JP2003251673A - Method for manufacturing heat-resistant sheet and molded body of polyethylene terephthalate polyester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide heat-resistant sheets and molded bodies useful in such fields as everyday items, civil engineering and construction materials, electronic and electric members and automotive members by using polyethylene terephthalate (PET) polyesters modified to a long chain branched structure and block-copolymerized with another polyester or a polyolefin. <P>SOLUTION: A mixture comprising (a) 100 pts.wt. PET polyester, (b) 0-100 pts.wt. other polyester or polyolefin containing carboxylic acid groups, (c) 1-15 pts.wt. master batch of a mixture with 0-75/100-25 weight ratio of at least a trifunctional epoxy compound/bifunctional epoxy compound as a bonding agent and (d) 0.25-10 pts.wt. master batch of a composite body of organic acid metal salts as a bonding catalyst, is modified to a long chain branched structure with a fast crystallization speed by a reaction extrusion method to prepare a block copolymer with a melt viscosity increased at least 10 times of a conventional PET with a linear structure. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inexpensive heat-resistant sheet of polyethylene terephthalate polyester having transparent heat resistance and opaque heat resistance which can withstand heating of a container and a microwave oven which can be heated and filled, and a method for producing a molded product.

[0002]

2. Description of the Related Art In recent years, as containers which can be heated and filled and which can withstand heating of a microwave oven, containers of tofu and natto having a heat resistance of about 80 to 90 ° C., bento containers of convenience stores having a heat resistance of about 110 to 130 ° C., etc. The demand for is rapidly increasing. Conventionally, polypropylene (PP), polystyrene (PS), polyethylene terephthalate (A-PET or C-PET), polybutylene terephthalate (PBT), and polycarbonate (PC) have been used as materials for these containers. These materials have advantages and disadvantages in terms of quality including heat resistance, price, environmental compatibility, and the like. For example, polypropylene (PP) is inexpensive and has good processability, but it is slightly inferior in transparency and elution of a stabilizer or the like is observed at high temperatures. The heat resistance of the microwave oven is about 120 ° C.
Polystyrene (PS) is cheap and has good processability and transparency, but it has a safety problem of residual monomer and is a little fragile. The heat resistance of the microwave oven is said to be deformed as a lunch container at about 110 ° C. It Polyethylene terephthalate (A-PET) has excellent transparency, strength, and environmental compatibility, but is slightly more expensive and has a heat resistance temperature of about 120
It has a weak point that whitening and embrittlement (C-PET formation) due to crystallization occur at ℃. Polyethylene terephthalate (C-PE
T) is excellent in heat resistance and environmental compatibility, but its use is limited due to special molding process, high price, and white opacity (for example, for microwave oven with heat resistance temperature of about 220 ° C.). In addition, polybutylene terephthalate (PBT) resin 70
~ 100 parts by weight and polyethylene terephthalate (PE
Although a composition comprising 30 to 0 parts by weight of T) -based resin has been successfully used as a sheet and container having a heat resistance of 140 ° C. (for example, the second
552328), the cost is higher because there are more PBTs than PET. Furthermore, polybutylene terephthalate (PBT) and polycarbonate (PC) are excellent in transparency, strength and heat resistance, but the cost of the sheet is extremely high since the raw material of the material is expensive, and it cannot meet the demand.

In recent years, from the viewpoint of resource saving and environmental protection, it is recognized worldwide that the used plastic products recovered from the factory production process and the general consumer market need to be reused. Films, sheets, etc.
Large-scale collection and reuse are being actively promoted, and it has become possible to obtain low-priced products at half the price of general-purpose resins. On the other hand, the used recovered pets have a lower molecular weight than the new pellets, and the molecular weight of the flakes (crushed materials) of the recovered PET bottles, which are derived in large quantities, is almost halved. Therefore, if only this is reused as the base resin, the molding processability is poor, the molded product is brittle and the impact resistance is poor, and the quality of the original PET bottle cannot be guaranteed. As a result, only fibers and low-quality sheets that can be molded even with a low molecular weight are obtained, and their reuse applications are limited to a narrow range. Further, since the transparent glassy PET-based polyester has a high glass transition temperature of 70 ° C. or higher, it is inferior in low-temperature brittleness (cold resistance) and impact resistance, so that it is difficult to develop new applications. On the other hand, polyolefins such as polyethylene and polypropylene are used in large amounts in films, sheets, containers, etc., but it is known that their rigidity and hardness are far inferior to those of hard PVC, PET polyester and polystyrene. .

As one of the methods for solving these problems, a method of recovering and increasing the molecular weight, that is, for PET type polyester, a method of recovering the molecular weight by solid phase polymerization, a chain extender (binder) and a polyester Known methods include a method of reacting terminal groups to increase the molecular weight, a method of adding another resin such as an elastomer to compensate for mechanical properties, and the like. Chain extender (binder) to increase molecular weight
As, isocyanate, oxazoline, epoxy,
It has been proposed to use a compound having a bond or a functional group such as aziridine or carbodiimide. However, there are strong restrictions from reactivity, heat resistance, stability, etc.
Those that have practicality are limited. Of these, epoxy compounds are relatively useful, and those containing a monoepoxy compound (JP-A-57-161124) and those containing a diepoxy compound (JP-A-7-16641).
9, Japanese Patent Publication No. 48-25074, Japanese Patent Publication No. 60
However, there are many problems in reaction rate, gel formation, melt viscosity, compatibility, thermal stability, physical properties of molded products, etc., and it was difficult to put them into practical use.

On the other hand, there has been proposed a method of increasing the molecular weight of the polyester by melt-mixing the recovered PET-based polyester with a bifunctional epoxy resin and a sterically hindered hydroxyphenylalkylphosphonic acid ester (Japanese Patent Laid-Open Publication No. Hei 8 (1998)). No. 5088776). Although this method has a relatively high reaction rate, the sterically hindered hydroxyphenylalkylphosphonate used is expensive, and in the industry where low cost recovery and circulation costs are required and the food packaging industry where safety is required, Practicality remains a challenge. Also,
The method proposed by the present inventors, in which a medium molecular weight PET-based polyester is used in combination with a bifunctional and polyfunctional epoxy compound, and melt-mixed and combined with a specific catalyst (P
CT WO98 / 44019) increased the molecular weight and melt tension of the polyester to enable foam molding (PCT WO00 / 20491), but the molded products are slightly brittle and have impact resistance and low temperature brittleness (cold resistance). It is completely insufficient for improvement. For example, as a frozen food material, a sheet molded body that does not crack at a low temperature of -20 to 30 ° C and has heat resistance of preferably 130 ° C, more preferably 230 ° C is required.

A blending method has also been proposed in which rubber, an elastomer, a soft metallocene-based polyethylene copolymer, etc. are blended with PET-based polyester, but in those cases, the compatibility is very poor, and the heat resistance and elastic modulus are very low. However, there was a problem in the drying property of the pellets. On the other hand, a blending method in which PET-based polyester is blended with polyethylene or polypropylene has been proposed, but it has not been practically used except for some applications because it has a definite poor mixability and compatibility. Further, the present inventors have previously proposed a medium-molecular-weight PET polyester and a carboxylic acid group-containing polyolefin by melt-mixing and binding reaction by using a bifunctional and polyfunctional epoxy compound in combination and a specific catalyst. The polyolefin-polyester block copolymer method (Japanese Patent Laid-Open No. 2001-122955) produced by the above method has a considerably improved impact resistance and low temperature brittleness (cold resistance) due to an increase in the amount of polyolefin, but is mixed. Gel and fish eyes are by-produced because of poor uniformity and uniformity, molding processability is not sufficient, and in the extreme case where the surface of the sheet molded body lacks barbs, it becomes a citron skin-like product. It was not enough.

[0007]

In order to realize the inexpensive heat-resistant sheet and the molded article of the above-mentioned problems, a recovered PET bottle and a recovered PET sheet which can be obtained at a half price of general-purpose resins may be used as a basic material. The molecular weight is too low to make a good quality sheet. Therefore, it is necessary to have a high molecular weight. However, since a linear structure is formed in the conventional solid-phase polymerization method, the crystallization speed is slow on the order of minutes when heat-fixing (heat setting) during sheet forming and pressure-pressing or vacuum-pressure forming of the sheet. It is difficult to realize a heat-resistant sheet and a molded body that require a long cycle and are inexpensive. On the other hand, the A-PET sheet that is not heat set does not have heat resistance because it has a crystallization zone at about 120 ° C. An object of the present invention is to provide an inexpensive heat-resistant sheet of polyethylene terephthalate-based polyester having transparent heat resistance and opaque heat resistance that can withstand heating of a container and a microwave oven that can be heated and filled, and a method for producing a molded product.

[0008]

As a result of intensive studies to solve the above problems, the present inventors have succeeded in dramatically improving the above problems and completed the present invention. . That is, an inexpensive recovered pet was used as the base material. The high molecular weight was made into a sheet in which the by-product of gel and fish eyes was dramatically reduced at high speed by adopting the masterbatch reactive extrusion method using a binder and a catalyst. In addition, a compound containing two epoxy groups in the molecule (2
A "long-chain branched structure" is introduced by using a compound (trifunctional or more: T) containing three or more epoxy groups in the molecule in the functional: D) to increase the T / D ratio and crystallize. The rate of conversion was increased. It is presumed that a compound having a trifunctional or higher functional epoxy group acts as a "molecular size crystallization nucleating agent". The long chain branched structure of the present invention,
It is possible to increase the melt viscosity by about 10 to 100 times due to the "entanglement effect" of the molecular chains as compared with the conventional linear structure, so a sheet with less drawdown during compressed air or vacuum compressed air molding is obtained. . Further, as in the case of polyethylene terephthalate polyester (component a),
By block-copolymerizing an aromatic polyester (B1 component) or a carboxylic acid-containing polyolefin (B2), it is possible to comprehensively crystallize during heat setting (heat setting) at the time of sheet molding and compressed air or vacuum compressed air molding of the sheet. We were able to speed up the conversion speed to the order of seconds.
Heat fixing (heat setting) is performed at about 90 to 100 ° C in the case of a container capable of heating and filling tofu and natto having a heat resistance of about 80 to 90 ° C, and a microwave oven with a heat resistance of about 110 to 130 ° C. In the case of a container such as a lunch box container of a convenience store that can withstand heating, it could be carried out at about 120 to 150 ° C. As a result, in the present invention, it is possible to enhance the productivity of the transparent heat-resistant and opaque heat-resistant polyethylene terephthalate-based polyester that can withstand the heating of a container and a microwave oven that can be heat-filled, and the productivity of a molded article, which is inexpensive. The method for producing a heat resistant sheet and a molded body has been completed.

That is, the present invention provides the following inventions. First, component A: (1) polyethylene terephthalate polyester a having a melt flow rate (JIS method: 280 ° C., load 2.16 Kg) of 40 to 200 g / 10 min: 100 parts by weight, (2) a molecule as a binder Compound b containing two epoxy groups in: 25-
100% by weight and a compound c containing 75 to 0% by weight of a compound containing 3 or more epoxy groups in the molecule d: 10 to 5
Binder masterbatch f: 1 to 10 parts by weight consisting of 0 parts by weight and substrate e: 100 parts by weight, (3) metal salt of organic acid g: 5 to 15 as a coupling reaction catalyst, and substrate h: 1
Catalyst masterbatch i consisting of 100 parts by weight:
0.25 to 10 parts by weight of a mixture, and B1 component: 0 to 100 parts by weight of an aromatic polyester having a melt flow rate (JIS method: 280 ° C., load 2.16 Kg) of 200 g / 10 minutes or less, A block copolymer having a melt flow rate of 60 g / 10 min or less is obtained by uniformly reacting by a reactive extrusion method while being melted at a temperature equal to or higher than its melting point and being degassed and dehydrated to 13.3 × 10 ³ Pa or less in a vacuum system. A transparent heat-resistant sheet of polyethylene terephthalate-based polyester, which is formed into a sheet to obtain a heat-formed body, and a method for producing the formed body.
Secondly, A component: (1) Melt flow rate (JIS
Method: 280 ° C., load 2.16 Kg) is 40 to 200 g /
10 minutes polyethylene terephthalate-based polyester a: 100 parts by weight, (2) compound b containing 2 epoxy groups in the molecule as a binder: 25 to 100% by weight and 3 or more epoxy groups in the molecule Compound c: a mixture of 75 to 0% by weight, d: 10 to 50 parts by weight of a base material, and a base material e: 100 parts by weight of a binder masterbatch f: 1 to 10 parts by weight, (3) an organic compound as a coupling reaction catalyst. A mixture composed of a catalyst masterbatch i: 0.25 to 10 parts by weight, which is composed of an acid metal salt g: 5 to 15 and a substrate h: 100 parts by weight, and a B2 component: a melt flow rate (JIS method: 280 ℃, load 2.16Kg) is 2
A polyolefin containing 0 to 100 parts by weight of one or more carboxylic acid groups in a molecule of 00 g / 10 min or less is melted at a temperature of its melting point or higher and 13.3 × in a vacuum system.
A melt flow rate of 60 g / 10 by performing a uniform reaction by reactive extrusion while degassing and dehydrating to 10 ³ Pa or less.
An opaque heat-resistant sheet of polyethylene terephthalate-based polyester and a method for producing a molded article, which comprises forming a block copolymer having a content of not more than 5 minutes, molding the sheet into a sheet, and then forming the sheet into a heat-molded article. Thirdly, any one of 1 and 2 above
The block copolymer produced by the method described in the item 1. is once pelletized, and 100 parts by weight of the block copolymer and a lubricant of 0.
A method for producing a heat-resistant sheet of polyethylene terephthalate-based polyester and a molded article, which comprises molding a mixture of 0. 1 to 1 part by weight into a sheet to obtain a heat-molded article. Fourthly, the polyethylene terephthalate polyester a is selected from the group consisting of polyethylene terephthalate having an intrinsic viscosity of 0.50 to 0.90 dl / g, polyethylene terephthalate aromatic polyester, and polyethylene terephthalate aromatic polyester molded product recycle product. A method for producing a heat-resistant sheet of polyethylene terephthalate-based polyester and a molded article according to any one of 1 to 3 above, which contains at least one kind. Fifthly, the compound b having two epoxy groups in the molecule as a binder is an aliphatic ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, alicyclic hydrogenated bisphenol A diether. 1 above, which contains at least one selected from the group consisting of glycidyl ether and aromatic bisphenol A / diglycidyl ether
A heat-resistant sheet of polyethylene terephthalate-based polyester according to any one of 1 to 3 and a method for producing a molded article. Sixth, the compound c containing 3 or more epoxy groups in the molecule as a binder is a fat-proof trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, epoxidized soybean oil, epoxidized flaxseed. 1 above containing at least one selected from the group consisting of oil, heterocyclic triglycidyl isocyanurate and aromatic phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisresorcinol tetraglycidyl ether ~ 3
10. A method for producing a heat-resistant sheet and a molded product of the polyethylene terephthalate polyester according to any one of 1.
Seventh, a complex containing at least two or more selected from the group consisting of lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt, zinc salt and manganese salt of stearic acid or acetic acid as the binding reaction catalyst g. A heat-resistant sheet of polyethylene terephthalate-based polyester according to any one of the above 1 to 3, and a method for producing a molded article. Eighth, the B1 component
(1) Dry or undried polyethylene terephthalate, polybutylene terephthalate, cyclohexanedimethanol-based co-condensed polyester, polyethylene terephthalate-based molded product having a melt flow rate (JIS method: 280 ° C., load 2.16 Kg) of 200 g / 10 minutes or less A heat-resistant sheet of polyethylene terephthalate-based polyester and a molded article according to any one of 1 to 3 above, which contains at least one selected from the group consisting of a recycled material and a reactant of component A. Manufacturing method. 9th
In addition, the component B2 is a polyolefin containing one or more carboxylic acid groups in the molecule, and polyethylene, polypropylene, or ethylene propylene copolymer in which maleic anhydride or an ethylene-based monomer containing a carboxylic acid group is copolymerized A method for producing a heat-resistant sheet of polyethylene terephthalate-based polyester and a molded article according to any one of 1 to 3 above, which contains at least one selected from the group consisting of a polymer and a mixture thereof. . Tenth, while manufacturing the block copolymer of the component A and the component B1 or the component B2 by a reactive extrusion apparatus, the component B1 or the component B2 is newly additionally supplied to the mold to form a 2 type 2 layer 2 type 3 layer.
A heat-resistant sheet of polyethylene terephthalate-based polyester according to any one of 1 to 9 above, which is formed into a layer or a multi-layered sheet to produce a heat-molded article, and a method for producing a molded article. Eleventh, the heat-resistant sheet of polyethylene terephthalate-based polyester and the method for producing a molded article according to any one of 1 to 10 above, wherein a roll temperature in extrusion molding of the sheet is 30 to 150 ° C. Twelfth, the heat-resistant sheet of polyethylene terephthalate-based polyester and the method for producing a molded article according to any one of the above items 1 to 11, wherein the mold temperature in sheet heat molding is 90 to 150 ° C.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the aromatic saturated polyester a as a raw material prepolymer of the component A is PET.
Polyethylene terephthalate (PET), which is mass-produced worldwide as the aromatic aromatic polyester, or a copolymer thereof can be used. Polyethylene terephthalate (PET or PET) is preferred. PET of the present invention
The aromatic aromatic polyester is dissolved in a 1,1,2,2-tetrachloroethane / phenol (1: 1) mixed solvent to give 2
Intrinsic viscosity (IV value) measured at 5 ° C is 0.50 dl / g
Above (This is JIS method, temperature 280 ℃, load 2.16
Melt flow rate (MFR) in kgf is about 21
This corresponds to 0 g / 10 minutes or less. Same below. ) Is preferred and 0.60 dl / g or more (MFR is about 13
0 g / 10 minutes or less) is more preferable. When the intrinsic viscosity is less than 0.50 dl / g, it is difficult to obtain a high molecular weight and a high melt viscosity even by the present invention, and the obtained polyester-polyethylene block copolymer does not necessarily have excellent moldability and physical properties. There is a fear that it cannot be given. The upper limit of the intrinsic viscosity is not particularly limited, but is usually 0.90 dl / g (MFR is about 25 g / 10 minutes or more), preferably 0.80 dl / g (MFR is about 45 g.
/ 10 minutes or more).

In reality, PET collected and collected in large quantities
Frequent polyester flake or pellets of polyester are often used as prepolymers. Usually, since the intrinsic viscosity of the PET bottle is relatively high, the intrinsic viscosity of the recovered product is also high, generally 0.60 to
0.80 dl / g (MFR 130-45 g / 10
Min), especially 0.65 to 0.75 dl / g (MFR 10
0-55 g / 10 minutes). Generally, the flakes of collected PET bottles are supplied in a paper bag product containing 20 kg and a flexible container product containing 600 kg.
It is about 0 to 6,000 ppm (0.3 to 0.6% by weight). Of course, a large amount is collected from the vacuum pressure molding plant.
-PET sheet skeleton flakes are also suitable as the saturated polyester of the raw material of the present invention.

The B1 component of the present invention has a (1) melt flow rate (JIS method: 280 ° C., load 2.16 Kg) of 2
At least one selected from the group consisting of dry or undried polyethylene terephthalate of not more than 00 g / 10 minutes, polybutylene terephthalate, cyclohexanedimethanol co-condensed polyester, polyethylene terephthalate molded article recycle product, and reactant of component A. Those containing can be used.

The polyolefin containing one or more carboxylic acid groups in the molecule of the component B2 of the present invention is a polyethylene or ethylene propylene copolymer in which maleic anhydride or an ethylene-based monomer containing a carboxylic acid group is copolymerized. Polymers, polypropylene and mixtures thereof. Further, it is possible to use a polyolefin in which a carboxylic acid group is introduced by adding maleic anhydride and an organic peroxide to polyethylene or polypropylene and performing a heat reaction treatment. Further, a partially saponified product of ethylene / alkyl acrylate copolymer can be used. For example, as an example of a commercially available product, a copolymer of polyethylene, alkyl acrylate, maleic anhydride, etc. of Japan Polyolefin Co., Ltd. (Rex Pearl ET series: MFR at 190 ° C.)
8 to 80 g / 10 minutes, melting point 70 to 98 ° C., content of alkyl acrylate of several 1 to several 10% by weight, content of maleic anhydride of several weight%) can be used. In addition, the company's polyolefin / maleic anhydride graft copolymer adtex series: PP type (230 ° C MF
R2-25g / 10 minutes, melting point 145-162 ° C), HD
Type (MFR at 190 ℃ 0.2-0.5g / 10 minutes,
Melting point 130-135 ° C), LDPE type (190 ° C MFR 1.0-11g / 10 min, melting point 102-106)
℃) and LLDPE type (MFR 1.0 at 190 ℃)
˜5.5 g / 10 min, melting point 110-122 ° C.) can be used.

The binder of the present invention is a compound containing two (b) and optionally more than three (d) epoxy groups in the molecule. Usually, examples of the compound b having an average of two epoxy groups in the molecule include aliphatic polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6- Hexamethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin
Diglycidyl ether, alicyclic hydrogenated bisphenol A / diglycidyl ether, hydrogenated isophthalic acid diglycidyl ester, 3,4-epoxy / cyclohexyl / methyl-3,4-epoxy / cyclohexane / carboxylate, bis ( 3,4-epoxy cyclohexyl) adipate or heterocyclic diglycidyl hydantoin, diglycidyl oxyalkyl hydantoin, or aromatic bisphenol A diglycidyl ether, bisphenol A diglycidyl ether initial condensation product, Diphenylmethane diglycidyl ether,
Examples thereof include terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, diglycidyl aniline and the like.

Examples of the compound c having an average of three epoxy groups in the molecule include aliphatic trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, and heterocyclic triglycidyl isocyanurate. Examples thereof include triglycidyl cyanurate, triglycidyl hydantoin, and aromatic triglycidyl para- or meta-aminophenol. Examples of the compound c having an average number of epoxy groups of 2.1 or more to several in the molecule such as diaminophenylmethane, tetraglycidyl bisaminomethylcyclohexane include phenol novolac epoxy resin, cresol novolac Epoxy resin and biphenyl dimethylene-based epoxy resin (for example, heat resistant epoxy resin NC-3000 series manufactured by Nippon Kayaku Co., Ltd.)
Etc. can be mentioned. As another example, an epoxy group in the molecule from Dow Chemical Company has an average of about 2.2,
There are 3.6, 3.8 and 5.5 on the market and these can be used.

The most important feature of the present invention is selection of the binder. By combining a compound having two epoxy groups in the molecule (bifunctional: D) with a compound having three or more epoxy groups in the molecule (trifunctional or more: T) as a binder A "branched structure" can be introduced to increase the T / D ratio and increase the crystallization rate. This is 3
It is presumed that a compound containing a functional or higher epoxy group acts as a “molecular size crystallization nucleating agent”. The long-chain branched structure of the present invention has a melt viscosity of about 10 to 100 due to the “entanglement effect” of molecular chains as compared with the conventional linear structure.
Since it is possible to double the number of sheets, a sheet with less drawdown can be obtained at the time of pressure or vacuum pressure forming.
In addition, polyethylene terephthalate polyester (a
Component), the aromatic polyester (B1 component) or the carboxylic acid-containing polyolefin (B
By block-copolymerizing 2), the crystallization speed can be comprehensively increased to the order of seconds in heat setting (heat setting) at the time of forming a sheet and pressure-pressing or vacuum-pressure forming the sheet. The epoxy group-containing compound d of the present invention is a compound (D) containing two epoxy groups in the molecule b: 100 to 0% by weight and a compound (T) containing more than 3 epoxy groups in the molecule. c: 0-10
0% by weight of the mixture. The increase of the latter (T) causes the resin swell and melt viscosity to rise sharply. The latter / the former weight ratio (T / D ratio) is usually 5/95 to 75/25, preferably 10/90 to 70/30, and more preferably 25 /.
It is 75-50 / 50. As the T / D ratio increases, the crystallization speed increases. When the T / D ratio is 5/95 or less, the effect is small, and when the T / D ratio is 75/25 or more, it is difficult to produce a polyester resin, and gel fish eyes are by-produced on the sheet, so that the product cannot be commercialized. The binder masterbatch is composed of 10 to 50 parts by weight of the mixture d and 100 parts by weight of the substrate e. The present mixture d is preferably 15 to 20 parts by weight. When the binder d is 10 parts by weight or less, the effect of the masterbatch i is small and the cost is high. When the binder d is 50 parts by weight or more, the masterbatch f is difficult to produce, and a gel is easily produced as a by-product in the binding reaction, which is not preferable.

A feature of the present invention is that the binder masterbatch f is used by utilizing the substrate e as a diluent in order to prevent the local reaction of the binder d which is a by-product of gel fish eyes of the sheet. Especially. As the substrate e,
Polyethylene terephthalate polyester having an intrinsic viscosity of 0.50 to 0.90 dl / g, recycled polyethylene terephthalate polyester molded product recirculation product, condensate of ethylene glycol, cyclohexane / dimethanol and terephthalic acid, etc. , Etc.), toluene, benzene, xylene and the like can be used. When the molded body needs transparency,
PET-based polyester and toluene, benzene, xylene and the like can be used. When the molded body does not need to be transparent, polyethylene acrylate resin (Nippon Polyolefin Co., Ltd., etc.) can be used.

The blending ratio of the binder masterbatch f is usually 1 to 10 parts by weight with respect to 100 parts by weight of the aromatic saturated polyester a, but preferably 2 to 5 with good dispersibility / mixability. It is around the weight part. As the ratio increases, MFR of polyester block copolymer of component A
And the melt viscosity can be increased.

Further preferred coupling reaction catalyst g in the present invention is a complex of a metal salt of a carboxylic acid and a masterbatch i thereof. It has been found in the present invention that the metal salts of carboxylic acids, when used alone, are not always suitable for the purpose of producing the polyesters of the present invention. Therefore, the binding reaction catalyst g is preferably a complex. For example, as a binary catalyst, lithium stearate / calcium stearate = 20/80 to 50/100, sodium stearate / calcium stearate = 20/80 to 50/10
0, manganese acetate / lithium stearate = 20 to 50
/ 100 or manganese acetate / calcium stearate = 20 to 50/100. On the other hand, for example, as a ternary catalyst, lithium stearate / sodium stearate / calcium stearate = 50/50/10
0, lithium stearate / sodium acetate / calcium stearate = 50/50/100 or lithium stearate / manganese acetate / calcium stearate = 50/50/100, etc., and a masterbatch i with a substrate h thereof. .

Another feature of the present invention is that the catalyst masterbatch i is utilized by using the substrate h as a diluent in order to prevent a local reaction around the catalyst g which is a by-product of gel / fisheye on the sheet. Is to use. Substrate h
As in the case of the substrate e, an intrinsic viscosity of 0.50 to 0.
90 dl / g polyethylene terephthalate aromatic polyester, recycled polyethylene terephthalate aromatic polyester molded product recycled product, condensate of ethylene glycol, cyclohexane / dimethanol and terephthalic acid (Pet Gee, etc. of Eastman) , Polyethylene acrylate resin (Japan Polyolefin Co., Ltd.) and polyacrylate resin (including copolymer)
Etc. can be used. When the molded body needs to be transparent, PET polyester and polyacrylate resin (including a copolymer) can be used. Polyethylene acrylate resin (Japan Polyolefin Co., Ltd., etc.) when the molded product does not require transparency
Etc. can be used. When the above-mentioned resin is not used as the base h, calcium stearate having a mild catalytic activity and a lubricant effect can be used.
The composition ratio of calcium stearate is 50 parts by weight or more with respect to the catalyst. Although this powdery composite catalyst has a problem of workability of powder scattering, it is inexpensive and suitable for small-scale production.

The composition ratio of the catalyst masterbatch i is usually 5 to 15 parts by weight of the catalyst g and 100 parts by weight of the substrate h, preferably the catalyst g: 7.5 to 12.5.
Parts by weight, more preferably 10 parts by weight of catalyst g and substrate h10.
0 parts by weight. When the catalyst g is 5 parts by weight or less, the effect of the catalyst masterbatch i is small and the cost is high. When the catalyst g is 15 parts by weight or more, the masterbatch i
Is difficult to produce, a gel is easily produced as a by-product in the binding reaction, and it causes hydrolysis of the resin during molding, which is not preferable. The amount of the catalyst masterbatch i used is usually 0.25 to 100 parts by weight of the saturated aromatic polyester a.
The amount is 10 parts by weight, but preferably about 0.5 to 2 parts by weight, which has good dispersibility / mixability.

The block copolymer of the present invention can be produced by the reactive extrusion method in addition to the method of simultaneously mixing the four components (1), (2), (3) and B1 or B2. And B1 aromatic polyester component or B
It is also possible to premix with the two polyolefin components under deaeration and dehydration, and then add (2) binder masterbatch f and (3) catalyst masterbatch i in a side feed system. In addition, (1) component a is degassed and dehydrated to mix (2) binder masterbatch f and (3) catalyst masterbatch i, and then B1 aromatic polyester component or B2 polyolefin component is side-fed. It is also possible to add. Further, even undried flake raw material can be used by appropriately degassing and dehydrating.

As the reactor for heating and melting, a single-screw extruder, a twin-screw extruder, a two-stage extruder and a kneader-ruder of a combination thereof, or a self-used extruder for producing polycondensation of PET polyester resin is used. A cleaning biaxial reaction device or the like can be used. Since the high temperature reaction method for producing the polyester resin of the present invention is carried out in an extruder in a short time of about 2 to 10 minutes, the L / D of the twin-screw extruder is preferably about 30 to 50. ,
Particularly, about 38 to 45 is preferable. According to the present invention, depending on the performance of the reactive extruder, generally a short time, for example 3
With a residence time of 0 second to 20 minutes, preferably 1 minute to 10 minutes, and particularly preferably 1.5 minutes to 5 minutes, the molecular weight of the saturated polyester a rapidly increases, and it is desired to block-copolymerize with the aromatic polyester or the polyolefin. Block copolymers of

In the above-mentioned reactor, generally, recovered PET bottle flakes or new polyester resin is preliminarily 110
Dry with hot air at ~ 140 ° C, water content 100 ~ 200ppm
And dried with dehumidified air to reduce the water content to 50
It is preferable to use the one reduced to ppm or less. Polyester resin usually adsorbs humidity in the air and is in the range of 3,500 to 6,000 ppm (0.35 to 5,000 ppm) depending on the environmental humidity.
It contains 0.60% by weight of water, and the object of the present invention can be stably achieved by performing the drying treatment as described above. On the other hand, when the recovered PET bottle flakes or new polyester resin is used as a raw material in an undried state, the vacuum line of the twin-screw extruder should be an oil seal type instead of a non-water seal type, and the vacuum degree of the first to third vents 13.
Immediately after the polyester resin is melted and melt-mixed by lowering it to 3 × 10 ³ Pa (100 mmHg) or less, preferably 2.6 × 10 ³ Pa (20 mmHg) or less, and more preferably 0.66 × 10 ³ pa (5 mmHg). It can be achieved by vacuum degassing and removing the moisture therein.

The method for molding and processing the polyester of the present invention is as follows:
It can be carried out according to the prior invention. That is, it can be formed into a sheet or a film at a forming temperature of usually about 260 to 290 ° C. When the extruder of the molding apparatus is a single screw, the pellets of the polyester of the present invention may stick to the screw groove, so that a lubricant such as calcium stearate can be mixed. Pellet 100
The lubricant may be used in an amount of 0.01 to 1 part by weight based on parts by weight.

In the polyester of the present invention, a block copolymer of the component A and the component B1 or the component B2 is produced by a reaction extrusion apparatus, a feed block type or a manifold type mold is used, and the component B1 is newly added from the outside. Alternatively, the component B2 may be additionally supplied to be molded into a two-kind two-layer, a two-kind three-layer, or a multi-layered sheet to manufacture a heat-molded body. At that time, the sheet layer of the collected pet is used on the inner surface so as not to come into direct contact with food.

In extrusion molding of a heat resistant sheet, the roll temperature involved in heating and fixing is extremely important. The temperature of the touch roll and the chill roll is usually 30 to 150.
C., preferably 60-140.degree. C. can be used.
The temperature of the touch roll and the chill roll is usually 30 to 150 ° C., preferably 60 to 140 ° C., as a roll temperature involved in heating and fixing once the sheet is formed.

The mold temperature in the pressure and vacuum pressure forming of the sheet is usually 60 to 150 ° C., preferably 90 to 14 ° C.
0 ° C. can be used.

[0029]

EXAMPLES The present invention will now be described in detail based on examples. Intrinsic viscosity (IV value), MFR (melt flow rate), swell (swelling degree), molecular weight, and melt viscosity of the aromatic saturated polyester, the carboxylic acid group-containing polyolefin or the block copolymer were evaluated. The evaluation methods for them are as follows. (1) Intrinsic viscosity: For aromatic saturated polyester, an equal weight of a mixed solvent of 1,1,2,2-tetrachloroethane and phenol was used, and the viscosity was measured with a Canon Fuenske viscometer at 25 ° C. (2) MFR: According to JIS K7210 condition 20,
For aromatic saturated polyester and polyolefin-polyester block copolymer compositions, a temperature of 280
The measurement was carried out under conditions of ° C and a load of 2.16 kg. In addition, polyethylene is measured at 190 ° C. and polypropylene is measured at 230 ° C. under a load of 2.16 kg. (3) Swell: Using a melt indexer for MFR, run down under conditions of temperature of 280 ° C. and load of 2.16 kg, cut when the sample droops 2.0 cm, and measure the diameter at 5.0 mm from the lower end. Was calculated by the following calculation formula. In addition, the said diameter was measured several times and the average value was employ | adopted. In addition, the numerical value of the following formula "2.09
“5” is the nozzle diameter of the melt indexer for MFR. Swell (%) = [(average diameter-2.095) /
2.095] × 100 (4) Molecular weight: The polyester was measured by the GPC method under the following conditions. (Main body) SYS made by Showa Denko KK
TEM-21, (column) Shodex KF-606
M (2) sample, reference side, (solvent) hexafluoroisopropyl alcohol, (column temperature) 4
0 ° C., (injection volume) 20 μl, flow rate: 0.6 ml / min,
(Polymer concentration) 0.15% by weight, (Detector) Shod
ex RI-74, (Molecular weight conversion standard) PMM
A: Shodex M-75 (5) Measurement of mechanical properties: Pre-heating the polymer with a press molding machine at 280 ° C. for 3 minutes, pressurizing at 60 atmospheres for 30 seconds, and pressing with water to a thickness of about 1 mm and about 3 mm. I made a plate. In the tensile test, according to JIS K7113, a press plate having a thickness of about 1 mm was punched out with a No. 2 dumbbell, and an autograph DSS2000 manufactured by Shimadzu Corporation was used.
Per minute. Izod impact test is JIS K7
According to No. 110, a press plate having a thickness of about 3 mm was processed into a No. 2 standard piece, which was notched. (6) Melt viscosity: 2 cm using DynAlyser DAR-100 manufactured by REOLOGICA of Sweden
It measured by applying the torsion vibration between hot plates at 280 degreeC in the nitrogen atmosphere for the test piece of square x thickness 2mm.

[Production Examples 1 to 5: binder master batches f1 to f5] Berstorff twin-screw extruder, caliber 43 m
m, L / D = 43, three-stage water-sealed vacuum evacuation, and clear flake (PE of PET bottle recycling Co., Ltd.)
Collected T bottle, intrinsic viscosity 0.75 dl / g, MFR
50 parts by weight of 56 g / 10 min) dried with hot air at 120 ° C. for about 12 hours and Petman 6763 from Eastman Company.
50 parts by weight of a dry bag product (IV 0.73, density 1.27) is set at a temperature of 260 ° C. and the screw rotation speed is 200 rp.
m, first vent about -600 mmHg, third vent about -6
While extruding at 70 mmHg and an automatic supply rate of 30 Kg / h, ethylene glycol diglycidyl ether, which is a bifunctional epoxy compound as a binder from the second vent hole (Epolite 40E of Kyoeisha Chemical Co., Ltd., epoxy equivalent 135 g / eq, pale yellow) 15 parts by weight of liquid was injected by a metering pump (Production Example 1, binder masterbatch f1: 2).
Functionality / 3 functionalities / ratio T / D = 0/100). Similarly, 75 parts by weight of ethylene glycol diglycidyl ether was added to trifunctional trimethylolpropane triglycidyl ether (Epolite 100M manufactured by Kyoeisha Chemical Co., Ltd.).
15 parts by weight of a mixture of 25 parts by weight of F, an epoxy equivalent of 150 g / eq, and a pale yellow liquid were injected with a metering pump (Production Example 2, binder masterbatch f2: T / D = 25/7).
5). Similarly, 15 parts by weight of a mixture of 50 parts by weight of trifunctional trimethylolpropane / triglycidyl ether was injected into 50 parts by weight of ethylene glycol diglycidyl ether by a metering pump (Production Example 3, binder masterbatch f3: T / D = 50/50). Similarly, 15 parts by weight of a mixture of 75 parts by weight of trifunctional trimethylolpropane / triglycidyl ether was injected into 25 parts by weight of ethylene glycol diglycidyl ether by a metering pump (Production Example 4, binder masterbatch f4: T /
D = 75/25). Similarly, 15 parts by weight of a mixture of 50 parts by weight of trifunctional trimethylolpropane triglycidyl ether was injected by a metering pump (Production Example 5, binder masterbatch f5: T / D = 100/0). Five strands flowing out from the die having a hole diameter of 3.5 mm were cooled with water and cut into pellets with a rotary cutter. 100 kg of each of the obtained pellets was hot-air dried at 140 ° C. for about 1 hour and then at 120 ° C. for about 12 hours and stored in a moisture-proof bag.

[Production Examples 6 to 7: Catalyst Masterbatch i
1-i2] Berstorff twin-screw extruder, caliber 43m
m, L / D = 43, three-stage water-sealed vacuum evacuation, and clear flake (PE of PET bottle recycling Co., Ltd.)
Collected T bottle, intrinsic viscosity 0.75 dl / g, MFR
56 g / 10 min) dry product 50 parts by weight Eastman Pet G6763 (IV 0.73, density 1.27) dry product 50 parts by weight, lithium stearate 2.5 parts by weight and sodium stearate 2.5. The composite catalyst of 1 part by weight and 5.0 parts by weight of calcium stearate was mixed in a tumbler (Production Example 6, composite catalyst masterbatch i1 :).
Li / Na / Ca = 25/25/50). Set temperature 26
0 ° C, screw rotation speed 200 rpm, first vent approx.-
While extruding at 630 mmHg, third vent of about -730 mmHg, and automatic supply rate of 30 Kg / h, 5 strands flowing out from the die hole diameter of 3.5 mm were cooled with water and cut with a rotary cutter to form pellets. Approximately 10 kg of each of the resulting pellets at 140 ° C for about 1 hour, then 120 ° C
And dried in hot air for about 12 hours and stored in a moisture-proof bag. On the other hand, a composite catalyst of 2.5 parts by weight of lithium stearate, 2.5 parts by weight of sodium stearate and 5.0 parts by weight of calcium stearate was mixed in a tumbler to carry out (Production Example 7, powdered composite catalyst). Masterbatch i2: Li /
Na / Ca = 25/25/50).

Examples 1 to 4 [Production Examples A1 to A4 of PET-based polyesters having different T / D ratios and sheet molding thereof] A-PET sheet flakes (recovered skeleton, intrinsic viscosity 0.71 dl / g,
100 parts by weight of undried product of MFR 60 g / 10 min), powdered composite catalyst masterbatch i2 (Production Example 7: Li / N)
a / Ca = 25/25/50) 0.10 parts by weight and binder masterbatch f1 (Production Example 1: T / D = 0/10)
0) 4.5 parts by weight were mixed with a tumbler. Twin screw extruder PCM-70 manufactured by Ikegai Co., Ltd., caliber 70 mm, L / D =
37, three-stage oil-sealed vacuuming is used, set temperature 280
C, screw rotation speed 100 rpm, first vent about -7
35mmHg, 2nd and 3rd vent about -750mmH
g, while extruding at an automatic supply rate of 50 kg / h, 10 strands flowing out from the die having a hole diameter of 2 mm were water-cooled and cut with a rotary cutter into pellets. The obtained pellets are heated at 140 ° C for about 1 hour and then at 120 ° C for about 1 hour.
It was dried with hot air for 2 hours and stored in a moisture-proof bag. The MFR of the obtained masterbatch method PET polyester A1 is 20.
It was g / 10 minutes (Example 1). By the same operation, T
PET-based polyesters having different / D ratios were produced. F2 as a binder masterbatch (Production Example 2: T / D = 25
/ 75) 4.0 parts by weight, f3 (Production Example 3: T / D = 50)
/ 50) 7.0 parts by weight, f4 (Production Example 4: T / D = 74
/ 25) 7.0 parts by weight were mixed by a tumbler. The MFR of the obtained masterbatch PET polyester was 18 g / 10 minutes for A2 (Example 2), 5.9 g / 10 minutes for A3 (Example 3), and 2.1 g / 10 minutes for A4. Example 4).

100 parts by weight of these four kinds of pellets were mixed with 0.2 part by weight of calcium stearate by a tumbler. Single screw extruder GS-65 manufactured by Ikegai Co., Ltd., caliber 65 m
m, horizontal extrusion T-die: 250 mm width, 2 mm interval, vertical 3
A thick sheet was formed using a stepped polishing roll. Set temperature 280 ℃, screw speed 60
rpm, automatic supply rate 30 Kg / h, roll temperature 30-
A transparent thick sheet having a width of 220 mm and a thickness of 1 to 1.5 mm was obtained at 50 ° C. Light cloudiness due to crystallization was observed on the A4 sheet. The results obtained by DSC are shown in Table 1 (ascending / descending speed under nitrogen of 10 ° C./min), but the A-PET of the present invention
It has been found that the sheet can double the crystallinity by increasing the T / D ratio. Further, the resin molding temperature and the isothermal crystallization time of 170 ° C., which is the average temperature of the chill roll, are about 30 seconds for the transparent thick sheet A3 manufactured in Example 3, whereas the commercially available A-PET sheet and the resin are several tens of minutes. It was late.

Table 1

Example 5 0.9 mm thick transparent thick sheet A manufactured in Example 2
2 by the air pressure molding method to make a coffee cup-shaped product with a molding pressure of 6
It was manufactured by rapid heating at atmospheric pressure and a temperature of 150 ° C. This transparent molded product showed heat resistance to withstand heating in a microwave oven.

Examples 6 to 7 [Production example of heat-resistant sheets B1 to B2 of PET-based polyester copolymerized with PBT] Clear flake of PET Bottle Recycle Co., Ltd. (collected PET bottle, intrinsic viscosity 0.75 dl) / G, MFR 56 g / 10 min) 100 parts by weight of undried product, Mitsubishi Rayon Co., Ltd. PBT 11
35 parts by weight of 00N (Example 6), 7.5 parts by weight of binder masterbatch (f2: T / D = 25/75), composite catalyst masterbatch (j2: Li / Na / Ca = 25 /).
25/50) 0.75 parts by weight, or PBT 1100
100 parts by weight of N (Example 7), 11 parts by weight of binder masterbatch (f2: T / D = 25/75), composite catalyst masterbatch (j2: Li / Na / Ca = 25/25).
/ 50) 0.75 parts by weight were mixed in a tumbler. Ikegai twin-screw extruder, caliber 70mm, L / D = 3
7, using a three-stage oil-sealed vacuum, set temperature 280 ℃,
Screw rotation speed 100 rpm, first vent about -735
mmHg, second and third vents about -750 mmHg,
While extruding at an automatic feed rate of 50 Kg / h, 10 strands flowing out from a die hole diameter of 2 mm were water-cooled and cut into pellets by a rotary cutter. The obtained pellets were dried with hot air at 140 ° C. for about 1 hour and then at 120 ° C. for about 12 hours and stored in a moisture-proof bag. Obtained masterbatch method PBT-polyester / block copolymers B1 to B
The MFR of 2 is 20 parts by weight of PBT (Example 6) 20
g / 10 minutes, PBT 100 parts by weight (Example 7) 25 g /
It was almost as designed in 10 minutes. On the other hand, PBT1100
N resin pellets and PET flakes / PBT1100N =
M of 100/50 parts by weight blend extrudate (Comparative Example 1)
FR is 70g / 10 minutes and 59g / 10 minutes respectively,
It was quite different from the resin of the present invention. According to the DSC measurement, the PET / PBT = 100/50 parts by weight blend (Comparative Example 1) shows that 214 ° C. (PBT) and 239 ° C. (PE
T) has a separate melting point, but the resin PET / P of the present invention
BT = 100/35 parts by weight of the copolymer (Example 6) was 2
It showed only one melting point at 30 ° C. The resin of the present invention is 26
A transparent sheet could be easily formed at 0 ° C.

Example 8 [Polyethylene-polyester block copolymer E1]
And multi-layered sheet molding] PET Bottle Recycle Co., Ltd.
100 parts by weight of uncured clear flake (recovered product of PET bottle, intrinsic viscosity 0.75 dl / g, MFR 56 g / 10 min), Lexpearl ET182 (polycarboxylic acid-containing polyethylene, MFR2) of Japan Polyolefin Co., Ltd.
80 ° C.-109, density 0.937, melting point 98 ° C.) 30 parts by weight, binder masterbatch (f2: T / D = 25/7)
5) 8.0 parts by weight of the composite catalyst masterbatch (i2:
0.75 parts by weight of Li / Na / Ca = 25/25/50) were mixed in a tumbler. Ikegai twin screw extruder PCM-
70, caliber 70 mm, L / D = 37, three-stage oil-sealed vacuum evacuation, set temperature 260 ° C., screw rotation speed 10
0 rpm, first vent about -735 mmHg, second and third vents about -750 mmHg, automatic feed rate 50 Kg
10 strands flowing out from the die having a hole diameter of 2 mm were water-cooled while being extruded at / h, and were cut into pellets by a rotary cutter. The obtained pellets were dried with hot air at 140 ° C. for about 1 hour and then at 120 ° C. for about 12 hours and stored in a moisture-proof bag. The MFR of the obtained masterbatch polyethylene-polyester block copolymer E1 was 3.5.
It was g / 10 minutes.

Polyethylene-polyester block copolymer E1 / polyester A1 = 50 / produced above
50 parts by weight of composition: 100 parts by weight and 0.2 part by weight of calcium stearate were mixed. A two-kind three-layer sheet was formed by a feed block type sheet forming apparatus manufactured by Soken Co., Ltd. Main single-screw extruder for block copolymer E1: caliber 3
0 mm, L / D = 38, set temperature 270 ° C., screw rotation speed 30 rpm, auxiliary single screw extruder for commercial PET (Unitika, intrinsic viscosity 0.83 dl / g): diameter 25 mm,
L / D = 25, set temperature 270 ° C., screw rotation speed 1
0 rpm, T die: 250 mm width, lip interval 1.0 m
m, vertical type, chill roll: horizontal three-stage hot water heating type was used. Main supply rate 6Kg / h, sub supply rate 0.6Kg / h
200m with almost no gel and fish eyes
It was possible to form a high-quality type 2 three-layer sheet with a white pearl length of m width and 0.4-0.6 mm thickness. Block copolymer E
There was no delamination between the 1 / polyester A1 (inside) and the commercially available PET (outside) with the gum tape. This sheet was heated and fixed by passing it through a heating roll at 110 ° C. Further, the compressed air molding container endured the filling temperature of tofu or natto at 83 ° C.

Example 9 [Polypropylene-polyester block copolymer P]
1 and multi-layered sheet molding] 100 parts by weight of PET flakes recycling Co., Ltd. clear flakes (collected PET bottles, intrinsic viscosity 0.75 dl / g, MFR 56 g / 10 min) undried products, Nippon Polyolefin Co., Ltd. ADTEX ER320P (carboxylic acid-containing polypropylene,
(MFR 230 ° C-20, density 0.91, melting point 159 ° C)
20 parts by weight, binder masterbatch (f2: T / D = 2
5/75) 8.7 parts by weight, composite catalyst masterbatch (i2: Li / Na / Ca = 25/25/50) 0.7
5 parts by weight were mixed in a tumbler. A twin-screw extruder PCM-70 made by Ikegai, caliber 70 mm, L / D = 37, three-stage oil-sealed vacuum evacuation, set temperature 280 ° C., screw rotation speed 100 rpm, first vent about −735 mmHg, second and While extruding at a third vent of about -750 mmHg and an automatic supply rate of 50 Kg / h, 10 strands flowing out from the die having a hole diameter of 2 mm were water-cooled and cut by a rotary cutter into pellets. The pellets obtained are 140 ° C
It was dried in hot air for about 1 hour and then at 120 ° C. for about 12 hours and stored in a moisture-proof bag. MFR of the obtained masterbatch polypropylene-polyester block copolymer P1
Was 16.8 g / 10 minutes. In the same manner as in Example 8, 100 parts by weight of the composition of polypropylene-polyester block copolymer P1 / polyester A1 = 50/50 parts by weight prepared above: 100 parts by weight and 0.2 part by weight of calcium stearate were mixed. A two-kind three-layer sheet was formed by a feed block type sheet forming apparatus manufactured by Soken Co., Ltd.
200mm with almost no by-product gel and fish eyes
Semi-transparent with a width of 0.4-0.6 mm and a high-class feeling 2
A seed 3-layer sheet was obtained. There was no delamination between the block copolymer P1 / polyester A1 (inside) and the commercially available PET (outside) with the gum tape. This sheet, 110 ℃
It was heat-fixed by passing it through the heating roll. In addition, the compressed air molding container has a filling temperature of 8 tofu or natto.
Withstood 3 ° C.

[0040]

INDUSTRIAL APPLICABILITY The inexpensive heat-resistant sheet and molded body of transparent heat-resistant and opaque heat-resistant polyethylene terephthalate polyester that can withstand heating of a heat-fillable container and a microwave oven of the present invention have physical properties of conventional PET resin. Since the above weaknesses have been improved, it can be expected to have a wide range of applications in addition to containers such as tofu and natto and bento containers for convenience stores. The molded product is excellent in heat resistance, mechanical strength such as tensile strength, and can be used for general food containers, packaging materials,
It is useful as a packaging material, a partition board, etc. in the fields of daily necessities, civil engineering and construction, electronic electrical machinery, automobile vehicle parts, packaging and the like. Further, a large amount of collected PET bottles can be effectively used as a prepolymer, which is socially beneficial. Further, even if incinerated after use, the calorific value of combustion is lower than that of polyethylene or polypropylene, the incinerator is less damaged, and no toxic gas is generated.

[0041]

[Brief description of drawings]

FIG. 1 is a view showing a skeleton structure of a polyethylene terephthalate-based polyester / block copolymer of the present invention.
Introducing a trifunctional binder and thereby a long chain branched structure,
It is the basis for accelerating crystallization speed and developing heat resistance.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // B29K 67:00 B29K 67:00 B29L 7:00 B29L 7:00 C08L 67:00 C08L 67:00 ( 72) Inventor Takashi Fujimaki 4-442 No. 634, Noba-cho, Konan-ku, Yokohama-shi, Kanagawa Prefecture (72) Takashi Nakamoto 2-8 F-term, Tennoji Kubori-cho, Osaka-shi, Osaka (reference) 4F071 AA14 AA43 AA46 AA75 AE02 AF30 AF45 AG05 AH04 AH05 BB06 BC01 BC04 4F207 AA24 AG01 AG03 AH54 AR07 KA01 KA17 KM05 KM15 4J029 AA03 AB01 AC03 AE03 BA03 CB06A JE04 KH00 KH01 4J031 AA12 AA49 AB01 AF11 AD01 AD03 AD03 AD01 AD03 AD03 AD03

Claims (12)

[Claims] 1. Component A: (1) Melt flow rate (JI
S method: 280 ° C., load 2.16 Kg) is 40 to 200 g
/ 10 minutes polyethylene terephthalate-based polyester a: 100 parts by weight, (2) compound b containing 2 epoxy groups in the molecule as a binder: 25 to 100% by weight, and 3 or more epoxy groups in the molecule Compound c: 75 to 0% by weight of a mixture d: 10 to 50 parts by weight of a base and 100 parts by weight of a base material e: a binder masterbatch f: 1 to 10 parts by weight, (3) a binding reaction catalyst As a catalyst masterbatch i: 0.25 to 10 composed of a metal salt of an organic acid g: 5 to 15 and a substrate h: 100 parts by weight
Aromatic polyesters 0 to 10 having a mixture composed of parts by weight and a B1 component: melt flow rate (JIS method: 280 ° C., load 2.16 Kg) of 200 g / 10 minutes or less.
A block having a melt flow rate of 60 g / 10 min or less is obtained by melting 0 part by weight at a temperature equal to or higher than its melting point and performing a uniform reaction by a reactive extrusion method while degassing and dehydrating to 13.3 × 10 ³ Pa or less in a vacuum system. A process for producing a transparent heat-resistant sheet of polyethylene terephthalate-based polyester, which comprises forming a copolymer into a sheet, and then forming the sheet into a heat-formed body. 2. Component A: (1) Melt flow rate (JI
S method: 280 ° C., load 2.16 Kg) is 40 to 200 g
/ 10 minutes polyethylene terephthalate-based polyester a: 100 parts by weight, (2) compound b containing 2 epoxy groups in the molecule as a binder: 25 to 100% by weight, and 3 or more epoxy groups in the molecule Compound c: 75 to 0% by weight of a mixture d: 10 to 50 parts by weight of a base material, and e: 100 parts by weight of a binder masterbatch f: 1 to 10 parts by weight, (3) as a binding reaction catalyst A mixture composed of a catalyst masterbatch i: 0.25 to 10 parts by weight composed of an organic acid metal salt g: 5 to 15 and a substrate h: 100 parts by weight, and a B2 component: melt flow rate (JIS method). : 280 ° C., load 2.16 kg) is 2
A polyolefin containing 0 to 100 parts by weight of one or more carboxylic acid groups in a molecule of 00 g / 10 min or less is melted at a temperature of its melting point or higher and 13.3 × in a vacuum system.
A melt flow rate of 60 g / 10 by performing a uniform reaction by reactive extrusion while degassing and dehydrating to 10 ³ Pa or less.
An opaque heat-resistant sheet of polyethylene terephthalate-based polyester and a method for producing a molded article, which comprises forming a block copolymer having a content of not more than 5 minutes, molding the sheet into a sheet, and then forming the sheet into a heat-molded article. 3. A mixture of 100 parts by weight of the block copolymer produced by the method according to claim 1 and 100 parts by weight thereof, and 0.01 to 1 part by weight of a lubricant. A heat-resistant sheet of polyethylene terephthalate-based polyester and a method for producing a molded article, characterized in that the sheet is molded into a sheet to obtain a heat-molded article. 4. A polyethylene terephthalate-based polyester a is selected from the group consisting of polyethylene terephthalate having an intrinsic viscosity of 0.50 to 0.90 dl / g, a polyethylene terephthalate-based aromatic polyester, and a recycled polyethylene terephthalate-based aromatic polyester molded product. The method for producing a heat-resistant sheet of polyethylene terephthalate-based polyester and a molded article according to any one of claims 1 to 3, further comprising at least one selected from the group consisting of: 5. A compound b containing two epoxy groups in the molecule as a binder is an aliphatic ethylene glycol.
Diglycidyl ether, polyethylene glycol diglycidyl ether, alicyclic hydrogenated bisphenol A
Diglycidyl ether and aromatic bisphenol A
-Contains at least one selected from the group consisting of diglycidyl ether.
10. A method for producing a heat-resistant sheet and a molded product of the polyethylene terephthalate polyester according to any one of 1. 6. A compound c containing 3 or more epoxy groups in the molecule as a binder is a fat-proof trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, epoxidized soybean oil, epoxidized. A linseed oil, a heterocyclic triglycidyl isocyanurate, an aromatic phenol novolac type epoxy resin, a cresol novolac type epoxy resin, and at least one selected from the group consisting of bisresorcinol tetraglycidyl ether. Item 1
4. A method for producing a heat-resistant sheet of polyethylene terephthalate polyester according to any one of 3 to 3, and a molded body. 7. A complex containing at least two or more selected from the group consisting of lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt, zinc salt and manganese salt of stearic acid or acetic acid as a binding reaction catalyst g. The method for producing a heat-resistant sheet of polyethylene terephthalate-based polyester according to any one of claims 1 to 3 and a molded article. 8. The B1 component has a melt flow rate (1) of 200 g (JIS method: 280 ° C., load 2.16 Kg).
/ 10 minutes or less of at least one selected from the group consisting of dry or undried polyethylene terephthalate, polybutylene terephthalate, cyclohexanedimethanol co-condensed polyester, polyethylene terephthalate molded article recirculation product, and reactant of component A. A heat-resistant sheet of polyethylene terephthalate-based polyester according to any one of claims 1 to 3, and a method for producing a molded article. 9. The component B2 is a polyolefin containing one or more carboxylic acid groups in the molecule, and polyethylene, polypropylene in which maleic anhydride or an ethylene-based monomer containing a carboxylic acid group is copolymerized. A heat-resistant sheet and molding of a polyethylene terephthalate-based polyester according to any one of claims 1 to 3, which comprises at least one selected from the group consisting of an ethylene-propylene copolymer and a mixture thereof. Body manufacturing method. 10. A method of producing a block copolymer of component A and component B1 or component B2 in a reactive extruder, while additionally supplying component B1 or component B2 to a mold, a two-kind two-layer structure,
A heat-resistant molded body is manufactured by molding into a two-kind three-layer or multi-layered sheet to manufacture a heat-molded body, and the heat-resistant sheet and molded body of the polyethylene terephthalate polyester according to any one of claims 1 to 9. Method. 11. A roll temperature in the extrusion molding of a sheet is 30 to 150 ° C., wherein the roll temperature is 30 to 150 ° C.
10. A method for producing a heat-resistant sheet and a molded product of the polyethylene terephthalate polyester according to any one of 1. 12. The mold temperature in sheet heat molding is 90.
It is -150 degreeC, The manufacturing method of the heat resistant sheet and molded object of the polyethylene terephthalate type polyester of any one of Claims 1-11 characterized by the above-mentioned.