TWI421261B - 防火性共聚物及包含其之阻燃熱塑性樹脂組成物 - Google Patents
防火性共聚物及包含其之阻燃熱塑性樹脂組成物 Download PDFInfo
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Description
本發明係關於一種防火性共聚物及包含其之阻燃熱塑性樹脂組成物。本發明尤指一種防火性共聚物及包含其之阻燃熱塑性樹脂,其中此防火性共聚物包含一具有特定結構之含乙烯基之磷單體以及一丙烯酸單體。
一般而言,丙烯酸單體樹脂具有良好的透明度、耐候性、機械特性、以及極佳的熱穩定性。因此,丙烯酸單體樹脂已廣泛的適用在電子產品、顯示器構件、光學材料、建築構件、以及汽車構件上,且亦同時應用在常見的模具上。丙烯酸樹脂尤其具有良好的抗刮性,故應用在電器或電子產品之外部構件上逐漸增長。然而,丙烯酸樹脂基本上是為一種易燃物質,造成丙烯酸樹脂的應用範圍有所限制。
即使提出混合一添加劑型阻燃劑之方法,以改善丙烯酸樹脂之阻燃性,然而為了要達到預設之阻燃性,仍必須混合大量的阻燃劑,且此方法亦因阻燃性的溶解而具有外觀不佳的問題。再者,此方法亦會造成以丙烯酸為主的樹脂,其透明度、耐熱性、及機械特性劣化等問題。
因此,提出在聚合物鏈中添加磷阻燃劑之方法,以解決這些問題。
美國專利第4,035,571號揭露一種防火性共聚物,其係由不飽和單體、二(烴基)乙烯基膦酸酯(bis(hydrocarbyl)vinyl phosphonate)、以及丙烯酸或甲基丙烯酸所共聚而成。
然而,此方法面臨必須使用大量的二(烴基)乙烯基膦酸酯才能得到足夠阻燃性之問題,這會造成機械特性不佳且亦造成應用上的限制。
因此,本發明之發明者發展出一種防火性共聚物及包含其之阻燃熱塑性樹脂組成物,其是將具有特定結構之含乙烯基之磷單體(磷含量為18至30重量百分比)與甲基丙烯酸單體共聚而成,除了能維持機械特性外,亦具有相同良好的防火性、透明度、以及抗刮性。
本發明之主要目的係在提供一種具有良好阻燃性之熱塑性樹脂組成物。
本發明之另一目的係在提供一種具有良好透明度及抗刮性且同時具有良好阻燃性之熱塑性樹脂組成物。
本發明之再一目的係在提供一種對生態環境無害之熱塑性樹脂組成物,當其燃燒時不會產生如戴奧辛、呋喃、或鹵化氫氣體等有毒氣體。
本發明之更一目的係在提供一種物理特性協調性良好之熱塑性樹脂組成物。
本發明其他的目的及優點,可透過揭露的內容及申請專利範圍而更加明瞭。
本發明一實施態樣係在提供一種防火性共聚物,其包含重複單元(a)約80至99重量百分比之甲基丙烯酸((meth)acrylic)單體;以及(b)約1至20重量百分比之含乙烯基(vinyl)之磷(phosphorous)單體。
在本發明示例性實施例中,含乙烯基之磷單體(b)可包含約18至30重量百分比之磷。
本發明另一實施態樣係關於一種防火性共聚物之製備方法,此方法包括:在一自由基起始劑之存在下,於溫度約60至90℃下,共聚合一甲基丙烯酸單體及一含乙烯基之磷單體1至6小時。
再者,本發明提供一種包含前述防火性共聚物之阻燃熱塑性樹脂組成物。此樹脂組成物,以一3mm厚之測試樣品經Nippon Denshoku霧度計測量後,樹脂組成物之霧度可為2%或以下;經JIS K 5401測量後,樹脂組成物之鉛筆硬度約為2H;以一1/8"厚之測試樣品經ASTM D-256測量後,樹脂組成物之艾氏(Izod)衝擊強度約為1.3 kgf.cm/cm或以上;以1/4"厚之測試樣品經ASTM D-1525測量後,樹脂組成物之耐熱度(VST)約為97℃或以上;且以2.0mm厚之測試樣品經UL 94測試後,樹脂組成物之阻燃性為V-2、V-1或V-0。
本發明之樹脂組成物可更包括一添加物,而此添加物係選自由抗衝擊改質劑(impact modifier)、抗滴垂劑(anti-dripping agent)、酚樹脂(phenol resin)、阻燃劑(flame
retardant)、助阻燃劑(flame retardant aid)、潤滑劑(lubricant)、抗氧化劑(antioxidant)、塑化劑(plasticizer)、熱穩定劑(thermal stabilizer)、光穩定劑(light stabilizer)、色素(pigment)、染料(dye)、無機填充劑(inorganic filler)及其混合物所組成之群組。
於本發明示例性實施例中,抗衝擊改質劑之使用量,可佔100重量份之防火性共聚物之約30重量份或以下。而橡膠改性接枝共聚物可作為抗衝擊改質劑。
於本發明示例性實施例中,抗滴垂劑之使用量,可佔100重量份之防火性共聚物之約2重量份或以下。
在一實施例中,酚樹脂之使用量,可佔100重量份之防火性共聚物之約1至20重量份。
於另一實施例中,此樹脂組成物以一3mm厚之測試樣品經Nippon Denshoku霧度計測量後,樹脂組成物之霧度可約為17%或以下;經JIS K 5401測量後,樹脂組成物之鉛筆硬度約為2H;以一1/8"厚之測試樣品經ASTM D-256測量後,樹脂組成物之艾氏衝擊強度約為1.3 kgf.cm/cm或以上;以1/4"厚之測試樣品經ASTM D-1525測量後,樹脂組成物之耐熱度(VST)為約95℃或以上;且以2.0mm厚之測試樣品經UL 94測試後,樹脂組成物之阻燃性為V-2、V-1或V-0。
再者,本發明提供一種此樹脂組成物之模具。
本發明之防火性共聚物包括重複單元(a)甲基丙烯酸單體以及(b)含乙烯基之磷單體。
甲基丙烯酸單體(a)之示例可包括但不限制於丙烯酸酯(acrylate)、丙烯酸烷酯(alkyl acrylate)、甲基丙烯酸酯((meth)acrylate)、甲基丙烯酸烷酯(alkyl(meth)acrylate)、或甲基丙烯酸。這些可單獨或相互混合使用。較佳為甲基丙烯酸單體可為甲基丙烯酸酯((meth)acrylate)、甲基丙烯酸甲酯(methyl(meth)acrylate)、甲基丙烯酸乙酯(ethyl(meth)acrylate)、甲基丙烯酸丙酯(propyl(meth)acrylate)、甲基丙烯酸丁酯(butyl(meth)acrylate)、甲基丙烯酸戊酯(pentyl(meth)acrylate)、甲基丙烯酸環己酯(cyclohexyl(meth)acrylate)、甲基丙烯酸正己酯(n-hexyl(meth)acrylate)、甲基丙烯酸環氧丙酯(glycidyl(meth)acrylate)、甲基丙烯酸((meth)acrylic acid)或其混合物。
含乙烯基之磷單體(b)可選自於如化學式1至4所示之化合物中之一者或多者。
(在上述化學式1至4中,R1
為氫或甲基,R2
及R3
係獨立為甲基或乙基,且n為0或1)。
化學式1所示之化合物例子可為二甲基乙烯基氧化膦(dimethylvinylphosphineoxide)、乙基甲基乙烯基氧化膦(ethylmethylvinylphosphineoxide)、二乙基乙烯基氧化膦(diethylvinylphosphineoxide)、二甲基2-甲基乙烯基氧化膦(dimethyl 2-methylvinylphosphineoxide)、乙基甲基2-甲基乙烯基氧化膦(ethylmethyl 2-methylvinylphosphineoxide)、二乙基2-甲基乙烯基氧化膦(diethyl 2-methylvinylphosphineoxide)、二甲基乙烯基次膦酸酯(dimethylvinylphosphinate)、乙基甲基乙烯基次膦酸酯(ethylmethylvinylphosphinate)、二乙基乙烯基次膦酸酯(diethylvinylphosphinate)、二甲基2-甲基乙烯基次膦酸酯(dimethyl 2-methylvinylphosphinate)、乙基甲基2-甲基乙烯基次膦酸酯(ethylmethyl 2-methylvinylphosphinate)、二乙基2-甲基乙烯基次膦酸酯(diethyl 2-methylvinylphosphinate)、二甲基乙烯基膦酸酯(dimethylvinylphosphonate)、乙基甲基乙烯基膦酸酯(ethylmethylvinylphosphonate)、二乙基乙烯基膦酸酯(diethylvinylphosphonate)、二甲基2-甲基乙烯基膦酸酯(dimethyl 2-methylvinylphosphonate)、乙基甲基2-甲基乙烯基膦酸酯(ethylmethyl 2-methylvinylphosphonate)、或二乙基2-甲基乙烯基膦酸酯(diethyl 2-methylvinylphosphonate)。
化學式2所示之化合物例子可為烯丙基二甲基氧化膦(allyldimethylphosphineoxide)、烯丙基甲基乙基氧化膦(allylmethylethylphosphineoxide)、烯丙基二乙基氧化膦(allyldiethylphosphineoxide)、2-甲基烯丙基二甲基氧化膦(2-methylallyldimethylphosphineoxide)、2-甲基烯丙基甲基乙基氧化膦(2-methylallylmethylethylphosphineoxide)、2-甲基烯丙基二乙基氧化膦(2-methylallyldiethylphosphineoxide)、烯丙基二甲基次膦酸酯(allyldimethylphosphinate)、烯丙基甲基乙基次膦酸酯(allylmethylethylphosphinate)、烯丙基二乙基次膦酸酯(allyldiethylphosphinate)、2-甲基戊基二甲基次膦酸酯(2-methylanyldimethylphosphinate)、2-甲基烯丙基甲基乙基次膦酸酯(2-methylallylmethylethylphosphinate)、2-甲基烯丙基二乙基次膦酸酯(2-methylallyldiethylphosphinate)、烯丙基二甲基膦酸酯(allyldimethylphosphonate)、烯丙基甲基乙基膦酸酯(allylmethylethylphosphonate)、烯丙基二乙基膦酸酯(allyldiethylphosphonate)、2-甲基烯丙基二甲基膦酸酯(2-methylallyldimethylphosphonate)、2-甲基烯丙基甲基乙基膦酸酯(2-methylallylmethylethylphosphonate)、或2-甲基烯丙基二乙基膦酸酯(2-methylallyldiethylphosphonate)。
化學式3所示之化合物例子可為乙烯基二甲基次膦酸酯(vinyldimethylphosphinate)、乙烯基乙基甲基次膦酸酯(vinylethylmethylphosphinate)、乙烯基二乙基次膦酸酯
(vinyldiethylphosphinate)、2-甲基乙烯基二甲基次膦酸酯(2-methylvinyldimethylphosphinate)、2-甲基乙烯基甲機乙基次膦酸酯(2-methylvinylmethylethylphosphinate)、2-甲基乙烯基二乙基次膦酸酯(2-methylvinyldiethylphosphinate)、乙烯基二甲基膦酸酯(vinyldimethylphosphonate)、乙烯基乙基甲基膦酸酯(vinylethylmethylphosphonate)、乙烯基二乙基膦酸酯(vinyldiethylphosphonate)、2-甲基乙烯基二甲基膦酸酯(2-methylvinyldimethylphosphonate)、2-甲基乙烯基乙基甲基膦酸酯(2-methylvinylethylmethylphosphonate)、2-甲基乙烯基二乙基膦酸酯(2-methylvinyldiethylphosphonate)、二甲基乙烯基磷酸酯(dimethylvinylphosphate)、乙基甲基乙烯基磷酸酯(ethylmethylvinylphosphate)、二乙基乙烯基磷酸酯(diethylvinylphosphate)、二甲基2-甲基乙烯基磷酸酯(dimethyl 2-methylvinylphosphate)、乙基甲基2-甲基乙烯基磷酸酯(ethylmethyl 2-methylvinylphosphate)、或二乙基2-甲基乙烯基磷酸酯(diethyl 2-methylvinylphosphate)。
化學式4所示之化合物例子可為烯丙基二甲基次膦酸酯(allyldimethylphosphinate)、烯丙基乙基甲基次膦酸酯(allylethylmethylphosphinate)、烯丙基二乙基次膦酸酯(allyldiethylphosphinate)、2-甲基烯丙基二甲基次膦酸酯(2-methylallyldimethylphosphinate)、2-甲基烯丙基甲基乙基次膦酸酯(2-methylallylmethylethylphosphinate)、2-甲基烯丙基二乙基次膦酸酯(2-methylallyldiethylphosphinate)、
烯丙基二甲基膦酸酯(allyldimethylphosphonate)、烯丙基乙基甲基膦酸酯(allylethylmethylphosphonate)、烯丙基二乙基膦酸酯(allyldiethylphosphonate)、2-甲基烯丙基二甲基膦酸酯(2-methylallyldimethylphosphonate)、2-甲基烯丙基乙基甲基膦酸酯(2-methylallylethylmethylphosphonate)、2-甲基烯丙基二乙基膦酸酯(2-methylallyldiethylphosphonate)、烯丙基二甲基磷酸酯(allyldimethylphosphate)、烯丙基乙基甲基磷酸酯(allylethylmethylphosphate)、烯丙基二乙基磷酸酯(allyldiethylphosphate)、2-甲基烯丙基二甲基磷酸酯(2-methylallyldimethylphosphate)、2-甲基烯丙基乙基甲基磷酸酯(2-methylallylethylmethylphosphate)、或2-甲基烯丙基二乙基磷酸酯(2-methylallyldiethylphosphate)。
含乙烯基之磷單體(b)之結構中,較佳可包含約18至30重量百分比之磷,且更佳包含約20至29重量百分比之磷。若乙烯基磷化合物中所使用的磷含量少於約18重量百分比時,共聚物則無法具有足夠的阻燃性。再者,若乙烯基磷化合物中所使用的磷含量高於30重量百分比時,則可能造成相容性降低。
於本發明一實施例中,共聚物可包含約80至90重量百分比之甲基丙烯酸單體及約5至20重量百分比之含乙烯基之磷單體之重複單元。當含乙烯基之磷單體的使用量在上述範圍中時,可得到高阻燃性及良好的機械特性。且更佳為具有約85至95重量百分比之甲基丙烯酸單體及約5至15
重量百分比之含乙烯基之磷單體。
含乙烯基之磷單體(c)之較佳示例可為二甲基乙烯基膦酸酯(DMVP)。含乙烯基之磷單體(c)之製備方法已揭露在日本專利第3836459號,而此篇專利所有的內容皆可併入本發明以供參考。
本發明之防火性共聚物可使用一般的共聚合反應來製造,其中含乙烯基之磷單體是在自由基起始劑的存在下添加至甲基丙烯酸單體中。既然含乙烯基之磷單體具有可聚合之乙烯基基團,則含乙烯基之磷單體與甲基丙烯酸單體可一同形成主鏈。當共聚合時,可選擇添加一包含單體之不飽和基團,如芳香族乙烯基單體。在最後共聚物的重複單元可達到上述之比例之前,藉由添加包含單體之不飽和基團,可控制甲基丙烯酸單體及含乙烯基之磷單體的含量。
於本發明一實施例中,可將甲基丙烯酸單體及含乙烯基之磷單體添加至一反應器中,接著在起始劑的存在下,於約60至90℃下共聚合約1-6小時。
可適用的起始劑可為,但不限於:如過氧化苯甲醯(benzoyl peroxide, BPO)、過氧化二異丙苯(dicumylperoxide, DCP)、二-第三丁基過氧化物(di-tert-butylperoxide, DTBP)、偶氮二異丁腈(azobisisobutyronitrile, AIBN)、及其相似物之自由基起始劑。
本發明之防火性共聚物可使用在一般的丙烯酸樹脂中。例如,防火性共聚物可單獨使用、或與其他樹脂或添
加物混合作為熱塑性樹脂組成物,以改善衝擊強度及阻燃性。
本發明之阻燃熱塑性樹脂組成物視需要可更包含一抗衝擊改質劑。此抗衝擊改質劑可藉由將樹脂聚合物與乙烯基單體接枝製備而成。此抗衝擊改質劑的製備可藉由將一芳香族乙烯基單體及選擇性一可共聚合之單體,接枝共聚合至一橡膠聚合物上。
此橡膠可選自由以二烯為主(diene-based)之橡膠,如聚丁二烯橡膠(polybutadiene rubber)、聚(苯乙烯-丁二烯)橡膠(poly(styrene-butadiene)rubber)、及聚(丙烯腈-丁二烯)橡膠(poly(acrylonitrile-butadiene)rubber);添加氫至二烯橡膠之飽和橡膠;異戊二烯橡膠(isoprene rubber);丙烯酸橡膠(acrylic rubber);矽橡膠(silicon rubber);乙烯/丙烯橡膠(ethylene/propylene rubber);以及乙烯-丙烯-二烯三元共聚物(ethylene-propylene-diene terpolymer, EPDM)所組成之群組中至少一橡膠聚合物。在這些橡膠中,較佳為以二烯為主之橡膠,更佳為以丁二烯為主之橡膠。橡膠的含量較佳係佔100重量百分比之接枝共聚物樹脂之約5至約65重量百分比。若考慮到模具之衝擊強度及外觀,橡膠共聚物的平均粒徑較佳可為約0.1至4μm。抗衝擊改質劑之使用量,可佔100重量份之防火性共聚物之約30重量份或以下,較佳約0.1至20重量份,而更佳約0.5至15重量份。若抗衝擊改質劑的使用量高於30重量份時,則可能造成阻燃性降低。
本發明之阻燃熱塑性樹脂組成物視需要可更包含一抗滴垂劑。此抗滴垂劑可為一種添加劑,其在與樹脂混合之後能以纖維狀的型態存在於樹脂中。抗滴垂劑的例子可為以氟為主的樹脂,如聚四氟乙烯(polytetrafluoroethylene)、四氟乙烯(tetrafluoroethylene)及六氟乙烯(hexafluoropropylene)之共聚物、四氟乙烯及全氟烷基乙烯基醚(perfluoroalkylvinylether)之氟化碳樹脂(fluorinated carbon resin)、以及聚偏二氟乙烯(polyvinylidenefluoride)。
抗滴垂劑的使用量範圍較佳可佔100重量份之防火共聚物之約2重量份或以下。當抗滴垂劑的使用量超過2重量份時,可能造成衝擊強度的劣化。在以氟為主的樹脂中,最佳為聚四氟乙烯。
本發明之樹脂組成物可更包括一作為形成焦炭劑之酚樹脂。由於酚樹脂於低溫下(約300至450℃)可形成一焦炭,因此在燃燒初期可有效的在表面上形成焦炭。
酚樹脂一般可分為熱固型(resol-type)酚樹脂以及熱塑型(novolak-type)酚樹脂。在本發明中,熱塑型酚樹脂尤其較熱固型酚樹脂更佳。熱塑型酚樹脂可包括酚甲醛(phenol formaldehyde)熱塑樹脂、第三丁基酚甲醛(tertiarybutylphenol formaldehyde)熱塑樹脂、對辛基酚甲醛(para octylphenol formaldehyde)熱塑樹脂、對氰酚甲醛(para
cyanophenol formaldehyde)熱塑樹脂、酚類環氧(phenolepoxy)熱塑樹脂、及其混合物。熱塑型酚樹脂之平均分子量(Mw)較佳為約300至約10,000。
在100重量份之防火性共聚物中,酚樹脂可包含約1至約20重量份,且較佳約1至約10重量份。若酚樹脂的含量多於約20重量份,則會造成機械特性劣化,以及耐候性較差。
本發明之樹脂組成物可更包括一添加物,其係選自由阻燃劑(flame retardant)、助阻燃劑(flame retardant aid)、潤滑劑(lubricant)、抗氧化劑(antioxidant)、塑化劑(plasticizer)、熱穩定劑(thermal stabilizer)、光穩定劑(light stabilizer)、無機填充劑(inorganic filler)、色素(pigment)、及染料(dye)所組成之群組。這些添加物可單獨使用或相互混合使用。
阻燃劑可為一磷阻燃劑或一鹵素阻燃劑,且較佳為磷阻燃劑。磷阻燃劑的例子可包括紅磷(red phosphorus)、磷酸酯(phosphate)、膦酸酯(phosphonate)、次膦酸酯(phosphinate)、膦氧化物(phosphine oxide)、磷氮基化合物(phosphazene)、其金屬鹽類、及其相似物。其中,最佳為芳香族磷酸酯(phosphate)化合物。
阻燃劑較佳的使用範圍,係為在每100重量份之防火性共聚物中,阻燃劑為約30重量份或以下,且更佳約為0.1至15重量份,而最佳約為0.3至10重量份。若阻燃劑的含量多於30重量份,則可能會造成阻燃性及衝擊強度等機械性質劣化。
本發明之樹脂組成物可由一般製程方法來製造。例如,所有的成分及添加物可混合在一起然後經過擠壓機擠壓,而可製備成顆粒狀。
再者,本發明之樹脂組成物可使用在各種模具產品中。特別是,此樹脂組成物適用在電子或電器產品上,如家庭用電視、電腦、音響組、冷氣機、自動化辦公裝置、及其相似物。
本發明可參考下列的實施例而更佳明瞭,這些實施例僅為了說明的目的,而不應視為用來限制本發明的範圍,且本發明的範圍如申請專利範圍所定義。
將90重量份的甲基丙烯酸甲酯、10重量份之二甲基乙烯基膦酸酯(含22.76重量百分比的磷)、及0.3重量份之過氧化苯甲醯添加至一反應器中,於80℃下反應3小時。將所製成的聚合物至於真空烘箱中乾燥,得到一阻燃PMMA共聚物(VP-PMMA)。接著,將此VP-PMMA共聚物經過一雙螺旋擠壓機,於200至260℃下擠壓成顆粒狀物。使用一8 oz之射出成型機,在250℃下且活塞筒溫度為60℃時,將顆粒狀物製成測試模具。
實施例2的實施方法與實施例1相同,除了更添加5重量份之EXL-2602(甲基丙烯酸甲酯-丁二烯-丙烯酸共聚物)(MRC Co.製造)作為一抗衝擊改質劑。
實施例3的實施方法與實施例2相同,除了更添加0.5重量份之聚四氟乙烯(Mitsui-Dupont公司製造之鐵氟龍30J)作為一抗滴垂劑。
實施例4的實施方法與實施例1相同,除了更添加0.5重量份之聚四氟乙烯(Mitsui-Dupont公司製造之鐵氟龍30J)作為一抗滴垂劑。
比較例1的實施方法與實施例1相同,除了使用75重量份之不含二甲基乙烯基膦酸酯之習知PMMA共聚物(韓國LG Chem Co.製造之L-84)取代本發明之阻燃PMMA共聚物,且添加25重量份之間苯二酚二(2,6二甲基苯基磷酸酯)(resorcinol bis(2,6dimethylphenylphosphate),日本Daihachi Chemical Co.製造之PX-200)作為一阻燃劑。
比較例2的比較方法與比較例1相同,除了更添加5重量份之EXL-2602(甲基丙烯酸甲酯-丁二烯-丙烯酸共聚物)(MRC Co.製造)作為一抗衝擊改質劑。
比較例3的比較方法與比較例2相同,除了更添加0.5重量份之聚四氟乙烯(Mitsui-Dupont公司製造之鐵氟龍30J)作為一抗滴垂劑。
比較例4的比較方法與比較例1相同,除了更添加0.5重量份之聚四氟乙烯(Mitsui-Dupont公司製造之鐵氟龍30J)作為一抗滴垂劑。
利用下述方法測試比較例及實施例製造之測試模具之物理特性,而測試結果如下表1所示。
(1)霧度(%):霧度(%)的測量,是以一3mm厚之測試樣品經Nippon Denshoku霧度計測量而得。
(2)鉛筆硬度:在23℃及相對溼度為50%下暴露48小時後,使用JIS K 5401,測量10×10 cm2
的模具之鉛筆硬度。利用3B、2B、B、HB、F、H、2H、3H等測量其抗刮性。H越高表示抗刮性越佳,B越高表示抗刮性越差。
(3)艾氏衝擊強度:缺口艾氏衝擊強度之測量是使用ASTM D-256(1/8 inch, kgf.cm/cm)。
(4)耐熱度(VST):域克軟化溫度(Vicat Softening Temperature)的測量是在5 kgf負載(℃)下,使用ASTM D-1525(1/4" inch, kgf.cm/cm)測量而得。
(5)阻燃性:阻燃性的測量,以2.0 mm厚之測試樣品經UL 94測量而得。
如表1所示,實施例1因低霧度而具有良好的透明度、鉛筆硬度、及耐熱度。實施例2因其包含一抗衝擊改質劑而具有較低但已足夠的透明度,且具有良好均勻的物理特性,如衝擊強度及阻燃性。使用PTFE作為抗滴垂劑之實施例3至4,其物理特性有稍微的改變,且相較於實施例1至2,實施例3至4之防火性提升到V1及V0。反之,使用習知PMMA之比較例1至4,即使其具有與實施例1至4等量的磷,比較
例1至4仍具有較差的阻燃性(flame retardancy)及較差的抗燃性(flame resistance)。且其抗燃性亦大大的降低。
綜上所述,本發明揭露特定的較佳實施例,然本技術領域之通常知識者皆了解,各種改變及修飾均可在不偏離本發明之精神與範圍下進行,且本發明之精神與範圍應以申請專利範圍所定義為基準。
Claims (13)
- 一種防火性共聚物,其包括重複單元:(A)80至99重量百分比之甲基丙烯酸((meth)acrylic)單體;以及(B)1至20重量百分比之含乙烯基(vinyl)之磷(phosphorous)單體,其中該含乙烯基之磷單體係選自於如化學式2及4所示之化合物中之至少一者:
- 如申請專利範圍第1項所述之防火性共聚物,其中該含乙烯基之磷單體(B)包含18至30重量百分比之磷。
- 如申請專利範圍第1項所述之防火性共聚物,其中該甲基丙烯酸單體(A)係選自由甲基丙烯酸酯((meth)acrylate)、甲基丙烯酸甲酯(methyl(meth)acrylate)、甲基丙烯酸乙酯(ethyl(meth)acrylate)、甲基丙烯酸丙酯(propyl(meth)acrylate)、甲基丙烯酸丁酯(butyl(meth)acrylate)、甲基丙烯酸戊酯(pentyl(meth)acrylate)、甲基丙烯酸環己酯(cyclohexyl(meth)acrylate)、甲基丙烯酸正己酯 (n-hexyl(meth)acrylate)、甲基丙烯酸環氧丙酯(glycidyl(meth)acrylate)、甲基丙烯酸((meth)acrylic acid)及其混合物所組成之群組。
- 一種阻燃熱塑性樹脂組成物,其包括如申請專利範圍第1至3項中任一項所述之防火性共聚物。
- 如申請專利範圍第4項所述之阻燃熱塑性樹脂組成物,其中該樹脂組成物以一3mm厚之測試樣品經Nippon Denshoku霧度計測量後,該樹脂組成物之霧度為2%或以下;經JIS K 5401測量後,該樹脂組成物之鉛筆硬度為2H;以一1/8”厚之測試樣品經ASTM D-256測量後,該樹脂組成物之艾氏(Izod)衝擊強度為1.3kgf.cm/cm或以上;以1/4”厚之測試樣品經ASTM D-1525測量後,該樹脂組成物之耐熱度(VST)為97℃或以上;且以2.0mm厚之測試樣品經UL 94測試後,該樹脂組成物之阻燃性為V-2、V-1或V-0。
- 一種模具,其係使用如申請專利範圍第4項所述之阻燃熱塑性樹脂組成物所製成。
- 如申請專利範圍第4項所述之阻燃熱塑性樹脂組成物,其更包括至少一添加物,該添加物係選自由抗衝擊改質劑(impact modifier)、抗滴垂劑(anti-dripping agent)、酚樹脂(phenol resin)、阻燃劑(flame retardant)、助阻燃劑(flame retardant aid)、潤滑劑(lubricant)、抗氧化劑(antioxidant)、塑化劑(plasticizer)、熱穩定劑(thermal stabilizer)、光穩定劑(light stabilizer)、色素(pigment)、染 料(dye)、無機填充劑(inorganic filler)及其混合物所組成之群組。
- 如申請專利範圍第7項所述之阻燃熱塑性樹脂組成物,其中該抗衝擊改質劑之使用量,係佔100重量份之防火性共聚物之30重量份或以下。
- 如申請專利範圍第7項所述之阻燃熱塑性樹脂組成物,其中該抗滴垂劑之使用量,係佔100重量份之防火性共聚物之2重量份或以下。
- 如申請專利範圍第7項所述之阻燃熱塑性樹脂組成物,其中該酚樹脂之使用量,係佔100重量份之防火性共聚物之1至20重量份或以下。
- 如申請專利範圍第7項所述之阻燃熱塑性樹脂組成物,其中該樹脂組成物以一3mm厚之測試樣品經Nippon Denshoku霧度計測量後,該樹脂組成物之霧度為17%或以下;經JIS K 5401測量後,該樹脂組成物之鉛筆硬度為2H;以一1/8”厚之測試樣品經ASTM D-256測量後,該樹脂組成物之艾氏衝擊強度為1.3kgf.cm/cm或以上;以1/4”厚之測試樣品經ASTM D-1525測量後,該樹脂組成物之耐熱度(VST)為95℃或以上;且以2.0mm厚之測試樣品經UL 94測試後,該樹脂組成物之阻燃性為V-2、V-1或V-0。
- 一種模具,其係使用如申請專利範圍第7項所述之阻燃熱塑性樹脂組成物所製成。
- 一種防火性共聚物之製備方法,其包括:在一自由基起始劑之存在下,於60至90℃下,將一甲基丙烯酸單體與一含乙烯基之磷單體進行共聚合1至6小時。
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KR101653023B1 (ko) * | 2009-06-26 | 2016-08-31 | 다우 글로벌 테크놀로지스 엘엘씨 | 에폭시화 노볼락 함유 열가소성 조성물 |
CA2778120C (en) * | 2009-10-28 | 2016-10-25 | Dow Global Technologies Llc | Thermoplastic polyurethane composition with high insulation resistance |
CN101717469B (zh) * | 2009-12-10 | 2012-01-04 | 天津工业大学 | 一种阻燃丙烯腈共聚物及其制备方法 |
WO2011147068A1 (en) * | 2010-05-24 | 2011-12-01 | Dow Global Technologies Llc | HALOGEN-FREE, FLAME RETARDANT COMPOSITION COMPRISING CROSSLINKED SILANE-g-EVA |
KR101293787B1 (ko) | 2010-07-28 | 2013-08-06 | 제일모직주식회사 | 난연성 및 내열성이 우수한 투명 열가소성 수지 조성물 |
KR101351614B1 (ko) | 2010-11-05 | 2014-02-17 | 제일모직주식회사 | 난연 내스크래치성 폴리카보네이트 수지 조성물 |
KR101374360B1 (ko) | 2010-12-14 | 2014-03-18 | 제일모직주식회사 | 난연 내스크래치성 폴리카보네이트 수지 조성물 |
KR101411004B1 (ko) * | 2010-12-23 | 2014-06-23 | 제일모직주식회사 | 아크릴계 공중합체 수지 조성물 |
KR20130002789A (ko) | 2011-06-29 | 2013-01-08 | 제일모직주식회사 | 컬러필터용 감광성 수지 조성물 및 이를 이용한 컬러필터 |
TW201420614A (zh) * | 2012-11-20 | 2014-06-01 | Ind Tech Res Inst | 無鹵難燃壓克力樹脂及成形物件 |
KR101674990B1 (ko) | 2012-12-07 | 2016-11-10 | 제일모직 주식회사 | 컬러필터용 감광성 수지 조성물 및 이를 이용한 컬러필터 |
JP6740101B2 (ja) * | 2016-11-24 | 2020-08-12 | 丸善石油化学株式会社 | 難燃性組成物及びそれを含む難燃性基材並びに難燃性基材の製造方法 |
KR101872623B1 (ko) * | 2016-12-22 | 2018-06-29 | (주)협진화학 | 전도성 수성 난연 수지 조성물 및 이의 제조 방법 |
JP6918717B2 (ja) * | 2018-02-02 | 2021-08-11 | 丸善石油化学株式会社 | 難燃性組成物および難燃性基材 |
JP7294317B2 (ja) * | 2018-03-08 | 2023-06-20 | Tdk株式会社 | 樹脂組成物、樹脂シート、樹脂硬化物および樹脂基板 |
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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Family Cites Families (2)
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US4035571A (en) | 1974-06-10 | 1977-07-12 | Stauffer Chemical Company | Fire retardant copolymers |
JP3336459B2 (ja) | 1999-09-24 | 2002-10-21 | 株式会社ニコン | 露光装置、及び該装置を用いるデバイス製造方法 |
-
2007
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Non-Patent Citations (1)
Title |
---|
B. J. Muray,"Homo- and copolymerization of vinyl phosphates and phosphonates",Journal of Polymer Science Part C, Vol. 16 Issue. 4, pages 1869-1886., 1967 * |
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