WO2003059994A1 - Polyester moule - Google Patents

Polyester moule Download PDF

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Publication number
WO2003059994A1
WO2003059994A1 PCT/JP2002/009097 JP0209097W WO03059994A1 WO 2003059994 A1 WO2003059994 A1 WO 2003059994A1 JP 0209097 W JP0209097 W JP 0209097W WO 03059994 A1 WO03059994 A1 WO 03059994A1
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Prior art keywords
structural unit
polyester
block copolymer
molded article
molecular weight
Prior art date
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PCT/JP2002/009097
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English (en)
Japanese (ja)
Inventor
Makoto Tokumizu
Takeshi Nii
Kousuke Tonami
Nobuhisa Takayama
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Mitsubishi Rayon Co., Ltd.
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Application filed by Mitsubishi Rayon Co., Ltd. filed Critical Mitsubishi Rayon Co., Ltd.
Publication of WO2003059994A1 publication Critical patent/WO2003059994A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances

Definitions

  • the present invention relates to a polyester molded article such as a sheet, a film, miscellaneous goods, home appliances, and automobile parts obtained by extrusion molding, injection molding, blow molding, calendar molding, and the like.
  • Thermoplastic elastomers have excellent productivity as a substitute material for soft vinyl chloride resin, and are being widely used in automotive parts, office equipment, home appliances parts, medical parts, sheets, films, miscellaneous goods, etc., and materials expected in the future It is.
  • Examples thereof include gen-based, hydrogen-added gen-based (hydrogen-added derivatives of Bier aromatic compound-conjugated gen compound block copolymer), polyolefin-based, polyester-based, and polyamide-based.
  • these molding materials have drawbacks in terms of scratch resistance, flexibility, processability, economy, and recyclability.
  • the olefin-based elastomer is relatively inexpensive and has excellent weather resistance and heat resistance, but has problems in flexibility and scratch resistance
  • the gen-based elastomer has problems in weather resistance
  • the polyamide-based elastomer has problems such as high cost. is there.
  • Some proposals have also been made for hydrogenated jen systems.
  • Japanese Patent Application Laid-Open Nos. 50-14742, 52-65551, and 58-24664 each disclose hydrogenated block copolymers. Discloses a composition in which a rubber softener and an olefin resin are blended. However, these compositions were also inferior in scratch resistance, like the olefin-based elastomer.
  • polyesters are known as thermoplastic elastomers with excellent environmental resistance and mechanical strength.
  • block copolymers containing polybutylene terephthalate (PBT) and polytetramethylene ether glycol (PTMG) as their main components have an excellent balance of performance, and are used in automobiles and home appliances. Used in the field.
  • PBT polybutylene terephthalate
  • PTMG polytetramethylene ether glycol
  • Such a block copolymer is disclosed, for example, in JP-B-49-13 As disclosed in, for example, US Pat. No. 1,558,878, it is manufactured by an industrially advantageous melt polymerization method.
  • thermoplastic elastomer generally has low transparency and is often opaque. Even if a block copolymer having relatively high transparency is used, it is very difficult to maintain the transparency for a long time and to maintain the heat resistance and chemical resistance as well as the transparency. I got it.
  • Japanese Patent Application Laid-Open No. 10-237167 discloses a molded article comprising a block copolymer using polyethylene terephthalate / polyethylene naphthalate as a hard segment.
  • a block copolymer is molded under quenching conditions, a transparent molded article can be obtained, but there is a problem that the crystallization of the polyester gradually progresses and whitens over time.
  • Japanese Patent Application Laid-Open No. 10-182954 discloses a composition in which a metal salt is blended with a block copolymer. However, such a composition gradually absorbs moisture, so Under an environment other than a dry atmosphere, whitening occurs over time.
  • Japanese Patent Publication No. 47-37040 discloses a block copolymer comprising a lactone and a polyester.
  • the block copolymer is prepared by dissolving the block copolymer in an inert solvent. It was obtained by on-polymerization, and a functional group other than an ester group was inserted between the lactone and the polyether. As a result, the resulting polyester copolymer had poor heat resistance and the like.
  • the terminal of the polyether serves as an initiator, the content of the polyether cannot be increased due to the relationship with the molecular weight of the produced polymer, so that flexibility cannot be imparted.
  • the total light transmittance required for parts that require visibility is generally 75% or more. If the total light transmittance of a thermoplastic elastomer molded article is higher than this value, although it is industrially useful, such as soft-brushed hippopotamus, switches, panels, and color tape with good visibility, it has excellent transparency.
  • existing polyesters have low heat resistance of less than 100 ° C, while existing polyesters have excellent heat resistance and chemical resistance.They are opaque, and thermoplastic elastomers with a good balance of transparency, heat resistance and chemical resistance are required. Was desired. Disclosure of the invention
  • An object of the present invention is to industrially provide a polyester molded article having excellent heat resistance and chemical resistance while maintaining transparency for a long time.
  • the polyester molded article of the present invention comprises a structural unit (A) having a unit having at least one ester bond in the repeating unit as a main component, and a functional group capable of forming an ester having a number average molecular weight in the range of 600 to 100,000.
  • a block copolymer comprising a structural unit (B) derived from a compound having a group at both ends, and having a compression set of 5 to 65% measured according to JIS-K-1262. It is characterized by being in the range, being an elastic body, and having a total light transmittance of 75% or more measured according to JIS-K-7361-1.
  • the structural unit (A) has a unit represented by the following formula (1) as a main component, has a glass transition temperature (Tg) of 0 or less, and has a number average molecular weight in the range of 600 to 100000, and can form an ester.
  • Tg glass transition temperature
  • the content of the structural unit (A) is preferably 10 to 70% by mass.
  • each of X and Y represents hydrogen, an alkyl group, or a phenyl group.
  • N is 5 to 5000.
  • Z is a direct bond, an alkylene group having 1 to 6 carbon atoms, One of phenylene groups is shown.
  • X and Y in the formula (1) are a methyl group and Z is a methylene group.
  • the structural unit (C) composed of a polyfunctional component is added to the structural unit (A) in an amount of 0.0. It may be constituted by containing 5 to 2 mol%.
  • the method for producing the aliphatic polyester block copolymer of the polyester molded article of the present invention comprises: a structural unit (A) having a unit represented by the following formula (1) as a main component; and a glass transition temperature (Tg) of o: And a structural unit (B) derived from a compound having a number-average molecular weight in the range of 600 to 100000 and having a functional group capable of forming an ester at both terminals, and comprising the structural unit (A)
  • X and Y each represent a hydrogen, an alkyl group, or a phenyl group.
  • N is 5 to 5000.
  • Z is a direct bond, an alkylene group having 1 to 6 carbon atoms, One of phenylene groups is shown.
  • X and Y in the above formula (1) are a methyl group and Z is a methylene group.
  • the aliphatic block copolymer may be configured to contain the structural unit (C) composed of a polyfunctional component in an amount of 0.05 to 2 mol% with respect to the structural unit (A).
  • the polyester molded article of the present invention is characterized in that the MFR measured according to ASTM D1238 is 3 to 300 g / 10 min.
  • the haze measured according to JIS-K-7136 is 50 or less, and the yellowness index described in JIS-K-7105 is 30 or less.
  • the aliphatic polyester block copolymer of the polyester molded article of the present invention is as follows:
  • the cyclic polyester represented by the above formula (2) is contained in the aliphatic polyester in a content of 0.0005.05% by mass.
  • each of X and Y represents hydrogen, an alkyl group, or a phenyl group.
  • M is an integer of 2 or more.
  • Z is a direct bond, an alkylene group having 1 to 6 carbon atoms, Shows any of the len groups.
  • the aliphatic polyester block copolymer preferably contains a cyclic trimer represented by the following formula (3) in an amount of 0.001 to 0.05% by mass in the aliphatic polyester.
  • the structural unit (B) of the polyester molded article of the present invention is a unit derived from polyolefin, polyoxyalkylenedarilicol, polydimethylsiloxane, or polyester.
  • the polyester molded article of the present invention comprises a block copolymer containing the structural unit (A) and the structural unit (B), and the structural unit (A) is an ester bond in the repeating unit.
  • the main component is a unit having at least one
  • the constitutional unit (A) of the block copolymer in the present invention preferably contains, as a main component, a unit represented by the following formula (1).
  • X and Y each represent any of hydrogen, an alkyl group and a phenyl group.
  • X and Y may be the same or different, but are preferably the same substituent because the block copolymer has excellent heat resistance.
  • n is 5 to 500. When n is less than 5, the heat resistance of the block copolymer becomes insufficient. On the other hand, when it exceeds 50,000, the fluidity of the block copolymer decreases and moldability deteriorates. It is preferable that n is 5 to 500, because both the heat resistance and the fluidity of the block copolymer are excellent, and it is more preferably 10 to 200,000.
  • Z represents a direct bond, an alkylene group having 1 to 6 carbon atoms, or a phenylene group.
  • Z may be a mere direct bond, but when Z is an alkylene group or a phenylene group having 1 to 6 carbon atoms, the reaction is easy when forming a block copolymer. Therefore, it is preferable. Further, the alkylene group having 1 to 6 carbon atoms may have a branched structure. Further, when the carbon number exceeds 6, the heat resistance tends to be poor.
  • polyester molded article of the present invention since such a component is contained as the structural unit (A), it is particularly excellent in heat resistance, excellent in transparency for a long time, and excellent in flexibility. Become.
  • the unit of the above formula (1) which is a main constituent of the structural unit (A) include a hydroxypivalic acid unit in which X and Y are methyl groups, Z is a methylene group, X is hydrogen, and Y is A hydroxyisobutyric acid unit in which Z is a methylene group, a glycolic acid unit in which X and Y are hydrogen and Z is a direct bond, a propanoic acid unit in which X and Y are hydrogen and Z is a methylene group, X and Y are hydrogen and Z is a dimethylene butyrate unit; X and Y are hydrogen and Z is a trimethylene group valerate unit; X and Y are hydrogen, ⁇ ⁇ is a tetramethylene group, cabronic acid unit, X is hydrogen, ⁇ is a methyl group, ⁇ is a direct bond, lactic acid unit X is hydrogen, ⁇ is a phenyl group, and ⁇ is a direct bond Is
  • the method for producing polypivalolactone is preferably one obtained by polymerizing hydroxypivalic acid or its ester or pivalolactone. More preferably, a polymer of hydroxypivalic acid or an ester thereof is preferably used as a main component of the structural unit (II) in that a starting material produced industrially can be used.
  • the unit represented by the formula (1) may be composed of one type of compound or a plurality of compounds as long as the melting point of the block copolymer is not significantly reduced.
  • they may be composed solely of hydroxypivalic acid or an ester thereof, or may be combined with another compound capable of forming a unit of the formula (1).
  • the structural unit (II) contains the unit represented by the above formula (1) as a main component, but may contain other copolymer components as long as the melting point of the block copolymer is not significantly reduced.
  • the molecular weight of the target block copolymer can be increased.
  • copolymerization components include dicarboxylic acids, diols, hydroxycarboxylic acids and their esterified products.
  • dicarboxylic acids examples include oxalic acid, malonic acid, succinic acid, daltaric acid, adipic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 5-sulfo Sodium isophthalate and their lower alkyl esters, aryl esters, ester carbonates and acid halides are preferably used.
  • diols examples include ethylene diol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanedyl, 1,6-hexane.
  • hydroxycarboxylic acid hydroxybenzoic acid and their lower alkyl esters, aryl esters, carbonates, and acid halides are preferably used. These copolymer components may be used alone or in combination of two or more.
  • copolymer components When these copolymer components are used, they are usually used in an amount of 20% by mass or less in the component (A).
  • the structural unit (B) constituting the block copolymer in the present invention is derived from a compound having a functional group capable of forming an ester at both terminals.
  • the functional group capable of forming an ester include a hydroxyl group, a propyloxyl group, a methyl carboxylate group, an ethyl carboxylate group, a propyl carboxylate group, and an acetyloxy group.
  • the main chain skeleton is composed of polyolefin, polyoxyalkylene glycol, polydimethylsiloxane, polyester, polycarbonate, polybutadiene, hydrogenated polybutadiene, or the like, and the both ends are functional groups capable of forming the above ester. And those consisting of Further, these compounds may be composed of one kind or a plurality of compounds.
  • the compound having a main chain skeleton made of polyolefin is not limited as long as it has a functional group capable of forming an ester at both ends of a linear or branched polyolefin.
  • the number average molecular weight of the compound having a main chain skeleton of polyolefin is 600 to 1
  • the preferred molecular weight is in the range of 150 to 100,000, more preferably in the range of 2000 to 100,000, and most preferably in the range of 2000 to 100,000. It is in the range of 0.
  • the structural unit (B) is composed of such polyolefin-derived units.
  • the water resistance and weather resistance of the ester molded body are improved and the specific gravity can be reduced.
  • it can be preferably used for sheet, film, miscellaneous goods, home appliances, and automobile parts that come into contact with light or water.
  • Examples of the compound having a main chain skeleton of polyolefin include a hydroxyl group-containing polyolefin such as Polytail (trademark) (manufactured by Mitsubishi Chemical Corporation).
  • Compounds having a main chain skeleton of polyoxyalkylene glycol include polytetramethylene glycol, 3-methyltetrahydrofuran copolymerized polytetramethylene glycol, polyethylene glycol, polypropylene glycol, and polypyrene. Things.
  • the number average molecular weight of the compound having a main chain skeleton composed of polyoxyalkylene glycol is preferably from 600 to 100,000. If the number average molecular weight is less than 600, heat resistance becomes insufficient, and if it exceeds 100000, fluidity becomes insufficient.
  • the preferred range of the molecular weight is 1500 to 1000, more preferably 2000 to
  • the structural unit (B) is composed of such a unit derived from polyoxyalkylene glycol, polyoxyalkylene glycol is inexpensive, so that the production cost of the polyester molded article is reduced, which is industrially advantageous. is there.
  • it can be preferably used for applications requiring a particularly low price among sheets, films, miscellaneous goods, home appliances, electric and electronic parts, and automobile parts.
  • Examples of the compound having a main chain skeleton of polydimethylsiloxane include a compound represented by the following formula (4).
  • C and D are a hydroxyl group, carboxylic acid group, methyl carboxylate group or the like capable of forming an ester. These may be the same or different groups.
  • 1 is not limited, but is preferably from 8 to 500, more preferably from 8 to 200, and still more preferably from 10 to 80. If 1 is less than 8, polyester In some cases, the heat resistance and flexibility of the molded article may be insufficient. On the other hand, if 1 exceeds 500, the compatibility with the component represented by the formula (1) may decrease. When 1 is in the range of 8 to 500, the heat resistance and flexibility of the polyester molded article are excellent, and the compatibility between the structural unit (A) and the structural unit (B) is particularly good.
  • a and B in the formula (4) are an alkyl group or an oxyalkyl group, preferably an alkyl group having 4 or more carbon atoms or an oxyalkyl group. Among them, an alkyl group having 4 or more carbon atoms is preferable because the polyester molded article has excellent weather resistance.
  • the structural unit (B) is composed of such a unit derived from polydimethylsiloxane, the low-temperature properties of the polyester molded article are particularly excellent.
  • it is preferably used for sheets, films, miscellaneous goods, home electric appliances, and automobile parts in which cold resistance is particularly required.
  • Examples of the compound having a main chain skeleton of polyester include a compound obtained by ring-opening polymerization of a lactone such as polycaprolactone and valerolactone, and a condensate of a dicarboxylic acid and a diol.
  • a lactone such as polycaprolactone and valerolactone
  • a condensate of a dicarboxylic acid and a diol examples of the compound having a main chain skeleton of polyester.
  • the dicarboxylic acid and the diol the same compounds as those exemplified as the copolymerization component contained in the structural unit (A) can be used.
  • the number average molecular weight of the compound having a main chain skeleton of polyester is preferably 600 to 100,000. When the number average molecular weight is less than 600, heat resistance becomes insufficient, and when it exceeds 100,000, fluidity becomes insufficient.
  • the preferred molecular weight range is from 1500 to: L00000, more preferably from 2,000 to 100,000, most preferably from 2,000 to 10,000.
  • the polyester molded article has particularly excellent weather resistance and heat resistance, and can be manufactured at low cost.
  • the polyester molded article can be preferably used for seats, films, miscellaneous goods, home appliances, and automobile parts, particularly those used outdoors or in high-temperature parts.
  • Examples of the compound having a main chain skeleton composed of polypropionate include a polymer of cyclic polycarbonate, a condensate of glycol and phosgene, and a copolymer of forceprolactone. More specifically, polydimethyltrimethylene force, polymonomethyltrimethylene force, polytrimethylene carbonate, polyhexamone Tylene carbonate and the like. These compounds may be homopolymers or copolymers and may contain aromatics.
  • the number average molecular weight of the compound whose main chain skeleton is made of polycarbonate is preferably from 600 to 100,000. When the number average molecular weight is less than 600, the heat resistance becomes insufficient, and when it exceeds 100000, the fluidity becomes insufficient.
  • the preferred molecular weight is in the range of 1,500 to 100,000, more preferably in the range of 2000 to 100,000, and most preferably in the range of 2000 to 10,000.
  • the heat resistance of the polyester molded article is particularly excellent.
  • it can be preferably used for sheet, film, miscellaneous goods, home appliances, electric / electronic parts, and automobile parts, particularly those used in high-temperature parts.
  • the glass transition temperature (Tg) is preferably 0 ° C or less. When the Tg is 0 ° C or less, it is preferable because the resilience and flexibility of the polyester molded article are excellent.
  • the block copolymer in the present invention is constituted by including the structural unit (A) and the structural unit (B), and the mass ratio of the structural unit (A) is preferably in a range of 10 to 70% by mass. More preferably, it is 15 to 70% by mass, and still more preferably 20 to 50% by mass. If the structural unit (A) is less than 10% by mass, the heat resistance of the polyester molded product may be insufficient, while if it exceeds 70% by mass, the resilience and flexibility of the polyester molded product may be reduced. When the structural unit (A) is from 10 to 90% by mass, the heat resistance, rebound resilience, and flexibility of the polyester molded article are all excellent, which is preferable.
  • the block copolymer in the present invention is constituted by containing the structural unit (A) and the structural unit (B), and further comprises the structural unit (C) composed of a polyfunctional component according to the above constitution. It is preferable to contain 0.05 to 2 mol% with respect to the unit (A). When such a structural unit (C) is contained, the polymerization time for producing the block copolymer of the polyester molded article can be shortened, and the balance between the fluidity and the tensile properties of the block copolymer is more excellent.
  • polyfunctional component examples include polyhydric alcohols such as trimethylolpropane and pentaeristol, and polyhydric alcohols such as pyromellitic acid and anhydride, trimellitic acid and so on.
  • polyhydric alcohols such as trimethylolpropane and pentaeristol
  • polyhydric alcohols such as pyromellitic acid and anhydride, trimellitic acid and so on.
  • examples thereof include compounds containing a trivalent or more polyvalent carboxylic acid such as an anhydride thereof, an anhydride thereof, dimethyl sodium sulfoisophthalate, and a compound containing a bifunctional or more functional epoxy group, oxazoline group, carbodiimide group and the like.
  • the method for producing the block copolymer used in the polyester molded article of the present invention is not particularly limited, and examples thereof include a melt polycondensation method.
  • the structural unit (A) is a methyl group and X and Y in the above formula (1) are methyl groups and Z is a methylene group
  • hydroxypivalic acid or hydroxypivalic acid ester can be industrially easily obtained.
  • the polymerization can be performed by a known polyester polymerization method, and may be continuous polymerization or batch polymerization.
  • the raw materials constituting the block copolymer are all charged at once into a reactor in which nitrogen is introduced, and transesterification is performed at a temperature of about 160 to 240 ° C., and then 240 T, 0 Polycondensation may be performed under conditions such as 13 kPa or less, or a polymer that constitutes the structural unit (A) may be prepared in advance by polymerizing hydroxypivalic acid, hydroxypivalic acid ester, pivalolactone, etc. Thereafter, a method of polycondensing the polymer and the compound constituting the structural unit (B) with the compound constituting the structural unit (C) used as necessary may be used.
  • the obtained polymer is discharged into water and pelletized to obtain a target block copolymer. Further, a polymer constituting the structural unit (A), a compound constituting the structural unit (B), and a compound constituting the structural unit (C) used as required are reacted in an extruder, and A method of manufacturing the target object may be used.
  • the molecular weight of the target block copolymer can be increased by combining the amount of the hydroxyl group and the amount of the propyloxyl group in the charged composition.
  • dicarboxylic acid, diol, or the like examples include the above-mentioned dicarboxylic acids and diols.
  • the following metal compounds are added to the block copolymer of the polyester molded product in which the total mass of the metals is finally obtained in 0.1.
  • the transesterification reaction or polycondensation can be carried out with high yield.
  • These metal compounds need only be added at least in the step of transesterification. For example, they can be supplied at the stage of charging the raw materials, or can be supplied at the time of transesterification.
  • Suitable metal compounds used include at least one selected from the group consisting of antimony, germanium, titanium, manganese, magnesium, calcium, strontium, barium, sodium, cobalt, aluminum, gallium, iron, tin, zinc, and boron.
  • examples of such compounds include fatty acid salts such as acetates of these metals, carbonates of these elements, sulfates of these elements, nitrates of these elements, and halogens such as chlorides.
  • the titanium compound is particularly preferably a tetraalkyl titanate such as tetrabutyl titanate or tetramethyl titanate, or a metal oxalate such as titanium oxalate.
  • dibutyltin oxide dibutyltin dilaurate and the like are preferable.
  • Examples of the aluminum compound include fatty acid aluminum salts such as aluminum acetate, aluminum carbonate, aluminum chloride, and acetyl acetonate salt of aluminum.
  • Aluminum acetate or aluminum carbonate is particularly preferable.
  • Examples of the barium compound include barium salts of fatty acids such as barium acetate, barium carbonate, barium chloride, and acetyl acetonate of barium. Barium acetate or barium carbonate is particularly preferable.
  • cobalt compound examples include a cobalt salt of a fatty acid such as cobalt acetate, cobalt carbonate, cobalt chloride, and acetyl acetonate salt of cobalt, and particularly preferably cobalt acetate or cobalt carbonate.
  • a cobalt salt of a fatty acid such as cobalt acetate, cobalt carbonate, cobalt chloride, and acetyl acetonate salt of cobalt, and particularly preferably cobalt acetate or cobalt carbonate.
  • magnesium compound examples include magnesium salts of fatty acids such as magnesium acetate, magnesium carbonate, magnesium chloride, and acetyl acetonate salt of magnesium. Particularly preferred is magnesium acetate or magnesium carbonate.
  • the manganese compound examples include manganese salts of fatty acids such as manganese acetate, manganese carbonate, manganese chloride, and acetyl acetonate salt of manganese. Particularly, manganese acetate or manganese carbonate is preferable.
  • strontium compound examples include a strontium salt of a fatty acid such as strontium acetate, strontium carbonate, strontium chloride, and an acetyl acetonate salt of strontium.
  • strontium acetate and strontium carbonate are particularly preferable.
  • Examples of the zinc compound include zinc salts of fatty acids such as zinc acetate and the like, zinc carbonate, zinc chloride, and acetyl acetonate salt of zinc. Particularly preferred are zinc acetate and zinc carbonate.
  • antimony compound examples include antimony dioxide and antimony acetate.
  • germanium dioxide is used as a germanium compound
  • calcium carbonate or calcium acetate is used as a calcium compound
  • sodium methylate is used as a sodium compound
  • gallium trichloride or gallium oxide is used as a gallium compound
  • acetic acid is used as an iron compound.
  • compounds of iron and boron include boron oxide.
  • These metal compounds can be used alone or in combination of two or more.
  • a stabilizer may be used if necessary.
  • the stabilizer include phosphates such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, and tricresyl phosphate; triphenyl phosphate, tris dodecyl phosphate, and tris.
  • Phosphite esters such as nonylphenyl phosphate; acid phosphate esters such as methyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, dibutyl phosphate, monobutyl phosphate, octyl phosphate and the like
  • Phosphorus compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid, and polyphosphoric acid are used.
  • the block copolymer of the present invention thus produced includes, for example, Known stabilizers such as heat stabilizers and light stabilizers may be added.
  • Known stabilizers such as heat stabilizers and light stabilizers may be added.
  • the heat stabilizer include phenol compounds such as 4,4-bis (2,6-di-tert-butylphenol) and amines such as N, N-bis (mononaphthyl) -p-phenylenediamine. And diazolyl thionate.
  • the light stabilizer include, for example, substituted benzophenones and benzotriazole compounds.
  • the melt viscosity of the block copolymer in the present invention is expressed by a melt flow rate (MFR) measured according to ASTM D 1238, and a preferable range of MFR is 3 to 3 OO gZl Omin. Is 5 to 250 gZl Omin., More preferably 10 to 250 gZl Omin. If the MFR is less than 3 gZl 0 min., The injection moldability is poor, and short shots tend to occur. If the MFR exceeds 300 g / 10 minutes, the molded product tends to have poor tensile properties.
  • MFR melt flow rate
  • the polyester molded article of the present invention is an elastic body, and has a compression set of 5 to 65% as measured according to JIS-K-6262. If the compression set is less than 5%, the moldability tends to be poor. On the other hand, if the compression set exceeds 65%, the rubber elasticity tends to be low, and the applications in which the molded article can be used tend to be limited. Furthermore, if it cannot be measured by the measurement method of JIS-K-1262, it is out of the definition of an elastic body and is not suitable for use as a thermoplastic elastomer. More preferably, the compression set is in the range of 25 to 60%, and still more preferably in the range of 30 to 55%.
  • the polyester molded article of the present invention has a total light transmittance of 75% or more as measured according to JIS-K-7361-1. Although the total light transmittance depends on the surface condition of the measured object, it is obtained from a specimen that has not been subjected to surface processing or surface treatment, and the upper limit is 93% in theory.
  • the total light transmittance is less than 75%, the transparency of the molded product is low, and the applications that can be used industrially are limited. A more preferable range of the total light transmittance is 80% or more. It is preferable that the haze of the polyester molded article of the present invention, measured according to JIS-K-7136, is 50 or less, since a molded article with good visibility can be obtained. More preferably, the haze value is 35 or less. In addition, JIS—K— It is preferable that the described yellowness index (hereinafter, YI) is 30 or less because the appearance of the molded article is maintained. More preferably, YI is 20 or less, further preferably 10 or less. In the aliphatic polyester block copolymer of the polyester molded article of the present invention, the content of the cyclic represented by the following formula (2) is preferably 0.05% by mass or less.
  • each of X and Y represents hydrogen, an alkyl group, or a phenyl group.
  • M is an integer of 2 or more.
  • Z is a direct bond, an alkylene group having 1 to 6 carbon atoms, Represents one of the len groups.
  • the cyclic body in the aliphatic polyester block copolymer exceeds 0.05% by mass, when the aliphatic polyester resin is molded, the cyclic body may bleed out over time.
  • the preferred content of the cyclic is 0.03% by mass or less, more preferably 0.01% by mass or less.
  • a crystal nucleating agent, an organic or inorganic reinforcing fiber, an organic or inorganic powder, and the like are added to the polyester molded article of the present invention. May be.
  • the polyester molded article of the present invention can be formed into a container by, for example, injection molding, formed into a sheet or the like by extrusion, or formed into a container or the like by professional molding. It can be formed into a shape. After forming the molded product, annealing treatment is further performed to promote crystallization of the structural unit (A) and to stabilize it. May be enhanced.
  • polyester molded article Since such a polyester molded article has excellent transparency, its transparency lasts for a long time, and is also excellent in flexibility and chemical resistance, it has been conventionally used for both soft vinyl chloride resin and styrene-butadiene-styrene block.
  • Polymers and their hydrogenated products, aliphatic polyester copolymers, and polyolefins are preferably used for applications where elastomers and the like have been used, that is, for automobile parts such as sheets, films, sundries and the like.
  • a resin is obtained by blending the block copolymer of the polyester molded product with a resin such as polyester, polypropylene resin, polyamide, polyolefin, polystyrene, polymethyl methacrylate, or polychlorinated biel as a modifier.
  • a resin composition excellent in these properties can be produced.
  • Extrusion molding Formed into a sheet shape with a thickness of 200 x m at 250 ° C by a film forming machine combining a 4 ⁇ ⁇ single screw extruder and a ⁇ -die.
  • JISK 6301 using a sample obtained by stacking samples obtained by press molding or injection molding so that the overall thickness becomes 4 mm or more, measure the JISA type term and indicate the index of flexibility.
  • a 2 mm thick sample obtained by press molding was cut into a strip of 3 Omm x 5 mm, and the end of the sample was fixed at 1 Omm, left in an oven at 120: for 1 hour, and did not sag more than 5 mm Is indicated by ⁇ in the table, and those hanging 5 mm or more are indicated by X in the table.
  • a 200-m-thick sheet-like sample obtained by extrusion molding or a 3.2-mm-thick test piece obtained by injection molding was measured in accordance with ASTM D-638.
  • the residual elongation after 200% tension was determined by elongating the sample at 23 ° C for 5 minutes while maintaining the sample at 200% tension for 5 minutes, and then releasing the sample for 30 minutes.
  • the resulting aliphatic polyester was dissolved in black-mouthed form, and the carrier gas was changed to helium using gas chromatography-(Hewlett Packard HP6890, capillary column ( ⁇ 5, length 30 m, film thickness 0.25 m)). The amount was determined at 1.5 mmZm in. And at a temperature of 200 ° C. using methyl palmitate as an internal standard.
  • Total light transmittance, haze The total light transmittance was measured using a haze meter at 23 ° C. on a 3 mm thick, 5 Omm ⁇ 5 Omm flat plate sample obtained by injection molding in accordance with JIS-K-7361.
  • the haze value was measured using the same apparatus and the same test piece in accordance with JIS-K-7136.
  • JIS-K-6262 a sample of 2 mm thickness obtained by press molding was punched out to a diameter of 13 mm to form three small laminated test pieces, which were compressed by 15% using a 5.3 mm spacer. This was held for 70 and 22 hours, and after 30 minutes, the thickness of the test piece was calculated from the measured value.
  • the resin (A-1) was confirmed to have an ester exchange rate of 97% or more based on the melting point, viscosity, and the like determined by DSC.
  • the calculated number average molecular weight at this time is 3290, and n in Equation 1 is 32.
  • the pressure inside the system was reduced to 0.13 kPa or less over 1 hour at 240 ° C., and polycondensation was performed while maintaining the reduced pressure for 2 hours.
  • the produced polymer was discharged into water under nitrogen pressure, and pelletized to obtain 1210 g of a polymer. This was dissolved in black-mouthed form and the number average molecular weight measured by polystyrene standard was 35000 and the molecular weight distribution was 1.8.
  • the polymer was subjected to dynamic viscoelasticity measurement, and the Tg derived from the structural unit ( ⁇ ) determined from the peak of t a ⁇ ⁇ was 143 ° C.
  • the content of the structural unit (A) was 32% by mass.
  • the polymer thus obtained was dried at 0.3 kPa, 120 ° C for 5 hours, and then 200 m thick at 250 t using a 4 Omm single screw extruder and T-die. Into a sheet. In addition, press molding and injection molding were performed at 240 ° C, and test specimens having a predetermined thickness were prepared and evaluated. Tables 1 and 2 show the results.
  • the pressure inside the system was reduced to 0.13 kPa or less at 240 ° C. over 30 minutes, and polycondensation was performed while maintaining the reduced pressure for 2 hours.
  • the produced polymer was discharged into water under nitrogen pressure, and pelletized to obtain 1180 g of a polymer. This to the black mouth Holm Melted, the number average molecular weight measured by polystyrene standard was 28000, and molecular weight distribution was 2.2.
  • the pressure inside the system was reduced to 0.13 kPa or less over 30 minutes at 240 ° C.
  • Polycondensation was performed while maintaining the reduced pressure for 2 hours.
  • the produced polymer was discharged into water under nitrogen pressure, and pelletized to obtain 1280 g of a polymer. This was dissolved in black-mouthed form and the number average molecular weight measured by polystyrene standard was 32,000, and the molecular weight distribution was 1.9.
  • the polyester molded article of Comparative Example has insufficient transparency, and the polyester molded article of Comparative Example 2 in which the molecular weight of the structural unit ( ⁇ ) is less than 600 is flexible. In addition, residual elongation due to tension and compression set are large. On the other hand, the polyester molded articles of the present invention were all excellent in heat resistance, maintained high transparency, and also excellent in flexibility and chemical resistance.
  • the pressure inside the system was reduced to 0.13 kPa or less over 1 hour at 240, and the polycondensation was performed while maintaining the reduced pressure for 2 hours.
  • the produced polymer was discharged into water under nitrogen pressure, and was pelletized to obtain 4500 g of a polymer. This was dissolved in black-mouthed form and the number average molecular weight measured by polystyrene standard was 35000 and the molecular weight distribution was 1.8.
  • the structural unit (A) having a hydroxypivalic acid unit as a main component in the obtained polymer was calculated to have a molecular weight of 2600 from the melting point of the form-insoluble portion of the polymer by DSC measurement, and n was 26.
  • the dynamic viscoelasticity of this polymer was measured, and the Tg derived from the structural unit (B) determined from the peak of tan ⁇ 5 was _40 ° C.
  • the structural unit (B) is composed of a compound composed of polytetramethylene glycol (PTG4000 having a number average molecular weight of 4000) and dimethyl adipate, both ends of which are ester-forming functional groups.
  • the molecular weight is 4100.
  • the pressure inside the system was reduced to 0.13 kPa or less over 30 minutes at 24 Ot: and the polycondensation was performed while maintaining the reduced pressure for 2 hours.
  • the produced polymer was discharged into water under nitrogen pressure, and pelletized to obtain 85 g of a polymer. This was dissolved in black-mouthed form, and the number average molecular weight measured by polystyrene standard was 28000 and the molecular weight distribution was 2.2.
  • the dynamic viscoelasticity of this polymer was measured, and the Tg derived from the structural unit ( ⁇ ) determined from the peak of ta ⁇ ⁇ was ⁇ 55 ° C.
  • the structural unit (B) is composed of a compound composed of polytetramethylene glycol (PTG4000 having a number average molecular weight of 4,000) and dimethyl adipate, both ends of which are ester-forming functional groups, Its number average molecular weight is 8200.
  • the pressure inside the system was reduced to 0.13 kPa or less over 30 minutes with 24 O :, and polycondensation was performed while maintaining the reduced pressure for 2 hours.
  • the produced polymer was discharged into water under nitrogen pressure, and pelletized to obtain 93 g of a polymer. This was dissolved in black hole form, and the number average molecular weight measured by polystyrene standard was 30,000 and the molecular weight distribution was 1.9.
  • (B) consists of a compound composed of polytetramethylene glycol (PTG 20000 having a number average molecular weight of 2000) and dimethyl adipate, both ends of which are ester-forming functional groups, and whose number average molecular weight is 2 is 100.
  • Example 2 The polymer obtained in Example 1 was dried at 0.3 kPa and 120 ° C for 5 hours, and then dried at 250 ° C using a film forming machine combining a 40 mm ⁇ single screw extruder and a T-die. The test piece was formed into a sheet having a thickness of zm and evaluated. The results are shown in Table 4. [Comparative Example 3]
  • Table 3 shows the proportion (calculated value) of titanium in titanium tetrabutoxide added as a catalyst in the obtained polymer.
  • the produced polymer was discharged into water under nitrogen pressure and pelletized to obtain 92 g of a polymer. This was dissolved in black hole form and the number average molecular weight measured by polystyrene standard was 32,000, and the molecular weight distribution was 1.7.
  • Table 3 shows the proportion (calculated value) of titanium in titanium tetrabutoxide added as a catalyst in the obtained polymer.
  • Polyester Elastomer P-40B (Toyobo Co., Ltd.) is dried at 0.3 kPa and 120 ° C for 5 hours, and then 250 ° by a 4 ⁇ ⁇ single screw extruder and T-die. C was molded into a sheet 200 m thick to form a test piece, and this test piece was evaluated. The results are shown in Table 4. Table 3
  • the polyester molded article of the comparative example is insufficient in any of flexibility, transparency, and heat resistance, whereas the polyester molded article copolymer of the present invention is heat resistant. Excellent in transparency, high transparency was maintained, and flexibility and chemical resistance were also good.
  • Table 4 shows that the polyester elastomer, which had excellent heat resistance among the existing thermoplastic elastomers, maintained its strength and was excellent in residual elongation and transparency.
  • the pressure inside the system was reduced to 0.13 kPa or less over 1 hour, and polycondensation was performed while maintaining the reduced pressure for 3 hours.
  • the produced polymer was discharged into water under nitrogen pressure, pelletized, and dried at 100 ° C. and 0.1 kPa or less for 48 hours to obtain 1500 g of a polymer. This was dissolved in black hole form, and the number average molecular weight measured with a polystyrene standard was 51,000, and the molecular weight distribution was 3.0.
  • Methyl hydroxypivalate 1 980 g (14.8 mol), PTG2000 (Hodogaya Chemical, number average molecular weight 2000) 1 125 g (0.563 mol), dimethyl adipate 67 g (0.385 mol), trimellit 22.9 g (0.119 mo 1) of acid anhydride, tetrakis [methylene (3,5-di-t-butyl) as stabilizer
  • the pressure inside the system was reduced to 0.13 kPa or less at 240 ° C. over 1 hour, and polycondensation was performed while maintaining the reduced pressure for 2 hours.
  • the polymer produced was discharged into water under nitrogen pressure, pelletized, dried at 120 kPa or less at 0.3 kPa or less for 5 hours.
  • the polyester molded article of the comparative example has a high cyclic trimer content and causes bleeding, whereas the polyester molded article of the present invention maintains high transparency and is more flexible.
  • the mechanical properties were also good.
  • Methyl hydroxybivalate 69.3 g (0.525 mol 1), Polytel (trademark) HA (manufactured by Mitsubishi Chemical, number average molecular weight 2000) 50 g (0.025 mol 1), dimethyl adipate 4.4 g (0.025 mol), and titanium tetrabutoxide (0.1 lg (1 000 ppm per polymer)) as a catalyst was charged into a reactor introduced with nitrogen, and methanol was removed at 160 to 240 ° C for 3 hours. While proceeding the reaction. Then, the pressure inside the system was reduced to ImmHg or less over 1 hour at 240 ° C, and polycondensation was performed while maintaining the reduced pressure for 2 hours.
  • the produced polymer was discharged into water under nitrogen pressure, and was pelletized to obtain 88 g of a polymer. Dissolve this in black mouth form, and police The number average molecular weight measured with a styrene standard was 30,000, and the molecular weight distribution was 1.8.
  • the pressure inside the system was reduced to ImmHg or less at 240 ° C. over 30 minutes, and polycondensation was performed while maintaining the reduced pressure for 2 hours.
  • the produced polymer was discharged into water under nitrogen pressure, and was pelletized to obtain 92 g of a polymer. This was dissolved in black hole form, and the number average molecular weight measured by polystyrene standard was 32,000 and the molecular weight distribution was 1.7.
  • the pressure inside the system was reduced to ImmHg or less over 30 minutes at 240, and the polycondensation was performed while maintaining the reduced pressure for 2 hours.
  • the produced polymer was discharged into water under nitrogen pressure, and pelletized to obtain 91 g of a polymer. This was dissolved in black hole form, and the number average molecular weight measured by polystyrene standard was 32,000 and the molecular weight distribution was 1.7.
  • the pressure in the system was reduced to ImmHg or less, and the mixture was stirred for 1 hour to perform polycondensation.
  • the produced polymer was discharged into water under nitrogen pressure, and pelletized to obtain 91 g of a polymer. This was dissolved in a black hole form, and the number average molecular weight measured by a polystyrene standard was 28,000, and the molecular weight distribution was 2.0.
  • the dynamic viscosity was measured for this polymer, and the Tg derived from the copolymer of adipic acid and 3-methyl-1,5-pentanedyl, which is the component ⁇ , determined from the peak of ta ⁇ ⁇ was one. 25 ° C.
  • the polymer obtained was discharged into water under nitrogen pressure and pelletized to obtain 9725 g of a polymer. It was dissolved in black-mouthed form and the number average molecular weight measured by polystyrene standards was 38,000 and the molecular weight distribution was 1.7.
  • the resulting polymer was discharged into water under nitrogen pressure and pelletized to obtain 97 g of a polymer. This was dissolved in black hole form and the number average molecular weight measured by polystyrene standard was 36,000, and the molecular weight distribution was 1.7.
  • the polyester molded article of the present invention has excellent heat resistance, good transparency, and high transparency.
  • hoses such as fire hoses and hydraulic hoses, gas pipe linings, traction rope jackets, corrugated tubes, pneumatic tubes, bicycle airless tubes, soccer pole tubes and other tubes, Bells for conveyor belts, V belts, timing belts, etc.
  • Sheets such as sheets for civil engineering, waterproofing, building materials, etc., films such as laminated films for food packaging, flexible couplings, door latch strikers, rebound studs, emblems, ski shoes, golf poles, shoe inners, watch bands, hot springs Miscellaneous goods such as Tokara bottles, bottle stoppers, combs, brushes, buttons, toys, etc., electrical and electronic parts such as telephone line curl cords, optical fiber coatings, cable covers, cable jackets, cable liners, back-up rings, etc.
  • Medical parts such as balloons and catheters, joint materials, sealing materials for electronic components, packing, dust seals, pumps, seals for diaphragms, membranes, accumulators, and other interior parts, pump parts, seatbell ratchet parts, AT Slide plate, constant velocity joint And pinion boots, suspension boots, McPherson strut covers, floats, gears, leaf spring bushings, pole joint retainers, joint bushings, airbag covers, steering rod covers, window glass anti-skid rolls, jumper bumpers , Side trim * Auto parts such as molds, grommets, tire inserts, etc., polymer blends, grips, cushions, stoppers, goggles, PC mice, sports equipment, vibration control materials, elastomers such as sound insulation materials, sound quality improvement materials, etc. It can be used for a wide range of applications such as resin modifiers and compatibilizers for one product, and is extremely useful as an industrial resin.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne un moulage en polyester présentant des propriétés de transparence de longue durée et une résistance thermique et chimique satisfaisante. Le moulage selon l'invention est obtenu par la mise en oeuvre de procédés industriels. Ce moulage en polyester contient un copolymère bloc constitué d'une unité structurelle (A) comprenant comme constituant principal des motifs répétés présentant au moins une liaison ester, et d'une unité structurelle (B) dérivée d'un composé présentant un poids moléculaire moyen compris entre 600 et 100 000 et contenant un groupe fonctionnel formant un ester au niveau de chaque extrémité. Le moulage selon l'invention est un élastomère présentant une rémanence à la compression comprise entre 5 et 65 %, telle que mesurée en fonction de JIS-K-6262. Ce moulage présente également une transmittance de la lumière totale de 75 % ou supérieure, telle que mesurée en fonction de JIS-K-7361-1.
PCT/JP2002/009097 2002-01-10 2002-09-06 Polyester moule WO2003059994A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8287685B2 (en) 2006-12-06 2012-10-16 Dow Corning Corporation Airbag and process for its assembly

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51106194A (ja) * 1975-03-14 1976-09-20 Teijin Ltd Horiesuterudanseitaino seizoho
EP0108912A2 (fr) * 1982-11-12 1984-05-23 American Cyanamid Company Copolymères blocs d'acide polyglycolique et de polyalkylèneglycol, et leur méthode de fabrication
US4699967A (en) * 1985-01-30 1987-10-13 Bayer Aktiengesellschaft Polysiloxane block copolymers
EP0712880A2 (fr) * 1994-11-17 1996-05-22 Mitsui Toatsu Chemicals, Incorporated Procédé de préparation de copolyesters en bloc dégradables
EP0778306A2 (fr) * 1995-12-05 1997-06-11 Mitsui Toatsu Chemicals, Incorporated Polyestercarbonates séquencés aliphatiques-aromatiques dégradables et leur préparation
EP0893463A1 (fr) * 1996-12-30 1999-01-27 Daicel Chemical Industries, Ltd. Elastomeres polyesters, procedes de preparation et compositions de ces elastomeres
JPH11323107A (ja) * 1998-05-15 1999-11-26 Kuraray Co Ltd ポリエステル系重合体組成物
JP2000212407A (ja) * 1999-01-27 2000-08-02 Sekisui Chem Co Ltd エステル系エラストマ―
JP2002069192A (ja) * 2000-08-31 2002-03-08 Shimadzu Corp 架橋型軟質乳酸系ポリマーの製造方法及びその組成物
JP2002265611A (ja) * 2001-03-07 2002-09-18 Mitsubishi Rayon Co Ltd ポリエステル系ブロック共重合体
JP2002292665A (ja) * 2001-03-29 2002-10-09 Dainippon Ink & Chem Inc 乳酸系ポリマーシートの製造法

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51106194A (ja) * 1975-03-14 1976-09-20 Teijin Ltd Horiesuterudanseitaino seizoho
EP0108912A2 (fr) * 1982-11-12 1984-05-23 American Cyanamid Company Copolymères blocs d'acide polyglycolique et de polyalkylèneglycol, et leur méthode de fabrication
US4699967A (en) * 1985-01-30 1987-10-13 Bayer Aktiengesellschaft Polysiloxane block copolymers
EP0712880A2 (fr) * 1994-11-17 1996-05-22 Mitsui Toatsu Chemicals, Incorporated Procédé de préparation de copolyesters en bloc dégradables
EP0778306A2 (fr) * 1995-12-05 1997-06-11 Mitsui Toatsu Chemicals, Incorporated Polyestercarbonates séquencés aliphatiques-aromatiques dégradables et leur préparation
EP0893463A1 (fr) * 1996-12-30 1999-01-27 Daicel Chemical Industries, Ltd. Elastomeres polyesters, procedes de preparation et compositions de ces elastomeres
JPH11323107A (ja) * 1998-05-15 1999-11-26 Kuraray Co Ltd ポリエステル系重合体組成物
JP2000212407A (ja) * 1999-01-27 2000-08-02 Sekisui Chem Co Ltd エステル系エラストマ―
JP2002069192A (ja) * 2000-08-31 2002-03-08 Shimadzu Corp 架橋型軟質乳酸系ポリマーの製造方法及びその組成物
JP2002265611A (ja) * 2001-03-07 2002-09-18 Mitsubishi Rayon Co Ltd ポリエステル系ブロック共重合体
JP2002292665A (ja) * 2001-03-29 2002-10-09 Dainippon Ink & Chem Inc 乳酸系ポリマーシートの製造法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8287685B2 (en) 2006-12-06 2012-10-16 Dow Corning Corporation Airbag and process for its assembly

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