JP5034145B2 - Polyester film - Google Patents

Description

【００８５】
【表２】

【００８６】
【表３】

【００８７】
尚、表中の記号は次の通りである。
【００８８】
ＥＧ：エチレングリコール
ＰＧ：プロパンジオール（１，３−プロパンジオール）
ＤＥＧ：ジエチレングリコール
ＢＧ：ブタンジオール
ＰＥＴ／ＣＨＤＭ：シクロヘキサンジメタノール共重合ＰＥＴ
【００８９】
【発明の効果】
本発明によれば、エチレングリコール、ブタンジオール、プロパンジオールから選択されるグリコール成分を少なくとも２種類以上含有するポリエステルフィルム中に含まれる触媒金属元素の濃度とリン元素の濃度の比Ｍ／Ｐを１以下とし、８０℃におけるフィルムの平均破断伸度を８００％以上とすることにより、成形、加工、印刷製品または成形、加工、印刷時の工程フィルムとして好適なポリエステルフィルムを提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyester film.
[0002]
More specifically, the present invention relates to a polyester film suitable as a process film at the time of molding, processing, printing product or molding, processing, and printing because it is excellent in moldability, workability, and printability.
[0003]
[Prior art]
Conventionally, as a material excellent in molding, processing, and printability, there has been a polyvinyl chloride film, but since a halogen element is contained in the constituent components of the polymer, harmful components such as dioxin are generated during incineration. Is a problem.
[0004]
As a method for solving this problem, a soft polyolefin film described in JP-A-9-132682, JP-A-9-226071 or the like, or JP-A-3-231929, JP-A-3-231930, etc. A polyester film copolymerized with a long-chain aliphatic dicarboxylic acid and a polyester film copolymerized with an alicyclic glycol and the like have been proposed. The flexible polyolefin film has flexibility, but it cannot be said that the moldability and processability are sufficient, and the polyester film copolymerized with a long-chain aliphatic dicarboxylic acid or alicyclic glycol has poor cost performance, especially alicyclic. Glycol copolymerized polyester has low solvent resistance, so it cannot be said that it is sufficiently satisfactory in terms of whitening and residual solvent during printing, and various molding and processing machines also have high stress during molding. It was not at a level that could be adapted to. In addition, an amorphous PET (polyethylene terephthalate) film generally called an A-PET film has high stress during molding and processing, and when it is molded at a high temperature to reduce the stress, wrinkles of the film due to softening and whitening due to crystallization occur. There was a problem.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to eliminate the above-mentioned problems of the prior art, and to provide a polyester film excellent in formability, workability, and printability.
[0006]
[Means for Solving the Problems]
The object of the present invention described above is a polyester A containing at least two kinds of glycol components selected from ethylene glycol, butanediol, and propanediol, and satisfies the following formula (1).And the average breaking elongation of the film at 80 ° C. is 800% or more.This is achieved by a polyester film characterized in that.
[0007]
M / P ≦ 1 (1)
(In the formula, M represents the concentration of the catalytic metal element remaining in the polyester A (mmol%), and P represents the concentration of the phosphorus element remaining in the polyester A (mmol%).)
As a result of intensive studies, the present invention combines a specific glycol component and makes the amount of catalytic metal and phosphorus in a specific range, thereby providing a polyester film with excellent cost performance and good moldability, workability, and printability. It has been found that it can be obtained.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Polyester A in the present invention has at least two types of glycol components selected from ethylene glycol, butanediol, and propanediol as structural units of the polyester, in that the moldability, processability, and printability are good. It is necessary that the polyester is contained above.
[0009]
In particular, in applications in which formability, processability, and printability are important, it is preferable that 10 to 90 mol% of the glycol component of polyester A is ethylene glycol. It is more preferable that 20-90 mol% of the glycol component of polyester A is ethylene glycol, and it is especially preferable that 25-85 mol% is ethylene glycol in the point which makes the moldability of 100 degrees C or less and workability favorable. preferable.
[0010]
In particular, it is preferable to contain all of ethylene glycol, butanediol, and propanediol as the glycol component in terms of improving moldability, processability, and printability. In that case, when the mol% of ethylene glycol, butanediol, and propanediol is X, Y, and Z, respectively, it is preferable that X + Z−Y is 0 or more.
[0011]
It is preferable that 10 to 90 mol% of the glycol component of polyester A is a glycol selected from butanediol and / or propanediol, in terms of improving moldability and processability at 100 ° C. or less, and 10 to 80 mol. More preferably,% is a glycol selected from butanediol and / or propanediol, and 15-75 mol% is particularly preferably a glycol selected from butanediol and / or propanediol. Butanediol and propanediol may be used in combination.
[0012]
Furthermore, as other glycol components, for example, aliphatic glycols such as pentanediol, hexanediol and neopentyl glycol; alicyclic glycols such as cyclohexanedimethanol; bisphenols (bisphenol A, bisphenol S) Etc.), 1,3-bis (2-hydroxyethoxy), 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, bis [4- (2-hydroxyethoxy) ) Phenyl] sulfone, 2,2-bis (4-β-hydroxyethoxyphenyl) propane, hydroquinone, resorcin and other aromatic glycols; diethylene glycol, polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol and the like. it can. The amount of diethylene glycol contained is preferably 0.1 to 10 mol% in terms of moldability, processability and printability, and further 0.3 to 5 mol% in terms of preventing deterioration of weather resistance. preferable.
[0013]
Examples of the acid component of polyester A include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sodiumsulfoisophthalic acid, and phthalic acid. , Oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, cyclohexyne dicarboxylic acid and other alicyclic dicarboxylic acids, p-oxybenzoic acid and other oxycarboxylic acids An acid etc. can be mentioned. In terms of heat resistance, moldability, processability, and printability, terephthalic acid, isophthalic acid, adipic acid and the like can be preferably used.
[0014]
As a means for containing at least two kinds of glycol components selected from ethylene glycol, butanediol, and propanediol in the polyester A of the present invention, a technique of adding these glycols during polymerization to obtain a copolymerized polyester, an extruder And a method obtained by blending a plurality of polyesters. At this time, the film using the copolyester deteriorates the solvent resistance, printability, heat resistance, and the like. Therefore, a film made of a blend of a plurality of polyesters is preferable. Furthermore, PET (polyethylene terephthalate), PPT (polypropylene terephthalate) ) And a blend of two or more resins selected from PBT (polybutylene terephthalate) are preferable. Here, PET, PPT, and PBT include those obtained by copolymerizing the above acid component and / or glycol component at a low rate of 20 mol% or less, more preferably 10 mol% or less, and particularly preferably 5% or less. In particular, in terms of moldability and whitening resistance, a blend of PET and PPT is preferable, and a blend polyester composed of 40 to 90% by weight of PET and 10 to 60% by weight of PPT is particularly preferable.
[0015]
It is necessary for the polyester film of the present invention that polyester A satisfies the following formula (1) in order to reduce variations in heat resistance, solvent resistance, printability, and quality.
[0016]
M / P ≦ 1 (1)
(In the formula, M represents the concentration of the catalytic metal element remaining in the polyester A (mmol%), and P represents the concentration of the phosphorus element remaining in the polyester A (mmol%).)
Here, these metal element concentrations and phosphorus element concentrations are expressed as concentrations per unit (mole) of repeating units of polyester.
[0017]
M / P is preferably 0.0001 or more and less than 1, more preferably 0.001 or more and 0.8 or less, and particularly preferably 0.01 or more and 0.6 or less.
[0018]
By controlling M / P ≦ 1, it is possible to increase the thermal stability, suppress the transesterification of the blend polymer, and suppress the lowering of the melting point due to the heat treatment. As a result, the above-mentioned characteristics can be improved.
[0019]
In the present invention, when producing polyester A, conventionally used reaction catalysts and anti-coloring agents can be used. Examples of reaction catalysts include alkaline earth metal compounds, zinc compounds, lead compounds, A manganese compound, a cobalt compound, an aluminum compound, an antimony compound, a titanium compound, or the like can be used. As a coloring inhibitor, for example, a phosphorus compound or the like can be used. Preferably, it is usually preferable to add an antimony compound, a germanium compound, or a titanium compound as a polymerization catalyst at an arbitrary stage before the production of the polyester is completed. As such a method, for example, when a germanium compound is taken as an example, a germanium compound powder is added as it is, or, as described in Japanese Patent Publication No. 54-22234, a glycosylated starting material for polyester. A method in which a germanium compound is dissolved and added to the component can be used.
[0020]
Examples of germanium compounds include germanium dioxide, germanium hydroxide containing crystal water, or germanium alkoxide compounds such as germanium tetramethoxide, germanium tetraethoxide, germanium tetrabutoxide, germanium ethyleneglycoxide, germanium phenolate, germanium β- Germanium phenoxide compounds such as naphtholate, phosphorus-containing germanium compounds such as germanium phosphate and germanium phosphite, germanium acetate, and the like can be used. Of these, germanium dioxide is preferable.
[0021]
Although it does not specifically limit as an antimony compound, For example, antimony oxides, such as antimony trioxide, an antimony acetate, etc. can be used.
[0022]
The titanium compound is not particularly limited, but alkyl titanate compounds such as tetraethyl titanate and tetrabutyl titanate, and complex oxides of titanium and elements selected from silicon, zirconium and aluminum elements can be preferably used.
[0023]
The phosphorus compound added as a heat stabilizer to the polyester in the present invention is not particularly limited, but phosphoric acid, phosphorous acid, phosphoric acid ester and the like are preferable.
[0024]
In particular, a phosphorus compound having a molecular weight of 300 or more, particularly preferably 400 or more is preferably used from the viewpoint of suppressing bleeding out during film formation. Examples of phosphorus compounds having a molecular weight of 300 or more include stearyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and stearyl phosphate particularly suppresses bleed out. From the point of view, it is preferable.
[0025]
The content (addition amount) of the phosphorus compound to be added to the polyester A is preferably 20 to 1000 mmol%, more preferably 90 to 1000% in terms of the phosphorus element amount from the viewpoint of thermal stability, color tone, and the like. It is 900 mmol%, particularly preferably in the range of 120 to 800 mmol%.
[0026]
Furthermore, as a method for adding the phosphorus compound, either a method of adding at the time of polymerization or a method of adding by adding to the extruder together with the polymer may be used. In general, when a large amount of a phosphorus compound is added during polymerization, the polymerization reaction is inhibited. Therefore, a method in which the polyester is added to an extruder together with a normal polyester in the range of M / P> 1 is preferable.
As the melting point of the polyester A, it is preferable that at least one melting point peak in DSC is in the range of 220 ° C. or higher and 280 ° C. or lower, and one of the melting point peaks is 230 ° C. or higher and 270 ° C. or lower in view of heat resistance and printability. It is more preferable that one of the melting point peaks is 245 ° C. or higher and 260 ° C. or lower. Furthermore, it is preferable that the melting point peak in DSC is one from the viewpoint that moldability is particularly good.
[0027]
Here, the peak of the crystal melting curve in the present invention is a crystal melting peak due to the polymer constituting the film, and the film (5 mg) was measured at a heating rate of 20 ° C./min in a nitrogen atmosphere in DSC. This is the minimum point of the endothermic curve obtained from the DSC curve, that is, the point at which the differential value becomes zero. A shoulder peak (minimum peak) having a heat of fusion of 2 J / g or more partially overlapping one endothermic curve is also regarded as an independent crystal melting curve peak. That is, what shows a substantially single peak in the present invention means that there is only a single minimum point of a crystal melting peak having a heat of fusion of 2 J / g or more.
[0028]
The intrinsic viscosity of the polyester A is preferably 0.5 to 1.5. In particular, in applications where a thin film is required in terms of moldability and processability, the intrinsic viscosity of the polyester A is 0.6 to 1.3. It is more preferable that the intrinsic viscosity is 0.7 to 1.0.
[0029]
The polyester film of the present invention has an average elongation at break of 800% or more at 80 ° C. in order to improve various molding and workability.is necessary. Here, the average breaking elongation of the film is 10 times in width and 100 mm in length when stretched at 300 mm / min to measure the breaking elongation in the vertical and horizontal directions 10 times each, and the maximum and minimum in each direction. It is an average value excluding points. The average breaking elongation at 80 ° C. is more preferably 900% or more, and particularly preferably 1000% or more and 2000% or less.
[0030]
The polyester film according to the present invention preferably contains 1 to 60% by weight of a plasticizer having a molecular weight of 3000 or less from the viewpoint of further improving moldability and workability and improving the flexibility of the film. In particular, in terms of improving flexibility, it is preferable to contain 5 to 60% by weight of a plasticizer having a molecular weight of 3000 or less. The plasticizer preferably has a freezing point of 30 ° C. or lower, more preferably 20 ° C. or lower, particularly preferably 10 ° C. or lower.
[0031]
The type of plasticizer is not particularly limited, but is a compound having a molecular weight of 3000 or less. Examples of the plasticizer include adipic acid plasticizers, phosphorus plasticizers, polyether plasticizers, trimellitic acid plasticizers, and phthalic acid. A plasticizer can be used. These plasticizers are preferably introduced with a functional group blocking group that suppresses the reaction with polyester A. As the plasticizer used in the present invention, an ester plasticizer is particularly preferable from the viewpoint of heat resistance and moldability. As the ester plasticizer, those having a hydroxyl value of 0 to 20 (mg / g) are preferred from the viewpoint of heat resistance, and those having 0 to 15 (mg / g) are more preferred. The acid value is preferably 0 to 5 (mg / g), particularly preferably 0 to 3 (mg / g).
[0032]
Examples of the method of adding the plasticizer include a method of batch addition before or after the polymerization reaction, a method using a vent type extruder, a method of adding from a screw or a tube wall using a liquid feed pump, and the like.
[0033]
In the present invention, when the polyester B layer is combined with at least one side of the above-described A layer mainly composed of the polyester A, the bleed-out resistance of the plasticizer, handling property, non-adhesiveness at the time of processing can be improved. Moreover, since new functions such as thermal adhesiveness can be imparted, it is more preferable.
[0034]
The A layer containing polyester A as the main constituent component and the B layer containing polyester B as the main constituent component can be arbitrarily combined. For example, it is possible to make a composite such as polyester A / polyester B, polyester A / polyester B / polyester A, polyester B / polyester A / polyester B, and the like.
[0035]
At this time, polyester A / polyester B in which polyester B is laminated on at least one surface, in terms of improving the bleed-out resistance, handling properties, non-tackiness during processing, or thermal adhesive properties of the plasticizers listed above, More preferably, a configuration of polyester B / polyester A / polyester B in which polyester B is laminated on both sides is preferable.
[0036]
Examples of the acid component of polyester B include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sodiumsulfoisophthalic acid, and phthalic acid. , Oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, cyclohexyne dicarboxylic acid and other alicyclic dicarboxylic acids, p-oxybenzoic acid and other oxycarboxylic acids An acid etc. can be mentioned. In terms of heat resistance, moldability, processability, and printability, terephthalic acid, isophthalic acid, adipic acid and the like can be preferably used.
[0037]
Examples of the glycol component of polyester B include aliphatic glycols such as ethylene glycol, propanediol, butanediol pentanediol, hexanediol and neopentyl glycol; alicyclic glycols such as cyclohexanedimethanol. Bisphenols (bisphenol A, bisphenol S, etc.), 1,3-bis (2-hydroxyethoxy), 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, Aromatic glycols such as bis [4- (2-hydroxyethoxy) phenyl] sulfone, 2,2-bis (4-β-hydroxyethoxyphenyl) propane, hydroquinone, resorcin; diethylene glycol, polyethylene glycol, polytrimethylene glycol, polythene It can be exemplified La glycol and the like. The amount of diethylene glycol contained is preferably 0.1 to 10 mol% in terms of moldability, processability and printability, and further 0.3 to 5 mol% in terms of preventing deterioration of weather resistance. preferable.
[0038]
Particularly for applications requiring formability and workability, the intrinsic viscosity of polyester B is preferably 0.5 to 1.5, more preferably 0.6 to 1.3, and It is especially preferable that it is 7-1.0.
[0039]
As for polyester B, it is preferable that M / P ≦ 1, similarly to polyester A, more preferably the range of M / P is 0.0001 or more and less than 1, more preferably 0.001 or more and 0.8 or less. Most preferably, it is 0.01 or more and 0.6 or less.
[0040]
In particular, the thickness of the polyester B layer is preferably 0.1 μm or more and 1 mm or less from the viewpoint of improving the bleed-out resistance of the plasticizer, the handleability of the film, the non-adhesiveness during processing, and the like. More preferably, they are 1 micrometer or more and 1 mm or less.
[0041]
Furthermore, in the present invention, particles may be added to each layer in order to improve the handling and processability of the film.
[0042]
Specifically, the inorganic particles include wet and dry silica, colloidal silica, aluminum silicate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, alumina, mica, kaolin, clay, titanium oxide, zirconia, hydroxyapatite and the like. Can be used.
[0043]
As the organic particles, various organic polymer particles can be used. As the type thereof, particles having any composition may be used as long as at least a part thereof is insoluble in polyester. In addition, as the material of such particles, various materials such as polyimide, polyamideimide, polymethyl methacrylate, formaldehyde resin, phenol resin, cross-linked polystyrene, and silicone resin can be used. Vinyl-based crosslinked polymer particles and crosslinked polystyrene particles are particularly preferable because particles having a uniform particle size distribution can be easily obtained.
[0044]
The particles are added to polyester A and / or polyester B, and the average particle diameter of the particles is preferably 0.01 to 10 μm. Especially in applications where workability is important, the average particle diameter is 0.1 to 5 μm. It is preferable to contain particles.
[0045]
When particles are added to each layer, the amount of particles added is preferably 0.01 to 70% by weight.
[0046]
Furthermore, each layer may contain a component imparting low surface energy such as wax and silicone, and the amount added is preferably 0.01 to 1% by weight in each layer.
[0047]
In terms of improving the beauty, it is preferable to use a filter that cuts coarse particles of 30 μm or less and foreign matters, and particularly a filter that cuts 20 μm or less when the thermoplastic composition is melt-extruded.
[0048]
Furthermore, the content of acetaldehyde in the film is preferably 100 ppm or less, more preferably 50 ppm or less, and particularly preferably 30 ppm or less in terms of reducing the odor during molding and processing or reducing the odor as a product. Is desirable.
[0049]
The method for reducing the content of acetaldehyde in the film is not particularly limited. For example, in order to remove acetaldehyde generated by thermal decomposition when the polyester is produced by a polycondensation reaction, the polyester is reduced under reduced pressure or not. A method in which heat treatment is performed at a temperature below the melting point of the polyester in an active gas atmosphere, preferably a method in which the polyester is solid-phase polymerized at a temperature of 150 ° C. or higher and below the melting point in a reduced pressure or inert gas atmosphere; For example, a method of melt extrusion using the polymer, a method of extruding in a short time by reducing the extrusion temperature as much as possible when the polymer is melt-extruded can be used.
[0050]
The thickness of the polyester film according to the present invention is preferably 10 to 2000 μm, more preferably 20 to 1000 μm, in terms of moldability and processability.
[0051]
The method for producing a polyester film according to the present invention is not particularly limited, but as an example of mixing polyester terephthalate containing particles, polypropylene terephthalate, polybutylene terephthalate as polyester A, a mixture of polyester and optionally a phosphorus compound After being dried or dried, it is supplied to a single-screw or twin-screw melt extruder, extruded into a sheet from a slit die, dropped between nip rolls, closely contacted with a casting drum, cooled and solidified, and an unstretched sheet obtain. At this time, it is preferable to reduce the diameter of the nip roll and / or increase the roll temperature in order to produce a film of 150 μm or less. In reducing the diameter of the nip roll, the diameter is preferably 400 mm or less, particularly preferably 300 mm or less. The roll temperature is preferably increased from 40 ° C to 150 ° C, more preferably from 50 ° C to 140 ° C. The obtained sheet, which may be roughened to make the film non-tacky, is rolled into a roll sheet to obtain a product.
[0052]
Further, the close contact with the casting drum by the electrostatic application method can be stably cooled, and thus can be more preferably used in terms of maintaining the flatness during the heat processing.
[0053]
In particular, in applications in which formability and workability are important, it is preferable to produce an unstretched film as described above.
[0054]
On the other hand, in applications where heat resistance is important, there is a method for obtaining a film having a desired elongation at break by stretching and heat-treating the unstretched sheet in the longitudinal direction and / or width direction of the film, if necessary. . Preferably, the tenter method is preferred in terms of film quality. After stretching in the longitudinal direction, a sequential biaxial stretching method in which the film is stretched in the width direction, and a simultaneous biaxial stretching method in which the longitudinal direction and the width direction are stretched almost simultaneously. Is desirable. The draw ratio is preferably 1.5 to 5.0 times, more preferably 1.5 to 4.0 times in each direction. Either the stretching ratio in the longitudinal direction or the width direction may be increased or the stretching ratio may be the same. The stretching speed is desirably 1000% / min to 1000000% / min, and it is particularly preferable to form a film at a longitudinal stretching speed of 300000% / min or less. The stretching temperature can be any temperature as long as it is 100 ° C. or higher and 150 ° C. or lower, but glass transition temperature + 20 ° C. to 60 ° C. is preferable.
[0055]
Further, after this, the film is heat-treated, and this heat treatment can be carried out by any conventionally known method such as heating on a heated roll. The heat treatment temperature can be any temperature between 60 ° C. and 250 ° C., preferably 150 to 240 ° C. Moreover, although heat processing time can be made arbitrary, 0.1 to 60 second is preferable, More preferably, it is 1 to 20 second.
[0056]
The heat treatment may be performed while relaxing the film in the longitudinal direction and / or the width direction. Furthermore, re-stretching may be performed once or more in each direction, and then heat treatment may be performed.
[0057]
The thickness of the polyester film according to the present invention is preferably 10 to 2000 μm, more preferably 20 to 1000 μm, in terms of moldability and processability.
[0058]
The polyester film of the present invention may be subjected to corona discharge treatment, coating treatment, or the like before winding or after winding, if necessary, in order to improve processability and adhesion. At this time, the surface energy is preferably 40 to 60 mN / m, and more preferably 45 to 60 mN / m.
[0059]
The polyester film according to the present invention is preferably used as an unstretched film when emphasizing moldability and workability, but when used with uniaxial stretching or biaxial stretching, the moldability and workability are pointed out. The plane orientation coefficient is preferably 0.03 to 0.14. In particular, in applications where film formability and heat resistance are required, the plane orientation coefficient is preferably 0.03 to 0.145, more preferably 0.04 to 0.14, particularly preferably 0.05 to. 0.13. Here, the plane orientation coefficient is nMD for the longitudinal refractive index of the film, nTD for the width direction refractive index of the film, and nZD for the film thickness direction refractive index, and the plane orientation coefficient fn = (nMD + nTD) / It is represented by 2-nZD.
[0060]
The polyester film according to the present invention is used for applications that are molded and processed with a single layer, a non-metal or a laminated structure with a metal material because it is excellent in moldability, workability, and printability. Yes, the purpose of use is not particularly limited, but when used in a laminated manner, the non-metallic material is preferably paper, non-woven fabric, glass, or polymer material in terms of reducing the weight of the final product. On the other hand, in applications where the strength of the material is required, it can be used in a configuration in which the present film is laminated with a metal or glass reinforced polymer.
[0061]
The polyester film according to the present invention may be partially melted by heat and adhered to another material, or an adhesive layer may be provided on the film of the present invention or another material in advance. Further, an adhesive layer, a printed layer, or the like may be formed between other materials in the laminated configuration.
[0062]
As molding and processing methods, laminate molding, vacuum forming, pressure forming, vacuum pressure forming, drawing, bending, or a combination or combination of these forming methods or other processing methods may be applied alone or in plural. The molding and processing method is not particularly limited.
[0063]
When used alone, it may be subjected to molding processing such as vacuum forming, pressure forming, vacuum pressure forming, draw forming, folding forming, and overhang forming one or more times, and the forming method is not particularly limited. .
[0064]
【Example】
Hereinafter, the present invention will be described in detail by way of examples. Various characteristics were measured and evaluated by the following methods.
(1) Intrinsic viscosity of polyester
The polyester was dissolved in orthochlorophenol and measured at 25 ° C.
(2) Catalyst metal and amount of phosphorus in polyester
It was determined by fluorescent X-ray analysis. The quantification was performed by preparing a sample containing a certain amount of each metal element and creating a reference line.
(3) Melting point of polyester film
The polyester film was measured at a rate of temperature increase of 10 ° C./min with a differential scanning calorimeter (DSC type 2 manufactured by Perkin Elmer), and the melting peak temperature was taken as the melting point.
(4) Refractive index of film
Measurement was performed using an Abbe refractometer using sodium D-line (wavelength 589 nm) as a light source. The plane orientation coefficient is nMD as the longitudinal refractive index of the film, nTD as the refractive index in the width direction of the film, and nZD as the refractive index in the thickness direction of the film as follows: plane orientation coefficient fn = (nMD + nTD) / 2−nZD expressed.
(5) Average particle size
Cut the film cross section to create an ultrathin section, take a photograph with a transmission electron microscope at a magnification of about 5000 to 20000, measure the equivalent circle diameter of each particle dispersed in the polyester A, and determine the average particle diameter It was.
(6) Average breaking elongation
Measurement was performed at 80 ° C. using a Tensilon (tensile tester). For measurement, the film was kept at the measurement temperature for 30 seconds, the tensile rate was 300 mm / min, the width was 10 mm, the sample length was 50 mm, and the breaking elongation (%) in the film longitudinal direction and width direction was measured at 10 points, and the average value was obtained. It was.
(7) Pneumatic formability
The temperature was changed from 80 to 130 ° C., and the moldability was judged with a pressure molding machine. The state when molded under the best temperature conditions was determined as follows.
[0065]
(Double-circle): The corner was shape | molded sharply and the thickness after shaping | molding was also uniform.
[0066]
○: The corners were slightly rounded, but the thickness after molding was uniform.
[0067]
Δ: Slightly rounded corners and slightly non-uniform thickness after molding.
[0068]
X: The thickness after molding was non-uniform, wrinkled or whitened.
(8) Printability
A solvent-based ink containing ethyl acetate and toluene was gravure coated and the appearance after drying at 80 ° C. was confirmed.
[0069]
A: No whitening and good aesthetics
○: Some whitening is observed, but there is no beauty issue
Δ: Whitening is observed and beauty is reduced
×: Whitened greatly, appearance changed greatly
(9) Embossability
The polyester film of the present invention and a commercially available PET biaxially stretched film (“Lumirror” manufactured by Toray Industries Inc., S type 75 μm) are bonded with a urethane adhesive using ethyl acetate as a solvent, and dried at 80 ° C. Then, the polyester film side of the present invention is heated by roll heating (100 ° C.) and immediately before heating by condensing type radiation, and after passing through an embossing roll (50 μm high unevenness), a cooling roll (40 ° C.) It was cooled with. The radiation heating setting was changed and the best condition was evaluated. The embossability of the obtained film was determined as follows. The beauty was determined by the absence of color change, wrinkles, and no glare.
[0070]
A: The uneven shape of the embossing roll is excellently formed on the film side, both large and small. Good beauty.
[0071]
○: A large portion of the embossing roll having a large uneven shape is formed on the film side. There is almost no change in beauty.
[0072]
(Triangle | delta): Although the uneven | corrugated shape of an embossing roll is formed in the film side, an unevenness | corrugation is slightly shallow.
A change in beauty is also observed.
[0073]
X: The embossing roll has an uneven shape on the film side, but the unevenness is shallow, and the change in beauty is large.
[0074]
Example 1
After performing a transesterification reaction by adding a titanium catalyst as a catalyst to dimethyl terephthalate and propylene glycol, a polycondensation reaction was performed by adding phosphoric acid (molecular weight 98) as a thermal stabilizer to obtain a polyester composition I (catalyst metal) Element amount: 13 mmol%, phosphorus element amount: 3 mmol%). Further, the polyester composition I was melted by providing two vacuum vents (5 Torr) with a twin-screw extruder, and a predetermined amount of powdered crosslinked polystyrene particles (average particle size 6 μm) was added. The polymer physical property of the polyester composition was an intrinsic viscosity of 0.90. Furthermore, after adding a manganese catalyst as a catalyst to dimethyl terephthalate and ethylene glycol, and performing a transesterification reaction, antimony trioxide as a polymerization catalyst and phosphoric acid (molecular weight 98) as a heat stabilizer are added, and a polycondensation reaction is performed to obtain a polyester composition. Compound II was obtained (amount of catalytic metal element: 70 mmol%, amount of phosphorus element: 100 mmol%). The polymer physical property of the polyester composition was an intrinsic viscosity of 0.71.
[0075]
The polyester composition I and the polyester composition II obtained as described above were chip-blended so as to have the composition shown in Table 1. Then, it vacuum-dried at 150 degreeC, supplied to the extruder, and after discharging from a nozzle | cap | die by a conventional method, it cooled and solidified with the mirror surface cooling drum, applying an electrostatic, and obtained the 100-micrometer unstretched film. Table 1 shows the physical properties, moldability, printability, and processability of the obtained film. As can be seen from Table 1, it was found that the moldability, printability and processability were excellent.
[0076]
Example 2
The composition of the particles and polyester was changed as shown in Table 1, and a phosphorus compound (Adekastab AX-71 (stearyl phosphoric acid, average molecular weight 490) manufactured by Asahi Denka Kogyo Co., Ltd.) was melted and extruded into a polyester with a feeder in an undried state. Weighed to add 625 mmol% phosphorus element, polyester I (catalyst metal element amount: 13 mmol%, phosphorus element amount: 3 mmol%) and polyester II (catalyst metal element amount: 88 mmol%, phosphorus element amount 27) A certain amount of the mixture (mol%) was fed into a twin-screw extruder (three vacuum vents after polyester melting) at a feeder using a feeder, and melt extrusion was performed at 270 ° C. Example 1 except that the film was cast with a nip roll (diameter 250 mm) with a cooling drum at 0 ° C. to obtain a 100 μm film. To obtain a film in the like.
[0077]
Example 3
Film formation was carried out in the same manner as in Example 2 except that the amount of the polyester I particles, polyester I, II, and phosphorus compound was changed and polyethylene glycol dibenzoate (molecular weight 600) was added in a 5 wt% liquid form. . In particular, workability was improved.
[0078]
Example 4
The plasticizer of Example 3 is 10% by weight, the polyester particles are removed from the polyester A, the composite structure is B / A / B (composite ratio: 1: 10: 1), and the polyester of the B layer is implemented. A film was obtained in the same manner as in Example 1 except that the polyester used in Example 1 was formed into a composite film and a 60 μm film was obtained. The obtained film was particularly excellent in printability.
[0079]
Comparative Example 4
In Example 4, a biaxially stretched film with a polyester A plasticizer of 5% by weight, a longitudinal stretching temperature of 80 ° C., a stretching ratio of 3.1 times, a transverse stretching temperature of 100 ° C., 2.8 times, and a heat treatment temperature of 230 ° C. Got. Although the moldability decreased, the printability was excellent.
[0080]
Example 6
As polyester I, PBT (inherent viscosity 1.0, Ti catalyst: 50 mmol%, phosphorus 30 mmol%) was used to obtain a film in which the particles and blend amount were changed.
[0081]
Comparative Example 1
A film was obtained in the same manner as in Example 2 except that only polyester II was used in Example 1, particles were added during polymerization of polyester II, and film formation was performed with a roll diameter of 450 mm and a casting temperature of 20 ° C. . As a result, as shown in Table 3, the moldability and workability were greatly reduced.
[0082]
Comparative Example 2
A film having a thickness of 60 μm was obtained in the same manner as in Example 1 using cyclohexanedimethanol 30 mol% copolymerized PET as the polyester. As a result, as shown in Table 3, the printability was greatly reduced.
[0083]
Comparative Example 3
Film formation was performed in the same manner as in Example 6 except that the blend amount was changed so that M / P was 2. As a result, as shown in Table 3, moldability and printability were greatly reduced.
[0084]
[Table 1]

[0085]
[Table 2]

[0086]
[Table 3]

[0087]
The symbols in the table are as follows.
[0088]
EG: Ethylene glycol
PG: propanediol (1,3-propanediol)
DEG: Diethylene glycol
BG: Butanediol
PET / CHDM: cyclohexanedimethanol copolymerized PET
[0089]
【The invention's effect】
According to the present invention, the concentration of the catalytic metal element contained in the polyester film containing at least two glycol components selected from ethylene glycol, butanediol, and propanediol and the phosphorus elementofConcentration ratio M / P is 1 or lessThe average breaking elongation of the film at 80 ° C. is 800% or more.By this, the polyester film suitable as a process film at the time of shaping | molding, a process, a printed product or a shaping | molding, a process, and printing can be provided.

Claims (5)

A polyester B containing at least two types of glycol components selected from ethylene glycol, butanediol, and propanediol is a constituent component, and a polyester B layer is composited on at least one side of a polyester A layer that satisfies the following formula (1). The polyester film characterized by having an average breaking elongation of the film at 80 ° C. of 800% or more.
M / P <1 (1)
(In the formula, M represents the concentration of the catalytic metal element remaining in the polyester A (mmol%), and P represents the concentration of the phosphorus element remaining in the polyester A (mmol%).) The polyester film according to claim 1, wherein 10 to 90 mol% of the glycol component of polyester A is ethylene glycol, and 10 to 90 mol% is butanediol and / or propanediol. The polyester film according to claim 1 or 2, wherein the polyester A is formed by blending two or more resins selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate. The polyester film according to claim 3, wherein the polyester A is a blend of 40 to 90% by weight of polyethylene terephthalate and 10 to 60% by weight of polypropylene terephthalate. The polyester film according to claim 1, wherein at least one of melting point peaks in DSC of polyester A is 220 ° C. or higher and 280 ° C. or lower.