WO2003059994A1

WO2003059994A1 - Molded polyester

Info

Publication number: WO2003059994A1
Application number: PCT/JP2002/009097
Authority: WO
Inventors: Makoto Tokumizu; Takeshi Nii; Kousuke Tonami; Nobuhisa Takayama
Original assignee: Mitsubishi Rayon Co., Ltd.
Priority date: 2002-01-10
Filing date: 2002-09-06
Publication date: 2003-07-24

Abstract

A polyester molding retaining transparency over long and satisfactory in heat resistance and chemical resistance is industrially provided. The polyester molding comprises a block copolymer which is made up of a structural unit (A) comprising as a major component repeating units having at least one ester bond therein and a structural unit (B) derived from a compound having a number-average molecular weight of 600 to 100,000 and having an ester-forming functional group at each end, is an elastomer having a compression set as measured in accordance with JIS-K-6262 of 5 to 65%, and has a total light transmittance as measured in accordance with JIS-K-7361-1 of 75% or higher.

Description

Description Polyester molded body Technical field

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. Background art

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. However, at present, these molding materials have drawbacks in terms of scratch resistance, flexibility, processability, economy, and recyclability. In other words, 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, and the polyamide-based elastomer has problems such as high cost. is there. Some proposals have also been made for hydrogenated jen systems. For example, 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. In contrast, polyesters are known as thermoplastic elastomers with excellent environmental resistance and mechanical strength. In particular, 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. 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.

However, a molded article made of such a block copolymer known as a 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.

For example, 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. When such 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.

In addition, by using a polyester that is as amorphous as possible, a block copolymer having relatively high transparency can be obtained. However, such a block copolymer had insufficient heat resistance and chemical resistance, and also had insufficient recovery elasticity.

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. In addition, since 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.

On the other hand, the total light transmittance required for parts that require visibility, such as sunset panels, 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. Units derived from compounds having various functional groups at both ends

(B), and the content of the structural unit (A) is preferably 10 to 70% by mass.

(In the formula (1), 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.)

Further, it is preferable that X and Y in the formula (1) are a methyl group and Z is a methylene group.

In addition, 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) A method for producing an aliphatic polyester block copolymer having an amount of 10 to 70% by mass, comprising: antimony, germanium, titanium, manganese, magnesium, calcium, strontium, barium, sodium, cobalt, aluminum, and gallium. A compound of at least one metal selected from the group consisting of iron, tin, zinc, and boron; Characterized in that it has added to the ester exchange reaction to process so that Le block copolymer 0. l~1 000 p pm.

(In the formula (1), 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.)

It is preferable that X and Y in the above formula (1) are a methyl group and Z is a methylene group.

Further, 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.

In addition, 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.

(In the formula (2), 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.

It is preferable that the structural unit (B) of the polyester molded article of the present invention is a unit derived from polyolefin, polyoxyalkylenedarilicol, polydimethylsiloxane, or polyester. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

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

If no ester bond is contained in the repeating unit, heat resistance and transparency are insufficient, It tends to be one of the high costs industrially.

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).

In the above 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. Further, in the equation (1), 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.

In the formula (1), 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.

In the 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.

Specific examples of 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, ブロ is a tetramethylene group, cabronic acid unit, X is hydrogen, Υ is a methyl group, Ζ is a direct bond, lactic acid unit X is hydrogen, Υ is a phenyl group, and Ζ is a direct bond Is a mandelic acid unit, X is hydrogen, Υ is a phenyl group, Ζ is a methylene group, a tropic acid unit, X and Υ are phenyl groups, and Ζ is a direct bond. it can. Of these, a hydroxypivalic acid unit is preferred because of ease of synthesis.

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.

Further, 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. For example, 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).

In addition, 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. For example, when producing a block copolymer, by combining the amount of hydroxyl group and the amount of carboxyl group in the charged composition, the molecular weight of the target block copolymer can be increased.

Other copolymerization components include dicarboxylic acids, diols, hydroxycarboxylic acids and their esterified products.

Examples of dicarboxylic acids 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. Examples of diols include ethylene diol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanedyl, 1,6-hexane. Diol, 1,71-heptandiol, 1,8-octanediol, 1,9-nonanediol 1,10-decanediol, neopentyldaricol, 3-methyl-1,5-pentanediol, Mouth hexane 1,2-diol, cyclohexane 1,3-diol, cyclohexane 1,4-diol, cyclohexane 1,4-dimethanol, hydroquinone, 4,4-diphenol . As examples of the 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.

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. Specific examples of 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.

As such a compound, 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

0 0 0 0 0 is preferred. When the number average molecular weight is less than 600, heat resistance becomes insufficient,

If it exceeds 100 000, the fluidity becomes insufficient. 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.

If the structural unit (B) is composed of such polyolefin-derived units, There are advantages that the water resistance and weather resistance of the ester molded body are improved and the specific gravity can be reduced. For example, 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

It is in the range of 1000, most preferably in the range of 2000 to 10000. Further, when 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. For example, 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).

(

In the 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.

Further, 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.

When 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. For example, 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. As 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.

When the structural unit (B) is composed of a unit derived from polyester, the polyester molded article has particularly excellent weather resistance and heat resistance, and can be manufactured at low cost. For example, it 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.

When the structural unit (B) is composed of units derived from polyacrylonitrile, the heat resistance of the polyester molded article is particularly excellent. For example, 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.

These compounds may be used alone or in combination of two or more. Further, 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.

Further, 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.

Examples of the polyfunctional component include polyhydric alcohols such as trimethylolpropane and pentaeristol, and 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. For example, when 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. There is no need to use an organic solvent during the reaction as in the case of anionic polymerization and cationic polymerization, and a block copolymer having more excellent heat resistance can be obtained.

The polymerization can be performed by a known polyester polymerization method, and may be continuous polymerization or batch polymerization.

For example, 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. After such a reaction, 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.

When the target block copolymer is produced, 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. In order to match the amount of hydroxyl groups with the amount of hydroxyl groups, use dicarboxylic acid, diol, or the like. Specific examples of these include the above-mentioned dicarboxylic acids and diols.

In these polymerization steps, in particular, 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. When it is added so as to be 100 ppm, preferably 1 to 500 ppm, 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. Compounds, acetyl acetonate salts of these elements, oxides of these elements, and the like.

Among them, the titanium compound is particularly preferably a tetraalkyl titanate such as tetrabutyl titanate or tetramethyl titanate, or a metal oxalate such as titanium oxalate.

As the tin compound, 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.

Examples of the cobalt compound 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.

Examples of the magnesium compound 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. Examples of the manganese compound 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.

Examples of the strontium compound 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.

Examples of the antimony compound include antimony dioxide and antimony acetate.

Also, 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, and acetic acid is used as an iron compound. Examples of compounds of iron and boron include boron oxide.

These metal compounds can be used alone or in combination of two or more.

In the polycondensation reaction, a stabilizer may be used if necessary. Examples of 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. Examples of 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. Examples of 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.

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.

If 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.

(In the formula (2), 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.) "

When the content of 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.

Further, in order to further enhance the balance between the heat resistance and the flexibility of the block copolymer, 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.

When compounding the above-mentioned stabilizer, crystal nucleating agent, reinforcing fiber, powder and the like, various known methods can be used to uniformly mix them. For example, a method of mixing with a double blender or a repump blender, or a method of melt-kneading and granulating the resin mixed by such a method using a single-screw extruder, a twin-screw extruder, a vented extruder, or the like. It is also possible to employ.

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.

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. In addition, 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 is obtained. By modifying the impact resistance, chemical resistance, slidability, and the like, a resin composition excellent in these properties can be produced. Example

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the contents of the examples.

[Test example]

Press molding; press molding the obtained polymer at 240

Injection molding; Injection molding of the obtained polymer at 220

Extrusion molding: Formed into a sheet shape with a thickness of 200 x m at 250 ° C by a film forming machine combining a 4Οιηηι φ single screw extruder and a Τ-die.

The flexibility, transparency, heat resistance, tensile properties and the like of this sample were measured by the following methods.

(1) Flexibility (in the table, indicated by Shore A hardness)

In accordance with 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. And

(2) Transparency

The appearance of the sample obtained by press molding or injection molding was visually evaluated. The long-term transparency was evaluated by (1) a sample immersed in 70-minute warm water for 3 days, and (2) a sample left at room temperature for 1 month. (3) Heat resistance

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 〇 in the table, and those hanging 5 mm or more are indicated by X in the table.

(4) Tensile properties

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. In addition, 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.

(5) Cyclic trimer content

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 (ΗΡ5, 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.

(6) Chemical resistance

The tensile strength retention of the sample after immersion in toluene at 23 ° C for 24 hours is 9

Those that could be maintained at 0% or more are indicated by 〇 in the table, and those that could not be maintained are indicated by X. Alternatively, a 2 mm thick sample obtained by press molding was subjected to acetone rubbing at 23 ° C. and visually evaluated.

(7) NMR

(i) Dissolve the sample in black-mouthed form, centrifuge, and remove

1 R was tested.

(ii) Deuterated chloroform was added to the sample, filtered, and subjected to NMR.

(iii) The sample was hydrolyzed with 3N KOHZ ethanol in a pressure vessel at 105 ° C for 12 hrs. The mixture was neutralized with hydrochloric acid, and the resulting salt was separated by suction filtration (Glass Fill Yuichi) and the filtrate was concentrated. Getyl ether and water were added, and the mixture was extracted with a separating funnel. The ether phase was concentrated, dried in vacuo and subjected to NMR.

(8) 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.

(9) Y I

According to JIS—K—7105, a 3 mm-thick, 50 mm × 50 mm plate sample was measured at 23 ° C. all at once.

(1 0) MF R

According to ASTM D 1238, it was measured at 190 ° C. under a load of 21.2N (2.16 kg) using a melt indexer.

(1 1) Compression set

According to 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.

[Production Example 1]

132 g (0.1 mol) of methyl hydroxypivalate and 0.132 g of titanium tetrabutoxide were placed in a reaction vessel, and transesterification was performed at 160 to 200 ° C for 2 hours under a nitrogen atmosphere. After raising the temperature of the reaction system to 240 ° C in 30 minutes, the pressure inside the system was reduced from normal pressure to 0.13 kPa or less over 2 hours, and the polycondensation reaction was performed for 2 hours. .

When the melt viscosity of the obtained resin was measured by a rheometer, it was 1 Pa · s at 240 ° C. Let the obtained resin be (A-1).

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.

[Example 1]

792 g (5.9 mol) of methyl hydroxypivalate, PTG4000 (protected) 900 g (0.225 mo 1) of Tsuchiya Chemical, number average molecular weight 4000), 26.7 g (0.153 mol) of dimethyl adipate, and 9.15 g (0.15 g) of trimellitic anhydride 048 mol), tetrakis [methylene (3,5-di-tert-butyl-1-hydroxyhydrocinnamate)] methane (6 g) as a stabilizer, and titanium tetrabutoxide (1.5 g) as a catalyst were introduced with nitrogen. The reactor was charged and the reaction was carried out at 160 to 240 ° C for 3 hours while removing methanol.

Next, 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 (Β) determined from the peak of t a η δ was 143 ° C. When this polymer was analyzed by NMR, 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.

[Example 2]

444 g of the resin (A-1) obtained in Production Example 1, 1050 g of PTG4000 (manufactured by Hodogaya Chemical Co., Ltd., number average molecular weight 4000), 36.4 g of dimethyl adipate, and 6 of trimellitic anhydride 8.4 g, tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane as a stabilizer, 6 g of methane, and 1.5 g of titanium tetrabutoxide as a catalyst were introduced with nitrogen. The reaction vessel was charged and the reaction proceeded at 160 ° C to 240 ° C for 1 hour while removing methanol. Next, 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 dynamic viscoelasticity of this polymer was measured, and the T g derived from the structural unit (Β) determined from the peak of t a η δ was 1 45 ° C. When this polymer was analyzed by NMR, the content of the structural unit (A) was 23% by mass. The thus obtained polymer was molded and evaluated in the same manner as in Example 1, and the results are shown in Tables 1 and 2.

[Comparative Example 1]

387.1 g (1.99 m'ol) of dimethyl terephthalate, 269.5 g (2.99 mol) of 1,4-tetramethylenglycol, PTG4000 (polytetramethylene glycol manufactured by Hodogaya Chemical, number average molecular weight) Reaction with 500 g of 4000), 5 g of tetrakis [methylene (3,5-di-tert-butyl-4-cinnamate)] methane as stabilizer and 0.31 g of titanium tetrabutoxide as catalyst The mixture was charged in a kettle, and the reaction was carried out at 160 to 240 ° C. for 2 hours while removing methanol to obtain 880 g of a reactive product. The number average molecular weight was 39,000, and the molecular weight distribution was 2.0, as determined by dissolving it in a gel form and using polystyrene standards.

The thus obtained polymer was molded and evaluated in the same manner as in Example 1, and the results are shown in Tables 1 and 2.

[Comparative Example 2]

444 g of resin (A-1) obtained in Production Example 1, 1050 g of ぺ Spore HP-1 000 (Toagosei Co., Ltd., number average molecular weight 538), 339.8 g of dimethyl adipate as a stabilizer Tetrakis [methylene (3,5-di-t-butyl_4-hydroxyhydrocinnamate)] methane (6 g) and titanium tetrabutoxide (1.5 g) as a catalyst were charged into a nitrogen-introduced reaction vessel, and 160 ° ( The reaction was proceeded while removing methanol for 1 hour at 240 to 240 ° C.

Then, 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 dynamic viscoelasticity of this polymer was measured, and the T g derived from the structural unit (Β) determined from the peak of ta η δ was 11 ° C. When this polymer was analyzed by NMR, the content of the structural unit (A) was 25% by mass. The polymer obtained in this manner was molded and evaluated in the same manner as in Example 1, and the results were evaluated.

1 and Table 2.

table 1

transparency

All rays

Shore A MFR 70 ° C hot water Chemical resistant

Transmittance heat resistance

Hardness (g / 10min.) After 3 days

(%)

Appearance

80

230 Transparent Transparent 88 〇例 Example 1

Implementation 87

200 Transparent Transparent 83 〇〇 Example 1

Comparison

83 135 Opaque Opaque 27 〇例 Example 1

Comparison

90 190 Translucent Translucent 60 〇〇 Example 2 Table 2

As is clear from Tables 1 and 2, 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 (Β) 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.

[Example 3]

Methyl hydroxypivalate 2200 g (16.4 mol), PTG4000 (Hodogaya Chemical, number average molecular weight 4000) 2500 g (0.625 mol), dimethyl adipate 74 g (0.425 mol), trimellitic anhydride 25.5 g (0.133mo 1) 4.0 g of titanium tetrabutoxide as a catalyst was charged into a reaction vessel into which nitrogen had been introduced, and the reaction was carried out at 160 to 240 ° C for 3 hours while removing methanol. .

Next, 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. Here, 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.

Further, when this polymer was analyzed by NMR, the content of the structural unit (A) was 29% by mass. Table 3 shows the proportion (calculated value) of titanium in titanium tetrabutoxide added as a catalyst in the obtained polymer.

The obtained polymer was molded and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[Example 4]

51.7 g of the resin (A-1) obtained in Production Example 1, 50 g of PTG4000 (manufactured by Hodogaya Chemical Co., Ltd., number average molecular weight 4000), 2.92 g of dimethyl adipate, and titanium tet as a catalyst 0.05 g of rabtoxide was charged into a reaction vessel into which nitrogen had been introduced, and the reaction was carried out at 160 to 240 for 1 hour while removing methanol.

Then, 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 (Β) determined from the peak of ta η δ was −55 ° C. Here, 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.

Further, when this polymer was analyzed by NMR, the content of the structural unit (A) was 27% by mass. Table 3 shows the ratio (calculated value) of titanium in titanium tetrabutoxide added as a catalyst in the obtained polymer. The obtained polymer was molded and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[Example 5]

51.7 g of the resin (A-1) obtained in Production Example 1, 50 g of PTG 2000 (manufactured by Hodogaya Chemical, number average molecular weight 2000), 4.4 g of dimethyl adipate, and manganese acetate as a catalyst 0.05 g was charged into a reaction vessel into which nitrogen had been introduced, and heated at 160 °. The reaction was allowed to proceed while removing methanol for 1 hour at a temperature of from 240 ° C.

Next, 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.

The dynamic viscosity of this polymer was measured, and the Tg derived from the structural unit (B) determined from the peak of t an <5 was 140. Also, here the structural unit

(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.

When this polymer was analyzed by NMR, the content of the structural unit (A) was 38% by mass. Table 3 shows the proportion (calculated value) of titanium in titanium tetrabutoxide added as a catalyst in the obtained polymer.

[Example 6]

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 φ 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]

75.3 g of PTG4000 (polytetramethylene glycol manufactured by Hodogaya Chemical, number average molecular weight 4000), 4.4 g of adipic acid, and 0.055 g of titanium tetrabutoxide as a catalyst were charged into a reactor introduced with nitrogen. The reaction was allowed to proceed while removing methanol at 240 ° C. for 2 hours at 160 ° C. to obtain 67.6 g of a reaction product. The number average molecular weight was 8,300 as measured by polystyrene standard after dissolving in black hole form, and the molecular weight distribution was 1.9.

This was reacted with an equivalent amount of tetrabutylammonium butoxide to synthesize a corresponding ammonium salt, which was used as a 0.01 mol Z 1 benzene solution.

176 g of anhydrous benzene is added to the reactor purged with nitrogen. Then, 12.6 g of the above-mentioned polyester ester benzene solution was added, and benzene was refluxed under stirring. Pivalolactone (41.0 g) was added thereto, and the mixture was refluxed for 6 hours. The resulting polymer was separated by filtration, and dried at 0.3 kPa, 120 for 5 hours to obtain 40.5 g of white granules. Was. This was dissolved in black hole form, and the number average molecular weight measured by polystyrene standard was 39,000 and the molecular weight distribution was 1.6.

When this polymer was analyzed by NMR, the content of the structural unit (A) was 97.5% by mass. Table 3 shows the proportion (calculated value) of titanium in titanium tetrabutoxide added as a catalyst in the obtained polymer.

[Comparative Example 4]

78.2 g of dimethyl terephthalate, 71.4 g of 1,6-hexanediol, and 0.05 g of titanium tetrabutoxide as a catalyst were charged into a reaction vessel into which nitrogen had been introduced. The reaction proceeded while removing methanol for hours. After methanol has distilled over 23.3 g (90% of the theoretical distillation amount), the pressure in the system was reduced to 0.13 kPa or less at 240 ° C for 30 minutes, and the pressure was reduced for 2 hours. Perform condensation. The resulting polymer is discharged into water under nitrogen pressure and pelletized to obtain 93 A polymer was obtained. The number average molecular weight was 36,000, and the molecular weight distribution was 1.7, as determined by dissolving in black mouth form and measuring with polystyrene standards.

The dynamic viscoelasticity of this polymer was measured, and the T g determined from the peak of t a η <5 was 7 ° C.

Table 3 shows the proportion (calculated value) of titanium in titanium tetrabutoxide added as a catalyst in the obtained polymer.

[Comparative Example 5]

51.7 g of the resin (A-1) obtained in Production Example 1, 50 g of Spore HP-1000 (manufactured by Toagosei Co., Ltd., number average molecular weight 538), 50 g, 16.4 g of dimethyl adipate, catalyst 0.05 g of titanium tetrabutoxide was charged into a reaction vessel into which nitrogen had been introduced, and the reaction was carried out at 160 to 240 ° C for 1 hour while removing methanol. Next, 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 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.

[Comparative Example 6].

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 製 πιπιφ 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

*) Amount of catalyst metal-[Amount of catalyst compound charged] I (Amount of polymer obtained)] X [Metal element / Catalyst compound] χ 100 000 (ppm)

Table 4

As is clear from 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.

[Example 7]

Methyl hydroxypivalate 1980 g (14.8mo1), PTG 2000 (protected Tsuchiya Chemical, number average molecular weight 2000) 1 125 g (0.563 mol), dimethyl adipate 67 g (0.385 mol 1), trimellitic anhydride 22.9 g (0.119 mol 1), stabilizer 10.9 g of tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] me and tan, and 1.36 g of titanium tetrabutoxide as a catalyst were charged into a reactor introduced with nitrogen. The reaction proceeded while removing methanol for 3 hours at 160 ° C to 240 ° C in a nitrogen stream of 500 ml / min.

Next, 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.

Note that the dynamic viscoelasticity of this polymer was measured, and the Tg derived from PTG2000 determined from the peak of t a η δ was −40 ° C. The obtained polymer was molded and evaluated in the same manner as in Example 1. Table 5 shows the results.

[Comparative Example 7]

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

4-Hydroxyhydrocinnamate)] 10.9 g of methane and 1.36 g of titanium tetrabutoxide as a catalyst are charged into a reaction vessel introduced with nitrogen and reacted at 160 to 240 ° C for 3 hours while removing methanol. Advanced.

Then, 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.

500 g of polymer were obtained. This was dissolved in black hole form, and the number average molecular weight measured by polystyrene standard was 50,000 and the molecular weight distribution was 3.2. The dynamic viscoelasticity of this polymer was measured, and the Tg derived from PTG 2000 determined from the peak of ta η δ was −40 ° C.

The obtained polymer was molded and evaluated in the same manner as in Example 1. Table 5 shows the results. Table 5

As is clear from Table 5, 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.

The obtained polymer was molded and evaluated in the same manner as in Example 1. Table 6 shows the results.

[Example 8]

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 dynamic viscosity of this polymer was measured, and the Tg derived from Polytail (trademark), which is the component Β, determined from the peak of t a η δ was 130 ° C.

[Example 9]

51.7 g of the resin (A-1) obtained in Production Example 1, 50 g of PTG4000 (polytetramethylene glycol manufactured by Hodogaya Chemical, number average molecular weight 4000), 1.74 g of dimethyl adipate, and titanium as a catalyst 0.05 g of tetrabutoxide (50 Op pm vs. polymer) was charged into a reaction vessel into which nitrogen had been introduced, and the reaction was carried out at 160 ° to 240 ° 0 for 1 hour while removing methanol.

Next, 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.

+ In addition, the dynamic viscoelasticity of this polymer was measured, and the Tg derived from P TG4000, which is the component 求め obtained from the peak of t a η δ, was _40. The obtained polymer was molded and evaluated in the same manner as in Example 1. Table 6 shows the results.

[Example 10]

51.7 g of the resin (A-1) obtained in Production Example 1, 50 g of polydimethylsiloxane modified at both ends with methyl undecenoate (number average molecular weight 2200), 4.0 g of dimethyl adipate Then, 0.05 g of titanium tetrabutoxide (5 OO ppm vs. polymer) as a catalyst is charged into a reaction vessel into which nitrogen has been introduced, and then heated from 160 ° C to 240 ° C. The reaction proceeded while removing methanol for 1 hour.

Then, 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 dynamic viscoelasticity of this polymer was measured, and the Tg derived from polydimethylsiloxane, which is the component Β, determined from the peak of ta η δ was −80 ° C.

[Example 11]

38 g of dimethyl adipate, 36.2 g of 3-methyl-1,5-pentanediol, and 0.025 of titanium tetrabutoxide (500 ppm vs. polymer) as a catalyst are charged into a nitrogen-introduced reaction vessel and heated from 160 ° C to 240 ° C. The reaction proceeded while removing methanol for 2 hours. Then, the pressure in 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. Thereafter, the pressure was released, and then (A-1) (50 g) was added and stirred for 30 minutes. Then, 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 Β, determined from the peak of ta η δ was one. 25 ° C.

The obtained polymer was molded and evaluated in the same manner as in Example 1. Table 6 shows the results. [Comparative Example 8]

3400 g of dimethyl terephthalate, 2270 g of 1,4-butanediol, 6000 g of PTG 2000 (polytetramethylene glycol manufactured by Hodogaya Chemical Co., Ltd., number average molecular weight 4000), 6000 g of titanium tetrabutoxide as a catalyst (500 gpm The polymer was charged into a reaction vessel into which nitrogen had been introduced, and the reaction was carried out at 160 to 240 ° C for 2 hours while removing methanol. Then, the pressure inside the system was reduced to ImmHg or less over 30 minutes at 24, and the polycondensation was performed while maintaining the reduced pressure for 2 hours. 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.

[Comparative Example 9]

17 g of dimethyl terephthalate, 17 g of dimethyl isophthalate, 22.7 g of 1,4-butanediol, 60 g of PTG 2000 (polytetramethylene glycol manufactured by Hodogaya Chemical, number average molecular weight 2000), As a catalyst, 0.05 g of titanium tetrabutoxide (500 ppm vs. polymer) was charged into a reaction vessel into which nitrogen had been introduced, and the reaction was carried out at 160 to 240 ° C. for 3 hours while removing methanol. Next, the pressure inside the system is reduced to 1 mmHg or less over 30 minutes at 240, and the polycondensation is performed while maintaining the reduced pressure for 2 hours. 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.

[Comparative Example 10]

100 g of Himilan (trademark) 1707 (Ionomer resin manufactured by DuPont-Mitsui Polychemicals) was dry-blended with 1900 g of the polymer obtained in Comparative Example 8, and extruded at 24 Ot: using a small twin-screw extruder. Pelletized sample 00 g of the polymer was obtained.

The obtained polymer was molded and evaluated in the same manner as in Example 1. Table 6 shows the results. Table 6

As is clear from Table 6, all of the polyester molded articles obtained in the examples were excellent in heat resistance, maintained high transparency, and had good flexibility and chemical resistance. Industrial applications

The polyester molded article of the present invention has excellent heat resistance, good transparency, and high transparency. In addition, because of its excellent flexibility and chemical resistance, 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.

Claims

The scope of the claims

1. Structural unit (A) whose main component is a unit having at least one ester bond in the repeating unit, and 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 ends. It is an elastic material having a compression set of 5 to 65% measured in accordance with JIS-K-6262 in the range of 5 to 65%. JIS -K- 736

A molded polyester product having a total light transmittance of at least 75% as measured according to 1-1.

2. Structural unit (A) whose main component is the unit represented by the following formula (1), glass transition temperature (Tg) is 0 ° C or less, and number average molecular weight is in the range of 600 to 100000. An aliphatic polyester block copolymer comprising a structural unit (B) derived from a compound having a functional group capable of forming an ester at both terminals, and the structural unit (A) The amount is 10 to 70% by mass, the compression set measured according to JIS-K-6262 is in the range of 5 to 65%, the material is elastic, and JIS-K-736 1-1 A polyester molded article having a total light transmittance of 75% or more as measured according to (1).

(In the formula (1), X and Υ each represent one of hydrogen, an alkyl group, and a phenyl group. Η is 5 to 5000. また is a direct bond, an alkylene group having 1 to 6 carbon atoms, One of phenylene groups is shown.)

3. The polyester molded article according to claim 2, wherein in the formula (1), X and Υ are methyl groups, and Ζ is a methylene group.

4. The polyester molded article according to claim 1, comprising a structural unit (C) comprising a polyfunctional component in an amount of 0.05 to 2 mol% based on the structural unit (A).

5. Structural unit (A) whose unit is the unit represented by the following formula (1) as a component (A) and ester with a glass transition temperature (Tg) of 0 ° C or less and a number average molecular weight in the range of 600 to 100000 An aliphatic polyester block comprising a structural unit (B) derived from a compound having a functional group that can be formed at both ends, and the content of the structural unit (A) is 10 to 70% by mass. A method for producing a copolymer, selected from the group consisting of antimony, germanium, titanium, manganese, magnesium, calcium, strontium, barium, sodium, cobalt, aluminum, gallium, iron, tin, zinc, and boron. At least one metal compound is added so that the total mass of the metal is 0.1 to 1000 ppm in the formed aliphatic polyester block copolymer, and transesterification is performed. Method for manufacturing an aliphatic polyester block copolymer characterized by having a degree.

(In the formula (1), 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, Shows any of phenylene groups.)

6. The method for producing an aliphatic polyester block copolymer according to claim 5, wherein X and Y in the formula (1) are methyl groups, and Z is a methylene group.

7. The aliphatic block copolymer is configured to contain a structural unit (C) composed of a polyfunctional component in an amount of 0.05 to 2 mol% with respect to the structural unit (A). 7. The method for producing an aliphatic polyester block copolymer according to claim 5, wherein

8. The polyester molded article according to claim 1, wherein the MFR of the block copolymer measured according to ASTM D1238 is 3 to 300 _g / 10min.

9. 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, wherein the yellowness index is 30 or less. The polyester molded article according to 1.

10. The polyester according to claim 2 or 4, wherein the aliphatic polyester block copolymer contains 0.05% by mass or less of a cyclic body represented by the following formula (2) in the aliphatic polyester. Molded body.

(In the formula (2), X and Y each represent any of hydrogen, an alkyl group, and 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.)

1. The aliphatic polyester block copolymer according to claim 3, wherein a cyclic trimer represented by the following formula (3) is contained in the aliphatic polyester in an amount of 0.05% by mass or less. The polyester molded article according to the above.

12. The polyester molded article according to claim 1, wherein the structural unit (B) is a unit derived from polyolefin.

13. The polyester molded article according to claim 1, wherein the structural unit (B) is a unit derived from polyoxyalkylene glycol.

14. The polyester molded article according to claim 1, wherein the structural unit (B) is a unit derived from polydimethylsiloxane.

1 5. The polyester molded article according to any one of claims 1 to 4, wherein the structural unit (B) is a unit derived from polyester.