CA2625894A1 - Thermoplastic polyester blend and process for producing heat-shrinkable tube by using the same - Google Patents
Thermoplastic polyester blend and process for producing heat-shrinkable tube by using the same Download PDFInfo
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- CA2625894A1 CA2625894A1 CA002625894A CA2625894A CA2625894A1 CA 2625894 A1 CA2625894 A1 CA 2625894A1 CA 002625894 A CA002625894 A CA 002625894A CA 2625894 A CA2625894 A CA 2625894A CA 2625894 A1 CA2625894 A1 CA 2625894A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/016—Flame-proofing or flame-retarding additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
A heat-shrinkable tube is made of a novel thermoplastic polyester blend which comprises component (A) from 5 to 95 wt %, based upon the total weight of components (A) and (B), of homopolymerized or copolymerized polyethylene terephthalate (PET) with an intrinsic viscosity of from 0.8 to 1.2 dl/g; and component (B) from 95 to 5 wt %, based upon the total weight of components (A) and (B), of polytrimethylene terephthalate (PTT) with an intrinsic viscosity of from 0.8 to 1.2 dl/g; and the heat-shrinkable tube after heating in hot water has a shrinkage from 5% to 15% in machine direction (MD) and a shrinkage greater than 35% in transverse direction (TD).
Description
THERMOPLASTIC POLYESTER BLEND AND PROCESS FOR
PRODUCING HEAT-SHRINKABLE TUBE BY USING THE SAME
BACKGROUND OF THE PRESENT INVENTION
1. Field of the Present Invention The present invention relates to a thermoplastic polymer blends suitable for producing heat-shrinkable tube, more particularly, to a thermoplastic polymer blends comprising component (A) from 5 to 95 wt %, based upon the total weight of components (A) and (B), of homopolymerized or copolymerized polyethylene terephthalate ( PET ) with an intrinsic viscosity of from 0.8 to 1.2 dl/g; and component (B) from 95 to 5 wt %, based upon the total weight of components (A) and (B), of polytrimethylene terephthalate (PTT) with an intrinsic viscosity of from 0.8 to 1.2 dl/g.
PRODUCING HEAT-SHRINKABLE TUBE BY USING THE SAME
BACKGROUND OF THE PRESENT INVENTION
1. Field of the Present Invention The present invention relates to a thermoplastic polymer blends suitable for producing heat-shrinkable tube, more particularly, to a thermoplastic polymer blends comprising component (A) from 5 to 95 wt %, based upon the total weight of components (A) and (B), of homopolymerized or copolymerized polyethylene terephthalate ( PET ) with an intrinsic viscosity of from 0.8 to 1.2 dl/g; and component (B) from 95 to 5 wt %, based upon the total weight of components (A) and (B), of polytrimethylene terephthalate (PTT) with an intrinsic viscosity of from 0.8 to 1.2 dl/g.
2. Description of Prior Art The heat-shrinkable tube is commonly made of PVC and used an exterior covering for protecting and tightly fitting on electronic parts for a long time. However, PVC if burned incompletely will produce environmental hormones such as dioxins which are seriously harmful to human health, so that the European countries and Japan already issue a ban on prohibiting the use of PVC on electric equipment.
For solving the problem of heat-shrinkable tube made of PVC, on US Patent No.
5,368,811 had disclosed a kind of polyester and a process for producing a heat-shrinkable polyester tube made of the polyester and suitable as an exterior covering for capacitors. The polyester disclosed on the patent was formed by a mixture containing polyethylene terephthalate (PET) of 20-70 wt% and copolyester of 30-80 wt%. And, the copolyester was obtained from the reaction of the mixture containing pure terephthalic acid (PTA) of 65-95 wt% based on the diacid and isophthalic acid (IPA) of 5-35 wt% as well as ethylene glycol.
Besides, the polyester disclosed on US Patent No. 5,368,811 may be used for producing unstretched tube by employing melt-extrusion method, and the unstretched tube so obtained was rapidly quenched and reheated to 72-98 C, then the unstretched tube undergoes biaxial stretching to achieve at a stretching ratio of from 1.0 to 1.4 times in the longitudinal direction (MD) and at a stretching ratio of from 1.3 to 2.2 times in the radial direction (TD) simultaneously. Finally, the stretched heat-shrinkable tube is cooled and wound into roll stock.
The heat-shrinkable polyester tube made by the method of the aforesaid US
patent having a crystallinity of not higher than 20%, a shrinkage of 5-26% in MD and a shrinkage of at least 25% in TD shall be achieved after it is heated in hot water with temperature of 98 2 C
for 10 seconds. And, heat-shrinkable polyester tube when used as an exterior covering for capacitors through heat-shrinking process may show a perfect covering condition for the capacitors.
Another US Patent No. 5,403,454 had disclosed a production method for improving the printability of a heat-shrinkable polyester tube. The heat-shrinkable polyester tube made of a blend comprising 20-99.5% by weight of a polyester containing polyethylene terephthalate and 0.5%-80% by weight of a polyester copolymer containing polyethylene glycol as the glycol component, wherein the polyethylene glycol content in the polyester co-polymer is within a range of from 0.1 to 4% by weight, and a discharge energy of from 100 to 800 W.min/m2 is applied to the surface of the tube for the corona discharge treatment to improve the printability of the heat-shrinkable polyester tube.
Further US Patent No.5,718,953 had disclosed a process for producing heat-shrinkable tube which is formed substantially from a polyphenylene sulfide through melt-extrusion method to obtain an unstretched tube, then the unstretched tube undergoes biaxial stretching under temperature of 85-105 C to achieve at a stretching ratio of from 1.05 to 4.5 times in the longitudinal direction (MD) and at a stretching ratio of from 1.3 to 4.5 times in the radial direction (TD) simultaneously.
The heat-shrinkable polyester tube made by the method of the US patent having a shrinkage of 25 -80% in TD shall be achieved after it is heated in hot water with temperature of 98 2 C for 30 seconds. In addition, when a capacitor is covered with the heat-shrinkable tube, and heated under temperature of 180 C for 20 seconds to have the heat-shrinkable tube tightly wraps and fits on the capacitor due to heat-shrinking. The capacitor is further heated in an oven with temperature of 160 C for 3 minutes and, after then, the capacitor is removed from the oven. It is found that no any defect of wrinkle, inflation, falling off or deformation happened on the heat-shrinkable tube covered and protected on the capacitor.
Further another US Patent 6,528,133 had disclosed a polyester heat-shrinkable tube for coating electrolytic condenser made from a resin composition comprising 80 to 99 wt % of a copolymerized polyester resin with an intrinsic viscosity of 0.65 to 1.0 dl/g and 1 to 20 wt %
of polybutylene terephthalate resin, wherein the copolymerized polyester resin with inherent viscosity of 0.65-1.0 dl/g comprises I to 15 mol % of polyethylene naphthalate and 85 to 90 mol % of polyethylene terephthalate.
Besides, the polyester disclosed on US Patent No. 6,528,133 may be used for producing unstretched tube by employing melt-extrusion method, and the unstretched tube so obtained was rapidly quenched and reheated to a temperature level higher than the Glass Transition Temperature (Tg), meanwhile a biaxial stretching is followed to get at a stretching ratio of from 1.0 to 1.5 times in the longitudinal direction (MD) and at a stretching ratio of from 1.7 to 2.5 times in the radial direction (TD) simultaneously. Finally, the stretched heat-shrinkable tube is cooled and wound it into roll stock The heat-shrinkable polyester tube made by the method of the US patent having a shrinkage of 5-15% in MD and a shrinkage of 40-60% in TD shall be achieved after it is heated in hot water with temperature of 98 C for 30 seconds. In addition, when a capacitor is covered with the heat-shrinkable tube, and heated under temperature of 260-280 C for 8 seconds to have the heat-shrinkable tube tightly wraps and fits on the capacitor due to heat-shrinking. The capacitor is further heated in an oven with temperature of 170 5 C for 3 minutes and followed by heating the capacitor in hot water with temperature of 100 2 C for minutes, after then, the capacitor is picked out. It is found that no any defect of wrinkle, inflation, falling off or deformation happened on the heat-shrinkable tube covered and protected on the capacitor.
Although the above-mentioned prior arts all have shown that polyester can be used for producing heat-shrinkable tube, both the method disclosed on US Patent No.
5,368,811 and 5,403,454 didn't disclose the heat aging resistance of the heat-shrinkable tube when it is actually used as an exterior covering for capacitors through heat-shrinking process. Further, the US Patent No. 6,528,133 disclosed the condition and procedure for testing the heat resistance of the heat-shrinkable tube which include heating the capacitor covered with the heat-shrinkable tube in an oven with temperature of 170 5 C for 3 minutes and heating the same capacitor in hot water with temperature of 100 2 C for 10 minutes.
Another US Patent No. 5,718,953 disclosed a heat-shrinkable tube made of polyethylene sulfide and possessed good heat aging resistance, yet its cost is relatively high.
In addition, none of Patents mentioned above discloses that a polyester blend mixed with polytrimethylene Terephthalate (PTT) shall be more suitable to produce the heat-shrinkable tube having much better improved quality for protecting and covering on electronic parts.
SUMMARY OF THE PRESENT INVENTION
The major purpose of the invention is to disclose a thermoplastic polyester blend suitable for producing heat-shrinkable tube comprising component (A) from 5 to 95 wt %, based upon the total weight of components (A) and (B), of homopolymerized or copolymerized polyethylene terephthalate (PET) with an intrinsic viscosity of from 0.8 to 1.2 dl/g; and component (B) from 95 to 5 wt %, based upon the total weight of components (A) and (B), of polytrimethylene terephthalate (PTT) with an intrinsic viscosity of from 0.8 to 1.2 dl/g.
The minor purpose of the invention is that either component (A) or components (B) of the thermoplastic polyester blend may further contain inorganic granules or additives so that the heat-shrinkable tube made of the thermoplastic polyester blend shall be more easily unwinding after it wound into roll stock, this makes the heat-shrinkable tube more suitable for high speed heat-shrinking covering process.
Another purpose of the invention is to disclose a process for producing a heat-shrinkable tube made of the thermoplastic polyester blend of the invention, which comprises extruding a thermoplastic polyester blend to form a unstretched tube, quenching the tube, through blow-expansion process stretching the tube at a temperature level higher than glass transition temperature (Tg) at a stretching ratio of from 1.0 to 3.0 times in machine direction (MD) and at a stretching ratio of from 1.3 to 4.5 times in transverse direction (TD) simultaneously, and quenching the stretched tube. And, the heat-shrinkable tube obtained after heating in hot water has a shrinkage from 5% to 15% in machine direction (MD) and a shrinkage greater than 35%
in transverse direction (TD).
Further another purpose of the invention is that the heat-shrinkable tube made of the thermoplastic polyester blend of the invention, when fits on the surface of an object by heat-shrinking, may provide the superior effect of enabling a perfect outward appearance without defect, particularly after the object covered with the heat-shrinkable tube of the invention is heated in an oven with temperature of 180 C for 30 minutes, or 105 C for 3 hours, or 250 C for 3 minutes, the heat-shrinkable tube of the invention still maintains a perfect covering condition without deformation of wrinkle, inflation, loose, falling off, crack or standing up.
For solving the problem of heat-shrinkable tube made of PVC, on US Patent No.
5,368,811 had disclosed a kind of polyester and a process for producing a heat-shrinkable polyester tube made of the polyester and suitable as an exterior covering for capacitors. The polyester disclosed on the patent was formed by a mixture containing polyethylene terephthalate (PET) of 20-70 wt% and copolyester of 30-80 wt%. And, the copolyester was obtained from the reaction of the mixture containing pure terephthalic acid (PTA) of 65-95 wt% based on the diacid and isophthalic acid (IPA) of 5-35 wt% as well as ethylene glycol.
Besides, the polyester disclosed on US Patent No. 5,368,811 may be used for producing unstretched tube by employing melt-extrusion method, and the unstretched tube so obtained was rapidly quenched and reheated to 72-98 C, then the unstretched tube undergoes biaxial stretching to achieve at a stretching ratio of from 1.0 to 1.4 times in the longitudinal direction (MD) and at a stretching ratio of from 1.3 to 2.2 times in the radial direction (TD) simultaneously. Finally, the stretched heat-shrinkable tube is cooled and wound into roll stock.
The heat-shrinkable polyester tube made by the method of the aforesaid US
patent having a crystallinity of not higher than 20%, a shrinkage of 5-26% in MD and a shrinkage of at least 25% in TD shall be achieved after it is heated in hot water with temperature of 98 2 C
for 10 seconds. And, heat-shrinkable polyester tube when used as an exterior covering for capacitors through heat-shrinking process may show a perfect covering condition for the capacitors.
Another US Patent No. 5,403,454 had disclosed a production method for improving the printability of a heat-shrinkable polyester tube. The heat-shrinkable polyester tube made of a blend comprising 20-99.5% by weight of a polyester containing polyethylene terephthalate and 0.5%-80% by weight of a polyester copolymer containing polyethylene glycol as the glycol component, wherein the polyethylene glycol content in the polyester co-polymer is within a range of from 0.1 to 4% by weight, and a discharge energy of from 100 to 800 W.min/m2 is applied to the surface of the tube for the corona discharge treatment to improve the printability of the heat-shrinkable polyester tube.
Further US Patent No.5,718,953 had disclosed a process for producing heat-shrinkable tube which is formed substantially from a polyphenylene sulfide through melt-extrusion method to obtain an unstretched tube, then the unstretched tube undergoes biaxial stretching under temperature of 85-105 C to achieve at a stretching ratio of from 1.05 to 4.5 times in the longitudinal direction (MD) and at a stretching ratio of from 1.3 to 4.5 times in the radial direction (TD) simultaneously.
The heat-shrinkable polyester tube made by the method of the US patent having a shrinkage of 25 -80% in TD shall be achieved after it is heated in hot water with temperature of 98 2 C for 30 seconds. In addition, when a capacitor is covered with the heat-shrinkable tube, and heated under temperature of 180 C for 20 seconds to have the heat-shrinkable tube tightly wraps and fits on the capacitor due to heat-shrinking. The capacitor is further heated in an oven with temperature of 160 C for 3 minutes and, after then, the capacitor is removed from the oven. It is found that no any defect of wrinkle, inflation, falling off or deformation happened on the heat-shrinkable tube covered and protected on the capacitor.
Further another US Patent 6,528,133 had disclosed a polyester heat-shrinkable tube for coating electrolytic condenser made from a resin composition comprising 80 to 99 wt % of a copolymerized polyester resin with an intrinsic viscosity of 0.65 to 1.0 dl/g and 1 to 20 wt %
of polybutylene terephthalate resin, wherein the copolymerized polyester resin with inherent viscosity of 0.65-1.0 dl/g comprises I to 15 mol % of polyethylene naphthalate and 85 to 90 mol % of polyethylene terephthalate.
Besides, the polyester disclosed on US Patent No. 6,528,133 may be used for producing unstretched tube by employing melt-extrusion method, and the unstretched tube so obtained was rapidly quenched and reheated to a temperature level higher than the Glass Transition Temperature (Tg), meanwhile a biaxial stretching is followed to get at a stretching ratio of from 1.0 to 1.5 times in the longitudinal direction (MD) and at a stretching ratio of from 1.7 to 2.5 times in the radial direction (TD) simultaneously. Finally, the stretched heat-shrinkable tube is cooled and wound it into roll stock The heat-shrinkable polyester tube made by the method of the US patent having a shrinkage of 5-15% in MD and a shrinkage of 40-60% in TD shall be achieved after it is heated in hot water with temperature of 98 C for 30 seconds. In addition, when a capacitor is covered with the heat-shrinkable tube, and heated under temperature of 260-280 C for 8 seconds to have the heat-shrinkable tube tightly wraps and fits on the capacitor due to heat-shrinking. The capacitor is further heated in an oven with temperature of 170 5 C for 3 minutes and followed by heating the capacitor in hot water with temperature of 100 2 C for minutes, after then, the capacitor is picked out. It is found that no any defect of wrinkle, inflation, falling off or deformation happened on the heat-shrinkable tube covered and protected on the capacitor.
Although the above-mentioned prior arts all have shown that polyester can be used for producing heat-shrinkable tube, both the method disclosed on US Patent No.
5,368,811 and 5,403,454 didn't disclose the heat aging resistance of the heat-shrinkable tube when it is actually used as an exterior covering for capacitors through heat-shrinking process. Further, the US Patent No. 6,528,133 disclosed the condition and procedure for testing the heat resistance of the heat-shrinkable tube which include heating the capacitor covered with the heat-shrinkable tube in an oven with temperature of 170 5 C for 3 minutes and heating the same capacitor in hot water with temperature of 100 2 C for 10 minutes.
Another US Patent No. 5,718,953 disclosed a heat-shrinkable tube made of polyethylene sulfide and possessed good heat aging resistance, yet its cost is relatively high.
In addition, none of Patents mentioned above discloses that a polyester blend mixed with polytrimethylene Terephthalate (PTT) shall be more suitable to produce the heat-shrinkable tube having much better improved quality for protecting and covering on electronic parts.
SUMMARY OF THE PRESENT INVENTION
The major purpose of the invention is to disclose a thermoplastic polyester blend suitable for producing heat-shrinkable tube comprising component (A) from 5 to 95 wt %, based upon the total weight of components (A) and (B), of homopolymerized or copolymerized polyethylene terephthalate (PET) with an intrinsic viscosity of from 0.8 to 1.2 dl/g; and component (B) from 95 to 5 wt %, based upon the total weight of components (A) and (B), of polytrimethylene terephthalate (PTT) with an intrinsic viscosity of from 0.8 to 1.2 dl/g.
The minor purpose of the invention is that either component (A) or components (B) of the thermoplastic polyester blend may further contain inorganic granules or additives so that the heat-shrinkable tube made of the thermoplastic polyester blend shall be more easily unwinding after it wound into roll stock, this makes the heat-shrinkable tube more suitable for high speed heat-shrinking covering process.
Another purpose of the invention is to disclose a process for producing a heat-shrinkable tube made of the thermoplastic polyester blend of the invention, which comprises extruding a thermoplastic polyester blend to form a unstretched tube, quenching the tube, through blow-expansion process stretching the tube at a temperature level higher than glass transition temperature (Tg) at a stretching ratio of from 1.0 to 3.0 times in machine direction (MD) and at a stretching ratio of from 1.3 to 4.5 times in transverse direction (TD) simultaneously, and quenching the stretched tube. And, the heat-shrinkable tube obtained after heating in hot water has a shrinkage from 5% to 15% in machine direction (MD) and a shrinkage greater than 35%
in transverse direction (TD).
Further another purpose of the invention is that the heat-shrinkable tube made of the thermoplastic polyester blend of the invention, when fits on the surface of an object by heat-shrinking, may provide the superior effect of enabling a perfect outward appearance without defect, particularly after the object covered with the heat-shrinkable tube of the invention is heated in an oven with temperature of 180 C for 30 minutes, or 105 C for 3 hours, or 250 C for 3 minutes, the heat-shrinkable tube of the invention still maintains a perfect covering condition without deformation of wrinkle, inflation, loose, falling off, crack or standing up.
DETAILED DESCRITION OF THE PREFERRED EMBODIMENTS
The invention disclosed a novel thermoplastic polyester blend suitable for producing heat-shrinkable tube which comprises component (A) from 5 to 95 wt %, based upon the total weight of components (A) and (B), of homopolymerized or copolymerized polyethylene terephthalate (PET) with an intrinsic viscosity of from 0.8 to 1.2 dl/g; and component (B) from 95 to 5 wt %, based upon the total weight of components (A) and (B), of polytrimethylene terephthalate (PTT) with an intrinsic viscosity of from 0.8 to 1.2 dl/g.
The component (A) of the invention may be made from the traditional method of synthesizing polyester such as PTA process or DMT process. When the component (A) is made from the PTA process, the diacid and diol are used to undergo direct esterification without the need of any catalyst. The gaseous mixture of ethylene glycol and water produced during esterification shall be separated in a distillation tower for having the separated ethylene glycol reflows into a reactor, and then polymerization catalyst is added into the reactor before completion of the esterification reaction. The catalyst selected for the reaction shall be the antimony catalyst or germanium catalyst or titanium catalyst or their mixture.
Then stabilizing agent containing phosphorus, such as phosphoric acid, and the inorganic granules, such as titanium dioxide, barium sulfate, calcium carbonate or silicon dioxide, shall be added in the reactor after the end of esterificaiton reaction but before the polymerization starts.. Then the mixture in the reactor undergoes polymerization reaction under vacuum environment. When the viscosity of the copolyester reaches a level higher than 0.6 dl/g, the product of the copolyester is removed from the reactor, and rapidly quenched, and then cut into as granulated copolyester.
When the component (A) is made from the DMT process, both the diacid in the form of ester and the diol are used to undergo an ester-exchange reaction. Before the reaction starts, an ester exchange catalyst such as manganese acetate shall be added in. The methyl alcohol produced in the reaction separated from the distillation tower will not flow back to an ester-exchange tank. When the predetermined theoretical amount of methyl alcohol of 98% is removed and collected, the stabilizer containing phosphorus shall be added in to enable the ester-exchange catalyst to become inactive, and then add the polymerization catalyst selected from the catalysts group comprising antimony catalyst, germanium catalyst, titanium catalyst and their mixture. The polymerization reaction undergoes in the vacuum state environment.
When the viscosity of the copolyester reaches a level higher than 0.6 dl/g, the product is removed from the reactor, and quickly quenched, and cut into as granules.
For making the component (A) of the invention, the granulated copolyester obtained from the PTA process or the DMT process mentioned above must undergo a melt-polymerization process to directly raise its inherent viscosity higher than 0.8 dl/g, or further undergo a solid polymerization reaction to raise its inherent viscosity to a level within the range of 0.80-1.20 dl/g to obtain the desired component (A) of the present invention.
Accordingly, the component (A) of the present invention shall has an inherent viscosity within the range of 0.8-1.2 dl/g. If a heat-shrinkable tube is made of the component (A) with inherent viscosity lower than 0.8 dl/g through melt-extruding process, the produced heat-shrinkable tube shall be resulted in a defect of uneven wall thickness during producing process. On the contrary, if the heat-shrinkable tube is made of the component (A) with inherent viscosity higher than 1.2 dl/g, the melt-extruding apparatus for producing the heat-shrinkable tube shall be born much higher loads to melt-extrude the heat-shrinkable tube with predetermined wall thickness.
When the PTA process is employed to synthesize the component (A) of the present invention, the diacid component used in the process contains the major component of pure terephthalic acid or further contains isophthalic acid of 5 to 15 mole % based on the diacid.
In addition, the diacid component used in the process may further contain other minor component such as 2,6-naphthylene dicarboxylic acid or the ester type compound thereof in an amount of not higher than 8 mole% based on the component (A).
Moreover, if the component (A) of the present invention contains isophthalic acid in an amount higher than 15 mole % as based on the component of diacid, the component (A) will be in the amorphous state that causes the component (A) is so easily become agglomerate during undergoing a solid polymerization for increasing inherent viscosity of the component (A).
The diol component used in the above-mentioned PTA process for forming the component (A) of the invention is mainly the ethylene glycol, but the diol component may further contain at least one of other kinds of diol component selected from the group comprising diethylene glycol, cyclohexane dimethanal, propanediol, 2,2-dimethyl-1,3-propanediol (NPG), 2-butyl-2 -ethyl- 1, 3 -propanediol (BEPG) and butylene glycol. However, these minor components are not the necessary components which, if selected as the minor components, shall not exceed 15 mole %, preferably not exceed 10 mole %, as based on the total diol contained. If the amount of minor component contained exceeds 15 mole % as based on the total diol, the component (A) will be in the amorphous state that caused it unable to undergo solid polymerization process to increase its inherent viscosity.
The preferred method for synthesizing the component (A) of the invention is adding inorganic granules during the melt-condensation polymerization stage. The inorganic granules used in the invention shall be the one or more than one selected from the group comprising titanium dioxide, barium sulfate, calcium carbonate and silicon dioxide or their mixture, more preferably, titanium dioxide or barium sulfate shall be chosen as the additive. The amount of the inorganic granules to be added in is between 0.005 -0.5wt% as based on the weight of the component (A), and the size of the inorganic granules shall be less than 1 micron ( m), preferably, between 0.1-0.5 micron.
The purpose of the above-mentioned inorganic granules added during the melt-condensation polymerization stage for synthesizing the component (A) of the invention is to enable a more easy unwinding of the heat-shrinkable tube of the invention after wound into roll stock so that the heat-shrinkable tube of the invention can be imparted the merit of being suitable for high speed heat-shrinking covering process.
The component (A) of the invention may be added with other additives according to the actual needs during processing. These additives include such as halogen-free flame retardant, dyeing pigment, antioxidant, lubricant, ultraviolet absorption or anti-static agent.
Similarly, the component (B) disclosed on the present invention is also made from the traditional method of synthesizing polyester such as PTA process or DMT
process. When the component (A) is made from the PTA process, the purified terephthalic acid (PTA) and propylene glycol are used to undergo direct esterification without the need of any catalyst.
The gaseous mixture of ethylene glycol and water produced during esterification shall be separated in a distillation tower for having the separated ethylene glycol reflows into a reactor, and then polymerization catalyst is added into the reactor before completion of the esterification reaction. The catalyst selected for the reaction shall be the antimony catalyst or germanium catalyst or titanium catalyst or their mixture. Then stabilizing agent containing phosphorus, such as phosphoric acid, and the inorganic granules, such as titanium dioxide, barium sulfate, calcium carbonate or silicon dioxide, shall be added in the reactor after the end of esterificaiton reaction but before the polymerization starts.. Then the mixture in the reactor undergoes polymerization reaction under vacuum environment. When the viscosity of the copolyester reaches a level higher than 0.6 dl/g, the product of the copolyester is removed from the reactor, and rapidly quenched, and then cut into as granulated copolyester.
When the component (B) is made from the DMT process, both the diacid in the form of ester and the diol are used to undergo an ester-exchange reaction. Before the reaction starts, an ester exchange catalyst such as manganese acetate shall be added in. The methyl alcohol produced in the reaction separated from the distillation tower will not flow back to an ester-exchange tank. When the predetermined theoretical amount of methyl alcohol of 98% is removed and collected, the stabilizer containing phosphorus shall be added in to enable the ester-exchange catalyst to become inactive, and then add the polymerization catalyst selected from the catalysts group comprising antimony catalyst, germanium catalyst, titanium catalyst and their mixture. The polymerization reaction undergoes in the vacuum state environment.
When the viscosity of the copolyester reaches a level higher than 0.6 dl/g, the product is removed from the reactor, and quickly quenched, and cut into as granules.
For making the component (B) of the invention, the granulated copolyester obtained from the PTA process or the DMT process mentioned above must undergo a melt-polymerization process to directly raise its inherent viscosity to a level within the range of 0.75-1.20 dl/g, or must undergo a melt-polyrnerization process to raise its inherent viscosity to 0.8 dl/g first and then further undergo a solid polymerization reaction to raise its inherent viscosity to a level within the range of 0.80-1.20 dl/g to obtain the desired component (B) of the present invention.
Accordingly, the component (B) of the present invention shall has an inherent viscosity within the range of 0.8-1.2 dl/g. If a heat-shrinkable tube is made of the component (B) with inherent viscosity lower than 0.8 dl/g through melt-extruding process, the produced heat-shrinkable tube shall be resulted in a defect of uneven wall thickness during producing process. On the contrary, if the heat-shrinkable tube is made of the component (B) with inherent viscosity higher than 1.2 dl/g, the melt-extruding apparatus for producing the heat-shrinkable tube shall be born much higher loads to melt-extrude the heat-shrinkable tube with predetermined wall thickness.
The preferred method for synthesizing the component (B) of the invention is adding inorganic granules during the melt-condensation polymerization stage. The inorganic granules used in the invention shall be the one or more than one selected from the group comprising titanium dioxide, barium sulfate, calcium carbonate and silicon dioxide or their mixture, more preferably, titanium dioxide or barium sulfate shall be chosen as the additive. The amount of the inorganic granules to be added in is between 0.005 -0.5wt% as based on the weight of the component (B), and the size of the inorganic granules shall be less than 1 micron ( m), preferably, between 0.1-0.5 micron. While it is not necessarily both the component (A) and the component (B) of the invention should be added inorganic granules.
The component (B) of the invention may be added with other additives according to the actual needs during processing. These additives include such as halogen-free flame retardant, dyeing pigment, antioxidant, lubricant, ultraviolet absorption or anti-static agent etc. While it is not necessarily both the component (A) and the component (B) of the invention should be added the additives mentioned above.
Those additives, including titanium dioxide, barium sulfate, calcium carbonate, silicon dioxide, halogen-free flame retardant, dyeing pigment, antioxidant, lubricant, ultraviolet absorption or anti-static agent mentioned above, may also be added in melt-extrusion process of making the heat-shrinkable tube of the invention other than in melt-condensation polymerization for synthesizing either the component (A) or the component (B) of the invention.
In the following description is to illustrate a method for producing heat-shrinkable tube made of the thermoplastic polyester blend disclosed on the present invention.
There are three methods of making a melted colloid from evenly mixing component (A) with component (B), the first method is that to measure a quantification of component (A) and component (B) respectively, and let the measurable component (A) and component (B) be evenly blended as a kind of thermoplastic polyester blend with a mixing apparatus through physical blending process.
After completely dry the thermoplastic polyester blend comprising component (A) and component (B) of the invention in a drying device provided with an environment containing dehumidified air under temperature of 150-170 C for a period of 4-6 hours, then the dried thermoplastic polyester blend is continuously carried into an extruding machine and melted as a melted colloid having been evenly mixed with component (A) and component (B) by the extruding machine reached a pre-determined melting temperature higher than the melting point (Tm).
The second method is that let component (A) and component (B) of the invention be respectively dried in a drying device provided with an environment containing dehumidified air under temperature of 150-170 C for a period of 4-6 hours. After then, further let the dried component (A) and the dried component (b) by way of a measurable weight or volume continuously be poured into a mixing apparatus for evenly blending as a kind of thermoplastic polyester blend. Let the dried thermoplastic polyester blend be continuously carried into an extruding machine and melted as a melted colloid having been evenly mixed with component (A) and component (B) by the extruding machine reached a pre-determined melting temperature higher than the melting point (Tm).
The third method is that let component (A) and component (B) of the invention be respectively dried in a drying device provided with an environment containing dehumidified air under temperature of 150-170 C for a period of 4-6 hours. After then, further let the dried component (A) and the dried component (B) be continuously carried into a different extruding machine each reached a pre-determined melting temperature higher than the melting point (Tm) and melted as a melted colloid respectively.
The melted colloid of component (A) and the melted colloid of component (B) are further pumped with a measurable quantity by a gear pump respectively and carried into a mixing apparatus for evenly blending as a kind of a melted colloid having been evenly mixed with component (A) and component (B).
The thermoplastic polyester blend of the invention comprises component (A) from 5 to 95 wt %, based upon the total weight of components (A) and (B), of homopolymerized or copolymerized polyethylene terephthalate (PET) and component (B) from 95 to 5 wt %, based upon the total weight of components (A) and (B), of polytrimethylene terephthalate (PTT).
The thermoplastic polyester blend of the invention may be added in inorganic granules and/or additives, and the total amount of component (A), component (B) inorganic granules and/or additives should be 100 wt %.
Accordingly, after the melted colloid evenly mixed with component (A) and component (B) is pushed to pass the annular opening of the extruding die, it is rapidly quenched by cooling air or water to form a unstretched circular tube, then the tube is transported by a set of feed roller into hot water or infrared ray tube for heating to a temperature level higher than the Glass Transition Temperature, and then introduce compressed air to blow the unstretched tube through blowing-expansion process to make the unstretched tube formed as a heat-shrinkable tube with pre-determined diameter which is then drain by a set of cooling nip roller, and wound into roll stock of heat-shrinkable tube. And, through the above-mentioned process a stretching in transverse direction (TD) is achieved in blow-expansion step, and a stretching in machine direction (MD) is achieved due to the speed difference between the pair of nip roller and the pair of feed roller.
Since the heat-shrinkable tube after the biaxial drawing is rapidly quenched, it may shrink in both of the transverse direction (TD) and machine direction (MD) after cooling, these enable the heat-shrinkable tube to be suitable as an exterior covering for electronic parts.
The thickness of the heat-shrinkable tube of the invention is between 20-200 micron, and the diameter of the tube is preferably between 4-400mm.
The heat-shrinkable tube made of the thermoplastic polyester blend as disclosed in the invention has a stretching ratio in machine direction (MD) equals the proportion of the drawing speed of the heat shrinkable tube after stretching to the feeding speed of the unstretched tube, and has a stretching ratio in transverse direction (TD) equals the proportion of tube diameter after blow-expansion to the unstretched tube diameter.
When the heat-shrinkable tube is made of the thermoplastic polyester blend of the invention, the preferred temperature for blowing-expansion process is between 85-105 C, the stretching ratio in machine direction (MD) is preferably between 1.0-3.0 times and the stretching ratio in transverse direction (TD) is preferably between 1.3-4.5 times.
The heat-shrinkable tube made of the thermoplastic polyester blend of the invention after heated in hot water with temperature of 100 C for 30 seconds should present a heat-shrinkage in machine-direction (MD) between 5%-15% and in transverse direction (TD) higher than 35%. If the heat-shrinkage in machine direction (MD) is less than 5%, the edge portions of the heat-shrinkable tube will unable to tightly fit on the surface of the electronic parts, whereas if the heat-shrinkable in machine direction (MD) is greater than 15%, a deformation and dislocation of the heat-shrinkage tube will be caused when the electronic parts are covered with the heat-shrinkable tube. And, if the heat-shrinkage in transverse direction (TD) is less than 35%, it is likely that the heat-shrinkable tube is unable to tightly fit on the surface of the electronic parts.
Therefore, heat the electronic parts having covered with the heat-shrinkable tube of the invention to a temperature level higher than 90 C will cause the heat-shrinkable tube evenly shrunk and tightly fit on the surface of the electronic parts as an exterior covering for the electronic parts.
If the electronic parts is covered with the heat-shrinkable tube of the invention, after heating in oven with temperature of 180 C for 30 minutes, or after heating in oven with temperature of 105 C for 3 hours, or after heating in oven with temperature of 250 C for 3 minutes, the result showed that the heat-shrinkable tube of the invention keep an excellently tight and secure fitting on the surface of the electronic parts without defects of wrinkle, inflation, loose, falling off, crack or standing up.
The heat-shrinkable tube made of the thennoplastic polyester blend of the invention, if after printed and then washed with acetone, still showed that no any printing character become dim or unclear.
The heat-shrinkable tube made of the thermoplastic polyester blend of the invention is easily cut off by a blade so that the heat-shrinkable tube of the invention is suitable for high speed heat-shrinking covering process.
In the following are several examples of embodiment of the invention and comparative examples for further describing the invention. However these examples are not for limiting the scope of patent right of the invention.
EXAMPLE OF EMBODIMENT
Component (A 1) Measure bis-hydroxyethyl terephthalate monomer (BHET) of 10.81 parts by weight and ethylene glycol (EG) of 3,243 parts by weight, and then put these materials into a reactor. The esterification reaction started when the temperature went up to a level over 190 C . The reaction pressure was 1.0-1.5kg/cm2. The reaction continued for 180 minutes to have the rate of esterification reached 95%, then added titanium dioxide, phosphoric acid stabilizer, manganese acetate catalyst of 0.035 parts by weight, and then lower the inner pressure to an approximately vacuum state of 1 torr with temperature between 250-280 C until the viscosity of the reactant reached a level over 0.60 dl/g. Then the reactant was unloaded from the reactor and cooled to form cylinder shaped amorphous granules; the amorphous granules so obtained were further loaded in a solid polymerization reactor where the polyester granules continued to react under temperature between 190-220 C , with the reactor equipment filled with nitrogen gas or made into approximately vacuum state to raise the viscosity of the polyester granules to 0.95 dl/g.
The polyester granules obtained are assigned as a component (Al) which is a kind of homopolymer.
Component (A2Z
Measure bis-hydroxyethyl terephtalate monomer (BHET) of 10.27 parts by weight, isophthalic acid (IPA) of 0.432 parts by weight and ethylene glycol (EG) of 3,243 parts by weight, then put these materials into a reactor for melt polymerization process reaction. Use the same method as that of component (Al) made to obtain a desired cylinder shaped amorphous granules and then further loaded in a solid polymerization reactor to raise the viscosity of the polyester granules to 0.83 dl/g.
The polyester granules obtained are assigned as a component (A2) which contains 5 mol% of isophthalic acid (IPA).
Component (A3) Measure bis-hydroxyethyl terephtalate monomer (BHET) of 9.73 parts by weight and isophthalic acid (IPA) of 0.864 parts by weight, then put these materials into a reactor for melt polymerization process reaction.
After completion of the melt polymerization reaction, the solid polymerization was followed to raise the viscosity of the polyester granules to 0.90 dl/g.
The polyester granules obtained are assigned as a component (A3) which contains 10 mol% of isophthalic acid (IPA).
Component (A4) Measure bis-hydroxyethyl terephtalate monomer (BHET) of 9.186 parts by weight and isophthalic acid (IPA) of 1.296 parts by weight, then put these materials into a reactor for melt polymerization process reaction.
After completion of the melt polymerization reaction, the viscosity of the reactant in the reactor is reached to 0.70 dl/g, and then the solid polymerization was followed to raise the viscosity of the polyester granules to 1.20 dl/g.
The polyester granules obtained contains some agglomerates occurred during solid polymerization. The polyester granules finally obtained after the agglomerates wholly removed through a sieving machine are assigned as a component (A4) which contains 15 mol% of isophthalic acid (IPA).
Component (A5) Measure bis-hydroxyethyl terephtalate monomer (BHET) of 8.970 parts by weight, isophthalic acid (IPA) of 1.470 parts by weight and ethylene glycol (EG) of 3,243 parts by weight, then put these materials into a reactor for melt polymerization process reaction.
After completion of the melt polymerization reaction, the viscosity of the reactant in the reactor is reached to 0.75 dl/g, and then the solid polymerization was followed to obtain a kind of polyester granules.
The polyester granules obtained contains serious agglomerates after completion of the solid polymerization. Pick up part of the polyester granules no containing agglomerates and analyze the viscosity of the picked polyester granules.
The polyester granules finally obtained with an intrinsic viscosity of 1.0 dl/g are assigned as a component (A5) which contains 17 mol% of isophthalic acid (IPA).
Component (B 1) Measure purified terephthalic acid (PTA) of 81 parts by weight and 1,3-propanediol of 37 parts by weight, and put these materials into a reactor to undergo a direct esterification.
The reactant after completion of the direct esterification in the reactor further undergoes a polymerization reaction under vacuum environment so that a polytrimethylene terephthalate (PTT) with an intrinsic viscosity of 0.75 dl/g is then obtained and assigned as a component (B 1).
Component (B2) The component (B 1) of polytrimethylene terephthalate (PTT) with an intrinsic viscosity of 0.75 dl/g further undergoes a solid polymerization under temperature between 190-220 C
with the reactor filled with nitrogen gas or made into approximately vacuum state to raise the viscosity of the polytrimethylene terephthalate (PTT) to 0.80 dl/g.
And, the polytrimethylene terephthalate (PTT) obtained are assigned as a component (B2).
Component (B3) The component (B 1) of polytrimethylene terephthalate (PTT) with an intrinsic viscosity of 0.75 dl/g further undergoes a solid polymerization under temperature between 190-220 C
with the reactor filled with nitrogen gas or made into approximately vacuum state to raise the viscosity of the polytrimethylene terephthalate (PTT) to 1.0 dl/g.
And, the polytrimethylene terephthalate (PTT) obtained are assigned as a component (B3).
Component (B4) The component (B1) of polytrimethylene terephthalate (PTT) with an intrinsic viscosity of 0.75 dl/g further undergoes a solid polymerization under temperature between 190-220 C
with the reactor filled with nitrogen gas or made into approximately vacuum state to raise the viscosity of the polytrimethylene terephthalate (PTT) to 1.2 dl/g.
And, the polytrimethylene terephthalate (PTT) obtained are assigned as a component (B4).
Component (B5) The component (B 1) of polytrimethylene terephthalate (PTT) with an intrinsic viscosity of 0.75 dl/g further undergoes a solid polymerization under temperature between 190-220 C
with the reactor filled with nitrogen gas or made into approximately vacuum state to raise the viscosity of the polytrimethylene terephthalate (PTT) to 1.2 dl/g.
And, the polytrimethylene terephthalate (PTT) obtained are assigned as a component (B5).
ExMIe 1 Measured component (Al) of 5 parts by weight and component (B2) of 95 parts by weight, and then evenly blended component (Al) with component (B2) as a kind of thermoplastic polyester blend through a mixing apparatus.
Dried the thermoplastic polyester blend by moisture-free air with temperature of 150 C
for 4 hours, then fed the thermoplastic polyester blend into a extruding machine for melt-extruding processing under temperature of 250-270 C, having the melted colloid passed through an extruding die with annular opening to form unstretched tube which was immediately quenched in cooling water tank followed by employing a pair of feed roller with rotating speed of 100 rpm to transport the unstretched tube to pass a heater where the tube was heated to a temperature between 90-100 C . Then compressed air was introduced to have the unstretched tube to expand through blow-expansion process to obtain a tube with a diameter 1.3 times that of the original unstretched tube, then the expanded tubing was drawn by a pair of nip roller with rotating speed of 105 rpm to obtain a desired heat-shrinkable tube.
A series of test were then followed to verify the quality of the heat-shrinkable tube produced by the above-mentioned process.
The test includes tube-blowing stability test; perfectness of covering appearance test by heating the tube in an oven with temperature of 105 C for 3 hrs, 180 C for 30 minutes and 250 C for 3 minutes, and the test of perfectness of print character after washing the printed tube with acetone.
Further, another test for cutting with ease is to test the heat-shrinkable tube made of the thermoplastic polyester blend of the invention is easily cut off by a blade and also test the cutting section existed on the heat-shrinkable is kept flatness or not.
All the test results are shown in Table 1.
Example 2 Use the same method as that of Example 1 except measuring component (Al) of 95 parts by weight and component (B2) of 5 parts by weight.
The test results are shown in Table 1.
Example 3 Use the same method as that of Example 1 except measuring component (A2) of 5 parts by weight and component (B3) of 95 parts by weight.
The test results are shown in Table 1.
Example 4 Use the same method as that of Example I except measuring component (A2) of 95 parts by weight and component (B3) of 5 parts by weight.
The test results are shown in Table 1.
Example 5 Use the same method as that of Example I except measuring component (A3) of 5 parts by weight and component (B4) of 95 parts by weight.
The test results are shown in Table 1.
Example 6 Use the same method as that of Example 1 except measuring component (A3) of 80 parts by weight and component (B4) of 20 parts by weight.
The test results are shown in Table 1.
Example 7 Use the same method as that of Example 1 except measuring component (A3) of 95 parts by weight and component (B4) of 5 parts by weight.
The test results are shown in Table 1.
Example 8 Use the same method as that of Example 1 except measuring component (A4) of 5 parts by weight and component (B4) of 95 parts by weight.
The test results are shown in Table 1.
Example 9 Use the same method as that of Example 1 except measuring component (A4) of 95 parts by weight and component (B4) of 5 parts by weight.
The test results are shown in Table 1.
Comparative example I
A heat-shrinkable tube is only made of component (Al) but produced by the same method as that of Example I
The test results are shown in Table 1.
Comparative example 2 A heat-shrinkable tube is only made of component (A2) but produced by the same method as that of Example 1 The test results are shown in Table 1.
Comparative example 3 A heat-shrinkable tube is only made of component (A3) but produced by the same method as that of Example 1 The test results are shown in Table 1.
Comparative example 4 A heat-shrinkable tube is only made of component (A4) but produced by the same method as that of Example I
The test results are shown in Table 1.
Comparative example 5 A heat-shrinkable tube is only made of component (A5) but produced by the same method as that of Example 1 The test results are shown in Table 1.
Comparative example 6 A heat-shrinkable tube is only made of component (B3) but produced by the same method as that of Example I
The test results are shown in Table 1.
Comparative example 7 A heat-shrinkable tube is made of component (A3) of 97 parts by weight and component (B3) of 3 parts by weight but produced by the same method as that of Example 1 The test results are shown in Table 1.
Comparative example 8 A heat-shrinkable tube is made of component (A3) of 3 parts by weight and component (B3) of 97 parts by weight but produced by the same method as that of Example The test results are shown in Table 1.
Comparative example 9 A heat-shrinkable tube is made of component (A3) of 97 parts by weight and component (B5) of 3 parts by weight but produced by the same method as that of Example I
The test results are shown in Table 1.
Comparative example 10 A heat-shrinkable tube is made of component (A3) of 97 parts by weight and component (B 1) of 3 parts by weight but produced by the same method as that of Example The test results are shown in Table 1.
Discussion of the test results The heat-shrinkable tubes made of thermoplastic polyester blend shown in Table 1 all have superior properties including in tube-blowing stability, in perfectness of covering appearance no matter by heating in oven with temperature of 105 C for 3 hrs, 180 C for 30 minutes and 250 C for 3 minutes, in perfectness of the print character on tube after washing with acetone, and particularly in the test for cutting with ease and flatness.
Table 1 tube-blowing perfectness of covering resistance to Component a earance test for cutting stability pp acetone washing, with ease and (A) (B) (uniformity of 105 180 250 (perfectness of flatness example wt% wt% thickness) x 3hr x 30min x 3min print character) Example I Al B2 Example 2 A1 B2 Example 3 A2 B3 Example 4 A2 B3 Example 5 A3 B4 Example 6 A3 B4 Example 7 A3 B4 Example 8 A4 B4 Example 9 A4 B4 Compa. Al - x x x example 1 100 Compa. A2 - A X X X
example 2 100 Compa. A3 x x example 3 100 Compa. A4 x x example 4 100 Compa. A5 A X X
example 5 100 Compa. B3 x x x x example 6 100 Compa. A3 B3 A A X X
example 7 97 3 Compa. A3 B3 x x x x example 8 3 97 Compa. A3 B5 x x example 9 97 3 Compa. A3 B l x x example 10 97 3 The content of each individual component shown in table 1 is based on the content of thermoplastic polyester blend. The symbol used in the table shall represent the following:
Represents Good; A: Represents average; x: Represents No Good
The invention disclosed a novel thermoplastic polyester blend suitable for producing heat-shrinkable tube which comprises component (A) from 5 to 95 wt %, based upon the total weight of components (A) and (B), of homopolymerized or copolymerized polyethylene terephthalate (PET) with an intrinsic viscosity of from 0.8 to 1.2 dl/g; and component (B) from 95 to 5 wt %, based upon the total weight of components (A) and (B), of polytrimethylene terephthalate (PTT) with an intrinsic viscosity of from 0.8 to 1.2 dl/g.
The component (A) of the invention may be made from the traditional method of synthesizing polyester such as PTA process or DMT process. When the component (A) is made from the PTA process, the diacid and diol are used to undergo direct esterification without the need of any catalyst. The gaseous mixture of ethylene glycol and water produced during esterification shall be separated in a distillation tower for having the separated ethylene glycol reflows into a reactor, and then polymerization catalyst is added into the reactor before completion of the esterification reaction. The catalyst selected for the reaction shall be the antimony catalyst or germanium catalyst or titanium catalyst or their mixture.
Then stabilizing agent containing phosphorus, such as phosphoric acid, and the inorganic granules, such as titanium dioxide, barium sulfate, calcium carbonate or silicon dioxide, shall be added in the reactor after the end of esterificaiton reaction but before the polymerization starts.. Then the mixture in the reactor undergoes polymerization reaction under vacuum environment. When the viscosity of the copolyester reaches a level higher than 0.6 dl/g, the product of the copolyester is removed from the reactor, and rapidly quenched, and then cut into as granulated copolyester.
When the component (A) is made from the DMT process, both the diacid in the form of ester and the diol are used to undergo an ester-exchange reaction. Before the reaction starts, an ester exchange catalyst such as manganese acetate shall be added in. The methyl alcohol produced in the reaction separated from the distillation tower will not flow back to an ester-exchange tank. When the predetermined theoretical amount of methyl alcohol of 98% is removed and collected, the stabilizer containing phosphorus shall be added in to enable the ester-exchange catalyst to become inactive, and then add the polymerization catalyst selected from the catalysts group comprising antimony catalyst, germanium catalyst, titanium catalyst and their mixture. The polymerization reaction undergoes in the vacuum state environment.
When the viscosity of the copolyester reaches a level higher than 0.6 dl/g, the product is removed from the reactor, and quickly quenched, and cut into as granules.
For making the component (A) of the invention, the granulated copolyester obtained from the PTA process or the DMT process mentioned above must undergo a melt-polymerization process to directly raise its inherent viscosity higher than 0.8 dl/g, or further undergo a solid polymerization reaction to raise its inherent viscosity to a level within the range of 0.80-1.20 dl/g to obtain the desired component (A) of the present invention.
Accordingly, the component (A) of the present invention shall has an inherent viscosity within the range of 0.8-1.2 dl/g. If a heat-shrinkable tube is made of the component (A) with inherent viscosity lower than 0.8 dl/g through melt-extruding process, the produced heat-shrinkable tube shall be resulted in a defect of uneven wall thickness during producing process. On the contrary, if the heat-shrinkable tube is made of the component (A) with inherent viscosity higher than 1.2 dl/g, the melt-extruding apparatus for producing the heat-shrinkable tube shall be born much higher loads to melt-extrude the heat-shrinkable tube with predetermined wall thickness.
When the PTA process is employed to synthesize the component (A) of the present invention, the diacid component used in the process contains the major component of pure terephthalic acid or further contains isophthalic acid of 5 to 15 mole % based on the diacid.
In addition, the diacid component used in the process may further contain other minor component such as 2,6-naphthylene dicarboxylic acid or the ester type compound thereof in an amount of not higher than 8 mole% based on the component (A).
Moreover, if the component (A) of the present invention contains isophthalic acid in an amount higher than 15 mole % as based on the component of diacid, the component (A) will be in the amorphous state that causes the component (A) is so easily become agglomerate during undergoing a solid polymerization for increasing inherent viscosity of the component (A).
The diol component used in the above-mentioned PTA process for forming the component (A) of the invention is mainly the ethylene glycol, but the diol component may further contain at least one of other kinds of diol component selected from the group comprising diethylene glycol, cyclohexane dimethanal, propanediol, 2,2-dimethyl-1,3-propanediol (NPG), 2-butyl-2 -ethyl- 1, 3 -propanediol (BEPG) and butylene glycol. However, these minor components are not the necessary components which, if selected as the minor components, shall not exceed 15 mole %, preferably not exceed 10 mole %, as based on the total diol contained. If the amount of minor component contained exceeds 15 mole % as based on the total diol, the component (A) will be in the amorphous state that caused it unable to undergo solid polymerization process to increase its inherent viscosity.
The preferred method for synthesizing the component (A) of the invention is adding inorganic granules during the melt-condensation polymerization stage. The inorganic granules used in the invention shall be the one or more than one selected from the group comprising titanium dioxide, barium sulfate, calcium carbonate and silicon dioxide or their mixture, more preferably, titanium dioxide or barium sulfate shall be chosen as the additive. The amount of the inorganic granules to be added in is between 0.005 -0.5wt% as based on the weight of the component (A), and the size of the inorganic granules shall be less than 1 micron ( m), preferably, between 0.1-0.5 micron.
The purpose of the above-mentioned inorganic granules added during the melt-condensation polymerization stage for synthesizing the component (A) of the invention is to enable a more easy unwinding of the heat-shrinkable tube of the invention after wound into roll stock so that the heat-shrinkable tube of the invention can be imparted the merit of being suitable for high speed heat-shrinking covering process.
The component (A) of the invention may be added with other additives according to the actual needs during processing. These additives include such as halogen-free flame retardant, dyeing pigment, antioxidant, lubricant, ultraviolet absorption or anti-static agent.
Similarly, the component (B) disclosed on the present invention is also made from the traditional method of synthesizing polyester such as PTA process or DMT
process. When the component (A) is made from the PTA process, the purified terephthalic acid (PTA) and propylene glycol are used to undergo direct esterification without the need of any catalyst.
The gaseous mixture of ethylene glycol and water produced during esterification shall be separated in a distillation tower for having the separated ethylene glycol reflows into a reactor, and then polymerization catalyst is added into the reactor before completion of the esterification reaction. The catalyst selected for the reaction shall be the antimony catalyst or germanium catalyst or titanium catalyst or their mixture. Then stabilizing agent containing phosphorus, such as phosphoric acid, and the inorganic granules, such as titanium dioxide, barium sulfate, calcium carbonate or silicon dioxide, shall be added in the reactor after the end of esterificaiton reaction but before the polymerization starts.. Then the mixture in the reactor undergoes polymerization reaction under vacuum environment. When the viscosity of the copolyester reaches a level higher than 0.6 dl/g, the product of the copolyester is removed from the reactor, and rapidly quenched, and then cut into as granulated copolyester.
When the component (B) is made from the DMT process, both the diacid in the form of ester and the diol are used to undergo an ester-exchange reaction. Before the reaction starts, an ester exchange catalyst such as manganese acetate shall be added in. The methyl alcohol produced in the reaction separated from the distillation tower will not flow back to an ester-exchange tank. When the predetermined theoretical amount of methyl alcohol of 98% is removed and collected, the stabilizer containing phosphorus shall be added in to enable the ester-exchange catalyst to become inactive, and then add the polymerization catalyst selected from the catalysts group comprising antimony catalyst, germanium catalyst, titanium catalyst and their mixture. The polymerization reaction undergoes in the vacuum state environment.
When the viscosity of the copolyester reaches a level higher than 0.6 dl/g, the product is removed from the reactor, and quickly quenched, and cut into as granules.
For making the component (B) of the invention, the granulated copolyester obtained from the PTA process or the DMT process mentioned above must undergo a melt-polymerization process to directly raise its inherent viscosity to a level within the range of 0.75-1.20 dl/g, or must undergo a melt-polyrnerization process to raise its inherent viscosity to 0.8 dl/g first and then further undergo a solid polymerization reaction to raise its inherent viscosity to a level within the range of 0.80-1.20 dl/g to obtain the desired component (B) of the present invention.
Accordingly, the component (B) of the present invention shall has an inherent viscosity within the range of 0.8-1.2 dl/g. If a heat-shrinkable tube is made of the component (B) with inherent viscosity lower than 0.8 dl/g through melt-extruding process, the produced heat-shrinkable tube shall be resulted in a defect of uneven wall thickness during producing process. On the contrary, if the heat-shrinkable tube is made of the component (B) with inherent viscosity higher than 1.2 dl/g, the melt-extruding apparatus for producing the heat-shrinkable tube shall be born much higher loads to melt-extrude the heat-shrinkable tube with predetermined wall thickness.
The preferred method for synthesizing the component (B) of the invention is adding inorganic granules during the melt-condensation polymerization stage. The inorganic granules used in the invention shall be the one or more than one selected from the group comprising titanium dioxide, barium sulfate, calcium carbonate and silicon dioxide or their mixture, more preferably, titanium dioxide or barium sulfate shall be chosen as the additive. The amount of the inorganic granules to be added in is between 0.005 -0.5wt% as based on the weight of the component (B), and the size of the inorganic granules shall be less than 1 micron ( m), preferably, between 0.1-0.5 micron. While it is not necessarily both the component (A) and the component (B) of the invention should be added inorganic granules.
The component (B) of the invention may be added with other additives according to the actual needs during processing. These additives include such as halogen-free flame retardant, dyeing pigment, antioxidant, lubricant, ultraviolet absorption or anti-static agent etc. While it is not necessarily both the component (A) and the component (B) of the invention should be added the additives mentioned above.
Those additives, including titanium dioxide, barium sulfate, calcium carbonate, silicon dioxide, halogen-free flame retardant, dyeing pigment, antioxidant, lubricant, ultraviolet absorption or anti-static agent mentioned above, may also be added in melt-extrusion process of making the heat-shrinkable tube of the invention other than in melt-condensation polymerization for synthesizing either the component (A) or the component (B) of the invention.
In the following description is to illustrate a method for producing heat-shrinkable tube made of the thermoplastic polyester blend disclosed on the present invention.
There are three methods of making a melted colloid from evenly mixing component (A) with component (B), the first method is that to measure a quantification of component (A) and component (B) respectively, and let the measurable component (A) and component (B) be evenly blended as a kind of thermoplastic polyester blend with a mixing apparatus through physical blending process.
After completely dry the thermoplastic polyester blend comprising component (A) and component (B) of the invention in a drying device provided with an environment containing dehumidified air under temperature of 150-170 C for a period of 4-6 hours, then the dried thermoplastic polyester blend is continuously carried into an extruding machine and melted as a melted colloid having been evenly mixed with component (A) and component (B) by the extruding machine reached a pre-determined melting temperature higher than the melting point (Tm).
The second method is that let component (A) and component (B) of the invention be respectively dried in a drying device provided with an environment containing dehumidified air under temperature of 150-170 C for a period of 4-6 hours. After then, further let the dried component (A) and the dried component (b) by way of a measurable weight or volume continuously be poured into a mixing apparatus for evenly blending as a kind of thermoplastic polyester blend. Let the dried thermoplastic polyester blend be continuously carried into an extruding machine and melted as a melted colloid having been evenly mixed with component (A) and component (B) by the extruding machine reached a pre-determined melting temperature higher than the melting point (Tm).
The third method is that let component (A) and component (B) of the invention be respectively dried in a drying device provided with an environment containing dehumidified air under temperature of 150-170 C for a period of 4-6 hours. After then, further let the dried component (A) and the dried component (B) be continuously carried into a different extruding machine each reached a pre-determined melting temperature higher than the melting point (Tm) and melted as a melted colloid respectively.
The melted colloid of component (A) and the melted colloid of component (B) are further pumped with a measurable quantity by a gear pump respectively and carried into a mixing apparatus for evenly blending as a kind of a melted colloid having been evenly mixed with component (A) and component (B).
The thermoplastic polyester blend of the invention comprises component (A) from 5 to 95 wt %, based upon the total weight of components (A) and (B), of homopolymerized or copolymerized polyethylene terephthalate (PET) and component (B) from 95 to 5 wt %, based upon the total weight of components (A) and (B), of polytrimethylene terephthalate (PTT).
The thermoplastic polyester blend of the invention may be added in inorganic granules and/or additives, and the total amount of component (A), component (B) inorganic granules and/or additives should be 100 wt %.
Accordingly, after the melted colloid evenly mixed with component (A) and component (B) is pushed to pass the annular opening of the extruding die, it is rapidly quenched by cooling air or water to form a unstretched circular tube, then the tube is transported by a set of feed roller into hot water or infrared ray tube for heating to a temperature level higher than the Glass Transition Temperature, and then introduce compressed air to blow the unstretched tube through blowing-expansion process to make the unstretched tube formed as a heat-shrinkable tube with pre-determined diameter which is then drain by a set of cooling nip roller, and wound into roll stock of heat-shrinkable tube. And, through the above-mentioned process a stretching in transverse direction (TD) is achieved in blow-expansion step, and a stretching in machine direction (MD) is achieved due to the speed difference between the pair of nip roller and the pair of feed roller.
Since the heat-shrinkable tube after the biaxial drawing is rapidly quenched, it may shrink in both of the transverse direction (TD) and machine direction (MD) after cooling, these enable the heat-shrinkable tube to be suitable as an exterior covering for electronic parts.
The thickness of the heat-shrinkable tube of the invention is between 20-200 micron, and the diameter of the tube is preferably between 4-400mm.
The heat-shrinkable tube made of the thermoplastic polyester blend as disclosed in the invention has a stretching ratio in machine direction (MD) equals the proportion of the drawing speed of the heat shrinkable tube after stretching to the feeding speed of the unstretched tube, and has a stretching ratio in transverse direction (TD) equals the proportion of tube diameter after blow-expansion to the unstretched tube diameter.
When the heat-shrinkable tube is made of the thermoplastic polyester blend of the invention, the preferred temperature for blowing-expansion process is between 85-105 C, the stretching ratio in machine direction (MD) is preferably between 1.0-3.0 times and the stretching ratio in transverse direction (TD) is preferably between 1.3-4.5 times.
The heat-shrinkable tube made of the thermoplastic polyester blend of the invention after heated in hot water with temperature of 100 C for 30 seconds should present a heat-shrinkage in machine-direction (MD) between 5%-15% and in transverse direction (TD) higher than 35%. If the heat-shrinkage in machine direction (MD) is less than 5%, the edge portions of the heat-shrinkable tube will unable to tightly fit on the surface of the electronic parts, whereas if the heat-shrinkable in machine direction (MD) is greater than 15%, a deformation and dislocation of the heat-shrinkage tube will be caused when the electronic parts are covered with the heat-shrinkable tube. And, if the heat-shrinkage in transverse direction (TD) is less than 35%, it is likely that the heat-shrinkable tube is unable to tightly fit on the surface of the electronic parts.
Therefore, heat the electronic parts having covered with the heat-shrinkable tube of the invention to a temperature level higher than 90 C will cause the heat-shrinkable tube evenly shrunk and tightly fit on the surface of the electronic parts as an exterior covering for the electronic parts.
If the electronic parts is covered with the heat-shrinkable tube of the invention, after heating in oven with temperature of 180 C for 30 minutes, or after heating in oven with temperature of 105 C for 3 hours, or after heating in oven with temperature of 250 C for 3 minutes, the result showed that the heat-shrinkable tube of the invention keep an excellently tight and secure fitting on the surface of the electronic parts without defects of wrinkle, inflation, loose, falling off, crack or standing up.
The heat-shrinkable tube made of the thennoplastic polyester blend of the invention, if after printed and then washed with acetone, still showed that no any printing character become dim or unclear.
The heat-shrinkable tube made of the thermoplastic polyester blend of the invention is easily cut off by a blade so that the heat-shrinkable tube of the invention is suitable for high speed heat-shrinking covering process.
In the following are several examples of embodiment of the invention and comparative examples for further describing the invention. However these examples are not for limiting the scope of patent right of the invention.
EXAMPLE OF EMBODIMENT
Component (A 1) Measure bis-hydroxyethyl terephthalate monomer (BHET) of 10.81 parts by weight and ethylene glycol (EG) of 3,243 parts by weight, and then put these materials into a reactor. The esterification reaction started when the temperature went up to a level over 190 C . The reaction pressure was 1.0-1.5kg/cm2. The reaction continued for 180 minutes to have the rate of esterification reached 95%, then added titanium dioxide, phosphoric acid stabilizer, manganese acetate catalyst of 0.035 parts by weight, and then lower the inner pressure to an approximately vacuum state of 1 torr with temperature between 250-280 C until the viscosity of the reactant reached a level over 0.60 dl/g. Then the reactant was unloaded from the reactor and cooled to form cylinder shaped amorphous granules; the amorphous granules so obtained were further loaded in a solid polymerization reactor where the polyester granules continued to react under temperature between 190-220 C , with the reactor equipment filled with nitrogen gas or made into approximately vacuum state to raise the viscosity of the polyester granules to 0.95 dl/g.
The polyester granules obtained are assigned as a component (Al) which is a kind of homopolymer.
Component (A2Z
Measure bis-hydroxyethyl terephtalate monomer (BHET) of 10.27 parts by weight, isophthalic acid (IPA) of 0.432 parts by weight and ethylene glycol (EG) of 3,243 parts by weight, then put these materials into a reactor for melt polymerization process reaction. Use the same method as that of component (Al) made to obtain a desired cylinder shaped amorphous granules and then further loaded in a solid polymerization reactor to raise the viscosity of the polyester granules to 0.83 dl/g.
The polyester granules obtained are assigned as a component (A2) which contains 5 mol% of isophthalic acid (IPA).
Component (A3) Measure bis-hydroxyethyl terephtalate monomer (BHET) of 9.73 parts by weight and isophthalic acid (IPA) of 0.864 parts by weight, then put these materials into a reactor for melt polymerization process reaction.
After completion of the melt polymerization reaction, the solid polymerization was followed to raise the viscosity of the polyester granules to 0.90 dl/g.
The polyester granules obtained are assigned as a component (A3) which contains 10 mol% of isophthalic acid (IPA).
Component (A4) Measure bis-hydroxyethyl terephtalate monomer (BHET) of 9.186 parts by weight and isophthalic acid (IPA) of 1.296 parts by weight, then put these materials into a reactor for melt polymerization process reaction.
After completion of the melt polymerization reaction, the viscosity of the reactant in the reactor is reached to 0.70 dl/g, and then the solid polymerization was followed to raise the viscosity of the polyester granules to 1.20 dl/g.
The polyester granules obtained contains some agglomerates occurred during solid polymerization. The polyester granules finally obtained after the agglomerates wholly removed through a sieving machine are assigned as a component (A4) which contains 15 mol% of isophthalic acid (IPA).
Component (A5) Measure bis-hydroxyethyl terephtalate monomer (BHET) of 8.970 parts by weight, isophthalic acid (IPA) of 1.470 parts by weight and ethylene glycol (EG) of 3,243 parts by weight, then put these materials into a reactor for melt polymerization process reaction.
After completion of the melt polymerization reaction, the viscosity of the reactant in the reactor is reached to 0.75 dl/g, and then the solid polymerization was followed to obtain a kind of polyester granules.
The polyester granules obtained contains serious agglomerates after completion of the solid polymerization. Pick up part of the polyester granules no containing agglomerates and analyze the viscosity of the picked polyester granules.
The polyester granules finally obtained with an intrinsic viscosity of 1.0 dl/g are assigned as a component (A5) which contains 17 mol% of isophthalic acid (IPA).
Component (B 1) Measure purified terephthalic acid (PTA) of 81 parts by weight and 1,3-propanediol of 37 parts by weight, and put these materials into a reactor to undergo a direct esterification.
The reactant after completion of the direct esterification in the reactor further undergoes a polymerization reaction under vacuum environment so that a polytrimethylene terephthalate (PTT) with an intrinsic viscosity of 0.75 dl/g is then obtained and assigned as a component (B 1).
Component (B2) The component (B 1) of polytrimethylene terephthalate (PTT) with an intrinsic viscosity of 0.75 dl/g further undergoes a solid polymerization under temperature between 190-220 C
with the reactor filled with nitrogen gas or made into approximately vacuum state to raise the viscosity of the polytrimethylene terephthalate (PTT) to 0.80 dl/g.
And, the polytrimethylene terephthalate (PTT) obtained are assigned as a component (B2).
Component (B3) The component (B 1) of polytrimethylene terephthalate (PTT) with an intrinsic viscosity of 0.75 dl/g further undergoes a solid polymerization under temperature between 190-220 C
with the reactor filled with nitrogen gas or made into approximately vacuum state to raise the viscosity of the polytrimethylene terephthalate (PTT) to 1.0 dl/g.
And, the polytrimethylene terephthalate (PTT) obtained are assigned as a component (B3).
Component (B4) The component (B1) of polytrimethylene terephthalate (PTT) with an intrinsic viscosity of 0.75 dl/g further undergoes a solid polymerization under temperature between 190-220 C
with the reactor filled with nitrogen gas or made into approximately vacuum state to raise the viscosity of the polytrimethylene terephthalate (PTT) to 1.2 dl/g.
And, the polytrimethylene terephthalate (PTT) obtained are assigned as a component (B4).
Component (B5) The component (B 1) of polytrimethylene terephthalate (PTT) with an intrinsic viscosity of 0.75 dl/g further undergoes a solid polymerization under temperature between 190-220 C
with the reactor filled with nitrogen gas or made into approximately vacuum state to raise the viscosity of the polytrimethylene terephthalate (PTT) to 1.2 dl/g.
And, the polytrimethylene terephthalate (PTT) obtained are assigned as a component (B5).
ExMIe 1 Measured component (Al) of 5 parts by weight and component (B2) of 95 parts by weight, and then evenly blended component (Al) with component (B2) as a kind of thermoplastic polyester blend through a mixing apparatus.
Dried the thermoplastic polyester blend by moisture-free air with temperature of 150 C
for 4 hours, then fed the thermoplastic polyester blend into a extruding machine for melt-extruding processing under temperature of 250-270 C, having the melted colloid passed through an extruding die with annular opening to form unstretched tube which was immediately quenched in cooling water tank followed by employing a pair of feed roller with rotating speed of 100 rpm to transport the unstretched tube to pass a heater where the tube was heated to a temperature between 90-100 C . Then compressed air was introduced to have the unstretched tube to expand through blow-expansion process to obtain a tube with a diameter 1.3 times that of the original unstretched tube, then the expanded tubing was drawn by a pair of nip roller with rotating speed of 105 rpm to obtain a desired heat-shrinkable tube.
A series of test were then followed to verify the quality of the heat-shrinkable tube produced by the above-mentioned process.
The test includes tube-blowing stability test; perfectness of covering appearance test by heating the tube in an oven with temperature of 105 C for 3 hrs, 180 C for 30 minutes and 250 C for 3 minutes, and the test of perfectness of print character after washing the printed tube with acetone.
Further, another test for cutting with ease is to test the heat-shrinkable tube made of the thermoplastic polyester blend of the invention is easily cut off by a blade and also test the cutting section existed on the heat-shrinkable is kept flatness or not.
All the test results are shown in Table 1.
Example 2 Use the same method as that of Example 1 except measuring component (Al) of 95 parts by weight and component (B2) of 5 parts by weight.
The test results are shown in Table 1.
Example 3 Use the same method as that of Example 1 except measuring component (A2) of 5 parts by weight and component (B3) of 95 parts by weight.
The test results are shown in Table 1.
Example 4 Use the same method as that of Example I except measuring component (A2) of 95 parts by weight and component (B3) of 5 parts by weight.
The test results are shown in Table 1.
Example 5 Use the same method as that of Example I except measuring component (A3) of 5 parts by weight and component (B4) of 95 parts by weight.
The test results are shown in Table 1.
Example 6 Use the same method as that of Example 1 except measuring component (A3) of 80 parts by weight and component (B4) of 20 parts by weight.
The test results are shown in Table 1.
Example 7 Use the same method as that of Example 1 except measuring component (A3) of 95 parts by weight and component (B4) of 5 parts by weight.
The test results are shown in Table 1.
Example 8 Use the same method as that of Example 1 except measuring component (A4) of 5 parts by weight and component (B4) of 95 parts by weight.
The test results are shown in Table 1.
Example 9 Use the same method as that of Example 1 except measuring component (A4) of 95 parts by weight and component (B4) of 5 parts by weight.
The test results are shown in Table 1.
Comparative example I
A heat-shrinkable tube is only made of component (Al) but produced by the same method as that of Example I
The test results are shown in Table 1.
Comparative example 2 A heat-shrinkable tube is only made of component (A2) but produced by the same method as that of Example 1 The test results are shown in Table 1.
Comparative example 3 A heat-shrinkable tube is only made of component (A3) but produced by the same method as that of Example 1 The test results are shown in Table 1.
Comparative example 4 A heat-shrinkable tube is only made of component (A4) but produced by the same method as that of Example I
The test results are shown in Table 1.
Comparative example 5 A heat-shrinkable tube is only made of component (A5) but produced by the same method as that of Example 1 The test results are shown in Table 1.
Comparative example 6 A heat-shrinkable tube is only made of component (B3) but produced by the same method as that of Example I
The test results are shown in Table 1.
Comparative example 7 A heat-shrinkable tube is made of component (A3) of 97 parts by weight and component (B3) of 3 parts by weight but produced by the same method as that of Example 1 The test results are shown in Table 1.
Comparative example 8 A heat-shrinkable tube is made of component (A3) of 3 parts by weight and component (B3) of 97 parts by weight but produced by the same method as that of Example The test results are shown in Table 1.
Comparative example 9 A heat-shrinkable tube is made of component (A3) of 97 parts by weight and component (B5) of 3 parts by weight but produced by the same method as that of Example I
The test results are shown in Table 1.
Comparative example 10 A heat-shrinkable tube is made of component (A3) of 97 parts by weight and component (B 1) of 3 parts by weight but produced by the same method as that of Example The test results are shown in Table 1.
Discussion of the test results The heat-shrinkable tubes made of thermoplastic polyester blend shown in Table 1 all have superior properties including in tube-blowing stability, in perfectness of covering appearance no matter by heating in oven with temperature of 105 C for 3 hrs, 180 C for 30 minutes and 250 C for 3 minutes, in perfectness of the print character on tube after washing with acetone, and particularly in the test for cutting with ease and flatness.
Table 1 tube-blowing perfectness of covering resistance to Component a earance test for cutting stability pp acetone washing, with ease and (A) (B) (uniformity of 105 180 250 (perfectness of flatness example wt% wt% thickness) x 3hr x 30min x 3min print character) Example I Al B2 Example 2 A1 B2 Example 3 A2 B3 Example 4 A2 B3 Example 5 A3 B4 Example 6 A3 B4 Example 7 A3 B4 Example 8 A4 B4 Example 9 A4 B4 Compa. Al - x x x example 1 100 Compa. A2 - A X X X
example 2 100 Compa. A3 x x example 3 100 Compa. A4 x x example 4 100 Compa. A5 A X X
example 5 100 Compa. B3 x x x x example 6 100 Compa. A3 B3 A A X X
example 7 97 3 Compa. A3 B3 x x x x example 8 3 97 Compa. A3 B5 x x example 9 97 3 Compa. A3 B l x x example 10 97 3 The content of each individual component shown in table 1 is based on the content of thermoplastic polyester blend. The symbol used in the table shall represent the following:
Represents Good; A: Represents average; x: Represents No Good
Claims (6)
1. A thermoplastic polyester blend suitable for producing heat-shrinkable tube comprising component (A) from 5 to 95 wt %, based upon the total weight of components (A) and (B), of homopolymerized or copolymerized polyethylene terephthalate ( PET
) with an intrinsic viscosity of from 0.8 to 1.2 dl/g; and component (B) from 95 to 5 wt %, based upon the total weight of components (A) and (B), of polytrimethylene terephthalate (PTT) with an intrinsic viscosity of from 0.8 to 1.2 dl/g.
) with an intrinsic viscosity of from 0.8 to 1.2 dl/g; and component (B) from 95 to 5 wt %, based upon the total weight of components (A) and (B), of polytrimethylene terephthalate (PTT) with an intrinsic viscosity of from 0.8 to 1.2 dl/g.
2. The thermoplastic polyester blend as described in claim 1, wherein the component (A) obtained by having pure terephthalic acid (PTA) or ester thereof react with diol, and wherein the diol comprises a major component of ethylene glycol (EG) and at least one minor diol component selected from a group consisting of diethylene glycol, cyclohexane dimethanol (CHDM), propanediol, 2,2-dimethyl-1,3-propanediol (NPG), 2-butyl-2-ethyl-1,3-propanediol (BEPG) and butylene glycol, and the content of the minor diol component is, based on the total diol, less than 10 mole%.
3. The thermoplastic polyester blend as described in claims 1 or 2, wherein one of the components (A) and (B) contains one or more types of inorganic granules from 0.005 to 0.5 wt % based upon the total weight of components (A) and (B), and the inorganic granules selected from a group consisting of titanium dioxide, barium sulfate, calcium carbonate and silicon dioxide and limited with size less than 1 micron.
4. The thermoplastic polyester blend as described in claims 1 or 2, wherein one of the components (A) and (B) contains halogen-free flame retardant.
5. A process for producing a heat-shrinkable tube after heating in hot water having a shrinkage from 5% to 15% in machine direction (MD) and a shrinkage greater than 35% in transverse direction (TD), which comprises extruding a thermoplastic polyester blend to form a unstretched tube, quenching the tube, through blow-expansion process stretching the tube at a temperature level higher than glass transition temperature (Tg) at a stretching ratio of from 1.0 to 3.0 times in machine direction (MD) and at a stretching ratio of from 1.3 to 4.5 times in transverse direction (TD) simultaneously, and quenching the stretched tube, wherein the thermoplastic polyester blend comprising component (A) from 5 to 95 wt %, based upon the total weight of components (A) and (B), of homopolymerized or copolymerized polyethylene terephthalate ( PET ) with an intrinsic viscosity of from 0.8 to 1.2 dl/g; and component (B) from 95 to 5 wt %, based upon the total weight of components (A) and (B), of polytrimethylene terephthalate ( PTT) with an intrinsic viscosity of from 0.8 to 1.2 dl/g.
6. The process for producing the heat-shrinkable tube as described in claim 5, wherein the heat-shrinkable tube obtained therefrom, after used as an exterior covering tightly fit on an electronic parts and heated to a temperature of 180°C for 30 minutes, or 105°C for 3 hours, or 250°C for 3 minutes, still maintains a perfect covering condition without deformation of wrinkle, inflation, loose, falling off, crack or standing up.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| CN200710088300.X | 2007-03-22 | ||
| CNB200710088300XA CN100543061C (en) | 2007-03-22 | 2007-03-22 | A kind of mixed state thermoplastic polyester and the thermal contraction casing tube that uses this polyester to make |
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| CA2625894A1 true CA2625894A1 (en) | 2008-09-22 |
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| CA002625894A Abandoned CA2625894A1 (en) | 2007-03-22 | 2008-03-17 | Thermoplastic polyester blend and process for producing heat-shrinkable tube by using the same |
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| Country | Link |
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| JP (1) | JP2008231423A (en) |
| KR (1) | KR20080086359A (en) |
| CN (1) | CN100543061C (en) |
| CA (1) | CA2625894A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9789670B2 (en) | 2009-08-11 | 2017-10-17 | Nissin Foods Holdings Co., Ltd. | Heat-sealable laminate and method for producing same |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100989116B1 (en) | 2008-09-02 | 2010-10-20 | 제일모직주식회사 | Environmental-friendly polylactic acid resin composition |
| CN102660004B (en) * | 2012-05-08 | 2014-02-26 | 姚榕楠 | Method for preparing neopentyl glycol (NPG) and SiO2 copolymerization-modified polyethylene terephthalate glycol (PETG) polyester |
| TWI555773B (en) * | 2013-10-23 | 2016-11-01 | Nanya Plastics Corp | A phosphorus-containing thermoplastic polyester and a phosphorus-containing heat-shrinkable sleeve |
| TWI672326B (en) * | 2017-06-30 | 2019-09-21 | 遠東新世紀股份有限公司 | Method for preparing polyester for reducing diethylene glycol content in polyester |
| TWI672325B (en) * | 2018-08-16 | 2019-09-21 | 遠東新世紀股份有限公司 | Polyester polyol, manufacturing method thereof, polyurethane foaming material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5985387A (en) * | 1998-01-30 | 1999-11-16 | Toyo Boseki Kabushiki Kaisha | Thermo-shrinkable polyester film |
| US6663977B2 (en) * | 2000-03-07 | 2003-12-16 | E.I. Du Pont De Numours And Company | Low temperature heat-sealable polyester film and method for producing the same |
| JP2002120268A (en) * | 2000-10-16 | 2002-04-23 | Toray Ind Inc | Polyester film and manufacturing method therefor |
| JP2002179814A (en) * | 2000-12-11 | 2002-06-26 | Toray Ind Inc | Polyester film and decorative film |
| JP4243797B2 (en) * | 2003-03-14 | 2009-03-25 | 三菱樹脂株式会社 | Heat shrinkable polyester tube |
| JP4260719B2 (en) * | 2004-10-25 | 2009-04-30 | 南亜塑膠工業股▲ふん▼有限公司 | Copolyester and heat shrinkable tube manufacturing method using the copolyester |
-
2007
- 2007-03-22 CN CNB200710088300XA patent/CN100543061C/en active Active
-
2008
- 2008-03-12 JP JP2008062392A patent/JP2008231423A/en active Pending
- 2008-03-17 CA CA002625894A patent/CA2625894A1/en not_active Abandoned
- 2008-03-18 KR KR1020080024957A patent/KR20080086359A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9789670B2 (en) | 2009-08-11 | 2017-10-17 | Nissin Foods Holdings Co., Ltd. | Heat-sealable laminate and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20080086359A (en) | 2008-09-25 |
| JP2008231423A (en) | 2008-10-02 |
| CN101029121A (en) | 2007-09-05 |
| CN100543061C (en) | 2009-09-23 |
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