TWI414571B - 光安定劑乳化組成物,及含有其之水系塗覆劑組成物 - Google Patents
光安定劑乳化組成物,及含有其之水系塗覆劑組成物 Download PDFInfo
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- TWI414571B TWI414571B TW094124759A TW94124759A TWI414571B TW I414571 B TWI414571 B TW I414571B TW 094124759 A TW094124759 A TW 094124759A TW 94124759 A TW94124759 A TW 94124759A TW I414571 B TWI414571 B TW I414571B
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- Prior art keywords
- light stabilizer
- group
- composition
- aqueous coating
- tert
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- 239000000203 mixture Substances 0.000 title claims abstract description 68
- 239000004611 light stabiliser Substances 0.000 title claims abstract description 67
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- 238000000576 coating method Methods 0.000 claims abstract description 28
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- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
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- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 3
- 239000003381 stabilizer Substances 0.000 claims description 13
- 125000002947 alkylene group Chemical group 0.000 claims description 12
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
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Description
本發明係有關賦予各種水系塗覆劑組成物耐候性之光安定劑乳化組成物以及含有該光安定劑乳化組成物之水系塗覆劑組成物。
自近年的環境問題,不使用有機溶劑,改使用水的塗覆劑組成物增加。如此的塗覆劑組成物,可列舉如水系塗料、水系油墨、光學用塗覆劑、纖維用藥劑、紙用藥劑等用途。
此等用途所使用的塗覆劑組成物,為提高所形成塗膜的耐候性,有添加紫外線吸收劑或自由基互補劑等的光安定劑的情形。但是此等光安定劑,通常由於為油溶性的有機化合物,添加於水系組成物時,已配合之光安定劑不能良好的分散,所形成的塗膜不具充分的耐候性為其問題。又,添加光安定劑之塗覆劑組成物於保管中光安定劑分離,有保存安定性差的問題。
所以,例如使用水系塗覆劑的用途,已知於聚合水系乳膠之步驟添加光安定劑。例如在專利文獻1揭示,將(甲基)丙烯酸酯單體(1)30~96重量%(質量%),特定的聚合性羧酸(2)的單獨或2種類以上的混合物1~10重量%(質量%),聚合性乳化劑(3)1~10重量%(質量%),二苯甲酮系或苯并三唑系聚合性光安定劑(4)1~20重量%(質量%),及1分子中至少具有1個環氧丙基之有機烷氧基矽烷化合物(5)1~30重量%(質量%)所成合計為100重量%(質量%)的單體混合物,與含鹼係數(PKb)為8以上的受阻胺系安定劑(HALS)(6)0.1~5重量%(質量%)之混合物乳化聚合所成之丙烯基聚矽氧乳膠組成物(如申請專利範圍第1項)。又,專利文獻2揭示,由(A)氟化烯烴系共聚物乳膠,及(B)含有(a)具有環烷基之聚合性不飽和單體5~70重量%(質量%),及(b)其他聚合性不飽和單體30~95重量%(質量%)所成單體混合物,與(c)紫外線吸收及/或光安定劑的混合物乳化聚合所得,含紫外線吸收劑及/或光安定劑之共聚合乳膠為特徵的水性塗料組成物(如申請專利範圍第1項)。又,專利文獻2的〔0016〕段落亦揭示水楊酸衍生物、二苯甲酮系、苯并三唑系等的紫外線吸收劑,或受阻胺衍生物等的光安定劑。
又,已知首先將光安定劑於水乳化或分散,再添加至水系乳膠之方法。例如專利文獻3揭示,含有光安定劑與乳化劑及水,含上述光安定劑20~85質量%為特徵之光安定性水性乳膠(如申請專利範圍第1項);上述光安定劑為三嗪系紫外線吸收劑為特徵之上述光安定劑水性乳膠(如申請專利範圍第3項)。該光安定性水性乳膠由於可在水性乳膠或水系塗覆劑組成物後添加,具有非常簡單,且容易發揮耐候性的功能的利點。
專利文獻1:日本特開平11-080486號公報申請專利範圍專利文獻2:日本特開2002-285045號公報申請專利範圍〔0016〕專利文獻3:日本特開2003-261759號公報申請專利範圍
但是,依專利文獻1及2,光安定劑可均勻的分散於水系乳膠內,由於光安定劑進入乳膠粒子內,有不能賦予所形成的塗膜充分耐候性的問題。
又上述專利文獻3,乳化或分散光安定劑的光安定劑水性乳膠的保存安定性差,不能長期間將光安定劑乳化於水中。因此,於水系塗覆劑組成物添加光安定劑乳化組成物時,此等被分離,不能均勻混合為其問題。又,使用配合該光安定劑水性乳膠的水系塗覆劑組成物形成塗膜時,塗膜的諸物性,例如光澤等有惡化的問題。
因此,本發明的目的為提供長期保存安定性良好,且添加於水系塗覆劑組成物,所形成的塗膜的諸特性亦不降低之光安定劑乳化組成物,以及含該光安定劑乳化組成物之水系塗覆劑組成物。
所以本發明者等由配合持有特定構造乳化劑,發現可提供長期保存安定性良好,添加於水系塗覆劑組成物,其所形成的塗膜之諸特性亦不降低的光安定劑乳化組成物,完成本發明。
即,本發明的光安定劑乳化組成物,係含有具反應2種以上的環氧烷之聚醚鏈之親水基,具碳數1~30的烴基的乳化劑之疏水基,與光安定劑及/或紫外線吸收劑(以下本說明書總稱為「光安定劑等」)、及水為其特徵。
又,本發明的水系塗覆劑組成物係含有上述光安定劑乳化組成物為其特徵。
又,本發明的塗裝品係具有由上述水系塗覆劑組成物所形成的塗膜為其特徵。
本發明的光安定劑乳化組成物,係長期保存安定性良好,且添加於水系塗覆劑組成物,所形成的塗膜的諸特性亦不降低,發揮可提高塗膜耐候性的效果。
本發明具反應2種以上的環氧烷之聚醚鏈之親水基,具碳數1~30的烴基的乳化劑之疏水基可舉例如聚環氧乙烷聚環氧丙烷嵌段或無規共聚物的烷基(或鏈烯基)醚、聚環氧乙烷聚環氧丙嵌段或無規共聚物的烷基(或鏈烯基)的苯醚、聚環氧乙烷聚環氧丙烷段或無規共聚物的多糖或單糖或低聚糖醚等醚類;聚環氧乙烷聚環氧丙烷嵌段或無規共聚物的脂肪酸酯,上述醚類之脂肪酸酯化反應物等的酯類。
此等化合物中,特別理想者為下述一般式(1)所示之化合物:RO-(AO)n
-H (1)(式中,R為碳數8~30的烴基,A為碳數2~4的2種以上的伸烷基,伸乙基為全體的50莫耳%以上,n為8~80之數)於上述一般式(1)R為碳數3~30的烴基。此等的烴基可列舉如烷基、鏈烯基、芳基等。
烷基可列舉如辛基、2-乙基己基、s-辛基、壬基、s-壬基、癸基、s-癸基、十一烷基、s-十一烷基、十二烷基、s-十二烷基、十三烷基、異十三烷基、s-十三烷基、十四烷基、s-十四烷基、十六烷基、s-十六烷基、硬脂基、廿烷基、廿二烷基、廿四烷基、卅烷基、2-丁基辛基、2-丁基癸基、2-己基辛基、2-己基癸基、2-辛基癸基、2-己基十二烷基、2-辛基十二烷基、2-癸基十四烷基、2-十二烷基十六烷基、2-十六烷基十八烷基、2-十四烷基十八烷基、甲基分枝-異硬脂基、廿烷基、廿一烷基、廿二烷基、廿二烷基、廿四烷基、廿五烷基、廿六烷基、廿七烷基、廿八烷基、廿九烷基等。
鏈烯基可列舉如辛烯基、壬烯基、癸烯基、十一烷烯基、十四烷烯基、油烯基等。
芳基可列舉如二甲苯基、枯基、三甲苯基、苯乙基、苯乙烯基、二苯甲基、三苯甲基、乙基苯基、丙基苯基、丁基苯基、戊基苯基、己基苯基、十一烷基苯基、十二烷基苯基、苯乙烯化苯基p-枯基苯基、二苯基、苄基苯基、α-萘基、β-萘基等。
此等烴基中,R以不含苯環之烷基、鏈烯基為理想。又,碳數以8~24者為佳,8~20者更佳。
其次,於上述一般式(1),A為碳數2~4的2種以上的伸烷基,A可列舉如伸乙基、伸丙基、伸甲基乙基、伸丁基、1-甲基伸丙基、2-甲基伸丙基、乙基伸乙基等,此等可由環氧乙烷、環氧丙烷、環氧丁烷、四氫呋喃(1,4-環氧丁烷)導入。
A為2種以上的伸烷基者,任組合均佳,由環氧乙烷導入之伸乙基,與其他環氧烷所導入之伸烷基的組合為理想。與伸乙基組合之其他環氧烷,以環氧丙烷、環氧丁烷為理想,以環氧丙烷為最理想。加成之環氧烷的聚合型態無特別的限制,以環氧乙烷與其他1種或2種以上的環氧烷的無規共聚合、嵌段共聚合或無規/嵌段共聚合等為佳。其中,依光安定劑乳化組成物的安定性觀點亦以無規共聚合為佳。
又,自乳化性的觀點,A中伸乙基所佔的比例以全體的50莫耳%以上為,理想為50~99莫耳%,更理想為60~95莫耳%,最理想為68~92莫耳%。伸乙基的比例未達50莫耳%時,不能充分發揮乳化劑的性能,光安定劑不能均勻的乳化情形不理想。又,伸乙基為100莫耳%時,不能充分發揮乳化劑的性能,光安定劑不能均勻的乳化情形不理想。又,伸乙基為100莫耳%時,由於融點變高,因析出等保存安定性變差,又,添加於水系塗覆劑組成物將其塗膜時,所形成的塗膜物性,例如由於塗料等的光澤等變差不理想。
又,於上述一般式(1),n為8~80的數,理想為8~70,更理想為10~60,最理想為10~50。n未達8時,乳化劑的性能不能充分的發揮,n超過80時,乳化安定性有變差的情形。
本發明的光安定劑乳化組成物,係含有如上述一般式(1)所示乳化劑,水、與光安定劑等的組成物。此處,光安定劑可使用受阻胺系光安定劑等,或二苯甲酮類、苯并三唑類、三嗪類、苯甲酸酯類、草醯替苯胺類、氰基丙烯酸酯類等的紫外線吸收劑。
受阻胺類系光安定劑可列舉如2,2,6,6-四甲基-4-哌啶基硬脂酸酯、1,2,2,6,6-五甲基-4-哌啶基苯甲酸酯、N-(2,2,6,6-四甲基-4-哌啶基)十二烷基琥珀酸醯亞胺、1-〔(3,5-二-s-丁基-4-羥基苯基)丙酸基乙基〕-2,2,6,6-四甲基-4-哌啶基-(3,5-s-丁基-4-羥基苯基)丙酸酯、雙(2,2,6,6-基-4-哌啶基)癸二酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)-2-丁基-2-(3,5-二-s-丁基-4-羥基苯基)丙二酸酯、N,N’-雙(2,2,6,6,-四甲基-4-哌啶基)六伸甲基二胺、四(2,2,6,6-四甲基-4-哌啶基)丁烷四羧酸酯、四(1,2,2,6,6-五甲基-4-哌啶基)丁烷四羧酸酯、雙(2,2,6,6-四甲基-4-哌啶基)二(十三烷基)丁烷四羧酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)二(十三烷基)丁烷四羧酸酯、3,9-雙〔1,1-二甲基-2-{三(2,2,6,6-四甲基-4-哌啶氧基羰氧基)丁基羰氧基}乙基〕-2,4,8,10-四噁基螺〔5.5〕十一烷、3,9-雙〔1,1-二甲基-2-{三(1,2,2,6,6-五甲基-4-哌啶氧基羰氧基)丁基羰氧基}乙基〕-2,4,8,10-四噁基螺〔5.5〕十一烷、1,5,8,12-四〔4,6-雙{N-(2,2,6,6-四甲基-4-哌啶基)丁基胺基}-1,3,5-三嗪-2-醯〕-1,5,8,12-四迭氮基癸烷、1,6,11-三〔{4,6-(N-丁基-N-(1,2,2,6,6-五甲基哌啶基-4-醯)胺基)-1,3,5-三嗪-2-醯}胺基〕十一烷、1-(2-羥基乙基)-2,2,6,6-四甲基-4-哌啶醇/琥珀酸二甲基縮合物、2叔辛基胺基-4,6-二氯-s-三嗪/N,N’-雙(2,2,6,6-四甲基-4-哌啶基)六伸甲基二胺縮合物、N,N’-雙(2,2,6,6-四甲基-4-哌啶基)六伸甲基二胺/二溴乙烷縮合物等。
又,紫外線吸收劑可列舉如2,4-羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-辛氧基二苯甲酮、5,5’-伸甲基雙(2-羥基-4-甲氧基二苯甲酮)等的2-羥基二苯甲酮類,2-(2-羥基-5-甲基苯基)苯并三唑、2-(2-羥基-5-s-辛基苯基)苯并三唑、2-(2-羥基-3,5-二-t-丁基苯基)-5-氯苯并三唑、2-(2-羥基-3-叔丁基-5-甲基苯基)-5-氯苯并三唑、2-(2-羥基-3,5-二枯基苯基)苯并三唑、2,2’-伸甲基雙(4-叔辛基-6-苯并三唑苯酚)、2-(2-羥基-3-叔丁基-5-羧基苯基)苯并三唑的聚乙二醇酯、2-〔2-羥基-3-(丙烯醯氧基乙基)-5-甲基苯基〕苯并三唑、2-〔2-羥基-3-(2-甲基丙烯醯氧基乙基)-5-叔丁基苯基〕苯并三唑、2-〔2-羥基-3-(2-甲基丙烯醯氧基乙基)-5-s-辛基苯基〕苯并三唑、2-〔2-羥基-3-(2-甲基丙烯氧基乙基)-5-s-丁基苯基〕氯苯并三唑、2-〔2-羥基-5-(2-甲基丙烯氧基乙基)-苯基〕苯并三唑、2-〔2-羥基-3-t-胺基-5-(2-甲基丙烯氧基乙基)-苯基〕苯并三唑、2-〔2-羥基-3-叔丁基-5-(3-甲基丙烯氧基乙基)-苯基〕-5-氯苯并三唑、2-〔2-羥基-4-(2-甲基丙烯氧基甲基)-苯基〕苯并三唑、2-〔2-羥基-4-(3-甲基丙烯氧基-2-羥基丙基)-苯基〕苯并三唑、2-〔2-羥基-4-(3-甲基丙烯氧基乙丙)-苯基〕苯并三唑等的2-(2-羥基苯基)苯并三唑類;2-(2-羥基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三嗪、2-(2-羥基-4-己氧基苯基)-4,6-二苯基-1,3,5-三嗪、2-(2-羥基-4-辛氧基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2-〔2-羥基-4-(3-C1 2
~C1 3
混合烷氧基-2-羥基丙氧基)苯基〕-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羥基-4-(2-丙烯醯氧基)苯基)-4,6-雙(4-甲基苯基)-1,3,5-三嗪、2-〔2-羥基-4-(2-乙醯氧基乙氧基)苯基〕-4,6-雙苯基-1,3,5-三嗪、2-(2,4-二羥基-3烯丙基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2,4,6-三(2-羥基-3-甲基-4-己氧基苯基)-1,3,5-三嗪、2-(2-羥基苯基)-4,6-二芳基-1,3,5-三嗪等的三嗪類;3-水楊酸苯酯、間苯二酚單苯甲酸酯、2,4-二-t-丁基苯基-3,5-二-叔丁基-4-羥基苯甲酸酯、十六烷基-3,5-t-基-4-羥基苯甲酸酯,硬脂基(3,5-二-t-丁基-4-羥基苯甲酸酯等的苯甲酸酯類;2-乙基-2’-乙氧基草醯替苯胺、2-乙氧基-4’-十二烷基草醯替苯胺等的取代草醯替苯胺類;乙基-α-氰基-β,β-二苯基丙烯酸酯、甲基-2-氰基-3-甲基-3-(p-甲氧基苯基)丙烯酸酯等的氰基丙烯酸酯類等。
此等的受阻胺系光安定劑或紫外線吸收劑,因應必要可使用其之任一方,亦可并用二種類以上,依乳化安定性的觀點,以使用受阻胺系光安定劑為理想。
本發明的光安定乳化組成物係使用乳化劑及水,將光安定劑等安定的乳化、分散之乳化組成物,含有光安定劑等20~80質量%,理想為30~70質量%,更理想為35~65質量%。光安定劑等未達20質量%時,為賦予水性塗覆劑組成物充分的耐候性必要大量添加,其結果水性塗覆劑組成物為大量的水所稀釋,由於對塗膜形成有不良影響不理想。又,光安定劑等超過80質量%時,由於光安定劑乳化組成物的安定性有下降情形不理想。
於本發明的光安定劑乳化組成物可使用的乳化劑,對光安定劑等而言以使用1~40質量%為理想,更理想為2~30質量%,最理想為5~20質量%。少於1質量%時,有不能充分乳化的情形,超過40質量%時,將添加之水性塗覆劑組成物塗膜時的塗膜物性,例如因耐水性惡化不理想。
製造本發明的光安定劑乳化組成物的方法,例如有轉相乳化法、機械強制乳化法等。可使用任一方法,為得到保存安定性高的乳化組成物,以轉相乳化法乳化者為理想。又,為實施此等的乳化法使用的機器,例如可使用高速回轉的螺旋槳攪拌、均質混合機〔日本特殊機化工業(股)製〕、高壓均質機、超音波式乳化機等。
本發明的光安定乳化組成物,為水系組成物者可任意的添加,提高塗膜耐候性為最大的目的,以添加於耐候性必要之水系塗覆劑組成物為理想。此等必要耐候性的水系塗覆劑組成物,可列舉如使用水系塗料等的樹脂乳膠組成物、染料或顏色等的著色劑之水系油墨組成物,噴墨用紙或熱感紙、壁紙等的紙用水系塗覆劑組成物,木材或地磚,緩衝地板等的地板用塗覆劑組成物,纖維用水系塗覆劑組成物、光學記錄載體的保護層等的光學用水系塗覆劑組成物,金屬或玻璃等的保護或修蝕為目的之水系塗覆劑組成物等。
本發明的光安定劑乳化組成物,100質量份此等水系塗覆劑組成物而言,光安定劑乳化組成物中添加的光安定劑成為0.01~5質量份為理想,0.03~3質量份為更理想,0.05~3質量份為最理想。未達0.01質量份時,雖添加亦不能得到充分的耐候性的情形,超過5質量份時,由於塗膜的耐水性有惡化的情形不理想。
本發明的光安定劑乳化組成物,因應必要,在不妨礙本發明的效果範圍可添加界面活性劑、抗氧化劑、溶劑、防腐劑等。
界面活性可使用非離子界面活性劑、陰離子界面活性劑、陽離子界面活性劑、兩性界面活性劑等。
非離子界面活性劑可舉例如聚環氧乙烷十一烷醚、聚環氧乙烷十二烷醚、聚環氧乙烷十三烷醚、聚環氧乙烷十四烷醚、聚環氧乙烷十五烷醚、聚環氧乙烷油醚、聚環氧乙烷壬基苯醚等的聚環氧乙烷醚類;聚環氧乙烷油酸酯、聚環氧乙烷月桂酸山梨糖酯、聚環氧乙烷油酸山梨糖酯等的聚環氧乙烷酯類;聚環氧乙烷聚環氧丙烷嵌段共聚物的Pluronic型界面活性劑等。
陰離子界面活性劑可舉例如上述非離子界面活性劑及醇類的硫酸酯鹽、磺酸酯鹽、磷酸酯鹽等,或脂肪酸皂等。
陽離子界面活性劑可舉例如,四烷基銨鹽、烷基吡啶鎓鹽、醯亞胺鹽(iminium)等。
兩性界面活性劑可舉例如氨基酸型兩性界面活性劑、甜菜鹼型兩性界面活性劑、硫酸酯鹽型兩性界面活性劑、磺酸鹽型兩性界面活性劑、磷酸酯鹽型兩性界面活性劑等。
抗氧化劑可舉磷系抗氧化劑、苯酚系抗氧化劑、硫系抗氧化劑、胺系抗氧化劑等。
磷系抗氧化劑可舉例如三苯基磷酸酯、三(2,4-二-叔丁基苯基)磷酸酯、三(2,5-二-叔丁基苯基)磷酸酯、三(壬基苯基)磷酸酯、三(二壬基苯基)磷酸酯、三(單,二混合壬基苯基)磷酸酯、二苯基酸式磷酸酯、2,2’-伸甲基雙(4,6-t-基苯基)辛基磷酸酯、二苯基癸基磷酸酯、二苯基辛基磷酸酯、二(壬基苯基)季戊四醇二磷酸酯、苯基二異癸基磷酸酯、三丁基磷酸酯、三(乙基己基)磷酸酯、三癸基磷酸酯、三月桂基磷酸酯、二丁基酸式磷酸酯、二月桂基酸式磷酸酯、三月桂基三硫磷酸酯、雙(新戊二醇).1,4-環己烷二甲基二磷酸酯、雙(2,4-二-叔丁基苯基)季戊四醇二磷酸酯、雙(2,5-二-叔丁基苯基)季戊四醇二磷酸酯、雙(2,6-二-叔丁基-4-甲基苯基)季戊四醇二磷酸酯、雙(2,4-二枯基苯基)季戊四醇二磷酸酯、二硬脂基季戊四醇二磷酸酯、四(C1 2
~C1 5
混合烷基)-4,4’-異丙叉基二苯基磷酸酯、雙〔2,2’-伸甲基雙(4,6-二戊基苯基)〕.異丙叉二苯基磷酸酯、肆十三烷基.4,4’-丁叉雙(2-叔丁基-5-甲基苯酚)二磷酸酯、六(十三烷基).1,1,3-三(2-甲基-5-叔丁基-4-羥基苯基)丁烷.三磷酸酯、四(2,4-二-叔丁基苯基)二伸苯基二磷酸酯、三(2-〔(2,4,7,9-四-叔丁基二苯并〔d,f〕〔1,3,2-dioxaphosphepine-6-醯〕)羥基〕乙基)胺、9,10-二氫-9-噁基-10-磷菲-10-氧化物、2-丁基-2-乙基丙二醇.2,46-三-叔丁基酚酮單磷酸酯等。
苯酚系抗氧化劑可舉例如2,6-二-叔丁基-p-甲酚、2,6-二苯基-4-十八烷氧基苯酚、硬脂基(3,5-二-叔丁基-4-羥基苯基)丙酸酯、二硬脂基(3,5-二-叔丁基-4-羥基苄基)膦酸酯、十三烷基.3,5-二-叔丁基-4-羥基苄基硫醋酸酯、硫二伸乙基雙〔(3,5-二-叔丁基-4-羥基苯基)丙酸酯、4,4’-硫雙(6-叔丁基-m-甲酚)、2-辛基硫化物4,6-二(3,5-叔丁基-4-羥基苯氧基)-s-三嗪、2,2’-(3,5-伸甲基(4-甲基-6-叔丁基苯酚)、雙(3,3-雙(4-羥基-3-叔丁基苯基)丁炔酸)甘醇酯4,4’-丁叉基雙(2,6-二_t-丁基苯酚)、4,4’-丁叉基雙(6-叔丁基-3-甲基苯酚)、2,2’-乙叉基雙(4,6-二-叔丁基-苯酚)、1,1,3-三(2-甲基-4-羥基-5-叔丁基苯基)丁烷、雙〔2-叔丁基-4-甲基-6-(2-羥基-3-叔丁基-5-甲基苄基)苯基〕對苯二甲酸酯、1,3,5-三(2,6-二-甲基-3-羥基-4-叔丁基苄基)異氰酸酯、1,3,5-三(3,5-二-叔丁基-4-羥基苄基)氰酸酯、1,3,5-三(3,5-二-叔丁基-4-羥基苄基)-2,4,6-三甲基苯、1,3,5-三〔(3,5-叔丁基-4-羥基苯基)丙酸基乙基〕異氰酸酯、四〔伸甲基-3-(3’,5’-二-叔丁基-4’-羥苯基)丙酸酯〕甲烷、2-t-丁基-4-甲基-6-(2-丙烯醯氧基-3-叔丁基-5-甲基苄基)苯酚、3,9-雙〔2-(3-叔丁基-4-羥基-5-甲基氫肉桂醯氧基)-1,1-二甲基乙基〕-2,4,8,10-四噁螺〔5.5〕十一烷、三乙二醇雙〔β-(3-叔丁基-4-羥基-5-甲基苯基〕丙酸酯)、生育酚或其衍生物等。
硫系抗氧化劑可舉例如硫二丙酸的二月桂酯、二肉豆蒄基、肉豆蒄基硬脂基、二硬脂基酯等的二烷基硫丙酸酯類及季戊四醇四(β-十二烷基甲基羥基丙酸酯)等的聚醇的β-烷基巰基丙酸酯類。
胺系抗氧化劑可舉例如1-萘基胺、苯基-1-萘基胺、p-辛基苯基-1-萘基胺、p-壬基苯基-1-萘基胺、p-十二烷基苯基-1-萘基胺、苯基-2-萘基胺等的萘基胺系抗氧化劑;N,N’-二異丙基-p-伸苯基二胺、N,N’-二異丁基-p-伸苯基二胺、N,N’-二苯基-p-伸苯基二胺、N,N”-二-β-萘基-p-伸苯基二胺、N-苯基-N’-異丙基-p-伸苯基二胺、N-環己基-N’-苯基-p-伸苯基二胺、N-1,3-二甲基丁基-N’-苯基-p-伸苯基二胺、二辛基-p-伸基二胺、苯基己基-p-伸苯基二胺、苯基辛基-p-伸苯基二胺等的伸苯基二胺系抗氧化劑;二吡啶基胺、二苯基胺、p,p’-二-n-丁基二苯基胺、p,p’-二-叔丁基二苯基胺、p,p’-二叔戊基二苯基胺、p,p’-二辛基二苯基胺、p,p’-二壬基二苯基胺、p,p’-二癸基二苯基胺、p,p’-二十二烷基二苯基胺、p,p’-二硬脂基二苯基胺、p,p’-二甲氧基二苯基胺、4,4’-雙(4-α,α-二甲基苄基)二苯基胺、p-異丙氧基二苯基胺、二吡啶基胺等的二苯基胺系抗氧化物;吩噻嗪、N-甲基吩噻嗪、N-乙基吩噻嗪、3,7-二辛基吩噻嗪、吩噻嗪二羧酸酯、吩硒嗪等的吩噻嗪系抗氧化劑。
溶劑可列舉如甲醇、乙醇、丙醇、異丙醇、丁醇、異丁醇、叔丁酸、甲基溶纖素、乙基溶纖素、丁基溶纖素等的水溶性醇。
防腐劑可舉例如對羥基苯甲酸酯類、第四級氨鹽類、吡啶鎓鹽類、甘油脂肪酸酯類、甘油烷基醇、辛二醇所代表的甘醇類、藻朊酸鈉類、兒苯酸類等。
本發明的光安定劑乳化組成物,可賦予各種水系塗覆劑組成物耐候性,例如可適合於水系塗料等的樹脂乳膠組成物、染料或顏色等的著色劑之水系油墨組成物,噴墨用紙或熱感紙、壁紙等的紙用水系塗覆劑組成物,木材或地磚,緩衝地板等的地板用塗覆劑組成物,纖維用水系塗覆劑組成物、光學記錄載體的保護層等的光學用水系塗覆劑組成物,金屬或玻璃等的保護或修蝕為目的之水系塗覆劑組成物等的使用。
又,本發明的水系塗覆劑組成物,例如可由水系塗料等的樹脂乳膠組成物、染料或顏色等的著色劑之水系油墨組成物,噴墨用紙或熱感紙、壁紙等的紙用水系塗覆劑組成物,木材或地磚,緩衝地板等的地板用塗覆劑組成物,纖維用水系塗覆劑組成物、光學記錄載體的保護層等的光學用水系塗覆劑組成物,金屬或玻璃等的保護或修蝕為目的之水系塗覆劑組成物等的水系塗覆劑組成物添加本發明的光安定劑乳化組成物而得。於100質量份水性塗覆組成物添加本發明的光安定劑組成物使光安定劑成為0.001~5質量份為理想。
本發明的水系塗覆劑組成物,依必要亦可添加造膜助劑、顏料、染料、無機填充劑、有機填充劑、分散劑、黏度調整劑、消泡劑、可塑劑、硬化劑、硬化促進劑、聚合防止劑、pH調整劑、吸氧劑、防腐劑等。
本發明的水系塗覆劑組成物,可直接或介由底塗塗覆於木材、紙、纖維、混凝土、水泥、石材、陶瓷、玻璃、塑膠類、金屬等的各種基材的表面。塗敷方法可藉由噴霧塗覆、毛刷塗覆、輥輪塗覆、淋液塗覆、浸漬塗覆、電鍍塗覆、列印機等的印字,筆等的筆記用具之印字等,可使用習如的方法塗覆或印字。
本發明的塗裝品,係具有自本發明的水系塗覆劑組成物所形成的膜者,例如建築物的外壁或內裝、屋頂、地板;汽車的外裝或內裝;衣料製品;皮革製品;人工皮革製品;噴墨用紙或熱感紙等的紙類;家庭用或辦公用的機器類;透鏡或塑膠薄膜、基板、光碟等的光學材料等。
以下以實施例詳細說明本發明的安定劑乳化組成物、及水系塗覆劑組成物。又,以下的實施例中,%無特別記載為質量基準。
<乳化劑>A1:十三烷醇12EO/3PO無規共聚物A2:十三烷醇25EO/3PO無規共聚物A3:十三烷醇50EO/5PO無規共聚物A4:十三烷醇11EO/5PO無規共聚物A5:十三烷醇15EO/3PO無規共聚物A6:月桂醇15EO/3PO無規共聚物A7:月桂醇8EO/3PO無規共聚物A8:油醇20EO/4PO無規共聚物A9:2-乙基己基酸的15EO/3PO無規共聚物A10:丁醇6EO/2PO嵌段共聚物A11:己醇10EO/3PO無規共聚物A12:十三烷醇5EO/2PO無規共聚物A13:十三烷醇80EO/20PO無規共聚物B1:十三烷醇25 EO B2:月桂醇12EO B3:月桂醇3EO的硫酸酯鈉鹽B4:H-(EO)8 0
-(PO)3 0
-(EO)8 0
-H B5:四十烷醇30EO/8PO無規共聚(Tetracontanol:碳數40的醇)
<光安定劑等>C1:
〔式中,R為下述的基(A)或(B):-C1 3
H2 7
,(A)/(B)=1/1(莫耳比)〕C2:
〔式中,R為下述的基(A’)或(B):-C1 3
H2 7
,(A’)/(B)=1/3(莫耳比)〕
C3:
C4:
<光安定劑乳化組成物的製造方法>具備均質混合機與昇溫裝置之1000 ml的容器,裝入光安定劑等的乳化劑,以均質混合機混合而昇溫至60~70℃。將指定量的水在目視容器內的情形下緩緩的投入,投入某定量的水時,自W/O乳膠轉相為O/W乳膠。確認其後,將溫度冷卻至30~40℃,將殘留的水全數加入,再繼續攪拌2小時得到乳化劑組成物。又,光安定劑等與乳化劑的種類與量,及水量如表1所示。
<保存安定性試驗>將所得的光安定劑乳化劑組成物80 ml,投入100 ml的玻璃密閉容器,於50℃的恒溫槽保管30天,觀察10天、20天、25天、30天後的乳化組成物的外觀。結果記載於表2。又表2中,◎:均勻,○:表面稍有分離,△:表面明確的分離,×:全體不均勻或可見大部份分離,××:完全分離。
<塗膜試驗>於市售的亮光塗料(Audicoat G;日本:油墨)添加光安定乳化組成物使光安定劑成為1質量%,攪拌至均勻後,使用10 mil的製膜器於玻璃基板上形成塗膜。將塗膜乾燥後,使用Gloss meter(日本電色VG 2000)測定塗膜的亮度,自添加光安定劑前的塗料亮度,減去添加後的亮度,將其作為亮度下降值。亮度下降值越小,原塗料的亮度越不降低,為性能佳。結果如表2。
Claims (6)
- 一種光安定劑乳化組成物,其特徵為含有:具使2種以上環氧烷反應之聚醚鏈作為親水基,具碳數1~30的烴基作為疏水基之乳化劑,與光安定劑及/或紫外線吸收劑、及水;其中前述乳化劑為下述一般式(1)所示RO-(AO)n -H (1)(式中,R為碳數8~30的烴基,A為碳數2~4的2種以上的伸烷基,伸乙基為全體的50莫耳%以上,n為8~80之數),前述乳化組成物的含量,相對於前述光安定劑及/或前述紫外線吸收劑為1~40質量%的範圍內,前述光安定劑及/或前述紫外線吸收劑的含量為20~80質量%的範圍內。
- 如申請專利範圍第1項之光安定劑乳化組成物,其中一般式(1)之R為碳數8~20的烷基或鏈烯基。
- 如申請專利範圍第1項之光安定劑乳化組成物,其中一般式(1)之A為伸乙基與伸丙基的無規聚合物。
- 如申請專利範圍第1項之光安定劑乳化組成物,其中光安定劑為受阻胺。
- 一種水系塗覆劑組成物,其特徵為含有如申請專利範圍第1~4項中任一項之光安定劑乳化組成物。
- 一種塗裝物,其特徵為具有由申請專利範圍第5項的水系塗覆劑組成物所成之塗膜。
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US20070240615A1 (en) | 2007-10-18 |
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