TW202219186A - 生物分解性樹脂水系分散體及其製造方法,及使用生物分解性樹脂水系分散體的食品包裝用紙 - Google Patents
生物分解性樹脂水系分散體及其製造方法,及使用生物分解性樹脂水系分散體的食品包裝用紙 Download PDFInfo
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- TW202219186A TW202219186A TW110133050A TW110133050A TW202219186A TW 202219186 A TW202219186 A TW 202219186A TW 110133050 A TW110133050 A TW 110133050A TW 110133050 A TW110133050 A TW 110133050A TW 202219186 A TW202219186 A TW 202219186A
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- Prior art keywords
- biodegradable resin
- aqueous
- anionic compound
- dispersion
- sodium
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Abstract
本發明提供一種生物分解性樹脂水系分散體及其製造方法,前述生物分解性樹脂水系分散體係具有穩定之分散性,不會降低生物分解性而可提升紙製品等的熱封性。
本發明之生物分解性樹脂水系分散體,係含有生物分解性樹脂與陰離子性化合物的生物分解性樹脂水系分散體,其中,前述陰離子性化合物的1質量%水溶液中的pH為7以上。
Description
本發明係關於一種生物分解性樹脂水系分散體及其製造方法,及使用生物分解性樹脂水系分散體的食品包裝用紙。
以往已知具有耐油性及熱封(heat seal)性的食品包裝用紙。具體而言,以往的食品包裝紙中係例如以聚丙烯(PP)或聚乙烯(PE)對紙實施積層(laminate)加工,藉此賦予耐油性和熱封性。
另一方面,在近年來環境意識的提高及海洋塑膠垃圾問題之背景下,替代塑膠之材料的需求正在提高。其中,正在尋求於塑膠使用比例高的食品包裝用途方面的替代物,在食品包裝用紙方面也正在進行具有生物分解性而且能夠替代PP或PE的材料之開發。
例如,有人提出了作為具有生物分解性的材料之生物分解性樹脂水系分散體(例如,專利文獻1至5)。此等生物分解性樹脂水系分散體中,係使用靜電交互作用更優異的陰離子性化合物來作為分散劑。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開平10-101911號公報
[專利文獻2]日本特開2004-035811號公報
[專利文獻3]日本特開2004-168927號公報
[專利文獻4]日本特開2004-323640號公報
[專利文獻5]國際公開第2016/080530號
然而,生物分解性樹脂水系分散體中,若未使用適當之pH範圍的陰離子性化合物,則生物分解性樹脂的分散性會變差,生物分解性樹脂的粒徑無法變小,故在塗佈至紙製品的情況下,會有難以確保充分的熱封性之問題。而且,如專利文獻1至5的以往之生物分解性樹脂水系分散體並未著眼於陰離子性化合物的pH範圍,而是使用pH範圍不適當的陰離子性化合物,因此難以得到穩定的分散體,關於熱封性尚有改善的空間。
再者,為了將生物分解性樹脂水系分散體使用於食品包裝,必須為基於食品衛生法規之食品、添加物等的判斷基準、FDA(美國食品醫藥品局)的
使用許可清單中收錄的物質。因此,開發食品包裝用的新穎生物分解性樹脂水系分散體時,亦必須考量在能夠使用之材料方面有所限制。
本發明係有鑒於以上情況而完成,其課題在於提供一種生物分解性樹脂水系分散體及其製造方法,該生物分解性樹脂水系分散體具有穩定之分散性,不會降低生物分解性而可提升紙製品等的熱封性。又,一課題在於提供一種具有生物分解性且熱封性優異的食品包裝用紙。
為了解決上述課題,本發明之生物分解性樹脂水系分散體係含有生物分解性樹脂與陰離子性化合物者,其中,前述陰離子性化合物的1質量%水溶液中的pH為7以上。
該生物分解性樹脂水系分散體中,前述陰離子性化合物較佳為選自構成脂肪酸的碳數為12至16之脂肪酸鹽、十四烯磺酸鈉、聚磷酸鈉、羧甲基纖維素鈉、烷基苯磺酸鈉、聚丙烯酸鈉的至少1種。
該生物分解性樹脂水系分散體中,前述陰離子性化合物較佳為選自構成脂肪酸的碳數為12至16之脂肪酸鹽、十四烯磺酸鈉、聚磷酸鈉、羧甲基纖維素鈉、聚丙烯酸鈉的至少1種。
該生物分解性樹脂水系分散體中,前述陰離子性化合物較佳為選自構成脂肪酸的碳數為12至16之脂肪酸鹽、十四烯磺酸鈉、聚丙烯酸鈉的至少1種。
該生物分解性樹脂水系分散體中,前述陰離子性化合物較佳為選自構成脂肪酸的碳數為12至16之脂肪酸鹽、聚丙烯酸鈉的至少1種。
該生物分解性樹脂水系分散體中,前述陰離子性化合物的重量平均分子量較佳為1萬至2000萬。
該生物分解性樹脂水系分散體中,較佳為含有作為分散穩定劑的皂化度70至90%之聚乙烯醇及作為黏度調整劑的選自瓜爾膠、阿拉伯膠、三仙膠之至少1種,
前述陰離子性化合物(A)與前述聚乙烯醇(B)的質量比(A/B)在1/2至1/99的範圍內,
相對於前述生物分解性樹脂之前述黏度調整劑的添加量為0.05至1.0質量%。
該生物分解性樹脂水系分散體中,前述生物分解性樹脂較佳為聚乳酸。
本發明之食品包裝用紙係使用前述生物分解性樹脂水系分散體。
本發明之生物分解性樹脂水系分散體的製造方法係含有生物分解性樹脂與陰離子性化合物的生物分解性樹脂水系分散體的製造方法,其中包含:分散步驟,係至少使已溶解之前述生物分解性樹脂與前述陰離子性化合物分散於溶劑中而得到分散液;
前述陰離子性化合物的1質量%水溶液中的pH為7以上,
前述分散步驟的前述分散液的pH為4至9。
本發明之生物分解性樹脂水系分散體係藉由前述製造方法而得。
本發明之生物分解性樹脂分散體具有穩定之分散性,不會降低生物分解性,且可提升纖維製品或紙製品等的熱封性。本發明之生物分解性樹脂分散體的製造方法可確實地得到前述生物分解性樹脂分散體。本發明之食品包裝用紙具有生物分解性,且熱封性優異。
以下對於本發明之生物分解性樹脂水系分散體及其製造方法,以及食品包裝用紙之一實施型態進行說明。
本發明之生物分解性樹脂水系分散體(以下有記載為「水系分散體」之情形)係含有生物分解性樹脂與陰離子性化合物(分散劑)。
又,本發明之生物分解性樹脂水系分散體的製造方法包含分散步驟,該分散步驟係至少使已溶解之生物分解性樹脂與陰離子性化合物分散於溶劑中而得到分散液。
生物分解性樹脂並無特別限定,但可列舉例如:聚乳酸、乳酸與其他羥基羧酸的共聚物、聚丁二酸丁二醇酯(polybutylene succinate)、聚丁二酸/己二酸丁二醇酯(polybutylene succinate adipate)、聚丁二酸乙二醇酯、聚己二酸丁二醇酯等二元酸聚酯;聚己內酯、己內酯與其他羥基羧酸的共聚物、聚羥基丁酸酯、聚羥基丁酸酯與其他羥基羧酸的共聚物、聚羥基丁酸、聚羥基丁酸與其他羥基羧酸的共聚物等。此等可單獨使用或混合2種以上使用。其中,從樹脂的耐熱性、耐水性、耐溶劑性、光澤等的觀點來看,生物分解性樹脂較佳為聚乳酸、乳酸與其他羥基羧酸的共聚物、聚丁二酸丁二醇酯、聚丁二酸/己二酸丁二醇酯、聚己內酯,更佳為聚乳酸。
作為聚乳酸,D-乳酸含有率較佳為1至30莫耳%,更佳為5至20莫耳%。
又,生物分解性樹脂的數量平均分子量較佳在5000至100萬的範圍內,更佳在1萬至30萬的範圍內。
就乳酸與其他羥基羧酸的共聚物而言,其他羥基羧酸係可列舉:乙醇酸、2-羥基丁酸、2-羥基戊酸、2-羥基己酸、2-羥基庚酸、2-羥基辛酸、2-羥基-2-甲基丙酸、2-羥基-2-甲基丁酸、2-羥基-2-乙基丁酸、2-羥基-2-甲基戊酸、2-羥基-2-乙基戊酸、2-羥基-2-丙基戊酸、2-羥基-2-丁基戊酸、2-羥基-2-甲基己酸、2-羥基-2-乙基己酸、2-羥基-2-丙基己酸、2-羥基-2-丁基己酸、2-羥基-2-戊基己酸、2-羥基-2-甲基庚酸、2-羥基-2-乙基庚酸、2-羥基-2-丙基庚酸、2-羥基-2-丁基庚酸、2-羥基-2-甲基辛酸、3-羥基丙酸、4-羥基丁酸、5-羥基戊酸、6-羥基己酸、7-羥基庚酸等。
乳酸及羥基羧酸有為D體、L體、D/L體等型態之情形,惟係任一型態均可,並無限制。
陰離子性化合物的1質量%水溶液中的pH為7以上。具體而言,陰離子性化合物的1質量%水溶液中的pH較佳為7至11,更佳為pH8至10,又更佳為pH9至10。若選擇滿足此範圍的陰離子性化合物,則可適當調整分散步驟中的分散液之pH,藉此,仄他(ζ)電位(zeta potential)變得容易成為適當的值,結果係可進一步提高分散穩定性等。因此,可提升使用生物分解性樹脂水系分散液而得之紙製品等的耐水性、熱封性。另一方面,若陰離子性化合物的1質量%水溶液中的pH未達7,則仄他電位會偏離適當的值之範圍,由此導致粒子間的互斥力變弱而凝聚,分散液的穩定性降低。
陰離子性化合物並無特別限定,但可列舉例如:構成脂肪酸的碳數為12至16之脂肪酸鹽、十四烯磺酸鈉、聚磷酸鈉、羧甲基纖維素鈉、烷基苯磺酸鈉、聚丙烯酸鈉等。其中,從分散穩定性優異的觀點來看,較佳為十四烯磺
酸鈉、聚磷酸鈉、羧甲基纖維素鈉、烷基苯磺酸鈉、聚丙烯酸鈉,更佳為聚丙烯酸鈉。
從提升使用生物分解性樹脂水系分散液而得之紙製品等的熱封性的觀點來看,較佳為選自構成脂肪酸的碳數為12至16之脂肪酸鹽、十四烯磺酸鈉、聚磷酸鈉、羧甲基纖維素鈉、聚丙烯酸鈉的至少1種,更佳為選自構成脂肪酸的碳數為12至16之脂肪酸鹽、十四烯磺酸鈉、聚丙烯酸鈉的至少1種,又更佳為選自構成脂肪酸的碳數為12至16之脂肪酸鹽、聚丙烯酸鈉的至少1種。
陰離子性化合物的重量平均分子量可列舉100至2500萬的範圍,但從生物分解性樹脂水系分散體的分散穩定性及抑制增黏的觀點來看,較佳為1萬至2000萬,更佳為10萬至1000萬。此外,重量平均分子量例如可利用凝膠滲透層析法(GPC),藉由與已知分子量的標準物質進行比較而求得。
相對於生物分解性樹脂的含量,陰離子性化合物的含量較佳為0.01至5.0質量%。更佳為0.01至2.0質量%,又更佳為0.01至1.0質量%,特佳為0.01至0.8質量%。若為0.01質量%以上,則分散穩定性等的效果會進一步提升,若為5.0質量%以下,則容易穩定地控制水系分散體的黏度,同時可提升使用該生物分解性樹脂水系分散液而得之紙製品等的耐水性、熱封性。
於生物分解性樹脂水系分散體中,係可視需求而添加上述陰離子性化合物以外的界面活性劑、塑化劑、黏度調整劑等。
作為前述陰離子性化合物以外的界面活性劑係可列舉:陰離子性界面活性劑、陽離子性界面活性劑、非離子界面活性劑、兩性界面活性劑、高分子界面活性劑等。
陰離子性界面活性劑並無特別限定,但可列舉例如:脂肪酸鹽、高級醇硫酸酯鹽、液體脂肪油硫酸酯鹽、脂肪族胺及脂肪族醯胺的硫酸鹽、脂肪醇磷酸酯鹽、烷基苯磺酸鹽、脂肪族醯胺磺酸鹽、二元脂肪酸酯的磺酸鹽等。
作為陽離子性界面活性劑,可列舉例如:烷基胺鹽類、四級銨鹽類、烷基吡啶鎓鹽、脂肪酸三乙醇胺單酯鹽、烷基聚氧乙烯胺等。
作為非離子系界面活性劑,可列舉例如:聚氧乙烯烷醚、聚氧乙烯烷基酚醚、聚氧乙烯烷基酯、山梨醇酐烷基酯、聚氧乙烯山梨醇酐烷基酯等。
高分子界面活性劑可列舉:陰離子性高分子、陽離子性高分子、非離子高分子、兩性高分子等。此等高分子界面活性劑可為水溶性,可列舉例如:聚丙烯酸鹽、聚甲基丙烯酸鹽、聚丙烯醯胺、丙烯酸/甲基丙烯酸烷酯共聚物、丙烯酸鹽/丙烯醯胺共聚物、甲基丙烯酸鹽/丙烯醯胺共聚物、二異丁烯/順丁烯二酸共聚物、烷基乙烯醚/順丁烯二酸共聚物、順丁烯二酸化聚丁烯、順丁烯二酸化聚丁二烯、聚甲基乙烯醚、聚乙烯吡咯啶酮、聚苯乙烯磺酸鹽、陽離子化纖維素、羧甲基纖維素、藻酸鹽、聚乙烯醇等。此等之中,從安全性、供給方面的觀點來看,較佳為非離子高分子。
生物分解性樹脂水系分散體較佳為包含非離子高分子的聚乙烯醇作為分散穩定劑。聚乙烯醇的皂化度較佳為70至90%,數量平均分子量較佳為5至30萬。聚乙烯醇的皂化度可從聚乙烯醇的羥價算出。藉由摻混聚乙烯醇,可使生物分解性樹脂粒子穩定地分散於溶劑中。
(A)陰離子性化合物(分散劑)與(B)聚乙烯醇(分散穩定劑)的質量比(A/B)較佳係在1/2至1/99的範圍內。更佳係在1/5至1/99的範圍內,又更佳在1/10至1/99的範圍內。若質量比(A/B)在此範圍內,則容易分散,分散後的穩
定性亦提升,故可提升使用生物分解性樹脂水系分散液而得之紙製品等的耐水性、熱封性。
又,相對於生物分解性樹脂的質量,(A)陰離子性化合物(分散劑)與(B)聚乙烯醇(分散穩定劑)的總質量較佳係在0.1至20質量%的範圍內。更佳為0.5至20質量%,又更佳係在1至20質量%的範圍內。若(A)陰離子性化合物與(B)聚乙烯醇的總質量為0.1質量%以上,則容易均勻地攪拌、分散,又,若為20質量%以下,則可降低因過剩地添加分散劑所致之無效率性並且可以將對耐水性造成的影響抑制於較小。
然後,(A)陰離子性化合物(分散劑)、(B)聚乙烯醇(分散穩定劑)及生物分解性樹脂的總質量,以相對於水的質量比計係在2/8至/6/4的範圍內亦為較佳。若該質量比為2/8以上,則生物分解性樹脂變成高含量,故有效率,若為6/4以下,則變得容易均勻地攪拌、分散,水系分散體的穩定性亦提升。因此,可提升使用生物分解性樹脂水系分散液而得之紙製品等的耐水性、熱封性。
塑化劑可列舉:檸檬酸三乙酯、檸檬酸三丁酯、乙醯檸檬酸三乙酯、乙醯檸檬酸三丁酯等檸檬酸衍生物;二乙二醇二乙酸酯、三乙二醇二乙酸酯、三乙二醇二丙酸酯等醚酯衍生物;甘油三乙酸酯、甘油三丙酸酯、甘油三丁酸酯等甘油衍生物;乙基鄰苯二甲醯基甘醇酸乙酯、乙基鄰苯二甲醯基甘醇酸丁酯、丁基鄰苯二甲醯基甘醇酸丁酯等苯二甲酸衍生物;己二酸與2-(2乙氧基甲氧基)乙醇及苯甲醇的混合酯、己二酸與1,4-丁二醇的縮合物等己二酸衍生物;聚己內酯、聚丙內酯等聚羥基羧酸等。此等之中,從成膜性提升效果高的觀點來看,特佳為使用了己二酸衍生物、苯二甲酸衍生物者。生物分解性樹脂每100重量份,
塑化劑的添加量較佳為5至40重量份。若為5重量份以上,則更能發揮塑化效果,若為40重量份以下,則可抑制發生塑化劑的滲出。
黏度調整劑可列舉:甲基纖維素、羧甲基纖維素、羥乙基纖維素、羥乙基甲基纖維素、羥丙基甲基纖維素等纖維素衍生物;陽離子化澱粉、醚化澱粉等澱粉衍生物;阿拉伯膠、瓜爾膠、三仙膠等植物膠;酪蛋白、幾丁聚醣(chitosan)、幾丁質(chitin)等動物性高分子等,其中,較佳為瓜爾膠、阿拉伯膠、三仙膠。相對於生物分解性樹脂,黏度調整劑的添加量較佳為0.05至1.0質量%。若為0.05質量%以上,則黏度調整效果提升,若為1.0質量%以下,則容易穩定地控制水系分散體的黏度。
在一較佳實施型態中,生物分解性樹脂水系分散體係含有為分散穩定劑的皂化度70至90%之聚乙烯醇與為黏度調整劑的選自瓜爾膠、阿拉伯膠、三仙膠之至少1種,其中,相對於陰離子性化合物(A)之聚乙烯醇(B)的質量比(A/B)係在1/2至1/99的範圍內,相對於前述生物分解性樹脂,黏度調整劑的添加量為0.05至1.0質量%。關於聚乙烯醇(B)的較佳例係如前述。
生物分解性樹脂水系分散體的黏度較佳係在0.1至10Pa.s的範圍內。較佳為0.1Pa.s以上、10Pa.s以下。例如,若生物分解性樹脂水系分散體的黏度未達0.1Pa.s,則會由於相分離、樹脂粒子的不均勻化或沉澱等而變得難以維持良好的分散狀態,有必須使用均質機或高壓乳化機等分散裝置等進行強力攪拌的疑慮。該強力攪拌中,係施加強的剪力來將吸附於分散粒子上之分散劑分子剝離,就結果而言,亦有粒徑分布變廣或分散本身變得困難的疑慮。另一方面,若生物分解性樹脂水系分散體的黏度超過10Pa.s,則會有因溶液黏度變得過高而變得無法良好地分散的疑慮。
又,為了改善表面平滑性、撥水性、脫模性等,亦可使本發明之生物分解性樹脂水系分散體中含有天然蠟、合成蠟等蠟類。天然蠟可列舉:小燭樹蠟(candelilla wax)、棕櫚蠟(carnauba wax)、米糠蠟、木蠟、荷荷巴固體蠟等植物系天然蠟;蜂蠟、羊毛脂、鯨蠟等動物系天然蠟;褐煤蠟(montan wax)、地蠟(ozokerite)、純地蠟(ceresin)等礦物系天然蠟;石蠟、微晶蠟(microcrystalline wax)、石油蠟(petroleum wax)等石油系天然蠟等。又,合成蠟可列舉:費托蠟(Fischer-Tropsch wax)、聚乙烯蠟等合成烴類;褐煤蠟衍生物、石蠟衍生物、微晶蠟衍生物等改質蠟;硬化蓖麻油、硬化蓖麻油衍生物等氫化蠟;12-羥基硬脂酸、硬脂酸醯胺、鄰苯二甲酸酐醯亞胺等。
生物分解性樹脂水系分散體所包含之生物分解性樹脂為粒子狀,粒子的平均粒徑較佳為在0.1至500μm的範圍內,更佳為在0.5至50μm的範圍內,又更佳為在0.5至10μm的範圍內。
接著,對於本發明之生物分解性樹脂水系分散體的製造方法之一實施型態進行說明。
本發明之生物分解性樹脂水系分散體的製造方法包含分散步驟,該分散步驟係至少使已溶解之生物分解性樹脂與陰離子性化合物分散於溶劑中而得到分散液。
如上所述,陰離子性化合物的1質量%水溶液中的pH為7以上。
分散步驟的分散液例如可藉由將溶劑、生物分解性樹脂、陰離子性化合物及視需求之其他材料一起進行混合攪拌而得到。
具體而言,第一係例如可列舉加壓分散法,其係使用具有攪拌裝置之密封槽,同時加入生物分解性樹脂、陰離子性化合物、聚乙烯醇、黏度調整劑及水,進行加熱攪拌同時加壓而使生物分解性樹脂分散。
第二係例如可列舉直接分散法,其係在保持於加壓下之熱水中將包含生物分解性樹脂、陰離子性化合物、視需求之聚乙烯醇、以及黏度調整劑之熔融物進行添加攪拌,而使其分散。
第三係例如可列舉相轉換法(phase inversion method),其係使生物分解性樹脂加熱熔融,並於其中將包含陰離子性化合物、視需求之聚乙烯醇、以及黏度調整劑之水溶液進行添加攪拌,而使生物分解性樹脂分散於水中。
第四係例如可列舉將有機溶劑、水、生物分解性樹脂、陰離子性化合物、視需求之聚乙烯醇、以及黏度調整劑進行添加攪拌而使其分散後,將有機溶劑去除的方法。
第五係例如可列舉在生物分解性樹脂的有機溶劑溶液中將包含陰離子性化合物、視需求之聚乙烯醇、以及黏度調整劑之水溶液進行添加攪拌而使其分散之後,將有機溶劑去除的方法。
就第一至第五的方法以外的方法而言,只要是可以得到生物分解性樹脂之水系分散體的方法,便可適當採用。
更具體而言,若是考量能夠適應生物分解性樹脂之廣泛種類之點、水解的進行等,就得到分散液的方法而言,例如較佳為下述方法:於具有攪拌裝置之密封槽中,加入有機溶劑、水、生物分解性樹脂、陰離子性化合物、視需求之聚乙烯醇、以及黏度調整劑,一邊攪拌一邊升溫,使固體原料溶解、分散後,進行冷卻,之後在減壓下將有機溶劑去除。
又,較佳為下述方法:在具有攪拌裝置之密封槽中加入有機溶劑、生物分解性樹脂並進行攪拌升溫,而溶解成生物分解性樹脂溶解溶液,於另一攪拌槽中加入水、陰離子性化合物、視需求之聚乙烯醇、以及黏度調整劑而溶解成水溶液,並將溶解成之水溶液添加至密封槽中,於攪拌同時升溫至樹脂溶解溫度以上而使其分散後,進行冷卻,之後,在減壓下將有機溶劑去除。
在此等方法中,有機溶劑可列舉:如甲酸甲酯、甲酸乙酯、甲酸丙酯、甲酸丁酯等甲酸酯類,乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯等乙酸酯類的酯系有機溶劑;氯仿、四氯化碳等氯系有機溶劑;苯、甲苯、二甲苯等芳香族烴等,但較佳為樹脂的溶解性良好的酯系有機溶劑,特佳為甲酸酯類、乙酸酯類。
本發明之生物分解性樹脂水系分散體的製造方法中,分散步驟的分散液的pH為4至9,較佳4至6。藉由使pH在此範圍內,仄他電位容易成為適當的值,聚合物粒子彼此會適當地互斥等,結果係可得到具有穩定之分散性的生物分解性樹脂水系分散體。具體而言,生物分解性樹脂水系分散體的仄他電位較佳為-30mV以下,更佳為-40mV以下。基本上,仄他電位若在此等值以下,則經時穩定性會更會良好。仄他電位並無特別的下限,但在通常的製備中係例如為-50mV以上。又,較佳係在轉相乳化後去除有機溶劑,使溶劑殘存量為1000ppm以下。
本發明之生物分解性樹脂分散體具有穩定之分散性,不會降低生物分解性,且可在塗佈至纖維製品或紙製品等時提升紙製品等的熱封性。因此,在產業上於各種用途係極為有用且能夠實際應用。
使用本發明之生物分解性樹脂分散體的用途並無特別限定,可列舉例如食品包裝用紙。此外,本發明之生物分解性樹脂分散體還可用於液晶顯示裝置用間隔物、色劑用添加劑、電子照片顯影用色劑、塗料等的流變改質劑/添加劑、對於粉體塗料用材料、汽車材料、建築材料等成形品的機械特性改良劑、薄膜、紙、纖維等的機械特性改良劑、快速原型(rapid prototyping)、快速製造(rapid manufacturing)等的樹脂成形體用原料、溢料成形(flush molding)用材料、塑溶膠(plastic sol)用糊狀樹脂(paste resin)、堵粉材料、粉體之流動性/平滑性提升劑、潤滑劑、橡膠摻混劑、研磨劑、增黏劑、過濾劑及過濾助劑、膠化劑、凝聚劑、吸油劑、脫模劑、塑膠薄膜/片料之滑動性提升劑、抗結塊劑、光澤調節劑、消光完善加工劑、光擴散劑、表面高硬度提升劑、韌性提升劑、層析用填充劑、微膠囊用助劑、藥物遞送系統/診斷藥等的醫療用材料、醫療用診斷檢查劑、香料/農藥之保持劑、化學反應用觸媒及其擔載體、氣體吸附劑、離子交換樹脂、陶瓷加工用燒結材料、測量/分析用之標準粒子、食品工業領域用之粒子等。
本發明之生物分解性樹脂水系分散體及其製造方法,及使用生物分解性樹脂水系分散體的食品包裝用紙,並不限定於以上的實施型態。
[實施例]
以下係連同實施例一起詳細說明本發明之生物分解性樹脂水系分散體等,但本發明並不限定於以下的實施例。
1.生物分解性樹脂分散體的調製
在實施例及比較例中,係使用以下成分來作為生物分解性樹脂、1質量%水溶液中的pH為7以上的陰離子性化合物(分散劑(A))或前述陰離子性化合物以外的界面活性劑(分散劑(A))、聚乙烯醇(分散穩定劑(B))、黏度調整劑。
[生物分解性樹脂]
生物分解性樹脂A:聚乳酸
生物分解性樹脂B:聚丁二酸丁二醇酯
生物分解性樹脂C:聚丁二酸/己二酸丁二醇酯
生物分解性樹脂D:聚己內酯
[1質量%水溶液中的pH為7以上的陰離子性化合物]
陰離子性化合物A:聚丙烯酸鈉(重量平均分子量50萬)
陰離子性化合物B:聚丙烯酸鈉(重量平均分子量300萬至500萬)
陰離子性化合物C:脂肪酸(C12、14、16)鈉
陰離子性高分子化合物D:十四烯磺酸鈉
陰離子性化合物E:聚磷酸鈉
陰離子性化合物F:羧甲基纖維素鈉
陰離子性化合物G:烷基苯磺酸鈉
[前述陰離子性化合物以外的界面活性劑(陰離子性化合物)]
陰離子性化合物H:聚丙烯醯胺-丙烯酸鈉(重量平均分子量1600萬至1700萬)
陰離子性化合物I:丙烯醯胺-甲基丙烯酸共聚物(重量平均分子量2000萬)
陰離子性化合物J:甲基丙烯酸-丙烯醯胺(重量平均分子量400萬)
陰離子性化合物K:藻酸鈉
[聚乙烯醇]
聚乙烯醇A:皂化度80%,數量平均分子量10萬
聚乙烯醇B:皂化度99%,數量平均分子量9萬
[黏度調整劑]
黏度調整劑A:三仙膠(DSP GOKYO FOOD & CHEMICAL CO.,LTD.製,Echo Gum)
黏度調整劑B:瓜爾膠(三榮源F.F.I.製,Bistop D20)
黏度調整劑C:阿拉伯膠(三榮藥品貿易股份有限公司製,Arabicol SS)
<實施例1至15、比較例1至4>
將表1、表2所示之成分以表1、表2所示之比例加入密封分散槽,而在使用生物分解性樹脂A、C、D的情況下加熱至65℃,在使用生物分解性樹脂B的情況下加熱至120℃,並藉由使用預定之攪拌分散裝置的分散方法進行分散1小時後,快速冷卻至40℃。之後,在減壓下去除乙酸乙酯,而得到生物分解性樹脂水系分散體。
又,針對調製生物分解性樹脂水系分散體時的分散步驟中(混合攪拌時的加熱分散、冷卻後)及水系分散體(去除乙酸乙酯後)的黏度、穩定性,係以下述方式進行測量、評估。
[pH]
使用堀場製作所股份有限公司製之玻璃電極式氫濃度計pH METER 9615S-10D,於25℃進行測量。
[仄他電位(mV)]
針對在各生物分解性樹脂水系分散體中添加水稀釋至固體成分1質量%而成者,使用Malvern公司製Zetasizer Nano ZS測量裝置來測量仄他電位。此外,係於25℃進行測量。
[平均粒徑(μm)]
粒子的平均粒徑,使用雷射繞射型粒度分布測定裝置(島津製作所股份有限公司製,SALD-2300型,折射率1.45-0.00i)進行測量。
[離心分離]
使用KUBOTA製桌上型離心機Model 4000,實施3500rpm離心分離20分鐘。之後,將所得之樣本的分離情況以下述4階段進行評估,◎:分離未達10%;○:分離10%以上且未達30%;△:分離30%以上且未達50%;×:50%以上。
[穩定性試驗:於25℃靜置]
將各生物分解性樹脂水系分散體放入100ml玻璃容器,以25℃恆溫槽保管。將保管14天後的分離情況以下述4階段進行評估:◎:分離未達10%;○:分離10%以上且未達30%;△:分離30%以上且未達50%;×:50%以上。
[穩定性試驗:於40℃靜置]
將各生物分解性樹脂水系分散體放入100ml玻璃容器,以40℃恆溫槽保管。將保管14天後的分離情況以下述4階段進行評估:◎:分離未達10%;○:分離10%以上且未達30%;△:分離30%以上且未達50%;×:50%以上。
[熱封性:剝離強度(N/m)]
於裁切成25mm×200mm的小片牛皮紙(基重70g/m2)的25mm×150mm部分,以棒塗裝置No.20塗佈上述實施例1至15及比較例1至4的水系分散體,於25℃、40%RH乾燥24小時後,將2片試片以塗佈面貼合的方式夾於鐵版,並以羽島股份有限公司製之全自動轉印壓製機:HP-84於180℃、300g/cm2的條件壓製3分鐘,藉此得到試片。將所得之試片靜置1天後,依據JISK6854-3,使用東洋精機股份有限公司製之拉伸試驗機:Strograph E3,以拉伸速度10mm/分鐘測量剝離強度(N/m)。
[耐水性試驗]
於裁切成130mm×130mm的小片牛皮紙(基重70g/m2)上,以棒塗裝置No.20塗佈上述實施例1至15及比較例1至4的水系分散體,並於25℃、40%RH乾燥24小時後,以羽島股份有限公司製全自動轉印壓製機:HP-84於180℃、300g/cm2的條件壓製3分鐘,藉此得到試片。耐水性的評估係依據JIS-P-8140,以吸水量(g/m2)進行判斷。
評估基準◎:0至5;○5至10;△10至20;×:20以上。
結果係示於表1A至1C、表2及表3。
如表1A、表1B所示,確認到在包含1質量%水溶液中的pH為7以上之陰離子性化合物的生物分解性樹脂水系分散體且分散步驟的分散液之pH為4以上的實施例1至15中,係穩定性、熱封性為優異。
另一方面,確認到在包含1質量%水溶液中的pH未達7之陰離子性化合物的生物分解性樹脂水系分散體且分散步驟的分散液之pH未達4的比較例1至4中,係穩定性、熱封性不充分。
又,如表3所示,於包含1質量%水溶液中的pH為7以上之陰離子性化合物的生物分解性樹脂水系分散體之中,在經塗佈包含聚丙烯酸鈉之生物分解性樹脂水系分散體而成的牛皮紙亦確認到耐水性的提升。
Claims (10)
- 一種生物分解性樹脂水系分散體,係含有生物分解性樹脂與陰離子性化合物,其中,前述陰離子性化合物的1質量%水溶液中的pH為7以上。
- 如請求項1所述之生物分解性樹脂水系分散體,其中,前述陰離子性化合物係選自構成脂肪酸的碳數為12至16之脂肪酸鹽、十四烯磺酸鈉、聚磷酸鈉、羧甲基纖維素鈉、烷基苯磺酸鈉、聚丙烯酸鈉的至少1種。
- 如請求項1所述之生物分解性樹脂水系分散體,其中,前述陰離子性化合物係選自構成脂肪酸的碳數為12至16之脂肪酸鹽、十四烯磺酸鈉、聚磷酸鈉、羧甲基纖維素鈉、聚丙烯酸鈉的至少1種。
- 如請求項1所述之生物分解性樹脂水系分散體,其中,前述陰離子性化合物係選自構成脂肪酸的碳數為12至16之脂肪酸鹽、十四烯磺酸鈉、聚丙烯酸鈉的至少1種。
- 如請求項1所述之生物分解性樹脂水系分散體,其中,前述陰離子性化合物係選自構成脂肪酸的碳數為12至16之脂肪酸鹽、聚丙烯酸鈉的至少1種。
- 如請求項1所述之生物分解性樹脂水系分散體,其中,前述陰離子性化合物的重量平均分子量為1萬至2000萬。
- 如請求項1至5中任一項所述之生物分解性樹脂水系分散體,其含有作為分散穩定劑的皂化度70至90%之聚乙烯醇及作為黏度調整劑的選自瓜爾膠、阿拉伯膠、三仙膠之至少1種;前述陰離子性化合物(A)與前述聚乙烯醇(B)的質量比(A/B)在1/2至1/99的範圍內,相對於前述生物分解性樹脂之前述黏度調整劑的添加量為0.05至1.0質量%。
- 如請求項1至7中任一項所述之生物分解性樹脂水系分散體,其中,前述生物分解性樹脂為聚乳酸。
- 一種食品包裝用紙,其係使用請求項1至8中任一項所述之生物分解性樹脂水系分散體。
- 一種生物分解性樹脂水系分散體的製造方法,前述生物分解性樹脂水系分散體係含有生物分解性樹脂與陰離子性化合物,前述製造方法中包含分散步驟,該分散步驟係至少使已溶解之前述生物分解性樹脂與前述陰離子性化合物分散於溶劑中,而得到分散液;前述陰離子性化合物的1質量%水溶液中的pH為7以上,前述分散步驟的前述分散液的pH為4至9。
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