TWI471353B - 共聚酯樹脂及使用其之物體 - Google Patents
共聚酯樹脂及使用其之物體 Download PDFInfo
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- TWI471353B TWI471353B TW98140558A TW98140558A TWI471353B TW I471353 B TWI471353 B TW I471353B TW 98140558 A TW98140558 A TW 98140558A TW 98140558 A TW98140558 A TW 98140558A TW I471353 B TWI471353 B TW I471353B
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- copolyester resin
- cyclohexanedimethanol
- shrinkage
- diol
- mol
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- 229920005989 resin Polymers 0.000 title claims description 28
- 239000011347 resin Substances 0.000 title claims description 28
- 229920001634 Copolyester Polymers 0.000 title claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 22
- 150000002009 diols Chemical class 0.000 claims description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 13
- 229920006257 Heat-shrinkable film Polymers 0.000 claims description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- -1 cyclohexanedimethanol compound Chemical class 0.000 claims description 8
- 230000000977 initiatory effect Effects 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000001746 injection moulding Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000006068 polycondensation reaction Methods 0.000 description 9
- 238000005886 esterification reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 239000000155 melt Substances 0.000 description 5
- 229920006267 polyester film Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical class OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- IHEDBVUTTQXGSJ-UHFFFAOYSA-M 2-[bis(2-oxidoethyl)amino]ethanolate;titanium(4+);hydroxide Chemical compound [OH-].[Ti+4].[O-]CCN(CC[O-])CC[O-] IHEDBVUTTQXGSJ-UHFFFAOYSA-M 0.000 description 1
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 1
- OQLZINXFSUDMHM-UHFFFAOYSA-N Acetamidine Chemical compound CC(N)=N OQLZINXFSUDMHM-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- XDODWINGEHBYRT-UHFFFAOYSA-N [2-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCCC1CO XDODWINGEHBYRT-UHFFFAOYSA-N 0.000 description 1
- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- TZWGXFOSKIHUPW-UHFFFAOYSA-L cobalt(2+);propanoate Chemical compound [Co+2].CCC([O-])=O.CCC([O-])=O TZWGXFOSKIHUPW-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002908 osmium compounds Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
-
- 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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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
本申請案係主張2008年11月28日提申之韓國專利申請案10-2008-119620的權益，其發明名稱為「共聚酯樹脂及使用其之物體」，在此合併作為整體參酌。
本發明係關於一種1,4-環己烷二甲醇之共聚酯樹脂及其所製成之膜，尤指一種適用於標籤目的之熱縮性聚酯類樹脂組成物及使用其之膜。
熱縮塑料物具有遇熱收縮之性質，其已廣泛用於薄膜，如熱縮包裝、熱縮標籤等。尤其，聚氯乙烯(PVC)類、聚苯乙烯類或聚酯類塑料膜可用於標記或蓋封各種容器，或用於直接包裝。
然而，一旦焚燒聚氯乙烯類膜，就會產生導致戴奧辛及氯化氫氣體的物質，故就環境觀點而言，其使用受到限制。再者，當PET容器或類似物使用該產品作為熱縮標籤時，則會有回收容器時必須將標籤與容器分開的麻煩。
此外，雖然聚苯乙烯類膜進行熱縮時具有優異的加工穩定性及好的外觀，但其耐化性差，導致於印刷時需使用具有特定組成之墨水。再者，該膜有儲存穩定性不佳而導致室溫下自動皺縮的問題，因而出現尺寸變形的不佳狀況。
因此，需要一種無上述問題之聚酯樹脂所製成之薄膜，以取代上述兩種膜而作為熱縮標籤。再者，隨著PET容器使用的增加，易於回收且回收時無需額外將標籤分開之聚酯膜使用的機會亦隨之增加。
然而，習知熱縮聚酯膜之收縮特性仍有待改善。尤其，由於該聚酯膜於收縮時會發生嚴重改變，其收縮過程可能會使該膜皺縮或不均勻地收縮，導致成型過程中常發生形狀偏離預定設計的不佳狀況。又，相較於PVC類或聚苯乙烯膜，聚酯膜低溫收縮性較差。因此，聚酯膜應在高溫下進行收縮。此時，可能發生PET容器變形或變白的不佳狀況。
據此，鑑於相關領域所遭遇的問題，本發明欲提供一種共聚酯樹脂及包含其之熱縮膜，其可改善不佳的低溫收縮性，縮短週期時間，並改善使用熱縮標籤進行成型時的產品成型性(moldability)。
本發明之一態樣係提供一種共聚酯樹脂，其包括芳香族二羧酸組成；及二醇組成，其包括10-80mol%的1,4-環己烷二甲醇、0.1-30mol%下式1所示之環己烷二甲醇類化合物、及使二醇組成總量達100mol%之餘量乙二醇。
於式1中，m為1至10的整數。
本發明另一態樣係提供一種藉由對上述共聚酯樹脂進行擠壓或射出成型而製得之物體。
下文將詳細敘述本發明。
製備本發明1,4-環己烷二甲醇之共聚酯樹脂時，使用由式1所示之環己烷二甲醇類衍生物所組成之二醇，俾使製得之共聚酯樹脂具有足夠高的成型性，得以製成低溫下可進行熱縮的薄膜。又，本發明提供一種使用該共聚酯樹脂之物體。
本發明共聚酯樹脂係藉由酯化而後聚縮合法而製得。
酯化可以批次或連續步驟進行。雖然可分開加入各別材料，但較理想係將呈漿狀之對苯二甲酸加至二元醇(glycol)中。
具體而言，芳香族二羧酸組成會與包括乙二醇及1,4-環己烷二甲醇的二元醇組成進行反應。該二羧酸組成可包括對苯二甲酸。
二元醇組成相對於二羧酸組成物之添加莫耳比率為1.2至3.0，俾使酯化反應可於230-260℃、1.0-3.0kg/cm2
的條件下進行。據此，酯化的反應溫度可設為240-260℃，尤其是245-255℃，但本發明並不侷限於此。
酯化反應的時間一般係設定於100-300分鐘，其可根據反應溫度、壓力、及二元醇相對於二羧酸之莫耳比作適當的改變，但本發明並不侷限於此。
二元醇化合物(用於改善僅由對苯二甲酸及乙二醇組成之均聚物成型性或其他性質)舉例可包括1,4-環己烷二甲醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、2,2-二甲基-1,3-丙二醇、1,6-己二醇、1,2-環己二醇、1,4-環己二醇、1,2-環己烷二甲醇及1,3-環己烷二甲醇。尤其有用的是1,4-環己烷二甲醇，以作為改善均聚物特性之二元醇化合物。
於本發明中，1,4-環己烷二甲醇可為順式(cis)異構物、反式(trans)異構物或兩種異構物的混合物，且其含量可類似於最終聚合物中理想的莫耳百分比(mol%)，尤其是二醇組成總量之10-80mol%，以避免成型性因結晶而降低。再者，考慮到1,4-環己烷二甲醇的含量，加入本發明二醇組成中之乙二醇，俾使相對於二羧酸組成之二醇組成總量達100mol%。
雖然酯化反應不需要催化劑，但可選擇性加入催化劑，以縮短反應時間。
於本發明中，由環己烷二甲醇類衍生物所構成之二醇如下式1所示。
於式1中，m為1至10的整數。
以二醇組成總量為基準，式1所示之二醇含量為0.1-30mol%。若上述二醇的含量小於0.1mol%，則難以確定加入式1的二醇會改善特性。相反地，若上述二醇的含量大於30mol%，則耐熱性會過度下降，進而導致其作為熱縮膜之應用性降低。
當以式1所示之二醇取代對苯二甲酸構成之共聚酯樹脂中部分二羧酸組成時，會降低熱縮膜的收縮起始溫度，因而可縮短流程的週期時間，以改善生產率。再者，由於進行低溫收縮時收縮速度變得緩慢，故可有效控制製程，以降低瑕疵率。式1所示之二醇化合物舉例可包括二環己烷二甲醇、三環己烷二甲醇、四環己烷二甲醇、五環己烷二甲醇及其混合物。
完成酯化步驟後，再進行聚縮合反應。進行聚酯樹脂之聚縮合反應時，可選擇性使用典型的組成，包括聚縮合催化劑、穩定劑及染色劑。
可用於本發明之聚縮合催化劑包括，但不限於，鈦、鍺、銻化合物。
鈦類催化劑係作為由對苯二甲酸及15%以上(以對苯二甲酸的重量為基準)1,4-環己烷二甲醇製成共聚酯樹脂之聚縮合催化劑。即使鈦類催化劑使用量低於銻類催化劑，仍可進行反應。又，相較於鍺類催化劑，鈦類催化劑較不昂貴。
用於本發明之鈦類催化劑舉例可包括四乙基鈦酸酯、乙醯三丙基鈦酸酯(acetyltripropyl titanate)、四丙基鈦酸酯、四丁基鈦酸酯、聚丁基鈦酸酯(polybutyl titanate)、2-乙基己基鈦酸酯(2-ethylhexyl titanate)、辛二醇鈦酸酯(octyleneglycol titanate)、乳酸鈦酸酯(lactate titanate)、三乙醇胺鈦酸酯、乙醯丙酮基鈦酸酯(acetylacetonate titanate)、乙基乙醯乙酯鈦酸酯(ethylacetoacetic ester titanate)、異硬脂酸鈦酸酯(isostearyl titanate)、二氧化鈦、二氧化鈦與二氧化矽的共沉澱物、及二氧化鈦及二氧化鋯的共沉澱物。
影響最終聚合物顏色之聚縮合催化劑含量可根據所求顏色及穩定劑與染色劑的種類變化。就鈦元素量而言，基於最終聚合物的重量，聚縮合催化劑使用量可為1-100ppm，較佳為1-50ppm；而就矽元素量而言，則可為10ppm以下。若鈦元素量少於1ppm，則無法達到所求的聚合度。相反地，若鈦元素量大於100ppm，則最終聚合物為黃色，而無法獲得所求顏色。
再者，可使用穩定劑及染色劑作為額外的添加劑。
可用於本發明之穩定劑可包括磷酸、磷酸三甲酯、磷酸三乙脂、磷醯基乙酸三乙酯(triethylphosphonoacetate)，就磷元素量而言，基於最終聚合物的重量，其使用量可為10-100ppm。若穩定劑含量低於10ppm，則難以得到所求的鮮亮色彩。相反地，若其含量大於100ppm，則無法達到所求的聚合度。
本發明中可用於改善顏色之染色劑可包括典型染色劑，如醋酸鈷及丙酸鈷，基於最終聚合物的重量，其使用量可為0-100ppm。
除了上述舉例之染色劑外，亦可使用任何習知的有機化合物。
加入該些組成後，可於260-290℃，400-0.1mmHg之減壓條件下，進行聚縮合步驟，但本發明並不侷限於此。
聚縮合反應的進行時間為達所求極限黏度(intrinsic viscosity)之所需時間，而反應溫度則設定於260-290℃，較佳為260-280℃，更佳為265-275℃。
又，聚縮合反應係於400-0.1mmHg之減壓條件下進行，以移除二元醇副產物，進而獲得1,4-環己烷二甲醇之共聚酯樹脂。
如上所述，本發明共聚酯樹脂具有低收縮起始溫度，故其收縮速度慢，因而可有效控制製程，俾使其具有足夠高的成型性，以降低瑕疵率。因此，該共聚酯樹脂係透過擠壓及拉伸而成型，進而獲得具有高成型性之物體，如熱縮膜。
透過下述說明用之實施例及比較例，可更加瞭解本發明，但不應解釋為侷限本發明。
實施例及比較例中的特性係根據下述方式量測。
◎玻璃轉移溫度(Tg)：Tg係使用購自TA儀器公司之微差掃瞄熱卡計(differential scanning calorimeter)而測得。
◎熱縮速率：將樣品裁切為10cm X 10cm尺寸之方型，並於無負載之條件下，浸入於下表1所示溫度之溫水中，遂而發生熱縮，而後，浸入25℃的水中達10秒後，測量樣品的長度及厚度，再代入下述方程式中。
熱縮速率(%)=100X(收縮前長度-收縮後長度)/(收縮前長度)
◎熔融阻抗力(Ωcm)：將成對電極板插入於275℃下熔融的薄片或薄膜中，並施加120V的電壓。測量此時的電流值，而後，將該值代入下述方程式中，以獲得熔融阻抗力Si(melt resistivity,Ωcm)。
Si=(A/I)X(V/io)
其中A為電極面積(cm2
)，I為電極間的距離(cm)，V為電壓(V)，而io為電流(A)。
[實施例]
實施例1
將6mol的對苯二甲酸、138g的1,4-環己烷二甲醇、502g的乙二醇及188g的二環己烷二甲醇加至裝有攪拌器及排出式冷凝器(discharge condenser)之3L反應瓶中，並混合進行反應，且溫度逐漸提升至255℃。
藉此，將所生成的水排出，以進行酯化反應。生成並排出水後，將所形成的酯化產物轉置於裝有攪拌器、冷凝器及真空系統的反應瓶中。
將0.5g的鈦酸四丁酯、0.4g的磷酸三乙酯及0.5g的醋酸鈷加至酯化產物中。當反應瓶內溫度曲240℃提升至275℃時，由大氣壓力減壓40分鐘，以達50mmHg之低真空條件，藉此移除乙二醇。接著，逐漸減壓至0.1mmHg，以於高真空條件下進行反應，直到獲得所求之極限黏度。將反應產物移出反應瓶，並裁切為片狀。
將製得的1,4-環己烷二甲醇之共聚酯樹脂製成熱縮膜，而後根據上述方法測量該膜之玻璃轉移溫度、收縮起始溫度、熱縮速率及熔融阻抗力。結果如下表1所示。
實施例2
除了加入268g的二環己烷二甲醇外，其共聚酯樹脂之製備方法如實施例1所述。由共聚酯樹脂製得熱縮膜後，測量玻璃轉移溫度、收縮起始溫度、熱縮速率及熔融阻抗力。結果如下表1所示。
實施例3
除了加入210g的三環己烷二甲醇外，其共聚酯樹脂之製備方法如實施例1所述。由共聚酯樹脂製得熱縮膜後，測量玻璃轉移溫度、收縮起始溫度、熱縮速率及熔融阻抗力。結果如下表1所示。
比較例1
除了未加入二環己烷二甲醇外，其共聚酯樹脂之製備方法如實施例1所述。由共聚酯樹脂製得熱縮膜後，測量玻璃轉移溫度、收縮起始溫度、熱縮速率及熔融阻抗力。結果如下表1所示。
比較例2
由PVC樹脂製得熱縮膜後，測量玻璃轉移溫度、收縮起始溫度、熱縮速率及熔融阻抗力。結果如下表1所示。
如上所述，本發明提供一種共聚酯樹脂及使用其之物體。於本發明中，該共聚酯樹脂包括一特定環己烷二甲醇類化合物，俾以降低收縮起始溫度，因而可於低溫下發生熱縮(類似於PVC)，進而避免膜熱縮時PET容器變形或變白。再者，可輕易控制收縮速率，進而減少成型瑕疵。
雖然本發明實施例已揭示共聚酯樹脂及使用其之物體作為說明用，但本領域之人士應瞭解，可進行各種不同修飾、添增及置換，其不背離隨後申請專利範圍所揭示之本發明範疇及精神。據此，該些修飾、添增及置換皆應落於本發明之範疇中。
Claims (7)
- 一種共聚酯樹脂，用於一種熱縮膜，包括芳香族二羧酸組成；及二醇組成，其包括10-80mol%的1,4-環己烷二甲醇、0.1-30mol%下式1所示之環己烷二甲醇類化合物、及使該二醇組成總量達100mol%之餘量乙二醇：
- 如申請專利範圍第1項所述之共聚酯樹脂，其中，該式1所示之化合物包括選自由：二環己烷二甲醇、三環己烷二甲醇及其混合物所組群組中之一者或以上。
- 如申請專利範圍第1項所述之共聚酯樹脂，其中，該芳香族二羧酸組成包括對苯二甲酸。
- 一種物體，其係藉由對如申請專利範圍第1項至第3項中任一項所述之共聚酯樹脂進行擠壓或射出成型而製得。
- 如申請專利範圍第4項所述之物體，其中，該物體為一熱縮膜。
- 如申請專利範圍第4項所述之物體，其中，該物體之收縮起始溫度為60℃以下，且60℃下之最大熱縮速率為2%或以上。
- 如申請專利範圍第4項所述之物體，其中，該物體85℃下之最大熱縮速率為50%或以上。
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| JP6367934B2 (ja) | 2013-06-17 | 2018-08-01 | エスケー ケミカルズ カンパニー リミテッド | 共重合ポリエステル樹脂を含む熱収縮フィルム |
| WO2015004313A1 (en) * | 2013-07-12 | 2015-01-15 | Upm Raflatac Oy | A thermally shrinkable plastic film and an item comprising the same |
| US10388705B2 (en) * | 2014-05-27 | 2019-08-20 | Lg Display Co., Ltd. | Display panel and method for manufacturing thereof |
| KR102251211B1 (ko) * | 2014-08-19 | 2021-05-11 | 에스케이케미칼 주식회사 | 폴리에스테르계 열수축 필름 |
| KR102193168B1 (ko) * | 2014-08-26 | 2020-12-18 | 에스케이케미칼 주식회사 | 폴리에스테르 수지 조성물 및 이의 제조 방법 |
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| US6924349B2 (en) * | 2003-06-23 | 2005-08-02 | Sk Chemicals Co., Ltd. | Copolyester resin and articles using the same |
| US20050026088A1 (en) * | 2003-08-01 | 2005-02-03 | Eastman Kodak Company | Process for rapid annealing of a polyester film base to control film curl |
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| EP2360202A2 (en) | 2011-08-24 |
| US20110230634A1 (en) | 2011-09-22 |
| ES2535017T3 (es) | 2015-05-04 |
| TW201020273A (en) | 2010-06-01 |
| KR20100060848A (ko) | 2010-06-07 |
| CN102227462A (zh) | 2011-10-26 |
| US8557951B2 (en) | 2013-10-15 |
| CN102227462B (zh) | 2013-08-28 |
| WO2010062082A2 (ko) | 2010-06-03 |
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