TW202407025A - 樹脂組成物及熱熔黏接劑組成物 - Google Patents
樹脂組成物及熱熔黏接劑組成物 Download PDFInfo
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- TW202407025A TW202407025A TW112118841A TW112118841A TW202407025A TW 202407025 A TW202407025 A TW 202407025A TW 112118841 A TW112118841 A TW 112118841A TW 112118841 A TW112118841 A TW 112118841A TW 202407025 A TW202407025 A TW 202407025A
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- polyolefin resin
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- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
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Abstract
本發明之課題係提供維持低壓成形優良的樹脂之流動性及黏接性的狀態下,水蒸氣阻隔性優良的樹脂組成物。解決該課題之手段為一種樹脂組成物,包含聚烯烴樹脂(A)、酸改性聚烯烴樹脂(B)、黏接賦予材(C)及填料(D),令聚烯烴樹脂(A)、酸改性聚烯烴樹脂(B)及黏接賦予材(C)之合計為100質量份時,黏接賦予材(C)的含量為10~50質量份,填料(D)的含量為1~13質量份,該填料(D)為板狀。
Description
本發明關於樹脂組成物。更詳細來說,關於流動性、黏接性及水蒸氣阻隔性優良的樹脂組成物及熱熔黏接劑組成物。
就使用於汽車、電器等的電氣電子零件之密封所使用的絕緣性樹脂而言,一般會使用二液硬化型環氧樹脂、矽樹脂,但考量需要長時間之步驟、也有可能因硬化時之收縮應力而導致電氣電子零件破壞,故近年已知有藉由使用熱塑性樹脂之低壓成形所為之電氣電子零件的密封。
考量電絕緣性、耐水性、耐久性、熔融黏度之觀點,聚酯樹脂係作為理想的材料而被使用作為電氣電子零件之密封樹脂,但在為了減少對電氣電子零件之損壞的低溫、低壓成形中,電氣電子零件與密封樹脂的黏接性會變得不足,常有作為目的之電絕緣性、防水性無法充分發揮的情況。因此,從提高黏接性之觀點,已有人積極地探討摻合具有官能基之黏接賦予材等的嘗試(例如專利文獻1)。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開2004-210893號公報
[發明所欲解決之課題]
近年,電氣電子零件中,除了如上述要求的物性,亦需要高度的水蒸氣阻隔性,如專利文獻1使用摻合了黏接賦予材的熱塑性樹脂的情況,雖然黏接性有所改善,但有無法保證水蒸氣阻隔性之問題。習知技術中,尚未有人提案尤其在維持低壓成形優良的樹脂之流動性的狀態下,可兼顧水蒸氣阻隔性的密封用樹脂組成物。
本發明係以該習知技術之課題為背景而成。即,本發明的目的係提供維持低壓成形優良的樹脂之流動性及黏接性的狀態下,水蒸氣阻隔性優良的樹脂組成物。
[解決課題之手段]
本發明人們辛勤探討後之結果發現,利用如下所示之手段可解決上述課題,乃至完成本發明。即本發明係由如下構成而成。
[1] 一種樹脂組成物,包含聚烯烴樹脂(A)、酸改性聚烯烴樹脂(B)、黏接賦予材(C)及填料(D),令聚烯烴樹脂(A)、酸改性聚烯烴樹脂(B)及黏接賦予材(C)之合計為100質量份時,黏接賦予材(C)的含量為10~50質量份,填料(D)的含量為1~13質量份,該填料(D)為板狀。
[2] 如[1]之樹脂組成物,其中該聚烯烴樹脂(A)包含聚丙烯樹脂,還包含乙烯-α-烯烴共聚物及丙烯-α-烯烴共聚物中之至少一者。
[3] 如[1]或[2]之樹脂組成物,其中該酸改性聚烯烴樹脂(B)的熔點為100℃以上。
[4] 如[1]或[2]之樹脂組成物,其中該黏接賦予材(C)的羥基價為1~100KOHmg/g。
[5] 如[1]或[2]之樹脂組成物,其中令聚烯烴樹脂(A)、酸改性聚烯烴樹脂(B)及黏接賦予材(C)之合計為100質量份時,聚烯烴樹脂(A)的含量為49~70質量份,酸改性聚烯烴樹脂(B)的含量為1~30質量份。
[6] 一種熱熔黏接劑組成物,含有如[1]或[2]之樹脂組成物。
[發明之效果]
本發明的樹脂組成物表現優良的流動性及黏接性,還有優良的水蒸氣阻隔性。因此,藉由作為需要高度防水的製品的密封材使用,能夠製造滿足水蒸氣阻隔性的製品。尤其本發明的樹脂組成物,可以作為熱熔黏接劑使用,尤其於電氣電子零件的密封用途係理想的。
以下詳述本發明。
<聚烯烴樹脂(A)>
本發明的樹脂組成物含有聚烯烴樹脂(A)。由於含有聚烯烴樹脂(A),可以提供樹脂組成物良好的水蒸氣阻隔性。本發明中使用的聚烯烴樹脂(A)沒有特別受限,考量水蒸氣阻隔性之觀點,宜為聚丙烯樹脂。又,考量對金屬、膜的黏接性之觀點,宜為乙烯-α-烯烴共聚物、丙烯-α-烯烴共聚物。為了高度兼顧水蒸氣阻隔性及黏接性,可以將聚丙烯樹脂與乙烯-α-烯烴共聚物、丙烯-α-烯烴共聚物一起使用。於此,聚丙烯樹脂係指主要由丙烯單元構成,即所謂的同元聚丙烯,不包含丙烯以外的α-烯烴等共聚合成分,即使包含亦最多僅為1莫耳%之程度。又,聚烯烴樹脂(A)不屬於後述酸改性聚烯烴樹脂(B),其係指未經酸改性者。
將聚丙烯樹脂與乙烯-α-烯烴共聚物及/或丙烯-α-烯烴共聚物(以下合併稱為烯烴共聚物)一起使用的情形中,聚丙烯樹脂/烯烴共聚物的較佳摻合比率為質量比20/80~80/20,更佳為30/70~70/30,再更佳為40/60~60/40。
本發明中使用的聚烯烴樹脂(A),藉由JIS K 7210-1:2014(試驗溫度190℃,標準荷重2.16kg)測定的熔融流體速率(以下簡稱為MFR),宜為10~70g/10分。MFR未達10g/10分為因熔融黏度太高而樹脂的流動性降低,可能有損成形性,若MFR超過70g/10分,則為黏度低,樹脂組成物非常容易軟化,機械物性可能會劣化。聚烯烴樹脂(A)包含複數種的聚烯烴樹脂的情形中,各聚烯烴樹脂宜在上述範圍內。
本發明的樹脂組成物作為熱熔黏接劑使用的情形中,為了盡可能不發生樹脂熱劣化地成形,需要於210~240℃的快速熔融,故聚烯烴樹脂(A)之熔點的上限為210℃係理想的。較佳為200℃以下,更佳為190℃以下。下限宜為90℃以上,更佳為100℃以上,再更佳為110℃以上,特別佳為120℃以上。若比所屬用途需要的耐熱溫度高5~10℃則為較佳。聚烯烴樹脂(A)包含複數種的聚烯烴樹脂的情形中,宜為各聚烯烴樹脂在上述範圍內。
<酸改性聚烯烴樹脂(B)>
本發明的樹脂組成物含有酸改性聚烯烴樹脂(B)。藉由含有酸改性聚烯烴樹脂(B),可以提供聚烯烴樹脂(A)與黏接賦予材(C)及填料(D)的良好相溶性,其結果,於可對於樹脂組成物賦予合適的流動性、黏接性、水蒸氣阻隔性。酸改性聚烯烴樹脂(B)沒有特別受限,若為具有聚烯烴片段及羧酸片段的樹脂即可,例如可列舉乙烯-乙酸乙烯酯-馬來酸酐三元共聚物、乙烯-丙烯酸乙酯-馬來酸酐三元共聚物等乙烯-不飽和羧酸共聚物、馬來酸酐接枝改性聚丙烯、馬來酸酐接枝改性丙烯-α-烯烴共聚物等不飽和羧酸接枝改性聚烯烴樹脂等。其中較佳的酸改性聚烯烴樹脂可列舉馬來酸酐改性聚丙烯。
本發明中使用的酸改性聚烯烴樹脂(B)的熔點宜為100℃以上,110℃以上更佳,120℃以上再更佳。又160℃以下較佳,150℃以下更佳。酸改性聚烯烴樹脂(B)的熔點若為前述下限値以上則樹脂組成物的耐熱性為良好的,若為前述上限値以下則樹脂組成物成形時的流動性變得良好。
本發明的樹脂組成物中之酸改性聚烯烴樹脂(B)的含量,令聚烯烴樹脂(A)、酸改性聚烯烴樹脂(B)及黏接賦予材(C)之合計為100質量份時,為1質量份以上較佳,3質量份以上更佳,5質量份以上再更佳。又30質量份以下較佳,25質量份以下更佳,20質量份以下再更佳。若酸改性聚烯烴樹脂(B)的含有比率為前述下限値以上,則聚烯烴樹脂(A)與黏接賦予材(C)及填料(D)的相溶性變得良好。又,若酸改性聚烯烴樹脂(B)的含有比率為前述上限値以下,則成形性、機械特性變得良好。
<黏接賦予材(C)>
本發明的樹脂組成物含有黏接賦予材(C)。藉由含有黏接賦予材(C),除了樹脂組成物作為密封劑使用時可以提供良好的黏接性,尚可以使樹脂組成物的流動性適當地提升。本發明中使用的黏接賦予材(C)沒有特別受限,可以使用苯酚化合物、二甲苯改性酚醛樹脂、萜烯改性酚醛樹脂、將萜烯改性酚醛樹脂予以氫化處理的氫化萜烯改性酚醛樹脂等。尤其,考量與聚烯烴樹脂(A)的相溶性之觀點,二甲苯改性酚醛樹脂、萜烯改性酚醛樹脂為較佳。
本發明中使用的黏接賦予材(C)具有羥基較佳。藉由黏接賦予材(C)具有羥基,可以發揮對基材的潤濕性提升的效果,且與基材的黏接性提升,使絕緣性提升。黏接賦予材(C)的羥基價宜為1KOHmg/g以上,更佳為30KOHmg/g以上,50KOHmg/g以上再更佳。又,100KOHmg/g以下較佳,更佳為90KOHmg/g以下,再更佳為80KOHmg/g以下,70KOHmg/g以下特別佳。若羥基價為前述上限値以下,則可以使黏接性提升,同時適當地維持透濕度。
本發明的樹脂組成物中黏接賦予材(C)的含量,令聚烯烴樹脂(A)、酸改性聚烯烴樹脂(B)及黏接賦予材(C)之合計為100質量份時,為10質量份以上較佳,20質量份以上更佳。又,50質量份以下較佳,40質量份以下更佳,30質量份以下再更佳。若黏接賦予材(C)的含量在前述範圍內,可以展現特別良好的黏接性。又,可抑制由於樹脂組成物柔軟性降低、脆化而致的黏接性降低等。
<填料(D)>
本發明的樹脂組成物含有填料(D)。藉由含有填料(D),可以提供樹脂組成物良好的水蒸氣阻隔性。本發明中使用的填料(D)沒有特別受限,可以使用玻璃珠、碳酸鈣、高嶺土、滑石、玻璃纖維、碳纖維、黏土等。本發明中使用的填料(D)為板狀,尤其於使水蒸氣阻隔性提升之點較佳。於此,板狀係指與填料的寬度及深度相比高度極小的如板之形狀。填料(D)的縱橫比宜為3至500。若填料(D)的縱橫比太低則有水蒸氣阻隔性降低的情況,若縱橫比太高則有分散性惡化、機械特性降低的情況。
本發明的樹脂組成物中填料(D)的含量,令聚烯烴樹脂(A)、酸改性聚烯烴樹脂(B)及黏接賦予材(C)之合計為100質量份時,為1質量份以上較佳,3質量份以上更佳,再更佳為5質量份以上。若填料(D)的含量為前述下限値以上,則水蒸氣阻隔性變得良好。又,有樹脂組成物的機械特性變得良好、剪切黏接強度提升的情況。又,填料(D)的含量為13質量份以下較佳,10質量份以下更佳,再更佳為8質量份以下。若填料(D)的含量為前述上限値以下,則黏接性變得良好。
本發明的樹脂組成物中的填料(D)之粒徑(D50),沒有特別受限,可為1~100μm。粒徑(D50),一般來說,可以利用雷射繞射法、動態光散射法測定。
<樹脂組成物>
本發明的樹脂組成物至少包含前述聚烯烴樹脂(A)、酸改性聚烯烴樹脂(B)、黏接賦予材(C)及填料(D)。再者取決於需要,可包含抗氧化劑等各種添加劑。
本發明的樹脂組成物於230℃的熔融黏度為5~1000dPa・s係理想的。樹脂組成物的熔融黏度可以藉由聚烯烴樹脂(A)、酸改性聚烯烴樹脂(B)、黏接賦予材(C)及填料(D)的種類及摻合比率適當地調整而達成。且於此,於230℃的熔融黏度為如以下測定的値。即,樹脂組成物於含水率0.1%以下進行乾燥,然後利用島津製作所股份公司製流動性測定儀(型號CFT-500C),使加熱至230℃安定的樹脂組成物通過具有1.0mm孔徑、厚度10mm的模具以98N/cm
2的壓力通過時的黏度的測定値。若為1000dPa・s以上的高熔融黏度,可以得到高樹脂凝聚力、耐久性,但用於對複雜形狀的零件密封時需要高壓射出成型,會發生零件的破壞。藉由使用具有1000dPa・s以下、較佳為900dPa・s以下的熔融黏度的樹脂組成物,以0.1~20MPa之較低射出壓力,可得到電絕緣性優良的製品,同時亦未損特性。又,考量樹脂組成物注入操作之觀點,於230℃的熔融黏度較低者為較佳,若考量樹脂組成物的黏接性、凝聚力,下限為5dPa・s以上係理想的,更佳為10dPa・s以上,再更佳為30dPa・s以上,最佳為50dPa・s以上。
本發明的樹脂組成物還可包含抗氧化劑。本發明中使用的抗氧化劑,若可以防止聚烯烴樹脂(A)的氧化則沒有特別受限,可以使用受阻酚(hindered phenol)系抗氧化劑、磷系抗氧化劑、硫醚系抗氧化劑等。例如就受阻酚系而言,可列舉1,3,5-三(3,5-二-第三丁基-4-羥基苄基)異氰酸酯、1,1,3-三(4-羥基-2-甲基-5-第三丁基苯基)丁烷、1,1-雙(3-第三丁基-6-甲基-4-羥基苯基)丁烷、3,5-雙(1,1-二甲基乙基)-4-羥基-苯基丙酸、季戊四醇四(3,5-二-第三丁基-4-羥基苯基)丙酯、3-(1,1-二甲基乙基)-4-羥基-5-甲基-苯基丙酸、3,9-雙[1,1-二甲基-2-[(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基]乙基]-2,4,8,10-四氧雜螺[5.5]十一烷、1,3,5-三甲基-2,4,6-三(3’,5’-二-第三丁基-4’-羥基苄基)苯,就磷系而言,3,9-雙(對壬基苯氧基)-2,4,8,10-四氧-3,9-二磷雜螺[5.5]十一烷、3,9-雙(十八烷氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、亞磷酸三(單壬基苯基)酯、三苯氧基膦、亞磷酸異癸酯、亞磷酸異癸基苯基酯、亞磷酸二苯基2-乙基己基酯、亞磷酸二壬基苯基雙(壬基苯基)酯、1,1,3-三(2-甲基-4-二(十三烷基)亞磷酸酯-5-第三丁基苯基)丁烷、亞磷酸三(2,4-二第三丁基苯基)酯、新戊四醇雙(2,4-二第三丁基苯基亞磷酸酯)、2,2’-亞甲基雙(4,6-二第三丁基苯基)2-乙基己基亞磷酸酯、雙(2,6-二第三丁基-4-甲基苯基)新戊四醇二亞磷酸酯,就硫醚系而言可列舉4,4’-硫代雙[2-第三丁基-5-甲基苯酚]雙[3-(十二烷基硫基)丙酸酯]、硫代雙[2-(1,1-二甲基乙基)-5-甲基-4,1-伸苯基]雙[3-(十四烷基硫基)-丙酸酯]、新戊四醇四(3-正十二烷基硫基丙酸酯)、硫代雙(十三烷基)酯,該等可以單獨使用或複合使用。
抗氧化劑的含量相對於聚烯烴樹脂(A)、酸改性聚烯烴樹脂(B)及黏接賦予材(C)之合計為100質量份宜為0.1質量份以上,更佳為0.2質量份以上,再更佳為0.3質量份以上。若含量太少,會有對於高溫下之長期耐久性造成不良影響的情況。又5質量份以下為較佳,更佳為3質量份以下,再更佳為1質量份以下。若含量過多,會有對黏接性、阻燃性等造成不良影響的情況。
本發明的樹脂組成物中,在不損害本發明的效果之範圍內,即使摻合不屬於聚烯烴樹脂(A)、酸改性聚烯烴樹脂(B)、黏接賦予材(C)及填料(D)中任一者的聚醯胺、聚碳酸酯、丙烯酸、乙烯醋酸乙烯酯等其他樹脂、異氰酸酯化合物、三聚氰胺等硬化劑、碳黑、氧化鈦等顏料、三氧化銻、溴化聚苯乙烯等阻燃劑亦完全無妨。藉由摻合該等成分,可改良黏接性、柔軟性、耐久性等。該情況的聚烯烴樹脂相對於本發明的樹脂組成物整體含有20~50質量%為較佳,更佳為30~50質量%。若聚烯烴樹脂(A)的含量太少,聚烯烴樹脂(A)本身具有的優良的水蒸氣阻隔性、耐久性會有降低的傾向,若太多,柔軟性、黏接性會有降低的傾向。
此外,本發明之樹脂組成物需要耐候性時,宜添加光安定劑。就光安定劑而言,例如可列舉苯并三唑系光安定劑、二苯甲酮系光安定劑、受阻胺系光安定劑、鎳系光安定劑、苯甲酸酯系光安定劑等。就苯并三唑系光安定劑而言,可列舉2-(3,5-二(第三戊基)-2’羥基苯基)苯并三唑、2-(2-羥基-5-第三辛基苯基)苯并三唑、2-(2’-羥基-3’-第三丁基-5’-甲基苯基)-5-氯苯并三唑、2-(2H-苯并三唑-2-基)對甲酚、2-(2’-羥基-5’-甲基苯基)苯并三唑、2,4-二(第三丁基)-6-(5-氯苯并三唑-2-基)苯酚、2-[2-羥基-3,5-二(1,1-二甲基苄基)]-2H-苯并三唑等。就二苯甲酮系光安定劑而言,可列舉2-羥基-4-(辛氧基)二苯甲酮、2,4-二羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-甲氧基-二苯甲酮-5-磺酸、2-羥基-4-正十二烷氧基二苯甲酮、雙(5-苯甲醯基-4-羥基-2-甲氧基苯基)甲烷、2-2’-二羥基-4-甲氧基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基二苯甲酮等。就受阻胺系光安定劑而言,可列舉雙(2,2,6,6-四甲基-4-哌啶基)癸二酸、琥珀酸二甲酯/1-(2-羥基乙基)-4-羥基-2,2,6,6-四甲基哌啶聚縮物、聚[{6-(1,1,3,3-四甲基丁基)胺基-1,3,5-三𠯤-2,4-二基}{(2,2,6,6-四甲基-4-哌啶基)亞胺基}六亞甲基(2,2,6,6-四甲基-4-哌啶基)亞胺基}]、1,3,5-三(3,5-二(第三丁基)-4-羥基苄基)-均三𠯤-2,4,6(1H,3H,5H)三酮、三(4-第三丁基-3-羥基-2,6-二甲基苄基-均三𠯤-2,4,6-(1H,3H,5H)三酮等。就鎳系光安定劑而言,可列舉[2,2’-硫代-雙(4-第三辛基酚根)]-2-乙基己基胺-鎳-(II)、鎳二丁基二硫代胺甲酸鹽、[2’,2’-硫代-雙(4-第三辛基酚根)]正丁基胺-鎳等。就苯甲酸酯系光安定劑而言,可列舉2,4-二(第三丁基)苯基-3,5’-二(第三丁基)‐4’‐羥基苯甲酸酯等。這些光安定劑可單獨使用或複合使用。添加時的添加量相對於樹脂組成物整體,宜為0.1質量%以上且5質量%以下。若未達0.1質量%,則會有缺乏耐侯性效果之情況。若超過5質量%,則會有對黏接性等造成不良影響之情況。
<熱熔黏接劑組成物>
本發明的樹脂組成物,可以作為熱熔黏接劑組成物使用。就熱熔黏接劑組成物而言,可以適當地作為例如電氣電子零件用的密封劑使用。就使用方法的具體例而言,藉由在設置了欲防水的製品的模具中注入本發明的樹脂組成物,可以得到密封了前述製品的成型體。更具體而言,使用螺桿型的熱熔成型加工用器具時,可於180~250℃前後加熱熔融,並通過射出噴嘴注入模具,其後經過一定的冷卻時間後,將成型物從模具去除而得到成型物。
熱熔成型加工用器具的型號沒有特別受限,可列舉井元製作所製立式擠壓成型機IMC-18F9、日精樹脂工業公司製混合式小型立式射出成形機STX20等。
[實施例]
為了更詳細地說明本發明而於以下列舉實施例、比較例,本發明不受實施例任何限定。另外,實施例、比較例中記載的各測定値藉由下列方法測定。
<熔點、玻璃轉移溫度的測定>
利用精工電子工業股份公司製的示差掃描熱量分析計「DSC220型」,將測定樣本5mg放入鋁盤,壓蓋密封,先以20℃/min的升溫速度加熱至230℃並熔融。然後,使用液態氮以20℃/min冷卻至-130℃,保持5分鐘後,從-130℃至230℃,以20℃/min的升溫速度進行測定。將得到的曲線如圖1所示之於DSC表現反曲點的部分之得自於反曲點前的基線之切線(1)與得自於反曲點後的基線之切線(2)的交點定義為玻璃轉移溫度(Tg),並將吸熱峰的極小點(圖內×記號)定義為熔點(Tm)。
<熔融特性>
利用島津製作所製流動性測定儀(CFT-500C型),於已設定至230℃的加熱體中央缸體中填充已乾燥至含水率0.1%以下的共聚合聚酯樹脂或樹脂組成物。填充經過1分鐘後,藉由柱塞對樣本施加荷重,以壓力1MPa由缸體底部的模具(孔徑:1.0mm,厚度:10mm)擠出已熔融的樣本,記錄柱塞的降下距離及降下時間,並計算於230℃的熔融黏度。由熔融黏度的値,藉由下述評價基準評價熔融特性(流動性)。
評價基準 〇:熔融黏度 5dPa・s以上且未達800dPa・s
△:熔融黏度 800dPa・s以上且未達1000dPa・s
×:熔融黏度 1000dPa・s以上
<水蒸氣阻隔性>
使用熱壓機(Tester產業股份公司製SA-303)以進行熱壓,製作樹脂膜厚度約120μm的樹脂組成物膜。
熱壓條件為溫度200℃、壓力10MPa、加壓時間30秒。將經熱壓的膜使用剪切機切出根據JIS Z0208:1976的試驗片。然後,設定膜於JIS Z0208:1976所規定的治具,於25℃90%相對濕度(RH)環境下靜置合計96小時。
從試驗開始24小時後、48小時後、72小時後及96小時後取出樣品測定質量。由從24小時後至48小時後之間、從48小時後至72小時後之間及從72小時後至96小時後之間之氯化鈣吸水的質量計算各自的透濕度(水蒸氣阻隔性),並將3個透濕度的値之平均値定義為透濕度。
透濕度藉由下式求得。
透濕度(g/(m
2・24h))=(240×m)/(t×s)
m:進行試驗之最後2個秤量間所增加質量之合計(mg)
t:進行試驗之最後2個秤量間的時間之合計(h)
s:透濕面積(cm
2)
評價基準 〇:透濕度 未達1.0(g/(m
2・24h))
△:透濕度 1.0(g/(m
2・24h))以上而未達1.5(g/(m
2・24h))
×:透濕度 1.5(g/(m
2・24h))以上
<黏接性試驗(剪切黏接強度)>
剪切黏接強度試驗片的製作方法
將基材(鋁基板:A5052(厚度:0.5mm))裁切為70mm×25mm及40mm×25mm之大小,表面以丙酮擦拭以去除油分。然後以該基材的鋁面與已熔融的樹脂組成物接觸的方式,使基材彼此有長度10mm部分重疊,並以寬度為25mm,成形的樹脂組成物厚度1mm的方式固定於剪切黏接試驗用模具內部。然後使用螺桿型熱熔成型加工用器具(井元製作所製立式低壓擠壓成型機IMC-18F9),注入含水率為0.1%以下的樹脂組成物,進行成型。成型條件為成型樹脂溫度240℃、成型壓力4.0MPa、保持的壓力4.0MPa、保持壓力的時間20秒、噴吐旋轉設定為80%(最大噴吐為100%)。將成型物從模具取下,得到以各基材夾持已成形的樹脂組成物而成的剪切黏接強度試驗片(基材/樹脂組成物層/基材)。
剪切黏接強度試驗方法
前述剪切黏接強度試驗片於23℃、相對濕度50%的環境氣體下保存24小時。然後,使用Autograph(島津製作所股份公司製AG-IS),以夾具夾持各基材並於剪切方向使樹脂組成物層剝離,測定剪切黏接強度。拉伸速度設為50mm/分。
評價基準 ○:剪切黏接強度2.0MPa以上
△:剪切黏接強度1.0MPa以上且未達2.0MPa
×:剪切黏接強度未達1.0MPa
<實施例1~11、比較例1~5>
按表1中記載的比例,藉由將聚烯烴樹脂(A)、酸改性聚烯烴樹脂(B)、黏接賦予材(C)及填料(D)使用雙軸擠壓機於模具溫度160℃~220℃進行熔融混練,得到樹脂組成物(S-1)~(S-16)。藉由另外記載的方法,評價樹脂組成物的熔融特性、水蒸氣阻隔性、剪切黏接強度。評價結果如以下表1。
[表1]
表1中使用的聚烯烴樹脂、酸改性聚烯烴樹脂、黏接賦予材及填料如下。
聚烯烴樹脂(A-1):J107G,Prime Polymer(股)製,同元聚丙烯樹脂,熔點:165℃,密度:0.90g/cm
3聚烯烴樹脂(A-2):EUL731,住友化學(股)製,乙烯-α-烯烴共聚物,熔點:113~117℃,密度:0.90g/cm
3聚烯烴樹脂(A-3):Tafmer PN-20300,三井化學(股)製,丙烯-α-烯烴共聚物,熔點:160℃,密度:0.87g/cm
3酸改性聚烯烴樹脂(B-1):PMA H1100P,東洋紡(股)製,酸改性聚丙烯樹脂,熔點:147℃,分子量Mw:74000
酸改性聚烯烴樹脂(B-2):PMA F2,東洋紡(股)製,酸改性聚丙烯樹脂,熔點:120℃,分子量Mw:70000
黏接賦予材(C-1): YS Polystar T160,Yasuhara chemical(股)製,萜烯改性酚醛樹脂,羥基價:60KOHmg/g
黏接賦予材(C-2):YS Polystar G150,Yasuhara chemical (股)製,萜烯改性酚醛樹脂,羥基價:140KOHmg/g
填料(D-1):K-1,日本Talc(股)製,Talc,板狀,粒徑(D50):8.0μm
填料(D-2):I.44P,Volclay Japan(股)製,蒙脫石,板狀,尺寸:14-18μm
填料(D-3):BYK-MAX CT 4255,BYK Japan(股)製,蒙脫石,板狀,粒徑(D50):未達40μm
填料(D-4):UBS-0005E,Unitika(股)製,玻璃珠,球狀,粒徑:5μm以下
由表1可知,實施例1~11的樹脂組成物,水蒸氣阻隔性、剪切黏接強度及熔融特性之各特性皆為優良的結果。另一方面,比較例1由於不含填料,故水蒸氣阻隔性不良。比較例2為填料含量多,而沒有黏接性。比較例3為黏接賦予劑少,熔融黏度上升,且黏接性不良。比較例4由於黏接賦予劑太多,反而黏接性降低,此外水蒸氣阻隔性亦降低。比較例5由於含有球狀填料,故水蒸氣阻隔性降低。
[產業上利用性]
本發明的樹脂組成物由於製品成形時的熔融黏度低,對鋁基板的黏接性優良,水蒸氣阻隔性亦優良,故作為防水用途的熱熔黏接劑組成物係有用。
[圖1] 圖1顯示以示差掃描熱量分析計測定的圖表之示意圖。
Claims (6)
- 一種樹脂組成物,包含聚烯烴樹脂(A)、酸改性聚烯烴樹脂(B)、黏接賦予材(C)及填料(D),令聚烯烴樹脂(A)、酸改性聚烯烴樹脂(B)及黏接賦予材(C)之合計為100質量份時,黏接賦予材(C)的含量為10~50質量份,填料(D)的含量為1~13質量份,該填料(D)為板狀。
- 如請求項1之樹脂組成物,其中該聚烯烴樹脂(A)包含聚丙烯樹脂,還包含乙烯-α-烯烴共聚物及丙烯-α-烯烴共聚物中之至少一者。
- 如請求項1或2之樹脂組成物,其中該酸改性聚烯烴樹脂(B)的熔點為100℃以上。
- 如請求項1或2之樹脂組成物,其中該黏接賦予材(C)的羥基價為1~100KOHmg/g。
- 如請求項1或2之樹脂組成物,其中令聚烯烴樹脂(A)、酸改性聚烯烴樹脂(B)及黏接賦予材(C)之合計為100質量份時,聚烯烴樹脂(A)的含量為49~70質量份,酸改性聚烯烴樹脂(B)的含量為1~30質量份。
- 一種熱熔黏接劑組成物,含有如請求項1或2之樹脂組成物。
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