JPH11335540A - Polyester composition and film resulted therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To plan improving smoothness, wear resistance, flavor, adhesion and impact resistance by adding certain indeterminate and/or coherent inorganic particles to polyesters. SOLUTION: Indeterminate and/or coherent inorganic particles which have water contents of 0.5% or less and a peak between 50-80 ppm in spectra at<13> C-NMR measurements, is obtained by heat mixing at least 50 deg.C for at least 5 min inorganic particles which are BET specific surface of 30-1,000 m<2> /g of at least a one compound selected from silicon dioxide, aluminum oxide, calcium phosphate, magnesium oxide, metal carbonates and silicates, and which are an average secondary particle diameter of 0.001-10 μm, with 0.001-50 wt.% of glycol compounds. An objective polyester composition is prepared by adding 0.0001-10 wt.% of indeterminate and/or coherent inorganic particles, and is necessary, 1-500 ppm of at least one element selected from germanium, antimony and titanium, with polyesters which have diethylene glycol contents of 0.5-5 wt.% and a melting point of 100-270 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester composition and a film comprising the same. More specifically, the present invention relates to a polyester composition containing inorganic particles having excellent affinity for polyester, and transparency, slipperiness, abrasion resistance, and the like. The present invention relates to a film having excellent flavor, adhesion, and impact resistance. More specifically, for magnetic recording media,
The present invention relates to a polyester composition and a film suitable for electrical insulation, general industrial use, food packaging, and the like, and particularly suitably used for food packaging and for bonding metal plates for beverages, food metal cans, and the like. And a film comprising the same.

[0002]

2. Description of the Related Art Polyesters represented by polyethylene terephthalate have excellent physical and chemical properties and are widely used as fibers, films and other molded products. Among these molded products, films are used for magnetic recording media, for electrical insulation, for general industry, for food packaging, etc., but most of them are films made of homopolyester represented by polyethylene terephthalate. .

[0003] Films used in these applications, particularly for magnetic recording media, electrical insulation, general industrial use, etc., are used to improve the handleability and quality characteristics of these processed products, or in the process of producing films. Including fine particles such as inorganic particles in the polyester to form moderate unevenness on the film surface for imparting smoothness and abrasion resistance to the film or processed product for the process passability in the processing process. It has been known.

However, in the method in which the inorganic particles are simply contained in the polyester, the affinity between the inorganic particles and the polyester is not sufficient, so that peeling occurs at the interface between the particles and the polyester during stretching or the like, and voids are formed. I do. As a result, when the film is used for a magnetic recording medium, it may cause a loss of magnetic recording signals or cause electrical insulation. When used for applications, it may be a dielectric breakdown point or cause deterioration of electrical characteristics.

In order to solve such a drawback, for example, Japanese Patent Application Laid-Open No. 53-45396 discloses a method of treating silicon oxide with a quaternary ammonium compound for the purpose of improving slipperiness and transparency. In Japanese Patent Application Laid-Open No. 61-31429, in order to reduce coarse projections on the surface of a film, water in a water-dispersed sol of silicon dioxide is replaced with glycol in order to make the polyester into a single particle state without containing agglomerated particles. For heating an organosol obtained by heating
In Japanese Patent Application Laid-Open No. 3-221158, there is proposed a method in which an amorphous spherical inorganic oxide fine particle having a glycol bonded to a particle surface is contained for the purpose of improving slipperiness and surface smoothness.

In order to improve the affinity between the particles and the polyester, for example, JP-A-62-235353 and JP-A-1-92265 disclose surface treatment with a phosphorus compound and JP-A-4-28715. Has proposed a surface treatment using a monophthalic ester.

On the other hand, among the above-mentioned applications, it is known to use a film composed of a modified polyester obtained by copolymerizing a specific component with a homopolyester, in addition to a film composed of a homopolyester.

For example, there are known films for bonding metal plates for various kinds of metal cans for beverages. For use in this application, (1) adhesion to a metal plate, forming Excellent wear resistance during processing.

(2) The laminated film is not crystallized or deteriorated by heating such as drying, printing and baking, and retort sterilization after can making, and the film does not peel off, shrink, crack, or pinhole.

(3) The polyester film does not peel or crack due to impact on the metal can.

(4) The content of the can is not adsorbed on the polyester film by the scent component, or the flavor of the content is not impaired by the components or odors eluted from the polyester film (hereinafter referred to as flavor). Such characteristics are required.

In response to these requirements, Japanese Patent Application Laid-Open No. 2-573
39, JP-A-2-305827, JP-A-5
Japanese Patent Application No. -154971 proposes a film made of various copolymerized polyesters as a metal plate bonding film.

[0013]

However, according to the above-mentioned conventional method, the transparency, slipperiness, and abrasion resistance when used for magnetic recording media, electrical insulation, general industrial use, food packaging, etc. are sufficient. In addition, flavor, heat resistance, adhesiveness, for use in food packaging and metal plate bonding
Various properties such as impact resistance are not sufficient.

The present invention solves the above problems and provides excellent transparency, slipperiness, and abrasion resistance for use in magnetic recording media, electrical insulation, general industry, food packaging, and the like.
In particular, it has various properties such as excellent heat resistance, flavor, adhesiveness, impact resistance, etc., and also has good handleability of film processed products for use in food packaging and metal plate bonding. An object is to provide a polyester composition and a film.

[0015]

SUMMARY OF THE INVENTION The object of the present invention is to provide particles of polyester having a peak between 50 and 80 ppm in the spectrum of ¹³ C NMR measurement, and amorphous and / or agglomerated inorganic particles. And a film comprising the same.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester of the present invention is preferably composed of a dicarboxylic acid component and a glycol component. For example, an esterification or transesterification reaction of a dicarboxylic acid or an ester-forming derivative thereof with a glycol, and a subsequent reaction. It is produced by a polycondensation reaction. The type of polyester is not particularly limited as long as it can be formed into a molded product such as a film. Suitable polyesters that can be molded into molded articles such as films include those composed of an aromatic dicarboxylic acid as a dicarboxylic acid component and aliphatic glycol or alicyclic glycol as a glycol component, such as polyethylene terephthalate and polyglycol. -1,3-propylene terephthalate, polyethylene-1,2-bis (2-chlorophenoxy) ethane-4,4′-dicarboxylate,
Polyethylene-1,2-bis (phenoxy) ethane-
4,4'-dicarboxylate, polyethylene-2,6
-Naphthalene dicarboxylate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate and the like, among others, from the viewpoint of the abrasion resistance of the film,
Polyethylene terephthalate, poly-1,3-propylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate and polybutylene terephthalate are preferred.

The polyester of the present invention can be preferably a copolymerized polyester obtained by copolymerizing a dicarboxylic acid component and a glycol component other than the dicarboxylic acid component and the glycol component constituting the polyester described above. The dicarboxylic acid component and glycol component to be copolymerized are not particularly limited, but, for example, an acid component such as aromatic dicarboxylic acid, aliphatic dicarboxylic acid and alicyclic dicarboxylic acid, aromatic glycol, aliphatic glycol and Glycol components such as alicyclic glycols can be mentioned. Specifically, terephthalic acid,
Aromatic dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, phthalic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid,
Aliphatic dicarboxylic acids such as maleic acid and fumaric acid, 1,4
-Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and decalindicarboxylic acid and ester-forming derivatives derived therefrom. Among these dicarboxylic acid components, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; aliphatic dicarboxylic acids such as adipic acid, sebacic acid, and dimer acid; and ester-forming derivatives derived therefrom are metals. It is preferable from the viewpoints of heat resistance, flavor, adhesiveness, impact resistance and the like when used for a film for plate bonding.

The glycol components include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 1,10-
Examples thereof include aliphatic glycols such as decanediol, alicyclic glycols such as 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and hydrogenated bisphenol A. Among these glycol components, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,4-cyclohexane dimethanol are used for heat resistance, flavor, and the like when used for a metal plate bonding film and the like. It is preferable in terms of adhesiveness, impact resistance, and the like.

The above dicarboxylic acid component and glycol component may be used alone or in combination of two or more. Further, these copolymer components may be by-produced when producing the polyester.

The amount of the copolymer component is not particularly limited, but is preferably 50 mol% or less, more preferably 1 to 40 mol%, in view of the heat resistance, flavor, adhesion and impact resistance of the obtained film. Mol%, more preferably 2-3
0 mol%, particularly preferably 5 to 25 mol%. If the amount of the copolymer component exceeds the above range, the heat resistance and impact resistance of the film may be poor.

The polyester of the present invention has a diethylene glycol content of 0. 0 from the viewpoint of heat resistance, flavor properties, adhesiveness and the like when used for a film for bonding metal plates.
The content is preferably 5 to 5% by weight, more preferably 0.7 to 3% by weight, and still more preferably 0.8 to 2.5% by weight.

The melting point of the polyester of the present invention is not particularly limited. However, from the viewpoints of heat resistance, adhesiveness, impact resistance and the like when used for a film for bonding a metal plate, etc.
00-270 degreeC is preferable. More preferably 120 to 2
The temperature is 60 ° C, more preferably 140 to 245 ° C. If the melting point of the polyester is out of this range, properties such as heat resistance, flavor properties, and impact resistance may be poor.

The amorphous and / or agglomerated inorganic particles contained in the polyester of the present invention have a peak between 50 and 80 ppm in the spectrum in ¹³ C NMR measurement. This peak -OC _n H _m - are those attributable to binding, or -OC _n H _m OH bonds. In particular, ¹³
55 to 75 ppm in the spectrum in C NMR measurement
It is preferable to have two or more peaks between them.

The inorganic particles are amorphous and / or agglomerated and have a spectrum as determined by ¹³ C NMR measurement of 50%.
By having a peak between about 80 ppm, the affinity with the polyester is excellent, and the film made of the obtained polyester composition has excellent abrasion resistance. It also has excellent properties and impact resistance.

The method of causing the inorganic particles to have a peak between 50 and 80 ppm in the spectrum in ¹³ C NMR measurement is not particularly limited. For example, a method of surface-treating the inorganic particles with a glycol compound, specifically, Examples thereof include a method of mixing a glycol compound and inorganic particles, and a method of heating a glycol slurry of inorganic particles in which inorganic particles are dispersed in a glycol compound.

The glycol compounds used in this case include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, diethylene glycol,
Glycols used in producing the polyester of the present invention, such as 1,6-hexanediol and 1,10-decanediol, can be exemplified, and aliphatic glycol compounds are particularly preferred. Among these glycol compounds, Ethylene glycol, 1,3-propylene glycol, and 1,4-butanediol can be used. In particular, inorganic particles treated with ethylene glycol can be used in a metal plate laminating film or the like in terms of flavor and resistance. It is preferable in terms of abrasion, adhesion, impact resistance and the like. The above-mentioned glycol compounds may be used alone or in combination of two or more.

Separately, as a method for surface-treating the inorganic particles with a glycol compound, a pulverizer such as a roll mill, a high-speed rotary pulverizer, a jet mill or a mixer such as a Nauta mixer, a ribbon mixer, a Henschel mixer is used. Then, (1) heating the inorganic particles and the glycol compound with stirring, (2) heating the inorganic particles with stirring, and then adding the glycol compound to the inorganic particles by spraying or the like. At this time, the surface treatment conditions such as the amount of the glycol compound, the treatment temperature and the time can be appropriately set, and are not particularly limited. The amount of the glycol compound for surface-treating the inorganic particles is preferably 0.001% by weight or more, more preferably 1% by weight or more, still more preferably 5% by weight or more based on the inorganic particles.
Particularly preferably, it is at least 10% by weight. The treatment temperature is preferably 50 ° C. or higher, more preferably 100 ° C. or higher,
It is more preferably at least 150 ° C., particularly preferably at least the boiling point of glycol. Further, the processing time is preferably 0.5 minutes or more, more preferably 1 minute or more, and further preferably 5 minutes or more. Further, at the time of surface treatment, it is preferable to previously remove water from the inorganic particles in a dryer or in the above-described treatment step. The water content of the inorganic particles is not particularly limited, but may be 0.5% by weight or less. Preferably, more preferably 0.2% by weight or less, still more preferably 0.1% by weight.
1% by weight or less.

In order to surface-treat the inorganic particles with the glycol compound, the method of heating the glycol slurry of the inorganic particles in which the inorganic particles are dispersed in the glycol compound is performed under various conditions such as the concentration of the glycol slurry of the inorganic particles, The processing temperature and time can be appropriately set, and are not particularly limited. The concentration of the inorganic particles in the glycol compound is preferably 50% by weight or less, more preferably 30% by weight or less, and particularly preferably 20% by weight or less. The heat treatment temperature is preferably 50 ° C. or higher, more preferably 100 ° C. or higher, even more preferably 150 ° C. or higher,
Particularly preferably, it is higher than the boiling point of glycol. The heat treatment time is preferably 0.5 minutes or more, more preferably 1 minute or more, further preferably 5 minutes or more, and particularly preferably 30 minutes or more. At this time, the inorganic particles are dried in advance by a dryer or the like, and after removing water, the inorganic particles are dispersed in glycol and used or used, or in the heating step, the water in the glycol slurry of the inorganic particles is removed. Is preferred. The water content of the inorganic particles and the water content of the inorganic particles in the glycol slurry are not particularly limited, but the water content of the inorganic particles is preferably 0.5% by weight or less, more preferably 0.5% by weight or less.
2% by weight or less, more preferably 0.1% by weight or less, and the water content of the inorganic particles in the glycol slurry is 0.5% by weight.
% By weight or less, more preferably 0.2% by weight or less, and even more preferably 0.1% by weight or less. When the surface treatment conditions of the inorganic particles with the glycol compound, the amount of the glycol compound, the treatment temperature, the treatment time and the like are out of the range, when the inorganic particles are blended with the polyester, the transparency and the resistance of the film comprising the obtained polyester composition are improved. In the case of using a film for improving abrasion, particularly a film for bonding a metal plate, the effect of improving flavor, adhesion and impact resistance may be insufficient.

The inorganic particles contained in the polyester of the present invention are irregular and / or aggregated particles. With amorphous inorganic particles, the shape of each particle is spherical, polyhedral,
These are irregular particles such as cylinders. Further, the aggregated inorganic particles are aggregates of primary particles regardless of the shape of the primary particles. The state of formation of the aggregates of the primary particles is not particularly limited, but has an affinity for polyester, abrasion resistance of a film obtained from the polyester composition and flavor properties when used as a metal plate bonding film, adhesiveness, From the viewpoint of impact resistance, aggregates formed at intervals smaller than twice the primary particle diameter are preferable, and aggregates formed at intervals smaller than the primary particle diameter are more preferable. The aggregate at that time may be formed of two or more primary particles, and preferably three or more, more preferably five or more primary particles.

The content of the amorphous and / or aggregated inorganic particles contained in the polyester is not particularly limited, and the amorphous inorganic particles alone may be used. Only inorganic particles may be used, or these particles may be mixed. Excellent in compatibility with polyester, from the viewpoint of the abrasion resistance of the film obtained from the polyester composition and the flavor, adhesion, and impact resistance when used as a metal plate bonding film, aggregated inorganic particles are used. It is preferred to contain.

The amorphous and / or agglomerated inorganic particles of the present invention are not particularly limited, and include, for example, silicon dioxide, aluminum oxide, calcium phosphate, magnesium oxide, metal carbonate, silica and the like by a dry method or a wet method. Aluminum silicate, silicates such as magnesium silicate, barium sulfate, zinc sulfide, titanium dioxide and the like can be mentioned. Among them, the sliding property of the film, abrasion resistance, or the flavor property when it is used as a metal bonding film, From the viewpoint of adhesiveness, abrasion resistance, etc., from the group consisting of silicates such as silicon dioxide, aluminum oxide, calcium phosphate, magnesium oxide, metal carbonates, aluminum silicate and magnesium silicate by the dry method or the wet method. At least one inorganic particle selected from the group consisting of Particularly, in order to combine various properties of the obtained film, silicon dioxide of a dry method and / or a wet method is preferable. Further, fine particles composed of other inorganic particles and organic particles may be contained in addition to silicon dioxide.

In the present invention, the content of the polyester in the inorganic particles is not particularly limited, but may be 0.000.
It is preferably 1 to 10% by weight, more preferably 0.005% by weight.
10 to 10% by weight, more preferably 0.01 to 5% by weight,
Particularly preferably, it is 0.05 to 2% by weight. 0.000
If the amount is less than 1% by weight, the film may have poor slipperiness and wear resistance.

The particle size and specific surface area of the inorganic particles in the present invention are not particularly limited, but the average secondary particle size is preferably 0.001 to 10 μm, more preferably 0.01 to 10 μm. Yes, it is particularly preferable that the average secondary particle diameter is 0.02 to 5 μm in terms of the effect of imparting slipperiness to the film, and furthermore, the flavor and abrasion resistance when used as a film for bonding a metal plate. . Also,
The average primary particle diameter of the inorganic particles is not particularly limited, but from the viewpoint of flavor properties, abrasion resistance, and the like when used as a metal plate bonding film, is preferably 0.2 μm or less,
More preferably 0.1 μm or less, particularly preferably 0.0
5 μm or less. Furthermore, the specific surface area is 30-1000m
² / g is preferred, and more preferably 50 to 700 m ² / g.
Flavor if it is, more preferably 100~600m ² / g, it especially is 150~500m ² / g, sliding property and wear resistance of the film, further having a film laminated metal sheet Properties, impact resistance, adhesion,
It is preferable in terms of abrasion resistance and the like.

The method of blending the inorganic particles with the polyester in the present invention is not particularly limited. For example, (1) a method in which the inorganic particles are added at an arbitrary stage in the polyester production reaction step; A method of directly kneading the polyester with a blender, a mixer, or the like, and then melt-kneading the mixture using a normal single-screw or twin-screw extruder. (3) Directly or in advance using a blender, a mixer, etc. After mixing, a method of melt-kneading using an ordinary vent-type single-screw or twin-screw extruder can be used. Above all, the inorganic particles can be contained in the polyester with good dispersibility, and in terms of quality stability such as slipperiness and abrasion resistance of the obtained film,
The method (1) or (3) is preferred, and the method (1) is particularly preferred.

Specifically, a method of subjecting a polyester to an esterification reaction from a dicarboxylic acid and a glycol, followed by addition of inorganic particles at an optional stage during the production by a polycondensation reaction, and a method of forming the polyester into a dicarboxylic acid ester A method of adding inorganic particles at any stage during the production by a transesterification reaction between a hydrophilic derivative and glycol and a subsequent polycondensation reaction can be mentioned.As a method for adding inorganic particles, powder is added. The slurry may be added as a slurry in which inorganic particles are dispersed in a glycol used for producing a polyester, and is not particularly limited. The concentration of the inorganic particles in the slurry at this time is not particularly limited, but is preferably added at 50% by weight or less from the viewpoint of the dispersibility of the particles in the polyester.

As described above, the present invention provides a polyester having a spectrum of 50 to 80 based on ¹³ C NMR measurement.
A polyester composition containing particles having a peak between ppm and amorphous and / or aggregated inorganic particles, and a film comprising the same.

In the spectrum in ¹³ C NMR measurement, 5
Particles having a peak between 0 and 80 ppm and containing amorphous and / or aggregated inorganic particles are excellent in affinity between the inorganic particles and the polyester. The film obtained from the polyester composition of the present invention is excellent in transparency, slipperiness, abrasion resistance, flavor, and impact resistance, and is suitable for magnetic recording media, electric insulation, food packaging, general industrial use, and the like. In particular, it is suitably used for bonding metal plates for beverages, food metal cans and the like. In particular, in the case of inorganic particles having a large specific surface area or amorphous and / or agglomerated inorganic particles having a small average primary particle diameter, they are more excellent in abrasion resistance, flavor, adhesiveness and impact resistance.

The polyester composition of the present invention preferably contains 1 to 500 ppm of at least one element selected from germanium, antimony and titanium. More preferably, it is 2 to 400 ppm, and still more preferably, 3 to 300 ppm. If the amount of at least one element selected from germanium, antimony and titanium is less than 1 ppm, the effect of flavor may not be sufficient, and if it exceeds 500 ppm, foreign matters may be generated in the polyester and the nucleating agent In some cases, crystallization is likely to occur, and impact resistance may deteriorate. The polyester composition of the present invention contains at least one or more elements selected from germanium, antimony, and titanium in a specific amount, thereby improving flavor. Among these elements, germanium is particularly preferred.

The compound used for causing the polyester composition of the present invention to contain at least one element selected from germanium, antimony and titanium is not particularly limited. Examples of the germanium compound include germanium dioxide and crystallization water. Germanium oxides and hydroxides such as germanium hydroxide, germanium alkoxide compounds such as germanium tetramethoxide and germanium ethylene glycoloxide, phosphorus-containing germanium compounds such as germanium phosphate, and germanium acetate.

Examples of the antimony compound include diantimony trioxide and antimony acetate.

Examples of the titanium compound include oxides such as titanium dioxide, hydroxides such as titanium hydroxide, alkoxide compounds such as tetramethoxytitanate, tetraethoxytitanate and tetrabutoxytitanate, and glycooxide compounds such as tetrahydroxyethyltitanate. ,
Compounds such as phenoxide compounds and acetates can be mentioned.

The method for incorporating the above-mentioned elements into the polyester composition may be any conventionally known method, and is not particularly limited, but is preferably added at any stage of the polyester production process. In this case, it may be added as a polyester reaction catalyst.

In producing the polyester composition of the present invention, conventionally known reaction catalysts and coloring inhibitors can be used, and examples of the reaction catalyst include alkali metal compounds,
Alkaline earth metal compounds, zinc compounds, manganese compounds, cobalt compounds, aluminum compounds, and the like. Examples of the coloring inhibitor include phosphorus compounds.

The carboxyl terminal group concentration of the polyester composition and the film in the present invention is from 20 to 50 equivalents / polyester from the viewpoint of abrasion resistance or heat resistance, adhesion and impact resistance when used for laminating a metal plate. It is preferably 10 ⁶ g, more preferably 30 to 30 g.
50 is equivalent / polyester 10 ⁶ g, more preferably 35 to 50 equivalents / polyester 10 ⁶ g. If the carboxyl terminal group concentration is out of the range, properties such as adhesion and abrasion resistance may be poor.

The intrinsic viscosity of the polyester composition and the film in the present invention is determined to be 0. 0 in terms of strength and crystallinity, and not to cause cracks during forming of a metal can when used for laminating a metal plate. 5dl /
g or more, more preferably 0.55 to 1.5 d
l / g, and more preferably 0.6 to 1 dl / g.

When the polyester composition and film of the present invention are used especially for bonding metal plates, the content of acetaldehyde and the content of oligomers such as cyclic trimers should be smaller in view of flavor. Is desirable. The content of acetaldehyde is preferably at most 10 ppm, more preferably at most 8 ppm, further preferably at most 5 ppm. The content of the oligomer is preferably 0.9% by weight or less, more preferably 0.8% by weight or less, and further preferably 0.7% by weight or less. When the content of acetaldehyde or the content of the oligomer is out of the range, the flavor may be poor.

The method for reducing the content of acetaldehyde and the content of oligomer in the polyester composition or film is not particularly limited. For example, in order to remove acetaldehyde generated by thermal decomposition when producing a polyester by a polycondensation reaction or the like, a method of heat-treating the polyester composition under reduced pressure or an inert gas atmosphere at a temperature equal to or lower than the melting point and the obtained polyester. Examples of the method include a method of forming the composition into a film.Preferably, the polyester composition is subjected to solid-state polymerization at a temperature equal to or lower than the melting point under reduced pressure or an inert gas atmosphere, and the obtained polyester composition. The method of forming into a film is good.

The film produced from the polyester composition of the present invention may be an unstretched sheet or a uniaxially or biaxially stretched film.

A specific method for producing a film comprising the polyester composition of the present invention will be described. After drying, the polyester composition is melt-extruded into an unstretched sheet, and then biaxially stretched and heat-treated to form a film. The biaxial stretching may be any of longitudinal and transverse sequential stretching or biaxial simultaneous stretching. The stretching ratio is not particularly limited, but usually 2 to 5 times each in the longitudinal and transverse directions. After the biaxial stretching, the film may be further stretched in any of the longitudinal and transverse directions.

When the film of the present invention is used for laminating a metal plate, the film has good laminating properties and adhesion to a steel sheet.
From the viewpoint of moldability, the plane orientation coefficient is preferably from 0.08 to 0.15, more preferably from 0.09 to 0.14, even more preferably from 0.095 to 0.13.

The film of the present invention may be a laminated film comprising a layer comprising the polyester composition of the present invention and another polyester layer. The lamination structure at this time is not particularly limited as long as it is two or more layers. In particular, when the laminated film is used for bonding a metal plate, it is preferable that there is a difference with respect to the melting point of the polyester composition constituting the film of the present invention. It is more preferable because the adhesion to a plate, impact resistance, and heat resistance are improved. 1 to 50 in the laminated film
When a polyester layer having a melting point difference of ℃ is laminated with a metal plate, if the melting point of the polyester composition of the present invention is higher than the melting point, the heat resistance is improved; The performance is improved.

The thickness of the film of the present invention is not particularly limited, but is preferably 100 μm or less, and particularly 5 to 50 μm when used as a metal plate bonding film.
m, more preferably 10 to 30 μm.

Further, the polyester film of the present invention may be provided with an easy-adhesion layer on at least one surface for the adhesiveness of the film. The type of the easy-adhesion layer is not particularly limited, for example, acrylic resin, acrylic resin adjusted using acrylic acid, methyl methacrylate, methyl acrylate, etc., isophthalic acid, adipic acid, ethylene glycol, polyethylene glycol, etc. Polyurethane resin adjusted from
Terephthalic acid, 2,6-naphthalenedicarboxylic acid, 5-
Examples include polyester-based resins prepared using metal salts of sulfoisophthalic acid, isophthalic acid, adipic acid, ethylene glycol, polyethylene glycol, and the like. Among these, water-dispersible or water-soluble resins have adhesiveness and handleability. It is preferable from the point of view. The method for providing the easy-adhesion layer on at least one surface of the polyester film is not particularly limited. For example, in the process of producing the polyester film, the above-mentioned acrylic resin, polyurethane resin, aqueous dispersion or aqueous solution of the polyester resin, etc. Is preferably applied using a conventionally known reverse coating method, gravure coating method, die coating method, wire bar method or the like. The thickness of the easy-adhesion layer is not particularly limited, but is preferably in the range of 0.001 to 5 μm, more preferably 0.01 to 2 μm, and even more preferably 0.05 to 0. 5 μm is preferred.

The polyester composition and the film of the present invention may contain other thermoplastic resins such as polyethylene, polypropylene and polystyrene, and various additives such as carbodiimide and epoxy compounds. , An antioxidant, an antistatic agent, a surfactant, a pigment, a fluorescent whitening agent, and the like. In addition, an inorganic particle or an organic particle, for example, an organic particle having acrylic acid, styrene, or the like as a constituent component is appropriately contained as necessary. May be.

When the film of the present invention is used for bonding metal plates, a plate made of tin, steel, aluminum or the like is suitable as a metal plate for can making to be bonded. The bonding to the metal plate is performed, for example, by (1) heating the metal plate to a temperature equal to or higher than the melting point of the film, bonding the film, rapidly cooling the film, amorphizing the surface layer of the film in contact with the metal plate, and bringing the film into close contact. (2) An adhesive layer is provided on the film in advance, and this surface is bonded to a metal plate. As the adhesive layer, a resin adhesive, for example, an epoxy adhesive, an epoxy-ester adhesive, an alkyd adhesive, or the like can be used.

[0056]

The present invention will be described in more detail with reference to the following examples.

The characteristics in the examples were measured as follows.

A. Average primary particle diameter and average secondary particle diameter of inorganic particles The polyester composition and the cross section of the film are observed using a transmission electron microscope (TEM). The section thickness of the TEM was about 100 nm, and at least 100 particles were observed to determine the area average particle diameter.

B. Specific surface area of inorganic particles BET using Autosorb-1 manufactured by Kantachrome
The specific surface area was measured by the method.

C. ¹³ C NMR Measurement of Inorganic Particles The ¹³ C NMR measurement conditions of the inorganic particles are as follows, and the CPMAS or MAS spectrum is 50 to 80.
The peak between ppm was analyzed.

In the case where the inorganic particles for NMR measurement are powder, the inorganic particles are separated from the slurry according to the following method if the inorganic particles are in the form of a powder. The measurement was performed after vacuum drying at room temperature for 24 hours.

In the case of inorganic particles in the polyester composition, the measurement is performed after separation and drying by the following methods.

[Method of Separating Inorganic Particles in Glycol Slurry] Four times the amount of methanol relative to the amount of glycol slurry of inorganic particles is added, and centrifuged at 22,000 G for 60 minutes using an ultracentrifuge for separation. . After separation, the supernatant is removed by a gradient method to separate the inorganic particles. Next, in order to remove the glycol remaining in the obtained separated inorganic particles, the same amount of methanol as the liquid amount before separation was added to the separated inorganic particles, stirred for 30 minutes while applying ultrasonic waves, and then centrifuged again. Separate and remove the supernatant by decantation. This operation is repeated using gas chromatography until no glycol is detected using gas chromatography to obtain inorganic particles.

[Method of Separating Inorganic Particles in Polyester Composition] A polyester composition is treated with o-chlorophenol.
After dissolution, the obtained lysate is centrifuged using an ultracentrifuge for separation. After separation, the supernatant is removed by a gradient method to separate the inorganic particles. Next, in order to remove o-chlorophenol and polyester remaining in the obtained separated inorganic particles, to the separated inorganic particles, the same amount of o-chlorophenol as used for dissolving the polyester composition was added, Centrifuge again and remove the supernatant by decantation. Next, the same amount of methanol as used for dissolving the polyester composition is added to the obtained inorganic particles, and centrifuged again in the same manner as the inorganic particles in the above-mentioned glycol slurry to obtain inorganic particles.

Apparatus: Chemmagnetics CMX-300 Measurement nucleus: ¹³ C Observation range: 30030 Hz Sample rotation speed: 5 kHz Chemical shift standard: tetramethylsilane (external standard: 0.0 ppm)

D. Intrinsic viscosity of polyester composition Measured at 25 ° C using an o-chlorophenol solvent.

E. Melting point of polyester composition and film The polyester composition and the film were measured by a differential scanning calorimeter (DSC-4, manufactured by Perkin-Elmer Co., Ltd.) for 16 hours.
The measurement was performed at a heating rate of ° C./min.

F. Amount of Metal Element in Polyester Composition The intensity of each element of germanium, antimony, and titanium was quantified by fluorescent X-ray measurement in comparison with a calibration curve obtained from each standard substance.

G. Acetaldehyde content in polyester composition or film 2 g of fine powder of polyester composition or film was collected and charged into a pressure-resistant container together with ion-exchanged water.
After extraction with water for 60 minutes, the amount was determined by high-sensitivity gas chromatography.

H. Oligomer content in polyester composition or film 100 mg of the polyester composition or film was dissolved in 1 ml of orthochlorophenol, and the cyclic trimer was measured by liquid chromatography (Varian model 8500) to determine the amount of oligomer.

I. Slipperiness of Film The film was slit into a half-inch width, and the film was run in an atmosphere of 20 ° C. and 55 RH% using a tape running tester, and the initial slipperiness (μk) was determined by the following equation.

Μk = 0.733 log (T1 / T2) Here, T2 is the entrance tension and T1 is the exit tension. The guide diameter is 6 mmφ, the guide material is SUS27, the winding angle is 180 °, and the running speed is 3.3 cm / sec.

Those having the above μk of 0.35 or less have good slipperiness. Here, μk of 0.35 is a limit of whether the slipperiness when processing a film or as a product is extremely deteriorated.

J. Abrasion resistance of film A film obtained by slitting a film to a width of 1/2 inch was guided with a guide pin (surface roughness Ra10) using a tape running tester.
0 nm) (running speed 300 m / min, running frequency 1 time, winding angle 60 °, running tension 60 g). At this time, the scratches in the film were observed with a microscope, and the abrasion resistance was determined. If the number of scratches with a width of 2.5 μm or more is less than 3 per tape width, the wear resistance is good, and if it is 8 or more, the wear resistance is poor.

K. Plane orientation coefficient of film (fn) Plane orientation coefficient obtained from refractive index (Nx, Ny, Nz) in longitudinal, width and thickness directions using Abbe refractometer with sodium D line (wavelength 589 nm) as light source Was determined from the following equation.

Fn = [(Nx + Ny) / 2] -Nz

L. (A) Abrasion resistance of film The state of the film bonded to the metal can after molding was observed, and the sliding property was evaluated according to the following criteria.

◎: No scratches or shavings were found on the film. ：: Scratch and shavings are slightly observed in the film. C: Scratches and shavings are considerably observed in the film. ×: Many scratches and shavings are found on the film.

(B) Heat Resistance of Film The molded metal can was heated at 210 ° C. for 5 minutes, the state of the film bonded to the metal can was observed, and the heat resistance was evaluated according to the following criteria.

A: No peeling or shrinkage occurs on the film. ：: Peeling and shrinkage are slightly generated in the film. C: Peeling and shrinkage of the film considerably occur. X: The peeling and shrinkage of the film are remarkable.

(C) Impact Resistance of Film A molded metal can was filled with water and dropped on a marble from a height of 1 m. Ten metal cans were dropped, and an electric current test (ERV test) was performed on each metal can, and the impact resistance was evaluated based on the following criteria. In the energization test, a 1% aqueous solution of sodium chloride was filled in a metal can that was dropped, and the current flowing when a voltage of 6 V was applied between an electrode provided in the aqueous solution and the metal can was measured. is there.

◎: 9 or more current values of 0.2 mA or less ：: 7 to 8 current values of 0.2 mA or less Δ: 5 to 6 current values of 0.2 mA or less ×: Current value of 0.2 mA or less Less than 5

(D) Adhesiveness of film After laminating a film at a rate of 40 m / min and a steel sheet (0.2 mm thick) heated to the melting point of the film + 15 ° C.
The mixture was quenched in a water bath at ℃. The laminated steel sheet was cut to a width of 30 mm, and only the steel sheet was cut except for a part of the film.
The retort treatment was performed for 5 minutes. The evaluation was based on the peel length of the film from the steel sheet after retort.

◎: Peeling length less than 5 mm ：: Peeling length less than 5 mm to 5 mm or more Δ: Peeling length less than 15 mm to 10 mm or more ×: Peeling length of 15 mm or more

(E) Flavor properties of the film A film cut into a size of 150 mm × 450 mm was immersed in a perfume aqueous solution (a 20 ppm aqueous solution of d-limonene) for 5 days. The amount of adsorbed d-limonene (μg / g) per sample was quantified to evaluate the flavor of the film.

◎: Adsorption amount of d-limonene less than 20 ｄ: Adsorption amount of d-limonene 20 to 25 Δ: Adsorption amount of d-limonene 25 to 30 ×: Adsorption amount of d-limonene 30 or more A perfume aqueous solution (d-limonene 20
ppm aqueous solution), left for one month after sealing, and then opened, and the change in odor was evaluated by a sensory test according to the following criteria.

A: No change in odor was observed. ：: Little change in odor is observed. Δ: Change in odor observed. X: The change in odor is remarkable.

Example 1 Agglomerated silicon dioxide (average primary particle diameter 0.040 μm)
m, average secondary particle diameter 0.4 μm, specific surface area 200 m ² /
g) as an ethylene glycol slurry having a particle concentration of 10% by weight, charged in a heating vessel having a rectification column, heated while stirring, and when reaching the boiling point, removing water.
Heated for 2 hours. The water content in the obtained ethylene glycol containing silicon dioxide was 0.08% by weight. Next, using silicon dioxide separated from ethylene glycol, ¹³ C NMR measurement showed 66 ppm.
(Attributed to Si—O—CH ₂ — bond) and 63.5 pp
m (attributable to —CH ₂ OH bond).

On the other hand, 100 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol were subjected to a transesterification reaction in the usual manner using 0.06 part by weight of magnesium acetate tetrahydrate as a catalyst. After the transesterification reaction,
As a phosphorus compound, 0.012 parts by weight of phosphoric acid and 0.03 parts by weight of antimony trioxide are added, and then an ethylene glycol slurry of silicon dioxide surface-treated with ethylene glycol is added so as to be 0.20% by weight as silicon dioxide. did. Subsequently, a polycondensation reaction is carried out according to a conventional method, and an intrinsic viscosity of 0.62 dl / g, diethylene glycol 0.8% by weight, a carboxyl terminal group 25 equivalents / polymer 10 ⁶ g, an antimony element 250 ppm, and a melting point of 257 ° C.
Was obtained. Further, as a result of observing the particles in the obtained polyester composition using a transmission electron microscope (TEM), a large number of primary particles were present in an aggregated state at intervals smaller than twice the particle diameter.

Further, after sufficiently drying the obtained polyester composition, it is supplied to an extruder and melted at 290 ° C.
It was extruded into a sheet shape from a T-type die and cooled and solidified with a cooling drum at 30 ° C. to obtain an unstretched film. Next, the unstretched film is heated to 95 ° C. and stretched 3.5 times in the machine direction,
Further, it is heated to 100 ° C. and stretched 3.6 times in the transverse direction,
Heat treatment was performed at 00 ° C. to obtain a film having a thickness of 12 μm. The μk of the obtained film was 0.21, and the abrasion resistance evaluation was such that a scratch having a width of 2.5 μm or more
The book was excellent in both slipperiness and wear resistance.

Comparative Example 1 ¹³ C NMR without surface treatment with a glycol compound
A polyester composition and a film were obtained in the same manner as in Example 1, except that agglomerated silicon dioxide having no peak at 50 to 80 ppm in the spectrum in the measurement was used. The intrinsic viscosity of the polyester composition is 0.62 dl /
g, and μk of the obtained film is 0.33
In the abrasion resistance evaluation, ten scratches with a width of 2.5 μm or more per tape were inferior in abrasion resistance.

Example 2 An esterification reaction was carried out according to a conventional method using 76.1 parts by weight of terephthalic acid, 10.4 parts by weight of isophthalic acid, and 48.4 parts by weight of ethylene glycol. After completion of the esterification reaction, 0.012 parts by weight of phosphoric acid and 0.017 parts by weight of germanium dioxide are added as a phosphorus compound, and then 50 to 80 ppm in a spectrum by ¹³ C NMR measurement produced in the same manner as in Example 1. An ethylene glycol slurry of aggregated silicon dioxide having a peak was added so as to be 0.15% by weight as silicon dioxide. Subsequently, a polycondensation reaction is performed according to a conventional method, and the intrinsic viscosity is 0.64 dl.
/ G, and obtained diethylene glycol 1.1 wt%, the carboxyl terminal group 38 equivalents / polymer 10 ⁶ g, germanium element 40 ppm, the polyester composition having a melting point of 225 ° C..

Further, as a result of observing the particles in the obtained polyester composition using a transmission electron microscope (TEM),
Many primary particles were present in an aggregated state at intervals smaller than twice the particle diameter.

Next, the polyester composition was subjected to a solid-state polymerization reaction at 190 ° C. for 5 hours under a nitrogen flow to obtain an intrinsic viscosity of 0.6.
9 dl / g, diethylene glycol 1.1% by weight to obtain a carboxyl-terminal group 36 equivalents / polymer 10 ⁶ g, germanium element 40 ppm, mp 225 ° C., acetaldehyde content 3 ppm, oligomer content of 0.7% of the polyester composition.

On the other hand, after sufficiently drying the obtained polyester composition, it is supplied to an extruder and melted at 280 ° C.
It was extruded into a sheet from a die and cooled and solidified with a cooling drum at 30 ° C. to obtain an unstretched film. Next, the unstretched film was heated to 90 ° C and stretched 3.5 times in the machine direction, and further heated to 105 ° C and stretched 3.5 times in the transverse direction.
Heat treatment at 0 ° C., thickness 25 μm, plane orientation coefficient 0.1
10 films were obtained. Subsequently, the obtained film was bonded to a heated (melting point + 15 ° C.) steel sheet having a thickness of 0.20 mm, and rapidly cooled with water. Further, deep drawing was performed so that the inner side was a polyester film bonding surface, thereby producing a 55 mm diameter metal can. Various evaluations were performed on the obtained cans. The results are shown in Table 3. Wear resistance,
Flavor properties, adhesive properties, heat resistance, and impact resistance were all good.

Comparative Example 2 Silicon dioxide was not surface-treated with a glycol compound,
^A polyester composition and a film were obtained in the same manner as in Example 2, except that silicon dioxide having no peak at 50 to 80 ppm in the spectrum of ¹³ C NMR measurement was used.

The obtained film was bonded to a metal plate,
Tables 1, 2, and 3 show the characteristics after the metal can was manufactured. The abrasion resistance, flavor, adhesion and impact resistance were all poor.

Examples 3 to 7 Polyester compositions and films were obtained in the same manner as in Example 2 except that the type of polyester and the type of particles, the particle size, the content, and the metal catalyst were changed. Tables 1, 2, and 3 show the properties after the obtained film was bonded to a metal plate to produce a metal can.

All of the films within the scope of the present invention exhibited good abrasion resistance, flavor, adhesion, heat resistance and impact resistance.

[0100]

[Table 1]

[0101]

[Table 2]

[0102]

[Table 3]

Example 8 After the polyester compositions produced in Examples 2 and 3 were separately dried sufficiently, they were supplied to extruders, melted at 280 ° C., and co-extruded from dies adjacent to each other. Laminated, fused, and cooled and solidified to obtain an unstretched laminated film. Next, the unstretched film was heated to 90 ° C., stretched 3.5 times in the machine direction, further heated to 105 ° C., stretched 3.5 times in the transverse direction, and heat-treated at 190 ° C. A polyester composition layer of 15 μm, a polyester composition layer of Example 3 having a thickness of 5 μm, a total thickness of 20 μm, and a two-layer laminated film having a plane orientation coefficient of 0.120 were obtained. Subsequently, the obtained film was bonded to a heated 0.25 mm-thick steel surface (the melting point of the polyester composition of Example 3 + 15 ° C.) so that the polyester composition layer of Example 3 was formed, and then water was applied. Quenched. Further, deep drawing was performed so that the inner side was a polyester film bonding surface, thereby producing a 55 mm diameter metal can. Various evaluations were performed on the obtained cans. The film attached to the metal can after molding has scratches,
There was no shavings and no peeling or shrinkage was observed when heated at 210 ° C. for 5 minutes.
9 mA or less, peeling length 4 mm in adhesiveness evaluation
And also had excellent flavor.

Example 9 An agglomerated silicon dioxide (average primary particle diameter: 0.040 μm, average secondary particle diameter: 0.4 μm, specific surface area: 50 m ² / g) having a water content of 0.05% by weight was mixed with a container-fixed mixer ( (Kawata super mixer), the temperature was increased while stirring, and when the temperature in the can reached 200 ° C., ethylene glycol was added as a glycol while spraying so as to be 10% by weight with respect to silicon dioxide. . Thereafter, the mixture was mixed for 30 minutes to perform a surface treatment. Using the obtained silicon dioxide,
^{When 13} C NMR was measured, 66 ppm (Si-O-
CH ₂ —bond) and 63.5 ppm (—CH ₂ O)
(Attributed to H bond).

On the other hand, 76.1 parts by weight of terephthalic acid, 10.4 parts by weight of isophthalic acid, and 48.4 parts of ethylene glycol
The esterification reaction was carried out according to a conventional method using parts by weight.
After the completion of the esterification reaction, phosphoric acid 0.0
12 parts by weight and 0.017 parts by weight of germanium dioxide were added, and then an ethylene glycol slurry of silicon dioxide surface-treated with ethylene glycol was added so as to be 0.15% by weight as silicon dioxide. Subsequently, a polycondensation reaction is carried out according to a conventional method, and an intrinsic viscosity of 0.70 dl /
to give g, diethylene glycol 1.1 wt%, the carboxyl terminal group 38 equivalents / polymer 10 ⁶ g, germanium element 40 ppm, copolymerized polyester composition having a melting point of 225 ° C.. Further, as a result of observing the particles in the obtained polyester composition using a transmission electron microscope (TEM), a large number of primary particles were present in an aggregated state at intervals smaller than twice the particle diameter.

On the other hand, the obtained copolyester composition was sufficiently dried, supplied to an extruder, melted at 280 ° C., extruded into a sheet shape from a T-shaped die, cooled and solidified with a cooling drum at 30 ° C. A stretched film was obtained. Next, the unstretched film is heated to 90 ° C., stretched 3.5 times in the machine direction, further heated to 105 ° C., stretched 3.5 times in the transverse direction, and heat-treated at 190 ° C. to a thickness of 25 μm. A film having a plane orientation coefficient of 0.115 was obtained. Subsequently, the obtained film was heated (melting point + 15 ° C.) to a thickness of 0.20 mm.
And quenched with water. Further, deep drawing was performed so that the inner side was a polyester film bonding surface, thereby producing a 55 mm diameter metal can. The film bonded to the molded metal can has no scratches or shavings,
When heated at 210 ° C. for 5 minutes, no peeling or shrinkage was observed, 8 pieces of current value of 0.2 mA or less were evaluated in the impact resistance evaluation, and the peeling length was 4 mm in the adhesion evaluation, and the flavor was excellent. Was.

[0107]

According to the present invention, as described above, the polyester has a spectrum of 50 to 80 p in ¹³ C NMR measurement.
A polyester composition containing particles having a peak between pm and amorphous and / or aggregated inorganic particles, and a film comprising the same.

By containing the inorganic particles, a polyester composition excellent in affinity between the particles and the polyester can be obtained, and also excellent in transparency, slipperiness, abrasion resistance, flavor, adhesion, and impact resistance. Film can be obtained. The film can be suitably used for magnetic recording media, electrical insulation, general industrial use, food packaging, and the like,
In particular, it is suitable for food packaging and for bonding metal plates for beverages, food metal cans and the like.

Claims (17)

[Claims] 1. A polyester composition comprising particles having a peak between 50 and 80 ppm in the spectrum of ¹³ C NMR measurement of the polyester, and comprising amorphous and / or aggregated inorganic particles. 2. The inorganic particles have an average secondary particle diameter of 0.001.
The polyester composition according to claim 1, which has a thickness of from 10 to 10 µm. 3. The inorganic particles have a BET specific surface area of 30 to 10.
The polyester composition according to claim 1, wherein the polyester composition is 00 m ² / g. 4. The inorganic particles have an average primary particle diameter of 0.2 μm.
The polyester composition according to any one of claims 1 to 3, which is as follows. 5. The polyester composition according to claim 1, wherein the inorganic particles are at least one selected from silicon dioxide, aluminum oxide, calcium phosphate, magnesium oxide, metal carbonate, and silicate. Stuff. 6. The content of the inorganic particles is 0.0001 to 10
The polyester composition according to any one of claims 1 to 5, which is a percentage by weight. 7. The polyester composition according to claim 1, wherein the inorganic particles are surface-treated with a glycol compound. 8. The polyester composition according to claim 7, wherein the glycol compound is at least one glycol selected from aliphatic glycols. 9. The polyester composition according to claim 1, wherein the polyester is a polyester composed of an aromatic dicarboxylic acid component and a glycol component selected from an aliphatic glycol or an alicyclic glycol. Stuff. 10. Polyester is polyethylene terephthalate, poly-1,3-propylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate,
10. A polyester comprising at least one selected from the group consisting of polybutylene terephthalate.
The polyester composition according to item 1. 11. The polyester composition according to claim 1, wherein the polyester is a copolymerized polyester. 12. At least one element selected from germanium, antimony and titanium is from 1 to 500.
The polyester composition according to any one of claims 1 to 11, which contains ppm. 13. The polyester having a melting point of 100 to 270.
The polyester composition according to any one of claims 1 to 12, which is at 0 ° C. 14. A film comprising the polyester composition according to any one of claims 1 to 13. 15. A laminated polyester film in which at least one layer made of the composition according to claim 1 is arranged. 16. The film has a plane orientation coefficient of 0.08 or more.
16. The film according to claim 14 or 15, which has a value of 0.15. 17. A metal bonding film comprising the film according to any one of claims 14 to 16.