TW201307401A - 用於黏合劑配方中之乙烯基酯/乙烯共聚物分散體 - Google Patents
用於黏合劑配方中之乙烯基酯/乙烯共聚物分散體 Download PDFInfo
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- TW201307401A TW201307401A TW101120510A TW101120510A TW201307401A TW 201307401 A TW201307401 A TW 201307401A TW 101120510 A TW101120510 A TW 101120510A TW 101120510 A TW101120510 A TW 101120510A TW 201307401 A TW201307401 A TW 201307401A
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- polyvinyl alcohol
- dispersion according
- dispersion
- vinyl ester
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- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
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- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
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- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
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- 241000403354 Microplus Species 0.000 description 1
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- 239000004793 Polystyrene Substances 0.000 description 1
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
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- UJRDRFZCRQNLJM-UHFFFAOYSA-N methyl 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OC)=CC(N2N=C3C=CC=CC3=N2)=C1O UJRDRFZCRQNLJM-UHFFFAOYSA-N 0.000 description 1
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- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
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- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
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- 239000003505 polymerization initiator Substances 0.000 description 1
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- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- DEWNCLAWVNEDHG-UHFFFAOYSA-M sodium;2-(2-methylprop-2-enoyloxy)ethanesulfonate Chemical compound [Na+].CC(=C)C(=O)OCCS([O-])(=O)=O DEWNCLAWVNEDHG-UHFFFAOYSA-M 0.000 description 1
- AIWXQURDQHMMDO-UHFFFAOYSA-M sodium;hydrogen sulfite;propan-2-one Chemical compound [Na+].CC(C)=O.OS([O-])=O AIWXQURDQHMMDO-UHFFFAOYSA-M 0.000 description 1
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- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
- C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J131/00—Adhesives 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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
- C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09J131/04—Homopolymers or copolymers of vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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Abstract
一種乙烯基酯/乙烯共聚物之水性分散體,係藉由使包括乙烯基酯、乙烯及聚乙烯醇安定化系統之單體混合物進行乳液共聚合反應而製備,該聚乙烯醇安定化系統基本上由下述成分所組成:(a)基於單體總重之0.5至3重量%之具有水解度至少98莫耳%之第一聚乙烯醇,及(b)基於單體總重之1至4重量%之具有水解度為85至90莫耳%且重量平均分子量至少為85,000克/莫耳之第二聚乙烯醇。
Description
本發明係關於乙烯基酯/乙烯共聚物之水性分散體(aqueous dispersions)以及有關其於黏合劑配方中之用途。
含有乙烯基酯及乙烯之共聚物的水性分散體已充分悉知可用於製造用於木材、紙類及包裝工業中之黏合劑。基於此等用途,一般係於含有聚合起始劑及水可溶保護膠體尤其是藉由使聚乙酸乙醯酯水解所衍生之聚乙烯醇之水性介質中使共聚單體(comonomer)聚合。所得乳液聚合物接著可與部分或完全水解之聚乙烯醇一起調配而獲得具有各種性質之黏合劑組成物。
例如,美國專利號3,827,996揭示一種製備乙烯基酯聚合物之安定水性分散體,係在水性介質中,使乙烯基酯及乙烯在衍生自聚乙酸乙烯酯之部分水解之聚乙烯醇存在下共聚合,其中該聚乙烯醇具有約5至7莫耳%之平均乙酸乙烯酯含量,且基本上係由含有不少於0.5莫耳%且不多於16莫耳%之乙酸乙烯酯之聚乙烯醇分子所組成,且存在量係基於乙烯基酯重量之約2至10重量%。在實施例1中,該聚乙烯醇為具有乙酸乙烯酯含量為0.5至1莫耳%之聚乙烯醇與具有乙酸乙烯酯含量為12至16莫耳%之聚乙烯醇之摻合物。
美國專利號4,521,561揭示一種乙酸乙烯酯/乙烯共聚物乳液,其
包括由乙酸乙烯酯及乙烯在聚乙烯醇安定化系統存在下進行乳液聚合所製得之共聚物之水性膠體分散體,該聚乙烯醇安定化系統具有8至10莫耳%之乙酸乙烯酯殘留量,尤其包括具有3至6莫耳%乙酸乙烯酯含量之聚乙烯醇與具有10至14莫耳%乙酸乙烯酯含量之聚乙烯醇,以可產生8至10莫耳%之平均乙酸乙烯酯殘留量之比例混合之混合物。當該等乳液與部分或完全水解之聚乙烯醇摻合時,據稱可提供具有增進之塑化劑增稠性之黏合劑組成物。
美國專利號5,143,966揭示一種乙酸乙烯酯-乙烯共聚物乳液,係藉由使乙酸乙烯酯及乙烯在聚乙烯醇安定化系統存在下進行水性乳液共聚合而製備,該聚乙烯醇安定化系統基本上係由下述所構成:(a)0.2至1.5重量%之低分子量之部分(85-90莫耳%)水解之聚乙烯醇,(b)0.5至2.5重量%之中等分子量之部分(85-90莫耳%)水解之聚乙烯醇,及(c)1至4重量%之中度分子量及/或高分子量之完全(98-99+莫耳%)水解之聚乙烯醇,其重量百分比係基於乙酸乙烯酯單體重量。
美國專利號5,633,334揭示一種製備包括70至95重量%乙烯基酯及5至30重量%乙烯之乳液聚合物之方法,該聚合係在2至8重量%之保護膠體存在下進行,該保護膠體係由1至3重量%之80%經水解聚乙烯醇、0至2重量%之88%經水解之聚乙烯醇及1至3重量%之96%經水解之聚乙烯醇所組成,該摻合物具有85至88%之平均水解度。依據該等實施例中提出之數據,96%經水解聚乙烯醇(3.5至4重量份)含量越高及80%經水解聚乙烯醇(1至1.5重量份)含量越低,則乳液之塑化劑反應降低。
如前述某些參考文獻所述,用於黏合劑配方中之乙烯基酯/乙烯共聚物之安定化水性分散體之一重要性質,為當其與既定量塑化劑如鄰苯二甲酸二異丁酯(DiBP)混合時之其塑化劑反應或分散體黏度增加。此性質通常描述為黏度增加比(VIR,Viscosity Increasing Ratio)且係由添加特定量(5、10或15重量%)之DiBP後之分散體黏度除以純分散體黏度而決定。該性質具有重要性,係因為在實務上配方調配人員會以水來稀釋該共聚物分散體且添加塑化劑以產生所需黏度之
黏著劑,因而使得具有高VIR之分散體可減少其所需之高成本且具潛在毒性之塑化劑之量。
依據本發明,現已發現具有高初始黏度及高VIR之乙烯基酯/乙烯共聚物之安定化水性分散體可藉由在聚乙烯醇安定化系統存在下進行聚合反應而製得,該聚乙烯醇安定化系統基本上由下述成分所組成:約0.5至約3重量%之完全(98-99+莫耳%)經水解之聚乙烯醇,及約1至約4重量%之部分(85-90莫耳%)經水解且具有中等分子量及/或高分子量之聚乙烯醇,該等百分比係基於共聚物中存在之單體總重。較為所需地,該分散體具有低的甲醛含量及較大粒徑。
因此,一方面,本發明有關一種乙烯基酯/乙烯共聚物之水性分散體,係藉由使包括乙烯基酯、乙烯及聚乙烯醇安定化系統之單體混合物進行乳液共聚合反應而製備,該聚乙烯醇安定化系統基本上由下述成分所組成:(a)基於單體總重之約0.5至約3重量%之具有水解度至少98莫耳%之第一聚乙烯醇,及(b)基於單體總重之約1至約4重量%之具有水解度為約85至約90莫耳%且重量平均分子量至少為85,000克/莫耳之第二聚乙烯醇。
會較為便利合宜地,該安定化系統含有約1至約2重量%之該第一聚乙烯醇及通常約2至約3重量%之第二聚乙烯醇。典型上,該第二聚乙烯醇具有約85,000至約125,000克/莫耳之重量平均分子量。
會較為便利合宜地,該分散體當與10重量%鄰苯二甲酸二異丁酯混合時具有至少7之黏度增加比(VIR)。
會較為便利合宜地,該分散體在55%固體成分及25℃時具有至少4000毫帕.秒(mPas)之黏度。
一具體例中,該分散體含有少於10每百萬份(ppm)重量之甲醛及少於0.5重量ppm(ppmw)之界面活性劑。
典型上,該分散體之平均粒徑係介於約2至約10μm之間。
會較為便利合宜地,該共聚物含有自約5至約25重量%,如約10
至約20重量%,例如自約14至約16重量%之衍生自乙烯之單元。
一具體例中,該乙烯基酯包括C1-C13飽和羧酸之乙烯基酯,尤其是乙酸乙烯酯。
本文所描述之乙烯基酯/乙烯共聚物之安定化水性分散體具有可誘使分散體使用作為製造一般目的黏著劑中之黏合劑之高初始黏度及高黏度增加比(VIR)。
本文所稱之該“黏度增加比(Viscosity Increasing Ratio,VIR)”值係由添加既定量(10重量%)之鄰苯二甲酸二異丁酯(DiBP)後之分散體黏度除以純分散體黏度而決定。尤其,本分散體當與10重量%之DiBP混合時具有至少7之VIR。
本發明之乙烯基酯/乙烯共聚物係藉由使包括乙烯基酯、乙烯及一或多種選用之共聚單體(co-monomers)及特定之聚乙烯醇安定化系統之單體混合物進行乳液聚合反應而製備。
所用之乙烯基酯一般為具有1至13個碳原子,典型為2至8個碳原子之飽和羧酸之乙烯基酯,尤其是乙酸乙烯酯。該乙烯基酯之一般存在量,基於單體總重,係介於約75重量%及約95重量%之間。該乙烯成分之存在量通常為單體總重之自約5至約25重量%,如自約10至約20重量%,例如自約14至約16重量%。
除了乙烯基酯及乙烯以外,該單體混合物亦可包含添加一種或多種官能性單體(functional monomers)以改良最終共聚物分散體之性質。此等視情況存在之官能性共聚單體可包含乙烯基不飽和酸,如單-或二-羧酸、磺酸、膦酸(phosphonic acids)。在游離酸的位置,亦可使用其鹽,較佳者為鹼金屬鹽或銨鹽。此類型之視情況之官能性共聚單體實例包含丙烯酸、甲基丙烯酸、巴豆酸、馬來酸、富馬酸、衣康酸、乙烯基磺酸、乙烯基膦酸、苯乙烯磺酸、馬來酸及/或富馬酸與鏈長C1-C18之單元脂族飽和醇之單酯、及衣康酸與鏈長C1-C18之單元脂族飽和醇之單酯、以及其鹼金屬鹽及銨鹽、或磺基烷醇之(甲基)丙
烯酸酯,其實例為2-磺基乙基甲基丙烯酸鈉。
其他類型之適宜之選用官能性共聚單體包含具有至少一個醯胺基、環氧基、羥基、三烷氧基矽烷基或羰基知乙烯基不飽和共聚單體。尤其適宜者為乙烯基不飽和環氧化合物,如甲基丙烯酸縮水甘油酯或丙烯酸縮水甘油酯。亦適宜者為羥基化合物,包含甲基丙烯酸及丙烯酸C1-C9羥基烷酯,如丙烯酸及甲基丙烯酸之2-羥基乙酯、2-羥基丙酯或2-羥基丁酯。其他適宜之官能性共聚單體包含如二丙酮丙烯醯胺及丙烯酸乙醯基乙烯氧基乙酯及甲基丙烯酸乙醯基乙烯氧基乙酯;及乙烯性不飽和羧酸之醯胺如丙烯醯胺或甲基丙烯醯胺之化合物。
不應併入本文所用之乙烯基酯/乙烯共聚物中之一類型官能性共聚單體包括含有在自含有該共聚物之組成物形成塗層或黏著層時會產生甲醛之可交聯基團之任何共聚單體。因此,該共聚物分散體中之乙酸乙烯酯/乙烯共聚物應實質上不含此共聚單體,該共聚單體包含如N-羥甲基丙烯醯胺(NVA)或甚至是N-羥甲基丙烯醯胺之低甲醛變體如NMA-LF之一般交聯劑。
選用之官能性共聚單體可以基於共聚物中主要共聚單體總重之至多約5重量%之量併入本文所用之乙酸乙烯酯/乙烯乳液共聚物中。更好,選用之官能性共聚單體可包括基於共聚物中主要共聚單體總重之自約0.5至約2重量%之量。
用以製造本發明共聚物分散體之安定化系統為實質上包括下述成分之兩成分系統:(a)基於單體總重之約0.5至約3重量%,如含約1至約2重量%之具有水解度至少98莫耳%之第一聚乙烯醇,及(b)基於單體總重之約1至約4重量%,如約2至約3重量%之具有水解度為約85至約90莫耳%且重量平均分子量至少為85,000克/莫耳,如至少約85,000至約125,000克/莫耳之第二聚乙烯醇。具有水解度至少98莫耳%之市售聚乙烯醇之一實例為由Sekisui化學股份有限公司提供之Celvol 107。具有水解度約85至約90莫耳%且重量平均分子量至少為85,000克/莫耳之市售聚乙烯醇之一實例為亦由Sekisui化學股份有限公司提供之Celvol 523。
本文所述之安定化共聚物分散體可使用可產生呈水性乳膠形態之聚合物分散體製劑之乳液聚合程序製得。此類型之水性聚合物分散體之製劑已充分悉知且已描述於多數例中且因此為熟知本技藝者所悉知。此程序描述於例如美國專利號5,633,334及聚合物科學及工程百科全書(Encyclopedia of Polymer Science and Engineering),卷8,第659頁之後(1987)。該兩公開文獻之揭示全文併入本文供參考。
聚合反應可以任何本身已知之方式以不同單體組合以一、二或多階段進行,獲得具有均質或非均質如芯殼或半球體形態之顆粒之聚合物分散體。可利用任何反應器系統如批料、迴路、連續、級聯(cascade)反應器等。
聚合反應溫度通常在約20℃至約150℃之範圍,更好自50℃至約120℃。聚合反應若適當通常在加壓下進行,較好自約2至約150巴(bar),更好自約5至約100巴。
在涉及例如乙酸乙烯酯/乙烯共聚物分散體之典型之聚合程序中,可在水性介質中在至多約120巴之壓力下,在一或多種起始劑存在下,使乙酸乙烯酯、乙烯、安定化系統及其他共聚單體聚合。聚合反應容器中之水性反應混合物可藉由適當緩衝劑維持在pH約2至約7。
組合數種聚合成分亦即安定化系統、共聚單體、觸媒系統成分等之方式可廣泛變化。通常,可先在聚合反應容器中以隨後欲添加至容器中之各種其他聚合成分先形成含有至少部分安定化系統之水性介質。
共聚單體可連續、間歇或以單次饋入添加欲使用之全體量的共聚單體而添加至聚合反應容器中。共聚單體可以純單體使用或可呈預混合乳液之形式使用。作為共聚單體之乙烯可泵入聚合反應容器中且其內可維持在適當壓力。
如所述,乙烯基不飽和單體之聚合反應通常在至少一種用於該等共聚單體之自由基聚合反應之起始劑存在下進行。製備該分散體期間,用於該自由基聚合反映且用以起始及持續聚合反應之適宜起始
劑,包含可在異相(heterophase)系統中起始自由基水性聚合反應之悉知起始劑。該等起始劑可為過氧化物如鹼金屬及/或銨之過氧硫酸氫鹽、或偶氮化合物,更好為水可溶性偶氮化合物。
較佳具體例中,使用氧化還原起始劑。此等起始劑實例包含氧化成分如第三丁基過氧化物及/或過氧化氫與還原劑如硫化合物組合、或與抗壞血酸或與還原糖組合,該硫化合物之實例為羥基甲烷磺酸之鈉鹽、Brüggolit FF6及FF7、亞硫酸鈉、亞硫酸氫鈉、硫代硫酸鈉及丙酮-亞硫酸氫鈉加成物。
該方法中使用之起始劑或起始劑組合之量可在一般用於異相系統中之水性聚合之範圍內變化。通常所用起始劑之量將不超過欲共聚合之共聚單體總量之5重量%。所用起始劑基於欲共聚合之共聚單體總量之量較好為0.05至2.0重量%。
本文中,可使起始劑總量包含在聚合開始時饋入至該反應器之最初饋入物中。然而,較好在開始時最初饋入物包含一部分之起始劑,且剩餘在開始起始聚合後以一或多步驟或連續添加。亦可使用種晶乳膠例如以約聚合混合物之約0.5至約15重量%起始該乳液聚合。
本文所製備之共聚物分散體在55%固體成分及25℃下,通常具有以布魯克菲爾德(Brookfield)黏度計以適當轉子測量之至少4,000mPas,如約4,000至約20,000 mPas之黏度。黏度可藉由添加增稠劑及/或水至共聚物分散體中而調整。適當增稠劑可包含聚丙烯酸酯或聚胺基甲酸酯,如Borchigel L75®及Tafigel PUR 60®。或者,該共聚物分散可體實質上不含增稠劑。
聚合反應後,所得水性共聚物分散體之固體含量可藉由添加水或蒸餾移除水而調整至所需程度。通常,聚合後之聚合物固體含量之所需程度係聚合物分散體總重之自約40重量%至約70重量%,更好自約45重量%至約55重量%。
當調配成黏著劑時,本文所述之該水性乙烯基酯/乙烯共聚物分散體可與一般用於製造以分散體為主之黏著劑之添加劑組合。適宜添加劑包含例如成膜助劑如石油溶劑油(white spirit)、Texanol®、TxiB®、
丁基甘醇、丁基二甘醇、丁基二丙二醇、及丁基三丙二醇、甲苯;可塑劑如鄰苯二甲酸二甲酯、鄰苯二甲酸二丁酯、鄰苯二甲酸二異丁酯、己二酸二異丁酯、Coasol B®、Plastilit 3060®及Triazetin®;濕潤劑如AMP90®、TegoWet.280®、Fluowet PE®;增稠劑如聚丙烯酸酯或聚胺基甲酸酯,如Borchigel L759®及Tafigel PUR 60®;消泡劑如礦物油消泡劑或矽氧消泡劑;紫外線(UV)保護劑如Tinuvin 1130®,隨後添加之安定化聚合物如聚乙烯醇或纖維素醚,及一般調配黏著劑之典型類型之其他添加劑及助劑。
最終以分散體為主之黏著劑中之該等添加劑之分率可為基於該分散體之至多25重量%,較好2至15重量%,且尤其是5至10重量%。
可使用本發明黏著劑黏合之適宜基材實例包含金屬、塑膠、塗料表面、紙、織物、不織布或天然物質如木材。欲黏合之基材可帶有吸附性表面或疏水性表面。吸附性表面之實例為紙,包含紙板及卡紙及其他纖維片。疏水性表面實例為聚合物薄膜(如聚酯薄膜、聚烯烴薄膜如聚丙烯或聚乙烯,例如聚苯乙烯薄膜、乙酸酯薄膜)或具有UV清漆塗層之紙。實務上可有任何所需組合。本發明現將參考下列非限制性實施例更詳細加以說明。
於配備攪拌器之28升加壓容器中饋入下列:
.6.7公斤水
.5克乙酸鈉
.Celvol 107或205(量及種類如表1所示)
.Celvol 523(量如表1所示)
.Orotan 850ER聚羧酸分散劑(量如表1所示)
.45克磷酸(85%於水中)
.1克氯化鐵(III)(40%於水中)
將容器排空並沖入氮氣,打開攪拌器且於容器中饋入下列:
.6公斤乙酸乙烯酯
.2.3公斤乙烯
於兩個分別之添加容器中饋入下列之溶液:
容器1:還原劑
.0.6公斤水
.28克Brueggolit FF6®(有機次磺酸衍生物之鈉鹽)
.9克乙酸鈉,及
容器2:氧化劑
.0.6公斤水
.46克第三丁基過氧化物(70%於水中)
聚合反應在85℃藉由以240分鐘之期間添加各還原劑及氧化劑至反應器中而進行,且同時在100分鐘期間添加6公斤乙酸乙烯酯。所得批料移至後處理容器中,於該處藉由隨後以15分鐘期間,自另一添加容器將下列溶液添加於該後處理容器中而對該批料進行後處理:
容器3:還原劑
.0.2公斤水
.8克Brueggolit FF6®
.7克碳酸氫鈉,及
容器4:氧化劑
.0.1公斤水
.3克第三丁基過氧化物(70%於水中)
.7克過氧化氫(35%於水中)
添加5克消泡劑Agitan DF 6575 GM後,將該批料排放至容器中且將固體量調整製55%。接著測試各批料之最初黏度及在10重量%DiBp可塑劑之VIR且結果概述於表1。
重複實施例11之製程,但主要聚合步驟期間之氧化劑及還原劑之量增加如下:
容器1:還原劑
.0.68公斤水
.31.5克Brueggolit FF6®(有機次磺酸衍生物之鈉鹽)
.10.1克乙酸鈉,及
容器2:氧化劑
.0.68公斤水
.51.8克第三丁基過氧化物(70%於水中)
後處理期間使用之氧化劑及還原劑量與實施例11相同。
結果再次概述於表1。
使實施例11及11(重複)之產物進行下列測試,與市售黏著劑Celvolit® CP 149進行比較且結果概述於表2及3。
.固體含量
.耐熱性-此測試涉及對第一紙片施加75μm厚之相關黏著劑塗層且接著藉助輥立即將該第一紙片積層至第二紙片上。使該積層物在20℃乾燥至少24小時後,自該積層物切出2.5公分寬之測試紙條並置於烘箱中。將各積層測試紙條之一紙片夾住且將另一紙片連接至200克砝碼上,將烘箱之溫度以每30分鐘5℃之速度自30℃開始升溫。留意黏著劑不再將紙片黏合在一起且因此砝碼掉落之溫度(180°角剝離)且顯示於表2。
.最初及各種靜置時間後之在25℃之布魯克菲爾德黏度
.以10% DiBP可塑劑之黏度反應
.濕處黏及設置在Fipago上-而實施例11/10%DiBP分散體以4.71%蒸餾水稀釋至7200mPas且實施例11(重複)/10% DiBP分散體以4.32%蒸餾水稀釋至7160mPas。在此測試中,對紙片施加100μm厚之相關黏著劑塗層,且10秒後,藉助輥將該紙片積層於卡紙片上。在指定之關閉時間(在1秒開始)後,將連接在該紙片上之鐘擺釋放且測量自該卡紙分離該紙片所需之力(90°角剝離)。藉由逐漸增加該關閉時間且測量剝
離力,可決定黏著劑濕觸黏隨時間之發展。
.以Physica Rheolab MC 100、MS-Z4、DIN/SM 0-1000 1/s,斜度1-5-1分鐘測量流變學流動曲線-而Celvolit/DiPB分散體以4.27%蒸餾水稀釋至5510mPas,實施例11/10%DiBP分散體以4.71%蒸餾水稀釋至7200mPas且實施例11(重複)/10% DiBP分散體以4.32%蒸餾水稀釋至7160mPas。
.使用Malvern Mastersizer Microplus測量粒徑分佈
.對下列塑膠基板Genotherm GA 66(PVC)、Melinex(PET)及Acetat N 50(纖維素乙酸酯)之黏附-使測試涉及於紙或卡紙上施加75-100μm厚之相關黏著劑濕塗層且接著藉助輥立即將塑膠基材薄膜積層於紙片上。所得積層物儲存在天候控制室內至少3天且接著藉由手動剝離測試(90°及180°剝離)測定該積層物之黏著性質。表3所給之半定量結果使用下列範圍:100意指紙片纖維完全剝離,0意指基材間無黏著性且0跳動(0 zipping)意指該基材不具黏著性且不具凝聚性。
Claims (15)
- 一種乙烯基酯/乙烯共聚物之水性分散體,係藉由使包括乙烯基酯、乙烯及聚乙烯醇安定化系統之單體混合物進行乳液共聚合反應而製備,該聚乙烯醇安定化系統基本上由下述成分所組成:(a)基於單體總重之0.5至3重量%之具有水解度至少98莫耳%之第一聚乙烯醇,及(b)基於單體總重之1至4重量%之具有水解度為85至90莫耳%且重量平均分子量至少為85,000克/莫耳之第二聚乙烯醇。
- 如申請專利範圍第1項之分散體,其中該安定化系統含有基於單體混合物總重之1至2重量%之該第一聚乙烯醇。
- 如申請專利範圍第1或2項之分散體,其中該安定化系統含有基於單體混合物總重之2至3重量%之該第二聚乙烯醇。
- 如前述申請專利範圍任一項之分散體,其中該第二聚乙烯醇具有85,000至125,000克/莫耳之重量平均分子量。
- 如前述申請專利範圍任一項之分散體,當該分散體與10重量%之鄰苯二甲酸二異丁酯混合時具有至少7之黏度增加比(VIR)。
- 如前述申請專利範圍任一項之分散體,其在55%固體成分及25℃時具有至少4000毫帕.秒(mPas)之黏度。
- 如前述申請專利範圍任一項之分散體,其含有少於10重量ppm之甲醛。
- 如前述申請專利範圍任一項之分散體,其含有少於0.5重量ppm之界面活性劑。
- 如前述申請專利範圍任一項之分散體,其具有介於2至10 μm之平均粒徑。
- 如前述申請專利範圍任一項之分散體,其中該共聚物含有自5至25重量%之衍生自乙烯之單元。
- 如前述申請專利範圍任一項之分散體,其中該共聚物含有自10至20重量%之衍生自乙烯之單元。
- 如前述申請專利範圍任一項之分散體,其中該共聚物含有自14至16重量%之衍生自乙烯之單元。
- 如前述申請專利範圍任一項之分散體,其中該乙烯基酯包括C1-C13飽和羧酸之乙烯基酯。
- 如前述申請專利範圍任一項之分散體,其中該乙烯基酯包括乙酸乙烯酯。
- 一種如前述申請專利範圍任一項之分散體之用途,係用於黏合劑配方中。
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US9382341B2 (en) * | 2012-09-27 | 2016-07-05 | Wacker Chemical Corporation | Carpet coating composition |
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