JP2006008805A - Polyester resin molding - Google Patents

Polyester resin molding Download PDF

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Publication number
JP2006008805A
JP2006008805A JP2004186563A JP2004186563A JP2006008805A JP 2006008805 A JP2006008805 A JP 2006008805A JP 2004186563 A JP2004186563 A JP 2004186563A JP 2004186563 A JP2004186563 A JP 2004186563A JP 2006008805 A JP2006008805 A JP 2006008805A
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polyester resin
resin
vapor deposition
polyester
layer
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JP2004186563A
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Japanese (ja)
Inventor
Takashi Hirokane
Tsuyoshi Ikeda
Kosei Kawashima
Tomohito Koyama
Shojiro Kuwabara
智仁 小山
孝正 川嶋
岳志 広兼
章二郎 桑原
剛志 池田
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Mitsubishi Gas Chem Co Inc
三菱瓦斯化学株式会社
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Priority to JP2004186563A priority Critical patent/JP2006008805A/en
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester resin molding having a vapor deposition layer, which is excellent in heat resistance, gloss, heat seal property and the like. <P>SOLUTION: The polyester resin molding has a resin layer comprising a polyester resin (A) in which 5-80 mol% of the diol units is those having a cyclic acetal skeleton, and a vapor deposition layer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

      The present invention relates to a polyester resin molded article having a resin layer containing a polyester resin having a cyclic acetal skeleton in a diol unit and a vapor deposition layer.

  Polyethylene terephthalate films have toughness, electrical insulation, dimensional stability, chemical resistance, etc., and are excellent in cost performance, so they are used in a wide range of applications.

  On the other hand, vapor deposition can impart gas barrier properties, light shielding properties, heat shielding properties, metallic luster, electrical conductivity, etc. to the resin, and in combination with the above polyethylene terephthalate, gold and silver thread, stamping foil, vapor deposition capacitor, vapor deposition packaging material, It is used in various applications such as heat ray blocking film, transparent electrode film, magnetic tape.

  However, a polyethylene terephthalate film is generally produced by stretching and then crystallizing by heat setting. Since light scattering increases and the softening temperature increases with crystallization, the polyethylene terephthalate vapor-deposited film is also inferior in glossiness and heat-sealability, etc., and a sufficient decorative effect cannot be obtained, or a resin having heat-sealability is used. The fact is that there is a problem that it is necessary to laminate.

As a method for reducing the crystallinity of polyethylene terephthalate, it is conceivable to copolymerize isophthalic acid or 1,4-cyclohexanedimethanol. These copolymer polyester resins have a low glass transition temperature and are practically used as a film. It does not have heat resistance that can be tolerated (see Non-Patent Document 1).
Edited by Kazuo Yuki, Saturated Polyester Resin Handbook, p. 564-565, published by Nikkan Kogyo Shimbun, December 22, 1989

  In view of the circumstances as described above, an object of the present invention is to provide a polyester resin molded article having a vapor-deposited layer which is excellent in heat resistance, glossiness, heat sealability and the like.

As a result of intensive studies, the present inventors have found that a polyester resin molded article having a resin layer containing a polyester resin having a cyclic acetal skeleton in a specific proportion in a diol unit and a vapor deposition layer has heat resistance, glossiness, and heat sealability. As a result, the present inventors have found that it is a polyester resin molded article having a vapor-deposited layer that is excellent in the present invention.
That is, the present invention relates to a polyester resin molded article having a resin layer containing a polyester resin (A) in which 5 to 80 mol% of diol units are diol units having a cyclic acetal skeleton and a vapor deposition layer.
In the present invention, the dicarboxylic acid unit or diol unit of the polyester resin refers to a repeating unit by an ester bond, and names of the dicarboxylic acid or diol generated when the ester bond of the polyester resin is hydrolyzed are listed. Described as a dicarboxylic acid unit or a diol unit derived from

  The polyester resin molded article of the present invention is excellent in heat resistance, glossiness, and heat sealability, and can be suitably used in various applications in the form of films, sheets, etc., and the industrial significance of the present invention is great.

The present invention is described in detail below.
The polyester resin molding of the present invention includes a polyester resin having a resin layer and a vapor deposition layer, and having a cyclic acetal skeleton in the resin layer.

The diol unit having a cyclic acetal skeleton in the diol unit of the polyester resin (A) used in the present invention has the general formula (1):
Or general formula (2):
The diol unit derived from the compound represented by these is preferable. In the general formulas (1) and (2), R 1 and R 2 are each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and A hydrocarbon group selected from the group consisting of aromatic hydrocarbon groups having 6 to 10 carbon atoms, preferably a methylene group, an ethylene group, a propylene group, a butylene group, or a structural isomer thereof such as an isopropylene group or isobutylene Represents a group. R 3 is a carbon selected from the group consisting of an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms. It represents a hydrogen group, preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a structural isomer thereof such as an isopropyl group or an isobutyl group. As a compound of general formula (1) or (2), 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 5-methylol-5-ethyl-2- (1,1-dimethyl-2-hydroxyethyl) -1,3-dioxane and the like are particularly preferable.

  Further, the diol unit other than the diol unit having a cyclic acetal skeleton is not particularly limited, but ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Aliphatic diols such as diethylene glycol, propylene glycol and neopentyl glycol; 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-decahydronaphthalenediethanol, 1,3-decahydronaphthalenediethanol 1,4-decahydronaphthalene diethanol, 1,5-decahydronaphthalene diethanol, 1,6-decahydronaphthalene diethanol, 2,7-decahydronaphthalene diethanol, tetralin dimethanol, norbornane dimethyl Alicyclic diols such as diol, tricyclodecane dimethanol and pentacyclododecane dimethanol; polyether compounds such as polyethylene glycol, polypropylene glycol and polybutylene glycol; 2,2-bis (4-hydroxyphenyl) propane ( Bisphenol A), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (tetrabromobisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis ( 3-tertiarybutyl-4-hydroxyphenyl) propane Bis (hydroxyaryl) alkanes exemplified by 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenylpropane) and the like; 1,1 -Bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), 1,1-bis (3,5-dibromo-4-hydroxyphenyl) cyclohexane, 1,1 Bis (hydroxyaryl) cycloalkanes exemplified by bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane and the like; 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1- Bis (hydroxyaryl) arylalkyl exemplified by bis (4-hydroxyphenyl) diphenylmethane Dihydroxydiaryl ethers exemplified by 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether; 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy Dihydroxydiaryl sulfides exemplified by -3,3'-dimethyldiphenylsulfide and the like; dihydroxydiaryls exemplified by 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide and the like Sulfoxides; dihydroxydiaryl sulfones exemplified by 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone, etc .; hydroquinone, resorcin, 4,4′-dihi An alkylene oxide adduct of the bisphenols; an aromatic dihydroxy compound such as hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylbenzophenone; Examples thereof include a diol unit derived from an alkylene oxide adduct of an aromatic dihydroxy compound. Considering the mechanical strength, heat resistance, and availability of the diol of the polyester resin (A), diol units derived from ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, etc. A diol unit derived from ethylene glycol is particularly preferable.

  The dicarboxylic acid unit of the polyester resin (A) used in the present invention is not particularly limited, but succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid. Acid, cyclohexanedicarboxylic acid, decalin dicarboxylic acid, norbornane dicarboxylic acid, tricyclodecane dicarboxylic acid, pentacyclododecanedicarboxylic acid, 3,9-bis (1,1-dimethyl-2-carboxyethyl) -2,4,8, Dicarboxylic acids derived from aliphatic dicarboxylic acids such as 10-tetraoxaspiro [5.5] undecane and 5-carboxy-5-ethyl-2- (1,1-dimethyl-2-carboxyethyl) -1,3-dioxane Acid unit: terephthalic acid, isophthalic acid, phthalic acid, 2-methylterephric Phosphoric acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, tetralindicarboxylic acid Examples thereof include dicarboxylic acid units derived from aromatic dicarboxylic acids such as In view of the mechanical strength, heat resistance, and availability of the dicarboxylic acid of the polyester resin (A), dicarboxylic acid units derived from terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid are particularly preferable.

  The polyester resin (A) used in the present invention includes a monoalcohol unit such as butyl alcohol, hexyl alcohol, octyl alcohol, or trimethylol, in order to adjust melt viscoelasticity, molecular weight, etc. Trivalent or higher polyhydric alcohol units such as propane, glycerin, 1,3,5-pentanetriol and pentaerythritol, monocarboxylic acid units such as benzoic acid, propionic acid and butyric acid, and polyvalent such as trimellitic acid and pyromellitic acid It may contain oxyacid units such as carboxylic acid units, glycolic acid, lactic acid, hydroxybutyric acid, 2-hydroxyisobutyric acid, and hydroxybenzoic acid.

  In view of moldability, heat resistance, mechanical performance, hydrolysis resistance, etc., particularly in the polyester resin (A) used in the present invention, the diol unit having a cyclic acetal skeleton is 3,9-bis (1,1-dimethyl- 2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane units, diol units other than diol units having a cyclic acetal skeleton are ethylene glycol units, and dicarboxylic acid units are terephthalates One or more dicarboxylic acid units selected from an acid unit, an isophthalic acid unit, and a 2,6-naphthalenedicarboxylic acid unit are preferable.

  The ratio of the diol unit having a cyclic acetal skeleton in the polyester resin (A) in the present invention is preferably 5 to 80 mol%, more preferably 5 to 70 mol%, and particularly preferably 10 to 50 mol%. It is. When the ratio of the diol unit having a cyclic acetal skeleton is in the above range, the polyester resin (A) has low crystallinity and excellent transparency, and has a high glass transition temperature, and the heat resistance of the polyester resin molded article of the present invention, Excellent gloss.

  Although the heat resistance of the polyester resin (A) in this invention can be suitably selected according to a use, it is preferable that a glass transition temperature is 85-150 degreeC, More preferably, it is 90-140 degreeC, Most preferably, it is 95. ~ 130 ° C. When the glass transition temperature is within the above range, the polyester resin molded article of the present invention exhibits excellent heat resistance. Although the glass transition temperature varies depending on the type and proportion of the structural unit, the diol unit having a cyclic acetal skeleton is mainly 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10. A tetraoxaspiro [5.5] undecane unit, a diol constituent unit other than a diol unit having a cyclic acetal skeleton is an ethylene glycol unit, a dicarboxylic acid constituent unit is a terephthalic acid unit and / or 2,6-naphthalenedicarbon In the case of acid units, a glass transition temperature in the above range is achieved.

  The intrinsic viscosity of the polyester resin (A) used in the present invention can be appropriately selected according to the molding method and application. In general, polyester resin with low intrinsic viscosity is suitable for molding by injection molding, which requires heat fluidity, and is extremely limited for molding by extrusion molding or for applications where mechanical properties and chemical resistance are important. Polyester resins with high viscosity are often suitable. In the polyester resin (A) in the present invention, the measured value at 25 ° C. using a mixed solvent of phenol and 1,1,2,2-tetrachloroethane in a mass ratio of 6: 4 is 0.5 to 1.5 dl / g. It is preferable that it is the range of this, More preferably, it is 0.5-1.2 dl / g, More preferably, it is 0.6-1.0 dl / g. When the intrinsic viscosity is in this range, the polyester resin (A) of the present invention has an excellent balance between moldability and mechanical performance.

The melt viscosity of the polyester resin (A) used in the present invention can also be appropriately selected according to the molding method and application. As with the intrinsic viscosity, polyester resins with low melt viscosity are often suitable when molding by injection molding, which generally requires heat fluidity. When molding by extrusion molding, mechanical properties, chemical resistance, etc. Polyester resins having a high melt viscosity are often suitable for uses where importance is attached. The melt viscosity is preferably in the range of 500 to 7000 Pa · s, more preferably 700 to 5000 Pa · s at a temperature of 240 ° C. and a shear rate of 100 sec −1 . When melt viscosity exists in this range, the polyester resin (A) in this invention is excellent in the balance of a moldability and mechanical performance. The melt viscosity depends on the intrinsic viscosity of the polyester resin (A), but greatly depends on the structural unit. Specifically, the more the diol unit having a cyclic acetal skeleton, the higher the melt viscosity.

  The method for producing the polyester resin (A) in the present invention is not particularly limited, and conventionally known polyester production methods can be applied. Examples thereof include a melt polymerization method such as a transesterification method and a direct esterification method, or a solution polymerization method. Various known stabilizers such as transesterification catalysts, esterification catalysts, etherification inhibitors, heat stabilizers, light stabilizers, polymerization regulators, and the like used in the production can be used. It is appropriately selected according to the color tone of the resin, safety, thermal stability, weather resistance, elution property of the resin, and the like.

  The resin used for the resin layer may be only the polyester resin (A), but may be a resin composition containing a resin other than the polyester resin (A). The resin other than the polyester resin (A) may be appropriately selected depending on the required performance. For example, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, isophthalic acid copolymerized polyethylene terephthalate, 1,4-cyclohexanedimethanol copolymer Polyester resin excluding polyester resin (A) such as polymerized polyethylene terephthalate, polyethylene-2,6-naphthalate, polyarylate, liquid crystalline polyester, polyester elastomer, polycarbonate resin, polyethylene, maleic anhydride grafted ethylene-propylene rubber, ethylene-vinyl acetate Copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl alcohol copolymer, acrylic acid grafted ethylene-vinyl acetate copolymer, Polyolefin resins such as butadiene rubber, acrylic rubber and cyclic olefin polymer, vinyl resins such as polystyrene, ABS resin, styrene-maleic anhydride copolymer, polyamide resins such as nylon 6, nylon 6,6, nylon MXD6, Phenoxy resin, polysulfone, polyether sulfone, polyphenylene oxide and the like can be mentioned. In particular, when a polyester resin other than the polyester resin (A), a polycarbonate resin, or a polyamide resin is used, the resin composition becomes transparent, which is preferable. Two or more kinds of resins other than the polyester resin (A) may be used at the same time.

  When the resin composition containing the polyester resin (A) is used for the resin layer, the ratio of the polyester resin (A) to the total amount of the resin other than the polyester resin (A) and the polyester resin (A) is 5% by weight or more. More preferably, it is 10% by weight or more, and particularly preferably 20% by weight or more. When the ratio of the polyester resin (A) is in the above range, the resin composition preferably exhibits heat resistance, transparency and low crystallinity based on the polyester resin (A).

  Although the heat resistance of the resin composition containing a resin other than the polyester resin (A) contained in the resin layer can be appropriately selected depending on the application, the glass transition temperature is preferably 85 to 180 ° C, more preferably. Is 90 to 170 ° C, particularly preferably 95 to 160 ° C. When the glass transition temperature is within the above range, the polyester resin molded article of the present invention exhibits excellent heat resistance. The glass transition temperature in the above range is achieved by using a polyester resin (A) having a glass transition temperature of 85 to 150 ° C. and using polyarylate, polysulfone and polycarbonate having a high glass transition temperature.

  Furthermore, you may mix | blend an organic filler and / or an inorganic filler with the resin composition containing resin other than said polyester resin (A) or polyester resin (A) in a resin layer. The filler can be appropriately selected depending on the application. For example, as the organic filler, powdered fillers such as wood powder, bamboo powder, coconut shell powder, cork powder, and pulp powder, crosslinked polyester, polystyrene, styrene / acryl, urea resin, etc. Balun-like / spherical filler, carbon fiber, synthetic fiber, and fibrous filler such as natural fiber. In addition, as inorganic filler, powder fillers such as calcium carbonate, talc, kaolin clay, mica, nepheline cinnite, synthetic silicic acid, quartz powder, quartzite powder, caustic clay, barium sulfate, pumice powder, shirasu balun, glass balun, Examples include balun fillers such as fly ash balun, fiber fillers such as glass fiber, sepiolite, mineral fiber, and whiskers. Although the compounding quantity of an organic filler and / or an inorganic filler can be suitably selected according to a use, it is preferable that it is 0.01-20 weight% of a resin layer.

  As the material used for the vapor deposition layer of the polyester resin molding of the present invention, conventionally known materials can be used, and may be appropriately selected depending on the application and required performance. For example, carbon, metal, metal oxide, etc. However, aluminum, zinc, tin, copper, nickel, chromium, silver, gold, iron, bismuth, titanium, indium, palladium, vanadium, tungsten, manganese, tantalum, cobalt, oxidation are preferable because of the ease of vapor deposition. Aluminum, indium oxide, tin oxide, titanium oxide, silicon oxide, antimony oxide, bismuth oxide, and zinc oxide are used. Aluminum, zinc, aluminum oxide, indium oxide, and silicon oxide are used from various aspects such as performance and economy. Particularly preferably used.

  The thickness of the vapor deposition layer may be appropriately selected according to the required performance, but is preferably 5 to 200 nm. When it is in the above range, various performances such as gas barrier properties, metallic gloss, and printability are sufficiently exhibited.

  The method for forming the vapor deposition layer on the resin layer for producing the polyester resin molded body of the present invention is not particularly limited, and conventionally known methods can be applied. Specific examples include vacuum deposition, electron beam vacuum deposition, sputtering, ion plating, thermal CVD, plasma CVD, and photo CVD.

  The polyester resin molding of the present invention can take various forms depending on the application. Specific examples include films, sheets, hollow containers, fibers, foams, and the like having a vapor deposition layer, and pouches such as retort pouches, standing pouches, spout pouches, and vapor depositions formed from a film having a vapor deposition layer. Also included are sheet molded articles such as cups and trays formed from sheets having layers. It is easy to form a vapor deposition layer on a resin layer such as a film or a sheet, and a vapor deposition film or vapor deposition sheet having a resin layer containing a polyester resin (A) and a vapor deposition layer is preferable as the polyester resin molded body of the present invention.

  When the form of the polyester resin molding of the present invention is a vapor deposition film or a vapor deposition sheet, the thickness of the film or sheet used as the resin layer is preferably 2 to 800 μm, more preferably 5 to 600 μm, and particularly preferably 7 to 500 μm. It is. Moreover, it is preferable that the haze measured by JISK7105 is 2% or less, More preferably, it is 1% or less. When a film or sheet in the above range is used, the polyester resin molded article of the present invention is excellent in mechanical strength, gloss and the like. Furthermore, the film or sheet used as the resin layer may be unstretched or stretched. When the stretching treatment is performed, the mechanical strength, gas barrier property, and pinhole resistance are improved, and it can be suitably used for applications requiring these performances.

  When the above film or sheet is used, the glossiness of the polyester resin molded product of the present invention is increased. When the vapor deposition layer is made of metal, the glossiness (60 degrees) measured by JIS K 7105 is preferably 850% or more on the resin layer side and 750% or more on the vapor deposition layer side. When the glossiness is in the above range, the appearance is good and the product value is high.

  By using a resin layer containing a resin having a high glass transition temperature, the heat resistance of the polyester resin molded article of the present invention is increased. The thermal shrinkage rate when immersed in hot water at 85 ° C. for 10 seconds is preferably 1.5% or less, more preferably 1% or less, for an unstretched molded body. In the stretched molded article, it is preferably 5% or less, more preferably 2% or less, and particularly preferably 1% or less.

The polyester resin molded article of the present invention has a gas barrier property comparable to a vapor-deposited molded article of polyethylene terephthalate. Oxygen permeability of the polyester resin molding of the present invention is preferably 2 · day 2 cc / m when measured in accordance with JIS K7126 at a temperature 23 ° C., a humidity of 60%, more preferably 1 cc / m 2 · Less than a day. Further, the water vapor permeability is preferably 2 g / m 2 · day or less, more preferably 1 g / m 2 · day or less when measured according to JIS K7129 at a temperature of 40 ° C and a humidity of 90%.

  The heat sealability of the polyester resin molded body of the present invention is preferably 0.5 kgf / 15 mm or more, more preferably 0.7 kgf / 15 mm or more when heat sealed at 180 ° C. Such high peel strength cannot be achieved with highly crystalline polyethylene terephthalate.

  The polyester resin molding of the present invention may have two or more resin layers and vapor deposition layers, respectively. For example, a molded body in which a vapor deposition layer is provided on both surfaces of the resin layer may be used, and conversely, a molded body in which a resin layer is provided on both surfaces of the vapor deposition layer may be used. Moreover, the polyester resin molded body of the present invention may have a layer other than the resin layer and the vapor deposition layer, for example, an anchor layer for improving the adhesion between the resin layer and the vapor deposition layer, and a resin for protecting the vapor deposition layer. Examples thereof include a layer / coating layer, a printing layer, an adhesive / pressure-sensitive adhesive layer for application to other materials, a release film layer for protecting the adhesive / pressure-sensitive adhesive, and a resin layer for improving slipperiness.

  The polyester resin molded product of the present invention can be used for various applications. For example, hot stamping foil, full surface transfer cloth, label, namer, adhesive tape, decorative material, gold and silver thread, ornament, artificial flower, glitter, packaging material, solar control, heat insulating material, heat insulation sheet, agricultural reflective sheet, retroreflective film, Mirror, screen, condenser, discharge recording paper, diaphragm, radio wave shield, antistatic, electrostatic shield, surface heating element, flexible circuit, thin film switch, magnetic recording material, transparent conductive film, transparent heat insulation film, photosensitive film, current transfer Examples include a ribbon, an antireflection film, a holographic film, and a rainbow film.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by these examples.

Evaluation methods for the polyester resin, the unstretched sheet, and the stretched film are as follows.
(1) Ratio of diol units having a cyclic acetal skeleton The ratio of diol units having a cyclic acetal skeleton in the polyester resin (A) was calculated by 1 H-NMR measurement. The measuring apparatus used JNM-AL400 by JEOL Co., Ltd., and measured it at 400 MHz. Deuterated chloroform was used as the solvent.

(2) Glass transition temperature The glass transition temperature is DSC / TA-50WS manufactured by Shimadzu Corporation, about 10 mg of sample is put in an aluminum non-sealed container, and the temperature rise rate in a nitrogen gas (30 ml / min) stream is 20 ° C / min The temperature at which the difference between the baselines before and after the transition of the DSC curve changed by 1/2 was taken as the glass transition temperature.

(3) Intrinsic viscosity The intrinsic viscosity is 0.5 g of a sample dissolved in 120 g of a mixed solvent of phenol and 1,1,2,2-tetrachloroethane (mass ratio = 6: 4), filtered, cooled to 25 ° C. Prepared. The measurement was performed at a temperature of 25 ° C. using a capillary viscometer automatic measuring device SS-300-L1 manufactured by Shibayama Scientific Machinery Co., Ltd.

(4) Melt viscosity The intrinsic viscosity was measured using Toyo Seiki Seisakusho Co., Ltd., trade name: Capillograph 1C. The diameter of the capillary is 1 mm, the length is 10 mm, and the measurement conditions are a measurement temperature of 240 ° C., a preheating time of 3 minutes, and a shear rate of 100 sec −1 .

(5) Haze Measured according to JIS K7105. The measuring device is a fog value measuring device (model: COH-300A) manufactured by Nippon Denshoku Industries Co., Ltd.

(6) Glossiness Measured according to JIS K7105. The measuring device is a gloss meter (model: VG-2000) manufactured by Nippon Denshoku Industries Co., Ltd. The incident angle and the light receiving angle were measured at 60 degrees.

(7) Thermal contraction rate A 20 mm mark was made in parallel with the extrusion direction on the central part of a film or sheet cut out to 100 mm × 100 mm, and immersed in hot water at 85 ° C. for 10 seconds. The thermal contraction rate was calculated from the length of the marked portion after immersion by the following formula.
Thermal contraction rate (%) = ((20−length after immersion (mm)) / 20) × 100

(8) Oxygen permeability Measured according to JIS K7126. A measuring device manufactured by Modern Controls (model: OX-TRAN10 / 50A) was used. The measurement conditions are a temperature of 23 ° C. and a humidity of 60%.

(9) Water vapor permeability Measured according to JIS K7129. The measurement conditions are a temperature of 40 ° C. and a humidity of 90%.

(10) Heat-sealability The heat-seal property was evaluated by peel strength of a strip-shaped test piece having a width of 15 mm and heat-sealed at 180 ° C. and 2.5 kgf / cm 2 J for 2 seconds at a seal width of 10 mm. The peel strength was measured using Strograph V1-C manufactured by Toyo Seiki Seisakusho. Measurement conditions are a distance between chucks of 50 mm, a load of 10 kgf, a T-type peeling, and a peeling speed of 300 mm / min.

Raw material resin The resins used in Examples and Comparative Examples are described below.
(1) Polyethylene terephthalate: manufactured by Nippon Unipet Co., Ltd., RT-553 (indicated in the table: PET)
(2) Polyarylate resin: manufactured by Unitika Ltd., U-polymer U-100 (indicated in the table: PAR)
(3) Polycarbonate resin: Mitsubishi Engineering Plastics Co., Ltd., Iupilon E-2000 (indicated in the table: PC)
(4) Polyamide resin: MX Nylon 6011 (Mitsubishi Gas Chemical Co., Ltd., notation: PA)
(5) 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate: Eastman Chemical Co., Ltd., Easter PETG 6763 (indicated in the table: PETG)

<Production Examples 1-4>
[Production of polyester resin (A)]
The raw material monomers listed in Table 1 are charged into a 150 liter polyester production apparatus equipped with a packed column rectification tower, a partial condenser, a total condenser, a cold trap, a stirrer, a heating device, and a nitrogen introduction pipe, and a dicarboxylic acid component On the other hand, in the presence of 0.03 mol% of manganese acetate tetrahydrate, the temperature was raised to 215 ° C. in a nitrogen atmosphere to carry out a transesterification reaction. After the reaction conversion rate of the dicarboxylic acid component is set to 90% or more, 0.02 mol% of antimony (III) oxide and 0.06 mol% of trimethyl phosphate are added to the dicarboxylic acid component, and the temperature and pressure are gradually increased. And finally polycondensation was performed at 270 ° C. and 0.1 kPa or less. The reaction was terminated when a suitable melt viscosity was reached, and a polyester resin was obtained. The evaluation test results are shown in Table 1.
In addition, the meaning of the abbreviation in a table | surface is as follows.
DMT: dimethyl terephthalate EG: ethylene glycol SPG: 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane DOG: 5-methylol -5-ethyl-2- (1,1-dimethyl-2-hydroxyethyl) -1,3-dioxane

Table 1
Production Example Number Production Example 1 Production Example 2 Production Example 3 Production Example 4
Monomer charge (mole)
Dicarboxylic acid component (mol)
DMT 201.8 174.6 290.6 208.0
Diol component (mol)
SPG 62.6 80.3 17.6 0.0
EG 341.1 356.2 508.5 330.7
DOG 0.0 0.0 0.0 0.0 43.7
Evaluation result of polyester resin Ratio of diol unit having cyclic acetal skeleton (mol%)
31 46 6 19
Glass transition temperature (° C) 104 113 87 89
Intrinsic viscosity (dl / g) 0.70 0.66 0.65 0.73
Melt viscosity (Pa · s) 2150 2950 1590 2100

<Production Examples 5 to 13>
[Manufacture of sheets]
Polyester resins (Production Examples 12 and 13) other than the polyester resin (A) (Production Examples 5 to 7) or polyester compositions (Production Examples 8 to 11) and polyester resins (A) described in Table 1 ) Was used to obtain an unstretched sheet having a thickness of 200 μm using a twin screw extruder PTM-30 manufactured by Plastics Engineering Laboratory equipped with a T die. The evaluation test results are shown in Tables 2-4.

Table 2
Production Example Number Production Example 5 Production Example 6 Production Example 7 Production Example 8
Resin Polyester resin (A) (parts by weight)
Production Example 1 100 0 0 67
Production Example 2 0 100 0 0
Production Example 4 0 0 100 0
Resins other than polyester resin (A) (parts by weight)
PET 0 0 0 33
Evaluation result of sheet Glass transition temperature (° C) 93
Haze (%) 0.5 0.5 0.7 0.6

Table 3
Production Example Number Production Example 9 Production Example 10 Production Example 11 Production Example 12
Resin Polyester resin (A) (parts by weight)
Production Example 1 50 0 0 0
Production Example 2 0 60 0 0
Production Example 3 0 0 80 0
Resins other than polyester resin (A) (parts by weight)
PET 0 0 0 100
PAR 50 0 0 0
PC 0 40 0 0
PA 0 0 20 0
Evaluation result of sheet Glass transition temperature (° C.) 148 127 91 82
Haze (%) 0.5 0.4 1.8 0.7

Table 4
Production Example Number Production Example 13
Resin Resin other than polyester resin (A) (parts by weight)
PETG 100
Evaluation result of sheet Glass transition temperature (° C) 83
Haze (%) 0.6

<Production Examples 14 to 18>
[Manufacture of stretched film]
The unstretched sheets manufactured in Production Examples 5, 8, and 11-13 were simultaneously biaxially stretched using a biaxial stretching apparatus manufactured by Toyo Seiki Seisakusho. The stretch ratio was 3.8 times in the extrusion direction (MD) and the width direction (TD) of the unstretched film, and a stretched film having a thickness of 15 μm was produced. In Production Examples 15 to 17, heat setting was performed at 180 ° C. The evaluation results of the stretched film are shown in Tables 5 and 6.

Table 5
Production Example Number Production Example 14 Production Example 15 Production Example 16 Production Example 17
Sheet used Production Example 5 Production Example 8 Production Example 11 Production Example 12
Evaluation result of film
Haze (%) 0.5 0.9 0.9 3.2

Table 6
Production Example Number Production Example 18
Used sheet Production Example 13
Evaluation result of film
Haze (%) 0.5

<Examples 1-12>, <Comparative Examples 1-4>
[Manufacture of polyester resin moldings (vapor-deposited film, vapor-deposited sheet)]
The metal or metal oxide shown in Table 2 was vapor-deposited on the unstretched sheets and stretched films produced in Production Examples 5 to 7, 9, 10, and 12 to 18 to produce vapor deposited sheets and films. The evaluation results are shown in Tables 7-10.
In addition, the meaning of the abbreviation in a table | surface is as follows.
Al: Aluminum Al 2 O 3 : Aluminum oxide ITO: Indium tin oxide SiO 2 : Silicon oxide

Table 7
Example No. Example 1 Example 2 Example 3 Example 4
Sheet or Film Production Example 5 Production Example 6 Production Example 7 Production Example 9
Deposition layer Al Al Al 2 O 3 ITO
Evaluation result of polyester resin molding Glossiness (%)
Resin layer side 970 860 160 130
Deposition layer side 900 890 100 100
Thermal contraction rate (%) 0.1 0.0 0.7 0.0
Oxygen permeability (cc / m 2 · day) 0.8 0.9 0.7 0.6
Water vapor transmission rate (g / m 2 · day) 0.7 0.8 0.5 0.4
Heat sealability (kgf / 15mm)
1.2 1.0 1.3 0.7

Table 8
Example No. Example 5 Example 6 Example 7 Example 8
Sheet or Film Production Example 10 Production Example 14 Production Example 15 Production Example 16
Deposition layer Al Al Al Al SiO 2
Evaluation result of polyester resin molding Glossiness (%)
Resin layer side 850 910 855 145
Vapor layer side 770 850 790 110
Thermal contraction rate (%) 0.1 5.0 0.0 0.0
Oxygen permeability (cc / m 2 · day) 0.8 0.9 0.6 0.6
Water vapor permeability (g / m 2 · day) 0.8 0.7 0.6 0.4
Heat sealability (kgf / 15mm)
0.8 1.4 0.7 0.9

Table 9
Comparative Example No. Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4
Sheet or Film Production Example 12 Production Example 13 Production Example 17 Production Example 18
Deposition layer Al Al Al Al Al
Evaluation result of polyester resin molding Glossiness (%)
Resin layer side 830 910 810 850
Vapor layer side 720 850 670 770
Thermal contraction rate (%) 1.9 12.0 1.5 44.7
Oxygen permeability (cc / m 2 · day) 0.7 0.8 0.6 0.9
Water vapor transmission rate (g / m 2 · day) 0.4 0.8 0.4 0.9
Heat sealability (kgf / 15mm)
0.3 2.1 Less than 0.1 1.8

Claims (14)

  1. The polyester resin molding which has a resin layer and a vapor deposition layer containing the polyester resin (A) whose 5-80 mol% in a diol unit is a diol unit which has a cyclic acetal frame | skeleton.
  2. The diol unit having a cyclic acetal skeleton has the general formula (1):
    (In the formula, R 1 and R 2 are each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and 6 to 10 carbon atoms. Represents a hydrocarbon group selected from the group consisting of aromatic hydrocarbon groups.)
    Or general formula (2):
    (In the formula, R 1 is the same as above, R 3 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and 6 to 10 carbon atoms. Represents a hydrocarbon group selected from the group consisting of aromatic hydrocarbon groups of
    The polyester resin molded product according to claim 1, which is a diol unit derived from a diol represented by the formula:
  3. The diol unit having a cyclic acetal skeleton is 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane or 5-methylol-5 The polyester resin molded article according to claim 2, which is a diol unit derived from -ethyl-2- (1,1-dimethyl-2-hydroxyethyl) -1,3-dioxane.
  4. The resin layer containing the polyester resin (A) further includes a resin composition containing one or more resins selected from the polyester resin excluding the polyester resin (A), a polycarbonate resin, and a polyamide resin, and the resin composition in the resin layer The polyester resin molded article according to claim 1, wherein the ratio of the polyester resin (A) to the total amount of is 5% by weight or more.
  5. The polyester resin molded product according to claim 4, wherein the resin layer contains polyethylene terephthalate.
  6. The polyester resin molded product according to claim 1, wherein the polyester resin (A) contained in the resin layer has a glass transition temperature of 85 to 150 ° C.
  7. The polyester resin molded product according to claim 4, wherein the resin composition contained in the resin layer has a glass transition temperature of 85 to 180 ° C.
  8. The polyester resin molded product according to claim 1, wherein the resin layer contains an organic filler and / or an inorganic filler in a proportion of 0.01 to 20% by weight based on the total amount of the polyester resin (A) and the organic filler and / or the inorganic filler. .
  9. The polyester resin molded product according to claim 4, wherein the resin layer contains an organic filler and / or an inorganic filler in a proportion of 0.01 to 20% by weight based on the total amount of the resin composition and the organic filler and / or the inorganic filler.
  10. The material used for the vapor deposition layer is aluminum, zinc, tin, copper, nickel, chromium, silver, gold, iron, bismuth, titanium, indium, palladium, vanadium, tungsten, manganese, tantalum, cobalt, aluminum oxide, indium oxide, oxidation The polyester molded article according to claim 1, which is at least one selected from the group consisting of tin, titanium oxide, silicon oxide, antimony oxide, bismuth oxide, and zinc oxide.
  11. The polyester resin molding according to claim 1, wherein the vapor deposition layer is formed by a method selected from a vacuum vapor deposition method, an electron beam vacuum vapor deposition method, a sputtering method, an ion plating method, a thermal CVD method, a plasma CVD method, and a photo CVD method. .
  12. The polyester resin molded article according to claim 1, which is a vapor-deposited film or vapor-deposited sheet having a resin layer containing a polyester resin (A) and a vapor-deposited layer.
  13. The polyester resin molded article according to claim 12, which is a vapor-deposited film or vapor-deposited sheet deposited on a film or sheet having a thickness of 2 to 800 µm and a haze measured by JIS K 7105 of 2% or less.
  14. The polyester according to claim 12, wherein the vapor deposition layer is made of metal, and is a vapor deposition film or vapor deposition sheet having a gloss (60 degrees) measured by JIS K7105 of 700% or more on the resin layer side and 800% or more on the vapor deposition layer side. Resin molded body.
JP2004186563A 2004-06-24 2004-06-24 Polyester resin molding Pending JP2006008805A (en)

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Country Link
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007308675A (en) * 2006-04-17 2007-11-29 Mitsubishi Gas Chem Co Inc Transparent electroconductive film and low reflection touch panel using the same
WO2008075639A1 (en) * 2006-12-20 2008-06-26 Mitsubishi Gas Chemical Company, Inc. Prefilled syringe
JP2012214056A (en) * 2006-04-17 2012-11-08 Mitsubishi Gas Chemical Co Inc Transparent electroconductive film and low reflection touch panel using the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001014951A (en) * 1999-06-28 2001-01-19 Toyobo Co Ltd Transparent conductive film and touch panel
JP2003113295A (en) * 2001-05-24 2003-04-18 Mitsubishi Gas Chem Co Inc Polyester resin composition and molded article
JP2003292593A (en) * 2002-04-04 2003-10-15 Mitsubishi Gas Chem Co Inc Polyester resin

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001014951A (en) * 1999-06-28 2001-01-19 Toyobo Co Ltd Transparent conductive film and touch panel
JP2003113295A (en) * 2001-05-24 2003-04-18 Mitsubishi Gas Chem Co Inc Polyester resin composition and molded article
JP2003292593A (en) * 2002-04-04 2003-10-15 Mitsubishi Gas Chem Co Inc Polyester resin

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007308675A (en) * 2006-04-17 2007-11-29 Mitsubishi Gas Chem Co Inc Transparent electroconductive film and low reflection touch panel using the same
JP2012214056A (en) * 2006-04-17 2012-11-08 Mitsubishi Gas Chemical Co Inc Transparent electroconductive film and low reflection touch panel using the same
WO2008075639A1 (en) * 2006-12-20 2008-06-26 Mitsubishi Gas Chemical Company, Inc. Prefilled syringe
US8398600B2 (en) 2006-12-20 2013-03-19 Mitsubishi Gas Chemical Company, Inc. Prefilled syringe
TWI409089B (en) * 2006-12-20 2013-09-21 Mitsubishi Gas Chemical Co Prefilled syringe
JP5374159B2 (en) * 2006-12-20 2013-12-25 三菱瓦斯化学株式会社 Prefilled syringe

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