TWI461495B - 磷酸化聚酯及含彼之塗覆組合物 - Google Patents
磷酸化聚酯及含彼之塗覆組合物 Download PDFInfo
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- TWI461495B TWI461495B TW101118415A TW101118415A TWI461495B TW I461495 B TWI461495 B TW I461495B TW 101118415 A TW101118415 A TW 101118415A TW 101118415 A TW101118415 A TW 101118415A TW I461495 B TWI461495 B TW I461495B
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- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
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- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
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- 238000011109 contamination Methods 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- FDENMIUNZYEPDD-UHFFFAOYSA-L disodium [2-[4-(10-methylundecyl)-2-sulfonatooxyphenoxy]phenyl] sulfate Chemical compound [Na+].[Na+].CC(C)CCCCCCCCCc1ccc(Oc2ccccc2OS([O-])(=O)=O)c(OS([O-])(=O)=O)c1 FDENMIUNZYEPDD-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000008266 hair spray Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- IMTKRLUCQZWPRY-UHFFFAOYSA-N triazine-4-carbaldehyde Chemical compound O=CC1=CC=NN=N1 IMTKRLUCQZWPRY-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0218—Pretreatment, e.g. heating the substrate
- B05D3/0236—Pretreatment, e.g. heating the substrate with ovens
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
- B05D7/227—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes of containers, cans or the like
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
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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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy compounds
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- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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Description
本發明係關於磷酸化聚酯及含有該等聚酯之塗覆組合物。該等組合物適用於塗覆各種容器,諸如食品及飲料容器。
已使用多種塗料來塗覆食品及飲料容器之表面。舉例而言,有時使用線圈塗覆或片材塗覆操作來塗覆金屬罐,亦即用適合組合物塗覆適合基材(例如鋼或鋁)之平面或線圈或片材並且固化。接著,將經塗覆基材形成罐體或罐端。或者,可藉由例如噴霧及浸漬將塗覆組合物施加至所形成之罐子,接著固化。用於食品及飲料容器之塗料較佳應能夠高速施加至基材且在進行固化時提供所需最終用途中之必需性質。舉例而言,塗料應具有食品接觸安全性且對基材具有極佳黏著性。
許多用於食品及飲料容器之塗覆組合物係基於環氧樹脂,亦即雙酚A之聚縮水甘油醚。包裝塗料中呈以下形式之雙酚A會引發問題:雙酚A本身(BPA);其衍生物,諸如雙酚A二縮水甘油醚(BADGE)、酚醛環氧樹脂及用雙酚A與雙酚F製備之多元醇。雖然權衡迄今可得之科學證據後表明,可能自現存塗料中釋放之較小痕量BPA或BADGE不會對人類健康造成風險。然而,有人已認識到此等化合物對人類健康有害。因此,強烈需要自用於食品及飲料容器之塗料中消除此等化合物。因此,所需要者為以下用於食
品或飲料容器之包裝塗覆組合物,該組合物不含可提取量的BPA、BADGE或其他BPA衍生物,卻具有極佳性質,諸如對基材之極佳黏著性。
本發明提供一種塗覆組合物,其包含樹脂黏合劑及至多10重量%磷酸化聚酯;及經該塗覆組合物塗覆之物件。
磷酸化聚酯包含以下之反應產物:(a)聚酯,其具有2000至10,000之Mn、20至75之羥基數及15至25之酸值;該聚酯為以下之聚縮合物:(i)多元醇組分,其包含二醇與三醇之混合物;(ii)多元酸組分,其包含α,β-烯系不飽和多羧酸;及(b)亞磷酸。
經塗覆物件包含:(a)基材;及(b)由上文剛剛提及之塗覆組合物沈積於該基材上所得之塗層。
該塗覆組合物可經調配以使其實質上不含雙酚A(BPA)及其衍生物,諸如雙酚A二縮水甘油醚(BADGE)。
如本文所使用,除非另外明確規定,否則諸如彼等表達值、範圍、量或百分比之所有數字均可當作如同前面加上詞語「約」,即使該術語未明確出現。此外應注意,複數術語及/或短語涵蓋其單數等效物,反之亦然。舉例而言,「一種」聚合物、「一種」交聯劑及任一其他組分係
指一或多種此等組分。
當提及任何值之數值範圍時,該等範圍應理解為包括所述範圍最小值與最大值之間的各個及每個數字及/或分數。
如本文所用,術語「多元醇」或其變化形式廣泛指每分子具有平均兩個或兩個以上羥基之物質。術語「多羧酸」係指酸及其功能衍生物,包括存在酸之酸酐衍生物及具有1至4個碳原子之低碳數烷基酯。
如本文所用,術語「聚合物」廣泛指預聚物、寡聚物及均聚物及共聚物兩者。術語「樹脂」與「聚合物」可互換使用。
術語「丙烯酸」及「丙烯酸酯」可互換使用(除非互換使用會改變預定含義)且除非另外明確指示,否則包括丙烯酸、酸酐及其衍生物,諸如其C1
-C5
烷基酯、經低碳數烷基取代之丙烯酸,例如經C1
-C2
取代之丙烯酸,諸如甲基丙烯酸、乙基丙烯酸等;及其C1
-C5
烷基酯。術語「(甲基)丙烯酸」或「(甲基)丙烯酸酯」意欲涵蓋所指示物質之丙烯酸/丙烯酸酯及甲基丙烯酸/甲基丙烯酸酯形式,例如(甲基)丙烯酸酯單體。術語「丙烯酸聚合物」係指由一或多種丙烯酸單體製備之聚合物。
如本文所用,「一種」及「至少一種」及「一或多種」可互換使用。因此,舉例而言,包含「一種」聚合物之塗覆組合物可解釋為意謂該塗覆組合物包括「一或多種」聚合物。
如本文所用,藉由凝膠滲透層析法使用聚苯乙烯標準物來測定分子量。除非另外指示,否則分子量係基於數量平均值(Mn)。
磷酸化聚酯係藉由使前驅物聚酯樹脂與亞磷酸反應來製備。聚酯樹脂含有羥基官能基及羧酸官能基。聚酯樹脂通常具有每公克聚酯樹脂20至75 mg KOH之羥基數及每公克聚酯樹脂15至20 mg KOH之酸值;各值係基於非揮發性固體而量測。
聚酯樹脂具有2000至10,000 g/mol之數量平均分子量(Mn)。
適合聚酯樹脂通常藉由根據已知製程進行縮合(酯化)來製備[參看例如Zeno Wicks,Jr.,Frank N.Jones及S.Peter Pappas,Organic Coatings:Science and Technology
,第1卷,第122-132頁(John Wiley & Sons:New York,1992)]。聚酯樹脂通常來源於至少一種多官能基醇(多元醇)之混合物,一般為經多元酸或酸酐酯化之二醇及三醇之混合物。多元酸組分包含α,β-烯系不飽和多羧酸或酸酐。
聚酯樹脂通常係由α,β-烯系不飽和多羧酸通常與芳族及/或脂族多羧酸之混合物及多元醇組分(通常為二醇與三醇之混合物)製備。以所要比例組合多元醇及多羧酸且使用標準酯化(縮合)程序進行化學反應以獲得聚酯,該聚酯樹脂中具有羥基與羧酸基兩者。通常使用三醇來提供與線性聚酯相對之分枝聚酯。
適合多羧酸或酸酐之實例包括(但不限於)順丁烯二酸
酐、順丁烯二酸、反丁烯二酸、衣康酸、鄰苯二甲酸、鄰苯二甲酸酐、間苯二甲酸、苯偏三酸酐、對苯二甲酸、萘二甲酸、己二酸、壬二酸、丁二酸、癸二酸及其各種混合物。
芳族及/或脂族多羧酸在使用時係以多羧酸或酸酐之總重量計至多70重量%、通常50重量%至65重量%之量使用。
適合二醇、三醇及多元醇之實例包括(但不限於)乙二醇、丙二醇、1,3-丙二醇、甘油、二乙二醇、二丙二醇、三乙二醇、三羥甲基丙烷、三羥甲基乙烷、三丙二醇、新戊二醇、異戊四醇、1,4-丁二醇、三羥甲基丙烷、己二醇、環己二甲醇及聚乙二醇或聚丙二醇。
如上文所提及,多元醇組分為二醇與三醇之混合物。二醇與三醇之重量比通常在0.5至10:1範圍內。
多元醇組分與多羧酸之當量比為0.9至1.1:1.0。
與聚酯樹脂反應之亞磷酸可為次膦酸、膦酸或較佳為磷酸。磷酸可呈水溶液形式,例如85重量%水溶液或可為100%磷酸或過磷酸。該酸係以聚酯樹脂之每羥基當量約0.2至0.5當量磷酸,亦即每個羥基0.2至0.45個P-OH基團之量提供。
亞磷酸與聚酯樹脂之反應通常在有機溶劑中進行。有機溶劑通常為具有約65℃至250℃之沸點的芳族溶劑、酮或酯。適合溶劑之實例包括甲基乙基酮、甲基異丁基酮、乙二醇丁醚乙酸酯及乙酸甲氧基丙酯。用於該反應之有機溶
劑之含量通常為以亞磷酸、聚酯樹脂及有機溶劑之總重量計約20重量%至50重量%。
通常在50℃至95℃之溫度下混合反應物與有機溶劑,且一旦接觸反應物,將反應混合物維持於較佳為90℃至200℃之溫度。通常使反應進行約45分鐘至6小時之時期。
塗覆組合物中通常使用微量磷酸化聚酯,由此改良所得塗料對基材之黏著。磷酸化聚酯於塗覆組合物中之含量通常為以塗覆組合物中樹脂固體之重量計至多10重量%、較佳0.1重量%至5重量%。小於0.1重量%之量造成塗覆組合物對基材之黏著不良,而大於10重量%之量不提供額外優勢。
除磷酸化聚酯以外,塗覆組合物包含樹脂媒劑、有機溶劑及其他視情況可選成分。
樹脂媒劑較佳為丙烯酸聚合物及/或聚酯聚合物。丙烯酸聚合物較佳為來源於一或多種丙烯酸單體之聚合物。此外,可使用丙烯酸聚合物之摻合物。較佳單體為丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸戊酯、丙烯酸己酯、甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯、甲基丙烯酸戊酯及甲基丙烯酸己酯。丙烯酸聚合物亦可含有通常來源於經羥基取代之丙烯酸酯或甲基丙烯酸酯之羥基。實例包括丙烯酸羥基乙酯及甲基丙烯酸羥基丙酯。丙烯酸聚合物組分之重量平均分子量(Mw)較佳為至少5,000 g/mol,更佳為15,000 g/mol至100,000 g/mol。
丙烯酸聚合物通常具有30 mg KOH/g至70 mg KOH/g,諸如40 mg KOH/g至60 mg KOH/g之酸值;0 mg KOH/g至100 mg KOH/g,諸如0 mg KOH/g至70 mg KOH/g之羥值;及-20℃至+100℃,諸如+20℃至+70℃之玻璃轉移溫度(Tg)。
聚酯聚合物係藉由如上文所提及之此項技術中所熟知的製程來製備,包含一或多種多羧酸與一或多種多元醇之縮合聚合反應。適合多羧酸之實例為鄰苯二甲酸、間苯二甲酸、對苯二甲酸、1,4-環己二甲酸、丁二酸、癸二酸、甲基四氫鄰苯二甲酸、甲基六氫鄰苯二甲酸、四氫鄰苯二甲酸、十二烷二酸、己二酸、壬二酸、萘-二甲酸、苯均四酸、二聚脂肪酸及/或偏苯三酸。
多元醇組分係選自例如二醇或三醇。適合多元醇之實例包括乙二醇、1,3-丙二醇、二乙二醇、二丙二醇、三乙二醇、1,4-丁二醇、2-甲基-1,3-丙二醇、1,4-環己二甲醇、1,6-己二醇、新戊二醇、三羥甲基丙烷及甘油。聚酯聚合物較佳具有1000 g/mol至20,000 g/mol之數量平均分子量。
聚酯聚合物通常具有0 mg KOH/g至20 mg KOH/g,諸如0 mg KOH/g至5 mg KOH/g之酸值;50 mg KOH/g至200 mg KOH/g,諸如70 mg KOH/g至150 mg KOH/g之羥基數;-20℃至+50℃,諸如-10℃至+40℃之玻璃轉移溫度(Tg)。
通常固化劑存在於樹脂媒劑中,該等固化劑與丙烯酸及聚酯聚合物反應。適合固化劑為酚醛塑膠或酚-甲醛樹脂及胺基塑膠或三嗪-甲醛樹脂。酚-甲醛樹脂較佳屬於甲階
酚醛樹脂類型。適合酚之實例為苯酚本身、丁基苯酚、二甲苯酚及甲酚。通常使用甲酚-甲醛樹脂,該等類型通常經丁醇醚化。關於製備酚系樹脂之化學反應,參考「The Chemistry and Application of Phenolic Resins or Phenolplasts」,第V卷,第I部分,Dr.Oldring編;John Wiley & Sons/Cita Technology Limited,London,1997。市售酚系樹脂之實例為PHENODUR®
PR285及BR612,以及以商標BAKELITE®
銷售之樹脂,通常為BAKELITE 6581LB。
胺基塑膠樹脂之實例為由諸如三聚氰胺或苯并胍胺之三嗪與甲醛反應所形成者。較佳通常用甲醇、乙醇、丁醇(包括其混合物)將此等縮合物醚化。關於胺基塑膠樹脂之化學製備及用途,參看「The Chemistry and Applications of Amino Crosslinking Agents or Aminoplast」,第V卷,第II部分,第21頁及其後,Dr.Oldring編;John Wiley & Sons/Cita Technology Limited,London,1998。此等樹脂可以商標MAPRENAL®
(諸如MAPRENAL MF980)及商標CYMEL®
(諸如CYMEL 303及CYMEL 1128,獲自Cytec Industries)購得。
丙烯酸聚合物及/或聚酯聚合物之用量通常為40重量%至90重量%,較佳為30重量%至70重量%,且交聯劑之含量為5重量%至50重量%,較佳為20重量%至40重量%,該等重量百分比係以塗覆組合物中之總樹脂固體之重量計。
塗覆組合物中可包括視情況可選成分。通常,塗覆組合物將含有稀釋劑,諸如水或有機溶劑或水與有機溶劑之混
合物,以便溶解或分散樹脂黏合劑及磷酸化聚酯。選擇具有足夠揮發性以便在固化製程中(諸如在自175℃至205℃加熱約5分鐘至15分鐘期間)基本上完全自塗覆組合物中蒸發之有機溶劑。適合有機溶劑之實例為脂族烴,諸如礦油精及高閃點VM&P石腦油;芳族烴,諸如苯、甲苯、二甲苯及溶劑石腦油100、150、200及其類似物;醇,例如乙醇、正丙醇、異丙醇、正丁醇及其類似物;酮,諸如丙酮、環己酮、異丁基甲酮及其類似物;酯,諸如乙酸乙酯、乙酸丁酯及其類似物;二醇,諸如乙二醇丁醚、乙二醇醚,諸如甲氧基丙醇及乙二醇單甲醚及乙二醇單丁醚及其類似物。亦可使用各種有機溶劑之混合物。對於水性組合物,樹脂媒劑通常具有至少部分經胺中和以便有助於分散或溶解於水性介質中的酸基,諸如酸官能基丙烯酸聚合物。稀釋劑在存在時於塗覆組合物中之用量係以塗覆組合物之總重量計約20重量%至83重量%、較佳30重量%至70重量%。
塗覆組合物中可包括輔助樹脂(諸如聚醚多元醇及聚胺基甲酸酯多元醇)以將所得塗料之某些性質最優化。輔助樹脂在存在時之用量係以塗覆組合物之樹脂固體之重量計至多50重量%、通常2重量%至50重量%。
通常存在於塗覆組合物中之另一視情況可選成分為用於增加塗覆組合物之固化或交聯速率之催化劑。一般可使用酸催化劑且其含量通常為約0.05重量%至5重量%。適合催化劑之實例為十二烷基苯磺酸、甲磺酸、對甲苯磺酸、二
壬基萘二磺酸及苯基膦酸。已發現本發明塗覆組合物中之酸催化劑之量由於存在磷酸化聚酯而與正常所期望不同。此反應產物為酸性的,且已發現其有助於塗覆組合物之固化。
另一適用視情況可選成分為潤滑劑,例如蠟,其藉由賦予經塗覆金屬基材片以潤滑性而有助於製造金屬封閉物。較佳潤滑劑包括例如巴西棕櫚蠟及聚乙烯型潤滑劑。若使用,則潤滑劑較佳以塗覆組合物中之樹脂固體之重量計至少0.1重量%存在於塗覆組合物中。
另一適用視情況可選成分為顏料,諸如二氧化鈦。若使用,則顏料係以塗覆組合物中之固體總重量計不超過70重量%、較佳不超過40重量%之量存在於塗覆組合物中。
可視情況向塗覆組合物中添加界面活性劑以輔助流動及對基材之濕潤。適合界面活性劑之實例包括(但不限於)壬基苯酚聚醚及鹽。若使用,則界面活性劑之含量較佳為以塗覆組合物中之樹脂固體之重量計至少0.01%且不超過10%。
在某些實施例中,用於實施本發明之組合物實質上不含、可基本上不含且可完全不含雙酚A及其衍生物或殘餘物,包括雙酚A(「BPA」)及雙酚A二縮水甘油醚(「BADGE」)。該等組合物有時稱為「非有意BPA」,因為並非有意添加BPA,包括其衍生物或殘餘物,但其可能因不可避免之環境污染而以痕量存在。組合物亦可實質上不含且可基本上不含且可完全不含雙酚F及其衍生物或殘
餘物,包括雙酚F及雙酚F二縮水甘油醚(「BPFG」)。如本文所用之術語「實質上不含」意謂組合物含有小於1000百萬分率(ppm)之任何上述化合物衍生物或其殘餘物,「基本上不含」意謂小於100 ppm之任何上述化合物衍生物或其殘餘物,且「完全不含」意謂小於20 ppb(parts per billion)之任何上述化合物衍生物或其殘餘物。
本發明之塗覆組合物可施加於各種容器,且尤其非常適用於食品及飲料罐(例如兩片式罐、三片式罐等)。除食品及飲料容器以外,該塗覆組合物亦可施加於氣霧劑應用(諸如除臭劑及噴髮膠)之容器。
兩片式罐係藉由接合罐體(通常為拉製金屬體)與罐端(通常為拉製金屬端)來製造。本發明之塗料適用於食品或飲料接觸情形,且可用於該等罐子內側或外側上。其適用於噴霧施加、液體塗覆、洗塗覆(wash coating)、片材塗覆、上清漆塗覆(over varnish coating)及邊封塗覆。
噴霧塗覆包括將塗覆組合物引入預成形包裝容器內部。適合噴霧塗覆之典型預成形包裝容器包括食品罐、啤酒及飲料容器及其類似物。噴霧較佳利用能夠均勻塗覆預成形包裝容器內部之噴霧嘴。接著使噴霧預成形容器受熱以移除殘餘溶劑並硬化塗層。
線圈塗覆描述為通常利用由金屬(例如鋼或鋁)構成之連續線圈之輥式塗覆應用進行的塗覆。一旦塗覆,塗覆線圈經歷短期熱、紫外線及/或電磁固化週期,以便硬化(例如乾燥及固化)塗層。線圈塗覆提供經塗覆金屬(例如鋼及/或
鋁)基材,該等基材可加工成為成形物件,諸如兩片式拉製食品罐、三片式食品罐、食品罐端、薄壁拉伸罐(drawn and ironed can)、飲料罐端及其類似物。
洗塗覆在工業上描述為塗覆具有保護性塗料薄層之兩片式薄壁拉伸(「D&I」)罐之外部。此等D&I罐外部藉由使預成形兩片式D&I罐通過塗覆組合物簾幕下而經「洗塗覆」。在通過簾幕時將罐子倒置,亦即罐子開口端處於「向下」位置。此塗覆組合物簾幕呈現「瀑布樣」外觀。
一旦此等罐子通過此塗覆組合物簾幕下,液體塗料物質有效塗覆各罐子外部。使用「空氣刮刀」移除過量塗料。一旦向各罐子外部施加所要量之塗料,可使各罐子通過熱、紫外線及/或電磁固化烘箱以硬化(例如乾燥及固化)塗層。經塗覆罐子於固化烘箱區域內之滯留時間通常為1分鐘至5分鐘。此烘箱內之固化溫度通常將在150℃至220℃範圍內。
片材塗覆描述為塗覆已預先切成正方形或矩形「片材」之各別多種材料(例如鋼或鋁)片。此等片材之典型尺寸為約1平方公尺。塗覆後,將各片材固化。一旦硬化(例如乾燥及固化),收集經塗覆之基材片且進行製備以供隨後之加工。片材塗覆提供經塗覆金屬(例如鋼或鋁)基材,該基材可成功地加工為成形物件,諸如兩片式拉製食品罐、三片式食品罐、食品罐端、薄壁拉伸罐、飲料罐端及其類似物。
邊封塗覆描述為將液體塗料噴霧施加於成形三片式食品
罐之焊接區域上。當製備三片式食品罐時,將矩形經塗覆基材件形成為圓柱體。圓柱體之形成由於經由熱焊接焊接矩形之各側面而為永久性的。一旦焊接,各圓柱體通常可需要液體塗料層,該液體塗料層保護暴露之「焊縫」隨後免受所容納食品之腐蝕或其他作用。起此作用之液體塗料稱為「邊封塗漆(side seam stripe)」。典型邊封塗漆係經噴霧施加且經由焊接操作之餘熱以及小型熱、紫外線及/或電磁烘箱而快速固化。
提供以下實例以幫助理解本發明,且該等實例不應視為限制本發明之範疇。除非另外指示,否則所有份數及百分數皆以重量計。
由以下成分混合物製備磷酸化聚酯樹脂:
將前兩種成分裝入裝備有攪拌器、氮氣層及蒸餾裝置之反應容器中,且加熱至50℃。一旦達到該溫度,接著將下四種成分添加至容器中且緩慢加熱至蒸餾。在180℃至240℃範圍內之溫度下,在氮氣氛圍下將混合物酯化約十二(12)小時。
當混合物之酸值下降至約13.00 mg KOH/g時,將混合物冷卻至約160℃,接著併入Aromatic 100溶劑(亦即可購自Exxon Mobil之芳族烴溶劑摻合物)以供進行水共沸蒸餾,逐漸成為縮合副產物。此後添加磷酸溶液及水,且繼續進行水共沸蒸餾,直至混合物之酸值下降至20 mg KOH/g以下。接著將所得磷酸化聚酯樹脂溶解於2-丁氧基乙醇及二乙二醇單丁醚中,產生約50重量%固體之組合物。
所得磷酸化聚酯之數量平均分子量為約4500,酸值為約20且羥值為約45。
將11.01 g 85%正磷酸及14.24 g丁醇添加至燒瓶中。在氮氣惰性層下將混合物加熱至230℉(110℃)。當達到該溫度時,關閉氮氣層且經2小時10分鐘之時期饋入45.64 g雙酚A二縮水甘油醚(每當量環氧樹脂0.286當量磷酸)與22.53 g丁醇之預混物。在添加期間將批料溫度維持在245℉(118℃)以下。完成饋料後,向燒瓶中添加2.18 g丁醇且將溫度降至219℉(104℃)並且再維持2小時。再向燒瓶中添加2.76 g丁醇且所得反應產物具有55.92重量%之樹脂固體含
量。
基於包含聚酯多元醇之黏合劑及胺基塑膠及酚醛塑膠固化劑製備一系列容器塗覆組合物。一種組合物(實例1)含有磷酸化聚酯黏著促進劑,第二種組合物(實例2)含有雙酚A二縮水甘油醚(BADGE)黏著促進劑,且第三種組合物(實例3,對照)不含黏著促進劑。
隨適度攪動將該等成分添加至容器中,形成透明清漆。將各清漆下引於經鋅處理之鋁面板上,在電強制送風烘箱中烘烤,獲得450℉(232℃)之峰值金屬溫度。接著評估經固化塗層的黏著及白化(blushing)。結果報導於以下表I中。
1
每平方吋之塗層重量(毫克)。
2
將經甲基乙基酮(MEK)浸泡之棉墊在恆定壓力下在塗層上來回移動,直至塗層嚴重損壞。100次雙重摩擦後,
終止測試。
3
Dowfax清潔性測試:設計「Dowfax」測試用於量測塗層對沸騰清潔劑溶液之抗性。藉由將5 ml Dowfax 2A1(Dow Chemical之產品)混入3000 ml去離子水中來製備溶液。將經塗覆基材在沸騰Dowfax溶液中浸漬15分鐘。接著沖洗基材且在去離子水中冷卻,乾燥,接著對白化及黏著進行測試並分級。
4
3重量%乙酸水溶液。
5
製程或蒸餾抗性:此為經塗覆基材暴露於熱及壓力與諸如水之液體後之塗層完整性的量度。對於本發明之評估,將經塗覆基材浸入去離子水或pH 9水中,且經受121℃(250℉)之熱及1.05 kg/cm之壓力持續30分鐘。接著乾燥基材且測試黏著及白化。
6
白化抗性:白化抗性量測塗層抗各種溶液侵蝕之能力。通常由吸入塗膜中之水量來量測白化。當膜吸水時,其一般變得混濁或看起來呈白色。使用0至10之標度目測白化,其中等級「10」指示無白化,且等級「0」指示膜完全白化。
7
黏著:進行黏著測試以評定塗層是否黏著於經塗覆基材。根據ASTM D3359-測試方法B,使用獲自3M Company(Saint Paul,Minnesota)之Scotch 610膠帶來進行黏著測試。黏著一般在0至100之標度上分級,其中等級「100」指示無黏著破壞,且等級「90」指示90%塗層保持黏著。
Claims (20)
- 一種液體塗覆組合物,其包含:(a)樹脂黏合劑;(b)至多10重量%磷酸化聚酯,該磷酸化聚酯包含包括以下之反應產物:(i)聚酯,其具有2000至10,000之Mn、20至75之羥基數及15至25之酸值;該聚酯包含以下之聚縮合物:(A)多元醇組分,其包含二醇與三醇之混合物;(B)多元酸組分,其包含α,β-烯系不飽和多羧酸;及(ii)亞磷酸。
- 如請求項1之液體塗覆組合物,其中該多元醇組分包含視情況具有烷基分枝之脂族多元醇。
- 如請求項2之液體塗覆組合物,其中該三醇包含三羥甲基丙烷。
- 如請求項1之液體塗覆組合物,其中該多元酸組分包含脂族及/或芳族多羧酸與α,β-烯系不飽和多羧酸之混合物。
- 如請求項1之液體塗覆組合物,其中該α,β-烯系不飽和多羧酸包含順丁烯二酸。
- 如請求項1之液體塗覆組合物,其中該亞磷酸包含磷酸。
- 如請求項1之液體塗覆組合物,其中該亞磷酸之用量係每當量羥基0.2至0.5當量,亦即每個羥基0.2至0.5個P-OH。
- 如請求項1之液體塗覆組合物,其中該樹脂黏合劑包含丙烯酸聚合物及/或聚酯聚合物。
- 如請求項1之液體塗覆組合物,其進一步包含交聯劑。
- 如請求項9之液體塗覆組合物,其中該交聯劑包含胺基塑膠及/或酚醛塑膠。
- 如請求項1之液體塗覆組合物,其中該樹脂黏合劑之含量係以該液體塗覆組合物中之樹脂固體之重量計40重量%至90重量%。
- 如請求項9之液體塗覆組合物,其中該交聯劑之含量係以該液體塗覆組合物中之樹脂固體之重量計5重量%至50重量%。
- 一種經塗覆物件,其包含:(a)基材;及(b)由如請求項1之液體塗覆組合物沈積於該基材上所得之塗層。
- 如請求項13之經塗覆物件,其中該基材為容器。
- 如請求項14之經塗覆物件,其中該基材為用於食品或飲料之容器。
- 如請求項13之經塗覆物件,其中該基材為罐子。
- 如請求項16之經塗覆物件,其中該液體塗覆組合物係沈積於該罐子之外壁上。
- 如請求項16之經塗覆物件,其中該基材為罐端。
- 如請求項1之液體塗覆組合物,其實質上不含雙酚A及其衍生物。
- 如請求項1之液體塗覆組合物,其完全不含雙酚A及其衍生物。
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| US20070260003A1 (en) * | 2006-05-05 | 2007-11-08 | Cinoman Douglas S | Acid functional phosphorus-containing polyester powder compositions and powder coatings made therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| MX2013013652A (es) | 2014-05-01 |
| RU2013156831A (ru) | 2015-06-27 |
| US20120301647A1 (en) | 2012-11-29 |
| US10280332B2 (en) | 2019-05-07 |
| KR102143268B1 (ko) | 2020-08-28 |
| WO2012162301A1 (en) | 2012-11-29 |
| TW201307494A (zh) | 2013-02-16 |
| CA2836909A1 (en) | 2012-11-29 |
| EP2714535B1 (en) | 2015-09-30 |
| ZA201308774B (en) | 2016-01-27 |
| CN103619718A (zh) | 2014-03-05 |
| HK1194344A1 (zh) | 2014-10-17 |
| PL2714535T3 (pl) | 2016-02-29 |
| SG195058A1 (en) | 2013-12-30 |
| CN103619718B (zh) | 2016-04-13 |
| RU2571137C2 (ru) | 2015-12-20 |
| CA2836909C (en) | 2016-02-09 |
| PT2714535E (pt) | 2015-12-07 |
| MY161368A (en) | 2017-04-14 |
| ES2554233T3 (es) | 2015-12-17 |
| MX354114B (es) | 2018-02-08 |
| KR20170016022A (ko) | 2017-02-10 |
| KR20140013092A (ko) | 2014-02-04 |
| US20170081549A1 (en) | 2017-03-23 |
| NZ618116A (en) | 2015-06-26 |
| AU2012258930B2 (en) | 2015-06-11 |
| DK2714535T3 (en) | 2016-01-11 |
| BR112013030020A2 (pt) | 2016-09-13 |
| EP2714535A1 (en) | 2014-04-09 |
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