TWI402339B - 附著性衛浴設備清潔及芳香劑 - Google Patents
附著性衛浴設備清潔及芳香劑 Download PDFInfo
- Publication number
- TWI402339B TWI402339B TW094138945A TW94138945A TWI402339B TW I402339 B TWI402339 B TW I402339B TW 094138945 A TW094138945 A TW 094138945A TW 94138945 A TW94138945 A TW 94138945A TW I402339 B TWI402339 B TW I402339B
- Authority
- TW
- Taiwan
- Prior art keywords
- barium
- agent
- adhesive agent
- sanitizer
- weight
- Prior art date
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- 239000000853 adhesive Substances 0.000 title claims description 21
- 239000003205 fragrance Substances 0.000 title claims description 14
- 230000001070 adhesive effect Effects 0.000 title claims description 7
- 238000004140 cleaning Methods 0.000 title claims description 7
- -1 hydrate strontium strontium Chemical compound 0.000 claims description 60
- 239000003795 chemical substances by application Substances 0.000 claims description 58
- 239000003638 chemical reducing agent Substances 0.000 claims description 37
- 239000007844 bleaching agent Substances 0.000 claims description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 15
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910052788 barium Inorganic materials 0.000 claims description 11
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052797 bismuth Inorganic materials 0.000 claims description 10
- 239000002304 perfume Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000011010 flushing procedure Methods 0.000 claims description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 239000011630 iodine Substances 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 claims description 5
- ZCHPOKZMTJTNHI-UHFFFAOYSA-L barium(2+);sulfonatooxy sulfate Chemical compound [Ba+2].[O-]S(=O)(=O)OOS([O-])(=O)=O ZCHPOKZMTJTNHI-UHFFFAOYSA-L 0.000 claims description 5
- 239000002562 thickening agent Substances 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- FZIZEIAMIREUTN-UHFFFAOYSA-N azane;cerium(3+) Chemical compound N.[Ce+3] FZIZEIAMIREUTN-UHFFFAOYSA-N 0.000 claims description 4
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- 239000002904 solvent Substances 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 3
- 230000000249 desinfective effect Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 3
- 230000002335 preservative effect Effects 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 claims description 2
- KEPNSIARSTUPGS-UHFFFAOYSA-N 2-n,4-n,6-n-trichloro-1,3,5-triazine-2,4,6-triamine Chemical compound ClNC1=NC(NCl)=NC(NCl)=N1 KEPNSIARSTUPGS-UHFFFAOYSA-N 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
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- HPEWZLCIOKVLBZ-UHFFFAOYSA-N barium hypochlorite Chemical compound [Ba+2].Cl[O-].Cl[O-] HPEWZLCIOKVLBZ-UHFFFAOYSA-N 0.000 claims description 2
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- 239000005871 repellent Substances 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 4
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- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 claims 1
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- 125000000217 alkyl group Chemical group 0.000 description 21
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- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 12
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/015—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone
- A61L9/04—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating
- A61L9/05—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating specially adapted to be released by contact with a liquid, e.g. for toilets
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
-
- 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
-
- 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
- C11D3/395—Bleaching agents
- C11D3/3956—Liquid compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Description
本發明關於一種用於衛浴物品如馬桶便盆的附著性衛生劑，用於清洗、消毒/及或釋出芳香劑。
此衛生劑係粘性的(一般為糊狀的)凝膠體，它們由一相關之容器直接施在該衛浴物品的表面上，附著在該處，且在較多次沖刷過程後才會沖掉。一般，此衛生劑至少為部分地液態結晶者。
藉著使該衛生劑直接附著在衛浴物品表面，就不需設以附加的容器如所謂的「WC小籃」，這些WC小籃被使用者使用時，特別是在更換衛生劑以及在馬達修整時，顯得特別不衛生。
這種附著性衛生劑見於國際專利WO 99/66017。它們除了界面張力減少劑(Tenside)、水、及芳香劑外，還含附著性賦與劑，例如由非離子性界面張力減少劑如聚烷氧基烷選出，且係為粘稠性、固體或糊狀的藥劑。一項用偏光顯微鏡研究該文獻所發表的清潔劑的研究顯示，該藥劑含有液晶相，特別是由六方晶系構造構成者。
為了防止此附著性藥劑的表面乾掉，並提供一種美觀光滑的表面而不受沖刷次數影響，故在德專利DE 100 48 887 A1中提到另外將一種脂肪族的二元羥基、寡羥基、或多元羥基化合物或其醚加到此藥劑。
在歐洲專利EP 1 318 191提到一種衛生劑，它包含由含有寡聚或多聚氧化乙烯及/或寡聚及/或多聚氧化丙烯及/或寡聚及/或多聚氧化丁烯的嵌段聚合物、芳基乙醇酸塩或芳基芳基乙醇酸塩選出的化合物，當作粘著性賦與劑。
此習知之附著性衛生劑可用簡單而衛生的方式用一適當的裝置施覆、附著在衛生物品表面上，維持其形式且即使就水的作用下也不會整個被沖掉，因係在沖了許多次以後才漸漸地完全溶掉。
此外在德專利DE 103 56 25 4 A1發表了一種長附著性的衛生劑，它會有陰離子性界面張力減少劑及非離子性界面張力減少劑當作附著附與劑，並有矽酸塩當作稠化劑。
這種藥劑的特色為良好的便利性及良好的清潔作用。由於該藥劑可直接用，故不再需要使得使用者在補充裝注時接觸到可能受污染的馬桶小籃。且使用者可將該藥劑以其所希望的量施用且不受限於製造商所定的包裝量。
此習用之凝膠體狀藥劑的另一優點為：該藥劑的芳香劑釋出作用遠比清潔劑模製體為優。
為了改善清潔及消毒能力。在押出的清潔劑模製體係一如「邊緣藥劑塊」(Rimblock)式「槽中式藥劑塊」(In－Tank Block)，用會游離出滷素當作漂白劑。然而這種含有會釋出鹵素的物質的習知藥劑就穩定性方面而言會發生困難，如歐洲專利EP 0 462 643 A1、國際專利WO 92/18 605及EP 0 672 103 B1所述。在潮濕條件下，該習知之含有釋出鹵素的藥劑的藥劑塊中已會發現該可釋出鹵素的藥劑分解的情事，且該釋出鹵素的藥劑會與其他反應性成分不當地起反應，且在上述文獻中以及在許多其他刊物有許多主張，例如對漂白劑的分解，以及漂白劑對於該習知清潔劑中的其他敏感的物質的侵蝕的問題如何解決。而且由於這些困難，甚至還有人主張將清潔做成多相式，亦即具有一含漂白劑的相似及一個具有該敏感物質之不含漂白劑的相。
本發明的目的在提供一種廁所清洗劑及/或芳香劑，它具有高度清潔力及消毒力且使用上簡單而衛生。
出乎意料地，茲發現，儘管漂白劑如先前技術所知具不穩定性，但在潮濕環境卻能提供一種含漂白劑的藥劑，可直接施在衛生物品上(它含有水、附著性賦與劑及陰離子式界面張力減少劑)，它含有可釋出鹵素及/或氧的漂白劑。出乎意料地，該會釋出鹵素及/或氧的物質在該先前技術習知之高度不穩定性的問題在這種含有附著性賦與劑的凝膠狀清潔劑中，其不穩定性的問題並不發生或者至多只有一點點。
依本申請人看法，其原因可能是該會釋出鹵素或氧的物質之分解作用(它受粗糙表面催化)在此藥劑中由於受到凝膠體構造影響而不會發生。
在本發明的定義中，「會釋出鹵素的藥劑」係指令釋出鹵素：氯、溴、碘或其次鹵酸醯(Hypohalogenide，X2
O)的藥劑。
本發明的能釋出鹵素及/或氧的漂白劑係為以下化合物選出者：碳酸塩的過氧化水合物、過硼酸塩、過硫酸塩、過氧化重硫酸塩、過氧化磷酸塩、過氧化硝酸塩、肉霉酸塩(Caroate)、硝酸塩、連二亞硫酸塩(Dithionite)、次氯酸塩、氯酸塩、過錳酸塩的鹼金屬塩、銨塩或鹼出金屬塩。
此外還可為二氯異氰異氰酸塩(Dichlorisecyanurate)、三氯異氰尿、酸塩、二溴尿、酸塩、三溴異氰尿酸塩氯或溴的乙內醯脲(Hydantoin)、氯化之三烷基磷酸酯呈其鹼金屬塩、銨塩、鹼土金屬塩或游離酸的形式。
此外還可為過氧化氫、有機過氧化物、碘、碘PVP、溴、及單氯胺、及氯化之磷酸三鈉。次氯酸鈣、次氯酸氯、單氯胺(Monochloramine)、雙氯胺、[(單三氯)－四(單鉗二氯)]五異氰尿、酸塩、1,3－二氯－5,5－二甲基茚丹酮、對－甲苯硫、二氯醯胺、三氯蜜胺、N－氯胺、N－氯－琥珀酸亞醯胺、N,N’－二氯偶氮二碳酸醯胺、N－氯乙醯脲、N,N－二氯雙縮脲N,N－Dichlorbiurile)、氯化之二氰二醯胺及二氯乙二醇脲。
「鹼金屬塩」特宜為鈉塩及鉀塩，而「鹼土金屬塩」特宜為鈣塩。
用於當作漂白劑使用者特宜為過氧化氫。
本發明之可釋出鹵素或氧的藥劑在凝膠體中可含1~20重量%比例，其比例宜在2~15重量%之間，特宜在5~10重量%之間。
一般，這些化合物在凝膠體中大致穩定，然而如果想要的話，也可加入一穩定劑使漂白劑向前更進一步穩定化。所用穩定劑可為尿素巴比土酸、嫌水性化合物如礦油或其他不反應性嫌水性化合物例如第三醇、錯合的酯或酮。在某些狀況，這些嫌水性穩定劑也可同時為香水劑及/或溶解控制劑。所用穩定劑也可為鍺塩形成物，如磷酸、二磷酸鈉、錫酸塩、矽酸塩(如矽酸鹼土金屬塩)、EDTA、NTA及檸檬酸塩選出，例如在宜為釋出氧的漂白劑為過氧化氫的場合，係與一重金屬(它能催化分解作用)錯合。
特宜當作為本發明的漂白劑為過氧化氫，過氧化氫宜在濃度30%的水溶液中穩定化。過氧化氫可呈液體或水溶液形式直接用於製造此藥劑，而不須將塩或類似物溶解。此外，過氧化氫在凝膠體中出奇地穩定。此外，過氧化氫的氧化作用係比對應的釋出氯的物質更具選擇性。
過氧化氫的另一優點為：過氧化氫及其氧化產物(即氧)都是無色者，因此不會像使用以溴、碘為基礎的漂白劑那樣影響藥劑的外觀，在溴、碘漂白劑的場合在某些情況以後會使該藥劑變褐色。
但也可依所要的顏色及本色而定，而完全使用會釋出碘或溴的藥劑，特別是當該凝膠體含有敏感的成份時，因為釋出溴及碘的藥劑的氧化電位比釋出氯或氧的藥劑低。
為了防止凝膠體中的過氧化氫的催化分解作用，該凝膠體須不含重金屬，如錳礦(Braunstein)、Fe3 ＋
、Ca2 ＋
及不含I－
、IO3 －
。
如果凝膠體中的漂白劑的氧化力要增高，舉例而言，要使用新的反應載體的漂白劑如過硼酸塩，則可加入漂白活化劑，特別是以N－或O－丙烯醯化合物為基礎者，例如乙醯基乙烯二胺(TAED)，四乙醯基乙二醇脲(TAGU)、五丙醯基葡萄糖(PPG)或五乙醯基葡萄糖(PAG)。
此附著性賦與劑在有水存在的情形產生作用，使該藥劑附著在表面上。一般，它形成網狀構造，該構造給予該藥劑本身所需的耐模成形性，在沖刷水的強力作用下仍不變。
附著性賦與劑的分子係為較長鏈或長鏈的分子且大致為直鏈分子，它們至少為部分地親水性，因此至少包含一親水性的游離基或一親水性基團，可與水交換作用。
該附著性賦與劑宜為不分枝分子，俾能形成所要的交聯構造。
該附著性賦與劑可為整體親水性或部分親水部分嫌水性。
所用附著性賦與劑可為具一親水性端及一嫌水性端的有機分子。所用親水性游離基，舉例而言，為聚烷氧基團，且宜為聚乙氧、聚丙氧或聚丁氧基團式混合之聚烷氧基團，例如聚(乙氧丙氧)基團。特佳者係使用一種聚乙氧基團當作親水性端，它包含15~100個乙氧基團，且宜在25~55，尤宜35±5個乙氧基團。
所用之親水性端也可為陰離子基團，例如磺酸塩、碳酸塩或硫酸塩。
脂肪酸塩(特別是脂肪酸的鈉塩或鉀塩)也適合當作附著性賦與劑。
只要該附著性賦與劑分子也具有一嫌水性端，則特別是直鏈的烷基游離基也適合做嫌水性游離基，其中特別是偶數烷基游離基由於可生物分解性較佳，特別適合。為了使附著性賦與劑分子形成所要的網架構造，故分子須不分枝。
如果選用烷基團當作嫌水性游離基，則該烷基團游離基宜為至少具十二個碳原子者。特佳的結果係用C1 6
~C3 0
間的烷基鏈長者達成，尤其是C1 6
、C1 8
、C2 0
及C2 2
。
該附著性賦與劑也可含烷基苯游離基作為嫌水性游離基，例如十二烷基苯或類似游離基，一如附著性賦與劑十二烷基苯甲酸鈉的情形。
非離子界面張力減少劑及非離子性乳化劑構成附著性賦與劑的一大類。
依本發明，用於做非離子性界面張力減少劑者宜為烷氧基化的(且宜為乙烷氧基化及或丙烷氧基化，尤宜為乙烷氧基化的)初級直鏈醇。特別是脂肪族醇，及/或脂肪酸，它們宜為C8
~C2 2
，且尤宜C1 2
~C2 2
者，且平均使用5~120莫耳氧化乙烯(EO)及/或1~5莫耳氧化丙烯(PO)/每莫耳醇，其中該醇游離基為直鏈者，或者可在第二位置帶有甲基分枝，或者在混合物中含有直鏈及甲基分枝游離基，一如它們一般在氧烷游離基中存在者。但一般具有直鏈游離基(由C1 2
~C2 2
的醇構成者，例如由可可醇、棕櫚醇、脂肪醇、或油酸基醇構成，且平均為20~100－－尤宜20~80EO/每莫耳或醇構成)的乙醇酸醇特佳。這類較佳的乙氧基化的醇的例子為C1 2
~C1 4
的醇及/或酯肪醇，具有30、40、50或60EO單位，及它們的混合物。如有必要，所予之乙氧基化程度的統計上的平均值對於一特殊的產物可為一整數或一分數。較佳的乙氧基醇具有適當的均度分佈(低範圍乙氧基化，NRE)。
較佳的附著性賦與劑為聚烷氧基烷，且宜為具有35EO的烷基(C2 0
－C2 0
)乙氧基化物或具35EO的烷基(C2 2
)乙氧基化物與具30EO的烷基(C1 6
－C1 8
)乙氧基化物構成的混合物，但也可為烷基磺酸塩，如十二烷基苯磺酸鈉或烷基碳酸酯或烷基硫酸酯。
使用該附著性賦與劑：烷基(C2 2
)乙氧基酸酸酯(35EO)及烷基(C1 6
~C1 8
)乙氧基酸酯(30EO)的混合物，對於所要的沖刷次數，在減少劑量方面及該藥劑的耐久性方面有正面效果。此外，共同使用這些附著性賦與劑，可使該藥劑可以簡單地使用。
隨著烷氧基數目減少，該附著性賦與劑變得更親油脂性，如此，舉例而言，香精(Parfum)的溶解度及芳香作用強度可提高。
此外，依本發明較佳者為C1 2
~C2 2
脂肪酸單酯及雙脂[它們係10~150莫耳氧化乙烯在C3
~C6
多元醇(特別是乙二醇)上的添加(Anlagerung)產物，C8
~C2 2
烷基單醣苷及寡醣苷及其乙氧基化之類似物(Analoga)、20~150莫耳(特別是20~100M，主要為20~80M)的氧化乙烯在蓖麻油(Rizinusl)或是硬化蓖麻油上的添加產物]、C3
~C6
多元醇與C8
~C2 2
飽和脂肪酸脂(它們同樣地可用4~150莫耳的氧化乙烯及/或0~5莫耳的氧化丙烯作烷基化)。舉例而言，用40EO單元烷氧基化的硬化蓖麻油係以商品名稱EumulginHRE40(Cognis)販售。用60EO單元烷氧基化蓖麻油，舉例而言，係以商品名稱EumulginHRE60(Cognis)及CremophorCD60(巴斯地夫公司)販售。
另一類可依本發明使用的非離子性界面張力減少劑(它們可呈單獨之非離子性界面張力減少劑使用或與其他之非離子性界面張力減少劑組合使用)係為烷氧基化(且宜乙氧基化，或乙氧基化及丙氧基化)的脂肪酸烷基酯，且烷基鏈中宜有1~4個碳原子，特別是酯酸甲酯。
又一類可依本發明使用的非離子性的界面張力減少劑係為烷氧基聚糖苷(APG)。可用的烷基聚糖苷具通式R－O－(－G)2
，其中R代表一直鏈或分枝(宜在第二位置有甲基分枝)的飽和或不飽和的脂肪族游離基，具8~12個(且宜8~18個)碳原子，G表示一單醣之一用糖苷方式結合的游離基，Z為1~10之間的值。
另一類較宜使用之非離子式界面活性減少劑(它們可呈單獨之非離子性界面活性減少劑使用或與其他非離子性界面活性減少劑組合使用)係為烷氧基化(且宜乙氧基化，或乙氧基化及丙氧基化)的脂肪酸烷基酯，其烷基鏈中具有1~4個碳原子。
氧化胺基類型的非離子式界面活性減少劑，例如N－可可烷基N,N－二甲基胺氧及T－脂肪烷基－N,N－二羥基乙基胺氧、及脂肪酸烷醇醯胺也可適合。這種非離子性界面活性減少劑的量宜不多於乙氧基化的脂肪醇，特別是不多於其一半。
其他適合的界面活性減少劑係具通式(II)的多羥基脂肪酸醯胺：
其中RCO代表一C6
~C2 2
的脂肪族丙烯醯期游離基，R1
代表氫、一個C1
~C4
的烷基或羥烷基游離基，[Z]代表一具3~10個羥基的直鏈或分枝的C3
~C1 0
多烴基烷基游離基。該多羥基脂肪酸醯胺係為習知之物質，它們可用一般方式藉著還原性糖用氨、烷基胺、或醇胺作還原性胺基化，然後用一脂肪酸、一脂肪酸烷基酯或一脂肪酸氯醯作用丙烯醯化而得到。
屬於此類多羥基脂肪酸醯胺者還有式(III)的化合物：
其中R代表－C7
~C1 2
的直鏈或分枝的烷基或烯基游離基，R1
代表一C2
~C8
的直鏈或分枝或環狀的烷基游離基或芳基游離基，R2
代表一C1
~C8
的直鏈、分枝或環狀烷基游離基或氧烷基游離基，其中C1
~C4
烷基或苯基游離基較佳，[Z]代表一直鏈多羥基烷基，其烷基鏈用至少二個羥基取代或為此游離基之烷氧基化(且宜乙氧基化或丙氧基化)的衍生物。
該非離子性界面活性減少劑含在凝膠體中的濃度宜為10~60重量%，且宜10~30重量%，尤其是15~25重量%。
也可使用一些分子當作附著性賦與劑，它們在水性系統中一般當作稠化劑，例如親水性物質，如纖維素、多醣、澱粉、黃質(Xanthan)－膠、瓊脂－瓊脂、格蘭(Gellan)膠、膠－阿拉伯膠(Arabicum)、約翰尼斯麵包心屑(Johannisbrotkernmehl)或胍(Guar)－膠。
該附著性賦與劑之所要使用的濃度係與其親水性及其形成網格的能力有關。舉例而言，它們可為10~40重量%，且宜15~35重量%，尤宜2－~30重量%，這點特別在使用聚烷氧基烷時尤宜。
為了利用附著性賦與劑藉著水添加(Anlagerung)而提供所要數目的粘著位置，此配方中水含量至少要20重量%，且宜在35~65重量%，特別是4－~60重量%，水成分還與所用之附著性賦與劑的親水性有關。
此外－－特別是對於顏料及香料油－－舉例而言，可含烷醇胺、多元醇(多乙烯乙二醇、丙烯乙二醇，1,2－苷油與其他－價或多價的醇)當作溶劑。溶劑含量依所要溶解的成分的種類與量而定，且一般在0.5~5重量%範圍。
所用之界面張力減少劑可為所有習知之陰離子性及陽離子性或無定形(非晶質)的界面張力減少劑。
所用陰離子性的界面張力減少劑，舉例而言磺酸塩及硫酸塩類型者。在此，磺酸塩類型的界面張力減少劑宜為C9
－C1 3
烷基苯礦酸塩、烯磺酸塩(換言之係烷與烴烷的磺酸塩的混合物)及二磺酸塩(它們係藉著用氣態三氧化硫磺酸化而成末端或內部的雙鍵，然後將此磺酸化產物作鹼式或酸式水解而得)。
適合者還有一些烷礦酸塩，它們由C1 2
~C1 8
烷，例如先硫氯醯化或硫氧化(Sulfoxidotion)，隨後水解或中和而得到。同樣地適合者還有α－硫脂肪酸的酯(酯磺酸塩)，例如氫化之椰子油酸、棕櫚仁酸、脂肪酸的α－磺酸化甲基酯。
其他適合的陰離子式的界面張力減少劑為硫化之脂肪酸甘油酯。脂肪酸甘油脂指一酸、二酸、及三酸甘油酯及其混合物(如在製造時將單甘油用1~3莫耳脂肪酸酯化或三甘油酯(Triglycerid)用0.3~2莫耳甘油轉酯化時所得者)。在此，較佳的硫化脂肪酸甘油酯為C6
~C2 2
的飽和脂肪酸[例如己酸、辛酸、癸酸、肉荳蔻酸、肉桂酸、棕櫚酸、硬脂酸、山萮酸(廿二烷酸)]的硫化產物。
較佳之烷(烯)基硫酸塩為C1 2
~C1 8
脂肪酸[例如椰子油醇、脂肪醇、月桂醇、肉荳莞醇、十六烷醇或硬酯酸醇或C1 0
~C2 0
氧代醇]的硫酸半酯及這種鏈長的第二醇的半酯的鹼金屬塩(特別是鈉塩)。此外較佳者為上述鏈長度的烷(烯)基硫酸塩(它們含有一個合成之直鏈烷基游離基係以石化基礎製造者，且具有類似於以脂肪化學原料為基礎的適合化合物的分解性質)。基於洗濯技術的優點，較佳者為C1 2
~C1 8
烷基硫酯塩，且宜C1 2
~C1 3
，尤宜C1 4
~C1 5
烷基硫酸塩。適當的陰離子或界面張力減少劑還有2,3－烷基硫酸塩，它們可由硯殼油公司購得，商品名稱DAN。
且1~6莫耳氧化乙烯作乙氧基化的直鏈或分枝的C7
~C2 1
醇的硫酸單酯[例如2－甲基－分枝C9
~C1 1
醇用平均3.5莫耳氧化乙烯(EO)乙氧基化，或C1 2
~C1 8
脂肪醇用1~4EO乙氧基化]也適合。在此，它們由於其高起泡性質，只能以較少量使用。
其他適合的陰離子界面張力減少劑還有烷基硫琥珀酸塩，它們亦稱為硫琥珀酸塩或硫琥珀酸游離基，且它們為硫琥珀酸與醇(宜為脂肪醇，尤宜為乙氧基化的脂肪醇)的單脂及/或雙酯。較佳由硫琥珀酸塩含C8
~C1 8
脂肪酸游離基或其混合物。較佳的硫琥珀酸塩含一脂肪酸游離基(它由乙氧基化的脂肪酸衍生出，該脂肪醇本身係為非離子性的界面活性減少劑(其說明見下文)。在此特佳者還有一些硫琥珀酸塩，它們的脂肪酸游離基由具有受限之均勻性分佈的乙氧基化脂肪醇衍生出。同樣地，也可使用一些烷(烯)基琥珀酸或其塩，它們的烷(烯)基鏈中宜有8~18個碳原子。陰離子式表面張力減少劑可呈其鈉塩、鉀塩或銨塩形式及有機鹹(如單、雙、或三乙醇胺)的可溶塩形成式存在。該陰離子式界面性減少劑宜呈其鈉塩或鉀塩形式，尤其呈鈉塩形式。
依本發明，特宜使用做陰離子式界面活性減少劑為脂肪醇乙醚硫酸塩、烷基硫酸塩、烷基苯硫酸塩、及/或烷礦酸。該陰離子式表面張力減少劑在組成物中的含量宜為10~75重量%，且宜20~70%，尤宜30~70%，特宜40~65重量%。
除了本發明的成份，該衛生劑可含其他一般的成份，例如香精物質、消毒劑、防腐劑、如如異噻唑酮衍生物或泡沫穩定劑，如椰子脂酸醯胺丙基甜菜鹼或椰子脂酸醯酸胺丙基二甲基氧化胺、椰子脂酸單/雙乙醇醯胺或烷基聚醚甘油－醚硫酸塩。還有顏料及/或溶解石灰石或尿石的物質，特別是酸。
這些選擇之附加的香精料，係為先前技術習用者。其例子有天然子合成之香料。天然香料為花的萃取物(百合、薰衣草、玫瑰、茉莉、橙花(Neroli)、馬來番荔枝(Yiang－Yiang)、生莖(Stengel)與葉[牻牛兒苗(Geranium)、綠葉刺蕊草(Patchoali)、卑檸(Petitgrain)]、果實[大茴香(Anis)、芹葉、早芹菜類(Kmmel)杜松(Wacholder)]、果皮[佛手柑(Bergamotte)、檸檬(Zitrone)、柑橘(Orange)]、根[(Mecis)、獨活類(繖形科)(Angelika)、洋芹(Sellerie)、豆蔻實(Kardam)、閉鞘－薑－(Costus)、鳶尾(Iris)、菖蒲(Kalmus)]。木材[松子木(Pinienhotz)、檀香木(Sandelholz)、癒瘡木(Guajakholz)、杉木(Zedernholz)玫瑰木]葯草與草[艾(Estragon)、檸檬草(Lemongras)、紫蘇(Salbei)麝香草(Thymian)]、針葉與枝[針樅(Fichte)、樅(Tanne)、松(Kiefer)矮松(Latschen)]、樹脂與芳香樹脂(Balsam)、[白松香(Galbanum)、越列密脂(Elemi)、安息香(Benzoe)沒藥(Myrrhe)乳香(Olibanum)、臭苔味樹脂(Opoponax)]。此外還可考慮動物原料，例如靈貓麝香(Zibet)與(Castoreum)。典型之合成香料化合物有酯、醚、醛、酮、醇及烴類的產物。酯類香料的例子有乙酯苄酯、異丁酸苯氧乙酯、乙酸對－第三丁基環乙酯、乙酸里哪酯、乙酸二甲基苄基烯丙脂、乙酸苯基乙酯、苯甲酸里哪酯、甲酸苄酯、甘胺酸乙基甲基苯酯、丙酸烯丙基環己酯、丙酸肉桂烯丙脂及脂環酸苄酯。醚類例子有苄基乙基醚，醛例子有C8
~C1 8
的直鏈烷醛、檸檬醛(Citral)、香茅醛(Citronellal)香茅醛基氧基乙醛、環戊醛(Cyclamenaldehyd)、羥基香茅醛、百合醛(Lilial)及Bourgeonal；酮的例子有紫羅酮(Jonone，英：ionone)、鄰－異甲基酮及甲基雪松醛、屬萜烯醛含各有薄荷醇、茴香腦(Anethol)、香茅醇(Citronellol)、丁子香酚(Eugenol)、異丁子香酚、牻牛兒醇(Geraniol)、異哪醇、橙花醇(Nerol)、苯基乙基醇、四氫香葉烯醇及萜品醇(Terpineol)。屬烴類者為萜及香脂(Bolsam)。但宜使用不同香料(它們共同產生有反應的香氣指數)的混合物。
較低揮發性的麻醉性油(它們大多當作芳香成份使用)也適合作香精，例如紫蘇油(Salbeil)、甘菊油、丁香油、香蜂油、薄荷油、肉桂油、菩提花油、杜松子油、歪惕油(Vetiverl)、乳香油(Olibanl)、古蓬香脂油．．．．(Labolanuml)及薰衣草油。較宜者為佛手柑油、二氫香葉烯醇、百合醛、Lyral、香茅醇、苯基乙基醇、α－己基肉桂醛(α－Hexylzimtaldehyd)、痝牛兒醇、苄基丙醇、環戊醛、里哪醇、Boisambrene Forte、土荊芥油、吲哚、Hedione、Sandelice、檸檬油、紅橘油、柑橘油、烯丙基戊基乙二醇酸塩(Gyclovertal、薰衣草油、Muskateller、香油膏、β－Damascone、波蒡痝牛兒苗油、水楊酸環乙酯、Vertofix Coeur、Iso－E－Super、Fixolide NP、煤地衣基(Evernyl)、Iraldein γ、苯乙酸乙酯牻牛兒苗酯、乙酸苄酯、氧化玫瑰素、Romillat、Irotyl及Floramat、它們係單獨使用或混合使用。
劑量依所要芳香強度而定，且宜在5~15重量%，特宜在8~12重量%範圍。
所用香料要比在凝膠體中的芳香劑耐八得多。
也可在本發明及藥劑中加烯磺酸塩、醚硫酸塩及/或界面張力減少劑，特別是酸甲基牛磺素當作具有自淨作用的起泡劑。
為了防止該藥劑乾掉，該藥劑可另外含有(宜在5~15重量%的)脂肪族的二元、寡元或多元羥基化合物或其醚或由以下之物選出者：甘油、1,3－二羥基丙烷、1,3－或1,4－二羥基丁烷、1,3－二羥基異丁烷及/或五赤蘚糖。
如果要的話，此配方還可加入塩，例如硫酸鈉，以提高溶解速度。塩比例可高達10重量%，且宜高達5重量%。本發明的藥劑可用衛生方式不接觸與便盆接合(且可能受污染的)裝置而施覆並更新。
本發明藥劑的一主要優點在於，可依使用者意願一份份地釋出。如果使用者希望作更密集的清洗或廁所常常使用，且可對應地加重劑量。
本發明的藥劑也可用簡單方式同時施到衛生物品的各不同位置，例如在便盆右側左側達成均勻清淨效果。
所達成之附著性，在該衛生物品上，即使施在一垂直面上也是很好，使該藥劑甚至在沖刷水流的附加力量作用下也不會脫離。
本發明的衛生劑在較多次沖刷過程後才沖掉。沖刷過程的次數當然依各衛生劑的組成、施覆量及所施覆的衛生劑的幾何性質而定。
本發明的藥劑宜為一種軟膏狀糊狀及/或乳霜式及/或液晶式凝膠體，它宜具六方晶系構造，此凝膠體大致穩定，因此不會往下跑或滴落。
此凝膠體的附著性及形狀，儘管因水沖刷造成很大的能量(摩擦、變形)仍保持不變。此糊狀凝膠體宜含1~20重量%的漂白劑、約1重量%~25重量%(特別是5~15重量%)的芳香劑、1重量%~20重量%(特別是5~10重量%)的陰離子式界面張力減少劑、20重量%~40重量%的附著性賦與劑、1~20重量%間的保濕劑、0~1重量%的增稠劑、及0重量%~5重量%(且宜0~1重量%)的防腐劑、及約35~65重量%的水。
在此較佳實施例中，特別用烯磺酸塩、甲基牛磺素及醚硫酸塩當作陰離子界面活性減少劑。
當作陰離子式界面張力減少劑而同時有起泡劑作用者，顯示有效者特別是：烷基(C1 2
~C1 4
)聚乙基乙二醇(2EO)醚硫酸塩－三異丙醇銨塩。這種陰離子式界面活性減少界較佳，因為它在有烯磺酸塩或牛磺素存在時，也不會呈較高濃度跑出。
烷基(C1 6
~C1 8
)－乙氧酸塩(30EO)及烷基(C22)乙氧酸塩(35EO)宜當作附著性賦與劑及非離子性界面張力減少劑使用。此藥劑另含(宜為0~3重量%的)氧化胺，例如氧化椰子酸醯胺丙基二甲基胺(35%)(它由Rewo/Goldschmidt產銷，當作泡沫穩定劑，商品名稱Rewominox B204)及0~2重量%稠化劑(例如一種多醣，特別是一種黃素膠，例如由Rhodia產銷，商品名稱Rhodopol T)，所用防腐劑舉例而言，可用異噻唑酮衍生物。
此凝膠體宜可經由擠筒、注射、或藥筒方式放入便盆並流在該處，以附著供多次先後相隨的沖刷過程使用。
這種糊狀凝膠體在一Haake粘度劑、System Platte－Kegel Semsor PK 51°，剪刀降25秒－ 1
及20℃要測定的粘度至少要15,000mPas，一般至少50,000mPas，且宜至少90,000mPas特宜至少110,000mPas。
本發明在以下利用一實施例及一比較實驗說明。
粘性在20℃時的120,000mPas(Haake粘度計，System Platte－Kegel,Senson PK 51°,剪力降25秒－ 1
)所用烷基(C22)乙醇酸塩(35EO)係用廠商Dr.W.Kolb公司的Imbentim V001/99，所用烷基(C16~C18)乙醇酸塩(30EO)為廠商Dr.W.Kolb公司的Imbentim 1 68S/300，所用烷基(C12－C14)聚乙烯乙二醇(2EO)醚硫酸塩三異丙醇銨塩為廠商Condea公司的Marlinat 242/90 T，所用香精為廠商Quest International的Citrix Extra F548 373。
本發明的藥劑一直到完全溶解為止，凝膠體表面光滑透明，即使每天沖四次的低沖刷頻數亦然，溶解過程也和沖刷頻數無關。
製造配方1的凝膠體，在室內溫度及白日光下作8週之沈積。由此製造0.5%水溶液並利用測試條測定H2
O2
濃度。
所用證明方法係為過氧化物試驗Peroxide－Test“Merckoquant 1.10011”在此它係一種酶試驗，其中過氧化酶(POD)將過氧化物的氧傳到一有機還原氧化指示物並變成藍色氧化產品。
在此比起剛製的漂白劑凝膠體來，未發現H2
O2
還原情事。
此試驗顯示漂白劑在此藥劑中的沈積(保存)穩定性。
Claims (12)
- 一種用於作清洗及/或消毒及/或釋出芳香劑的附著性衛生劑，該衛生劑直接施到衛浴物品上，附著在該處，在較多數的沖刷過程後才會沖刷掉，且該衛生劑含有溶劑、界面張力減少劑(Tenside)及一種附著性賦與劑，由會釋出氧的藥劑選出的一種漂白劑，其中該衛生劑為一種液體結晶凝膠體。
- 如申請專利範圍第1項之附著性衛劑，其中：該衛生劑粘度至少15,000mPas(其測量用一種哈克粘度劑測，板錐系統，感測器PK 51°，在剪力降25/秒及室溫測)。
- 如申請專利範圍第1或第2項之附著性衛劑，其中：該溶劑為水。
- 如申請專利範圍第1或第2項之附著性衛劑，其中：該附著性賦與劑由非離子性界面強力減少劑構成。
- 如申請專利範圍第1或第2項之附著性衛劑，其中：該附著性賦與劑由非離子性乳化劑構成。
- 如申請專利範圍第1或第2項之附著性衛劑，其中：更包含以下之物的至少一種：稠化劑、染劑、防腐劑、芳香劑、漂白劑的穩定劑、漂白劑活化劑。
- 如申請專利範圍第1或第2項之附著性衛劑，其中：該漂白劑由以下之物選出過氧化水合物酸塩、過硼酸塩、過硫酸塩、過氧重硫酸塩、過氧化磷酸塩、過氧化硝 酸塩、過硫酸塩、硝酸塩、二硫代亞硫酸塩、次氯酸塩、氯酸塩、過錳酸塩，這些塩各呈其相關酸的鹼金屬塩、銨塩、或鹼土金屬塩形式；二氯異氰尿酸塩、三氯異氰尿酸塩、二溴異氰尿酸塩、三溴異氰尿酸塩、氯-溴海因、氯化之三鹼金屬磷酸塩，這些塩各呈其相關酸的鹼金屬塩、銨塩、鹼土金屬塩或呈其自由酸形式；過氧化氫、有機過氧化物、碘、碘PVP(聚乙烯基吡咯烷酮-碘)、溴單氯胺、氯化磷酸三鈉、單氯胺、雙氯胺、[(單氯)-四(單鈣二氯)]五異氰尿酸塩、1,3-二氯-5,5-二甲基因丹酮、對-甲苯磺酸二氯醯胺、三氯蜜胺、N-氯胺、N-氯琥珀醯胺、N,N-二氯偶氮二碳醯胺、N-氯乙醯脲、N,N-二氯雙脲、氯化之二氰二醯胺及二氯乙二醇脲。
- 如申請專利範圍第1或第2項之附著性衛劑，其中：該漂白劑的量在1~20重量%。
- 如申請專利範圍第8項之附著性衛劑，其中：該漂白劑的量為2-15重量%。
- 如申請專利範圍第9項之附著性衛劑，其中：該漂白劑的量為5-10重量%。
- 如申請專利範圍第6項之附著性衛劑，其中：該漂白劑的穩定劑，由尿素、巴比土酸、嫌水性化合物及錯塩形成物選出。
- 如申請專利範圍第1或第2項之衛生劑，其中：該衛生劑更包含5~15%重量的香水當作芳香劑。
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- 2005-11-03 US US11/791,402 patent/US20080255017A1/en not_active Abandoned
- 2005-11-03 EP EP05803485A patent/EP1817399B1/de not_active Expired - Lifetime
- 2005-11-03 WO PCT/EP2005/011770 patent/WO2006056301A1/de not_active Ceased
- 2005-11-03 DE DE502005010088T patent/DE502005010088D1/de not_active Expired - Lifetime
- 2005-11-03 AU AU2005309096A patent/AU2005309096A1/en not_active Abandoned
- 2005-11-07 TW TW094138945A patent/TWI402339B/zh not_active IP Right Cessation
- 2005-11-21 AR ARP050104867A patent/AR051773A1/es active IP Right Grant
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Also Published As
| Publication number | Publication date |
|---|---|
| US20080255017A1 (en) | 2008-10-16 |
| EP1817399B1 (de) | 2010-08-11 |
| AR051773A1 (es) | 2007-02-07 |
| TW200630480A (en) | 2006-09-01 |
| AU2005309096A1 (en) | 2006-06-01 |
| DE102004056554A1 (de) | 2006-05-24 |
| WO2006056301A1 (de) | 2006-06-01 |
| DE502005010088D1 (de) | 2010-09-23 |
| EP1817399A1 (de) | 2007-08-15 |
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| MM4A | Annulment or lapse of patent due to non-payment of fees |