TW200821152A - Water-soluble substrate with resistance to dissolution prior to being immersed in water - Google Patents

Water-soluble substrate with resistance to dissolution prior to being immersed in water Download PDF

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Publication number
TW200821152A
TW200821152A TW096124360A TW96124360A TW200821152A TW 200821152 A TW200821152 A TW 200821152A TW 096124360 A TW096124360 A TW 096124360A TW 96124360 A TW96124360 A TW 96124360A TW 200821152 A TW200821152 A TW 200821152A
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Taiwan
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water
coating
soluble
soluble substrate
substrate
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TW096124360A
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Chinese (zh)
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Vincenzo Catalfamo
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Procter & Gamble
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/043Improving the adhesiveness of the coatings per se, e.g. forming primers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Wrappers (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)
  • Paints Or Removers (AREA)

Abstract

A water-soluble substrate, and more particularly a water-soluble substrate that is resistant to contact with small amounts of water, and methods of making the same are disclosed. A coating which is less water-soluble than the water-soluble substrate and in the form of particles, is applied to and substantially covers at least one surface of the water-soluble substrate. The weight ratio of coating to water-soluble substrate is higher than 0.8. Articles, such as pouches, made from the water-soluble substrate, are also disclosed herein.

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200821152 九、發明說明 【發明所屬之技術領域】 本發明關於一種水溶性基質,且尤其是關於一種在浸 於水之前具有改進的抗溶解性之水溶性基質,及其製造方 法。本發明亦關於一種由此水溶性基質所製成之諸如囊袋 的物件。 φ 【先前技術】 水溶性基質已廣泛地接受作爲封裝材料。封裝材料包 括膜、薄片、吹製或模製之中空體(即小袋、囊袋及錠劑) 、瓶、容器及類似者。當用於特定類型之諸如小袋及囊袋 之物件的製備時,水溶性基質於暴露至少量水或高濕度的 情況下經常滲漏及/或變得黏滯。此可能造成其不適用於 封裝及儲存其中所包含的組成物。 最常見的消費者對於水溶性囊袋的抱怨爲,當水溶性 • 囊袋不慎與少量水接觸時之不預期的囊袋溶解,諸如於購 買後,水分經由潮濕的手部、高濕度、儲存期間之滲漏的 槽或管而進入販售及儲存囊袋用之外包裝。此可能造成水 溶性囊袋於使用前滲漏及/或彼此黏合。次常見的抱怨爲 ,於使用時水溶性囊袋無法完全溶解。因此,有必要提供 一種水溶性基質及由其所製成之諸如小袋及囊袋的物件, 其對暴露至少量水時具有改進的抗溶解性,然而於浸於諸 如淋洗及/或沖洗用水之水溶液時可極快速地溶解。 縮減水溶性基質的厚度爲另一趨勢,其不僅改進水溶 -4 - 200821152 性基質於使用時之溶解度,亦可以較低成本製造水溶性基 質及由其所製成的物件。然而,當水溶性基質較薄時,其 抗溶解性降低。在業界已有各種阻礙水溶性基質溶解的習 知方法。典型地,此等方法包括以水不溶性材料塗覆水溶 性基質。美國專利號6,5 09,0 72描述一種包含障壁塗層之 水溶性基材。此障壁塗層爲形成連續膜於水溶性基質上的 聚合型膜。WO 01/2 3460中描述另一讓渡予高氏(Kao)公司 φ 之障壁塗層的實例,其中以粒子化或纖維化之水不溶性材 料塗覆水溶性基質的表面,其中所使用之水不溶性材料的 含量爲0.1-80重量份/100重量份水溶性膜。前案之此等 障壁塗層係少量施用且相對於水溶性基質的厚度爲相當薄 者。然而,於暴露至意外之水接觸後,此等塗層可能不足 以提供該基質充分的抗溶解性。尤其是於使用薄水溶性基 質的情況中。 因此,本發明之一面向在於提供一種獨立於水溶性基 φ 質的厚度、在浸於水之前具有改進的抗溶解性,而當接續 地浸於諸如淋洗及/或沖洗用水的水溶液時可極快速地溶 解之水溶性基質。 【發明內容】 本發明關於一種水溶性基質,其包含第一表面、相對 於該第一表面的第二表面,及介於該第一及第二表面之間 的厚度,該水溶性基質具有一塗層,其被塗佈至並實質上 覆蓋該第一及第二表面之至少一者,其特徵在於塗層對水 -5- 200821152 溶性基質的重量比係大於0.80。 本發明亦關於一種物件,其包含此水溶性基質,及關 於一種此水溶性基質之製造方法。 【實施方式】 本發明關於一種水溶性基質,且尤其是關於一種在浸 於水之前具有改進的抗溶解性之水溶性基質,及其製造方 φ 法。本發明亦關於一種物件,其包含於此描述之水溶性基 質。 水溶性基質 第1圖顯示水溶性基質1 0的橫截面。水溶性基質1 0 具有第一表面12、相對於第一表面12之第二表面14以及 介於第一表面1 2及第二表面1 4之間的厚度1 6。水溶性基 質10可爲膜、薄片或泡沬形式,且包括編織或未編織結 ⑩構。 水溶性基質由聚合型材料所構成,且藉於此提出之使 用具有最大孔徑爲20微米之玻璃濾器的方法測量具有至 少50重量%的水溶度。基質之水溶度較佳爲至少75重量 %或更佳爲至少95重量%。 添加50公克:t 0·1公克的基質材料至預秤重的400 ml燒杯中,並加入245 ml ± 1 ml之25 °C的蒸餾水。以 設定爲600 rpm的磁性攪拌器將之劇烈攪拌持續30分鐘 。接著以具有上述定義孔徑(最大値20微米)之經折疊定性 200821152 燒結濾器過濾混合物。水分藉任何習知方式由收集濃液而 被乾燥,並測定剩餘材料的重量(其爲溶解的部份)。接著 可計算溶解度百分比。 典型地,每平方公尺之水溶性基質1〇具有自0.33至 1 667公克的基本重量,較佳爲每平方公尺33至〗67公克 。介於第一表面1 2及第二表面1 4之間的水溶性基質1 〇 的厚度之範圍可爲自約0.7 5微米至約1250微米,較佳自 φ 約10微米至約250微米,更佳自約25微米至約125微米 〇 適合使用作爲基質材料之較佳聚合物、共聚物或其衍 生物係選自聚乙烯醇(PVA)、聚乙烯吡咯烷酮、聚烷烯氧 化物、丙烯醯胺、丙烯酸、纖維素、纖維素醚、纖維素酯 、纖維素醯胺、聚乙酸乙烯酯、聚羧酸及鹽、聚胺基酸或 肽、聚醯胺、聚丙烯醯胺、順丁烯二酸/丙烯酸的共聚物 、包括澱粉及明膠的多醣、諸如黃樹膠及卡拉膠 φ (carragum)之天然樹膠、聚丙烯酸酯及水溶性丙烯酸酯共 聚物、甲基纖維素、羧甲基纖維素鈉、糊精、乙基纖維素 、羥乙基纖維素、羥丙基纖維素、麥芽糊精、聚甲基丙烯 酸酯、聚乙烯醇共聚物、羥丙基甲基纖維素(HPMC)及彼 等之混合物。最佳聚合物係聚乙烯醇。於基質中的聚合物 量較佳爲至少6 0 %。 市售之水溶性膜的實例有產品名爲Monosol Μ 8 63 0之 由位於美國印第安那州Gary之MonoSol LLC所販售的 PVA膜,以及相應溶解度及變形特徵之PVA膜。其他適 200821152 用於此的膜包括產品名爲PT膜或κ系列膜之由Aicello 所提供者,或由Kuraray所提供之VF-HP膜。 塗層 塗層係塗佈至並實質上覆蓋水溶性基質1 〇的至少第 一表面12或第二表面14。塗層可爲水溶性。然而其不似 水溶性基質1 〇般溶於水。根據上述方法進行測量,塗層 φ 之溶解度較佳低於75重量%。“實質上覆蓋”表示至少95 %,較佳至少9 9 %,最佳1 〇 〇 %的第一表面1 2或第二表 面1 4被塗層覆蓋。此確保於意外的與水接觸時,水將不 會到達水溶性基質1 〇的第一表面1 2或第二表面1 4,或是 到達該表面的水量不足以完全溶解水溶性基質1 〇。 施用的塗層之塗層對水溶性基質的重量比大於0.80 ( 即塗層重量:水溶性基質重量的比例)。塗層對水溶性基 質的重量比較佳爲至少〇· 85,更佳爲至少0.90,尤佳爲至 φ 少1.00,且可高達100,較佳達50,更佳達20,尤佳達 1 〇。此等含量的塗層使得較薄的水溶性基質1 〇得以被使 用,於與水意外接觸時其具有充分的抗溶解性,而當經塗 覆的基質浸於水中時對溶解度無負面影響。塗層對水溶性 基質之重量比的最佳範圍爲介於0.80及10之間,更佳自 〇_85至5,尤佳自〇·90至3,亦尤佳自1至2。 不受理論的限制’申請人認爲抗溶解性並不僅取決於 水溶性基質1 〇之厚度或溶解度,或是不僅取決於厚度、 溶解度或塗層之覆蓋範圍。相對的,結合的基質之總抗性 -8- 200821152 ,亦即具塗層塗覆其上之水溶性基質1 0以及水透過塗層 所產生之可獲得的通道而到達水溶性基質1 0的時間,係 決定的因素。因此,若水溶性基質1 0的厚度小,則塗層 對水溶性基質1 0的重量比需爲高,以賦予經塗覆的基質 充分的抗溶解性。 塗層可包含各種材料,且可以將於以下說明的各種形 式及方式進行塗覆。 Φ 於另一較佳實施例中,塗層20爲水不溶者。“水不溶 者”表不根據前述方法進行測量時溶解度小於5 0重量%。 塗層較佳具小於4 0重量%的水溶解度,更佳小於3 0重量 %,且最佳小於1 0重量%。水不溶性材料可爲水不溶性無 機材料或水不溶性有機材料。 水不溶性無機材料可爲沸石、膨土、滑石、雲母、高 嶺土、海泡石、矽石、碳酸鈣、氧化鈦、無水矽酸、羥基 磷灰1¾、酞花青藍、Helidone粉紅、Hansa橙、珠光材料 φ 等,而以沸石、膨土、滑石、雲母、高嶺土、矽石、氧化 鈦、聚矽氧等爲較佳者。 水不溶性有機材料可爲選自纖維素及/或其衍生物、 澱粉及/或其衍生物、種殻及/或其衍生物之天然聚合物。 以纖維素及/或其衍生物爲較佳者。 第3圖顯示水溶性基質1 〇之實施例,其中塗層20係 呈粒子24的形式。此等粒子具有500微米或以下的平均 直徑,較佳爲300微米或以下,尤佳爲自0.01至300微 米。於高度較佳實施例中,粒子24爲奈米尺寸範圍,平 -9 - 200821152 均粒徑爲自0.01至1微米。以奈米級尺寸粒子塗覆水溶 性基質10進一步提供之益處係使塗層呈透明,其係美學 上較佳者。 塗層20較佳爲撓性者。當透過用於印刷、片裂、縱 裂、復捲及其他典型轉化操作進行水溶性基質1 〇之轉化 時,或當製作諸如囊袋之包含水溶性基質1 0之物件時, 水溶性基質10典型地經拉伸。於基質10的某些區域,基 Φ 質10甚至可被延長達200 %或以上。此可能造成塗層破 裂而因此使水與水溶性基質1 0之表面接觸。因此,塗層 20較佳爲撓性者,且可經拉伸而不會破裂。塗層20較佳 可經延長至少20 %,更佳至少30 %,尤佳至少50 %,最 佳超過1 0 0 %且達到2 0 0 %而不會破裂。此撓性塗層的實 例爲Ideal Products LLC (印第安納州普利茅斯市)所販售 之產品名爲Sani-Tred 液態聚胺基甲酸酯塗 層,或Η M G A m e r i c a L L C (表現性塗層,南卡羅萊納州羅 # 巴克市)之產品名爲FlexithaneTM者。其他撓性塗層之實 例有JC Whitney Inc.(伊利諾州芝加哥市)所販售之丙燃酸 系之於低溫時爲撓性浸塗層。亦可使用此等塗層與任何前 述塗層之混合物。 根據本發明之塗層可呈不透明,但較佳呈透明或半透 明。亦爲較佳者爲經著色或三維的塗層,以產生諸如觸覺 (觸摸)效果或諸如圖示、漫畫、標籤、烙印、使用者指示 及類似者之視覺效果之外觀上的效果。 而當根據本發明之水溶性基質浸於水中時(即於所欲 -10- 200821152 使用基質且基質需被溶解之應用中),塗層無法充分阻抗 與水的接觸而確保基質快速溶解。 於如第2圖中所示之較佳實施例中,塗層20進一步 包含有包含具高水解度之PVA的組成物。用於塗層之 PVA水解度較佳大於97 %。當於水溶性基質中使用PVA 時,於塗層中所使用的PVA較佳具有較高的水解度。PVA 可爲PVA與諸如上述者之其他水溶性聚合物的混合物。 選擇性成分 於一些應用中可能需增進基質(於浸沒時)的溶解率。 可添加崩解劑至塗層以加速溶解浸於水中之水溶性基質1〇 。當存在時,塗層中崩解劑的量爲該塗層重量的自0.1至 3 0 %,較佳自1至15 %。可供選擇地,崩解劑亦可塗佈 至水溶性基質1 0的表面,相對於塗佈塗層之表面,或可 將其塗佈至水溶性基質1 0的兩個表面,或可將其合倂至 • 水溶性膜1 〇之中,或彼等之任何組合。可使用任何合適 的崩解劑。於此使用之崩解劑較佳爲玉米/馬鈴薯澱粉、 甲基纖維素(類)、礦物性黏土粉末、croscarmelose (經交 聯的纖維素)、crospovidine (經交聯的聚合物)、澱粉羥乙 酸鈉(經交聯的澱粉)。 水溶性基質所形成的組成物及自其所形成的水溶性基 質10亦可包含一或多種添加物或佐劑成分。舉例而言, 水溶性基質所形成的組成物及水溶性基質1 〇可含有··塑 化劑、潤滑劑、釋放劑、塡料、增效劑、抗阻塞劑、去增 -11 - 200821152 黏劑、消泡劑或其他功能性成分。於物件含有用於沖洗之 組成物的情況中,後者可包括欲輸送至沖洗用水之功能性 清潔劑添加物,例如有機聚合型分散劑或其他清潔劑添加 物。 合適的塑化劑包括,但不限於:丙三醇、甘油、二甘 油、羥丙基甘油、山梨醇、乙二醇、二乙二醇、三乙二醇 、四乙二醇、丙二醇、聚乙二醇、新戊二醇、三羥甲基丙 φ 烷、聚醚多元醇、乙醇胺及彼等之混合物。塑化劑可以任 何合適的含量被倂入水溶性基質1 0之中,而合適的含量 包括自約5重量%至約30重量%,或自約1 2重量%至約 20重量%的範圍中之含量。 * 合適的界面活性劑包括非離子性、陽離子性、陰離子 性及兩性離子類。合適的界面活性劑包括,但不限於,聚 氧乙烯化之聚氧丙二醇、乙醇乙氧基化物、烷基酚乙氧基 化物、三級炔屬二醇及烷基醯胺(非離子性)、聚氧乙烯化 • 之胺、四級銨鹽及四級化的聚氧乙烯化之胺(陽離子性)、 及胺氧化物、N-烷基甜菜鹼及磺基甜菜鹼(兩性離子性)。 界面活性劑可以任何合適的含量被倂入水溶性基質1 0之 中,丽合適的含量包括自約0.0 1重量%至約1重量%,或 自約0 · 1重量%至約0 · 6重量%的範圍中之含量。 合適的潤滑劑/釋放劑包括,但不限於,脂肪酸及其 鹽、脂肪醇、脂肪酯、脂肪胺、乙酸脂肪胺及脂肪醯胺。 潤滑劑/釋放劑可以任何合適的含量被倂入水溶性基質! 〇 之中,而合適的含量包括自約0.02重量%至約1 .5重量% -12- 200821152 ,或自約〇 . 04重量%至約0.1 5重量%的範圍中之含量。 合適的塡料、增效劑、抗阻塞劑、去增黏劑包括,但 不限於:澱粉、經改質的澱粉、交聯的聚乙烯基吡咯烷酮 、交聯的纖維素、微晶體纖維素、矽石、金屬氧化物、碳 酸鈣、滑石及雲母。塡料、增效劑、抗阻塞劑、去增黏劑 可以任何合適的含量存在水溶性基質1 〇之中,而合適的 ' 含量包括自約0.1重量%至約2 5重量%,較佳自約1重量 φ %至約1 5重量%的範圍中之含量。於澱粉不存在的情況中 ,可預期塡料\增效劑、抗阻塞劑、去增黏劑存在於自約 1重量%至5重量%的範圍中。 合適的消泡劑包括,但不限於,基於聚二甲基矽氧烷 及烴摻合物。消泡劑可以任何合適的含量存在水溶性基質 10之中,而合適的含量包括自約0.001重量%至約0.5重 量%,較佳自約0.01重量%至約0.1重量%的範圍中之含 量。 • 亦可倂入增益劑至塗層中。如此可經由諸如囊袋之物 件輸送與物件中之產物或組成物不相容的增益劑。可容納 於中空玻璃珠之中或塗覆至玻璃珠外表面之增益劑的實例 包括,但不限於,清潔劑、土壤懸浮劑、抗再沉積劑、光 學增亮劑、漂白劑、酵素、香味組成物、漂白活化劑及前 驅物、閃耀劑、肥皂泡抑制劑、織物照護組成物、表面滋 養組成物。舉例而言,當藉塗覆多層的塗層材料而產生塗 層時,可施加增益劑於塗層之間。 水溶性基質所形成的組成物係藉混合材料並於攪動混 -13- 200821152 合物的同時將溫度自約7〇〇F (約21〇c)升高至195〇F (約 90°C)直到完成溶液而製備。由基質所形成的組成物可製 成任何合適的形式(如膜或薄片)且可接續被形成爲任何合 適的產物(如單-或多-分室囊袋、小袋、袋等)。 水溶性基質的製造方法 於此描述之水溶性基質〗〇之製造方法有許多非用於 φ 限制的實施例。 於一實施例中’方法包含提供先前形成的水溶性基質 1 〇且塗佈塗層2 0至先前形成之水溶性基質1 〇的表面J 2 、1 4之至少一者。 塗層20可以數種不同的方法而塗佈至先前形成的水 溶性基質1 〇。於一非用以限制的實施例中,塗層20係以 粒子或粉末的形式而塗佈至先前形成之水溶性基質1 〇的 表面12、14之至少一者。粒子或粉末較佳經由噴射流或 φ 靜電地塗佈至水溶性基質1 0。因高速噴射流,一些粒子或 粉末被埋入基質中,藉此減少甚至是免除使用黏合劑的需 求。於靜電地塗佈粒子時通常亦不需要黏合劑。然而,仍 可使用黏合劑。於塗佈粒子之前可事先塗佈黏合劑至水溶 性基質1 0。或可供選擇地,黏合劑可與粒子混合並接著將 混合物添加至水溶性基質1 〇。 於本方法之另一非用於限制的實施例中,塗層20以 溶液形式塗佈至水溶性基質10之表面12、14之至少一者 ,接續並使其乾燥或進行乾燥製程。溶液可藉任何塗覆方 -14- 200821152 法而施加至膜上,包括噴霧、刀、桿、密接、狹縫、塗漆 、印刷及彼等之混合。於此以使用印刷爲較佳方法。印刷 爲完善建立且經濟的方法。印刷通常以墨水及染料執行並 用於賦予基質圖案與色彩,但於本發明的情況中,使用印 刷以沉積較少的水溶性材料至水溶性基質上。可使用任何 種類的印刷法,包括凹印輪轉法、微影法、膠版印刷、孔 版及網版印刷、噴墨印刷、凸印、移印及彼等的組合。 φ 此等實施例亦可包含於塗佈塗層20至先前形成的水 溶性基質1 〇之前,濕潤水溶性基質1 〇的表面1 2、14之 至少一者的一部份之步驟。濕潤水溶性基質1 0的表面12 、1 4之至少一者可用以至少部份地溶解基質1 0的表面1 2 、1 4之外部(亦即深入基質的部份厚度)。因部份地埋入於 基質中的塗層,水溶性基質1 0可至少部份溶解至任何合 適的深度。合適的深度包括,但不限於:總基質厚度16 的自約1 %至約40 %或約45 %、自約1 %至約30 %、自 φ 約1 %至約20 %、自約1 %至約15 %,及可供選擇地自約 1 %至約10 %。接著塗佈塗層20至基質10的表面12、14 之至少一者之部份經溶解的部份。此使塗層20被埋入基 質10的表面12、14之外部,且成爲基質10之更恆存的 部份。具有塗層20埋入其中的基質1 0之經濕潤的表面1 2 、14接續受到乾燥。本方法的此實施例亦可包含水溶性基 質1 〇經乾燥之後,移除至少一些水溶性基質1 0表面殘餘 之任何鬆動或過多塗層20的步驟,諸如藉擦淨或除塵基 質10之表面。 -15- 200821152 於另一實施例中,於將基質1 〇製成產物之後,可添 加塗層20至水溶性基質1 0。舉例而言,若使用水溶性基 質1 〇以形成含有組成物的水溶性囊袋,則於至少部份之 水溶性囊袋的表面上可添加塗層2 0至水溶性基質1 〇。 於此方法之另一非用於限制的實施例中,以多重施用 步驟塗佈塗層20。根據任何上述方法塗佈第一塗層至水溶 性基質10,且選擇性地使其乾燥。接續地,可添加另外的 Φ 一或更多塗層直至獲得所欲塗層厚度爲止,且選擇性地使 其乾燥。如此可於薄水溶性基質上產生相對厚的塗層。 於本方法之另一非用於限制之實施例中,可分別地形 成塗層,隨後並將其施加至水溶性基質的表面。 水溶性囊袋的製造方法 於此所描述之水溶性基質1 〇可形成物件,包括但不 限於使用水溶性基質10作爲包裝材料者。此等物件包括 # ’但不限於水溶性囊袋、小袋及其他容器。 可以任何業界知悉之合適的方式製作水溶性囊袋或其 他此等採用於此所描述之水溶性基質1 0之容器。可提供 具改進之抗溶解性的水溶性基質1 〇於形成彼之最終產物 之前或之後。於各情況下,於特定實施例中,當製作此等 物件時所欲者爲塗佈有塗層於基質1〇之表面12、14形成 物件的外部。 有許多用於製作水溶性囊袋的方法。此包括,但不限 於業界知悉之下列方法:直立式塡充封口製程、水平式塡 -16- 200821152 充封口製程及於圓形鼓輪表面上的模中形成囊袋。於直立 式塡充封口製程中,藉折疊基質而形成直立管。管的底部 經密封以形成開口囊袋。部份地塡充此囊袋使留下頂隙。 開口囊袋的頂部接續經密封以封閉囊袋,並形成下一個開 口囊袋。接續切割第一個囊袋並重複步驟。所形成的囊袋 通常爲枕狀。水平式塡充封口製程使用其中具有一系列模 之模具。於水平式塡充封口製程中,置放基質於模具中並 φ 形成開口囊袋於此等模中,其可接續經塡充、被另一基質 層覆蓋且經密封。於第三種方法(於圓形鼓輪表面上的模 中形成囊袋)中,將基質環繞鼓輪而形成袋,其通過塡充 機以塡充開口袋。塡充及密封發生於鼓輪之環形的最高點 (頂點),如典型地,恰於旋轉的鼓輪開始向下環型運動前 完成塡充,且恰於鼓輪開始其向下運動後完成密封。 於任何含有形成開口囊袋之步驟的製程中,可使用熱 成型、真空成型或兩者而初步地模製基質或將之形成爲開 • 口囊袋的形狀。熱成型包括以任何知悉方式,諸如使模接 觸加熱元件、或吹入熱氣或使用加熱燈以加熱模及/或基 質,施加熱而加熱模及/或基質。於真空成型的情況中, 採用真空係有助於驅動基質進入模中。於另一實施例中, 可結合兩種技術以形成囊袋,舉例而言,可藉真空成型形 成開口囊袋且提供熱以促進製程。接續以囊袋中所含有的 組成物塡充開口囊袋。 經塡充之開口囊袋接續可藉執行任何方法而被封閉。 於一些情況中,諸如於水平式囊袋形成製程中,封閉係藉 -17- 200821152 連續進料諸如水溶性基質之第二材料或基質至開口囊袋網 之上並接續將第一基質與第二基質一起密封而完成。第二 材料或基質可包含於此所描述的水溶性基質1 〇。可預期塗 佈有塗層之第二基質的表面經定向,以使其形成囊袋的外 表面。 於此製程中,第一及第二基質典型地經密封於模間區 域,並因此密封於形成於相鄰模中的囊袋之間。此密封可 Φ 藉任何方式完成。密封用方法包括熱密封、溶劑焊接以及 溶劑或濕密封。囊袋之經密封的網可接續經切割裝置而切 割,其切割網中囊袋成爲分別的囊袋。於Cat 1 in等人所發 表之美國專利申請序號 〇9/994,533、公開號 US 2002/0 1 6 9092 A1中進一步描述形成水溶性囊袋的方法。 物件之製造 如第4圖所顯示,本發明亦包括一種包含產物組成物 Φ 40及水溶性基質1 0的物件,而水溶性基質1 0可形成諸如 囊袋、小袋、膠囊、袋等之容器3 0以固持產物組成物。 可使用具有塗層2 0塗佈於其上的水溶性基質1 〇的表面以 形成容器3 0的外表面。水溶性基質i 〇可形成至少部份的 容器3 0,而容器3 0提供產物組成物4 0之單位劑量。 爲簡便說明之故,此處之物件將表示水溶性囊袋,然 而應要瞭解的是於此之論述亦適用於其他種類的容器。 由前述方法所形成的囊袋30可被形成爲任何適以固 持內含之組成物40的形式及形狀,直至欲自水溶性囊袋 -18- 200821152 3 0釋出組成物40爲至,諸如將水溶性囊袋3 〇浸於水中。 囊袋30可包含一或二或多個分室(亦即囊袋可爲多分室囊 袋)°於一實施例中,囊袋3〇可具有兩個或更多個通常呈 疊置關係的分室’且囊袋3〇包含通常相對於外壁之形成 囊袋3 0側部及一或多個內部份隔壁的上及下裙狀側壁, 以將不同分室彼此分離。若囊袋3 〇中所含有的組成物4 0 包含不同形式或組份,則組成物4〇的不同組份可存於水 φ 溶性囊袋3 0的不同分室中,且可藉水溶性材料之障壁彼 此分離。 囊袋或其他容器30可含有單位劑量之用作/用於洗衣 清潔劑組成物、自動洗碗機清潔劑組成物、硬表面清潔劑 、污漬去除劑 '纖維增效劑及/或纖維柔軟劑、食物及飲 料之一或多種組成物40,以及與少量水接觸可產生過早囊 袋溶解、非所欲囊袋滲漏及/或不預期囊袋間黏滯的新產 物形式。囊袋3 0中的組成物4〇可爲任何合適的形式,其 φ 包括但不限於:液體、液態膠、膠體、糊漿、乳油、固體 、顆粒、粉末等。可使用多分室囊袋30的不同分室以分 離不相容的成分。舉例而言,可預期將漂白劑與酵素分開 至分離的分室中。其他多分室形式的實施例可包括含有粉 末的分室結合含有液體的分室。於Smith等人的美國專利 6,67 0,3 1 4 B2中揭露另外的多分室水溶性囊袋的實例。 水溶性囊袋30可落入任何合適水溶液中(諸如熱或冷 水),隨後形成水溶性囊袋3 0的水溶性基質1 〇溶解以釋 出囊袋的內容物。 -19- 200821152 於此描述的水溶性基質1 〇亦可使用於包衣產品或其 他物件。此種產物之非用於限制的實例爲洗衣清潔錠劑或 自動洗碗機清潔錠劑。其他實例包括食物或飮料類的包衣 產品,其與少量水接觸時可能產生過早的溶解、非所欲滲 漏及/或不預期黏滯。 實例 爲獲得水溶性基質對意外與水接觸時之抗性,於水溶 性基質上形成PVA膜,諸如得自Dissolve) LLC (賓夕法尼 亞州克羅伊登市)之產品名爲基級D60S的基於纖維素料的 (紙)基質。此膜藉由以含有4 %的PVA水溶液塗佈紙基質 而製成,隨後並將之乾燥。所得的PVA膜之基本重量爲 約0.44 gsm,而厚度爲約0.33微米。 根據上述步驟製成之第一 PVA膜(A)係使用作爲比較 實例。 根據上述步驟而製成之第二(B)及第三(C) PVA膜係進 一步以塗層塗佈以製造根據本發明之水溶性基質。以得自 EIC之品名爲EC 007003之經微粒化PTFE粒子的水性懸 浮液塗覆PVA膜表面(相對於與紙基質接觸的表面)。樣本 B之塗層的基本重量爲15.90 gsm,而樣本C之塗層的基 本重量爲3 0.1 6 gsm,使得較不溶於水的材料對水溶性基 質的比例分別爲36及68。 如第5圖所示,各樣本5 0係附接至2 ’’中空塑膠管5 1 的一開口端並以橡皮圈52固定。將2公克重物53置放於 -20 - 200821152 管內。將具有面朝下之樣本的管降低1 ’’而進入燒杯54中 之室溫(2 0 - 2 5 D C)的水中。記錄自紙碰到水面直至重物穿過 樣本而落下的時間。此記錄的時間稱爲“斷裂時間”。斷裂 時間越大,則表示樣本對水的抗性越大。 爲比較之故,亦單獨測試紙基質(D)。 結果: 樣本 斷裂時間(秒) A 1 B 9 C 11 D 1BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a water-soluble matrix, and more particularly to a water-soluble substrate having improved resistance to solubility prior to immersion in water, and a process for its production. The invention also relates to an article such as a pouch made from such a water soluble matrix. φ [Prior Art] Water-soluble substrates have been widely accepted as encapsulating materials. The encapsulating material includes films, sheets, blown or molded hollow bodies (i.e., pouches, pouches, and lozenges), bottles, containers, and the like. When used in the preparation of articles of a particular type, such as pouches and pouches, the water soluble matrix often leaks and/or becomes viscous when exposed to at least a quantity of water or high humidity. This may render it unsuitable for packaging and storing the components contained therein. The most common consumer complaints about water-soluble pouches are that when the water-soluble pouch is inadvertently contacted with a small amount of water, the undesired pouch dissolves, such as after the purchase, the moisture passes through the wet hands, high humidity, The leaking tank or tube during storage enters the outer packaging for the sale and storage of the pouch. This may cause the water-soluble bladders to leak and/or adhere to each other prior to use. A common complaint is that the water-soluble bladder cannot be completely dissolved during use. Accordingly, it would be desirable to provide a water soluble matrix and articles made therefrom such as sachets and pouches that have improved resistance to dissolution when exposed to at least a quantity of water, yet are immersed in water such as rinsing and/or rinsing. The aqueous solution dissolves very quickly. Reducing the thickness of the water-soluble matrix is another tendency not only to improve the solubility of the water-soluble liquid in use, but also to produce a water-soluble base and articles made therefrom at a lower cost. However, when the water-soluble matrix is thin, its solubility resistance is lowered. There are various conventional methods in the industry that hinder the dissolution of water soluble matrices. Typically, such methods include coating a water soluble matrix with a water insoluble material. U.S. Patent No. 6,5,09,072 describes a water soluble substrate comprising a barrier coating. The barrier coating is a polymeric film that forms a continuous film on a water soluble substrate. Another example of a barrier coating imparted to Kao Corporation φ is described in WO 01/2 3460, in which a surface of a water-soluble matrix is coated with a particle-forming or fibrillated water-insoluble material, wherein the water-insoluble is used. The content of the material is from 0.1 to 80 parts by weight per 100 parts by weight of the water-soluble film. Such barrier coatings of the foregoing are applied in small amounts and are relatively thin relative to the thickness of the water soluble matrix. However, after exposure to accidental water contact, such coatings may not be sufficient to provide sufficient resistance to dissolution of the substrate. Especially in the case of using a thin water-soluble matrix. Accordingly, one aspect of the present invention is directed to providing a thickness independent of the water-soluble base φ, having improved resistance to dissolution prior to immersion in water, while continuously immersing in an aqueous solution such as rinsing and/or rinsing water. A water soluble matrix that dissolves very quickly. SUMMARY OF THE INVENTION The present invention is directed to a water-soluble substrate comprising a first surface, a second surface relative to the first surface, and a thickness between the first and second surfaces, the water-soluble substrate having a A coating that is applied to and substantially covers at least one of the first and second surfaces, wherein the weight ratio of the coating to the water-5-200821152 soluble matrix is greater than 0.80. The invention also relates to an article comprising the water soluble matrix and a method of making such a water soluble matrix. [Embodiment] The present invention relates to a water-soluble substrate, and more particularly to a water-soluble substrate having improved solubility resistance before immersion in water, and a method for producing the same. The invention also relates to an article comprising the water soluble matrix described herein. Water Soluble Substrate Figure 1 shows a cross section of a water soluble matrix 10 . The water soluble matrix 10 has a first surface 12, a second surface 14 relative to the first surface 12, and a thickness 16 between the first surface 12 and the second surface 14. The water soluble matrix 10 can be in the form of a film, sheet or foam and comprises a woven or unwoven structure. The water-soluble matrix is composed of a polymeric material, and the water solubility of at least 50% by weight is measured by the method proposed to use a glass filter having a maximum pore diameter of 20 μm. The water solubility of the substrate is preferably at least 75% by weight or more preferably at least 95% by weight. Add 50 g: t 0·1 g of matrix material to a pre-weighed 400 ml beaker and add 245 ml ± 1 ml of distilled water at 25 °C. The mixture was vigorously stirred for 30 minutes with a magnetic stirrer set at 600 rpm. The mixture was then filtered using a folded qualitative 200821152 sintered filter having the above defined pore size (maximum 値 20 microns). The moisture is dried by collecting the concentrate in any conventional manner, and the weight of the remaining material (which is the dissolved portion) is determined. The percent solubility can then be calculated. Typically, the water soluble matrix per square meter has a basis weight of from 0.33 to 1667 grams, preferably from 33 to 67 grams per square meter. The thickness of the water-soluble matrix 1 介于 between the first surface 12 and the second surface 14 may range from about 0.75 microns to about 1250 microns, preferably from about 10 microns to about 250 microns, more preferably Preferably, from about 25 microns to about 125 microns, a preferred polymer, copolymer or derivative thereof suitable for use as a matrix material is selected from the group consisting of polyvinyl alcohol (PVA), polyvinylpyrrolidone, polyalkylene oxide, acrylamide , acrylic acid, cellulose, cellulose ether, cellulose ester, cellulose decylamine, polyvinyl acetate, polycarboxylic acid and salt, polyamino acid or peptide, polyamine, polypropylene decylamine, maleic acid Acid/acrylic copolymers, polysaccharides including starch and gelatin, natural gums such as gum arabic and carragum, polyacrylates and water-soluble acrylate copolymers, methylcellulose, sodium carboxymethylcellulose , dextrin, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, maltodextrin, polymethacrylate, polyvinyl alcohol copolymer, hydroxypropyl methylcellulose (HPMC) and a mixture of such. The most preferred polymer is polyvinyl alcohol. The amount of polymer in the matrix is preferably at least 60%. An example of a commercially available water soluble film is the PVA film sold by MonoSol LLC of Gary, Indiana, USA, under the product name Monosol® 63 0 0, and a PVA film of corresponding solubility and deformation characteristics. Other suitable membranes for use in this product include those supplied by Aicello under the product name PT membrane or κ series membrane, or VF-HP membranes supplied by Kuraray. The coating is applied to and substantially covers at least the first surface 12 or the second surface 14 of the water soluble matrix 1 . The coating can be water soluble. However, it is not as soluble as water-soluble matrix. According to the above method, the solubility of the coating φ is preferably less than 75% by weight. "Substantially covered" means that at least 95%, preferably at least 99%, optimally 1% of the first surface 12 or the second surface 14 is covered by the coating. This ensures that upon accidental contact with water, the water will not reach the first surface 12 or the second surface 14 of the water-soluble substrate 1 or the amount of water reaching the surface will be insufficient to completely dissolve the water-soluble matrix. The weight ratio of the coating applied to the water-soluble matrix is greater than 0.80 (i.e., coating weight: ratio of water-soluble matrix weight). The weight of the coating to the water-soluble substrate is preferably at least 〇·85, more preferably at least 0.90, more preferably 1.00 less than 1.00, and may be as high as 100, preferably up to 50, more preferably up to 20, and particularly up to 1 〇. . These levels of coating allow the use of a thinner water-soluble matrix, which has sufficient resistance to solubility when in contact with water, and has no negative effect on solubility when the coated substrate is immersed in water. The optimum ratio of the weight ratio of the coating to the water-soluble matrix is between 0.80 and 10, more preferably from 〇85 to 5, particularly preferably from 90 to 3, and more preferably from 1 to 2. Without being bound by theory, the Applicant believes that the resistance to solubility does not depend solely on the thickness or solubility of the water-soluble matrix, or on the thickness, solubility or coverage of the coating. In contrast, the total resistance of the bound matrix is -8-200821152, that is, the water-soluble matrix 10 coated with the coating thereon and the water-permeable substrate can be passed through the coating to reach the water-soluble matrix 10 Time is the factor that determines. Therefore, if the thickness of the water-soluble matrix 10 is small, the weight ratio of the coating to the water-soluble matrix 10 is required to be high to impart sufficient solubility resistance to the coated substrate. The coating may comprise a variety of materials and may be applied in a variety of forms and manners as described below. Φ In another preferred embodiment, the coating 20 is water insoluble. The "water insoluble" table has a solubility of less than 50% by weight when measured according to the aforementioned method. The coating preferably has a water solubility of less than 40% by weight, more preferably less than 30% by weight, and most preferably less than 10% by weight. The water-insoluble material may be a water-insoluble inorganic material or a water-insoluble organic material. The water-insoluble inorganic material may be zeolite, bentonite, talc, mica, kaolin, sepiolite, vermiculite, calcium carbonate, titanium oxide, anhydrous citric acid, hydroxyapatite 13⁄4, phthalocyanine blue, Helidone pink, Hansa orange, The pearlescent material φ or the like is preferred, and zeolite, bentonite, talc, mica, kaolin, vermiculite, titanium oxide, polyoxymethylene or the like is preferred. The water-insoluble organic material may be a natural polymer selected from the group consisting of cellulose and/or its derivatives, starch and/or its derivatives, seed coats and/or derivatives thereof. Cellulose and/or its derivatives are preferred. Figure 3 shows an embodiment of a water soluble matrix 1 wherein the coating 20 is in the form of particles 24. These particles have an average diameter of 500 μm or less, preferably 300 μm or less, and more preferably from 0.01 to 300 μm. In a highly preferred embodiment, the particles 24 are in the nanometer size range and the average particle size of the flat -9 - 200821152 is from 0.01 to 1 micron. Coating the water-soluble matrix 10 with nano-sized particles further provides the benefit of making the coating transparent, which is aesthetically preferred. The coating 20 is preferably flexible. When the water-soluble matrix 1 is converted by printing, chipping, longitudinal cracking, rewinding, and other typical transformation operations, or when an article such as a pouch containing a water-soluble matrix 10 is produced, the water-soluble substrate 10 It is typically stretched. In certain regions of the substrate 10, the base Φ 10 can even be extended by up to 200% or more. This may cause the coating to break and thus bring the water into contact with the surface of the water-soluble substrate 10. Therefore, the coating 20 is preferably flexible and can be stretched without breaking. The coating 20 is preferably extended by at least 20%, more preferably at least 30%, particularly preferably at least 50%, most preferably more than 100% and up to 200% without breaking. An example of such a flexible coating is the product sold by Ideal Products LLC (Plymouth, IN) under the name Sani-Tred Liquid Polyurethane Coating, or Η MGA merica LLC (Expressive Coating, South Carolina) The product of RolleraneTM is the product of Lokner State. An example of other flexible coatings is the soft dip coating sold by JC Whitney Inc. (Chicago, Ill.) at low temperatures. Mixtures of these coatings with any of the foregoing coatings can also be used. The coating according to the invention may be opaque, but is preferably transparent or translucent. Also preferred are colored or three-dimensional coatings to produce an appearance such as a tactile (touch) effect or an appearance such as a graphic, a comic, a label, a branding, a user indication, and the like. Whereas when the water-soluble substrate according to the present invention is immersed in water (i.e., in the application where the substrate is used and the substrate needs to be dissolved), the coating does not sufficiently resist contact with water to ensure rapid dissolution of the substrate. In a preferred embodiment as shown in Figure 2, the coating 20 further comprises a composition comprising a PVA having a high degree of hydrolysis. The degree of hydrolysis of the PVA used for the coating is preferably greater than 97%. When PVA is used in a water-soluble matrix, the PVA used in the coating preferably has a higher degree of hydrolysis. The PVA can be a mixture of PVA with other water soluble polymers such as those described above. Selective Ingredients In some applications it may be desirable to increase the dissolution rate of the matrix (when immersed). A disintegrant can be added to the coating to accelerate dissolution of the water soluble matrix 1 浸 immersed in water. When present, the amount of disintegrant in the coating is from 0.1 to 30%, preferably from 1 to 15% by weight of the coating. Alternatively, the disintegrant may be applied to the surface of the water-soluble substrate 10, relative to the surface of the coating layer, or may be applied to both surfaces of the water-soluble substrate 10, or may be It is incorporated into the water-soluble film 1 ,, or any combination of them. Any suitable disintegrant can be used. The disintegrant used herein is preferably corn/potato starch, methyl cellulose (type), mineral clay powder, croscarmelose (crosslinked cellulose), crovovidine (crosslinked polymer), starch hydroxy Sodium acetate (crosslinked starch). The composition formed by the water-soluble matrix and the water-soluble substrate 10 formed therefrom may also contain one or more additives or adjuvant components. For example, the composition formed by the water-soluble matrix and the water-soluble matrix 1 may contain plasticizers, lubricants, release agents, tanning agents, synergists, anti-blocking agents, and de-increasing -11 - 200821152 Agent, defoamer or other functional ingredients. Where the article contains a composition for rinsing, the latter may include a functional detergent additive to be delivered to the rinsing water, such as an organic polymeric dispersant or other detergent additive. Suitable plasticizers include, but are not limited to, glycerol, glycerin, diglycerin, hydroxypropyl glycerol, sorbitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, poly Ethylene glycol, neopentyl glycol, trimethylolpropane alkane, polyether polyol, ethanolamine, and mixtures thereof. The plasticizer can be incorporated into the water soluble matrix 10 in any suitable amount, and suitable amounts include from about 5% by weight to about 30% by weight, or from about 12% by weight to about 20% by weight. content. * Suitable surfactants include nonionic, cationic, anionic and zwitterionic. Suitable surfactants include, but are not limited to, polyoxyethylated polyoxypropylene glycols, ethanol ethoxylates, alkylphenol ethoxylates, tertiary acetylenic diols, and alkylguanamines (nonionic) , polyoxyethyleneated amines, amines, quaternary ammonium salts and quaternized polyoxyethylated amines (cationic), and amine oxides, N-alkyl betaines and sultaines (zwitterionic) . The surfactant may be incorporated into the water-soluble matrix 10 in any suitable amount, and the suitable content includes from about 0.01% by weight to about 1% by weight, or from about 0. 1% by weight to about 0.6% by weight. The content in the range. Suitable lubricants/release agents include, but are not limited to, fatty acids and salts thereof, fatty alcohols, fatty esters, fatty amines, fatty amines and fatty amines. The lubricant/release agent can be incorporated into the water soluble matrix at any suitable level! In addition, a suitable content includes from about 0.02% by weight to about 1.5% by weight -12 to 200821152, or a content ranging from about 〇. 04% by weight to about 0.15% by weight. Suitable tanning agents, synergists, anti-blocking agents, de-tackifiers include, but are not limited to: starch, modified starch, cross-linked polyvinylpyrrolidone, crosslinked cellulose, microcrystalline cellulose , vermiculite, metal oxides, calcium carbonate, talc and mica. The dip, synergist, anti-blocking agent, de-tackifying agent may be present in the water-soluble matrix in any suitable amount, and suitable 'contents include from about 0.1% to about 25% by weight, preferably from Amount in the range of from about 1% by weight to about 15% by weight. In the case where starch is not present, it is expected that the pigment, synergist, anti-blocking agent, and detackifying agent are present in the range of from about 1% by weight to 5% by weight. Suitable antifoaming agents include, but are not limited to, polydimethyl methoxy oxane based and hydrocarbon blends. The antifoaming agent may be present in the water-soluble base 10 in any suitable amount, and a suitable amount includes a content in the range of from about 0.001% by weight to about 0.5% by weight, preferably from about 0.01% by weight to about 0.1% by weight. • The gain agent can also be incorporated into the coating. Thus, a benefit agent that is incompatible with the product or composition in the article can be delivered via an article such as a pouch. Examples of the gain agent that can be contained in the hollow glass beads or applied to the outer surface of the glass beads include, but are not limited to, detergents, soil suspending agents, antiredeposition agents, optical brighteners, bleaches, enzymes, fragrances Compositions, bleach activators and precursors, sparking agents, soap bubble inhibitors, fabric care compositions, surface nourishing compositions. For example, when a coating is applied by applying a plurality of layers of coating material, a reinforcing agent can be applied between the coatings. The water-soluble matrix is formed by mixing the material and agitating the mixture to a temperature of about 7 〇〇F (about 21 〇c) to 195 〇F (about 90 ° C) while stirring the mixture. Prepared until the solution is completed. The composition formed from the matrix can be formed into any suitable form (e.g., film or sheet) and can be subsequently formed into any suitable product (e.g., single- or multi-compartment pockets, sachets, pouches, etc.). Method of Making a Water-Soluble Matrix There are many embodiments of the water-soluble matrix described herein that are not used for the φ limitation. In one embodiment, the method comprises providing at least one of the previously formed water soluble matrix 1 and coating the coating 20 to the previously formed water soluble matrix 1 〇 surface J 2 , 14 . The coating 20 can be applied to the previously formed water-soluble matrix 1 数 in a number of different ways. In a non-limiting embodiment, the coating 20 is applied as a particle or powder to at least one of the surfaces 12, 14 of the previously formed water soluble matrix 1 . The particles or powder are preferably electrostatically applied to the water soluble matrix 10 via a jet or φ. Due to the high velocity jet, some particles or powder are embedded in the matrix, thereby reducing or even eliminating the need to use adhesives. Adhesives are generally not required when coating particles electrostatically. However, binders can still be used. The binder may be previously applied to the water-soluble matrix 10 prior to coating the particles. Alternatively, the binder may be mixed with the particles and then the mixture added to the water soluble matrix. In another non-limiting embodiment of the method, the coating 20 is applied as a solution to at least one of the surfaces 12, 14 of the water soluble substrate 10, followed by drying and drying. The solution can be applied to the film by any of the methods of application -14-200821152, including sprays, knives, rods, bonds, slits, lacquers, printing, and the like. Here, the use of printing is a preferred method. Printing is a well-established and economical approach. Printing is typically performed with inks and dyes and used to impart a matrix pattern and color, but in the context of the present invention, a print is used to deposit less water soluble material onto the water soluble substrate. Any type of printing method can be used, including gravure rotation, lithography, offset printing, stenciling and screen printing, inkjet printing, embossing, pad printing, and combinations thereof. φ These embodiments may also include the step of moisturizing a portion of at least one of the surfaces 1 2, 14 of the water-soluble substrate 1 prior to applying the coating 20 to the previously formed water-soluble substrate 1 . At least one of the surfaces 12, 14 of the wet water-soluble matrix 10 can be used to at least partially dissolve the exterior of the surface 1 2, 14 of the substrate 10 (i.e., deep into the thickness of the substrate). The water soluble matrix 10 can be at least partially dissolved to any suitable depth due to the coating partially embedded in the matrix. Suitable depths include, but are not limited to, from about 1% to about 40% or about 45% of the total matrix thickness 16, from about 1% to about 30%, from about 1% to about 20% from about φ, from about 1%. Up to about 15%, and optionally from about 1% to about 10%. The coating 20 is then applied to the partially dissolved portion of at least one of the surfaces 12, 14 of the substrate 10. This causes the coating 20 to be buried outside of the surfaces 12, 14 of the substrate 10 and to become a more permanent portion of the substrate 10. The wetted surfaces 1 2 , 14 of the substrate 10 having the coating 20 embedded therein are successively dried. This embodiment of the method may also comprise the step of removing any loose or excessive coating 20 remaining on at least some of the surface of the water-soluble matrix 10 after drying of the water-soluble matrix 1, such as by rubbing or dusting the surface of the substrate 10. . -15- 200821152 In another embodiment, after the substrate 1 is formed into a product, the coating 20 may be added to the water-soluble substrate 10. For example, if a water-soluble base is used to form a water-soluble bladder containing the composition, a coating 20 to a water-soluble base 1 can be added to the surface of at least a portion of the water-soluble bladder. In another embodiment of the method that is not intended to be limiting, the coating 20 is applied in multiple application steps. The first coating is applied to the water-soluble substrate 10 according to any of the above methods, and is selectively dried. Successively, additional Φ one or more coatings may be added until the desired coating thickness is obtained and selectively dried. This produces a relatively thick coating on a thin water soluble substrate. In another embodiment of the method that is not intended to be limiting, a coating may be separately formed and subsequently applied to the surface of the water soluble substrate. Method of Making a Water Soluble Pouch The water soluble matrix 1 described herein can be formed into articles including, but not limited to, water soluble matrix 10 as a packaging material. Such items include # ' but are not limited to water soluble pouches, sachets and other containers. The water soluble pouch or other container of the water soluble matrix 10 described herein can be made in any suitable manner known to the art. A water soluble matrix 1 having improved resistance to solubility can be provided before or after the formation of the final product. In each case, in a particular embodiment, when such articles are made, the desired surface is coated with a coating on the surface 12, 14 of the substrate 1 to form the exterior of the article. There are many methods for making water soluble pouches. This includes, but is not limited to, the following methods known to the industry: vertical upright sealing process, horizontal 塡 -16- 200821152 filling process and forming pockets in the mold on the surface of the circular drum. In the upright filling and sealing process, an upright tube is formed by folding the substrate. The bottom of the tube is sealed to form an open pocket. Partially filling this pocket leaves a top gap. The top of the open pouch is sealed to close the pouch and form the next open pouch. Continue to cut the first pocket and repeat the steps. The resulting pocket is usually pillow shaped. The horizontal fill-and-seal process uses a mold having a series of molds therein. In a horizontal fill-and-seal process, a substrate is placed in the mold and φ is formed into an open pocket in which the mold can be subsequently filled, covered by another substrate layer, and sealed. In a third method (forming a pocket in a mold on the surface of a circular drum), the substrate is wrapped around the drum to form a pocket which is passed through a tamping machine to fill the open pocket. The filling and sealing occurs at the highest point (apex) of the ring of the drum, as typically, just after the rotating drum begins to recharge before the downward ring motion, and just after the drum begins its downward motion seal. In any process comprising the step of forming an open pocket, the matrix may be initially molded or formed into the shape of an open pocket using thermoforming, vacuum forming or both. Thermoforming involves heating the mold and/or substrate in any known manner, such as by contacting the mold with a heating element, or by blowing hot air or using a heat lamp to heat the mold and/or substrate, applying heat. In the case of vacuum forming, the use of a vacuum system helps drive the substrate into the mold. In another embodiment, two techniques can be combined to form a pouch, for example, an open pouch can be formed by vacuum forming and heat is provided to facilitate the process. The sac is filled with the composition contained in the pouch to fill the open pouch. The spliced sac continuous sac can be closed by any method. In some cases, such as in a horizontal pouch forming process, the closure is continually fed a second material or matrix, such as a water soluble matrix, onto the open pocket web and continues to pass the first substrate with the -17-200821152 The two substrates are sealed together to complete. The second material or matrix can comprise the water soluble matrix 1 oxime described herein. It is contemplated that the surface of the coated second substrate is oriented such that it forms the outer surface of the bladder. In this process, the first and second substrates are typically sealed to the inter-die region and thus sealed between pockets formed in adjacent molds. This seal can be done in any way. Methods of sealing include heat sealing, solvent welding, and solvent or wet sealing. The sealed mesh of the pouch can be cut by the cutting device, which cuts the pouch into a separate pouch. A method of forming a water soluble pouch is further described in U.S. Patent Application Serial No. 9/994,533, the disclosure of which is incorporated herein by reference. Manufacture of the article As shown in Fig. 4, the present invention also includes an article comprising the product composition Φ 40 and the water-soluble matrix 10, and the water-soluble matrix 10 can form a container such as a pouch, a pouch, a capsule, a bag, or the like. 30 to retain the product composition. The surface of the water-soluble substrate 1 涂布 having the coating 20 coated thereon may be used to form the outer surface of the container 30. The water soluble matrix i 〇 can form at least a portion of the container 30 and the container 30 provides a unit dose of the product composition 40. For the sake of brevity, the items herein will refer to water soluble bladders, however it should be understood that the discussion herein also applies to other types of containers. The pouch 30 formed by the foregoing method can be formed into any form and shape suitable for holding the contained composition 40 until the composition 40 is to be released from the water-soluble pouch -18-200821152 30, such as Dip the water-soluble pouch 3 in water. The pouch 30 can include one or two or more compartments (i.e., the pouch can be a multi-compartment pouch). In one embodiment, the pouch 3 can have two or more compartments that are generally in a stacked relationship. And the bladder 3 includes upper and lower skirt-like sidewalls that generally form a pocket 30 side and one or more inner partitions relative to the outer wall to separate the different compartments from one another. If the composition 40 contained in the capsule 3 contains different forms or components, the different components of the composition 4〇 may be stored in different compartments of the water φ soluble capsule 30, and may be made of a water-soluble material. The barriers are separated from each other. The pouch or other container 30 may contain a unit dose for/for laundry detergent composition, automatic dishwashing detergent composition, hard surface cleaner, stain remover' fiber synergist and/or fiber softener One or more of the compositions 40 of foods and beverages, as well as contact with small amounts of water, can result in new forms of premature pouch dissolution, unwanted bladder leakage, and/or unanticipated viscosities between the pockets. The composition 4 of the pouch 30 may be in any suitable form including, but not limited to, liquid, liquid glue, colloid, paste, cream, solids, granules, powder, and the like. Different compartments of the multi-compartment pocket 30 can be used to separate incompatible ingredients. For example, bleach and enzyme can be expected to separate into separate compartments. Other embodiments in the form of multiple compartments may include compartments containing powder in combination with compartments containing liquids. An example of an additional multi-compartment water soluble pouch is disclosed in U.S. Patent 6,670,3, 4, B2 to Smith et al. The water soluble pouch 30 can fall into any suitable aqueous solution (such as hot or cold water), and the water soluble matrix 1 which then forms the water soluble pouch 30 dissolves to release the contents of the pouch. -19- 200821152 The water-soluble matrix 1 described herein can also be used in coated products or other articles. An example of such a product that is not used for limitation is a laundry cleaning lozenge or an automatic dishwasher cleaning lozenge. Other examples include food or tanning coated products which may cause premature dissolution, unwanted leakage, and/or unanticipated viscosities when contacted with small amounts of water. An example is to obtain a PVA film on a water-soluble substrate by obtaining a water-soluble matrix for accidental contact with water, such as a fiber based on the product grade D60S from Dissolve) LLC (Croiden, Pa.) The (paper) matrix of the material. This film was prepared by coating a paper substrate with a 4% aqueous solution of PVA, followed by drying. The resulting PVA film had a basis weight of about 0.44 gsm and a thickness of about 0.33 microns. The first PVA film (A) produced according to the above procedure was used as a comparative example. The second (B) and third (C) PVA films produced according to the above steps are further coated with a coating to produce a water-soluble substrate according to the present invention. The surface of the PVA film (relative to the surface in contact with the paper substrate) was coated with an aqueous suspension of micronized PTFE particles from EIC under the designation EC 007003. The coating of Sample B had a basis weight of 15.90 gsm, while the coating of Sample C had a basis weight of 3 0.1 6 gsm, such that the ratio of water-insoluble materials to water-soluble substrates was 36 and 68, respectively. As shown in Fig. 5, each sample 50 is attached to an open end of the 2'' hollow plastic tube 5 1 and fixed by a rubber band 52. Place 2 gram of weight 53 in the -20 - 200821152 tube. The tube with the face down sample was lowered 1 '' into the water at room temperature (20 - 2 5 D C) in beaker 54. Record the time from when the paper hits the surface of the water until the weight passes through the sample. The time of this record is called the "break time". The greater the break time, the greater the resistance of the sample to water. For comparison, the paper substrate (D) was also tested separately. Result: Sample Break time (seconds) A 1 B 9 C 11 D 1

於此揭露之尺寸與數値不應被視爲以所陳述之確切數 値進行嚴格限制。相反的,除非另行指明,各尺寸意謂所 陳述的數値及鄰近該數値之功能性相等範圍兩者。舉例而 言,若揭露之尺寸爲“4 0 mm”,其意謂“約4 0 mm”。 【圖式簡單說明】 第1圖顯示未經塗覆之水溶性基質的橫截面; 第2圖顯示根據本發明之水溶性基質之一實施例的橫 截面; 第3圖顯示根據本發明之水溶性基質之另一實施例的 橫截面; 第4圖顯示根據本發明之包含水溶性基質之物件的橫 -21 - 200821152 截面;以及 第5圖顯示測試方法之示意圖。 【主要元件符號說明】 1 0 :水溶性基質 1 2 :表面 1 4 :表面 ⑩ 1 6 :厚度 2 0 :塗層 2 4 :粒子 30 :容器 40 :產物組成物 5 〇 :樣本 5 1 :塑膠管 52 :橡皮圈 φ 5 3 :重物 54 :燒杯 -22-Dimensions and numbers disclosed herein are not to be considered as limiting the exact number stated. Conversely, unless otherwise indicated, each dimension means both the recited number and the functional equivalents of the number. For example, if the exposed size is “40 mm”, it means “about 40 mm”. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a cross section of an uncoated water-soluble substrate; Figure 2 shows a cross section of an embodiment of a water-soluble substrate according to the present invention; and Figure 3 shows a water-soluble solution according to the present invention. A cross-section of another embodiment of a substrate; Figure 4 shows a cross-section of the cross-section 21 - 200821152 of an article comprising a water-soluble matrix according to the present invention; and Figure 5 shows a schematic view of the test method. [Explanation of main component symbols] 1 0 : Water-soluble matrix 1 2 : Surface 1 4 : Surface 10 1 6 : Thickness 2 0 : Coating 2 4 : Particle 30 : Container 40 : Product composition 5 〇: Sample 5 1 : Plastic Tube 52: Rubber band φ 5 3 : Weight 54 : Beaker-22-

Claims (1)

200821152 十、申請專利範圍 1 · 一種水溶性基質,其包含第一表面、相對於該第一 表面的第二表面,及介於該第一表面及該第二表面之間的 厚度,該水溶性基質之塗層塗佈至並實質上覆蓋該第一或 第一表面之至少一者,其中該塗層對該水溶性基質的重量 比係大於約0.80,且其中該塗層係呈選自水不溶性無機材 料及水不溶性有機材料之複數粒子的形式。 2·根據申請專利範圍第1項之水溶性基質,其中該塗 層對該水溶性基質的該重量比係介於約0.80及約1〇〇之 3 ·根據申請專利範圍第1項之水溶性基質,其中該塗 層對該水溶性基質的該重量比係介於約〇·80及約1〇之間 〇 4 ·根據申請專利範圍第1項之水溶性基質,其中該塗 層對該水溶性基質的該重量比係自約〇.85至約5。 5. 根據申請專利範圍第1項之水溶性基質,其中介於 該第一表面及該第二表面之間的該厚度係自約0.75微米 至約1 250微米。 6. 根據申請專利範圍第!項之水溶性基質,其中該塗 層另外包含水解度爲至少約9 7 %的聚乙燒醇。 7·根據申請專利範圍第〗項之水溶性基質,其中該等 粒子包含的水不溶性有機材料係天然聚合物。 8 .根據申請專利範圍第i項之水溶性基質,其中該等 粒子的平均直徑爲約5 00微米或以下。 -23- 200821152 9.根據申請專利範圍第1項之水溶性基質,其中該等 粒子的平均直徑爲自約0 · 0 1至約1微米。 1 0.根據申請專利範圍第1項之水溶性基質’其中該 塗層另外包含可以被延長至少約20 %之撓性材料。 1 1 .根據申請專利範圍第〗項之水溶性基質,其中該 塗層係塗佈至並實質上覆蓋該第一及第二表面兩者。 12.根據申請專利範圍第1項之水溶性基質’其中該 φ 塗層係透明的或半透明的。 1 3 .根據申請專利範圍第1項之水溶性基質,其中該 塗層係經著色或三維者,且較佳包含圖示、漫畫、標籤、 烙印、使用者指示或彼等之任何組合。 14.根據申請專利範圍第1項之水溶性基質,其中該 塗層另外包含崩解劑。 1 5 . —種物件,其包含申請專利範圍第1項之水溶性 基質,其中該塗層塗佈至該第一及第二表面之至少一者而 • 形成該物件的外表面。 1 6.根據申請專利範圍第1 5項之物件,其中該水溶性 基質形成包含產物組成物之容器的至少一部份。 1 7· —種製造申請專利範圍第1項之水溶性基質之方 法,該水溶性基質包含第一表面及第二表面,該方法包含 塗佈複數粒子至該第一及第二表面之至少一者的步驟。 1 8 ·根據申請專利範圍第1 7項之方法,其中該等粒子 係經由噴射流或靜電地塗佈至該水溶性基質。 1 9 ·根據申請專利範圍第1 7項之方法,其中該等粒子 -24- 200821152 係經由噴霧、刀、桿、密接、狹縫、塗漆、印刷及彼等之 混合而塗佈至該水溶性基質。 2 0.根據申請專利範圍第17項之方法,其包含以下步 驟: a. 塗佈第一粒子塗層至水溶性基質; b. 選擇性地乾燥該第一塗層; c. 塗佈第二塗層至該第一塗層; d. 選擇性地乾燥該第二塗層。200821152 X. Patent Application No. 1 - A water-soluble substrate comprising a first surface, a second surface relative to the first surface, and a thickness between the first surface and the second surface, the water solubility Applying a coating of the substrate to and substantially covering at least one of the first or first surfaces, wherein the weight ratio of the coating to the water soluble substrate is greater than about 0.80, and wherein the coating is selected from the group consisting of water A form of a plurality of particles of an insoluble inorganic material and a water-insoluble organic material. 2. The water-soluble substrate according to claim 1, wherein the weight ratio of the coating to the water-soluble substrate is between about 0.80 and about 1 ·. The water-soluble according to claim 1 a matrix, wherein the weight ratio of the coating to the water-soluble substrate is between about 〇80 and about 1 〇4. According to the water-soluble substrate of claim 1, wherein the coating dissolves the water. The weight ratio of the matrix is from about 8585 to about 5. 5. The water soluble substrate of claim 1 wherein the thickness between the first surface and the second surface is from about 0.75 microns to about 1 250 microns. 6. According to the scope of the patent application! A water soluble substrate, wherein the coating additionally comprises a polyethyl alcohol having a degree of hydrolysis of at least about 97%. 7. The water-soluble substrate according to the scope of the patent application, wherein the water-insoluble organic material contained in the particles is a natural polymer. 8. The water-soluble base according to item i of the patent application, wherein the particles have an average diameter of about 500 microns or less. The water-soluble substrate according to claim 1, wherein the particles have an average diameter of from about 0. 01 to about 1 micron. 10. The water soluble substrate of claim 1 wherein the coating additionally comprises a flexible material which can be extended by at least about 20%. A water-soluble substrate according to claim IA, wherein the coating is applied to and substantially covers both the first and second surfaces. 12. The water-soluble substrate of claim 1 wherein the φ coating is transparent or translucent. The water-soluble substrate according to claim 1, wherein the coating is colored or three-dimensional, and preferably comprises a graphic, a comic, a label, a brand, a user indication, or any combination thereof. 14. The water soluble substrate of claim 1, wherein the coating further comprises a disintegrant. An article comprising the water-soluble substrate of claim 1 wherein the coating is applied to at least one of the first and second surfaces and • forms an outer surface of the article. 1 6. The article of claim 15 wherein the water soluble matrix forms at least a portion of a container comprising the product composition. A method for producing a water-soluble substrate according to claim 1, wherein the water-soluble substrate comprises a first surface and a second surface, the method comprising coating a plurality of particles to at least one of the first and second surfaces Steps. The method of claim 17, wherein the particles are applied to the water-soluble substrate via a jet or electrostatically. 1 9 · According to the method of claim 17, wherein the particles-24-200821152 are applied to the water by spraying, knife, rod, adhesion, slit, painting, printing and the like. Sexual matrix. The method of claim 17, comprising the steps of: a. coating a first particle coating to a water soluble matrix; b. selectively drying the first coating; c. coating a second Coating to the first coating; d. selectively drying the second coating. -25--25-
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JPS51138772A (en) * 1975-05-28 1976-11-30 Kuraray Co Method of modification of surface property of polyvinyl alcohol film
US4416791A (en) * 1981-11-11 1983-11-22 Lever Brothers Company Packaging film and packaging of detergent compositions therewith
JPS6429438A (en) * 1987-07-24 1989-01-31 Kao Corp Polyvinyl alcohol film
JPH01249343A (en) * 1988-03-30 1989-10-04 Kuraray Co Ltd Polyvinyl alcohol film with coated surface and its manufacture
JP2534313B2 (en) * 1988-04-12 1996-09-11 株式会社クラレ Surface-treated polypinyl alcohol film and its manufacturing method
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