TW200550B - - Google Patents
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- TW200550B TW200550B TW81102151A TW81102151A TW200550B TW 200550 B TW200550 B TW 200550B TW 81102151 A TW81102151 A TW 81102151A TW 81102151 A TW81102151 A TW 81102151A TW 200550 B TW200550 B TW 200550B
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3715—Polyesters or polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
- C11D3/0015—Softening compositions liquid
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
200550 A 6 _ η 6 五、發明説明(1) 抟銜齡皤 本發明係Μ於非離子糸寡聚物,其功能係作為經改良污 垢釋離劑(Sra’s)且係有用於洗滌姐成物中,詳细言之, 織品软化劑姐成物等。 發明背畺 若將嫌品(詳细言之,具有合成孅維成份之嫌品)沉浸 在家庭或公設拖中之水性洗滌或潤濕劑中,則產生“污垢 釋雜”效懕,其中水浴含有各棰不同聚合物或寡聚物系酯 之污垢釋離劑(Sra’s),典型係K低濃度,如每百萬人份 中佔5至幾拾份。聚合體或寡聚體沉積在織品表面Μ提供 污垢釋離精整物。污垢釋離係不同於普通洗滌清潔表面活 性劑及增滌劑之清潔效應之處在於彼具有多重清洗效應, 例如,經個別洗滌之織品歷經2、3或4次清洗、穿截循 環後傾向於更容易逐漸地加W清潔,而且亦經常獲得某些 污垢再沉積效益。污垢釋離對聚酯織品尤其顯著,但是對 聚酯/棉摻合品亦獲得良好结果。污垢釋離效益亦見諸於 (請先閱讀背而之这意事^再填寫本頁) 裝< 訂· 綠· 經濟部中央桴準局Α工消费合作社印3i 類,不用潔品 種整之施清織 物精上 S 之糸 成業質a'用子 姐 H lnsr作離 a 之些滌擾陽 Sr等某洗干在 般漿有之具係 一 上具式不式 在-中型在方 離妙件種係佳 釋經條此此更 垢、程具而者 污維製將,或 之纖在型上 , 。中、此典品下 品文妙。,織在 織下於佳中之存 系上同極件中之 酸滌不性事器劑 稀洗係 Η 何機性 丙性面加任滌活 及水方者在洗面 論在目前。在表 耐 項因同至劑 表紙張尺度遑用中®因家樣準(CNS)f4規格(210x29/公*) 81. 川,〇〇〇張(丨丨) 200550 A 6 Π 6 五、發明説明(2 )200550 A 6 _ η 6 5. Description of the invention (1) 芟 馬 隤 The present invention is based on non-ionic oligomer oligomers, its function is as an improved dirt release agent (Sra's) and it is used for washing sisters. In detail, the fabric softener is finished. In the invention, if the susceptible substance (specifically, the susceptible substance with synthetic dimensional ingredients) is immersed in the water-based washing or wetting agent in the household or public establishment, the effect of "dirt release" will be produced. The soil release agent (Sra's) containing different polymers or oligomer esters is typically a low K concentration, such as 5 to a few parts per million. Polymers or oligomers are deposited on the fabric surface M to provide soil release finish. The dirt release system is different from the cleaning effect of ordinary washing and cleaning surfactants and detergents in that it has multiple cleaning effects. For example, fabrics that have been washed individually tend to undergo 2, 3, or 4 times of washing and cutting cycles It is easier to add W for cleaning gradually, and some dirt redeposition benefits are often obtained. Dirt release is particularly noticeable for polyester fabrics, but good results are also obtained for polyester / cotton blends. The benefits of dirt release are also seen (please read the meaning of ^ first and then fill out this page). Install &Order; Green · Printed by the Central Bureau of Economic Affairs of the Ministry of Economic Affairs Α 工 consumer cooperatives, category 3i, without cleaning Shi Qing fabrics are fine with S's qualities a '. Use the sister H lnsr as a deodorant to disperse the sun, Sr, etc. Some of the clothes are dried and dried in the pulp. There is a style that is not in style-medium in the square. The wonderful article is a good way to explain the scriptures, which is more dirty, more complicated, and more effective in keeping the shape or shape. In the middle, the classics are excellent. , Weaving under the weaving Yu Jiazhong's system on the same pole pieces of acid-purifying agent agent Dilute washing system Η He organic Chrysanthemum surface is added as a living and water side in the face-washing theory at present. In the table of the same item to the paper sheet size in the use of the same standard in the home standard (CNS) f4 specifications (210x29 / g *) 81. Sichuan, 8000 Zhang (丨 丨) 200550 A 6 Π 6 V. Invention Description (2)
經濟部中央標準局BX工消^合作杜印M 軟化劑之存在下,Sra典型僅有限程度沉積在嫌品上。相 反的,工業精整普通在高度可控制製程設備(如浸染機) 中完成。 典型的嫌物係清潔的,且清潔劑或软化劑(若存在任一 種)之濃度傾向於低的,此係至少在此階段即欲將污垢釋 離處理皆用在織物底材上。 由於介於洗滌及工業精整技術方面係不同的*故介於姐 成物型式(如洗滌清潔劑、洗滌軟化劑、洗滌漂白劑等) 之間亦具有顯著不同。亦製得此種洗滌清潔姐成物而Μ各 種不同型式,如粒狀、液態、凝膠、糊狀-形式,及加入 有乾燥劑之產物。在洗滌技藝中之調配者譬覺到各種不同 \, 形式之洗滌姐成物具有固有的配方限制。例如*固體配方 姐成物所需成份一般係能夠分散或溶於水性清潔浴中,同 時液體配方共同所需成份係自由混合而不具過刺化學或物 理交互作用如相改變或沉澱。 特定言之,近代洗滌姐成物玆呈“濃縮”形式者愈加普 遍。例如,茲已有市售之液態織品软化劑所含腸離子軟化 劑成份之濃度大小而為迄今所得織品软化劑3倍Κ上。感 知此種组成物配方若要皆具自身穩定形式且具有合理粒度 範圍,則係困難的。當然,若欲將具有額外功能之成份( 如sra’s)併入此種姐成物中,則如何調製且揮發效能方面 更加困難。 因而持續進行有闞供使用於洗滌姐成物之有效、能相容 、易於調製之sra’s方面之研究。 ___ _ " ----- -4- (請先閱讀背而之¾意节¾#墦筠本頁) 裝· 訂 本紙51c尺度逍用中a國家樣毕(CNS) T4規格(210x297公釐) 81. 4. lO.OUOfSL (|() 200550 A 6 Π 6 五、發明説明(3 .〕 本發明提供育》f籃子系sra’s而適用於洗滌組成物中 ^ 。本發明亦珲避非雛子系s r a · s而特則有用於具有陽離子 糸織品軟化劑之結合物宁。此外,即使K軟化劑“濃縮劑 ”調製,於此之許多s r a · s也王窜過度增加液S1織品軟化 _姐成物之粘度。 昔甚坊轻 年12月8日頒予Gosselink及Diehl之美國專利 4,711,7 30號中係關於加蓋的1,2-丙烯對苯二甲酸酯-聚氧化乙烯對苯二甲酸酯聚酯類而有用於洗滌清潔劑及織 品軟化劑姐成物(包含濃縮劑)中且作為污垢釋離劑。 在此等範_中如Gossel丨nk及Diehl中所述額外參考文 件包含下列: L 存洗滌清潔劑組成物中所使用乙烯對笼二甲務酯/PRn 對荣二审Sg酷污诟煙件聚酯 (請先間讀背而之淺意事項4填筠本頁) 經濟部屮央櫺準局貝工消赀合作社印製 1978年9月 4,116,δ85 號 2 5 % ( Κ 0 . 5 % 二甲酸酯污垢 量為5,000至 潔劑姐成物進 之某些特定可 性劑和不超過 26日頒予Derstadt諸位之美國 中揭示之洗滌清潔劑姐成物而 至10%最佳)之乙烯對笨二甲 釋離聚酯,如MILEASET ,係 200,000(Μ 10,〇〇〇至 50,000較 一步含有5%至95% ( Μ 10% 相容醇硫酸酯及硫酸乙氧烷酯 10%之其它不相容的陰雜子系 專利 含有0. 15%至 酸酯/PEG對苯 具有平均分子 佳)。這些清 至25%最佳) 清潔劑表面活 表面活性劑, 本紙張尺度边用中B國家楳準(CNS) T4規怙(210父297公釐) 81. 4. 1(),〇〇〇張(ίί) 經沭部中央標準^β工消伢合作杜印製 200550 Λ fi ____Π6_五、發明説明(4 ) 如線性烷苯磺酸鹽。 1979年1月2日頒予Nicol之美國專利4,132,680號中 亦揭示洗滌清潔劑姐成物而具污垢釋雜性質,此含有2% 至95% ( Μ 至60%較佳)之清潔劑表面活性劑及0.15 %至25% (1 %至1〇%最佳)之乙烯對苯二甲酸酯/ PEG對 苯二甲酸酯(其箅耳比率為65: 35至80: 20)具有分子量 為10,000至50,000之污垢釋離聚酯,如《11^/^£1'。這些 姐成物進一步包括〇·〇5%至15% (以0.1%至5%最佳) 之成份而在水溶液中會產生具有1至3個(:8至(:24烷基之 四級銨陽雔子。由Nicol所教示之這些陽離子係為了改良 污垢釋離聚酯對經洗滌嫌品上之沉積。見其第11檷第14至 21行° L 亦楢加涠溻斋物中使闲聚酯Μ僂输污诟鐸餘袢曾 1981年5月15日頒予Becker諸位之加拿大專利第 1 , 100,262號中揭示之織品軟化劑姐成物係含有1 %至80 % ( Μ 5 %至50%較佳)之織品軟化劑如氛化二動物脂基 二甲酸銨而與0,5% 至25% (Ml%至10%較佳)之某些 特定膽酴脂肪酸醏類。這些軟化姐成物Μ包含0.5%至1〇 % .(以1 %至5%較佳)乙烯對笨二甲酸酯/ PEG對苯二甲 酸酯污垢釋離聚酯如PERMAL0SE或ZELC0N。 1975年7月8日頒予Basadur之美國專利3,893,929號 揭示之增加潤濕之酸糸溶液而含有從下列物質所製成污垢 釋離劑:二蘧基羧酸(以對苯二甲酸較佳)、一棰聚伸烷 -6 ** (請先閲讀背而之注意事項項寫本頁) 本紙張尺度逍用中8 8家楳毕〇:叫〒4規格(210><297公龙) 81. 4. ω,ϋϋΟ張(Η) 200550 A 6 Π 6 五、發明説明(5 ) 經濟部中央榀準局β工消伢合作社印51 二酵(M具有分子量為1,300至1,800之PEG較佳)及伸烷 二醇(乙二酵、丙二酵或丁二酵)。較佳的污垢釋離劑係 具有分子量為3,000至5,000。在這些姐成物中可含有陽離 子糸織品軟化劑如氛化二動物脂基二甲基銨,但據說並非 較佳“因為彼等在酸系出中傾向於阻緩污垢釋離劑沉積在 聚酯继維上”。見第7檷第54至59行。 1973年1月23日頒予Zenk之美國專利3,712,873號中揭 示藉噴灑或浸染(軋染)施用之織物處理組成物,此包括 1 %至5%在Basadur專利中所掲示型式之污垢釋離聚酯 。這些姐成物可額外含有至高達4%而具有1個Cie至 C2 2烷基之四级铵化合物。經說明此種四级銨化合物與聚 酯之结合物係作為改良經處理織品上之污垢釋離性質。 Zenk亦說明其它四级銨化合物(如氯化二動物脂基二甲基 銨)並不能得到相同的優效能。見第3檷第57至61頁。 L 聚酯#悄加乾憷畜物中夕闲徐W傅输污诟煜譃件皙 1980年12月9日頒予Rudy諸位之美國專利4,238,531號 中揭示增加乾燦產物係含有“分配劑”如聚乙二酵及施用 至織品上之佐劑而可為污垢釋離劑。所揭堊之污垢釋離劑 包括聚丙烯酸糸樹脂、聚乙烯醇及PERMALOSE TG聚酯(見 例8 )。 L 使用聚酯於镰品或辦物鹿捆滚液中,铧熟固化以德输 污垢蹭繾及/成杭靜雷袢晳 一Ί - (請先閲請背而之洼意亊項#填寫本頁) 裝- 訂- 本紙尺度遑用中8 S家標毕(CN5)T4規格(2丨0x297公Λ) 81. 4. ΙΟ,υυϋίί. (H) 200550 Λ (5η 6 經济部屮央榀準局β工消费合作社印51 五、發明説明(6 ) 1970年5月9日頒予Dunlop之美國專利3,512,920號中 所揭示低分子董伸烷二酵/聚伸烷二酵對苯二甲酸聚酯類 係使用於含有澱粉或纖維素衍生物之樹脂處理浴中,而熱 固化後,用以傳输污垢釋雛性質至棉/聚酯織品中。可用 以製成這些聚酯之伸烷二醇類包含乙二酵,1,2 -丙二酵 、1,3 -丙二酵、丁二醇及其混合物類。可使用之聚伸烷 二醇類包含PEG 、聚丁二醇及其混合物而具有平均分子量 為 200 至20,000 ( Μ 1,000 至5,000 較佳)。 1 968年12月7日頒予Me Intyre諸位之美國專利 3,416,952號中掲示之聚酯抗靜電試劑含有1個水可溶聚 合物糸基如聚氧化伸烷基而具有平均分子量為300至 6,000 。較佳的聚氧化伸烷基係PEG’S而具有平均分子量 為1,000至4,000 。進行處理而以在抗氧化劑之存在下施 用聚酯之水性散劑,接著加熱至超過90 =之溫度而在經過 處理物件上得到耐用的聚酿塗層。例6揭示一棰所形成之 此種聚酯而Μ將對苯二甲酸二甲酯、乙二酵及具有平均分 子量為350之0-甲基聚(氧化乙烯)二酵進行催化反應 。使用此種聚酯在苄酵中之20%溶液Μ傳输抗靜電性質至 聚酯鎌品上。例7揭示係使用類似聚酯之20%水溶液而將 抗靜電性質之聚酯織品上。 1984年1月24日頒予Stockburger之美國專利 4,427,557號揭示所示形成之低分子量共聚酯( 2,000至 1 0 , 000 )而以將乙二醇,一種PEG (具有平均分子量為 200至1,000),一種芳香族二羧酸(例如對笨二甲酸二甲 -8 - 本紙張尺度边用中a B家標寧(CNS)規格(2丨0X297公龙)~~ 81. 4. 10,000¾ (11) (請先間諸背而之注意事項Λ填寫本頁) 裝· 200550 Λ 6 Π 6 五、發明説明(7 ) 酯)及磺化芳香族二羧酸(例如5-磺酸間苯二甲酸二甲 酯)起反應。可將PEG部份取代而K PEG之單烷基醚如甲 基、乙基及丁基醚。將共聚酯之分散劑或溶液施用至織物 上,然後在升高溫度下(90勺至150 C)將彼加熱固化Μ傳 输用之污垢釋雔性質。亦見Me Intyre諸位之專利,其中例 2揭示係使用任意排列之共聚酯K傳輸抗靜電性質,形成 彼等而以將對笨二甲酸、間苯二甲酸二甲酯磺酸納、乙二 酵及具有平均分子悬為1,5 40之PEG。 此外,在聚酯技轻中有若干揭示,更特定言之,彼等低 分子量寡聚體類,而在洗滌產品中能作為sra’s 。稍早所 揭示者係闞於娌改良之聚醅型物質而不必為募聚體類而所 含部份不具有特定终端加蓋體。彼等係衍自乙二酵之聚醚 片段。見例如,1976年6月8日頒予Nicol諸位之美國專 利第3, 962,152號、1978年9月7日頒予Derstadt諸位之 美國專利第4, 116,885號、1981年5月5日頒予Becker諸 位之加拿大專利1,100,262號、1980年12月9日頒予Rudy 諸位之美國専利第4,238,531號及1986年9月24日為 Crossin所刊出之美國專利申請案第2,1 72,608號。 經濟部中央檫準局CX工消费合作社印製 最近在sra’s範畴中而用於洗滌清潔劑應用之發展包含 某些特定終端加蓋醅之寡聚體類,如下列這些頒予 Gosse link之美國專利中所揭示:見例如美國專利第 4,702,857(1987年10月27日頒予)。美國專利第 4,721,580號(1988年1月26日)和1989年10月31日予 Malc^onads、Trink及Gonsslink之美國專利 4,877,896 -9- 81. 4. 1(),000張 (請先閲讀背而之注意事項再碼寫本頁) 本紙張尺度逍R1中HB家樣導(CNS)肀4規格(210x2町公龙) 200550 Λ 6 Π 6 五、發明説明(8 ) 號0 經濟部屮央梂準局貝工消仲合作社印奴 本發明涵蓋污垢釋離劑而包括一種反應混合物之寡聚物 系酯化產物,此包括: U)任意地(但較佳者)一種(^至“烷氧基-終止(Μ 甲氧基终结者較佳)聚乙氧基單元 [^-(OCi^CHdx-O-來源或任意地併有少量丙氧基單 元之具终结之聚乙氧基單元之混合物; (b) —種對苯二甲醯基單元之來源,任意地,對苯二甲 醯基及少量間苯二甲醯基單元之混合體; (c) 一種聚(氧化乙烯)氧基單元[即 _(0CH2CH2)y-0-]之來源; (d) —種氧化異丙烯氧基單元之來源 即含 CH3 及 -0CHCH20-; (e) —種氧化乙烯氧基即-〇CH2CH2〇-來源; 該污垢釋離劑所具進一步特徵為所具氧化伸乙氧基單元 氧化異丙烯氧基單元之莫耳比率為至少約0.5: 1。 因此,於此之污垢釋離劑包括例如一種反應混合物之酯 反應產物包括: (a) CH3 (0CH2CH2)1Θ0Η ; -10- 本紙张尺度边用中國Η家楳準(CNS)甲4規格(210X297公龙) 81. 4. l(),〇U〇張(H) (請先閲請背而之注意事項洱填寫本頁) 200550 五、發明説明(9 ) (b) 對苯二甲酸二甲酯; (c) 聚乙二醇 1 500 (E34); (d) 1,2-丙二醇;及 (e) 乙二醇; 其中氧化乙烯氧基單元··氧化異丙烯氧基單元之莫耳比 率係至少約0 . 5 : 1,Μ至少約1 . 2 5 : 1較佳。 此種污垢釋離劑與sra's (上述Gosselink及Diehl美國 專利4,711,730號中所揭示)不同處在於彼等含有氧化物 乙烯氧基單元。本發明之sra's意外地具有此’730號專利 之這些具有較佳效能。 雖則不欲加K限制而以理論或構造考盧。咸信本發明較 佳s「a’s之特激為具式: - _0、 0 11 / \ |1 Ri〇-(CH2CH20)x cY^/V-CO-CH-CH^ - R2 _ m ο ο /1 /=Λ » C-^>-C - 0 (CHzCH^Jx-R1 —0 0 C-<^>-C0(CH2CHz0)y η 經濟部屮央標準扃员工消货合作社印51 (請先閱讀背而之洼意事項"塥寫本頁) 其中R1係低级(例如(^至(:4)烷基,詳细言之,甲基;且 R2係Η及CH3之混合體(即乙烯及異丙烯部份皆存在於分 子構造中),Μ提供氧化乙烯氧基:氧化異丙烯氧基之莫 耳比率為至少約0 . 5 : 1而Μ至少約1 . 2 5 : 1較佳。 在所繪之式中,X ,y ,m及η係整數而在下列範圍内 -11 - 本紙張尺度边用中H a家樣準(CNS)T4規格(210x297公龙) 8丨.4.丨0,000張(H) 200550 Λ 6 Β6 五、發明説明(10) 廣範圍 較佳範圍 最佳範圍 X 6至 100 6至43 12 至 30 y 6 至 100 12 至 77 12 至 50 m 0.75至30 1.5 至 25 2.25至20 η 0.25至20 0.5 至 15 0.75至12 m+n+l々 n + l 1至5 1.2至4.5 1 - 5至 4 (請先閲請背而之.注意事項.再硝筠本頁) 經濟部屮央標準局只工消费合作杜印驭 這些項目指出於MPEG單元插人之前之平均鄰接對苯二 甲酸酯單元之數目。 可知可將氧化乙烯氧基:氧化丙烯氧基單元之比率改變 Μ符合調製員所需。H與里匾_飲..'北..劑_之.—用途、方..面—、,此種 比率以至少約0 . 7 5 : 1較佳,而¥至少約1 . 2 5 ; 1更f。 供在ϋ里潔.麗進m,若以此種比率,則某些產物會 發生孩化,故調配員可選取稍低比率,例如,_ 0 . 5 : 1。、...... 本發明亦涵蓋洗滌组成物,如清潔劑、軟化劑、潤濕肋 劑等,包括至少約0.1重量% (而以約 0.2重量%至約10 重量%較佳)之前述s「a’s 。 於此較佳之織品軟化劑姐成物典型包括約0.3重量%至 « -12- 本紙5k尺度边用中®圉家樣苹(CNS)甲4規格(2〗0x297公;«:) 81. 4. Ιϋ,ΟϋΟ^ (11) 200550 Λ 6 ___ 五、發明説明(11) 約3重量% 2sra及約3重量%至約25重量%之織物軟化 劑成份。 一種可稀釋液體織物軟化劑姐成物濃縮液包括: (a) 約10重量%至約32重量%陽離子系織品软化劑; (b) 約4重量%至約20重量%咪唑餅織品軟化劑;且 (c) 約1重量%至約5重量%2sra 。 於此典型之洗滌清潔劑姐成物包括習知清潔劑表面活性 劑、任意的助洗劑、任意的載體、及約 0.1重量%至約10 重量%之5「3 。較佳的洗滌清潔劑包括約0.3重量%至約 3重量%之該污垢釋離劑及至少約3重量% ( Μ約3重量 %至約20重量%較佳)之脂肪酸多羥基醯胺表面活性劑, 詳细言之,C12至C1S脂肪酸Ν -甲基葡醣醯胺。 經將部中央標準局ΚΧ工消评合作社印" 本發明亦涵蓋一種方法用以對嫌品提供一種污垢釋離精 整而Μ該織品與水性介質[含有至少約2ppm(每百萬份佔 2份)前述s r* a ’ s ]。在一種較佳橫式中’此種方法包括Μ 继品與水浴[包括至少3ppm(W約4ρριπ至約25 ppm較佳 )之前述sra’s及至少約10 ppm(以約30 ppm至約10 ppm較 佳)之陽離子系軟化劑]相接觸而於從水浴分離織品之前 ,歷一段期間即至少約1分鐘(以約1分鐘至約1 〇分鐘較 佳)。(感滿意的是即使以較低的S「a’s湄度亦能有效進 行多重循環處理)。感滿意的是在習知的自動清洗機器中 於潤濕循環期間*能很容易進行此種方法。 於此全部百分比、比率及比例係Μ重量計’除非另加指 明。 -13- 81. 4. 10,000張(H) (請先閲讀背而之注急事項^項"本頁) 本紙5艮尺度遑用中a明家楳準(CNS)«P4規格(210x297公釐) 200550 Λ 6_η 6 五、發明説明(12) 經濟部屮央榣準局员工消费合作社印^ mm m 製得本發明之sra’s而M酯化前文所揭示之經取代羥基 -及羧酸鹽反應物。下列實例進一步說明了製備根據本發 明之s r a ’ s ,但並非藉此限制其範圍。II. 聚(乙二醅)甲辭(分芊S7 5 0)、 對笼二甲醸二甲酯、聚f 7,二醅)(分罕暑15 00) 、7,二醆孖丙二醅聚合物之合成 分別將下列物質加至裝有磁攪拌棒、經改良C 1 a i s e η接 頭、冷凝器(用於蒸餾裝置)、溫度計、及溫度控制器( THERM - 0 - WATCH > I2R)之250毫升大小3頸圓底燒瓶中 :分子量750之聚(乙二酵)甲醚(Aldrich ,50.0克, 0.067莫耳),對笨二甲酸二甲酯(35.6克,0.183莫耳 )、分子量 1500之聚(乙二醇)(Aldrich,50.0克,0.033 莫耳)、乙二醇(Baker,7.2 克,0.116 箅耳),1,2 -丙 二醇(Fisher·,8,9克,0.117莫耳)、水合氣化單丁基錫 (M&T化學公司出品,0. 30克,0.2%结!反應重量),及丁 基化羥基甲苯(Calbiochem,0.15克,0.1%缌反應重量 )。將此種混合物加熱至180 °C 且在氬氣下維持在此溫度 下過夜同時將甲醇及水從反應容器蒸餾出。由 13C-NMR(DMS〇-de)顯示在約52 ppm處具芦用於甲酯之殘留 共振。將溫度昇高至200t:歷5小時,然後加入額外的乙 二酵(7.2克,0.116奠耳)及丙二醇(8.9克,0.117箅耳) -1 4 - (請先閱讀背而之汶意事項扑填寫本頁) 本紙張尺度逍用中國國家楳毕(CNS)規格(210X297公龙) 81. 4·丨0,0⑻張(H) 200550 Λ 6 η 6 五、發明説明(13) 。將溫度降低至190C ,於此條件下將彼維持過夜。由 13C-NMR(DMS〇-de)顯示出此階段之反應已完成而Μ不見甲 酯之共振。將此物質轉送至1升大小單頸圓底燒瓶中而在 Kugelrohr裝置(Aldrich)内於約1.5毫米汞柱之下將此 逐步加熱至2 30 t 歷超過20分鐘並維持在此條件下歷1 + 時。然後.將燒瓶在抽興空下容許Μ空氣極快速冷卻至接近 室溫(約30分鐘)。反懕產得124.1克軟質棕色固艚。由 UMlHDMSO-de)顯示對於聚(氧化乙烯)片段在約3.5 ppm處有極密集共振,對於對笨二甲酸酯在約8.0 ppm處 有共振、對於雙重酯化丙二酵之甲基在約1.4 ppm處有共 振,且對於雙重酯化乙二醇在約4 . 7 p p m處有共振。由tb 較在1.4及4.7 ppm處之共振指出由乙二酵所衍生單元對 由丙二醇所衍生單元之莫耳比率係約2.2: 1。將此稱為 E/P比率。由其13C-NMR(DMS〇-de)亦與所要的聚合物構请 相一致顯示這些共振係在70.2 ppm (聚氧化乙烯部份)、 經濟部屮央標準局CX工消费合作社印奴 1 6 . 5 p p m (雙重酯化丙二醇之C Η 3 )、6 3 . 6 p P m (雙重酯化 乙二酵)、及 58_4ppra( (HO CH2CH2〇-)。由於對於乙二 酵(-C (0) OCHaCH^OH)之任何單醏在約60 ppm處或對於丙 二醇(_C(0)0CH(CH3)CH2OH )異構物系單酯之其一種之甲 基而在約20 ppm處皆不存在共振指出此具有高的聚合作用 程度。 可得到具有低E / P比率之寡聚物而以使用相同合成條件 除了降低了乙二酵:丙二酵之初比率以外。典型方式係以 初二酵比率為約0.25: 1而得到最终E/P比率為約〇·5 ·· -15- 本紙51尺度遍用中a B家炫箏(CHS)甲4規格(2丨0父297公龙) 81. 4. 10,000¾ (||) 200550 Λ 6 ΙΪ6 五、發明説明(14) m τ τ 7ι二酿、對茏二甲醏二甲8¾、聚(乙二醇)田糍(ϋ g 750)、聚(乙二酵)(分孑量15 00)及 1.2 -丙二醉 F/P=1.M 聚合物(夕会成) 將下表所列物質置於裝有磁攪拌器、加熱罩、内置溫度 計、蒸皤接頭、用於蒸餾之冷卻器装置、用於惰性氣膀人 口、及用於溫度控制之THERM-0-WATCH(I2R)等之5升大,j、 、3頸圓底燒瓶内: (請先間讀背而之注意卞項存项窵本頁) 經濟部中央樑準局只工消俾合作杜印魟 克數 莫耳數 來源 乙二酵 130.2 2.1 ·— — MCB 對苯二甲酸二甲酷 640.2 3.3 Aldrich 聚(乙二酵)甲醚(分子量750) 300 0.4 聯合碳化公司 聚(乙二醇)(分子量1500) 1500 1.0 聯合碳化公司 1,2-丙二醇 322 4.2 Fisher公司 水合氧化單丁基錫(FASCAT 4100) 5.5 M&T Chem公司 水基化羥基甲笨(ΒΗΤ) 3.2 Calbiochem 公司 將此系統攪拌而其溫度逐漸昇高至185t: 且維持在此條 件下歷28小時同時有甲酵從 反應物蒸 皤出。 然後將透明玻 璃通入管***至接近熗瓶底 部而將惰 性氣體 以高速通入並 -16- 81. 4. ΙΟ,ΟΟΟίΙ (Η) 本紙張尺度遑用中B B家樣準(CNS) Ή規格(210x297公*) 200550 五、發明説明(15) 經濟部屮央標準局β工消评合作社印製 昇高溫度至24010 。將此狀況捋鑛歷約13小時。容許將所 得聚合物冷卻而得約2400克軟質固體,若K在10%固體湄 度下進行試驗而Μ攪拌過夜,則絕大部份在室溫下係可溶 於水中。由1H-NMR(de-DMS0)顯示對於聚氧化乙烯部份在 約3. 45 ΡΡίπ處具有極密集共振、對於對笨二甲酸酯在約 8.05 ppm處具有複合或共振、對於經雙重酯化丙二醇之甲 基而於約1.4 ppm處有共振|且對於雙重酯化乙二酵而在 約4.7 ρρπ處有共振。由比較在1.4及4.7 ppm處之共振指 出由乙二酵所衍生單元對由丙二醇所衍生單元之莫耳比率 係約1.5: 1。此係指作為E/P比率。其13C-NMR(d--nMsm 数據亦與所需聚合物構造一致,而所顯示之共振處係分別 在:70.2 ppm (聚氧化乙烯部份)、16 ppm (經雙重酯化 丙二醇之CH3)、63.6 ppm (經雙重酯化乙二醇)、及在58 ppm處之一個極小尖峰(CH^OCH^O-)。由對於任何乙二酵單 酯(-ίΜίυοεΗζςϋ^ΟΗ)而在約60 ppm處或對於丙二酵之異 構物糸單酯(-C(0)0CH( CH3) CH2〇H)之其一·種而在約20 ppm 處皆不存在真正的共振指出此具高度聚合作用程度。 例T T T 乙二醇、對苯二甲梯二甲酯、聚(乙二甲糊(分孑a 7.5 00)、 聚(乙二酵)(分罕畺15 00)及 1.? -丙二醅夕帮 合物(会成1 將下表所列物質置於裝有磁攪拌器、加熱罩、内置溫度 計、蒸餾接頭、用於蒸餾之冷凝器装置、用於惰性氣體入 -17- (諳先閲讀背而之注意事嗲再填寫本頁) 裝_ *3r_ 本紙5艮尺度边用中8 Η家樣準(CNS) TM規格(210x297公*) 81. 4. ιο,υυο張(η) 200550 五、發明説明(16) 口、及THERM-0-WATCH(I2R)而用於溫度控制者等之5升大 小、3頸圓底燒瓶: 克數 莫耳數 來源 乙二酵 408 6.58 Fisher 對苯二甲酸二甲酯 1024 5.28 Aldrich 聚(乙二酵)甲醚(分子量750) 480 0.64 Aldrich 聚(乙二醇)(分子量1500) 2400 1.60 Aldrich 1,2-丙二醇 510 6.71 Ma 11 inkrodt 水合氧化單丁基錫(FASCAT 4100) 3 M8,T Chein 水基化羥基甲笨(BHT) 3 Calbiochem 經濟部中央標準局只工消"合作社印製 將糸統攪拌而於將溫度逐漸升高從175T:至195Ό歷超過 36小時期間後,收集到290克蒸餾物(絕大部係甲醇)。 然後將溫度升高至2101C 歷18小時而於此時收集到更多蒸 豳物。然後將透明玻璃入口管***至接近燒瓶底部並且將 惰性氣體K高速通過而將溫度維持在200C 。持績此種狀 況歷約4天而收集到少量額外蒸豳物。容許將所得聚合物 冷卻而得約3800克軟質固體,若以1〇%固體湄度進行試驗 而以攪拌過夜方式,則在室溫彼約65%可溶於水中。(在 較低固體含量之溶液中,則顯然可見頗高之溶解部份)。 由1-^1?((^-0>^0)顯示用於聚氧化乙烯部份而在約3.45 ppm處具有極密集共振、對於對笨二甲酸酯而在約8.〇5 -18- 81. 4. Ιϋ,ουο張(if) (請先閱^背而之迮意事"#项寫本頁) 本紙張尺度遑W中國國家樣準(CNS) Ή規格(210X297公釐) 200550 五、發明説明(17) (請先間讀背而之注意事項戽蜞寫本頁) PPm處具有複式共振、對於雙重酯化丙二酵之甲基則在約 1.4 ppm處有共振•且對於雙重醏化乙二酵則在約4.7 ppb處有共振。由比較在1.4及4.7 ppm處之共振指出由 乙二酵所衍生單元對由丙二酵所衍生單元之莫耳比率係約 2.6: 1。將此稱為E/P比率。由13C-NMR(d«-nMsm齡播浙 所要聚合物構造一致而顯示出下列共振:70.2 ppm (聚氬 化乙烯部份)、16 ppm (經雙重酯化丙二酵之CH,)、^ « PPm (繹雙重酯化之乙二酵)、及在58 ppm ( QiU〇CH2CH2〇-)有極细小尖峰。由於對於任何乙二酵( -C (0) OCH2 CJL2.O Η)之單酯而在約60 ppm處或對於一種丙二 醇之異構物糸單酯(_C(0)0CH( CLlaJ CH20H )而在約2 0 dd™ 皆不存在真正共振指出彼具高聚合作用度。 继品虚描昍成物 經濟部+央梂準局β工消件合作杜印鱿 可將根據本發明之sra's利用於各種不同環境中而於此 需要將污垢釋離精整傳输至織品中,詳细言之,在洗滌操 作中。例如,可將於此之sra’s直接加至自動清洗機器之 洗滌或潤濕浴中。或者於熨平操作期間,可將sra’s唄灑 至織品上。在其它模式中,在自動衣眼乾燥機中而於進行 洗滌乾煉操作期間,sra's會沉積在織品上。 在較佳模式中,於此之sra’s從含有織品软化劑(如在 技藝上廣為熟知之陽離子系織品钦化劑)之水浴中沉積在 纈品上。事實上,各種不同sra's可選自於此所掲示之這 些而與陽離子糸頗具相容性而即使“三重湄縮劑”液體織· -19- 81. 4. 10,(W0張(H) 各紙5fc尺度遏用中B國家樣準(CNS)T4規格(210X29?公*) 00550 Λ 6η 6 五、發明説明(18) (請先閱請背而之注意事項#堝寫本頁) 品软化劑產品已於最近流入市面也不會有害地增加粘度。 一般而言,具愈低分子量之sra's將產生具較低增加粘度 。因此,於此之較佳姐成物係皆能提供孅品钦化劑成份及 bra’s成份*且設計此K同時提供具有污垢釋雠調理之継 品软化(和抗靜電)益處。下列係欲協助調製員製造經結 合織品軟化劑/污垢釋離姐成物,但不欲藉Μ限制其範圍 〇 液體織品來化劑V 本發明之液體继品軟化劑姐成 、, 物包括前文所界定之有效數量的s「a’s 。所謂“有效數量 ”係依下列因素而定:所使用之特定sra’s 、特定形式之 嫌品軟化劑配方和所需效益。通常,若sra’s之含量係佔 姐成物之約0.01.重量至約10重量%,則彼係有效的。以污 垢釋離效益之項目而言•較佳的織品軟化劑姐成物包括約 0.1至約5重量%之sra’s ,但是典型包括約0.3至約3重 量%之這些化合物類。 經濟部中央標準扃员工消伢合作社印製 本發明之嫌品软化劑姐成物進一步包括約2至約50重量 % (以約3至約25重量%較佳)織品軟化劑成份。用於常 規強度(1倍)織品軟化劑姐成物方面,織品軟化劑成份 典型包括佔有姐成物之約3至約1 0重量%。用於經滬縮( 例如3倍)織品钦化劑姐成物方面,織品軟化劑成份典型 包括佔姐成物之約15至約25重量%。 織品軟化劑成份典型包括單-或雙(高級烷基)四級銨 鹽或此種鹽類之混合物。見1975年12月23日頒予Temple諸 -20- 81. 4. 10,000張(H) 本紙51尺度逍用中8 »家樣毕(CKS)甲4規格(210x297公*) 200550 A 6 Π 6 五、發明説明(19) - γ 位之美國專利3,928,213號,詳细言之,其第2檷第57行 至其第4檷第34行,和1983年8月16日頒予Burns之美國 專利4,399,045號,詳细言之,其第4檷第23行至第7檷 第2行(於此併於'本文供參考),此掲示合宜的四级銨鹽 類。於此四级銨鹽類上下文中所使用“高级烷基”係意指 烷基而具有8至30個碳原子,以12至22個碳原子較佳。此 類習知四级銨鹽之實例包括: 1 . 具有下式之單氮原子之四级銨鹽類: (請先閱讀背而之a意事項#堝寫本頁) 裝- 經濟部屮央楳準局员工消费合作社印奴 R. - N+ - R3 A' , 1 t R: 其中1^係脂肪族C12至C22烴基;R2係(^至“飽和榇某 或羥烷基。R2係選自Ri (較佳)或R2基且A係陰離子 四氯、溴或甲基硫酸根。 合宜單氮原子四级銨鹽之實例係氛化單動物脂基三甲 基銨(MTTMAC)、氯化雙動物脂基甲基銨(DTDMAC)、 甲基硫酸二動物脂基二甲基铵、氛化二(氫化動物脂 基)二甲基銨、氛化二(山裔基)二甲基銨、氯化二 (十六烷基)二甲基铵、氯化二(十八烷基)二甲基 銨、氯化二(二十烷基)二甲基銨、氯化二(二十二 烷基)二甲基銨、甲基硫酸二(氫化動物脂基)二甲 基銨、氯化二(十六烷基)二乙基銨、溴化二動物脂 訂_ 本紙張尺度逍用中®困家楛準(CNS)T4規格(210x297公龙) 8!. 4. 10,UUt)張(H) 200550 Λ 6 Π 6 經濟部屮央櫺準局貝工消"合作社印^ 五、發明説明(20) 基二丙基銨;氯化二(椰子烷基)二甲基銨;及其混 合物類。 2. 具下式之二醯胺四级銨鹽類: 0 R6 〇 R4 - C - NH - R3 - N+ - Rg - NH - C - R4 A- Rr 其中R4係脂肪族C12至C22烴基;R3及R5係各具有1至 3個碳原子之二價伸烷基;1?3係(:1至(^飽和烷某或羥 烷基;R7係Re或(CaH2e〇)bH部份,其中a係2或3且 b係1至約5 ;而A係陰離子。 合宜二醯胺四级銨鹽之例係甲基硫酸甲基雙(動物脂 醯胺乙基)(2 -羥乙基)铵、甲硫酸甲基雙(氫化 動物脂醯胺乙基)(2 -羥乙基)銨、及甲硫酸雙( 2-氫化動物脂醯胺乙基)乙氧化銨;這些物質係取 自Sherex化學公司而商品各分別為VARIS0FT 222、 VARIS0FT 220及 VARIS0FT 110 ; 3. 四鈒咪唑餅鹽如甲硫酸1 -甲基-1 -動物脂醯胺乙 基-2 -動物脂咪唑餅(MVARIS0FT 475之商品名稱 出售)、甲硫酸1-甲基-1-(氫化動物脂醯胺乙 基)-2 -動物脂基眯唑鉼(MVARIS0FT 445之商品 名稱出售)、1-伸乙基-雙(甲硫酸2 -動物脂-1 -甲基-咪唑餅)(以VAR IS0FT 61 12之商品名稱 -22- 冬紙5良尺度通用中S B家樣毕(〇^)干4規格(210x297公釐) 81. 4. 1(),000¾ (!|) (請先閲讀背而之注意事項Λ项寫本頁) 200550 Λ 6 Π 6 五、發明説明(21) 出售);且甲硫 動物脂醢胺乙基 VARIS0FT 3012 用於漘縮繊品软化 份包括:(A)約2至 0至約14重最%之二 量%之四级眯唑餅鹽 約15至約22.5重量% 國專利 4,399,045 1 織品軟化劑姐成物 系胺類,典型係作為 胺類具有下式: 酸1 -甲基-2 動物脂胺基)乙 之商品名稱出售 劑組成物方面, 約1 5重量%之單 醢胺四级銨鹽類 類;而A、B、 。見1 983年8月 ,將其内容-併於 亦^可包括某些特 與四鈒鞍鹽(類) -動物脂基-3 -「 基]眯哇餅(Μ )° 較佳的織品軟化劑成 氮四级銨邇類;(Β) ;(C)約2至約13重 及C之發類缌數量係 16日頒予Burins之美 本文併參考。定二(高级烷基)環 之混合物。這些環系 Z - Rf ? 先 閲 ή 背 而 之 -注 意 事 •項 本 Μ C I R« 經濟部中央標準局cx工消1-Ϊ-合作杜印¾ 其中c係2或3K2較佳;係單獨SCa$C3。烷基 、或烯羥基,以Cn至C22烷基較佳,K (:以至Cle怯甚审佯 ,或此種烷基之混合物類,如這些而得自椰子油,“軟質 ”(非硬化)動物脂,及硬化動物脂;CI係CH或n ,而Μ Ν較佳;Ζ係 23- 本紙張尺度逍用中a國家《準(CNS)T4規格(210X297公釐) 81. 4. 10,000張⑻ 五、發明説明()In the presence of BX Industrial Consumers, Central Bureau of Standards, Ministry of Economic Affairs ^ Cooperative Du Yin M softener, Sra typically deposits only on the suspects to a limited extent. Conversely, industrial finishing is usually done in highly controllable process equipment (such as dip dyeing machines). Typical suspects are clean, and the concentration of detergent or softener (if any) tends to be low. At least at this stage, the soil release treatment is intended to be used on fabric substrates. Due to the difference in washing and industrial finishing technology *, there are also significant differences between sister types (such as washing detergent, washing softener, washing bleach, etc.). This kind of washing and cleaning products and different types of M, such as granular, liquid, gel, paste-form, and products with desiccant are also prepared. The formulators in the washing technique have realized that different forms of washing sisters have inherent formula restrictions. For example, the solid ingredients required by the adult formula can generally be dispersed or dissolved in an aqueous cleaning bath. At the same time, the liquid ingredients together need the ingredients to be freely mixed without thorny chemical or physical interactions such as phase change or precipitation. In particular, the modern washing sisters are more and more popular in the form of "concentration". For example, the concentration of the intestinal ion softener component contained in the commercially available liquid fabric softener is 3 times higher than that of the fabric softener obtained so far. It is difficult to realize that the formulation of such a composition should have its own stable form and a reasonable particle size range. Of course, if you want to incorporate ingredients with additional functions (such as sra ’s) into this kind of finished product, it is more difficult to prepare and volatile performance. Therefore, continuous research on the effective, compatible, and easy-to-make sra ’s that are available for washing sisters ’products is continued. ___ _ " ----- -4- (please read the back-to-back ¾ 意 节 ¾ # 墦 筠 this page first) Binding and ordering paper 51c standard Chinese National Standard (CNS) T4 specification (210x297 ) 81. 4. lO.OUOfSL (| () 200550 A 6 Π 6 V. Description of the invention (3.) The present invention provides yuraf basket line sra's and is suitable for washing compositions ^. The present invention also avoids non- Chicks are sra · s and are especially used for the combination of cationic textile softener Ning. In addition, even if K softener "concentrate" is prepared, many of the sra · s are also excessively increased liquid S1 fabric softening _ The viscosity of the sister product. U.S. Patent No. 4,711,7 No. 30 issued to Gosselink and Diehl on December 8th, 2005, is related to the capped 1,2-propylene terephthalate-polyoxyethylene pair Phthalates are used in washing detergents and fabric softener products (including concentrates) and as a soil release agent. In this category, as described in Gossellnk and Diehl The reference documents include the following: L Ethylene p-Cage Dimethyl Ester / PRn Pyong Rong Second Examination Sg Cool Smudge Smoke Piece Polyester ( Read the back-to-back simple matters 4 and fill out this page) Printed by the Ministry of Economic Affairs, Pyongyang Bureau, Beigong Consumer Cooperative, September 4, 1978, No. 4, 116, δ 85 2 5% (Κ 0. 5% Diformate The amount of dirt is 5,000 to some specific agents into the detergent and the detergent and the detergent and detergent disclosed in the United States awarded to Derstadt on the 26th are best to 10%). A release polyester, such as MILEASET, is 200,000 (M 10, 000 to 50,000 in a step containing 5% to 95% (M 10% compatible alcohol sulfate and ethoxyalkyl sulfate 10% other incompatible The patent for Yin-Zhezizi contains 0.15% to ester / PEG-p-benzene with an average molecular weight). These are clear to 25%, the best) Detergent surface active surfactant, this paper scale is used in the national B standard (CNS) T4 regulation (210 father, 297 mm) 81.4.1 (), 〇〇〇 张 (ίί) Cooperated with the Central Standard of the Ministry of Economic Affairs ^ β 工 工 伢 Cooperated by Du Printed 200550 Λ fi ____ Π6_V. Invention Description (4) Such as linear alkane benzene sulfonate. US Patent No. 4,132,680 issued to Nicol on January 2, 1979 also discloses that the detergent and cleaning agent has dirt release properties , This contains 2% to 95% (M to 60% better) detergent surfactant and 0.15% to 25% (1% to 10% best) ethylene terephthalate / PEG p-benzene Dicarboxylic acid esters (with grate ratios of 65:35 to 80:20) have soil release polyesters with molecular weights of 10,000 to 50,000, such as "11 ^ / ^ £ 1 '. These sister products further include 〇5% 5% to 15% (preferably 0.1% to 5%) components and will produce 1 to 3 (: 8 to (: 24 alkyl quaternary ammonium) in aqueous solution陔 雔 子. These cations taught by Nicol are used to improve the deposition of dirt-releasing polyester on washed suspects. See its 11th line, lines 14 to 21 ° L. Polyester Μ 偻 潟 道 訟 多余 袢 was issued on May 15, 1981 to the Becker Canadian Patent No. 1, 100,262 disclosed in the fabric softener sister composition contains 1% to 80% (Μ 5% to 50% is better) fabric softener such as ammonium ditallow ammonium dicarboxylate with certain cholera fatty acid compounds ranging from 0.5% to 25% (Ml% to 10% is better). These softeners The product M contains 0.5% to 10%. (Preferably 1% to 5%) ethylene terephthalate / PEG terephthalate soil release polyester such as PERMAL0SE or ZELCON. July 1975 U.S. Patent No. 3,893,929, issued to Basadur on the 8th, discloses an acid-wet solution that increases wetting and contains a soil release agent made from the following substances: dimeric carboxylic acid (preferably terephthalic acid), one Polyalkylene -6 ** (Please read the precautions first to write this page) This paper is used for 8 to 8 years. The standard is called 〒4 specifications (210 > < 297 male dragon) 81. 4. ω, ϋϋΟ Zhang (Η) 200550 A 6 Π 6 V. Description of the invention (5) The Ministry of Economic Affairs, Central Bureau of Economy, Labor and Social Sciences, Co., Ltd. Printed 51. Two enzymes (M has a molecular weight of 1,300 PEG up to 1,800 is preferred) and alkylene glycol (glyoxygenation, malonylation or succinylation). The preferred soil release agent has a molecular weight of 3,000 to 5,000. These sister products may contain cationic textile softeners such as chlorinated ditallow dimethyl ammonium, but it is said to be unsatisfactory "because they tend to retard the deposition of dirt release agents in the polymer during acid extraction Ester follows the dimension. " See lines 54 to 59 on page 7. U.S. Patent No. 3,712,873 issued to Zenk on January 23, 1973 discloses a fabric treatment composition applied by spraying or dipping (pad dyeing), which includes 1% to 5% of the type of dirt release polymer shown in the Basadur patent ester. These sister products may additionally contain up to 4% of quaternary ammonium compounds with 1 Cie to C2 2 alkyl group. The combination of this quaternary ammonium compound and polyester has been shown to improve the soil release properties of the treated fabric. Zenk also shows that other quaternary ammonium compounds (such as ditallow dimethyl ammonium chloride) do not achieve the same superior efficacy. See pages 57 to 61 on page 3. L Polyester # Quietly added to the dry animals, the slack X, W, Fu, Shou, Yu, Yu, Xie, Xi, U.S. Patent No. 4,238,531 issued to Rudy on December 9, 1980, it was revealed that the added dry product contains "dispensing agent" Such as polyethylene glycol and adjuvant applied to fabrics can be used as soil release agent. The released dirt release agents include polyacrylic acid resin, polyvinyl alcohol and PERMALOSE TG polyester (see Example 8). L Use polyester in sickle products or deer skein roll liquid, curing and curing to transport dirt and rubbish and Cheng Hangjing Lei Huanxiyi-(please read first, please go back and back to the wayi 亊 item #fill this page ) 装 装-定-This paper standard is used in the 8 S home standard (CN5) T4 specification (2 丨 0x297 public Λ) 81. 4. ΙΟ, υυϋίί. (H) 200550 Λ (5η 6 Ministry of Economic Affairs Biyang Bureau Printed by the β Industry Consumer Cooperative 51 51. Description of the invention (6) The low-molecular-weight dioxin / polyoxanediase terephthalate polyesters disclosed in US Patent No. 3,512,920 issued to Dunlop on May 9, 1970 It is used in resin treatment baths containing starch or cellulose derivatives, and after heat curing, it is used to transfer the dirt release properties to cotton / polyester fabrics. It can be used to make these alkylene glycols Contains glyphosate, 1,2-propanediol, 1,3-propanediol, butanediol and their mixtures. The polyalkylene glycols that can be used include PEG, polybutanediol and their mixtures. The average molecular weight is 200 to 20,000 (M 1,000 to 5,000 is preferred). The polyester antistatic in US Patent No. 3,416,952 issued to Me Intyre on December 7, 968 The reagent contains 1 water-soluble polymer such as polyoxyalkylene and has an average molecular weight of 300 to 6,000. The preferred polyoxyalkylene is PEG'S and has an average molecular weight of 1,000 to 4,000. It is treated to Apply an aqueous powder of polyester in the presence of an antioxidant, and then heat to a temperature exceeding 90 = to obtain a durable polybrown coating on the treated object. Example 6 reveals the formation of this type of polyester. Dimethyl phthalate, ethylene fermentation and 0-methyl poly (ethylene oxide) fermentation with an average molecular weight of 350 are used for the catalytic reaction. Use this polyester in a 20% solution of benzyl fermentation M to transmit antistatic The properties are similar to polyester sickles. Example 7 discloses the use of a polyester-like 20% aqueous solution to apply antistatic properties to polyester fabrics. U.S. Patent No. 4,427,557 issued to Stockburger on January 24, 1984 was formed Low-molecular-weight copolyester (2,000 to 10,000) and ethylene glycol, a PEG (having an average molecular weight of 200 to 1,000), and an aromatic dicarboxylic acid (such as p-dibenzic acid dimethyl-8-this A B home for paper size Ning (CNS) specifications (2 丨 0X297 male dragon) ~~ 81. 4. 10,000¾ (11) (please pay attention to the considerations Λ fill in this page) Install · 200550 Λ 6 Π 6 V. Description of invention ( 7) Ester) and sulfonated aromatic dicarboxylic acid (such as dimethyl 5-sulfoisophthalate). It can be partially substituted with PEG and K PEG monoalkyl ether such as methyl, ethyl and Butyl ether. The dispersant or solution of the copolyester is applied to the fabric, and then it is heated at an elevated temperature (90 scoops to 150 C) to cure the soil release properties of the M transfer soil. See also the patents of Me Intyre, where Example 2 discloses the use of random arrangement of copolyester K to transmit antistatic properties to form them to convert para-dicarboxylic acid, dimethyl isophthalate sulfonate, and ethylenedioxide Yeast and PEG with an average molecular suspension of 1,5 40. In addition, there are several disclosures in polyester technology, more specifically, their low molecular weight oligomers, which can be used as sra's in washing products. It was disclosed earlier that it is a polyimide-type substance modified by Nai, and it does not need to be a recruiter and the contained part does not have a specific terminal cover. They are polyether fragments derived from glyphosate. See, for example, U.S. Patent No. 3,962,152 issued to Nicol on June 8, 1976, U.S. Patent No. 4,116,885 issued to Derstadt on September 7, 1978, and Becker issued on May 5, 1981 You Canadian Patent No. 1,100,262, U.S. Patent No. 4,238,531 issued to Rudy on December 9, 1980, and U.S. Patent Application No. 2,1 72,608 published by Crossin on September 24, 1986. The CX Industrial and Consumer Cooperative of the Ministry of Economic Affairs of the Ministry of Economic Affairs recently printed the sra's category for the development of detergent and detergent applications. It contains certain terminal-coated oligomers, such as the following awarded to Gosse link in the United States. Patent disclosure: See, for example, U.S. Patent No. 4,702,857 (issued October 27, 1987). U.S. Patent No. 4,721,580 (January 26, 1988) and U.S. Patent 4,877,896 -9-81.4.1 (), 000 to Malc ^ onads, Trink and Gonsslink on October 31, 1989 (please read the back Please note the code and write this page) The specifications of the HB family sample guide (CNS) in the paper standard R1 (210x2 Machiko) 200550 Λ 6 Π 6 V. Description of the invention (8) No. 0 The present invention covers dirt release agents and includes an oligomer esterification product of a reaction mixture, which includes: U) arbitrarily (but preferably) one (^ to "alkane Oxygen-terminated (M methoxy terminator is preferred) polyethoxy units [^-(OCi ^ CHdx-O-source or optionally with a small number of propoxy units with terminated polyethoxy units Mixture; (b) — source of terephthaloyl units, optionally, a mixture of terephthaloyl units and a small amount of m-xylylene units; (c) a poly (ethylene oxide) oxy group The source of the unit [ie _ (0CH2CH2) y-0-]; (d)-the source of the oxyisopropenyloxy unit contains CH3 and -0CHCH20-; (e)-the type of ethylene oxide Oxygen is the source of -〇CH2CH2〇-; the dirt release agent has a further feature of having a molar ratio of oxidized ethoxylated units to oxidized isopropenyloxy units of at least about 0.5: 1. Therefore, here The dirt release agent includes, for example, an ester reaction product of a reaction mixture including: (a) CH3 (0CH2CH2) 1Θ0Η; -10-This paper scale is used in China Η Jia 楳 quasi (CNS) A 4 specifications (210X297 male dragon) 81. 4. l (), 〇U〇 Zhang (H) (please read the back-up notes first and fill in this page) 200550 5. Description of the invention (9) (b) dimethyl terephthalate; (c) Polyethylene glycol 1 500 (E34); (d) 1,2-propanediol; and (e) ethylene glycol; wherein the molar ratio of oxyethyleneoxy units · oxypropyleneoxy units is at least about 0. 5: 1, M is preferably at least about 1.2 5: 1. Such soil release agent differs from sra's (disclosed in Gosselink and Diehl U.S. Patent No. 4,711,730 above) in that they contain oxide ethyleneoxy units. The sra's of the present invention unexpectedly have the better performance of the '730 patent. Although it is not intended to add the K limit, it is tested by theory or structure. .Xianxin's preferred s "a's special form of the invention is the formula:-_0, 0 11 / \ | 1 Ri〇- (CH2CH20) x cY ^ / V-CO-CH-CH ^-R2 _ m ο ο / 1 / = Λ »C-^ > -C-0 (CHzCH ^ Jx-R1 —0 0 C- < ^ > -C0 (CH2CHz0) y η Ministry of Economic Affairs Standards and Employee Consumers ’Cooperative Printing 51 (please read the back-to-back issues " 塥 write this page) where R1 is low-level (for example (^ to (: 4) Alkyl, in particular, methyl; and R2 is a mixture of H and CH3 (ie, both ethylene and isopropylene are present in the molecular structure), M provides oxyethyleneoxy: oxyisopropylene The molar ratio of oxy groups is at least about 0.5: 1 and M is preferably at least about 1.2 5: 1. In the formulae drawn, X, y, m and η are integers and are in the following ranges -11 -The size of the paper is used in the Ha Ha home sample standard (CNS) T4 specification (210x297 male dragon) 8 丨 .4. 丨 0,000 sheets (H) 200550 Λ 6 Β6 V. Description of the invention (10) The wide range is the best Best range X 6 to 100 6 to 43 12 to 30 y 6 to 100 12 to 77 12 to 50 m 0.75 to 30 1.5 to 25 2.25 to 20 η 0.25 to 20 0.5 to 15 0.75 to 12 m + n + l々n + l 1 to 5 1.2 to 4.5 1-5 to 4 (please read the information first, please note it. Note this page again) The Bureau of Standards, Ministry of Economic Affairs, only the consumer cooperation Du Yinyu These projects are pointed out to be inserted in the MPEG unit Average neighbor Connect the number of terephthalate units. It can be seen that the ratio of oxyethyleneoxy: oxypropyleneoxy units can be changed to meet the needs of the modulator. H and Li plaque_drink .. 'North..agent_the. —Uses, squares .. noodles—, this ratio is preferably at least about 0.7 5: 1, and ¥ at least about 1.2 5; 1 is more f. For the ϋ Li Jie. Li Jin m, if At such a ratio, some products may become childlike, so the blender may choose a slightly lower ratio, for example, _0.5: 1 ... The invention also covers washing compositions such as detergents, Softeners, wetting ribs, etc., include at least about 0.1% by weight (preferably from about 0.2% to about 10% by weight) of the aforementioned s "a's. Preferred fabric softeners here typically include about 0.3 Weight% up to «-12- This paper is used in the 5k-scale side-to-side model (CNS) A4 specifications (2〗 0x297 g;« :) 81. 4. Ιϋ, ΟϋΟ ^ (11) 200550 Λ 6 ___ V. DESCRIPTION OF THE INVENTION (11) About 3% by weight of 2sra and about 3% by weight to about 25% by weight of fabric softener ingredients. A dilute liquid fabric softener sister product concentrate includes: (a) about 10% by weight to about 32% % By weight cationic fabric softener; (b) about 4% by weight to about 20% by weight imidazole cake fabric softener; and (c) about 1% by weight to about 5% by weight 2sra. Typical detergent and detergent products here include conventional detergent surfactants, any builder, any carrier, and 5 "3 from about 0.1% to about 10% by weight. Preferred detergents are Including about 0.3% by weight to about 3% by weight of the soil release agent and at least about 3% by weight (M is about 3% by weight to about 20% by weight) fatty acid polyhydroxyamide surfactant, in detail , C12 to C1S fatty acid N-methyl glucosamine. Printed by the Ministry of Central Standards Bureau KX Industry and Consumers ’Cooperation Co., Ltd." The present invention also covers a method to provide a dirt release finishing for suspected products. With an aqueous medium [containing at least about 2 ppm (2 parts per million) of the aforementioned sr * a 's]. In a preferred horizontal mode, such a method includes Μ followers and a water bath [including at least 3 ppm (W about 4ρριπ To about 25 ppm, preferably) the aforementioned sra's and at least about 10 ppm (preferably from about 30 ppm to about 10 ppm) of the cationic softener] come into contact and separate the fabric from the water bath for a period of at least about 1 Minutes (preferably from about 1 minute to about 10 minutes). (Satisfied Even with a low S "a's Medo can also effectively perform multiple cycle processing). Satisfied with the conventional automatic cleaning machine during the wetting cycle * This method can be easily performed. Here all percentages, The ratios and ratios are based on the weight of the M 'unless otherwise specified. -13- 81. 4. 10,000 sheets (H) (please read the back-up notes ^ Item " this page) This paper is 5 gram size and is used in a Ming Family Standard (CNS) «P4 specification (210x297 mm) 200550 Λ 6_η 6 V. Description of the invention (12) Printed by the Employee Consumer Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs ^ mm m The sra's and M ester of the present invention were prepared The substituted hydroxy- and carboxylate reactants disclosed above. The following examples further illustrate the preparation of sra's in accordance with the present invention, but do not limit the scope thereof. II. Poly (ethylene dioxonate) S7 5 0), p-cage dimethyl dimethyl ester, poly f 7, di quinone) (sub-hanshan 15 00), 7, synthesis of bis bis propyl propylene dimer polymer respectively add the following substances to the magnetic Stirring rod, modified C 1 aise η joint, condenser (for distillation unit), thermometer, and temperature (THERM-0-WATCH > I2R) in a 250 ml 3-neck round bottom flask: poly (ethylene glycol) methyl ether with a molecular weight of 750 (Aldrich, 50.0 g, 0.067 mol), paraben dicarboxylic acid Methyl ester (35.6 g, 0.183 mol), poly (ethylene glycol) with a molecular weight of 1500 (Aldrich, 50.0 g, 0.033 mol), ethylene glycol (Baker, 7.2 g, 0.116 mg), 1,2-propanediol (Fisher, 8,9 grams, 0.117 mole), monobutyltin hydrated gas (produced by M & T Chemicals, 0.30 grams, 0.2% knot! Reaction weight), and butylated hydroxytoluene (Calbiochem, 0.15 g, 0.1% reaction weight). This mixture was heated to 180 ° C and maintained at this temperature under argon overnight while distilling methanol and water from the reaction vessel. 13C-NMR (DMS〇-de) shows that there is residual resonance of reed for methyl ester at about 52 ppm. Raise the temperature to 200t: for 5 hours, then add additional glyphosate (7.2 g, 0.116 mole) and propylene glycol (8.9 g, 0.117 mg ear) -1 4-(Please read the notes beforehand (Fill in this page) This paper uses the Chinese National Standard (CNS) (210X297 male dragon) for free use of the paper. 81. 4 · 丨 0,0⑻ Zhang (H) 200550 Λ 6 η 6 V. Description of the invention (13). Reduce the temperature to 190C, and maintain it overnight under this condition. 13C-NMR (DMS〇-de) shows that the reaction at this stage has been completed without methyl ester resonance. This material was transferred to a 1 liter single-neck round bottom flask and heated gradually to 2 30 t in a Kugelrohr apparatus (Aldrich) under about 1.5 mm Hg for more than 20 minutes and maintained under this condition for 1 + Hour. Then, the flask was allowed to cool down to near room temperature (approximately 30 minutes) under a vacuum. Nitrogen yielded 124.1 grams of soft brown solid stern. (UMLHDMSO-de) shows extremely dense resonance at about 3.5 ppm for poly (ethylene oxide) fragments, about 8.0 ppm for parabens, and about 2.00 for methyl esters of double esterified malonase There is resonance at 1.4 ppm and there is resonance at about 4.7 ppm for double esterified ethylene glycol. The resonance of tb at 1.4 and 4.7 ppm indicates that the molar ratio of units derived from glyphosate to units derived from propylene glycol is about 2.2: 1. This is called the E / P ratio. Its 13C-NMR (DMS〇-de) is also consistent with the desired polymer structure and shows that these resonances are at 70.2 ppm (polyethylene oxide part). . 5 ppm (C Η 3 of double esterified propylene glycol), 6 3 .6 p P m (double esterified glyphosate), and 58_4ppra ((HO CH2CH2〇-). Because for the ethylene glycol (-C (0 ) OCHaCH ^ OH) any single compound at about 60 ppm or for the propylene glycol (_C (0) 0CH (CH3) CH2OH) isomer is one of the methyl ester and there is no resonance at about 20 ppm It is pointed out that this has a high degree of polymerization. It is possible to obtain oligomers with a low E / P ratio and to use the same synthesis conditions in addition to reducing the initial ratio of glyphosate to malonylase. It is about 0.25: 1 and the final E / P ratio is about 〇.5. -15- 51 papers are widely used in a B home dazzle kite (CHS) A 4 specifications (2 father 0 father 297 male dragon) 81. 4. 10,000¾ (||) 200550 Λ 6 ΙΪ6 V. Description of the invention (14) m τ τ 7ι Two brews, p-dimethyme dimethicone 8¾, poly (ethylene glycol) Tianyu (ϋ g 750), poly (Ethyl yeast) ( The amount is 15 00) and 1.2-propanediazide F / P = 1.M polymer (Xihuicheng) Place the substances listed in the table below with a magnetic stirrer, heating hood, built-in thermometer, steamed joint, A 5-liter large, cooler device for distillation, for the inert gas tank, and THERM-0-WATCH (I2R) for temperature control, etc., j, 3 neck round bottom flask: (Please read in advance (Besides pay attention to the Bian item on this page.) The Central Bureau of Economics of the Ministry of Economic Affairs only works with the consumer to cooperate with Du Yinweig. The number of moles is derived from oxalase 130.2 2.1. — — MCB dimethyl terephthalate 640.2 3.3 Aldrich poly (Glyoxal) methyl ether (molecular weight 750) 300 0.4 United Carbonization Corporation poly (ethylene glycol) (molecular weight 1500) 1500 1.0 United Carbonization Corporation 1,2-propanediol 322 4.2 Fisher's hydrated monobutyltin oxide (FASCAT 4100) 5.5 M & T Chem company's water-based hydroxymethyl stupid (BHT) 3.2 Calbiochem company stirred this system and its temperature gradually increased to 185t: and maintained under this condition for 28 hours while there is formazan steamed from the reactant. Then Insert the transparent glass inlet tube close to the bottom of the bottle The inert gas is introduced at a high speed and the -16- 81. 4. ΙΟ, ΟΟΟΙ (Η) This paper size is used in the BB home sample standard (CNS) Ή specification (210x297 public *) 200550 V. Invention description (15) Printed by the β-Consumer Evaluation Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs to raise the temperature to 24010. It took about 13 hours to push this situation. The resulting polymer was allowed to cool to obtain about 2400 grams of soft solids. If K was tested at 10% solids and M was stirred overnight, most of it was soluble in water at room temperature. 1H-NMR (de-DMS0) showed a very dense resonance at about 3.45 ΡΡίπ for the polyethylene oxide moiety, a complex or resonance at about 8.05 ppm for parabens, and for double esterification The methyl group of propylene glycol has resonance at about 1.4 ppm | and has resonance at about 4.7 ρρπ for double esterification of glyphosate. Comparing the resonances at 1.4 and 4.7 ppm indicates that the molar ratio of units derived from glyphosate to units derived from propylene glycol is about 1.5: 1. This refers to the E / P ratio. The 13C-NMR (d--nMsm data is also consistent with the desired polymer structure, and the resonances shown are: 70.2 ppm (polyoxyethylene part), 16 ppm (CH3 after double esterification of propylene glycol ), 63.6 ppm (by double esterification of ethylene glycol), and a very small peak at 58 ppm (CH ^ OCH ^ O-). From about 60% for any oxalase monoester (-ίΜίυοεΗζςϋ ^ ΟΗ) There is no real resonance at about 20 ppm at the ppm or for one of the isomers of malonate (-C (0) 0CH (CH3) CH2〇H). This indicates a high degree of polymerization Extent of action. Examples TTT Ethylene glycol, dimethyl terephthalate, poly (glyoxal paste (p aa 7.5 00), poly (glyoxal) (p. 15 00) and 1.?- Methylenedioxiride complex (will be 1) Place the substances listed in the table below in a magnetic stirrer, heating hood, built-in thermometer, distillation joint, condenser device for distillation, for inert gas inlet-17- (Be sure to read the precautions first and then fill out this page) Install _ * 3r_ This paper is in 5 gram size and is used in the middle. 8 Η home sample standard (CNS) TM specifications (210x297 public *) 81. 4. ιο, υυο Zhang ( η) 20055 0 V. Description of the invention (16) Port, and THERM-0-WATCH (I2R) 5L size, 3-neck round bottom flask for temperature controllers etc .: Gram Molar number Source Glycogen 408 6.58 Fisher Dimethyl phthalate 1024 5.28 Aldrich poly (ethylene glycol) methyl ether (molecular weight 750) 480 0.64 Aldrich poly (ethylene glycol) (molecular weight 1500) 2400 1.60 Aldrich 1,2-propanediol 510 6.71 Ma 11 inkrodt hydrated oxidation mono Butyl tin (FASCAT 4100) 3 M8, T Chein Water-based hydroxymethyl stupid (BHT) 3 Calbiochem Central Bureau of Standards of the Ministry of Economic Affairs only "Consumer Printed by Cooperative Society" Stirs the system and gradually raises the temperature from 175T: to 195Ό After a period of more than 36 hours, 290 grams of distillate (mostly methanol) was collected. Then the temperature was raised to 2101C for 18 hours and more distillate was collected at this time. Then a transparent glass inlet tube was inserted Close to the bottom of the flask and passing the inert gas K at a high speed to maintain the temperature at 200 C. A small amount of additional steam was collected for about 4 days in this condition. Allowing the resulting polymer to cool to about 3800 grams of soft solids, If 1 % Solids was tested and stirred overnight, about 65% of them were soluble in water at room temperature. (In the lower solids solution, a relatively high dissolved part is clearly visible). It is shown by 1- ^ 1? ((^ -0> ^ 0) for the polyethylene oxide part with extremely dense resonance at about 3.45 ppm, and about 8.〇5 -18 for parabens -81. 4. Ιϋ, ουο Zhang (if) (please read ^ Backwards "# items to write this page) This paper size is not included in China National Standards (CNS) Ή specification (210X297mm) 200550 V. Description of the invention (17) (please read the notes on the back and write this page first) There is a double resonance at PPm, and about 1.4 ppm for the methyl ester of the double esterified malonase For the dual oxalase, there is resonance at about 4.7 ppb. Comparing the resonances at 1.4 and 4.7 ppm indicates that the molar ratio of units derived from oxalase to units derived from malonylase is approximately 2.6: 1. This is referred to as the E / P ratio. The 13C-NMR (d «-nMsm age sow the desired polymer structure is consistent and shows the following resonance: 70.2 ppm (polyargonated ethylene part), 16 ppm (after double Esterified malonase CH,), ^ «PPm (extracted double esterification of oxalase), and a very small peak at 58 ppm (QiU〇CH2CH2〇-). Since for any oxalase (-C ( 0) OCH2 CJL2.O Η) monoester at about 60 ppm or for a propylene glycol isomer 糸 monoester (_C (0) 0CH (CLlaJ CH20H) and at about 2 0 dd ™ there is no real resonance indicating that it has high polymerization Following the imaginary description of the Ministry of Economic Affairs and the Central Bureau of Industry and Commerce β-consumer cooperation Du Yinju can use the sra's according to the present invention in a variety of different environments where it is necessary to transfer the dirt release finishing to In the fabric, in detail, in the washing operation. For example, the sra's can be added directly to the washing or wetting bath of the automatic cleaning machine. Or during the ironing operation, the sra's can be sprinkled on the fabric In other modes, sra's will be deposited on the fabric during the washing and drying operation in the automatic eye dryer. In the preferred mode, the sra's will never contain fabric softener (as It is a well-known cationic fabric agent) deposited in the water bath in the water. In fact, a variety of different sra's can be selected from those shown here and is quite compatible with the cationic Shitou even if "triple shrinking agent" Liquid weave · -19- 81. 4. 10, (W0 Zhang (H) The 5fc scale of each paper is used in the national B standard (CNS) T4 specifications (210X29? Public *) 00550 Λ 6η 6 V. Description of the invention (18) (please read the back and forth precautions #pot write this page) product softening The product that has recently flowed into the market will not deleteriously increase the viscosity. Generally speaking, sra's with lower molecular weight will produce lower viscosity increase. Therefore, all of the better sister systems here can provide the ingredients of brazilian agent and bra ’s * and this K is designed to provide softening (and antistatic) benefits with dirt release conditioning. The following is intended to assist the modulator to manufacture the combined fabric softener / soil release agent, but does not intend to limit its scope by M. Liquid fabrics are used as agents V. The liquid secondary softener agent of the present invention, the objects include the foregoing The defined effective amount of s "a's. The so-called" effective amount "depends on the following factors: the specific sra's used, the specific form of the suspected softener formula and the required benefit. Generally, if the sra's content is accounted for by the sister From about 0.01% to about 10% by weight of the finished product, they are effective. In terms of soil release benefits, the preferred fabric softener sister products include about 0.1 to about 5% by weight of sra's, but Typically, these compounds include about 0.3 to about 3% by weight of these compounds. The Ministry of Economic Affairs, Central Standards, Employee Consumer Cooperatives of the invention printed the suspected softener of the present invention, further comprising about 2 to about 50% by weight (from about 3 to about 25% by weight is preferred) fabric softener component. Used in conventional strength (1 times) fabric softener composition, fabric softener composition typically includes about 3 to about 10% by weight of the fabric composition. Shanghai shrink For example, 3 times) fabric softener composition, the fabric softener composition typically includes about 15 to about 25% by weight of the fabric composition. The fabric softener composition typically includes mono- or bis (higher alkyl) quaternary ammonium Salt or a mixture of such salts. See December 20, 1975, issued to Temple -20-81. 4. 10,000 sheets (H) of this paper on 51 scales for easy use 8 »Home Samples (CKS) A 4 specifications ( 210x297 public *) 200550 A 6 Π 6 V. Description of the invention (19)-U.S. Patent No. 3,928,213 at position γ, in detail, its second line from line 57 to its fourth line from line 34, and August 1983 U.S. Patent No. 4,399,045 issued to Burns on May 16th, in detail, its fourth line from the 23rd line to the second line from the 7th line (herein and in this article for reference), which shows the appropriate quaternary ammonium salt "Higher alkyl" used in the context of quaternary ammonium salts means alkyl having 8 to 30 carbon atoms, preferably 12 to 22 carbon atoms. Such conventional quaternary ammonium salts Examples include: 1. Quaternary ammonium salts of the single nitrogen atom with the following formula: (please read the back-to-hand a meaning matter #pot to write this page) equipment-consumption by employees of the Bureau of Economics and Trade of the Ministry of Economic Affairs Cooperative Innu R.-N +-R3 A ', 1 t R: where 1 ^ is an aliphatic C12 to C22 hydrocarbon group; R2 is (^ to "saturated or a hydroxyalkyl group. R2 is selected from Ri (preferred) Or R2 group and A is an anion tetrachloro, bromine or methyl sulfate. Examples of suitable single nitrogen atom quaternary ammonium salts are atmospheric monotallow trimethyl ammonium (MTTMAC), ditallow tallow methyl chloride Ammonium (DTDMAC), ditallow methyl dimethyl sulfate, dimethyl ammonium bis (hydrogenated tallow) dimethyl ammonium, bis (ammonium based) dimethyl ammonium, di (16) Alkyl) dimethyl ammonium, bis (octadecyl) dimethyl ammonium chloride, bis (eicosyl) dimethyl ammonium chloride, bis (docosyl) dimethyl ammonium chloride , Di (hydrogenated tallow) dimethyl ammonium, di (hexadecyl) diethylammonium chloride, ditallow bromide _ This paper standard is used in Chinese ® Sleepy Family Shade Standard (CNS ) T4 specifications (210x297 male dragons) 8 !. 4. 10, UUt) Zhang (H) 200550 Λ 6 Π 6 Ministry of Economic Affairs, Ministry of Economic Affairs, Ministry of Economic Affairs, Beigong Consumer Co., Ltd. Printed by the cooperative ^ V. Description of the invention (20) Base 2 Propyl ammonium; bis (coconut alkyl) chloride Methyl chloride; and mixtures thereof class. 2. Quaternary ammonium salts of diamides with the following formula: 0 R6 〇R4-C-NH-R3-N +-Rg-NH-C-R4 A-Rr where R4 is an aliphatic C12 to C22 hydrocarbon group; R3 and R5 is a divalent alkylene group each having 1 to 3 carbon atoms; 1 to 3 series (: 1 to (^ saturated alkane or hydroxyalkyl; R7 is Re or (CaH2e〇) bH part, where a is 2 or 3 and b is from 1 to about 5; and A is an anion. An example of a suitable quaternary ammonium salt of diamide is methyl bis (tallowamide ethyl) (2-hydroxyethyl) ammonium methyl sulfate, Methyl bis (hydrogenated tallowamide ethyl) ammonium (2-hydroxyethyl) ammonium and bis (2-hydrogenated tallowamide ethyl) ammonium ethoxide; these substances were taken from Sherex Chemical Company The commodities are VARIS0FT 222, VARIS0FT 220 and VARIS0FT 110 respectively; 3. Tetraimidazole cake salt such as methyl 1-methyl-1 -tallowamide ethyl ethyl 2-tallowimidazole cake (trade name of MVARIS0FT 475 Sale), 1-methyl-1- (hydrogenated tallowamide ethyl ethyl) methylsulfate-2 -tallow fatty oxazolidine (sold under the trade name of MVARIS0FT 445), 1-ethylidene-bis (methylsulfate 2 -Tallow-1 -methyl-imidazole ) (With the trade name of VAR IS0FT 61 12-22- winter paper 5 good standard universal SB home sample (〇 ^) dry 4 specifications (210x297 mm) 81. 4. 1 (), 000¾ (! |) ( Please read the precautions and write this page first) 200550 Λ 6 Π 6 V. Description of the invention (21) Sale); and methionine tallow amine ethyl VARIS0FT 3012 is used to soften the softening products including: (A) About 2 to 0 to about 14% by weight of the second most amount of the fourth-grade zona azole salt about 15 to about 22.5% by weight National Patent 4,399,045 1 Fabric softener sister amines, typically as amines It has the following formula: acid 1-methyl-2 tallow amine group), the trade name of the sales agent composition of B, about 15% by weight of monoacetamide quaternary ammonium salts; and A, B,. See 1 In August 983, its content-and also included some special and four-saddle saddle salt (class)-animal fat base-3-"base] squint cake (Μ) ° The preferred fabric softener composition Nitrogen quaternary ammonium compounds; (B); (C) about 2 to about 13 weights and the number of hair types of C is awarded to Burins on the 16th of this article and reference. Ding two (higher alkyl) ring mixture. These Ring system Z-Rf ? Read first and then-Note: Items Μ C I R «Central Bureau of Standards of the Ministry of Economic Affairs cx 工 消 1-Ϊ-Cooperative Duin ¾ Where c is 2 or 3K2 is better; it is a separate SCa $ C3. Alkyl, or alkenyl hydroxy, preferably Cn to C22 alkyl, K (: even Cle timid, or a mixture of such alkyls, such as those obtained from coconut oil, "soft" (non-hardening) Animal fat, and hardened animal fat; CI is CH or n, and MN is better; Z is 23-the standard of this paper is used in a country "quasi (CNS) T4 specification (210X297 mm) 81. 4. 10,000 sheets ⑻ V. Description of invention ()
Ri〇-T-C- A 6 一B6 其中T係0或NR^,Ru係Η或 Cl至C4烷基,ΜΗ較佳; 且R1〇係二價“至“伸烷基或(C2H4〇)4基,其中d係數目 而為1至8,或冗係!?10 。 此種胺類之特殊例如下:1-動物脂醯胺乙基-2-動 物脂眯唑啉;1 - (2-C14-18 -烷基-醢胺乙基)-2 -Ci3-C17 -烷基。4,5-二氫咪唑;1-硬脂醣胺丙基 -2 -硬脂眯唑啉;及1 _動物脂醯胺丁基-2 -動物脂 六氫吡啶。 這些醢胺及彼等之製法在1985年3月28日由Koenig及 <^81^23〇8「1111提出申請之英國專利申請案8,508,130號 中有完整說明,於此併於本文供參考。(亦見美國專利 4,711,730 號,第 28櫊)。 可潠棰件的 1. 酸類及鹸類-若環系胺類係存在於織物炊化劑組份中 *則嫌物钦化劑姐成物之出對於適當分散胺類係重要 的。此.外,某些酸系出對於本發明污垢釋離化合物之 水解穩定性係較佳的。因而可將酸及/或醮加至姐成 物中之調整其出。酸或驗之用量偽於混合後•分散劑 之pH範圍係約2 . 5至約6 . 5 t 合宜酸類之實例包含無機礦物酸、羧酸,特定言之, 低分孑量((^至(:3)羧酸*及烷磺酸類。 {請先《讀背面之注意事項再瑱寫本頁) .¾. •打· •緣. 甲 4(210X 297公发) -21- 200550 Λ 6η 6 經洧部屮央櫺準届13:工消许合作杜印3i 五、發明説明(23) 低分子量((^至(:3)羧酸,及烷磺酸類。 合宜無機酸類包含HCl、H2S〇4、HN〇3及η3ρ〇4 。合宜 有機酸類包含甲酸、乙酸、甲磺酸及乙磺酸。較佳酸 類係氫氯酸、磷酸、甲酸及甲磺酸。 合宜鹼類包含NaOH及Ha2C〇3。 2. 有機溶劑-可調製本發明之織品软化劑姐成物而不必 使用任何有機溶劑。然而,存在有機溶劑(例如,具 低分子量而水可相混合之脂肪族醇類)無害於姐成物 之貯存穩定性、粘度、或軟化效能。此種溶劑之實例 包含乙酵及異丙醇。 典型得到四级銨鹽類(或環系胺)而K從B u 1 k化學公 司之供懕商而呈固體形式或作為在有機溶劑(例如異 丙醇)中之溶液。於製備姐成物並不需移除溶劑。事 實上,若真的需要,則可加人額外溶劑。 3. 任意的非離子系物-織品软化劑姐成物任意地含有如 已揭示供在软化劑姐成物中所使用之非離子糸物。此 種非離子系物及使用濃度在1984年6月12日頒予 MacGilp諸位之美國專利4,454,049號中已有揭示, 於此併於本文供參考。 於此適合用於織品軟化劑組成物之非離子系物之特別 包含甘油酯類(例如單硬脂酸甘油酯)、脂肪酵類( 例如硬脂酵)、及烷氧化脂肪醇類。若使用非離子系 物’則其典型用量範圍係佔姐成物之約0 . 5至約1 0重 量% ° ~ 2 5 - (請先ΜΙ1,?背而之-注悉亊項#填寫本頁) 裝· 線- 本紙5Jt尺度逍用中Η國家楳準(〇阳)肀4規格(210x297公龙) 81. 4. ΐο,ουο張(Η) 200550 Λ 6 Π 6 五、發明説明(24)Ri〇-TC-A 6-B6 where T is 0 or NR ^, Ru is Η or Cl to C4 alkyl, ΜΗ is preferred; and R1〇 is a divalent "to" alkyl or (C2H4〇) 4 group , Where d is the number from 1 to 8, or redundant! ? 10. Specific examples of such amines are as follows: 1-tallowamide ethyl-2-tallowoxazoline; 1- (2-C14-18-alkyl-acetaminoethyl) -2-Ci3-C17- alkyl. 4,5-dihydroimidazole; 1-stearylaminopropyl-2-stearic oxazoline; and 1_aniline fatty butylamine-2-butyl tallow hexahydropyridine. These amines and their preparation methods are fully described in British Patent Application No. 8,508,130 filed by Koenig and <^ 81 ^ 23〇8 "1111 on March 28, 1985, and are hereby incorporated by reference. (See also U.S. Patent No. 4,711,730, No. 28). 1. Acids and chrysanthemums that can be removed-if the ring system amines are present in the fabric cooking agent component *, the suspected agent is a chemical It is important to properly disperse amines. In addition, some acids are better for the hydrolytic stability of the soil release compound of the present invention. Therefore, acids and / or alcohols can be added to sister compounds Adjust the amount. The amount of acid or test is false after mixing. • The pH range of the dispersant is about 2.5 to about 6.5 t. Examples of suitable acids include inorganic mineral acids and carboxylic acids, in particular, low scores. Amount ((^ to (: 3) Carboxylic acid * and alkane sulfonic acid. {Please first read the precautions on the back and then write this page). ¾. • Hitting • • Edge. A 4 (210X 297 public)- 21- 200550 Λ 6η 6 approved by the central government of the Ministry of Industry and Commerce 13: Industry and Consumer Cooperation Du Yin 3i V. Description of the invention (23) Low molecular weight ((^ to (: 3) carboxylic acid, and alkane sulfonate Suitable inorganic acids include HCl, H2S〇4, HN〇3 and η3ρ〇4. Suitable organic acids include formic acid, acetic acid, methanesulfonic acid and ethanesulfonic acid. Preferred acids are hydrochloric acid, phosphoric acid, formic acid and methanesulfonic acid Acid. Convenient bases include NaOH and Ha2C〇3. 2. Organic solvent-The fabric softener composition of the present invention can be prepared without using any organic solvent. However, organic solvents exist (for example, with a low molecular weight and water-soluble phase) Mixed aliphatic alcohols) are not detrimental to the storage stability, viscosity, or softening performance of the adult products. Examples of such solvents include ethyl yeast and isopropyl alcohol. Typically, quaternary ammonium salts (or cyclic amines) are obtained. K is supplied in a solid form or as a solution in an organic solvent (such as isopropanol) from a supplier of B u 1 k Chemical Company. It is not necessary to remove the solvent in order to prepare the finished product. In fact, if really needed , Additional solvent can be added. 3. Any non-ionic system-fabric softener product can optionally contain non-ionic materials as disclosed for use in softener products. Such non-ionic system The substance and the use concentration were on June 12, 1984 U.S. Patent No. 4,454,049 issued to MacGilp has been disclosed herein and is hereby incorporated by reference. Non-ionics suitable for use in fabric softener compositions in particular include glycerides (eg glyceryl monostearate) Esters), lipases (e.g. stearase), and alkoxylated fatty alcohols. If non-ionics are used, the typical dosage range is about 0.5 to about 10% by weight ° ~ 2 5-(please start with ΙΙ1 ,? 背 而 之-注解 亊 项 #Fill in this page) 装 · 线-This paper 5Jt scale is easy to use in the Chinese National Standard (〇 阳) Yuan 4 specifications (210x297 male dragon) 81. 4. Zhang (Η) 200550 Λ 6 Π 6 V. Description of the invention (24)
經濟部屮央楛準局A工消许合作杜印M 雖然一般認定非離子糸物具有缅品軟化性質,而為了 計算嫌品软化劑成份在姐成物中之數量起見,故不認 為此係嫌品軟化劑成份之部份。 4r 任意的矽成份-嫌品軟化姐成物任意含有主要為線性 聚二烷基或烷基芳基矽氧烷之水性乳化劑,其中烷基 可具有1至5個碳原子而可將此全部或部份氟化。合 宜矽類係聚二甲基矽氧烷類而在25Ϊ:具有粒度範圍係 約100至約100,000厘泊,而以在約1,000至約 12,000厘伯之範圍較佳。 如在结合物中所使用矽飼之離子價特徴對於測定下列 性食方面係重要的:矽沉積程度及分佈均匀性和從此 所處理織品之性質。 具有陽離子条特微之矽類顯示出具加強沉積之傾向。 發現矽類之價值在於提供嫌品柔適感之益處而此具有 主要為線性特徴且以聚二烷基矽氧烷類較佳,其中烷 基Μ甲基最為普遍。在商業方面經常製造出此種矽聚 合賴而Μ使用強酸或強鹼觸媒而在非離子糸或混合的 非雕子糸一陰離子糸轧化劑***之存在下進行乳化 聚合作用。 任意的矽成份亦包括具陽離子特徵之矽而經界定為下 列之其一種:(a)主要係線性聚二(^至(^烷基-或匕 -烷基、芳基、聚矽氧烷,製得彼等而从使用陽雔子 系表面活性劑作為乳化劑進行乳化聚合作用;(b) α -W -二四級化二CiMCs或(^至“垸基、芳基矽氧烷 -26- (請先閲讀背而之>:t意事項Λ填艿本頁) 裝- 訂_ 線. 本紙張尺度边用中《明家«準(CNS) <P4規格(2丨0X297公*) 81. 4. 10,000¾ (I!) 200550 經濟部中央梂準局貝工消#合作社印則4 Λ 6 __Π_6_____ 五、發明説明(25) 聚合物;或(c)胺基官能基二(^至“烷基)或烷基 芳基矽氧烷聚合物,其中可將胺基加Μ取代且四鈒化 而其中取代程度(d.s.)之範圔係0.001至0.2,而Μ 0.01至0.073較佳;但是矽在251C之粘度為約1〇〇至 約100,000厘泊。 於此之織品軟化组成物可含有至高達約10% (約0.1知 至約5%較佳)的矽成份。 5. 其它任意成份-為了進一步改良於此嫌品軟化劑姐成 物之穗定性,且進一步調整彼等之粘度,這些姐成物 可含有相對少量之電解質(例如,0.1%至3%),如 NaCl,KC 1 、LiCl、MgCU 或 CaCl2° 織品軟化劑姐成物亦可任意含有已知適合用於嫌物軟 化劑中之其它成份。此類佐劑包含香料、防腐劑、殺 生物劑、色料、染料、殺徽菌劑、穩定劑、亮光劑及 不透明劑類。若使用這些佐劑,則常規將彼等以習知 濃度(大約0.1%至5%)加入。然而,在組成物中’ 所利用成份係為了 (增加)織品處理效應(例如利用 香料)*則將這些物質加入而以比常規澴度(相當於 產物之湄度)為高。 本發明液體缃品軟化劑姐成物之其餘物質係水。 下列說明前述型式之液體組成物。 -27- 本紙尺度遑用中BB家«準(CNS)f 4規格(210X297公*) 81. 4. 1(),000張(II) 200550 Λ 6 Π 6 五、發明説明(26) 例TV 製得Μ織品软化劑為基之姐成物而Μ從下列成份: 份 軍 t % 氛 化 二 動物 脂 基二甲基銨 4 .33 甲 硫 酸 卜甲 基 -1-動物脂醯胺乙基-2- 動 物 脂咪 唑 m (VARIS0FT 475) 1 .0 乙 醇 0 .7 異 丙 醇 0 .1 香 料 0 .42 染 料 0 .1 少 量 物 »<» 至高達 0 .1 水 餘 額 *指防腐劑、HaCl、NaOH、H2S〇4抗氧化劑溶液。 分別將例I及II中,重量% Ssra’s加至此和基底姐成 物中以提供織品软化/sra姐成物IVA及I VB。 (請先閲誚背而之注意事項/f填寫本頁) 裝· 訂 線.The Ministry of Economic Affairs, Ministry of Economic Affairs, Bureau of Engineering, A, Consumer, Cooperation, Du Yin, M. Although it is generally recognized that non-ionic materials have the softening properties of Burmese products, in order to calculate the amount of suspected softener components in the sister product, it is not considered this It is part of the suspected softener ingredients. 4r Any silicon component-the suspected softener is free of water-based emulsifiers containing mainly linear polydialkyl or alkylaryl siloxanes, where the alkyl group can have 1 to 5 carbon atoms and all Or partially fluorinated. It is suitable that the silicon-based polydimethylsiloxanes have a particle size in the range of about 100 to about 100,000 centipoise, and preferably in the range of about 1,000 to about 12,000 centipoise. The ion valence of the silicon feed as used in the combination is important for the determination of the following sexual foods: the degree of silicon deposition and the uniformity of distribution and the nature of the fabrics treated from then on. Silicones with ultra-fine cation strips show a tendency to enhance deposition. It is found that the value of silicon is to provide the benefit of softness of the suspected product. This has mainly linear characteristics and polydialkylsiloxanes are preferred, among which alkyl M groups are the most common. In the commercial aspect, such silicon polymerization is often produced, and M uses a strong acid or a strong base catalyst to emulsify and polymerize in the presence of a non-ionic or mixed non-carved and anionic milling agent system. Any silicon component also includes silicon with cationic characteristics and is defined as one of the following: (a) Mainly linear poly (^ to (^ alkyl- or d-alkyl, aryl, polysiloxane, They are prepared from emulsification polymerization using cationized surfactants as emulsifiers; (b) α-W-two or four quaternary CiMCs or (^ to "alkyl, arylsiloxane-26 -(Please read the back-to-back >: t notice Λ fill in this page) Binding-Order _ Line. This paper is used in the "Mingjia" standard (CNS) < P4 specification (2 丨 0X297 公 *) ) 81. 4. 10,000¾ (I!) 200550 Central Ministry of Economic Affairs Bei Gong Xiao # Cooperative seal 4 Λ 6 __Π_6 _____ V. Description of the invention (25) Polymer; or (c) Amino functional group di (^ To "alkyl" or alkylaryl siloxane polymers, in which the amine group can be substituted with M and tetramethylated and the degree of substitution (ds) ranges from 0.001 to 0.2, and M 0.01 to 0.073 is preferred ; But the viscosity of silicon at 251C is about 100 to about 100,000 centipoises. The fabric softening composition here may contain up to about 10% (about 0.1 to about 5% is preferred) of silicon components. 5. Other Ren Ingredients-In order to further improve the characterization of the spikes of the suspected softener sister products and further adjust their viscosity, these sister products may contain relatively small amounts of electrolytes (eg, 0.1% to 3%), such as NaCl, KC 1. LiCl, MgCU or CaCl2 ° Fabric softener can also contain any other ingredients known to be suitable for use as an analyte softener. Such adjuvants include fragrances, preservatives, biocides, colors, dyes , Antimicrobial agents, stabilizers, brighteners and opaque agents. If these adjuvants are used, they are usually added at a conventional concentration (approximately 0.1% to 5%). However, in the composition ' For the purpose of (increasing) the fabric treatment effect (for example, the use of fragrances) *, these substances are added to a higher degree than the conventional degree (equivalent to the majestic degree of the product). The remaining substances of the liquid softener of the present invention It is water. The following describes the liquid composition of the aforementioned type. -27- This paper uses standard BB standard (CNS) f 4 specifications (210X297 g *) 81. 4. 1 (), 000 sheets (II) 200550 Λ 6 Π 6 V. Description of the invention (26) Examples of TV made woven The softener is the base compound and M is composed of the following components: Serving t% Adiated Ditallowyl Dimethyl Ammonium 4.33 Methyl Sulfate Methyl Sulfate 1-Tallowyl Acetyl Ethyl Ethyl 2-Tallowyl Fatty Imidazole m (VARIS0FT 475) 1.0 Ethanol 0.7 Isopropyl alcohol 0.1 Fragrance 0.42 Dyes 0.1 Small amount »<» Up to 0.1 Water balance * Refers to preservatives, HaCl, NaOH, H2S〇4 Antioxidant solution. In Examples I and II, respectively,% by weight of Ssra's was added to this and the base compound to provide fabric softening / sra compound IVA and IVB. (Please read the precautions / f fill in this page first) Binding and threading.
經濟部屮央楳準局员工消费合作社印M 本紙尺度逍用中S »家樣準(CHS)肀4規格(210x297公龙) 8i. 4. 10,000¾ (||) Λ 6 Π 6 200550 五、發明説明(27) 例 V - V Τ Τ Τ 製得具常規強度及濃縮嫌品软化劑為基之姐成物而Μ從 下列成份: (請先閲讀背而之注意本項"碣寫本頁) 經濟部屮央梂準局β工消#合作社印31 *指CaCU 、染料、殺菌劑 分別將例I及例III之0.5重量%的3「3’5加至常規強度基 底姐成物V及VII中。而分別將例I及例II之具1.5重量% 之sra、加至經濃縮為基之姐成物VI及VIII中。 -29- ^_ia_ 車 * % V VI VII VIII 氯化二動物脂基二甲基銨 3.65 7.7 2.33 7.0 1-動物脂醮胺乙基-2- 動物脂咪唑拼 3.65 14.3 4 .33 3. 0 氯化動物脂基三甲基銨 0.5 0.5 — — 聚二甲基矽氧烷 (粘度為旳00厘泊) 0.2 0.6 1.33 4.0 香料 0.25 0.45 0.25 0.45 少量物* 0.13 0.13 0.13 0.13 HC 1 ---加 至fH 4 — — 水 ---η 額 — — 本紙5fc尺度边用中a國家標毕(CNS>甲4規格(210><297公;»:) 200550 Λ 6 Π 6 五、發明説明(28) 例1·Χ 製得一種經湄縮缃品软化劑為基之姐成物而以從下列成 份: m_fiL 雷昼% 氛化二氫化動物脂基二甲基銨 13 甲硫酸 1-甲基-1-動物脂醯胺乙基- 2- 動物脂咪唑餅 3 極性亮藍色染料 80 ppm CaC 1 2 0.265 香料 0.75 乙酵 0.92 異丙酵 1.36 水 餘額 分別將例I、II及III中具1.5重量% isra’s加至此種經 湄縮為基之姐成物Μ提供經濃縮軟化劑姐成物加上sra’s 之 IXA 、 IXB及 IXC 。 (請先間讀背而之注意事項再填寫本頁) 經濟部中央櫺準而A工消伢合作社印31 本Λ5艮尺度边用中國B家樣準(CNS) T4規格(210x297公;4) 81. 4. ΐυ,ουϋ張(π) 200550 A 6 η 6 五、發明説明(29) 例y 種較佳的軟化劑姐成物如下 昜软6R方之番畺% 經濟部屮央榀準局KX工消许合作社印製 侑葙合 DTDMAC _ 4.00 MTTMAC 0.67 VARIS0FT 475^ 2.00 水關座(Water Seat·) 純水 餘額 Si1icone DC-1520(抗起泡劑) 0.02 H C1 * * 0.35 Lytrο η 621 (染料) 0.75 S R A ϋ ϊ: * 2.25 加成後 KATHON(防腐劑) 0.04 聚(二甲基矽氧烷)***::= 0.20 香料 0.30 =:= 眯唑鉼織品軟化劑 ** 足以使最終產物之pH在3至3.5 。 依例I之方式製得;E/D比率1.5。 55%聚二甲J 矽氧烷(350 cps)乳化劑(在水中)。 將預混合物與水閥座(Water Seat)摻合,然後與加成後 之混合物相结合。 -31 - 冬紙張疋度遑用中B珲家標準(CNS)T4規格(210x297公;¢) (請先閲讀背而之&意事嘌#填寫本頁) 200550 Λ 6 Π 6 五、發明説明(30) 例X Τ 使用在例X中所說明成份,製得一種3倍濃縮之織品軟 化劑如卞。 m_ί2_ 預泯合物 DTDMAC VARIS0FT 475 水關座(Water Seat) 純水 Silicone DC-1520 WC\t ϋ Lytron 621(染料) SRA (E/P 1.5/每例 II) 加成後 KATHON 聚(二甲基矽氧烷) 香料 昜紡SF方夕重量% 14.67 6.00 餘額0.020.35 0.75 1.50 0.04 0.541.05 (請先閲請背而之泾意事嘈再项寫本頁} 裝· 訂_ 線_ 經濟部中央桴準局CX工消#合作杜印51 *足Μ使最終產物之出在3至3.5 -32- 本紙尺度逸用中Η B家煤华(CNS) 規格(210x297公龙) 8i. 4. 10,000¾ (If) Λ 6 Β6 200550 五、發明説明(31) (請先閱讀背而之-意亊項•再項"本頁) mmm m a 本發明之sra’s亦有用於某些特定洗滌清潔萷姐成物中 Μ提供污垢釋離性質。可使用這些姐成物作為洗滌清潔劑 、洗滌添加劑,及洗滌預處理劑。 本發明洗滌清潔劑姐成物包括污垢釋離成份而含有前文 所界定有效數量之sra’s 。所謂“有效數量”係依下列因 素而定所使用特定s r· a ’ s 、特定型式之清潔劑配方(液體 、粒劑等)及所要求益處。通常若s「a’s在姐成物中之含 量係佔約至約1〇雪量%,則彼係有效的。在污垢釋離 益處項目中,較佳的洗滌清潔劑姐成物可包括約0 . 1至約! 5重量%2sra’s ,但是典型包括約0.3至約3重量%之 〜·'--- 這些化合物類。 經濟部中央標準扃CX工消费合作社印製 用於_ γ清潔劑配方方面· sra成份典型包括sra化合 物加上任何保護性包衣物質。在製成粒狀清潔劑配方中, 可將sra曝S於高鐮性物質如NaOH及Κ0Η中。可將s「a’s (特定言之,具有較短骨幹之這些)降解而以鹼性環境, 詳细言之,出超過約8.5之這些。因此,較佳方式係將 sra’s包衣在一種物質中以保護彼等以避免粒狀清潔劑配 方之鹼性環境而仍允許將s「a’s分散於洗滌操作中。 合宜包衣物質包含非離子糸表面活性劑、聚乙二酵 (PEG)、脂肪酸、二酵及多元醇之脂肪酸酯類、陰離子糸 表面活性劑、膜形成聚合物及這些物質之混合物類。合宜 非離子糸表面活性劑包衣物質之例包含某些於後文所說明 之這些亦作為在姐成物中有用的清潔劑表面活性劑。合宜 -33- 各虼尺度逍用中国B家樣準(CNS) 規格(210x297公龙) 81. 4. ιυ,υυο張(II) 200550 Λ 6 Π 6 經#部屮央櫺準局CO:工消合作社印31 五、發明説明(32) PEG包衣物質之例係這些而具有平均分子量為約2,000至 15,000,以約3,000至約10,000較佳且Μ約4,000至約 8,000最佳。合宜脂肪酸包衣物筲之例係具有12至1δ個碳 原子之高鈒脂肪酸。合宜脂肪酸酯包衣物質之例包含山梨 糖苷脂肪酸酯(例如山梨糖苷單月桂酸酯)。合宜包衣物 質之其它例包含陰離子系表面活性劑及膜形成聚合物類, 此於1984年12月4日頒予Murphy諸位之美國專利 4,486,327號中有揭示,於此併於本文供參考。可將 sra's而根據在Murphy諸位專利中所揭示之方法包衣之。 用於液體清潔劑配方中,sra成份可包含由sra’s所姐 成或進一步包含水溶性有機溶劑或水溶助長劑以協助溶解 sra’s 。合宜有機溶劑係普通之芳香族而可包含苯甲酸乙 酯、苯氧基乙醇、鄰-甲基苯甲酸甲酯、2 -甲氧基苄酵 及四氫吡咯_。合宜水溶肋長物包含甲基加蓋PEG’S及較 短骨幹聚酯類。這些短骨幹聚酯類更能溶於水且因此其功 能係作為用於具較長骨幹而較少水不溶sra’s之水溶助長 劑。 用以製得含本發明sra's之液體清潔劑配方之有機溶劑 或水溶肋長劑之用量(或更羼所需用量)依下列因素而定 :所使用sra's 、詳细言之其部份係可溶於水、在洗滌清 潔劑糸统中所存在成份、及是否所需為各向同性之均匀液 體。用於各向同性液雅清潔劑配方中,為了儘可能將 sra’s溶解而有些時侯要求使用有機溶劑或水溶肋長劑。 而且咸信將sra’s溶於液體清潔劑配方中,使彼等更有效 -34- (請先閲讀背而之泾意事項#填筠本頁) 裝· 本紙張尺度边用中國Η家樣準(CNS)T4規格(210X297公;《:) 81. 4. 10,000». (II) Λ 6 Π 6 2〇〇55〇 五、發明説明(33) (請先閲讀背而之注意枣項*#碭寫本頁) 作為污垢釋離劑而Μ有利於溶於洗液中且因而吸附在標的 嫌品上。 本發明之洗滌姐成物以包括約5至約75重量%不具干援 性而羼非離子系清潔表面活性劑較佳。非雛子糸清潔表面 活性劑Κ佔有姐成物之約10至約40重量%更佳,而Κ約15 至約30重量%最佳。 一般而言,供本發明洗滌組成物中所使用之合宜非離子 \ 糸表面活性劑在1975年12月30日頒予LaughlU諸位之美國 —’一·· 一 專利3,929,678號之第13櫊第14行至第16檷第6行中有揭 示(於此併於本文供參考)。非離子糸表面活性劑所包含 類別係: 1. 烷基酚類之聚氧化乙烯縮合物。此種型式化合物之例 包括以壬基酚與每莫耳壬基酚約9.5莫耳環氧乙烷縮 合;十二烷基酚與每奠耳酚約12箅耳環氧乙烷縮合。 所取得此類物質如IGEPAL C0-630 (由GAF公司上市) 及 Triton X-45、 X-114、 X-100和 X-102 (全部由 Rohm & Haas公司上市)。 經沭部屮央楳準扃貝工消费合作社印製 2. 脂肪族酵類與約1至約25莫耳環氧乙烷之縮合產物。 脂肪族酵之烷基鏈可為直鏈或具側鏈、一鈒或二级, 而一般含有約8至約22個碳原子。此種乙氧化酵之例 包含十四烷酵與(每莫耳酵約10莫耳)環氧乙烷縮合 之縮合產物,且約9奠耳環氧乙烷與椰子酵(一種脂 肪酵之混合物,所具烷基鍵係可變的而畏度為從10至 14個碳原子)。市售此種型式之非離子糸表面活性劑 本紙張尺度遑用中as家«準(CNS)T4規格(210x297公釐) 81 moot)張(II) 200550 Λ 6η 6 經濟部屮央榀準局貝工消费合作杜印31 五、發明説明(34) 之例包含TERGITOL 15-S-9 (由聯合碳化公司上市) ' NE0D0L 45-9 、 NE0D0L 23-6.5 、 NE0D0L 45-7 ' 及NE0D0L 45-4 (由殻牌化學公司上市)和KYR0 Ε0Β (由P r 〇 c t e r & G a η b丨e公司上市)。 3. 由環氧乙烷與疏水系鹼所形成縮合產物而以將環氧丙 烷與丙二酵縮合。此種型式化合物之例包含某些特定 市售PLUR0NIC表面活性劑(由Wyandotte化學公司上 市)。 4. 由環氣乙烷與(瑁氧丙烷和乙二胺反應所得)產物之 縮合產物。此種非離子糸表面活性劑型式之實例包含 某些特定市售TETR0NIC化合物類(由Wyandotte化學 公司上市)。 5. 半極性非難子糸清潔劑表面活性劑包含水溶性氧化胺 類而含有1個具約10至18個碳原子之烷基部份及2個 部份而選自含有1至約3個碳原子之烷基及羥垸基所 姐成群姐;水溶性氧化磷而含有1個烷基部份(具約 10至18個碳原子)如2涸部份而選自含有約1至3個 碳原子之烷基及羥烷基所組成群姐;且水溶性磺氧化 物類而含有1個烷基部份(具有約10至18個碳原子) 及1個部份而選自具有約1至3個碳原子之烷基和羥 烷基所姐成群姐。較佳的氧化胺清潔劑表面活性劑係 氧化C10至C18烷基二甲基胺及氧化C8至C12烷氧基乙 基二羥乙基胺。 6. 烷基多釀類(1983年1月19日為Ramon A. Llenado刊 _ 3 6 - (請先閲讀背而之法意事項#Λδ寫本頁) 裝· 訂 線· 本紙ft尺度逡用中ΒΒ家標準(CNS)T4規格(210X297公 81. 4. 10,000¾ (I!) A 6 Π6 2〇055〇 五、發明説明(35) 出之歐洲專利申請案70, 074號中所揭示)係具有疏水 系基而含有約6至約30個碳原子(K約1〇至約16個碳 原子較佳)且一種多_,例如多葡萄糖苷,為親土糸 基而含有約1.5至約10 (M約1.5至約3較佳,以約 1.6至約2.6最佳)之醣單元。 7. 脂肪酸醢胺清潔劑表面活性劑(見美國專利 4,711,730號,第17櫊第35行,係用以說明此種表面 活性劑)。 8. 脂肪酸多羥基醯胺表面活性劑;見1960年12月20日頒 佈之美國專利2,965,576號;亦即大英國協專利 809 , 060 號。 供在本發明洗滌姐成物中所使用之較佳的非離子糸清潔 劑表面活性劑係乙氧化酵及烷基酚類,詳细言之,C12至 (:1Λ酵與每奠耳酵約3至約7莫耳環氧乙烷之縮合產物, 例如C12至C13酵與(每莫耳酵約6.5莫耳)環氧乙烷縮合。 N-烷基葡萄糖胺-醣胺型式表面活性劑[如在美國專利 2,965,576 及英國專利 809,060(E.R. Wilson)中所說明] 構成於此所使用其它類之較佳的非離子糸表面活性劑。 本發明之洗滌姐成物亦可包括0至約12重量% (M0-至 約10重量%較佳)合成陰離子糸清潔劑表面活性劑。這些 合成陰離子糸清潔劑表面活性劑包含有機硫酸反應產物之 水溶性鹽(典型為«(金屬、銨及羥烷基铵鹽類)而在彼等 分子構造中所具烷基係含有約10至約20個碳原子及硫酸酯 基之磺酸。(在所含“烷基”名稱係指醯基之烷基部份h -37-Printed by the Employee Consumers Cooperative of the Ministry of Economic Affairs of the Central Committee of the Ministry of Economic Affairs. Printed on this paper. S »Home Sample Standard (CHS) 4 specifications (210x297 male dragon) 8i. 4. 10,000¾ (||) Λ 6 Π 6 200550 V. Description of the invention (27) Example V-V Τ Τ Τ prepared with a conventional strength and concentrated suspect softener-based sister compound and M from the following ingredients: (please read the back and pay attention to this item " 碣 写 本Page) The Ministry of Economic Affairs, Ministry of Economic Affairs β 工 消 # Cooperative Society Seal 31 * Refers to CaCU, dyes, and fungicides adding 0.5% by weight 3 "3'5 of Example I and Example III to the conventional strength base sister product V" And VII. The 1.5% by weight sra of Example I and Example II were added to the concentrated sister products VI and VIII. -29- ^ _ia_ Che *% V VI VII VIII dichloride Tallow dimethyl ammonium 3.65 7.7 2.33 7.0 1-tallow fatty amine ethyl-2- tallow imidazoline 3.65 14.3 4 .33 3. 0 tallow trimethyl ammonium chloride 0.5 0.5 — — polydimethyl Siloxane (viscosity is 00 centipoise) 0.2 0.6 1.33 4.0 Perfume 0.25 0.45 0.25 0.45 Small amount * 0.13 0.13 0.13 0.13 HC 1 --- Add to fH 4--Water --- η Amount-The 5fc scale of the paper is used in the national standard of China (CNS > A 4 specifications (210 > < 297 public; »:) 200550 Λ 6 Π 6 V. Description of the invention (28) Example 1. Mae shrinkage softener is based on the elder sister's finished product and is based on the following ingredients: m_fiL ray day% Ammonia dihydrogenated tallow dimethyl ammonium 13 Methyl sulfate 1-methyl-1-tallow fatty amide ethyl ethyl- 2- Tallow fat imidazole cake 3 Polar bright blue dye 80 ppm CaC 1 2 0.265 Perfume 0.75 Ethanase 0.92 Isozyme 1.36 Water balance Add 1.5% by weight isra's in Examples I, II and III to this type Ji Jicheng Cheng M provides IXA, IXB, and IXC with concentrated softener and sra's. (Please read the precautions before filling out this page) Central Ministry of Economic Affairs and A Gongxiao Cooperative Society Printed in 31 copies of the Λ5 Gen scale using the Chinese B home sample standard (CNS) T4 specification (210x297 g; 4) 81. 4. Ιυ, ουϋ Zhang (π) 200550 A 6 η 6 V. Description of the invention (29) Example y species The preferred softener products are as follows: 6R Fang Ruan %% of the Ministry of Economic Affairs, Ministry of Economic Affairs, Central Bureau of Accreditation, KX Engineering Consumer Cooperative Cooperative, Cooperative Printed DDTMAC _ 4.00 MTTMAC 0.67 VARIS0FT 475 ^ 2.00 Water Seat (Water Seat ·) Pure water balance Si1icone DC-1520 (anti-foaming agent) 0.02 H C1 * * 0.35 Lytrο η 621 (dye) 0.75 SRA ϋ ϊ: * 2.25 KATHON (after addition) Preservative) 0.04 Poly (dimethylsiloxane) *** :: = 0.20 Perfume 0.30 =: = anazoyl fabric softener ** enough to make the pH of the final product between 3 and 3.5. Prepared as in Example I; E / D ratio 1.5. 55% polydimethyl J silicone (350 cps) emulsifier (in water). The premix is blended with the water seat and then combined with the added mixture. -31-B4 Hengjia Standard (CNS) T4 specification (210x297 g; ¢) (please read the first one and fill in this page) 200550 Λ 6 Π 6 V. Invention Description (30) Example X Τ Using the ingredients described in Example X, a 3-fold concentrated fabric softener such as Bian was prepared. m_ί2_ Pre-compound DTDMAC VARIS0FT 475 Water Seat Pure Water Silicone DC-1520 WC \ ly Lytron 621 (dye) SRA (E / P 1.5 / each case II) KATHON poly (dimethyl) after addition Siloxane) Perfume weaving SF Fangxi weight% 14.67 6.00 Balance 0.023.35 0.75 1.50 0.04 0.541.05 (please read the back-to-back information and write this page again) Install · Order _ Line _ Ministry of Economic Affairs The central government quasi-bureau CX 工 消 # Cooperation Du Yin 51 * Fully make the final product in the range of 3 to 3.5 -32- the size of the paper is used in the H B home coal (CNS) specifications (210x297 male dragon) 8i. 4. 10,000¾ (If) Λ 6 Β6 200550 V. Description of the invention (31) (please read the back-to-back item-then item " this page) mmm ma The sra's of the present invention can also be used for certain washing and cleaning The M in the sister product provides dirt release properties. These sister products can be used as a cleaning detergent, a detergent additive, and a washing pretreatment agent. The detergent cleaner product of the present invention includes a dirt release component and contains the above-defined effective The number of sra's. The so-called "effective number" is determined by the following factors. The specific sr. A's, special The type of cleansing agent formula (liquid, granules, etc.) and the required benefits. Generally, if the content of s "a's in the sister product is from about 10% to about 10% of snow, then they are effective. In the benefit project, the preferred detergent detergent composition may include about 0.1 to about 5 wt% 2sra's, but typically includes about 0.3 to about 3 wt% of these compounds. Economy Printed by the Ministry of Central Standards CX Industrial Consumer Cooperative for _ γ detergent formulations · sra ingredients typically include sra compounds plus any protective coating substances. In the formulation of granular detergents, sra can be exposed to High sickle substances such as NaOH and Κ0Η. S "a's (specifically, those with shorter backbones) can be degraded to an alkaline environment, in particular, those exceeding about 8.5. Therefore, it is preferable The way is to coat sra's in a substance to protect them from the alkaline environment of the granular detergent formulation and still allow the s "a's to be dispersed in the washing operation. Convenient coating substances include non-ionic Shito surfactant, Polyethylene glycol (PEG), fatty acid, two enzyme Fatty acid esters of polyhydric alcohols, anionic Shito surfactants, film-forming polymers, and mixtures of these substances. Examples of suitable nonionic Shito surfactant coating materials include some of those described below and are also used as sisters Useful detergent surfactants in adult products. Heyi-33- Chinese standard (CNS) specifications (210x297 male dragons) for various scales of Xiaoxiao 81. 4. ιυ, υυο Zhang (II) 200550 Λ 6 Π 6 By # 部 屮 央 擂 准 局 CO: Printed by the Industrial and Commercial Cooperatives 31 V. Description of the invention (32) Examples of PEG coating materials are those with an average molecular weight of about 2,000 to 15,000, preferably about 3,000 to about 10,000 and M About 4,000 to about 8,000 is best. An example of a suitable fatty acid wrapper is a high-gold fatty acid having 12 to 1δ carbon atoms. Examples of suitable fatty acid ester coating materials include sorbitan fatty acid esters (e.g. sorbitan monolaurate). Other examples of suitable packaging materials include anionic surfactants and film forming polymers, which are disclosed in U.S. Patent No. 4,486,327 issued to Murphy on December 4, 1984, and are incorporated herein by reference. Sra's can be coated according to the methods disclosed in Murphy patents. For use in liquid detergent formulations, the sra ingredients may contain sra ’s or may further contain water-soluble organic solvents or hydrotropes to assist in dissolving sra ’s. Suitable organic solvents are ordinary aromatics and may include ethyl benzoate, phenoxyethanol, methyl o-methylbenzoate, 2-methoxybenzyl yeast and tetrahydropyrrole. Suitable water-soluble ribs include methyl-capped PEG'S and shorter backbone polyesters. These short backbone polyesters are more soluble in water and therefore their function as hydrotropes for sra's with longer backbones and less water insolubility. The amount of organic solvent or water-soluble rib-lengthening agent used to prepare the liquid detergent formulation containing sra's of the present invention (or the amount needed) is determined by the following factors: the sra's used, part of it in detail It is soluble in water, the components present in the cleaning detergent system, and whether it is required to be an isotropic homogeneous liquid. It is used in the formulation of isotropic liquid cleaners. In order to dissolve sra ’s as much as possible, sometimes it is required to use organic solvents or water-soluble rib-lengthening agents. And Xianxin dissolves sra's in the liquid detergent formula to make them more effective. -34- (please read the back-to-back 泾 意 事 #fill this page) CNS) T4 specification (210X297; ":) 81. 4. 10,000». (II) Λ 6 Π 6 2〇〇55〇 V. Description of the invention (33) (Please read the notes and notes * # 砀Write this page) As a dirt release agent, M is beneficial to dissolve in the washing solution and thus adsorbed on the target suspect. The detergent product of the present invention preferably contains from about 5 to about 75% by weight of non-drying non-ionic cleaning surfactant. It is more preferable that the non-Hina Shito cleansing surfactant K accounts for about 10 to about 40% by weight of the adult product, and about 15 to about 30% by weight of K. Generally speaking, suitable nonionic surfactants for use in the detergent composition of the present invention were issued to LaughterU in the United States on December 30, 1975-'A ·· Patent No. 3,929,678, No.13, No.14 It is revealed in the 6th row to 16th row (here and for reference). The nonionic Shito surfactants include the following categories: 1. Polyethylene oxide condensates of alkylphenols. Examples of compounds of this type include the condensation of nonylphenol with about 9.5 moles of ethylene oxide per mole of nonylphenol; the condensation of dodecylphenol with about 12 moles of ethylene oxide per mole of phenol. Such materials as IGEPAL C0-630 (listed by GAF) and Triton X-45, X-114, X-100 and X-102 (all listed by Rohm & Haas). Printed by Shubei Biyang Bizhunbeigong Consumer Cooperatives 2. Condensation products of aliphatic enzymes and about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic yeast may be linear or have side chains, one or two, and generally contains about 8 to about 22 carbon atoms. Examples of such ethoxygenases include the condensation product of tetradecane fermentation and (about 10 moles per mole) ethylene oxide condensation, and about 9 moles of ethylene oxide and coconut yeast (a mixture of lipases, The alkyl bond system is variable and the degree of fear is from 10 to 14 carbon atoms). Commercially available non-ionic surfactants of this type are used in the paper as standard (CNS) T4 specifications (210x297 mm) 81 moot) Zhang (II) 200550 Λ 6η 6 Ministry of Economic Affairs Beigong Consumer Cooperation Du Yin 31 5. Examples of inventions (34) include TERGITOL 15-S-9 (listed by United Carbonization Corporation) 'NE0D0L 45-9, NE0D0L 23-6.5, NE0D0L 45-7' and NE0D0L 45- 4 (listed by Shell Chemical Company) and KYR0 Ε0Β (listed by Pr Octer & Ga η b 丨 e). 3. The condensation product formed by ethylene oxide and hydrophobic alkali to condense propylene oxide and malonylase. Examples of compounds of this type include certain specific commercially available PLURONIC surfactants (listed by Wyandotte Chemical Company). 4. The condensation product of ring gas ethane and (product from the reaction of oxipropane and ethylenediamine). Examples of such non-ionic Shito surfactant types include certain specific commercially available TETRONIC compounds (listed by Wyandotte Chemical Company). 5. The semi-polar non-difficult Shito detergent surfactant contains water-soluble amine oxides and contains 1 alkyl portion with about 10 to 18 carbon atoms and 2 portions selected from 1 to about 3 carbons Atom alkyl and hydroxyalkyl groups are sisters; water-soluble phosphorous oxide contains 1 alkyl part (with about 10 to 18 carbon atoms) such as 2 parts and is selected to contain about 1 to 3 Carbon atoms are composed of alkyl and hydroxyalkyl groups; and the water-soluble sulfoxides contain 1 alkyl part (having about 10 to 18 carbon atoms) and 1 part selected from having about 1 The sisters of alkyl and hydroxyalkyl groups up to 3 carbon atoms are group sisters. Preferred amine oxide detergent surfactants are C10 to C18 alkyl dimethylamine oxides and C8 to C12 alkoxyethyl dihydroxyethylamine oxides. 6. Alkyl polybranches (January 19, 1983 by Ramon A. Llenado _ 3 6-(please read back to the law of the intention # Λδ to write this page) Binding · Threading · ft scale of this paper China BB Standard (CNS) T4 specification (210X297 male 81. 4. 10,000¾ (I!) A 6 Π6 20055055, invention description (35) European Patent Application No. 70, 074 disclosed in (35) The system has a hydrophobic group and contains about 6 to about 30 carbon atoms (K is about 10 to about 16 carbon atoms is preferred) and a poly-, such as polyglucoside, is a philosophyl group and contains about 1.5 to about 10 (M is preferably about 1.5 to about 3, preferably about 1.6 to about 2.6) sugar units. 7. Fatty acid amidoamine detergent surfactant (see U.S. Patent No. 4,711,730, 17th line 35, It is used to illustrate such surfactants.) 8. Fatty acid polyhydroxyamide surfactant; see US Patent No. 2,965,576 issued on December 20, 1960; that is, Great Britain Association Patent No. 809,060. For this document Invented the preferred non-ionic Shitou detergent surfactants used in the cleaning of adult products are ethoxylated enzymes and alkylphenols. In detail, C12 to (: 1Λ yeast and Condensation products of about 3 to about 7 moles of ethylene oxide per mole of yeast, for example, condensation of C12 to C13 yeast with (about 6.5 moles of moles of ethylene oxide). N-alkylglucosamine-glycosamine type Surfactants [as described in U.S. Patent 2,965,576 and U.K. Patent 809,060 (ER Wilson)] constitute other types of preferred non-ionic surfactants used herein. The cleaning products of the present invention may also include 0 Up to about 12% by weight (M0 to about 10% by weight is preferred) synthetic anionic Shitou detergent surfactants. These synthetic anionic Shitou detergent surfactants include water-soluble salts of organic sulfuric acid reaction products (typically «(metal, Ammonium and hydroxyalkyl ammonium salts) and the alkyl groups in their molecular structures contain sulfonic acids containing about 10 to about 20 carbon atoms and sulfate groups. (The name "alkyl" contained in this group refers to amides) The alkyl part of the base h -37-
本紙張尺度遑用中a S家搽準(CNS)T4規格(2丨0x297公D (請先閱誚背而之¾.意事^#磺寫本頁) 裝· 訂 經濟部屮央槛準局β工消饨合作社印製 81. 4. 10,〇U(]張(H) A 6 Π 6 五、發明説明(36 ) 此種合成陰離子糸表面活性劑之例係烷基硫酸納及鉀, 詳油言之,這些得自將高级酵(含(:8至(:18個碳原子)硫 酸化和烷基苯磺酸納及鉀,其中烷基含有約9至約15個碳 原子,呈直鍵或具側鐽構形,例如在美國專利第 2,220,099及2, 477,383號中所說明之這些型式。在造些 表面活性劑諸類中係包含直鍵烷苯磺酸鹽,其中在烷基中 碳原子之平均數目係約11至13’縮寫成為至C13 LAS 。 經Μ部中央櫺準局cx工消伢合作杜印" (請先間讀背而之注意事項-洱蜞寫本頁) 合成陰離子糸表面活性劑亦包含:(:1〇至(:22烷基聚乙氧 化硫酸鹽;烷基甘油醚磺酸納;α -磺化脂肪酸酯之水溶 性鹽類而在其脂肪酸基中含有約6至20個碳原子且在酯基 中含有約1至10個碳原子;2 -醢氧基-烷-1 -磺酸之 水溶性鹽類而在醯基中含有約2至9個碳原子且在烷部份 含有約9至約23個碳原子;烷基醚硫酸鹽而在烷基中含有 約10至20個碳原子且約1至30莫耳之環氧化物;烯烴磺酸 鹽之水溶性鹽而含有約12至24個碳原子;/3 -烷氧基烷磺 酸鹽而在烷基中含有約1至3個碳原子且在烷部份含有約 8至20個碳原子。 本發明之洗滌姐成物亦包含兩性系,兩性離子系及陽離 子系清潔劑表面活性劑以及鹸金羼肥皂。 可廣泛地將兩性糸表面活性劑說明為二级或三级胺類之 脂肪族衍生物,或雜環系二级或三级胺之脂肪族衍生物類 ,其中脂肪族基可為直鏈或具側鐽且其中一個脂肪族取代 -38* 本紙尺度遑用中Β圃家樣準(CNS) Τ4規格(210X297公龙) 81. 4. 1〇,〇ϋΟ張(H) 200550 Λ 6 Π 6 五、發明説明(37) 經沭部屮央標準局员工消费合作社印利4 基含有約8至18個碳原子而至少一棰含有一個陰離子系水 溶解基,例如羧基、磺'酸根、硫酸根。見1975年12月30日 頒予Laughli η諸位之美國專利3,929,678號第19檷第18至 35行(於此併於本文供參考)而用於兩性系表面活性劑之 例。 可廣泛地將兩性離子系表面活性劑說明為二鈒及三级胺 類之衍生物類,雜環系二级及三級胺類之衍生物、或四鈒 銨、四级辚或三级磺化合物之衍生物類。見1 975年12月30 日頒予Laughlin諸位之美國專利3,929,678號第19檷第38 行至第22檷第48行(於此併於本文供參考)用於兩性離子 系表面活性劑之例。 合宜陽離子表面活性劑在1981年3月31日頒予Mu「phy之 美國專利4, 259,217號中有揭示,於此併於本文供參考。 有用的鹼金靨肥皂包含高级脂肪酸之納、鉀、銨及羥烷 基銨鹽類而此含有約8至約24個碳原子,Μ約10至約20個 碳原子較佳。 本發明之洗滌清潔劑組成物可任意包括無機或有機清潔 劑助洗劑以協肋控制礦物質硬度。此類助洗劑典型包括佔 有姐成物之至高達約60重量% ;助洗式液態配方一般包括 約1重量%至約25重量%之清潔劑助洗劑,Μ約3重量% 至約20重量%最佳,同時肋洗粒劑配方一般包括約5重量 %至約50重量%清潔劑助洗劑,以約10重量%至約30重量 %較佳。 廣泛各類清潔劑助洗劑在文件中係已知,故不必於此將 -39- (請先間讀背而之洼意事項#填寫本頁) 本紙尺度遑用中a a家榀準(CNS) 規格(2丨0X297公#) 81. 4. IO.UUOS. (Η) 200550 Λ 6 η 6 五、發明説明(38) 經濟部屮央標準扃只工消费合作杜印5ί 此類物質再全部列出、調配員例如可參照美画専利第 4,71 1,730 (始於第19欄)用於典型列出此類物質。然而 ,為了便於調配員起見,而並不欲藉此加Μ限制,而將某 些說明性合宜的清潔劑肋洗劑列於後文中。 合宜的清潔劑肋洗劑包括晶形鋁矽酸鹽離子交換物質, 典型係指“沸石A ” , “沸石P ”及‘沸石X ” ,詳细言 之,沸石而具有粒子大小為約0.1至約10微米。用於助洗 劑用途之最適當沸石係具有鈣維子交換速率為至少約4粒 /加侖/分鐘/克/加侖。非晶形鋁矽酸鹽類(詳妞言之 ,這些具有鎂離子交換速率為至少約1粒/加侖/分鏟/ 克/加侖)亦為有用的。鋁矽酸蘧離子交換物霣之製法在 美國專利3,985,669號中有說明。尤佳者係具下式之水合 鋁矽酸鹽: Nai2[(Al〇2)i2(Si〇2)i2].xH2〇 其中X係約20至約30,詳细言之,28。 其它清潔劑助洗劑包含水溶性餘金靨(或銨)之磷酸鹽 、多磷酸鹽、亞磷酸鹽、碳酸鹽、矽酸馥、乙酸鹽、多羥 基磺酸鹽且詳细言之,多羧酸鹽。各類多羧酸鹽助洗劑在 美國専利 3,308,067; 3,732,322; 4,144,226;及 4,246,495號中有揭示。氧代二丁二酸翹(又稱“氧合二 丁 二酸鹽(oxo disuccinates)” ],酒石酸薄,單-及二 -丁二酸鹽、和檸檬酸鹽為有用於此之較佳的多羧酸鹽肋 洗劑之特例。 於此之洗滌清潔劑姐成物亦任意包含粘土污ig移除及/ -40- (請先閲誚背而之注意市項-#項寫本頁) 裝 -訂- 緣· 本蛛张尺度遑用中國8家樣毕(CNS)T4規怙(210x297公;¢) 81. 4. lO.OUOfi. (H) 200550 Λ 6 Β6 五、發明説明(39 ) 或抗再沉積劑,而普通此類物質之使用範圍係佔姐成物之 約0.1重量%至約10重量%。此類物質包含各類乙氧化胺 類等,參照上述美國專利第4,711,730號。其它類較佳的 粘土污垢移除/抗再沉橫劑係陽離子系化合物而在198 4年 6月27日刊出之歐洲專利申# 1 1 1,965號中有揭示。此 類物質在上述美國專利4,711,730號中亦有頗詳细揭示。 其它任意成份[可含於本發明洗滌清潔劑姐成物中而且 K彼等習知技藝所建立濃度供使用(即約0重量%至約20 重畺%)]包含溶劑、漯白劑、漂白活化劑、腐蝕抑制作劑 、染料、填料、光學亮光劑、殺菌劑、出調整劑、酶、梅 安定劑、香料等。在完整配製好清潔劑姐成物中所含之此 種住意成份係一種分開的物質而以根調記員之目的而定。 形成用以具體化本發明sra’s之粒狀清潔劑姐成物而K 將sra’s乾煉混合至(由習知技藝所形成之)姐成物中, 所謂習知技藝即將其它個別成份在水中拌漿、然後霧化且 噴乾所得混合物,或Μ淘盤或滾茼而將成份製粒,或以流 動床方法。The size of this paper is in accordance with the specifications of China S Home Standard (CNS) T4 (2 丨 0x297 Gong D (please read it first and back ¾. 意 事 ^ # sulfu to write this page) Printed by the Bureau β Gongxiao Cooperative 81. 4. 10, 〇U (] Zhang (H) A 6 Π 6 V. Description of the invention (36) Examples of such synthetic anionic surfactants are sodium alkyl sulfate and potassium sulfate , In detail, these are derived from high-grade leaven (containing (: 8 to (: 18 carbon atoms) sulfated and sodium alkylbenzenesulfonate and potassium, wherein the alkyl group contains about 9 to about 15 carbon atoms, It has a straight bond or a lateral configuration, such as those described in U.S. Patent Nos. 2,220,099 and 2,477,383. Among these surfactants, straight bond alkane benzene sulfonates are included, in which The average number of carbon atoms in the group is abbreviated to about 11 to 13 'to C13 LAS. Cooperated with the Central Bureau of Cement of the Ministry of Industry, cx, industrial and consumer cooperation Du Yin " (please read the notes beforehand-Er Leng's writing Page) Synthetic anionic Shito surfactant also contains: (: 10 to (: 22 alkyl polyethoxylated sulfate; alkyl glyceryl ether sulfonate; α-sulfonated fatty acid ester water-soluble salt The fatty acid group contains about 6 to 20 carbon atoms and the ester group contains about 1 to 10 carbon atoms; the water-soluble salts of 2-acetoxy-alkane-sulfonic acid are in the acyl group Rings containing about 2 to 9 carbon atoms and about 9 to about 23 carbon atoms in the alkane portion; alkyl ether sulfates containing about 10 to 20 carbon atoms in the alkyl group and about 1 to 30 mole rings Oxides; water-soluble salts of olefin sulfonates containing about 12 to 24 carbon atoms; / 3-alkoxy alkane sulfonates containing about 1 to 3 carbon atoms in the alkyl group and containing in the alkane portion About 8 to 20 carbon atoms. The cleaning product of the present invention also includes amphoteric, zwitterionic and cationic detergent surfactants and Ejin soap. The amphoteric surfactants can be widely described as secondary Or aliphatic derivatives of tertiary amines, or aliphatic derivatives of heterocyclic secondary or tertiary amines, where the aliphatic group may be linear or with a side chain and one of the aliphatic substitutions -38 * This paper The scale is used in the CNB family standard (CNS) Τ4 specification (210X297 male dragon) 81.4.10, 〇ϋΟ Zhang (H) 200550 Λ 6 Π 6 V. Invention (37) The Indian Consumer ’s Cooperative Society of the Bureau of Standards and Economics of the Ministry of Economic Affairs of India contains about 8 to 18 carbon atoms and at least one contains an anionic water-soluble group, such as carboxyl, sulfonate, and sulfate. See 1975 US Patent No. 3,929,678 issued to Laughli η on December 30, lines 18 to 35 (herein and incorporated herein by reference) for examples of amphoteric surfactants. Zwitterionic surfaces can be widely used The description of the active agent is the derivatives of the second amines and tertiary amines, the derivatives of the second and third amines of the heterocyclic system, or the derivatives of the quaternary ammonium, quaternary sulfonate or tertiary sulfonate. See U.S. Patent No. 3,929,678 issued December 30, 1975 to Laughlin, No. 19, line 38 to 22, line 48 (herein and incorporated herein by reference) for examples of zwitterionic surfactants. Convenient cationic surfactants are disclosed in U.S. Patent No. 4,259,217 issued to Mu "phy on March 31, 1981, and are hereby incorporated by reference. Useful alkali soaps include sodium, potassium, Ammonium and hydroxyalkyl ammonium salts and this contains about 8 to about 24 carbon atoms, preferably about 10 to about 20 carbon atoms. The detergent composition of the present invention may optionally include inorganic or organic detergent builder Agents help to control the hardness of minerals. This type of builder typically includes up to about 60% by weight of the finished product; the liquid builder formula generally includes about 1% to about 25% by weight of detergent builder , Μ about 3% by weight to about 20% by weight is the best, while the rib detergent granules generally include about 5% by weight to about 50% by weight detergent builder, preferably from about 10% by weight to about 30% by weight. A wide range of cleaning agents and builders are known in the document, so there is no need to -39- (please read the back and the intention of the first time # fill in this page) This paper is not used in the standard aa family standard (CNS ) Specification (2 丨 0X297 公 #) 81. 4. IO.UUOS. (Η) 200550 Λ 6 η 6 V. Description of invention (38) The Ministry of Economic Affairs, Ministry of Economic Affairs and Economics, Duin 5 5 such substances are listed in full. For example, the deployment staff can refer to Meihuali No. 4,71 1,730 (from column 19) for typical listing of such substances. However, for the convenience of the deployment staff, and do not intend to impose restrictions on M, certain illustrative and suitable detergent rib lotions are listed below. Suitable detergent rib lotions include crystalline aluminosilicate Ion exchange materials typically refer to "zeolite A", "zeolite P" and 'zeolite X ". In detail, zeolite has a particle size of about 0.1 to about 10 microns. The most suitable zeolite for builder applications has a calcium dimensional exchange rate of at least about 4 particles / gallon / minute / gram / gallon. Amorphous aluminosilicates (in particular, these have a magnesium ion exchange rate of at least about 1 grain / gallon / minute shovel / gram / gallon) are also useful. The preparation method of aluminosilicate ion exchangers is described in US Patent No. 3,985,669. Particularly preferred is a hydrated aluminosilicate having the following formula: Nai2 [(Al〇2) i2 (Si〇2) i2]. XH2〇 where X is about 20 to about 30, in detail, 28. Other detergent builders include water-soluble phosphates, polyphosphates, phosphites, carbonates, silicates, acetates, polyhydroxysulfonates and more. Carboxylate. Various types of polycarboxylate builders are disclosed in U.S. Patent Nos. 3,308,067; 3,732,322; 4,144,226; and 4,246,495. Oxydisuccinate (also known as "oxo disuccinates"), tartaric acid is thin, mono- and di-succinates, and citrates are better for this purpose Special case of polycarboxylate rib lotion. The cleaning detergents here also contain clay dirt ig removal and / -40- (please read the first item and note the item ## to write this page) Binding-binding-margin · The scale of this spider is based on 8 Chinese standards (CNS) T4 regulations (210x297 g; ¢) 81. 4. lO.OUOfi. (H) 200550 Λ 6 Β6 V. Description of invention (39 ) Or anti-redeposition agent, and the general range of use of such substances is about 0.1% to about 10% by weight of the adult products. Such substances include various ethoxylated amines, etc., refer to the above-mentioned US Patent No. 4,711,730 Other types of preferred clay soil removal / anti-re-settling agents are cationic compounds and are disclosed in European Patent Application # 1 1 1,965 published on June 27, 1984. Such substances are disclosed in the aforementioned US patents There are also quite detailed disclosures in No. 4,711,730. Other arbitrary ingredients [may be contained in the detergent and cleaning agent composition of the present invention and built by K and their conventional skills Concentration for use (ie about 0% to about 20% by weight)] contains solvents, whitening agents, bleach activators, corrosion inhibitors, dyes, fillers, optical brighteners, fungicides, regulators, enzymes , Mayan stabilizers, perfumes, etc. The intentional ingredients contained in the complete cleansing agent are a separate substance and are used for the purpose of rooting the clerk. Formed to embody the sra's of the present invention The granular cleansing agent is a finished product and K mixes sra's dryly (to be formed by the conventional art) into the adult product. The so-called conventional art is to mix other individual ingredients in water, then atomize and spray dry. The mixture, or M pan or roll choke, granulates the ingredients, or in a fluid bed method.
經濟部中央榀準局3工消伢合作杜印M 液體配方可Κ單相(較佳)姐成物形式或以多相或“分 散劑”形成。分散散劑傳統係利用粘度改良劑以產製具有 塑膠切變特徴之糸統Κ維持安定的分散劑且防止相分離或 固體沉著。 雖則本發明之洗滌清潔劑姐成物在廣泛範圍清洗出内係 可操作的 > 若在液體中調製,則彼等特別通合提供接近中 性清洗cH,即在20¾水中之切出係約6.0至約8.5而其濃 -41 - 8】.4. 10,0U0張⑻ (請先間讀背而之:在意事項洱填讳本頁) 本紙張尺度遑用中國Η家樣毕(CNS)T4規格(2]0χ297公*) Λ 6 Π 6 200550 五、發明説明(40) 度係約0.1重量至約2重量%。此種配方亦需要接近中性 cHM確保用於sra's長期穩定性。在此種配方中,產物pH 以約6.5至約8.5較佳且約7.0至約8.0更佳。 下列係說明本發明洗滌清潔劑組成物利用s「a | s之特別 ,但並不欲藉此限制其範圜。The Ministry of Economic Affairs, Central Bureau of Economic Cooperation and Industry 3 cooperation of Du Yin M liquid formula can be formed in single-phase (preferred) form or in multi-phase or “dispersant”. Dispersion powders traditionally use viscosity modifiers to produce dispersants with plastic shear characteristics such as K to maintain stability and prevent phase separation or solid deposition. Although the cleaning detergent product of the present invention is operable in a wide range of washing out > if prepared in a liquid, they will provide a near-neutral cleaning cH, that is, a cut-off system in 20¾ water 6.0 to about 8.5 and its concentration -41-8]. 4. 10,0U0 sheets ⑻ (please read it back and forth: please pay attention to this matter and fill in this page) This paper size is based on the Chinese NH family sample (CNS) T4 specification (2) 0 × 297 g *) Λ 6 Π 6 200550 V. Description of the invention (40) Degree is about 0.1% to about 2% by weight. This formulation also needs to be close to neutral cHM to ensure long-term stability for sra's. In such formulations, the product pH is preferably from about 6.5 to about 8.5 and more preferably from about 7.0 to about 8.0. The following illustrates the particularity of the use of s "a | s in the detergent composition of the present invention, but it is not intended to limit its scope.
例XT T 一種液賭清潔劑姐成物如下: 成份 爾量% SRA* 1.0 C12烷乙氧基(1)硫酸納 9.5 C12至C13酵多乙氧化物 10.2 C12至C14N -甲基葡萄糖醢胺 7.0 乙酵 5.5 伸乙二胺四乙酸納 0.3 少量物及h2〇 餘額 (請先閲讀背而之注意苹項"項筠本頁)Example XT T The composition of a liquid detergent cleaner is as follows: Ingredients% SRA * 1.0 C12 Alkylethoxy (1) Sodium Sulfate 9.5 C12 to C13 Fermented Polyethoxylate 10.2 C12 to C14N-Methyl Glucose amine 7.0 Ethanol 5.5 Ethylenediaminetetraacetic acid sodium 0.3 small amount and h2〇 balance (please read the back of the note and the "Item" page)
* S R A係根據上例I 經濟部中央櫺準局员工消伢合作社印^ -42 - 81. 4. 10,000¾ (II) 本紙尺度这用中a困家標準(CHS)甲4規格(210x297公龙) 200550 經试部屮央櫺準局β工消许合作社印51 五、發明説明(41) 例 X Τ Τ Τ 一種粒狀清潔劑姐成物如下: S R A c12至c13酵多乙氧化物 MgS04 水合沸石4A ( 1至10微米) N a 2 C 0 3 NaHCOs Maxatase MP(—種蛋白酶) 亮光劑 水及少量物質 *SRA係根據上例II而將此包衣在具平均分子量8,000之 聚乙二醇中。 製得例X I 11之姐成物而Μ使用標準混合方法以併入s r a ο 如從前文所見,可將本發明之s r a ’ S利用於為織品料理 姐成物之調配員所熟悉之洗滌及钦化姐成物之型式中。在 另一種横式中•可將於此之sr a's直接加至例如與鎌品有 關之水性洗滌潤濕浴中。在仍屬其它横式中,可將於此之 sra’s可釋離地固定在層板底材上等,設計此係為了供使 用於自動衣服乾燦器中。可將在商業實務中廣為熟知型式 -43 - 莆量% 3 . 5 20 . 0 1.0 26 . 0 18.3 15.0 1 . 5 1 . 2 加至100 (請先間讀背而之注惠肀項洱巩窍本頁) 裝. 訂 -躁· 本JMfc尺度逍用中國Η家標準規格(210x297公;*) 81. 4. !(),〇(]〇張(||) 2〇〇55〇 Λ 6η 6 五、發明説明(42) 經濟部中央櫺準扃貝工消^合作社印製 之各類熾品軟化劑及/或抗靜電劑行可釋離地固定在此類 層板底材上。於使用時,將濕嫌品與層板底材滾動,藉此 造成將sra’s且(若存在)任意的織品軟化劑/抗靜電劑 從層板底材输送至嫌品表面上。於此亦預期到將sra's施 用至織品之這些及其它模式。 雖則前文實例說明了較佳之加蓋的sra’s ,下列說明了 任意不加蓋的sra's而此亦涵蓋於本發明中、如上所揭示 ,可知不加蓋sra’s可使用於洗滌配方中。 例X T V 合成由對苯二甲酸二甲酯、聚f7,二醅U分;量14 5 Q)、 乙二酵、及丙二醇(具E/P=2.?)^《日成夕不加著真聚物 將下列物質加至裝有磁播拌棒、經改良Claiseri接頭、 冷凝器(用於蒸餾之装置)、溫度計、及溫度控制器( THERM - 0 - WATCH > I2R)之250毫升大小3頸圚底燒瓶中 :分子量1450之聚乙二酵(聯合碳化公司出品,93 . 3克, 0.064莫耳),對苯二甲酸二甲醏(25.0克,0.129莫耳 )、乙二.酵(Baker,16·0 克,0.258 莫耳),1,2 -丙二酵 (Fisher,19.6克,0.258箅耳)、及水合氧化單丁基錫 (M&T Chemicals公司出品,0.27克,佔0.2%结[反應物重 量)。將此混合物在氬氣中加熱至1801C 後,維持在此溫 度下過夜,同時將反懕容器蒸餾出。由13C-NMR(DMS〇-de) 顯示出已完成此種反應階段而以在〜52 ppm處不見甲酯之 共振。將此棰物質轉送至500毫升大小圓底燒瓶中而在 -44- (請先WJift背而之注意亊項、再巩Λ本頁) 本紙張尺度逍用中BB家標毕(CNS>T 4規格(210x297公*) .81. 4. 10,(03張(If) Λ 6 η 6 200550 五、發明説明(43) (請先間婧背而之注意事項外瑱寫本頁)* SRA is based on the above example I. Printed by the Ministry of Economic Affairs, Central Bureau of Precincts, Consumer Cooperatives ^ -42-81. 4. 10,000¾ (II) This paper scale is used in the China Standard (CHS) Grade 4 (210x297 male dragon) ) 200550 Printed by the Ministry of Economics and Trade, Beta-Consumer Cooperative Society 51 V. Description of the invention (41) Example X Τ Τ Τ A granular detergent is as follows: SRA c12 to c13 yeast polyethoxide MgS04 hydration Zeolite 4A (1 to 10 microns) N a 2 C 0 3 NaHCOs Maxatase MP (a protease) brightener water and a small amount of substances * SRA is coated with polyethylene glycol with an average molecular weight of 8,000 according to Example II above in. The elder sister of Example XI 11 was prepared and M used a standard mixing method to incorporate sra. As seen from the foregoing, the sra's of the present invention can be used for washing and cleaning familiar to the fabricator of the elder sister In the form of the sister into things. In another horizontal mode, the sra's can be added directly to, for example, water-based washing and wetting baths related to sickle. In still other horizontal styles, the sra ’s can be releasably fixed to the laminate substrate, etc., designed for use in automatic clothes dryers. The well-known type in business practice can be added to -43-Pu% 3. 5 20. 0 1.0 26. 0 18.3 15.0 1. 5 1. 2 to 100 (please read back and note the benefit of the item (Gongqiao this page) Pack. Order-many. This JMfc standard is easy to use Chinese H home standard specifications (210x297 g; *) 81. 4.! (), 〇 () 〇 Zhang (||) 2〇〇55〇Λ 6η 6 V. Description of the invention (42) Various types of incandescent softeners and / or antistatic agents printed by the cooperative of the Central Ministry of Economic Affairs of the Ministry of Economic Affairs ^ Cooperative Society are releasably fixed on the substrate of such laminates. During use, the wet suspect and the laminate substrate are rolled, thereby causing sra's and (if present) any fabric softener / antistatic agent to be transported from the laminate substrate to the surface of the suspect. It is also expected here These and other modes of applying sra's to fabrics. Although the previous examples illustrate preferred sra's with capping, the following illustrates any sra's without capping and this is also covered by the present invention, as disclosed above, it is known that it is not capped sra's can be used in washing formulas. Example XTV synthesis is made from dimethyl terephthalate, poly f7, dioxin U; amount 14 5 Q), glyphosate, and propylene Alcohol (with E / P = 2.?) ^ "The following materials are added without the true polymer on a day to night, and the following materials are added to the magnetic stirrer, modified Claiseri joint, condenser (device for distillation), thermometer , And a temperature controller (THERM-0-WATCH > I2R) in a 250 ml size 3-neck squat bottom flask: polyethylene glycol with a molecular weight of 1,450 (by Union Carbide, 93.3 g, 0.064 mol), right Dimethyl phthalate (25.0 g, 0.129 mol), ethanediastase (Baker, 16.0 g, 0.258 mol), 1,2-propanediol (Fisher, 19.6 g, 0.258 mol), And hydrated monobutyltin oxide (produced by M & T Chemicals, 0.27 g, accounting for 0.2% of the weight of the reactants). After heating the mixture to 1801C in argon, it was maintained at this temperature overnight while distilling off the decanter vessel. 13C-NMR (DMS〇-de) showed that this reaction stage had been completed and the resonance of the methyl ester was not seen at ~ 52 ppm. Transfer this material to a 500-ml round-bottom flask at -44- (please pay attention to the items before WJift, and then consolidate this page) The standard of this paper is BB home standard (CNS > T 4 Specification (210x297 public *) .81. 4. 10, (03 sheets (If) Λ 6 η 6 200550 V. Description of the invention (43) (please pay attention to the matters needing attention before writing this page)
Kugelrohr装置(Aldrich)中且在約1毫米汞柱之下將彼 逐步加熱超過20分鐘後,維持在此條件下歷40分鐘。然後 在抽真空下將燒瓶W空氣快速冷卻至接近室溫(約需30分 鐘)。反應產生94.8克橙色軟質固體。由 ^-NMR (DHSO-de)顯示出用於-C(0) 0 C H z CHz.O C (0)-之共振 係在約63.2?01«處(二醏)’用於-〇(〇)(1]1^(^2[^之共振 係在約- 59.4 ρρπ處(單酯),及在約69.8 ppm處有大尖 峰代表聚(氧化乙烯)單元。二酯尖峰高度對單酯尖峰高 度之比率係約5.8 °由乙二醇單醏所姐成終端基之滿意濃 度顗示出產物係一棰低分子量聚合物。由 UMlUDMSO-de)光譜亦與所形成之低分子量聚合物一致 。在1 . 1至1 . 3 ppm區域之尖峰顯示出存在可覼濃度之丙二 酵單酯。量測用於乙二酵二酯伸甲基在約4.7 ppm處之尖 峰面積對用於丙二酵二酯之甲基在約1.4 ppm處之尖峰面 積之比率。由此計算出所併入乙二醇/丙二酵之莫耳比率 (E/P比率)係2.2: 1。試驗溶解度而以將少量物質在小瓶 中稱量。加人足夠純水Μ製得5重量%溶液,而劇烈攫拌 小瓶物質在這些條件下係可溶的。 經濟部中央榀準局β工消伢合作社印31 從前文可見,製得廣泛各類織品軟化劑姐成物及洗滌清 潔劑姐成物而以使用於此之sr,s 。事實上,一般所提供 之近代液體織品軟化劑係作為高液體(H20)瀟縮劑(5倍 至6倍),設計此係為了由消費者在家庭内Μ水稀釋之。 在基本上,將根據前文例XI之成份濃度加倍以提供此種高 濃縮劑。因此•姐成物包括約10重量%至約32重量%之陽 _ 4 5 _ 81. 4. lO.OUOijt (I!) 本ΙΜ艮尺度遑用中B S家樣毕(CNS)T4規格(210x297公釐) 200550 A 6η 6 五、發明説明(44 ) 離子糸嫌品軟化劑(例如DTDMAC),約4重量%至約20重量 %之咪唑拼嫌品軟化劑及約1重量%至約5重量%於此之 sra’s ,而此等皆涵蓋於本發明中。 關於洗滌清潔劑姐成物方面*極佳姐成物係包括約0.3 重量%至約3重量%於此乏sra’s,而且約3重量%至約 20重量%脂肪酸多羥基醢胺表面活性劑作為清潔劑表面活 性劑(見美國専利2,965,576而相當於上述大英國協專利 809,060號,於此併於本文供參考),較佳方式係结合者 約5重量%至約25重量%硫酸化或磺酸化陰離子系表面活 性劑如C12至C18烷基苯磺酸鹽,C12至Cie烷基乙氧基磺酸 鹽(平均E0 3至10 ;較佳),伴阐著習知數量(15%至50 %)之習知助洗劑,包含此種較佳的肋洗劑如沸石A、氧 代二丁二酸酯、及其混合物,此種姐成物之其餘部份係包 括具習知濃度之習知清潔劑成份。 (請先間讀背而之漾意事項4填ΑΓ本頁) 裝· 訂' 經濟部屮央櫺準扃一3:工消费合作社印31 -46- 本紙51尺度边用中《«家標準(CNS) T4規格(210X297公*) 81. 1(),01)0¾ (||)In the Kugelrohr apparatus (Aldrich) and gradually heating each other for more than 20 minutes under about 1 millimeter of mercury, it was maintained under this condition for 40 minutes. Then, under vacuum, the flask W was quickly cooled to near room temperature (about 30 minutes). The reaction yielded 94.8 grams of orange soft solid. ^ -NMR (DHSO-de) shows that the resonance system used for -C (0) 0 CH z CHz.OC (0)-is at about 63.2? 01 «at the place (diamide) 'for -〇 (〇) (1) The resonance of 1 ^ (^ 2 [^ is at about-59.4 ρρπ (monoester), and at about 69.8 ppm there is a large peak representing the poly (ethylene oxide) unit. The height of the diester peak versus the height of the monoester peak The ratio is about 5.8 °. The satisfactory concentration of the terminal group formed by ethylene glycol monoacetate shows that the product is a low molecular weight polymer. The spectrum from UMLUDMSO-de) is also consistent with the formed low molecular weight polymer. The peaks in the 1.1 to 1.3 ppm range indicate the presence of malonyl monoester at a concentrable concentration. The peak area measured for the methyl ester of oxalase at approximately 4.7 ppm is used for malonase The ratio of the peak area of the methyl ester of the diester at about 1.4 ppm. From this, the molar ratio of the incorporated ethylene glycol / malonate (E / P ratio) is 2.2: 1. The solubility is tested to The substance is weighed in a vial. Add enough pure water M to make a 5% by weight solution, and vigorously stir the vial of the substance to be soluble under these conditions. The Central Bureau of Economy, Ministry of Economic Affairs β 工 消 合Sheyin 31 As can be seen from the foregoing, a wide range of fabric softener and detergent detergent products have been prepared and used for sr, s. In fact, the modern liquid fabric softeners generally provided as high Liquid (H20) shrinking agent (5 times to 6 times), designed to be diluted by consumers in household M water. Basically, the concentration of ingredients according to the previous Example XI is doubled to provide this high concentration agent Therefore, the sister product includes about 10% to about 32% by weight of the sun _ 4 5 _ 81. 4. lO.OUOijt (I!) This ΙΜgun standard used in China BS home sample Bi (CNS) T4 specifications ( 210x297 mm) 200550 A 6η 6 V. Description of the invention (44) Ionite suspect softener (eg DTDMAC), about 4% to about 20% by weight imidazole and suspect softener and about 1% to about 5 Sra's by weight, and all of them are covered in the present invention. Regarding cleaning detergents and cleaning products * excellent cleaning products include about 0.3% to about 3% by weight of sra's, and about 3 Weight% to about 20% by weight fatty acid polyhydroxyacetamide surfactant as a detergent surfactant ( U.S. Patent No. 2,965,576, which is equivalent to the aforementioned Great Britain Association Patent No. 809,060, hereby incorporated herein by reference), the preferred method is a combination of about 5% to about 25% by weight sulfated or sulfonated anionic surfactant such as C12 To C18 alkyl benzene sulfonate, C12 to Cie alkyl ethoxy sulfonate (average E0 3 to 10; preferably), with a known amount (15% to 50%) of conventional builders , Containing such preferred rib lotions such as zeolite A, oxodisuccinate, and mixtures thereof, the remaining portion of this sister product includes conventional cleansing ingredients with known concentrations. (Please read the back-to-back issues 4 and fill in the ΑΓ page first) Binding · Ordering 'Ministry of Economic Affairs, Ministry of Economic Affairs and Industry 3: Printed by the Industrial and Consumer Cooperatives 31-46 CNS) T4 specification (210X297 male *) 81.1 (), 01) 0¾ (||)
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CZ276994A3 (en) * | 1992-05-12 | 1995-04-12 | Procter & Gamble | Concentrated agent for softening fabrics and containing biodegradable fabric softeners |
EP0686190A4 (en) * | 1993-02-26 | 1998-01-14 | Procter & Gamble | Laundry additives comprising encapsulated perfumes and modified polyesters |
DE4402852C1 (en) * | 1994-01-31 | 1995-02-16 | Henkel Kgaa | Detergent mixtures and the use thereof |
US5691298A (en) * | 1994-12-14 | 1997-11-25 | The Procter & Gamble Company | Ester oligomers suitable as soil release agents in detergent compositions |
DE69605532T3 (en) * | 1995-01-12 | 2004-04-08 | The Procter & Gamble Company, Cincinnati | STABILIZED LIQUID SOFTENER |
WO1997002337A1 (en) * | 1995-06-30 | 1997-01-23 | The Procter & Gamble Company | Liquid detergent compositions |
DE19616096A1 (en) * | 1996-04-23 | 1997-11-06 | Huels Chemische Werke Ag | Use of anionic gemini surfactants in formulations for washing, cleaning and personal care products |
WO1999041348A1 (en) * | 1998-02-11 | 1999-08-19 | Rhodia Chimie | Detergent compositions containing an amine silicone and a glucamide |
DE19811329C2 (en) * | 1998-03-16 | 2001-11-22 | Lifestyle Vertriebsgmbh | Flea control agents |
DE19826356A1 (en) * | 1998-06-12 | 1999-12-16 | Clariant Gmbh | Soil-removing oligoester |
WO2000042139A1 (en) * | 1999-01-11 | 2000-07-20 | The Procter & Gamble Company | Fabric care composition for directly applying to fabrics |
DE19959119A1 (en) * | 1999-12-08 | 2001-06-13 | Clariant Gmbh | Emulsions |
US6362158B1 (en) * | 2000-06-29 | 2002-03-26 | Colgate-Palmolive Co. | Multi-phase clear fabric softening composition |
US7655609B2 (en) | 2005-12-12 | 2010-02-02 | Milliken & Company | Soil release agent |
CN101400850B (en) * | 2006-01-18 | 2012-08-15 | 因维斯塔技术有限公司 | Non-textile polymer compositions and methods |
CN100519715C (en) * | 2006-05-11 | 2009-07-29 | 李伯林 | High molecular pollutant cleaning agent and preparation method thereof |
DE102008023803A1 (en) * | 2008-05-15 | 2009-11-26 | Clariant International Ltd. | Additives for detergents and cleaners |
US8900328B2 (en) * | 2009-03-16 | 2014-12-02 | The Procter & Gamble Company | Cleaning method |
WO2011000158A1 (en) * | 2009-07-01 | 2011-01-06 | Rhodia (China) Co., Ltd. | Process for producing polyether-polyester block copolymer |
EP2534206B1 (en) * | 2010-02-09 | 2014-04-02 | Unilever PLC | Dye polymers |
CN104508199B (en) * | 2012-06-15 | 2017-11-07 | 罗地亚经营管理公司 | Recover or increase the method for polyester textile water imbibition |
DE102012016462A1 (en) * | 2012-08-18 | 2014-02-20 | Clariant International Ltd. | Use of polyesters in detergents and cleaners |
WO2018067482A1 (en) * | 2016-10-03 | 2018-04-12 | The Procter & Gamble Company | Laundry detergent composition |
US10377977B2 (en) | 2016-11-01 | 2019-08-13 | The Procter & Gamble Company | Leuco polymers as bluing agents in laundry care compositions |
US10590275B2 (en) | 2016-11-01 | 2020-03-17 | Milliken & Company | Leuco polymers as bluing agents in laundry care compositions |
EP3835396A1 (en) * | 2019-12-09 | 2021-06-16 | The Procter & Gamble Company | A detergent composition comprising a polymer |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1534641A (en) * | 1977-05-04 | 1978-12-06 | Unilever Ltd | Detergent compositions for fabric washing |
DE3585505D1 (en) * | 1984-12-21 | 1992-04-09 | Procter & Gamble | BLOCK POLYESTER AND SIMILAR COMPOUNDS, USED AS A DETOIL REMOVER IN DETERGENT COMPOSITIONS. |
US4661267A (en) * | 1985-10-18 | 1987-04-28 | The Procter & Gamble Company | Fabric softener composition |
US4711730A (en) * | 1986-04-15 | 1987-12-08 | The Procter & Gamble Company | Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents |
GB8629936D0 (en) * | 1986-12-15 | 1987-01-28 | Procter & Gamble | Laundry compositions |
US4756850A (en) * | 1987-06-10 | 1988-07-12 | The Procter & Gamble Company | Articles and methods for treating fabrics |
-
1992
- 1992-03-18 CA CA 2106217 patent/CA2106217A1/en not_active Abandoned
- 1992-03-18 AU AU17532/92A patent/AU1753292A/en not_active Abandoned
- 1992-03-18 WO PCT/US1992/002256 patent/WO1992017523A1/en active Application Filing
- 1992-03-18 JP JP4509434A patent/JPH06506251A/en active Pending
- 1992-03-21 TW TW81102151A patent/TW200550B/zh active
- 1992-03-25 PT PT10029892A patent/PT100298A/en not_active Application Discontinuation
- 1992-03-27 AR AR32202692A patent/AR244788A1/en active
- 1992-03-27 NZ NZ24215092A patent/NZ242150A/en unknown
- 1992-03-27 MX MX9201415A patent/MX9201415A/en unknown
- 1992-03-28 CN CN 92103387 patent/CN1066680A/en active Pending
Also Published As
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NZ242150A (en) | 1995-04-27 |
WO1992017523A1 (en) | 1992-10-15 |
AR244788A1 (en) | 1993-11-30 |
MX9201415A (en) | 1992-10-01 |
PT100298A (en) | 1993-07-30 |
JPH06506251A (en) | 1994-07-14 |
AU1753292A (en) | 1992-11-02 |
CN1066680A (en) | 1992-12-02 |
CA2106217A1 (en) | 1992-09-29 |
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