is allowed to cool for 10 minutes under a nitrogen atmosphere, then transferred to a desiccator and allowed to cool to room temperature, and the weight is weighed to m2. Thereafter, the sample boat is placed in a muffle furnace and incinerated at 900 ° C. until there is no trace of carbon black. Cool the sample boat to room temperature in a desiccator and weigh it to m3. The content (mass%) of carbon black is calculated by the following (formula i), and the arithmetic average is used as the content (mass%).
(Formula i) (m2-m3) / m1 × 100
(5) Content of phosphorus element and antimony element in film The measurement was performed using a fluorescent X-ray analyzer (manufactured by Rigaku Corporation, model number: 3270).

(6) Flame retardancy Based on the UL-94 VTM method, the following method evaluated.

(I) Sample preparation A measurement sample (biaxially oriented polyester film) is cut into 20 cm x 5 cm.
Sample A left at 23 ° C. and 50% RH for 48 hours is sample A, temperature 70 ° C., left for 168 hours, then cooled to 23 ° C. and 20% RH or less for 4 hours as sample B, and 5 samples each. Prepare as a set.

(Ii) Measuring method A line is drawn at 125 mm from the bottom of the long side of each sample and wound around a rod having a diameter of 12.7 mm. In the 75mm part above the 125mm mark, stick with pressure sensitive tape and pull out the stick. The top of the sample is closed during the test so that there is no chimney effect. Next, each sample is set vertically, and absorbent cotton is placed 300 mm below. Using a Bunsen burner with a diameter of 9.5 mm and a flame length of 20 mm as a heating source so that the burner tube is located 10 mm from the lower end of the sample, a blue flame is indirectly flamed at the center of the lower end of the sample for 3 seconds. Measure the combustion time (t1) after the flame release. Then, as soon as the flame has disappeared, the indirect flame is again emitted for 3 seconds, and the combustion time (t2) and the fire type time (t3) after the second flame-off are measured. In addition, at the time of the first and second flame contact, observation is also made as to whether there was combustion that burned up to the 125 mm mark, and whether there was a burning fallen object that would ignite absorbent cotton. For sample A and sample B, the above measurement is performed for each set (five pieces).

(Iii) Evaluation of flame retardance Based on the following criteria, flame retardancy was evaluated as follows.
VTM-0: Satisfy any of the criteria (A), (I), (U), (E), (O).
VTM-1: Judgment criteria (A '), (I'), (U '), (E), (O) are all satisfied.
VTM-2: Satisfy any of the criteria (A '), (I'), (U '), (E).
No VTM: Does not correspond to any of VTM-0, VTM-1, and VTM-2.
Judgment criteria (A): The longer combustion time (t1) after the first flame-off of each sample or the combustion time (t2) after the second flame-off is 10 seconds or less in all samples.
Judgment criteria (A '): The longer the combustion time after the first flame release (t1) or the second combustion time after the flame release (t2) of each sample is 30 seconds or less.
Judgment criteria (I): The total of the burning time after flame removal per set (the total of the burning time after flame removal of five samples (t1 + t2)) is 50 seconds or less for both sample A and sample B.
Criteria (I '): The total burning time after flame removal per set (the total burning time after flame removal (t1 + t2) of 5 samples) is less than 250 seconds for both sample A and sample B .
Judgment standard (U): The total of the combustion time (t2) and the fire type time (t3) after the second flame-off is 30 seconds or less in all the samples.
Judgment standard (U '): The total of the combustion time (t2) and the fire type time (t3) after the second flame-off is 60 seconds or less in all the samples.
Criterion (E): Combustion or fire type is not reached in all samples up to the 125 mm mark.
Judgment criteria (O): Absorbent cotton is not ignited by the fall of the burned sample in all samples.

(7) Continuous productivity Continuous productivity is calculated by converting the number of film breaks per 24 hours when the film was formed for 48 hours under the conditions of the examples and comparative examples, and the examples and comparative examples. The film raw materials used in the above were judged on the basis of the following criteria using the increased filtration pressure when the filterability test was conducted under the following conditions.
S: Less than one break per 24 hours and an increase in filtration pressure of less than 80 kg / cm ² A: Less than one break per 24 hours and an increase in filtration pressure of 80 kg / cm ² or more and less than 100 kg / cm ² B : Less than one break per 24 hours and a filtration pressure increase value of 100 kg / cm ² or more and less than 120 kg / cm ² C: One or more breaks per 24 hours or a filtration pressure increase value of 120 kg / cm ² or more B is good, and S is the best among them.
<Conditions for filterability test>
The raw materials used in Examples and Comparative Examples are dried at 140 ° C. for 8 hours under reduced pressure of 133 Pa or less. Using a single-screw extruder, the pellets were dried using a X4 type 20 μm Dynaloy filter (filtration area 4.5 cm ² ) manufactured by Watanabe Seisakusho, polymer temperature 280 ° C., passing amount 10 g / Filter in minutes. From the start of filtration, the filtration pressure (R0) at the time when the polymer passage amount is 1200 g and the filtration pressure (R1) at the time of 8400 g are measured, and R1-R0 (kg / cm ² ) is defined as the filtration pressure increase value.

(8) Film thickness The film thickness was measured according to JIS C 2151 (2006) “micrometer method”. The measuring instrument used a micrometer, measured so that it may become substantially equal intervals along the product width direction, and made it the average value of 30 points | pieces of the width direction.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not necessarily limited to these.

(Reference Example 1) Production of polyethylene terephthalate resin A To a mixture of dimethyl terephthalate and ethylene glycol, 0.09% by weight of calcium acetate and 0.03% by weight of antimony trioxide with respect to dimethyl terephthalate were added. The temperature was raised by heating to conduct transesterification. Next, after adding 0.15% by weight of lithium acetate and 0.21% by weight of trimethyl phosphate to the raw material dimethyl terephthalate, the resulting transesterification product was transferred to a polymerization reaction tank, Subsequently, the reaction system was gradually depressurized while being heated and heated, and polymerization was performed at 290 ° C. under a reduced pressure of 1 mmHg by a conventional method to obtain polyethylene terephthalate (PET) having an intrinsic viscosity of 0.54 dl / g. The obtained PET polymer was heat-treated at a temperature of 225 ° C. for 35 hours under a reduced pressure of 1 mmHg or less using a rotary vacuum polymerization apparatus, and a polyethylene terephthalate resin A (PET) having a melting point of 255 ° C. and an intrinsic viscosity of 0.73 dl / g. Chip A) was obtained.

(Reference Example 2) Production of polyethylene terephthalate resin B To a mixture of dimethyl terephthalate and ethylene glycol, 0.06% by weight of magnesium acetate tetrahydrate was added to dimethyl terephthalate, and the temperature was raised by heating in a conventional manner to form an ester. An exchange reaction was performed. Next, 0.02% by weight of trimethyl phosphate was added to the obtained transesterification reaction product with respect to dimethyl terephthalate as a raw material, and 0.02% of germanium dioxide dissolved in ethylene glycol as a polymerization catalyst was finely dispersed and dissolved. After adding a solution in which wt% was dissolved in tetraethylammonium hydroxide, the mixture was further transferred to a polymerization reaction tank, and then the reaction system was gradually depressurized while heating to raise the temperature, and the reaction was carried out in a conventional manner at 280 ° C under a reduced pressure of 1 mmHg. A condensation reaction was performed. The obtained PET polymer was heat-treated at a temperature of 240 ° C. for 8 hours under a reduced pressure of 1 mmHg or less using a rotary vacuum polymerization apparatus, and a polyethylene terephthalate resin B (PET) having a melting point of 255 ° C. and an intrinsic viscosity of 0.76 dl / g. Chip B) was obtained.

Reference Example 3 Production of Carbon Black-Containing Polyester Resin Composition Master A Kneading paddle kneading 80% by weight of PET chip A prepared in Reference Example 1 and 20% by weight of furnace black (# 3030B) manufactured by Mitsubishi Chemical Corporation as carbon black particles. Are put into a co-rotating twin-screw kneading extruder with a vacuum vent (L / D = 40) provided with a part, residence time 90 seconds, screw rotation speed 300 rotations / minute, screw rotation speed fluctuation rate 4%, 290 It was melt extruded at ℃, discharged into a strand, cooled with water at a temperature of 25 ℃, and immediately cut to prepare a carbon black-containing polyester resin composition master A (master chip A) having an intrinsic viscosity of 0.58 dl / g. . The screw rotation speed N is an average value for 10 minutes. The fluctuation of the screw rotation speed is obtained by observing an oscilloscope capable of displaying a waveform representing the screw rotation speed with respect to time while measuring the current of the motor of the screw driving device. It was carried out by adjusting.

Reference Example 4 Production of Carbon Black-Containing Polyester Resin Composition Master B In Reference Example 3, the same procedure as in Reference Example 3, except that PET chip A prepared in Reference Example 1 was 90% by weight and carbon black was 10% by weight. A carbon black-containing polyester resin composition master B (master chip B) having an intrinsic viscosity of 0.63 dl / g was produced.

Reference Example 5 Production of Carbon Black-Containing Polyester Resin Composition Master C The same as Reference Example 3 except that in Reference Example 3, the PET chip A produced in Reference Example 1 was 94% by weight and the carbon black was 6% by weight. A carbon black-containing polyester resin composition master C (master chip C) having an intrinsic viscosity of 0.65 dl / g was produced.

Reference Example 6 Production of Carbon Black-Containing Polyester Resin Composition Master D In Reference Example 3, 78% by weight of PET chip A prepared in Reference Example 1, 20% by weight of carbon black, an olefin wax “Licowax PP230” (as a dispersant) A carbon black-containing polyester resin composition master D (master chip D) having an intrinsic viscosity of 0.55 dl / g was produced in the same manner as in Reference Example 3 except that 2% by weight of Clariant) was added.

Reference Example 7 Production of Carbon Black-Containing Polyester Resin Composition Master E In Reference Example 3, the same procedure as in Reference Example 3, except that PET chip B prepared in Reference Example 2 was 80% by weight and carbon black was 20% by weight. A carbon black-containing polyester resin composition master E (master chip E) having an intrinsic viscosity of 0.60 dl / g was produced.

Reference Example 8 Production of Phosphate Ester-Containing Polyester Resin Composition Master F 95% by weight of PET chip A prepared in Reference Example 1 and 5% by weight of condensed phosphate ester (PX200) manufactured by Daihachi Chemical Co. as a phosphate ester Charged into a co-rotating twin-screw kneading extruder with a vacuum vent (L / D = 40) equipped with a kneading paddle kneading section (L / D = 40), residence time 90 seconds, screw rotation speed 300 rotations / minute, screw rotation speed fluctuation rate 4%, melt-extruded at 290 ° C., discharged into a strand, cooled with water at a temperature of 25 ° C., and immediately cut to obtain a phosphate ester-containing polyester resin composition master F (master chip) having an intrinsic viscosity of 0.65 dl / g F) was prepared. The screw rotation speed N is an average value for 10 minutes. The fluctuation of the screw rotation speed is obtained by observing an oscilloscope capable of displaying a waveform representing the screw rotation speed with respect to time while measuring the current of the motor of the screw driving device. It was carried out by adjusting.

Reference Example 9 Production of Phosphate Ester-Containing Polyester Resin Composition Master G Same as Reference Example 8 except that in Reference Example 8, the PET chip A prepared in Reference Example 1 was 90% by weight and the phosphate ester was 10% by weight. Thus, a phosphoric ester-containing polyester resin composition master G (master chip G) having an intrinsic viscosity of 0.62 dl / g was produced.

Reference Example 10 Production of Phosphate Ester-Containing Polyester Resin Composition Master H Same as Reference Example 8 except that in Reference Example 8, the PET chip A prepared in Reference Example 1 was 80% by weight and the phosphate ester was 20% by weight. Thus, a phosphoric ester-containing polyester resin composition master H (master chip H) having an intrinsic viscosity of 0.53 dl / g was produced.

Reference Example 11 Production of Phosphate Ester-Containing Polyester Resin Composition Master I Same as Reference Example 8 except that in Reference Example 8, the PET chip B prepared in Reference Example 2 was 95% by weight and the phosphate ester was 5% by weight. Thus, a phosphoric ester-containing polyester resin composition master I (master chip I) having an intrinsic viscosity of 0.68 dl / g was produced.

Example 1
10% by weight of the master chip A obtained in Reference Example 3 and 90% by weight of the master chip F obtained in Reference Example 8 were vacuum-dried at a temperature of 180 ° C. for 2 hours. Subsequently, it supplied to the extruder under nitrogen atmosphere. Screw rotation speed of 300 rotations / minute, screw rotation speed fluctuation rate of 4%, polymer filtered through a filter at a temperature of 290 ° C, and then melt extruded from a T-die die set at a temperature of 280 ° C. While applying an electrostatic charge to the cast drum, it was closely cooled and solidified to produce an unstretched film.

  This unstretched film was stretched at a magnification of 3.3 times in the longitudinal direction of the film at a temperature of 90 ° C. using a difference in peripheral speed of the roll using a longitudinal stretching machine composed of a plurality of heated roll groups. . Thereafter, both ends of the film are gripped with a clip, guided to a tenter, stretched in the width direction of the film at a stretching temperature of 95 ° C. and a stretching ratio of 3.5 times, heat-treated at 225 ° C. for 8 seconds, and a thickness of 50 μm. A biaxially oriented polyester film was obtained.

  The characteristics of the obtained biaxially oriented polyester film are shown in the table.

(Examples 2-3, Comparative Example 2)
A biaxially oriented polyester film was obtained in the same manner as in Example 1 except that the fluctuation rate of the screw rotation number was changed as described in the table. The characteristics of the obtained biaxially oriented polyester film are shown in the table.

(Examples 4 to 5)
A biaxially oriented polyester film was obtained in the same manner as in Example 1 except that the contents of the master chip A and the master chip F and the fluctuation rate of the screw rotation speed were changed as shown in the table. The characteristics of the obtained biaxially oriented polyester film are shown in the table.

(Example 6)
A biaxially oriented polyester film was obtained in the same manner as in Example 1 except that the contents of the master chip A and the master chip F and the thickness of the film were changed to 200 μm. The characteristics of the obtained biaxially oriented polyester film are shown in the table.

(Example 7, Example 9)
A biaxially oriented polyester film was obtained in the same manner as in Example 1 except that the contents of the master chip A and master chip F were changed as shown in the table. The characteristics of the obtained biaxially oriented polyester film are shown in the table.

(Example 8)
A biaxially oriented polyester film was obtained in the same manner as in Example 1, except that 40% by weight of master chip A and 60% by weight of master chip G obtained in Reference Example 9 were used instead of master chip F. The characteristics of the obtained biaxially oriented polyester film are shown in the table.

(Example 10)
The same as in Example 1 except that 10% by weight of the master chip B obtained in Reference Example 4 was used instead of the master chip A, and 90% by weight of the master chip G obtained in Reference Example 9 was used instead of the master chip F. A biaxially oriented polyester film was obtained by this method. The characteristics of the obtained biaxially oriented polyester film are shown in the table.

(Example 11)
Instead of master chip A, the same as Example 1 except that 40% by weight of master chip C obtained in Reference Example 5 and 60% by weight of master chip G obtained in Reference Example 9 are used instead of master chip F. A biaxially oriented polyester film was obtained by this method. The characteristics of the obtained biaxially oriented polyester film are shown in the table.

(Example 12)
Example 10 is the same as Example 1 except that instead of the master chip A, 10% by weight of the master chip E obtained in Reference Example 7 and 90% by weight of the master chip I obtained in Reference Example 11 are used instead of the master chip F. A biaxially oriented polyester film was obtained by this method. The characteristics of the obtained biaxially oriented polyester film are shown in the table.

(Comparative Example 1)
A biaxially oriented polyester film was obtained in the same manner as in Example 1 except that 90% by weight of PET chip A obtained in Reference Example 1 was used instead of master chip F. The characteristics of the obtained biaxially oriented polyester film are shown in the table.

(Comparative Example 3)
Instead of the master chip F, the master chip H 90% by weight obtained in Reference Example 10 was used, and the change rate of the screw rotation speed was changed as described in the table. An oriented polyester film was obtained. The characteristics of the obtained biaxially oriented polyester film are shown in the table.

(Comparative Example 4)
A biaxially oriented polyester film was obtained in the same manner as in Example 1 except that 10% by weight of master chip D and 90% by weight of master chip F obtained in Reference Example 6 were used instead of master chip A. The characteristics of the obtained biaxially oriented polyester film are shown in the table.

(Comparative Example 5)
A biaxially oriented polyester film was obtained in the same manner as in Example 1, except that 60% by weight of master chip A and 40% by weight of master chip G obtained in Reference Example 9 were used instead of master chip F. The characteristics of the obtained biaxially oriented polyester film are shown in the table.

(Comparative Example 6)
A biaxially oriented polyester film was obtained in the same manner as in Example 1 except that 0.1% by weight of the master chip C obtained in Reference Example 5 and 99.9% by weight of the master chip F were used instead of the master chip A. It was. The characteristics of the obtained biaxially oriented polyester film are shown in the table.

According to the present invention, it is possible to provide a biaxially oriented polyester film that satisfies high light-shielding properties, concealability, and flame retardancy, and is excellent in continuous productivity. Furthermore, by using such a film, it is possible to provide a light shielding member for an optical device or a solar battery back sheet having both high light shielding properties and flame retardancy.

Claims (10)

A biaxially oriented polyester film satisfying the following (1) to (5).
(1) Carbon black particles are contained in the polyester resin composition constituting the film, and the content thereof is 0.01 to 10% by weight.
(2) The polyester resin composition constituting the film does not substantially contain a dispersant.
(3) The phosphorus resin is contained in the polyester resin composition constituting the film, and the content thereof is 0.01 to 5% by weight.
(4) Optical density spots are 0.10% or more and 50% or less.
(5) The flame retardancy calculated | required by the following method must be either VTM-0 or VTM-1.
<Flame retardancy evaluation method>
(I) Sample preparation A measurement sample (biaxially oriented polyester film) is cut into 20 cm x 5 cm.
Sample A left at 23 ° C. and 50% RH for 48 hours is sample A, temperature 70 ° C., left for 168 hours, then cooled to 23 ° C. and 20% RH or less for 4 hours as sample B, and 5 samples each. Prepare as a set.
(Ii) Measuring method A line is drawn in a direction parallel to the short side at 125 mm from the short side of each sample, and wound around a rod having a diameter of 12.7 mm so that the short side is in the vertical direction. In the 75mm part above the 125mm mark, stick with pressure sensitive tape and pull out the stick. The top of the sample is closed during the test so that there is no chimney effect. Next, each sample is set vertically, and absorbent cotton is placed 300 mm below. A bunsen burner with a diameter of 9.5 mm and a flame length of 20 mm is used as a heating source so that the burner tube is located 10 mm from the lower end of the sample. Measure the combustion time (t1) after the flame release. Then, as soon as the flame has disappeared, the indirect flame is again emitted for 3 seconds, and the combustion time (t2) and the fire type time (t3) after the second flame-off are measured. In addition, at the time of the first and second flame contact, observation is also made as to whether there was combustion that burned up to the 125 mm mark, and whether there was a burning fallen object that would ignite absorbent cotton. For sample A and sample B, the above measurement is performed for each set (five pieces).
(Iii) Evaluation of flame retardancy Based on the following criteria, flame retardancy is evaluated as follows.
VTM-0: Satisfy any of the criteria (A), (I), (U), (E), (O).
VTM-1: Judgment criteria (A '), (I'), (U '), (E), (O) are all satisfied.
VTM-2: Satisfy any of the criteria (A '), (I'), (U '), (E).
No VTM: Does not correspond to any of VTM-0, VTM-1, and VTM-2.
Criteria (A): In all samples, the longer combustion time (t1) after the first flame release or the second combustion time (t2) after the second flame release is 10 seconds or less.
Judgment criteria (A '): In all samples, the longer combustion time after the first flame release (t1) or the second combustion time after the flame release (t2) is 30 seconds or less.
Judgment criteria (I): The total of the burning time after flame removal per set (the total of the burning time after flame removal of five samples (t1 + t2)) is 50 seconds or less for both sample A and sample B.
Criteria (I '): The total burning time after flame removal per set (the total burning time after flame removal (t1 + t2) of 5 samples) is less than 250 seconds for both sample A and sample B .
Judgment standard (U): In all samples, the sum of the combustion time (t2) and the ignition time (t3) after the second flame-off is 30 seconds or less.
Judgment criteria (U '): In all samples, the sum of the combustion time (t2) and the ignition time (t3) after the second flame-off is 60 seconds or less.
Judgment criteria (e): In all samples, combustion or fire type does not reach the 125 mm mark.
Judgment criteria (O): In all samples, absorbent cotton is not ignited by the fall of the burned sample.   The biaxially oriented polyester film according to claim 1, wherein the polyester resin composition constituting the film contains an antimony element, and the content thereof is 0.005 to 0.1% by weight.   The biaxially oriented polyester film according to claim 1 or 2, obtained by adding a phosphate ester.   The biaxially oriented polyester film according to any one of claims 1 to 3, wherein the film has a thickness of 10 µm to 300 µm.   The biaxially oriented polyester film according to any one of claims 1 to 4, wherein the degree of uneven distribution of the carbon black particles contained in the polyester resin composition constituting the film is 0.10% or more and 20% or less.   The biaxially oriented polyester film according to any one of claims 1 to 5, which is used for either a light shielding member of an optical device or a solar battery backsheet. A method for producing a biaxially oriented polyester film comprising a step of melt-kneading a polyester resin composition and carbon black particles using a melt-kneading extruder, wherein the screw rotation speed of the melt-kneading extruder in the melt-kneading step is The biaxially oriented polyester film according to any one of claims 1 to 6, wherein when N ₁ (rpm) is set, a fluctuation of 0.01% or more and 10% or less is imparted to the screw rotation speed N _1. Manufacturing method. The manufacturing method of the biaxially-oriented polyester film of Claim 7 including the process of satisfy | filling following (6)-(7).
(6) Carbon black-containing polyester resin composition master (b) obtained by melting and kneading a polyester resin composition (a) having an intrinsic viscosity [η] of 0.70 dl / g or more and 0.90 dl / g or less and carbon black particles ) And a polyester resin composition master containing a phosphate ester obtained by melting and kneading a polyester resin composition (a) having an intrinsic viscosity [η] of 0.70 dl / g to 0.90 dl / g and a phosphate ester ( c) including a step of melt kneading and extruding.
(7) The screw rotation speed of the melt-kneading extruder in the step of melt-kneading the carbon black-containing polyester resin composition master (b) and the phosphate ester-containing polyester resin composition master (c) was N ₂ (rpm). When giving the screw rotation speed N ₂ a fluctuation of 0.01% or more and 10% or less. When producing the carbon black-containing polyester resin composition master (b), the intrinsic viscosity of the polyester resin of the polyester resin composition (a) before kneading and the resulting carbon black-containing polyester resin composition master (b) The method for producing a biaxially oriented polyester film according to claim 8, wherein the intrinsic viscosity of the polyester resin satisfies the following formula (8-1).
(8-1) 0.75 ≦ [η] b / [η] a ≦ 0.90
[Η] a: Intrinsic viscosity (dl / g) of the polyester resin of the polyester resin composition (a) of 0.7 dl / g or more
[Η] b: Intrinsic viscosity (dl / g) of the polyester resin of the carbon black-containing polyester resin composition master (b) When preparing the phosphate ester-containing polyester resin composition master (c), the intrinsic viscosity of the polyester resin of the polyester resin composition (a) before kneading and the resulting phosphate ester-containing polyester resin composition master (c The intrinsic viscosity of the polyester resin of) satisfies the following formula (9-1): The method for producing a biaxially oriented polyester film according to claim 8.
(9-1) 0.75 ≦ [η] c / [η] a ≦ 0.95
[Η] a: Intrinsic viscosity (dl / g) of the polyester resin of the polyester resin composition (a) of 0.7 dl / g or more
[Η] c: Intrinsic viscosity (dl / g) of polyester resin of phosphoric ester-containing polyester resin composition master (c)