TW202241990A - 聚酯樹脂組成物、水分散體、塗料組成物及塗膜 - Google Patents
聚酯樹脂組成物、水分散體、塗料組成物及塗膜 Download PDFInfo
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- TW202241990A TW202241990A TW111104262A TW111104262A TW202241990A TW 202241990 A TW202241990 A TW 202241990A TW 111104262 A TW111104262 A TW 111104262A TW 111104262 A TW111104262 A TW 111104262A TW 202241990 A TW202241990 A TW 202241990A
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- polyester resin
- resin composition
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Abstract
本發明之課題係提供可抑制有害的釋氣、能夠形成硬化性、耐蒸煮性、加工性等特性優良的塗膜之聚酯樹脂及聚酯樹脂組成物。
本發明之解決手段係一種聚酯樹脂組成物,特徵係含有聚酯樹脂(A)且滿足以下(i)~(iii)之要件。(i)聚酯樹脂(A)之酸價為100eq/ton以上。(ii)實質上不含有硬化劑。(iii)將聚酯樹脂組成物於240℃加熱處理1小時時之四氫呋喃不溶物為10質量%以上。
Description
本發明係關於聚酯樹脂組成物。詳細而言係關於適合罐用塗料之聚酯樹脂組成物,更詳細而言係關於適合用於被覆容納飲料、食品(以下統稱為飲食品)之罐的內面之聚酯樹脂組成物、及含有其之水分散體、塗料組成物、以及塗膜及具有該塗膜之金屬罐。
飲料罐、食品罐等金屬罐為了防止由食品所致之金屬之腐蝕(耐蝕性)、不損害內容物之味道、風味(味道性),會以有機樹脂進行塗佈。此等塗佈要求加工性、耐蝕性、對於金屬材料之密接性、硬化性等。此外根據用途,亦有在蒸煮殺菌等之高溫高濕度條件下施行塗佈之情形,即使在如此情形下,不僅要求塗膜要維持與金屬材料之密接性,亦要求尤其是應用在金屬蓋等之外面側時塗膜不會發生白化。
作為上述耐蝕性、味道性、可耐受罐之成形加工之塗料,以往係廣泛地使用環氧-酚系塗料、環氧-胺系塗料、環氧-丙烯酸系塗料等環氧系塗料、聚酯-酚系塗料、聚酯-胺系塗料等聚酯系塗料、及氯乙烯系塗料。但是,最近的研究中有人報告係環氧樹脂之原料之雙酚A可能會影響雌激素作用或胎兒、嬰幼兒的腦部。此外氯乙烯系塗料有安定劑之問題、在焚化時產生戴奧辛之問題。已知用來作為酚醛樹酯、胺樹脂等之原料而殘留在塗料中之甲醛,具有致癌性等對人體之有害性,並且對內容物之味道性有不良影響。此外亦有人擔心使用有機溶劑所導致之環境污染、對作業環境之影響。
由於擔心這些各種對於人體的不良影響,市場期望著不使用此等原料之水性塗料,但實際情況是無法得到滿足作為罐用途的性能。
考量如此之觀點,作為金屬容器或金屬蓋用之樹脂組成物,例如,有人提案使樹脂端部具有乙烯性雙鍵之聚酯樹脂上接枝聚合聚合性不飽和單體成分而形成之丙烯酸改性聚酯樹脂、及β-羥烷基醯胺交聯劑分散在水性介質中而形成之水性塗料組成物 (專利文獻1)。
此外,專利文獻2中有人提案由聚酯多元醇、及嵌段聚異氰酸酯硬化劑構成之塗料組成物。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開2001-81160號公報
[專利文獻2]日本特開2006-169535號公報
[發明所欲解決之課題]
然而,使用專利文獻1中記載之高酸價之丙烯酸改性聚酯樹脂時,無法得到充分的加工性。此外,β-羥烷基醯胺交聯劑之未反應物會殘留在塗膜中,且有硬化性、蒸煮白化性降低之問題。專利文獻2中記載之使聚酯與嵌段聚異氰酸酯反應而得之塗膜,有耐水性不良,將內容物進行殺菌時發生白化之問題。
本發明之目的係提供即使實質上不含有硬化劑,聚酯樹脂亦可單獨地硬化,故可抑制有害的釋氣,能夠形成硬化性、耐蒸煮性、加工性等特性優良之塗膜之聚酯樹脂及聚酯樹脂組成物。
[解決課題之手段]
本案發明人們針對上述進行了各種探討後,發現含有具有規定量之酸價的聚酯樹脂,且在進行規定之加熱處理時具有一定量以上之四氫呋喃不溶物之聚酯樹脂組成物,實質上不使用硬化劑而聚酯樹脂可單獨地硬化。並且發現藉由指定樹脂組成並控制觸媒量,可得到硬化性與加工性之平衡優良、不產生有害的釋氣、耐蒸煮性顯著改善之聚酯樹脂塗膜,而促成了本發明。即,本發明係由以下構成所形成。
[1]一種聚酯樹脂組成物,含有聚酯樹脂(A)且滿足以下(i)~(iii)之要件:
(i)聚酯樹脂(A)之酸價為100eq/ton以上;
(ii) 實質上不含有硬化劑;
(iii)將聚酯樹脂組成物於240℃加熱處理1小時時之四氫呋喃不溶物為10質量%以上。
[2]如上述[1]之聚酯樹脂組成物,其中,該聚酯樹脂(A)具有分支結構。
[3]如上述[1]或[2]之聚酯樹脂組成物,其中,該聚酯樹脂(A),就構成上述聚酯樹脂(A)之多元醇成分而言,具有具2個1級羥基且不具脂環結構之二醇(a),更具有具脂環結構之二醇(b)及具1個1級羥基及1個2級羥基且不具脂環結構之二醇(c)中之任一者或具有兩者。
[4]如上述[1]至[3]中之任一項之聚酯樹脂組成物,其中,該聚酯樹脂(A) ,作為構成上述聚酯樹脂(A)之多元羧酸成分,具有選自由己二酸、2,6-萘二羧酸及1,4-環己烷二羧酸構成之群組中之至少一種。
[5]如上述[1]至[4]中之任一項之聚酯樹脂組成物,其中,該聚酯樹脂(A) ,作為構成上述聚酯樹脂(A)之多元羧酸成分,具有不飽和二羧酸(d)。
[6]如上述[1]至[5]之聚酯樹脂組成物,其中,於150℃加熱處理30分鐘時之四氫呋喃不溶物未達10質量%,並且含有1種以上之觸媒(B)。
[7]如上述[6]之聚酯樹脂組成物,其中,相對於聚酯樹脂(A)100質量份,觸媒(B)之含量為0.01~0.5質量份。
[8]一種聚酯樹脂水分散體,含有如上述[1]至[7]中之任一項之聚酯樹脂組成物、及水性介質。
[9]一種塗料組成物,含有如上述[1]至[7]中之任一項之聚酯樹脂組成物或如上述[8]之聚酯樹脂水分散體中之任一者。
[10]一種塗膜,含有如上述[1]至[7]中之任一項之聚酯樹脂組成物。
[11]一種金屬罐,具有如上述[10]之塗膜。
[發明之效果]
本發明可提供不產生硬化劑導致之有害的釋氣、硬化性與加工性之平衡優良、耐蒸煮性顯著改善之聚酯樹脂組成物及其塗膜。
以下針對本發明之實施之形態詳細地進行說明。本發明之聚酯樹脂組成物,係特徵為含有聚酯樹脂(A)且滿足以下(i)~(iii)之要件之聚酯樹脂組成物。
<要件(i)>
針對要件(i)進行說明。聚酯樹脂(A)之酸價必須為100eq/ton以上。宜為200eq/ton以上,較宜為250eq/ton以上,更宜為300eq/ton以上。若未達上述則作為交聯點之羧基較少,故有時會有硬化性降低之情形。並且,若酸價未達上述條件,則有時會有加熱至240℃時熱分解反應會優先於硬化反應進行而加工性降低之情形。此外,藉由具有酸價為上述下限值以上,水性分散化會變得容易。酸價之上限值無特別限定,但為了減少酸加成反應時之酸成分之未反應物、寡聚物量,宜為1200eq/ton以下。
本發明中的聚酯樹脂(A)之酸價,能夠用任意方法賦予。賦予酸價之方法,有在聚縮合後期使多元羧酸酐進行加成反應之方法、於預聚物(寡聚物)之階段將其製成高酸價然後將其聚縮合而得到具有酸價之聚酯樹脂之方法等,考量操作之容易度、容易得到作為目標之酸價,前者之進行加成反應之方法為理想。
用以對本發明中的聚酯樹脂(A)賦予酸價之在分子內具有多元羧酸酐基之化合物之中,就羧酸單酸酐而言,例如,可舉例酞酸酐、琥珀酸酐、馬來酸酐、偏苯三甲酸酐、伊康酸酐、檸康酸酐、5-(2,5-二氧四氫糠基)-3-環己烯-1,2-二羧酸酐等一酸酐、六氫酞酸酐、四氫酞酸酐等,可從此等之中選擇1種或1種以上使用。其中,考量泛用性、經濟性之方面宜為偏苯三甲酸酐。
用以對本發明中的聚酯樹脂(A)賦予酸價之在分子內具有多元羧酸酐基之化合物之中,就羧酸多酸酐而言,例如有焦蜜石酸酐、1,2,3,4-丁烷四羧酸二酐、1,2,3,4-戊烷四羧酸二酐、3,3’,4,4’-二苯基酮四羧酸二酐、環戊烷四羧酸二酐、2,3,6,7-萘四羧酸二酐、1,2,5,6-萘四羧酸二酐、乙二醇雙偏苯三甲酸酯二酐、2,2’,3,3’-二苯基四羧酸二酐、噻吩-2,3,4,5-四羧酸二酐、乙烯四羧酸二酐、4,4’-氧二鄰苯二甲酸二酐、5-(2,5-二側氧基四氫-3-呋喃)-3-甲基-3-環己烯-1,2-二羧酸酐等,可從此等之中選擇1種或2種以上使用。其中,乙二醇雙偏苯三甲酸酯二酐為理想。
用以賦予上述酸價之在分子內具有多元羧酸酐基之化合物,可個別單獨使用羧酸單酸酐及羧酸多酸酐,亦可合併來使用。
<要件(ii)>
針對要件(ii)進行說明。本發明之聚酯樹脂組成物實質上不含有硬化劑。該「實質上不含有硬化劑」意思為「相對於聚酯樹脂(A)100質量份(換算固體成分),硬化劑含量未達1質量份 (換算固體成分)」。
此處硬化劑,係指與本發明中的聚酯樹脂(A)反應並形成交聯結構之既知的硬化劑,交聯結構之形態,例如可舉例由使聚酯樹脂中之不飽和雙鍵藉由自由基加成反應、陽離子加成反應、或陰離子加成反應等進行反應並生成分子間碳-碳鍵之反應、與聚酯樹脂中之多價羧酸基、多價醇基之縮合反應、聚合加成反應、或轉酯作用反應等所為之分子間鍵結之形成等。硬化劑,例如可舉例酚醛樹酯、胺樹脂、異氰酸酯化合物、環氧化合物、或β-羥醯胺化合物、含有不飽和鍵之樹脂等。
本發明之聚酯樹脂組成物中,硬化劑之含量,相對於聚酯樹脂(A)(固體成分)100質量份,係未達1質量份。未達0.5質量份為較佳、未達0.1質量份為更佳,不含有硬化劑為最佳。硬化劑之含量比上述範圍多時,不僅經濟性不良,亦有由硬化劑彼此之自我縮合反應所致之加工性降低、封端化劑之揮發、甲醛等有害的釋氣之產生、以及長期保存之穩定性不良之虞。
<要件(iii)>
針對要件(iii)進行說明。本發明之聚酯樹脂組成物,於240℃加熱處理1小時時之四氫呋喃不溶物必須為10質量%以上。藉由四氫呋喃(THF)不溶物為10質量%以上,可得到耐蒸煮性與加工性之平衡優良之聚酯樹脂組成物及其塗膜。THF不溶物宜為30質量%以上,較宜為50質量%以上,更宜為70質量%。未達10質量%則硬化性變得不充分,塗膜之強靭性不足,有耐蒸煮性降低、塗佈在金屬板進後無法耐受製成罐之成型加工之虞。
此處,「將聚酯樹脂組成物於240℃加熱處理1小時時之四氫呋喃不溶物為10質量%以上」,係指將聚酯樹脂組成物以乾燥後之厚度成為10μm之方式塗佈在銅箔上,於240℃加熱1小時,製成長10cm、寬2.5cm之尺寸之樣本之THF浸漬前質量定義為(X),在60ml之THF中於25℃、浸漬1小時後,於100℃、乾燥10分鐘後之樣本之質量定義為THF浸漬後質量(Y),經下式求得之THF不溶物為10質量%以上。
THF不溶物(質量%)=〔{(Y)-銅箔質量}/{(X)-銅箔質量}〕×100
此外,本發明之聚酯樹脂組成物,宜為於150℃加熱處理30分鐘時之THF不溶物為未達10質量%。較宜為未達5質量%,更宜為未達1質量%,亦可為0質量%。藉由在約150℃之較低溫的加熱條件下THF不溶物未達上述之值,可抑制溶解在溶劑時、或製成水分散體時凝聚物之產生。
本發明之聚酯樹脂組成物,藉由含有聚酯樹脂(A)且滿足上述(i)~(iii)之要件,即使實質上不使用硬化劑,聚酯樹脂亦可單獨地硬化。因此,本發明之聚酯樹脂組成物,亦可為不含有聚酯樹脂(A)以外之成分之聚酯樹脂(A)單獨的態樣。
<聚酯樹脂(A)>
接著針對本發明中的聚酯樹脂(A)進行說明。本發明中的聚酯樹脂(A),主要由多元羧酸成分及多元醇成分構成。
本發明中的聚酯樹脂(A),宜具有具2個1級羥基且不具脂環結構之二醇(a)(以下,有時稱作(a)成分)作為多元醇成分。聚酯樹脂(A)中的具2個1級羥基且不具脂環結構之二醇(a),可舉例例如乙二醇、1,3-丙二醇、2-丁基-2-乙基-1,3-丙二醇、2-甲基-1,3-丙二醇、新戊二醇、3-甲基-1,5-戊二醇、1,4-丁二醇、2,4-二乙基-1,5-戊二醇、1,6-己二醇、2-甲基-1,8-辛二醇、3-甲基-1,6-己二醇、4-甲基-1,7-庚二醇、4-甲基-1,8-辛二醇、1,9-壬二醇等脂肪族二醇、二甘醇、三乙二醇、聚乙二醇、聚丙二醇、聚丁二醇等聚醚二醇類等,可從此等之中選擇1種或1種以上使用。其中,宜使用乙二醇、2-甲基-1,3-丙二醇、1,6-己二醇。
聚酯樹脂(A)中的具2個1級羥基且不具脂環結構之二醇(a)之共聚合比率,宜為全部多元醇成分中的20~80莫耳%,較宜為20~60莫耳%,更宜為20~40莫耳%。若在上述範圍內,則硬化性、耐蒸煮性會變得良好。
本發明中的聚酯樹脂(A),宜具有具脂環結構之二醇(b)作為多元醇成分。藉由具有具脂環結構之二醇(b)(以下,有時稱作(b)成分),容易兼顧加工性及耐蒸煮性。本發明中的構成聚酯樹脂(A)之具脂環結構之二醇(b),例如可舉例1,2-環己烷二甲醇、1,3-環己烷二甲醇、1,4-環己烷二甲醇、三環癸烷二醇類、氫化雙酚類等,可從此等之中選擇1種或1種以上使用。其中,考量硬化性、加工性、耐蒸煮性之觀點,宜使用1,4-環己烷二甲醇。
本發明中的構成聚酯樹脂(A)之具脂環結構之二醇(b)之共聚合比率,宜為全部多元醇成分中的5~50莫耳%,較宜為10~40莫耳%,更宜為20~30莫耳%。若在上述範圍內,加工性會變得良好。
本發明中的聚酯樹脂(A),宜具有具1個1級羥基及1個2級羥基且不具脂環結構之二醇(c)(以下,有時稱作(c)成分)作為多元醇成分。本發明之聚酯樹脂(A)中的具1個1級羥基及1個2級羥基且不具脂環結構之二醇(c),例如可舉例1,2-丙二醇、1,2-丁二醇等,可從此等之中選擇1種或1種以上使用。其中,宜使用1,2-丙二醇。
本發明中的聚酯樹脂(A)中的具1個1級羥基及1個2級羥基且不具脂環結構之二醇(c)之共聚合比率,宜為全部多元醇成分中的5~75莫耳%,較宜為10~65莫耳%,更宜為15~50莫耳%。若在上述範圍內,硬化性、耐蒸煮性會變得良好。
本發明中的聚酯樹脂(A),宜具有上述(a)成分、與(b)成分及(c)成分中之任一者或兩者作為多元醇成分。據推測由於(a)成分容易形成酯鍵,另一方面(b)成分及(c)成分,酯鍵相較於(a)成分容易開裂,藉由具有(a)成分、與(b)成分或(c)成分,在加熱處理時酯鍵之再排列及再鍵結會被促進,THF不溶物會增加,可形成兼具硬化性、柔軟性意即加工性之塗膜。
本發明中的構成聚酯樹脂(A)之多元羧酸成分,例如可舉例對苯二甲酸、間苯二甲酸、鄰苯二甲酸、2,6-萘二羧酸、1,4-萘二羧酸、1,8-萘二羧酸等芳香族二羧酸成分等。此等可單獨使用或合併使用2種以上。其中宜為對苯二甲酸、2,6-萘二羧酸。
本發明中的構成聚酯樹脂(A)之其他的多元羧酸成分,例如可舉例脂肪族二羧酸成分、脂環族二羧酸成分。脂肪族二羧酸成分,可舉例琥珀酸、戊二酸、己二酸、壬二酸、癸二酸、十二烷二酸、二聚酸等。脂環族二羧酸成分,可舉例1,4-環己烷二羧酸、四氫苯二甲酸、六氫間苯二甲酸、1,2-環己烯二羧酸等。可從此等之中選擇1種或2種以上使用。其中,己二酸、1,4-環己烷二羧酸,考量反應性、經濟性之方面係理想。
在聚酯樹脂(A)中結構單元中具有脂肪族二羧酸成分、脂環族二羧酸成分時,此等之共聚合比率宜為多元羧酸成分中的5~40莫耳%。較宜為10~30莫耳%。若超出上述範圍則有時會有聚酯樹脂(A)之玻璃轉移溫度大幅降低且耐蒸煮性降低之情形。
本發明中的構成聚酯樹脂(A)之多元羧酸成分,亦宜含有不飽和二羧酸(d)作為結構單元。藉由具有不飽和二羧酸(d),可以藉由於加熱處理時不飽和鍵開裂所致之使分子間碳-碳鍵生成之反應來改善硬化性。上述不飽和二羧酸(d),例如可舉例富馬酸、馬來酸、伊康酸、檸康酸、2,5-降莰烷二羧酸及四氫苯二甲酸以及此等之酸酐,此等可使用一種或二種以上。
聚酯樹脂(A)中,在結構單元中具有不飽和二羧酸(d)時,不飽和二羧酸(d)之共聚合比率宜為多元羧酸成分中的5~20莫耳%。較宜為10~15莫耳%。藉由在上述範圍內,可兼顧加工性及硬化性。
本發明中的聚酯樹脂(A)宜具有分支結構。具有分支結構係指聚酯之主鏈上具有分支結構,針對在聚酯樹脂(A)中導入分支結構,可舉例在聚酯之聚縮合反應中,使3官能以上之成分作為多元羧酸成分及/或多元醇成分之一部份進行共聚合之方法。3官能以上之多元羧酸成分,可舉例例如偏苯三甲酸、焦蜜石酸、二苯基酮四羧酸等,3官能以上之多元醇可舉例甘油、三羥甲基乙烷、三羥甲基丙烷、甘露醇、山梨醇、新戊四醇、α-甲基葡萄糖苷等。藉由聚酯樹脂(A)具有分支結構,於加熱處理時酯鍵之再排列及再鍵結發生時之交聯密度會上升,故THF不溶物會增加而可使硬化性及加工性改善。
針對3官能以上之多元羧酸成分之共聚合比率,將全部多元羧酸成分定義為100莫耳%時,宜為0.1莫耳%以上,較宜為0.5莫耳%以上,更宜為1莫耳%以上。此外,宜為7莫耳%以下,較宜為6莫耳%以下,更宜為5莫耳%以下,特宜為4莫耳%以下。針對3官能以上之多元醇成分之共聚合比率,將全部多元醇成分定義為100莫耳%時,宜為0.1莫耳%以上,較宜為0.5莫耳%以上,更宜為1莫耳%以上。此外,宜為5莫耳%以下,較宜為3莫耳%以下,更宜為2莫耳%以下,特宜為1莫耳%以下。若多元羧酸成分及多元醇成分各自超出上述範圍,則有時會有失去聚酯樹脂之可撓性,加工性會降低、或聚酯在聚合時出現膠凝化之情形。
在本發明中的構成聚酯樹脂(A)之多元羧酸成分及多元醇成分,可使用衍生自生物質資源之原料。生物質資源,係指包含藉由植物的光合作用而將太陽的光能變換成澱粉、纖維素等之形態而經儲存者、攝食植物而生長發育的動物的身體、將植物體或動物體進行加工所製成之產品等。其中,較理想的生物質資源為植物資源,可舉例例如木材、稻草、稻殼、米糠、老米、玉米、甘蔗、木薯、西米、豆渣、玉米芯、木薯粉、甘蔗渣、植物油渣、塊莖塊根、蕎麥、黃豆、油脂、廢紙、製紙殘渣、水產品殘渣、家畜排泄物、污水污泥、食品廢棄物等。更宜為玉米、甘蔗、木薯、西米。
接著針對本發明中的聚酯樹脂(A)之製造方法進行說明。酯化/交換反應,係將全部單體成分及/或其低聚物加熱熔融並使其進行反應。酯化/交換反應溫度,宜為180~250℃,較宜為200~250℃。反應時間宜為1.5~10小時,較宜為3小時~6小時。另外,反應時間,係定義為從達到所需的反應溫度到隨後的聚縮合反應之時間。聚縮合反應,係在減壓下、以220~280℃的溫度,從於酯化反應得到之酯化物餾去多元醇成分,持續進行聚縮合反應直到達到期望的分子量。聚縮合之反應溫度,宜為220~280℃,較宜為240~275℃。減壓度,宜為130Pa以下。若減壓度不充分,則由於聚縮合時間有變長之傾向而並不理想。從大氣壓達到130Pa以下之減壓時間,宜為耗時30~180分鐘緩慢地進行減壓。
在酯化/交換反應及聚縮合反應時,因應需要使用鈦酸四丁酯等有機鈦酸化合物、二氧化鍺、氧化銻、辛酸錫等有機錫化合物來使聚合進行。考量反應活性之方面宜為有機鈦酸化合物,考量樹脂著色之方面宜為二氧化鍺。
本發明中的聚酯樹脂(A)之玻璃轉移溫度,就耐水性,尤其是塗膜之耐蒸煮性之觀點而言宜為40℃以上,較宜為60℃以上。玻璃轉移溫度之上限沒有特別限定,通常為130℃以下。
本發明中的聚酯樹脂(A)之還原黏度,宜為0.2~0.6dl/g,較宜為0.3~0.5dl/g。還原黏度為0.2dl/g以下則硬化性會變得不充分,此外塗膜之強靭性不足,塗佈在金屬板後有無法耐受製成罐之成型加工之虞。另一方面,若還原黏度為0.6dl/g以上則熔融黏度、溶液黏度會變高,不僅操作性會降低,由於羥基末端數減少而有變得無法充分地賦予酸價之虞。
<觸媒(B)>
本發明之聚酯樹脂組成物中,更宜含有觸媒(B)。藉由含有觸媒(B),可促進聚酯樹脂(A)之加熱處理時之自我交聯性,可增加THF不溶物,可改善硬化性。觸媒,例如可舉例硫酸、對甲苯磺酸、十二烷基苯磺酸、萘磺酸、二壬基萘磺酸、二壬基萘二磺酸、樟腦磺酸、磷酸等酸觸媒及將此等予以胺封端(添加胺而一部分中和)而成者、二月桂酸二丁基錫等有機錫化合物、四丁氧基鈦等鈦化合物、乙酸鋅等鋅化合物、氯化鉿-THF錯合物等鉿化合物、三氟甲磺酸鈧等稀土類化合物,可從此等之中使用1種、或合併使用2種以上。其中考量與聚酯樹脂(A)之相容性、衛生性之方面,十二烷基苯磺酸及其中和物為理想。
本發明之聚酯樹脂組成物中的聚酯樹脂(A)及觸媒(B)之摻合比,宜為(A)/(B)=100/0.01~0.5(質量比),更宜為100/0.05~0.4(質量比),最佳為100/0.1~0.3(質量比)。若在上述範圍內,可改善聚酯樹脂組成物之硬化性。
本發明之聚酯樹脂組成物中,觸媒(B)可包含在聚酯樹脂(A)中,亦可在之後添加。就避免聚酯樹脂(A)聚合時之膠凝化之觀點,宜在製造聚酯樹脂(A)後添加觸媒(B)。
本發明之聚酯樹脂組成物中亦可添加自由基聚合禁止劑(C)。主要係為了用來防止聚合聚酯樹脂(A)時之由不飽和鍵開裂所致之膠凝化,為了提高聚酯樹脂(A)之貯存穩定性,亦可在聚合後添加。自由基聚合禁止劑(C),可示例為酚系抗氧化劑、磷系抗氧化劑、胺系抗氧化劑、硫系抗氧化劑、無機化合物系抗氧化劑等公知者。
酚系抗氧化劑,可舉例2,5-二-第三丁基氫醌、4,4’-亞丁基雙(3-甲基-6-第三丁基苯酚)、1,1,3-參(2-甲基-4-羥基-5-第三丁基苯基)丁烷、1,3,5-三甲基-2,4,6-參(3,5-二-第三丁基-4-羥基苄基)苯、參(3,5-二-第三丁基-4-羥苯)異氰尿酸酯等、或此等之衍生物等。
磷系抗氧化劑,可舉例亞磷酸三(壬基苯)酯、亞磷酸三苯酯、亞磷酸二苯基異癸酯、亞磷酸三(十八基)酯、亞磷酸十三酯、亞磷酸二苯基癸酯、亞磷酸4,4’-亞丁基-雙(3-甲基-6-第三丁基苯基-二(十三基)酯、二亞磷酸二硬脂基新戊四醇酯、三硫代亞磷酸三月桂基酯等、或此等之衍生物等。
胺系抗氧化劑,可舉例苯基-β-萘胺、啡噻𠯤(phenothiazine)、N,N’-二苯基-對苯二胺、N,N’-二-β-萘基-對苯二胺、N-環己基-N’-苯基-對苯二胺、醛醇-α-萘胺、2,2,4-三甲基-1,2-二氫喹啉聚合物等、或此等之衍生物等。
硫系抗氧化劑,可舉例硫代雙(N-苯基-β-萘胺、2-巰基苯并噻唑、2-巰基苯并咪唑、二硫化四甲基秋蘭姆(Tetramethylthiuram disulfide)、異丙基黃原酸鎳(nickel isopropylxanthate)等、或此等之衍生物。
硝基化合物系抗氧化劑,可舉例1,3,5-三硝基苯、對亞硝基二苯胺、對亞硝基二甲苯胺、1-氯-3-硝基苯、鄰二硝基苯、間二硝基苯、對二硝基苯、對硝基苯甲酸、硝基苯、2-硝基-5-氰基噻吩等、或此等之衍生物。
無機化合物系抗氧化劑,可舉例FeCl3、Fe(CN)3、CuCl2、CoCl3、Co(ClO4)3、Co(NO3)3、Co2(SO4)3等。
本發明中使用之自由基聚合禁止劑(C),在上述抗氧化劑之中,就熱穩定性之觀點宜為酚系抗氧化劑、胺系抗氧化劑,熔點為120℃以上且分子量為200以上者為較佳,熔點為170℃以上者為更佳。具體而言,為啡噻𠯤、4,4’-亞丁基雙(3-甲基-6-第三丁基苯酚)等。
本發明之聚酯樹脂組成物中的聚酯樹脂(A)及自由基聚合禁止劑(C)之摻合比,宜為(A)/(C)=100/0.001~0.5(質量比),更宜為100/0.01~0.1(質量比),最佳為100/0.02~0.08(質量比)。藉由在上述範圍內,可抑制聚酯樹脂(A)製造中的膠凝化。
本發明之聚酯樹脂組成物中,配合要求之特性,可摻合氧化鈦、氧化矽等公知的無機顏料、磷酸及其酯化物、表面平滑劑、消泡劑、分散劑、潤滑劑等公知的添加劑。尤其是潤滑劑,對於為了賦予DI罐、DR(或DRD)罐等在成形時必須的塗膜之潤滑性係重要,可舉例如係多元醇化合物與脂肪酸之酯化物之脂肪酸酯蠟、矽系蠟、氟系蠟、聚乙烯等聚烯烴蠟、羊毛脂系蠟、褐煤蠟、微晶蠟等作為理想的潤滑劑。潤滑劑,可使用1種或混合2種以上使用。
本發明之聚酯樹脂組成物,可在經溶解於公知的有機溶劑中之狀態下進行塗料化。塗料化中使用之有機溶劑,例如可舉例甲苯、二甲苯、乙酸乙酯、乙酸丁酯、甲乙酮、甲基異丁基酮、環己酮、異佛爾酮、甲基賽珞蘇、丁基賽珞蘇、乙二醇單乙醚醋酸酯、二甘醇單乙醚醋酸酯、乙二醇單醋酸酯、甲醇、乙醇、丁醇、乙二醇單乙醚、乙二醇單丁醚、二甘醇單丁醚、SOLVESSO等。從此等之中,考慮溶解性、蒸發速度等,可選擇1種或2種以上使用。
本發明之聚酯樹脂組成物,可使用公知的粉碎方法進行粉體塗料化。公知的粉碎方法,例如可舉例粉碎法。粉碎法,係將本發明之聚酯樹脂組成物、根據需要之防鏽顏料及添加劑等之混合物,使用轉鼓混合機、亨舍爾混合機等混合機進行乾式混合,並藉由混練機進行熔融混練。混練機,例如可使用1軸或2軸之擠壓機、三輥研磨機、PLASTOMILL等一般的混練機。使混練物冷卻固化,並將固化物予以粗粉碎及細粉碎而得到粉碎物。粉碎機,例如,可舉例利用超音速噴射氣流來進行粉碎之噴射式粉碎機、及在高速旋轉的旋轉子(rotor)及固定子(liner)之間形成的空間中導入固化物並予以粉碎之衝擊式粉碎機。此外,亦可因應需要在粉碎物中進一步添加添加劑。可將粉碎物分級來將粉體調整至期望的粒徑及期望的粒徑分布而得到粉體塗料組成物。分級可使用可藉由離心力及風力所為之分級將過粉碎調色劑母粒去除之公知的分級機,例如可使用迴旋式風力分級機(旋轉式風力分級機)等。
本發明之聚酯樹脂組成物中,可摻合為了賦予塗膜可撓性、密接性等改質之其他的樹脂。作為其他的樹脂的例子,可舉例非晶性聚酯、結晶性聚酯、乙烯-聚合性不飽和羧酸共聚物、及乙烯-聚合性羧酸共聚物離子聚合物,藉由摻合選自此等中之至少1種以上之樹脂,有可賦予塗膜之可撓性及/或密接性之情形。
本發明之聚酯樹脂組成物,只要是可用於飲料罐、罐頭用罐、其蓋、罩蓋(cap)等之由金屬材料構成的金屬板,則可塗裝在其單面或是兩面,此外如有需要亦可塗裝在端面。上述金屬材料,例如可舉例馬口鐵、無錫鋼、鋁等。由此等金屬材料構成的金屬板,亦可使用事先施以了磷酸處理、鉻酸鉻酸鹽處理、磷酸鉻酸鹽處理、其他的防鏽處理劑所為之防蝕處理、為了改善塗膜之密接性之表面處理者。
可將本發明之聚酯樹脂組成物藉由輥塗機塗裝、噴霧塗裝等公知的塗裝方法塗裝於金屬板並硬化。塗裝膜厚並無特別限制,乾燥膜厚宜為3~18μm,更宜為5~15μm之範圍。塗膜之烘烤條件,通常係在約180~260℃之範圍進行約10分鐘~2小時,更宜為在約200~240℃之範圍進行約5分鐘~1小時。
<聚酯樹脂水分散體>
本發明之聚酯樹脂組成物,可分散在水性介質中並以聚酯樹脂水分散體的形式使用。
使本發明中使用之聚酯樹脂(A)水分散體化之方法,有將聚酯樹脂(A)溶解在會溶解聚酯樹脂(A)的水溶性有機溶劑中,並因應需要逐次加入鹼性化合物、水來進行分散之方法(a)、加入聚酯樹脂(A)及水、溶解聚酯樹脂(A)之水溶性有機溶劑、因應需要之鹼性化合物,並加熱來進行分散之方法(b)等。此外,欲將有機溶劑減量時、或欲將其完全去除來進行水分散體化時,亦可在使用具有100℃以下之沸點之有機溶劑進行分散後,加熱或在減壓下將溶劑去除。在聚酯樹脂(A)之情形,考量造膜性之觀點宜進行前者之方法(a)。
此情形下,聚酯樹脂(A)溶解時之溫度以40~160℃為佳,50~140℃為較佳,60~120℃為更佳,70~100℃為最佳。若未達40℃,則有時會有聚酯樹脂(A)之溶解變得不充分之情形,故無法充分地解開分子鏈彼此之糾纏,此外若超過160℃,則導致聚酯樹脂(A)之劣化之風險會提高。作為在40~160℃之溫度範圍內加熱因而可溶解聚酯樹脂(A)之有機溶劑,可舉例甲乙酮、二甲基乙醯胺、二甲基甲醯胺、N-甲基吡咯啶酮、四氫呋喃、1,4-二㗁烷、1,3-二㗁烷、1,3-二氧五環、1,2-己二醇、甲基賽珞蘇、丁基賽珞蘇、乙基卡必醇、丁基卡必醇、丙二醇單丙醚、丙二醇單丁醚、三乙二醇單丁醚等。其中,宜為甲乙酮、丁基賽珞蘇、丙二醇單丙醚、丙二醇單丁醚等。
於100℃以上溶解聚酯樹脂(A)之情形,必須將聚酯樹脂溶液之溫度冷卻至100℃以下後邊攪拌該樹脂溶液邊逐次添加水及因應需要之鹼性化合物來進行相轉移藉此得到水分散體。
作為在使本發明之聚酯樹脂(A)水分散體化時使用之鹼性化合物,宜為在塗膜形成時之乾燥、烘烤步驟會揮發之化合物,係使用氨及/或沸點為250℃以下之有機胺化合物等。宜可舉例如三乙胺、N,N-二乙基乙醇胺、N,N-二甲基乙醇胺、胺基乙醇胺、N-甲基-N,N-二乙醇胺、異丙胺、亞胺基雙丙胺、乙胺、二乙胺、3-乙氧基丙胺、3-二乙基胺丙胺、第二丁胺、丙胺、甲基胺丙胺、二甲基胺丙胺、甲基亞胺基雙丙胺、3-甲氧基丙胺、單乙醇胺、二乙醇胺、三乙醇胺、𠰌啉、N-甲基𠰌啉、N-乙基𠰌啉等。此等鹼性化合物,必須為至少能夠部分中和聚酯樹脂(A)之羧基的量,具體而言,相對於羧基當量添加0.5~1.5當量為理想。
本發明之聚酯樹脂水分散體之平均粒徑,會大幅地影響塗膜外觀、保存穩定性,故非常的重要,宜為30~250nm。更宜為50~200nm,特宜為70~150nm。若平均粒徑超過250nm,不僅分散穩定性會大幅地降低,造膜性亦會降低,故得到的皮膜之外觀會惡化。此外相反地若未達30nm,則有造膜性顯著地上升之傾向,因而在分散粒子間之融合、凝聚容易發生,結果引起增黏、分散不良之可能性會提高而並不理想。
本發明之聚酯樹脂水分散體,宜為以10~45質量%之樹脂固體成分濃度來製作。較宜為15~40質量%,更宜為20~35質量%之範圍。若樹脂固體成分濃度超過45質量%,則水分散體之黏度會變高,並且樹脂粒子間之凝聚變得容易發生,故分散穩定性會大幅地降低。此外未達10質量%時,則考量製造面、用途面之雙方面難以稱為實用。
本發明之聚酯樹脂水分散體,最適合用於食品、飲料用罐之內面塗料。為了作為食品、飲料用罐之內面塗料,因應目的有時會摻合各種添加劑。可將為了使塗佈性、塗膜之平滑性、外觀改善之調平劑、界面活性劑、為了防止塗膜之傷痕之潤滑劑、以及著色顏料、根據情形之聚酯樹脂(A)以外的聚酯樹脂、聚酯樹脂以外的樹脂,例如丙烯酸樹脂乳劑、聚胺酯樹脂乳劑等,在不損及食品衛生性、味道性等本發明之目的之範圍內予以摻合。
使用了本發明之聚酯樹脂水分散體之塗料,能夠藉由輪轉凹輥塗佈機、逗點式塗佈機(comma coater)、噴霧法等塗裝在鋁、不銹鋼、馬口鐵等之罐用金屬基材。膜厚並無特別限制,通常以乾燥膜厚計為3~18μm,更宜為5~15μm之範圍。塗膜之烘烤條件通常係在約180~260℃之範圍進行約10分鐘~2小時,更宜為在約200~240℃之範圍進行約5分鐘~1小時。
[實施例]
以下藉由實施例更詳細地說明本發明,但本發明並不受限於此等實施例。各種的特性之評價係依照下述方法。簡稱為「份」者係表示質量份,簡稱為「%」者係表示質量%。
<聚酯樹脂(A)>
(1)樹脂組成之測定
將聚酯樹脂(A)之試料溶解在氘代氯仿中,並使用VARIAN公司製核磁共振(NMR)裝置400-MR,進行1H-NMR分析。藉由其積分值比來求出莫耳比。
(2)還原黏度(單位:dl/g)之測定
將聚酯樹脂(A)之試料0.1g溶解在酚/四氯乙烷(質量比6/4)之混合溶劑25cc中,並於30℃進行測定。
(3)玻璃轉移溫度(Tg)之測定
藉由差示掃描型熱量計(SII公司、DSC-200)進行測定。將聚酯樹脂(A)之試料5mg裝入鋁製的押蓋型容器中並密封,使用液態氮冷卻至-50℃,然後以20℃/分昇溫至150℃。於此過程得到的吸熱曲線中,係取吸熱峰部出現前的基線與朝向吸熱峰部的切線之交點之溫度,定義為玻璃轉移溫度(Tg,單位:℃)。
(4)酸價之測定
將聚酯樹脂(A)之試料0.2g溶解在40ml之氯仿中,以0.01N之氫氧化鉀乙醇溶液進行滴定,求得每10
6g之聚酯樹脂的當量(eq/ton)。指示劑係使用酚酞。
<聚酯樹脂組成物之製作>
將聚酯樹脂(A)100質量份(固體成分)溶解在環己酮/SOLVESSO150=1/1(質量比)中以成為適合塗裝的黏度。依照表2及表3之摻合,得到聚酯樹脂組成物(固體成分約35質量%)。
(5)THF不溶物之測定
於240℃加熱處理1小時時之THF不溶物,係將聚酯樹脂組成物以在銅箔上乾燥後之厚度成為10μm之方式進行塗佈,於240℃加熱1小時,經製成長10cm、寬2.5cm之尺寸的樣本之THF浸漬前質量定義為(X),將於25℃、浸漬於60ml之THF中1小時後,以100℃乾燥10分鐘後的樣本之質量定義為THF浸漬後質量(Y),藉由下式求得。
THF不溶物(質量%)=〔{(Y)-銅箔質量}/{(X)-銅箔質量}〕×100
此外,於150℃加熱處理30分鐘時之THF不溶物,係將溫度設定為150℃且加熱30分鐘,除此之外,係以與上述相同之方式求得。
<試驗片之製作>
使用棒塗機,於馬口鐵板(JIS G 3303(2008) SPTE、70mm×150mm×0.3mm)之單面以聚酯樹脂組成物乾燥後之膜厚成為10±2μm之方式進行塗裝,烘烤條件設定為240℃(PMT:基材到達最高溫度)×1小時來進行硬化烘烤,並將其作為試驗片(以下稱作試驗片)。
(6)加工性之評價
將得到的試驗片以向硬化膜成為外側之方向施以180°折彎加工,針對折彎部產生的硬化膜之裂痕測定通電值藉此來進行評價。此外,折彎加工,係在中間沒有夾入任何東西(意即0T)來進行折彎。準備在鋁板製的電極(寬20mm、深度50mm、厚度0.5mm)上放置了浸泡過1%NaCl水溶液的海綿(寬20mm、深度50mm、厚度10mm)之物品,以與海綿的20mm的邊呈平行之方式使試驗片之折彎部之中央部附近與海綿接觸。在鋁板電極與試驗板之背面之非塗裝部之間施加5.0V的直流電壓,並測定通電值。通電值較小者意味折彎特性較良好。
(判定)
◎:未達 0.5mA
○:0.5mA以上且未達1.0mA
△:1.0mA以上且未達2.0mA
×:2.0mA以上
(7)硬化性之評價
將浸泡過甲乙酮的紗布氈以接觸1cm
2之方式推壓在試驗片之硬化膜面,施加500g之負重並進行摩擦試驗。將直到硬化膜剝落為止之次數(往返一次定義為一次),按以下基準進行評價。
(判定)
◎:即使50次以上塗膜亦不會剝落,於硬化膜未觀察到變化
○:於25~49次硬化膜會剝落而馬口鐵板會暴露
△:於16~24次硬化膜會剝落而馬口鐵板會暴露
×:於15次以下硬化膜會剝落而馬口鐵板會暴露
(8)耐蒸煮性之評價
將試驗片豎直放入不鏽鋼杯中,在其中注入離子交換水直到試驗片的一半高度,將其設置在蒸煮試驗機(TOMY工業(股)製 ES-315)的壓力釜之中,進行125℃×30分鐘之蒸煮處理。處理後之評價,係在認為會暴露在比通常對硬化膜而言更嚴苛的條件下之蒸氣接觸部分進行,以目視如下列方式判定硬化膜之白化、氣泡之狀態。
(判定)
◎:良好(沒有白化以及氣泡)
○:有輕微白化但沒有氣泡
△:有一些白化及/或一些氣泡
×:有顯著的白化及/或顯著的氣泡
聚酯樹脂(A)之合成例(a)
將對苯二甲酸二甲基740質量份、2,6-萘二羧酸二甲酯100質量份、偏苯三甲酸酐8質量份、乙二醇190質量份、1,2-丙二醇330質量份、1,4-環己烷二甲醇190質量份、作為觸媒之鈦酸正四丁酯(以下有時簡稱為TBT)0.4質量份(相對於全部酸成分為0.03莫耳%)進料在3L四口燒瓶中,邊耗時3小時緩慢地升溫至230℃邊進行酯化反應。然後使系統內緩慢地減壓,耗時1小時進行減壓聚合至10mmHg同時使溫度升溫至250℃,並且在1mmHg以下的真空下進行50分鐘後期聚合。當達到目標分子量後使其在氮氣環境下冷卻至210℃。然後投入偏苯三甲酸酐26質量份,在氮氣環境下,於200~230℃持續攪拌30分鐘。將其取出而得到聚酯樹脂(合成例(a))。得到的聚酯樹脂之還原黏度為0.33dl/g、玻璃轉移溫度(Tg)為65℃、酸價為300eq/t。
合成例(b)~(t)
與合成例(a)同樣地使用直接聚合法,但是變更進料組成,製造樹脂組成如表1所示的聚酯樹脂(合成例(b)~(t))。
[表1]
合成例 | a | b | c | d | e | f | g | h | i | j | k | l | m | n | o | p | q | r | s | t | ||
樹脂 組成 | 多元羧酸成分(莫耳%) | 對苯二甲酸 | 79 | 79 | 79 | 69 | 79 | 80 | 79 | 79 | 79 | 79 | 79 | 79 | 80 | 89 | 49 | 79 | 79 | 79 | 79 | 79 |
2,6-萘二羧酸 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 50 | 10 | 10 | 10 | 10 | 10 | |||
鄰苯二甲酸 | 10 | |||||||||||||||||||||
己二酸 | 10 | |||||||||||||||||||||
富馬酸 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | ||||
偏苯三甲酸酐 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | ||||
偏苯三甲酸酐(後加成) | 3 | 3 | 1 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 1 | 3 | 3 | 0.8 | 0.6 | 3 | ||
多元醇成分(莫耳%) | 乙二醇 | 35 | 35 | 35 | 70 | 35 | 80 | 50 | 20 | 80 | 25 | 35 | 35 | 50 | 50 | 35 | 35 | 30 | ||||
1,6-己二醇 | 30 | 40 | ||||||||||||||||||||
新戊二醇 | 50 | |||||||||||||||||||||
1,2-丙二醇 | 35 | 35 | 35 | 40 | 59 | 35 | 20 | 30 | 75 | 35 | 35 | 70 | 35 | 35 | 40 | |||||||
1,4-環己烷二甲醇 | 30 | 30 | 30 | 30 | 30 | 50 | 50 | 20 | 30 | 30 | 50 | 30 | 30 | 30 | 30 | |||||||
三環癸烷二甲醇 | 30 | |||||||||||||||||||||
三羥甲基丙烷 | 1 | |||||||||||||||||||||
樹脂特性 | 還原黏度 (dl/g) | 0.33 | 0.35 | 0.33 | 0.35 | 0.60 | 0.35 | 0.35 | 0.45 | 0.28 | 0.30 | 0.30 | 0.30 | 0.35 | 0.30 | 0.30 | 0.40 | 0.30 | 0.33 | 0.33 | 0.25 | |
酸價 (eq/ton) | 300 | 300 | 120 | 290 | 300 | 300 | 310 | 280 | 320 | 320 | 320 | 320 | 300 | 300 | 120 | 300 | 300 | 90 | 70 | 280 | ||
Tg (℃) | 65 | 65 | 65 | 60 | 45 | 40 | 78 | 60 | 80 | 80 | 70 | 85 | 65 | 75 | 95 | 60 | 90 | 65 | 65 | 65 |
使用得到的聚酯樹脂製作聚酯樹脂組成物,實施加工性、硬化性及耐蒸煮性之評價。聚酯樹脂組成物之摻合、及評價結果表示於表2及表3。
[表2]
項目 | 實施例 | ||||||||||||||||||
1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | |||
聚酯樹脂組成物 (固體質量比) | 樹脂 | 聚酯樹脂 | a 100 | b 100 | c 100 | d 100 | e 100 | f 100 | g 100 | h 100 | i 100 | j 100 | k 100 | l 100 | m 100 | n 100 | o 100 | p 100 | q 100 |
觸媒 | 十二烷基苯磺酸 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | |||||||
評價 | THF不溶物(質量%) <240℃ 1小時> | 70 | 90 | 60 | 90 | 90 | 80 | 90 | 80 | 80 | 80 | 80 | 80 | 60 | 45 | 20 | 45 | 40 | |
THF不溶物(質量%) <150℃ 30分鐘> | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | ||
加工性 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | △ | ○ | △ | ||
硬化性 | ◎ | ◎ | ○ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | ○ | ○ | ○ | ||
耐蒸煮性 | ○ | ◎ | ○ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | △ | △ | ○ | △ | △ |
[表3]
項目 | 比較例 | ||||
1 | 2 | 3 | |||
聚酯樹脂組成物 (固體質量比) | 樹脂 | 聚酯樹脂 | r 100 | s 100 | t 100 |
觸媒 | 十二烷基苯磺酸 | ||||
硬化劑 | PR-521 (※) | 5 | |||
評價 | THF不溶物(質量%) <240℃ 1小時> | 7 | 3 | 80 | |
THF不溶物(質量%) <150℃ 30分鐘> | 0 | 0 | 0 | ||
加工性 | × | × | × | ||
硬化性 | × | × | △ | ||
耐蒸煮性 | × | × | △ | ||
(※)PR-521:酚醛樹脂硬化劑(Allnex公司製 PHENODUR PR-521) |
由表2可明白,從使用了本發明之聚酯樹脂(A)之聚酯樹脂組成物得到之硬化膜(塗膜),其加工性、硬化性、耐蒸煮性皆優良。而如表3所示,比較例1、2由於聚酯樹脂之酸價低,硬化性變得不充分,加工性、耐蒸煮性亦不良。比較例3由於摻合了硬化劑,加工性不良。
[產業上利用性]
本發明製品係加工性、硬化性、耐蒸煮性優良的聚酯樹脂組成物,及聚酯樹脂水分散體、及含有其之塗料、塗膜,適合作為塗裝在食品、及飲料用金屬罐等之塗料之主劑。
Claims (11)
- 一種聚酯樹脂組成物,含有聚酯樹脂(A)且滿足以下(i)~(iii)之要件: (i)聚酯樹脂(A)之酸價為100eq/ton以上; (ii)實質上不含有硬化劑; (iii)將聚酯樹脂組成物於240℃加熱處理1小時時之四氫呋喃不溶物為10質量%以上。
- 如請求項1之聚酯樹脂組成物,其中,該聚酯樹脂(A)具有分支結構。
- 如請求項1或2之聚酯樹脂組成物,其中,該聚酯樹脂(A)中,就構成該聚酯樹脂(A)之多元醇成分而言,具有具2個1級羥基且不具脂環結構之二醇(a),更具有具脂環結構之二醇(b)及具1個1級羥基及1個2級羥基且不具脂環結構之二醇(c)中之任一者或兩者。
- 如請求項1或2之聚酯樹脂組成物,其中,該聚酯樹脂(A)中,作為構成該聚酯樹脂(A)之多元羧酸成分,含有選自由己二酸、2,6-萘二羧酸及1,4-環己烷二羧酸構成之群組中之至少一種。
- 如請求項1或2之聚酯樹脂組成物,其中,該聚酯樹脂(A)中,作為構成該聚酯樹脂(A)之多元羧酸成分,具有不飽和二羧酸(d)。
- 如請求項1或2之聚酯樹脂組成物,其中,於150℃加熱處理30分鐘時之四氫呋喃不溶物未達10質量%,且更含有1種以上之觸媒(B)。
- 如請求項6之聚酯樹脂組成物,其中,相對於聚酯樹脂(A)100質量份,觸媒(B)之含量為0.01~0.5質量份。
- 一種聚酯樹脂水分散體,含有如請求項1至7中之任一項之聚酯樹脂組成物及水性介質。
- 一種塗料組成物,含有如請求項1至7中之任一項之聚酯樹脂組成物或如請求項8之聚酯樹脂水分散體中之任一者。
- 一種塗膜,含有如請求項1至7中之任一項之聚酯樹脂組成物。
- 一種金屬罐,具有如請求項10之塗膜。
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US (1) | US20240110005A1 (zh) |
EP (1) | EP4289904A1 (zh) |
JP (1) | JPWO2022168910A1 (zh) |
KR (1) | KR20230142751A (zh) |
CN (1) | CN116848171A (zh) |
TW (1) | TW202241990A (zh) |
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JP3501234B2 (ja) * | 1993-01-05 | 2004-03-02 | 東洋紡績株式会社 | 共重合ポリエステル樹脂系水分散体及びその製造法 |
JP2001081160A (ja) | 1999-09-13 | 2001-03-27 | Unitika Ltd | 金属缶内面用の被膜形成用共重合ポリエステル樹脂、並びにこれを含有する塗料 |
JP2001106969A (ja) * | 1999-10-07 | 2001-04-17 | Toyobo Co Ltd | 3ピース缶内面用塗料樹脂組成物及びこれを塗布した缶内面用塗装金属板 |
JP4968993B2 (ja) * | 2000-09-28 | 2012-07-04 | ユニチカ株式会社 | ポリエステル樹脂水性分散体およびその製造方法 |
JP4310973B2 (ja) * | 2001-07-06 | 2009-08-12 | 東洋紡績株式会社 | 水分散型樹脂組成物、これを含む水分散型塗料、その塗料を用いた塗膜、その塗膜を用いた金属板および缶 |
DE102004060798A1 (de) | 2004-12-17 | 2006-06-29 | Bayer Materialscience Ag | Wässrige Beschichtungen für Nahrungsmittelbehälter |
JP5028842B2 (ja) * | 2006-04-12 | 2012-09-19 | 東洋紡績株式会社 | ポリエステル樹脂水分散体 |
JP2008007719A (ja) * | 2006-06-30 | 2008-01-17 | Toyobo Co Ltd | ポリエステル樹脂水分散体及びこれを用いた接着剤、コーティング剤、塗料 |
JP7329949B2 (ja) * | 2019-03-29 | 2023-08-21 | 東洋紡株式会社 | 組成物、積層体及び被覆金属製品 |
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- 2022-02-03 EP EP22749781.5A patent/EP4289904A1/en active Pending
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- 2022-02-03 CN CN202280013121.2A patent/CN116848171A/zh active Pending
- 2022-02-03 KR KR1020237029392A patent/KR20230142751A/ko unknown
- 2022-02-03 WO PCT/JP2022/004239 patent/WO2022168910A1/ja active Application Filing
- 2022-02-03 JP JP2022534326A patent/JPWO2022168910A1/ja active Pending
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WO2022168910A1 (ja) | 2022-08-11 |
CN116848171A (zh) | 2023-10-03 |
JPWO2022168910A1 (zh) | 2022-08-11 |
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