JP4267075B2 - Laundry detergent compositions having cellulosic polymers to provide appearance and integrity benefits to fabrics washed therewith - Google Patents
Laundry detergent compositions having cellulosic polymers to provide appearance and integrity benefits to fabrics washed therewith Download PDFInfo
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- JP4267075B2 JP4267075B2 JP53016998A JP53016998A JP4267075B2 JP 4267075 B2 JP4267075 B2 JP 4267075B2 JP 53016998 A JP53016998 A JP 53016998A JP 53016998 A JP53016998 A JP 53016998A JP 4267075 B2 JP4267075 B2 JP 4267075B2
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- alkyl
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- sulfate
- cellulose ether
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- 239000000203 mixture Substances 0.000 title claims description 102
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- 239000003599 detergent Substances 0.000 title claims description 80
- 230000008901 benefit Effects 0.000 title claims description 11
- 229920000642 polymer Polymers 0.000 title description 33
- 229920003086 cellulose ether Polymers 0.000 claims description 38
- -1 sodium alkyl sulfate Chemical class 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 20
- 239000004094 surface-active agent Substances 0.000 claims description 20
- 238000004140 cleaning Methods 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical class O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
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- 239000011591 potassium Substances 0.000 claims description 10
- 238000006467 substitution reaction Methods 0.000 claims description 10
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
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- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
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- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims 1
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- 150000001340 alkali metals Chemical class 0.000 description 3
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- 238000010191 image analysis Methods 0.000 description 3
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- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical class OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 2
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 2
- FAGGUIDTQQXDSJ-UHFFFAOYSA-N 3-benzoylazepan-2-one Chemical compound C=1C=CC=CC=1C(=O)C1CCCCNC1=O FAGGUIDTQQXDSJ-UHFFFAOYSA-N 0.000 description 2
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- 125000002877 alkyl aryl group Chemical group 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 2
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- 239000002304 perfume Substances 0.000 description 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229940044652 phenolsulfonate Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229940071207 sesquicarbonate Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- OAAFQHZBMJODBO-UHFFFAOYSA-J tetrasodium;hydrogen peroxide;phosphonato phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].OO.[O-]P([O-])(=O)OP([O-])([O-])=O OAAFQHZBMJODBO-UHFFFAOYSA-J 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
-
- 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
- C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/223—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin oxidised
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
-
- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
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- 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
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
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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
- 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
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- Detergent Compositions (AREA)
Description
技術分野
本発明は、外観および完全性の利益をこの組成物から調製された洗浄液中で洗濯された布帛および布類に付与するために特定の種類の変性セルロースエーテル物質を含有する液体または粒状形のいずれかのヘビーデューティー洗濯洗剤組成物に関する。
背景技術
勿論、布帛および布類、例えば、着古した衣料品および衣服を使用し且つ洗濯するくり返しサイクルは、不可避的に、そのように使用され且つ洗濯された布帛および布類アイテムの外観および完全性に悪影響を及ぼすであろうことは周知である。布帛および布類は、経時的に使用と共に着古されるものである。布帛および布類の洗濯は、通常の使用時にその中およびその上に蓄積する汚れおよびしみを除去することが必要である。しかしながら、多くのサイクルにわたっての洗濯操作自体は、このような布帛および布類の完全性および外観の劣化を一層悪くし且つ劣化の一因となることがある。
布帛完全性および外観の劣化は、数種の方式で現われることがある。短繊維は、洗濯の機械的作用によって織成／編成布帛／布類構造物から追い出される。これらの追い出された繊維は、布帛の表面上で可視であり且つ布帛の新しさの外観を減少する糸くず（lint）、毛羽（fuzz）または「毛玉（pill）」を形成することがある。更に、布帛および布類の反復洗濯、特に漂白剤含有洗濯製品での布帛および布類の反復洗濯は、布帛および布類から染料を除去することがあり且つ減少された色強度の結果および多くの場合には色相または色彩の変化の結果、退色された着古された外観を付与することがある。
前記のことからすれば、明らかに、このような洗剤製品を使用して洗濯される布帛および布類の繊維とそれら自体関連し、それによって外観を劣化する洗濯布帛／布類の傾向を減少するか最小限にするであろう洗濯洗剤製品に添加できる物質を同定する継続的ニーズがある。勿論、このような洗剤製品添加剤物質は、布帛クリーニング機能を遂行する洗濯洗剤の能力を不当に妨害せずに布帛外観および完全性に利益を与えることができるべきである。本発明は、この所望の方式で遂行する特定の種類のセルロース系物質を含有する洗剤組成物に係わる。
発明の開示
本発明の洗濯洗剤組成物は、洗剤界面活性剤約１〜８０重量％、有機または無機洗浄性ビルダー約０．１〜８０重量％および特定の種類の変性セルロースエーテル布帛処理剤約０．１〜８重量％を含む。洗剤界面活性剤および洗浄性ビルダー物質は、通常の洗濯洗剤製品で有用なもののいかなるものであることもできる。変性セルロースエーテル物質は、分子量約１０，０００〜２，０００，０００を有し且つ「発明を実施するための最良の形態」セクションに後述の一般式No.Ｉ、IIおよびIIIに対応する反復置換アンヒドログルコース単位を含むものである（後述の一般式中、置換基は置換セルロースエーテル重合体を生成するために反復するアンヒドログルコース環上の特定の位置で示す。これは、例示目的のみのためであること、およびこのような置換基はアンヒドログルコースの炭素原子のいかなるものの上でも見出されることがあることを理解すべきである）。
１つの有用な種類のセルロースエーテルは、疎水的に変性された非イオン物質からなる（アンヒドログルコース環アルキル置換はセルロースエーテルの約０．１〜５重量％である）。環置換基は、約１〜２０モルの量でアルコキシ化する。
第二の有用な種類のセルロースエーテルは、セルロースエーテルの約０．１〜５重量％のアンヒドログルコース環アルキル置換を有していてもよい陽イオンセルロースエーテル物質からなる。アンヒドログルコース環置換基は、アルコキシ化約１〜２０モルおよび第四級アンモニウム陽イオン部分約０．００５〜０．５モルを含有する。
第三の種類のセルロースエーテルは、セルロースエーテルの約０．１〜５重量％のアンヒドログルコース環アルキル置換を有していてもよい陰イオンセルロースエーテル物質からなる。また、このような陰イオン物質中のアンヒドログルコース環は、カルボキシメチル置換度約０．０５〜２．５を有する。非イオン変性セルロースエーテルと陽イオン変性セルロースエーテルと陰イオン変性セルロースエーテルとの組み合わせも、使用できる。
方法の態様においては、本発明は、布帛および布類を、有効量のここに記載の洗剤組成物から調製されるか、このような組成物の個々の成分から調製される水性洗浄または処理液中で洗濯するか処理することに関する。布帛および布類をこのような洗浄液中で洗濯した後、すすぎ、乾燥することは、布帛外観上の利益をそのように処理された布帛および布類物品に付与する。このような利益としては、改善された全外観、毛玉／毛羽減少、退色防止、改善された耐摩耗性、および／または高められた柔軟性が挙げることができる。
発明を実施するための最良の形態
前記のように、本発明の洗濯洗剤組成物は、必須に、洗剤界面活性剤、洗浄性ビルダーおよび布帛および布類を洗濯するために洗剤組成物の使用時に布帛外観および完全性を高めるのに役立つ或る変性セルロースエーテル布帛処理剤を含有する。これらの必須の洗剤組成物成分の各々、並びにこのような組成物用の任意成分およびこのような組成物の使用法は、次の通り詳細に記載する。与えるすべての％および比率は、特に断らない限り、重量基準である。
Ａ）洗剤界面活性剤
本発明の洗剤組成物は、必須に洗剤界面活性剤約１〜８０重量％を含む。好ましくは、このような組成物は、この界面活性剤約５〜５０重量％を含む。利用する洗剤界面活性剤は、陰イオン界面活性剤、非イオン界面活性剤、双性界面活性剤、両性界面活性剤または陽イオン界面活性剤型を有することができ、またはこれらの型の相容性混合物からなることができる。ここで有用な洗剤界面活性剤は、１９７２年５月２３日発行のノリスの米国特許第３，６６４，９６１号明細書、１９７５年１２月３０日発行のローリン等の米国特許第３，９１９，６７８号明細書、１９８０年９月１６日発行のコックレルの米国特許第４，２２２，９０５号明細書、および１９８０年１２月１６日発行のマーフイーの米国特許第４，２３９，６５９号明細書に記載されている。これらの特許のすべては、ここに参考文献として編入する。すべての界面活性剤のうち、陰イオン界面活性剤および非イオン界面活性剤が好ましい。
有用な陰イオン界面活性剤は、単独で数種の異なる型を有することができる。例えば、高級脂肪酸の水溶性塩、即ち、「石鹸」は、本組成物で有用な陰イオン界面活性剤である。これとしては、アルカリ金属石鹸、例えば、炭素数約８〜約２４、好ましくは炭素数約１２〜約１８の高級脂肪酸のナトリウム塩、カリウム塩、アンモニウム塩、およびアルキロールアンモニウム塩が挙げられる。石鹸は、油脂の直接ケン化により、または遊離脂肪酸の中和により生成できる。ヤシ油およびタローに由来する脂肪酸の混合物のナトリウム塩およびカリウム塩、即ち、ナトリウムまたはカリウムのタロー石鹸およびココナツ石鹸が、特に有用である。
ここで使用するのに好適である追加の非石鹸陰イオン界面活性剤としては、分子構造中に炭素数約１０〜約２０のアルキル基およびスルホン酸エステル基または硫酸エステル基を有する有機硫酸反応生成物の水溶性塩、好ましくはアルカリ金属塩、およびアンモニウム塩も挙げられる（「アルキル」なる用語にはアシル基のアルキル部分が包含される）。この群の合成界面活性剤の例は、（ａ）アルキル硫酸ナトリウム，アルキル硫酸カリウムおよびアルキル硫酸アンモニウム、特にタローまたはヤシ油のグリセリドを還元することにより生成されたものなどの高級アルコール（Ｃ8〜Ｃ18炭素原子）を硫酸化することによって得られるもの；（ｂ）アルキルポリエトキシレート硫酸ナトリウム、アルキルポリエトキシレート硫酸カリウムおよびアルキルポリエトキシレート硫酸アンモニウム、特にアルキル基が１０〜２２個、好ましくは１２〜１８個の炭素原子を有し且つポリエトキシレート鎖が１〜１５個、好ましくは１〜６個のエトキシレート部分を含有するもの；（ｃ）アルキル基が直鎖または分枝鎖配置に約９〜約１５個の炭素原子を有するアルキルベンゼンスルホン酸ナトリウムおよびアルキルベンゼンスルホン酸カリウム、例えば、米国特許第２，２２０，０９９号明細書および第２，４７７，３８３号明細書に記載の種類のものである。アルキル基中の炭素原子の平均数が約１１〜１３である線状直鎖アルキルベンゼンスルホネート（略称Ｃ11〜13ＬＡＳ）が、特に価値がある。
好ましい非イオン界面活性剤は、式 Ｒ1（ＯＣ2Ｈ4）nＯＨ（式中、Ｒ1はＣ10〜Ｃ16アルキル基またはＣ8〜Ｃ12アルキルフェニル基であり、ｎは３〜約８０である）のものである。Ｃ12〜Ｃ15アルコールとアルコール１モル当たり約５〜約２０モルのエチレンオキシドとの縮合物、例えば、アルコール１モル当たり約６．５モルのエチレンオキシドと縮合されたＣ12〜Ｃ13アルコールが、特に好ましい。
追加の好適な非イオン界面活性剤としては、式
Ｂ）洗浄性ビルダー
また、本発明の洗剤組成物は、必須に、洗浄性ビルダー約０．１〜８０重量％も含む。好ましくは、液体形のこのような組成物は、ビルダー成分約１〜１０重量％を含むであろう。好ましくは、粒状形のこのような組成物は、ビルダー成分約１〜５０重量％を含むであろう。洗浄性ビルダーは、技術上周知であり且つ、例えば、リン酸塩並びに各種の有機および無機無リンビルダーからなることができる。
ここで有用な水溶性無リン有機ビルダーとしては、各種のアルカリ金属、アンモニウムおよび置換アンモニウムのポリ酢酸塩、カルボン酸塩、ポリカルボン酸塩およびポリヒドロキシスルホン酸塩が挙げられる。ポリアセテートおよびポリカルボキシレートビルダーの例は、エチレンジアミン四酢酸、ニトリロ三酢酸、オキシジコハク酸、メリト酸、ベンゼンポリカルボン酸、およびクエン酸のナトリウム塩、カリウム塩、リチウム塩、アンモニウム塩および置換アンモニウム塩である。ここで使用するのに好適な他のポリカルボキシレートは、クラッチフィールドに１９７９年３月１３日発行の米国特許第４，１４４，２２６号明細書およびクラッチフィールド等に１９７９年３月２７日発行の米国特許第４，２４６，４９５号明細書（それらの両方ともここに参考文献として編入）に記載のポリアセタールカルボキシレートである。特に好ましいポリカルボキシレートビルダーは、オキシジスクシネートおよび１９８７年５月５日発行のブッシュ等の米国特許第４，６６３，０７１号明細書（その開示をここに参考文献として編入）に記載のタルトレートモノスクシネートとタルトレートジスクシネートとの組み合わせを含むエーテルカルボキシレートビルダー組成物である。
好適な無リン無機ビルダーの例としては、シリケート、アルミノシリケート、ボレートおよびカーボネートが挙げられる。ナトリウムおよびカリウムの炭酸塩、重炭酸塩、セスキ炭酸塩、四ホウ酸塩１０水和物、およびＳｉＯ2対アルカリ金属酸化物の重量比約０．５〜約４．０、好ましくは約１．０〜約２．４を有するシリケートが特に好ましい。ゼオライトを含めてアルミノシリケートも好ましい。このような物質および洗浄性ビルダーとしての用途は、コルキル等の米国特許第４，６０５，５０９号明細書（その開示をここに参考文献として編入）により十分に論じられている。また、結晶性層状シリケート、例えば、コルキル等の米国特許第４，６０５，５０９号明細書（ここに参考文献として編入）に論ずるものは、本発明の洗剤組成物で使用するのに好適である。
Ｃ）変性セルロース系重合体
本発明の洗剤組成物の第三必須成分は、１種以上の変性セルロース系重合体からなる。このような物質は、多数の外観上の利益を、このような変性セルロース系物質を含有する洗剤組成物から調製された水性洗浄液中で洗濯された布帛および布類に付与することが見出された。このような布帛外観上の利益としては、例えば、洗濯された布帛の改善された全外観、毛玉および毛羽の形成の減少、退色に対する保護、改善された耐摩耗性などが挙げることができる。本発明の組成物および方法で使用する変性セルロース系重合体は、このような物質が配合されている洗濯洗剤組成物によって与えられるクリーニング性能を許容できる程にほとんどまたは何も損失せずに、このような布帛外観上の利益を与えることができる。
ここで有用な変性セルロース系重合体は、非イオン型、陽イオン型または陰イオン型を有していてもよく、または本組成物の変性セルロース系重合体成分は、これらのセルロース系重合体型の組み合わせからなっていてもよい。本組成物の変性セルロース系重合体成分は、一般に、組成物の約０．１〜８重量％を占めるであろう。より好ましくは、このような変性セルロース系物質は、組成物の約０．５〜４重量％、最も好ましくは約１％〜３％を占めるであろう。
ここで使用するのに好適な１つの種類の変性セルロース系重合体は、分子量約１０，０００〜２，０００，０００、好ましくは約５０，０００〜１，０００，０００を有する疎水的に変性された非イオンセルロースエーテルからなる。疎水的に変性された非イオン物質は、次の通り一般式No.Ｉに対応する反復置換アンヒドログルコース単位を有する。
一般式No.Ｉ中、ＲはＨとＣ8〜Ｃ24アルキル、好ましくはＣ8〜Ｃ16アルキルとの組み合わせである。重合体のアンヒドログルコース環上のアルキル置換は、重合体物質の約０．１〜５重量％、より好ましくは約０．２〜２重量％である。また、一般式No.Ｉ中、Ｒ1はＨまたはメチルであり；ｘは約１〜２０、好ましくは約１〜１０である。
一般式No.Ｉの疎水的に変性された非イオンセルロースエーテルとしては、市販のものが挙げられ且つ市販の物質の通常の化学変性によって製造できる物質も挙げられる。一般式No.Ｉ型の市販のセルロースエーテルとしては、ハーキュレス・インコーポレーテッドによって市販されているポリサーフ（Polysurf）６７、ナトロゾル・プラス（Natrosol Plus）４３０およびナトロゾル・プラス３３０が挙げられる。
ここで使用するのに好適な別の種類の変性セルロース系重合体は、疎水的に変性してもよくまたは変性しなくともよく、分子量約１０，０００〜２，０００，０００、より好ましくは約１０，０００〜１，０００，０００を有する特定の陽イオンセルロースエーテルを含んでなる。これらの陽イオン物質は、次の通り一般式No.IIに対応する反復置換アンヒドログルコース単位を有する。
一般式No.II中、ＲはＨまたはＣ8〜Ｃ24アルキル、好ましくはＣ8〜Ｃ16アルキルである。重合体のアンヒドログルコース環上のアルキル置換は、重合体物質の約０．１〜５重量％、より好ましくは約０．２〜２重量％である。また、一般式No.II中、Ｒ2はＣＨ2ＣＨＯＨＣＨ2またはＣ8〜Ｃ24アルキル、好ましくはＣ8〜Ｃ16アルキルである。Ｒ3、Ｒ4およびＲ5は各々独立にメチル、エチルまたはフェニルである。Ｒ6はＨまたはメチルである。更に、一般式II中、ｘは約１〜２０、好ましくは約１〜１０であり；ｙは約０．００５〜０．５、好ましくは約０．００５〜０．１であり；ＺはＣｌ-またはＢｒ-である。
同様に、一般式No.IIの陽イオンセルロースエーテルとしては、市販のものが挙げられ且つ更に市販の物質の通常の化学変性によって製造できる物質が挙げられる。一般式No.II型の市販のセルロースエーテルとしては、ユニオン・カーバイド・コーポレーションによって市販されているＪＲ３０Ｍ、ＪＲ４００、ＪＲ１２５、ＬＲ４００およびＬＫ４００ウケア（UCARE）重合体が挙げられる。ここで使用するのに好適な第三の種類の変性セルロース重合体は、疎水的に変性してもよくまたは変性しなくともよく、分子量約１０，０００〜２，０００，０００、より好ましくは約５０，０００〜１，０００，０００を有する特定の陰イオンセルロースエーテルからなる。これらの陰イオン物質は、次の通り一般式No.IIIに対応する反復置換アンヒドログルコース単位を有する。
一般式No.III中、ＲはＨと（ａ）ＣＨ2ＣＯＯＡと場合によって（ｂ）Ｃ2〜Ｃ24アルキル、好ましくはＣ2〜Ｃ16アルキルとの組み合わせであり、ＡはＮａまたはＫである。重合体のアンヒドログルコース環上のアルキル置換は、重合体物質の約０．１〜５重量％、より好ましくは約０．２〜２重量％である。また、陰イオンセルロースエーテルは、カルボキシメチル置換度約０．０５〜２．５、より好ましくは約０．１〜１．０を有する。
また、一般式No.IIIの陰イオンセルロースエーテルとしては、市販の物質が挙げられ且つ更に市販の物質の通常の化学変性によって製造できるものが挙げられる。一般式No.III型の市販のセルロースエーテルとしては、ハーキュレス・インコーポレーテッドによって市販されているＣＭＣ７Ｈ、ＣＭＣ９９−７Ｍ、およびＣＭＣ９９−７Ｌ、およびペン・カルボースによって市販されているＣＭＣ Ｄ７２、ＣＭＣ Ｄ６５およびＣＭＣ ＤＨＴが挙げられる。
ここで有用な市販のセルロースエーテル物質は、それら自身、好適な天然セルロス源から誘導される。このような源としては、例えば、綿リンターおよび他の植物組織が挙げられる。本発明で使用する変性セルロースエーテルは、一般に、すべて水溶性物質である。それゆえ、それらは、所望ならば、このようなセルロース系重合体の水溶液の形で洗剤組成物調製で利用できる。
Ｄ）任意の洗剤成分
前記の必須の界面活性剤、ビルダーおよび変性セルロースエーテルに加えて、本発明の洗剤組成物は、いかなる数の追加の任意成分も包含できる。これらとしては、通常の洗剤組成物成分、例えば、漂白剤および漂白活性化剤、酵素および酵素安定剤、増泡剤または抑泡剤、曇り防止剤および耐食剤、汚れ沈殿防止剤、防汚剤、殺菌剤、ｐＨ調整剤、非ビルダーアルカリ度源、キレート化剤、有機および無機充填剤、溶媒、ハイドロトロープ、光学増白剤、染料および香料が挙げられる。
本発明の洗剤組成物への配合に好ましい任意成分は、漂白剤、例えば、過酸素漂白剤を含む。このような過酸素漂白剤は、性状が有機または無機であってもよい。無機過酸素漂白剤は、しばしば、漂白活性化剤と併用される。
有用な有機過酸素漂白剤は、ペルカルボン酸漂白剤およびそれらの塩を包含する。この種の漂白剤の好適な例としては、モノペルオキシフタル酸マグネシウム６水和物、ｍ−クロロ過安息香酸のマグネシウム塩、４−ノニルアミノ−４−オキソペルオキシ酪酸およびジペルオキシドデカンジオン酸が挙げられる。このような漂白剤は、１９８４年１１月２０日発行のハートマンの米国特許第４，４８３，７８１号明細書、１９８５年２月２０日公開のバンクス等の欧州特許出願ＥＰ−Ａ第１３３，３５４号明細書、および１９８３年１１月１日発行のチャング等の米国特許第４，４１２，９３４号明細書に開示されている。高度に好ましい漂白剤としては、バーンズ等に１９８７年１月６日発行の米国特許第４，６３４，５５１号明細書に記載のような６−ノニルアミノ−６−オキソペルオキシカプロン酸（ＮＡＰＡＡ）も挙げられる。
無機過酸素漂白剤も、一般に本発明の洗剤組成物で粒状形で使用してもよい。無機漂白剤は、事実、好ましい。このような無機過酸素化合物としては、アルカリ金属過ホウ酸塩および過炭酸塩物質が挙げられる。例えば、過ホウ酸ナトリウム（例えば、１水和物または４水和物）は、使用できる。好適な無機漂白剤としては、炭酸ナトリウム過酸化水素化物または炭酸カリウム過酸化水素化物および均等の「ペルカーボネート」漂白剤、ピロリン酸ナトリウム過酸化水素化物、尿素過酸化水素化物、および過酸化ナトリウムも挙げることができる。ペルサルフェート漂白剤〔例えば、デュポンによって商業上生産されているオキソン（OXONE）〕も、使用できる。しばしば、無機過酸素漂白剤は、シリケート、ボレート、サルフェートまたは水溶性界面活性剤で被覆するであろう。例えば、被覆ペルカーボネート粒子は、ＦＭＣ、ソルベイ・インターロックス、トーカイ・デンカ、デグッサなどの各種の商業的源から入手できる。
無機過酸素漂白剤、例えば、ペルボレート、ペルカーボネートなどは、好ましくは、漂白活性化剤と組み合わせ、このことは漂白活性化剤に対応するペルオキシ酸の水溶液中でのその場生成（即ち、布帛洗濯／漂白のために本組成物の使用時）をもたらす。活性化剤の各種の非限定例は、マオ等に１９９０年４月１０日発行の米国特許第４，９１５，８５４号明細書およびチャング等に１９８３年１１月１日発行の米国特許第４，４１２，９３４号明細書に開示されている。ノナノイルオキシベンゼンスルホネート（ＮＯＢＳ）およびテトラアセチルエチレンジアミン（ＴＡＥＤ）活性化剤が典型であり且つ好ましい。それらの混合物も、使用できる。ここで有用な他の典型的な漂白剤および活性化剤については前記米国特許第４，６３４，５５１号明細書も参照。
他の有用なアミド誘導漂白活性化剤は、式
Ｒ1Ｎ（Ｒ5）Ｃ（Ｏ）Ｒ2Ｃ（Ｏ）Ｌまたは
Ｒ1Ｃ（Ｏ）Ｎ（Ｒ5）Ｒ2Ｃ（Ｏ）Ｌ
（式中、Ｒ1は炭素数約６〜約１２のアルキル基であり、Ｒ2は炭素数１〜約６のアルキレンであり、Ｒ5はＨまたは炭素数約１〜約１０のアルキル、アリールまたはアルカリールであり、Ｌは好適な離脱基である）のものである。離脱基は、過加水分解陰イオンによる漂白活性化剤上への求核攻撃の結果として漂白活性化剤から置換される基である。好ましい離脱基は、フェノールスルホネートである。
前記式の漂白活性化剤の好ましい例としては、前記米国特許第４，６３４，５５１号明細書に記載のような（６−オクタンアミドカプロイル）オキシベンゼンスルホネート、（６−ノナンアミドカプロイル）オキシベンゼンスルホネート、（６−デカンアミドカプロイル）オキシベンゼンスルホネート、およびそれらの混合物が挙げられる。
別の種類の有用な漂白活性化剤は、１９９０年１０月３０日発行のホッジ等の米国特許第４，９６６，７２３号明細書（ここに参考文献として編入）に開示のベンゾオキサジン型の活性化剤からなる。ベンゾオキサジン型の高度に好ましい活性化剤は、式
なお別の種類の有用な漂白活性化剤としては、アシルラクタム活性化剤、特に式
利用するならば、過酸素漂白剤は、一般に、本発明の洗剤組成物の約２〜３０重量％を占めるであろう。より好ましくは、過酸素漂白剤は、組成物の約２〜２０重量％を占めるであろう。最も好ましくは、過酸素漂白剤は、本組成物の約３〜１５重量％程度で存在するであろう。利用するならば、漂白活性化剤は、本発明の洗剤組成物の約２〜１０重量％を占めることができる。しばしば、活性化剤は、漂白剤対活性化剤のモル比が約１：１から１０：１、より好ましくは約１．５：１から５：１であるように使用される。
本発明の洗剤組成物で高度に好ましい別の任意成分は、洗剤酵素成分である。酵素は、基体からのタンパク質をベースとするしみ、炭水化物をベースとするしみ、またはトリグリセリドをベースとするしみの除去、布帛洗濯における逃避染料移動の防止および布帛復元を含めて各種の目的で、本発明の洗剤組成物に配合できる。好適な酵素としては、いかなる好適な起源、例えば、植物、動物、細菌、真菌および酵母起源のプロテアーゼ、アミラーゼ、リパーゼ、セルラーゼ、ペルオキシダーゼ、およびそれらの混合物が挙げられる。好ましい選択は、因子、例えば、ｐＨ活性および／または安定性最適条件、熱安定性、活性洗剤、ビルダーなどに対する安定性によって影響される。この点で、細菌または真菌酵素、例えば、細菌アミラーゼおよびプロテアーゼ、および真菌セルラーゼが、好ましい。
ここで使用する「洗剤酵素」は、洗濯洗剤組成物中でクリーニング、しみ抜きまたは他の点で有益な効果を有する酵素を意味する。洗濯目的に好ましい酵素としては、限定せずに、プロテアーゼ、セルラーゼ、リパーゼ、アミラーゼおよびペルオキシダーゼが挙げられる。
酵素は、通常、洗剤組成物に「クリーニング有効量」を与えるのに十分な量で配合する。「クリーニング有効量」なる用語は、布帛などの基体上でクリーニング、しみ抜き、汚れ除去、増白、脱臭、または鮮度改良効果を生ずることができるいかなる量も意味する。現在市販の製剤の実用に関しては、典型的な量は、洗剤組成物１ｇ当たり活性酵素約５mgまで（重量）、より典型的には０．０１mg〜３mgである。換言すれば、本組成物は、典型的には、市販の酵素製剤０．００１〜５重量％、好ましくは０．０１〜１重量％を含むであろう。プロテアーゼ酵素は、通常、このような市販の製剤に組成物１ｇ当たり０．００５〜０．１アンソン（Anson）単位（ＡＵ）の活性を与えるのに十分な量で存在する。より多い活性成分量は、高濃縮洗剤処方物で望ましいことがある。
プロテアーゼの好適な例は、枯草菌およびB.licheniformisの特定の菌株から得られるズブチリシンである。１つの好適なプロテアーゼは、デンマークのノボ・インダストリーズＡ／Ｓ（以下「ノボ」）によって開発され且つエスペラーゼ（ESPERASE▲Ｒ▼）として販売されている８〜１２のｐＨ範囲全体にわたって最大活性を有するバチルスの菌株から得られる。この酵素および類似の酵素の調製は、ノボへの英国特許第１，２４３，７８４号明細書に記載されている。他の好適なプロテアーゼとしては、ノボからのアルカラーゼ（ALCALASE▲Ｒ▼）およびサビナーゼ（SAVINASE▲Ｒ▼）およびオランダのインターナショナル・バイオ−シンセティックス・インコーポレーテッドからのマキサターゼ（MAXATASE▲Ｒ▼）並びに１９８５年１月９日公開のＥＰ第１３０，７５６Ａ号明細書に開示のようなプロテアーゼＡおよび１９８７年４月２８日公開のＥＰ第３０３，７６１Ａ号明細書および１９８５年１月９日公開のＥＰ第１３０，７５６Ａ号明細書に開示のようなプロテアーゼＢが挙げられる。ノボへのＷＯ第９３１８１４０Ａ号明細書に記載のBacillus sp.ＮＣＩＭＢ４０３３８からの高ｐＨプロテアーゼも参照。プロテアーゼ、１種以上の他の酵素、および可逆プロテアーゼ抑制剤を含む酵素洗剤は、ノボへのＷＯ第９２０３５２９Ａ号明細書に記載されている。他の好ましいプロテアーゼとしては、プロクター・エンド・ギャンブルへのＷＯ第９５１０５９１Ａ号明細書のものが挙げられる。望まれる時には、減少された吸着および増大された加水分解を有するプロテアーゼは、プロクター・エンド・ギャンブルへのＷＯ第９５０７７９１号明細書に記載のように入手できる。ここで好適な洗剤用組換えトリプシン様プロテアーゼは、ノボへのＷＯ第９４２５５８３号明細書に記載されている。
本発明で使用できるセルラーゼとしては、細菌セルラーゼと真菌セルラーゼとの両方が挙げられる（好ましくは、５〜１０のｐＨ最適条件を有する）。
１９８４年３月６日発行のバーベスゴード等の米国特許第４，４３５，３０７号明細書は、Humicola insolensまたはHumicola菌株ＤＳＭ１８００またはアエロモナス属に属するセルラーゼ２１２産生真菌からの好適な真菌セルラーゼ、およびマリン軟体動物（Dolabella Auricula Solander）の肝膵臓から抽出されるセルラーゼを開示している。また、好適なセルラーゼは、英国特許第２．０７５．０２８号明細書、英国特許第２．０９５．２７５号明細書およびＤＥ−ＯＳ第２．２４７．８３２号明細書に開示されている。ケアザイム（CAREZYME▲Ｒ▼）およびセルザイム（CELLUZYME▲Ｒ▼）（ノボ）が特に有用である。ノボへのＷＯ第９１１７２４３号明細書も参照。
洗剤使用に好適なリパーゼ酵素としては、英国特許第１，３７２，０３４号明細書に開示のようなPseudomonas stutzeri ＡＴＣＣ１９．１５４などのPseudomonas群の微生物によって産生されるものが挙げられる。１９７８年２月２４日公開の特開昭５３−２０４８７号公報中のリパーゼも参照。このリパーゼは、日本の名古屋のあまの天野製薬株式会社から商品名リパーゼＰ「アマノ（Amano）」または「アマノ−Ｐ」で入手できる。他の好適な市販のリパーゼとしては、アマノ−ＣＥＳ、Chromobacter viscosum、例えば、日本の田方の東洋醸造株式会社からのChromobacter viscosum var.lipolyticum ＮＲＲＬＢ３６７３からのリパーゼ；米国のＵ．Ｓ．バイオケミカル・コーポレーションおよびオランダのディソイント・カンパニーからのChromobacter viscosumリパーゼ、およびPseudomonas gladioliからのリパーゼが挙げられる。Humicola lanuginosaに由来し且つノボから市販されているリポラーゼ（LIPOLASE▲Ｒ▼）酵素（ＥＰ第３４１，９４７号明細書も参照）は、ここで使用するのに好ましいリパーゼである。
本発明の酵素含有組成物は、場合によって、酵素安定化系約０．００１〜約１０重量％、好ましくは約０．００５〜約８重量％、最も好ましくは約０．０１〜約６重量％を含んでもよい。酵素安定化系は、洗剤酵素と相容性であるいかなる安定化系であることもできる。このような系は、他の処方物活性成分によって固有に与えることができ、または、例えば、処方業者により、または洗剤用酵素の製造業者により別個に添加できる。このような安定化系は、例えば、カルシウムイオン、ホウ酸、プロピレングリコール、短鎖カルボン酸、ボロン酸、およびそれらの混合物からなることができ且つ洗剤組成物の種類および物理的形に応じて異なる安定化問題を扱うように設計される。
Ｅ）洗剤組成物調製
本発明に係る洗剤組成物は、液体、ペーストまたは粒状形であることができる。このような組成物は、所要の濃度の必須成分および任意成分を好適な順序で通常の手段によって合わせることによって調製できる。
粒状組成物は、例えば、一般にベース粒状物成分（例えば、界面活性剤、ビルダー、水など）をスラリーとして合わせ、得られたスラリーを少量の残留水分（５〜１２％）に噴霧乾燥することによって調製する。残りの乾燥成分は、粒状粉末形で回転混合ドラム中で噴霧乾燥粒状物と混合でき且つ液体成分（例えば、必須のセルロース系重合体の有機溶液、酵素、バインダーおよび香料）は、得られた粒状物上に噴霧して完成洗剤組成物を調製できる。本発明に係る粒状組成物は、「コンパクト形」であることもでき、即ち、通常の粒状洗剤より比較的高い密度、即ち、５５０〜９５０ｇ／リットルを有していてもよい。このような場合には、本発明に係る粒状洗剤組成物は、通常の粒状洗剤と比較して少量の「無機充填剤」を含有するであろう。典型的な充填剤塩は、硫酸および塩化物のアルカリ土類金属塩、典型的には硫酸ナトリウムである。「コンパクト」洗剤は、典型的には、充填剤塩１０％以下を含む。
液体洗剤組成物は、必須成分および任意成分を所望の順序で合わせて所要の濃度の成分を含有する組成物を与えることによって調製できる。本発明に係る液体組成物も、「コンパクト形」であることができる。このような場合には、本発明に係る液体洗剤組成物は、通常の液体洗剤と比較して少量の水を含有するであろう。
セルロースエーテル成分の本発明の液体洗剤組成物への添加は、単純に所望のセルロースエーテルの水溶液を液体洗剤に入れることによって達成してもよい。セルロースエーテルは、液体洗剤製品の粘度または他のレオロジー特性を変更できる。それゆえ、使用するハイドロトロープおよび／または溶媒の種類および量を変更することによってセルロースーエーテル添加によってもたらされる液体洗剤製品のレオロジー変化を補償することが必要であることがある。
Ｆ）布帛洗濯法
また、本発明は、ここで使用するセルロース系重合体によって与えられる布帛外観上の利益を付与する方法で布帛を洗濯するための方法を提供する。このような方法は、これらの布帛を、前記の有効量の洗剤組成物から調製された水性洗浄液またはこのような組成物の個々の成分から調製された水性洗浄液と接触させることを利用する。本発明の組成物は布帛クリーニングおよび処理用の水性非攪拌ソーキング溶液を調製するためにも使用してもよいが、布帛と洗浄液との接触は、一般に、攪拌条件下で生ずるであろう。
攪拌は、好ましくは、良好なクリーニングのために洗濯機中で与えられる。洗浄後、好ましくは、ぬれた布帛を通常の布乾燥機中で乾燥する。洗濯機中の水性洗浄液中の液体または粒状洗剤組成物の有効量は、好ましくは、約５００〜約７０００ｐｐｍ、より好ましくは約１０００〜約３０００ｐｐｍである。
Ｇ）布帛コンディショニング
本発明の洗濯洗剤組成物の成分として前記の変性セルロースエーテルは、本発明の洗剤組成物態様の界面活性剤成分およびビルダー成分の不在下で布帛および布類を処理し且つコンディショニングするためにも使用してもよい。したがって、例えば、変性セルロースエーテルのみ単独からなるか変性セルロースエーテルの水溶液を含む布帛コンディショニング組成物は、前記の所望の布帛外観および完全性の利益を付与するために通常の家庭洗濯操作のすすぎサイクル時に添加してもよい。
例
下記の例は、本発明の組成物および方法を例示するが、本発明の範囲を限定したり、他の点で規定することを必ずしも意味しない。
例Ｉ
液体洗剤試験組成物調製
各種の変性セルロース系重合体を含有する数種のヘビーデューティー液体洗剤組成物を調製する。このような液体洗剤組成物は、すべて下記の基本処方を有する。
粒状洗剤試験組成物調製
各種の変性セルロース系重合体を含有する数種のヘビーデューティー粒状洗剤組成物を調製する。このような粒状洗剤組成物は、すべて下記の基本処方を有する。
試験組成物で使用するセルロース系重合体
例ＩおよびIIに記載の液体洗剤組成物および粒状洗剤組成物で使用する代表的な変性セルロース系重合体を表Ｃで特徴づける。表示の各種の置換基は、前記一般式No.Ｉ、IIおよびIIIからのものである。
例IV
全外観
全外観試験においては、セルロース系重合体を含有しないか例IIIのセルロース系重合体の１種を含有するかのいずれかの各種の試験組成物を使用して布帛を洗浄する。次いで、１０サイクル後そのように洗浄された布帛を、洗浄された布帛の全外観を評価する３人の判定者によって比較等級化する。それは、１つの属性、例えば、色、ピリング、毛羽などを評価するために特定の指示が与えられない限り評価すべきものに関する判定者の決定である。
全外観試験においては、シェフェスケールを使用して判定者の目視採択を表現する。
０＝差なし
１＝このものがより良いと思う（不確実）。
２＝このものが少し良いことを知る。
３＝このものがはるかに良いことを知る。
４＝このものが大いに良いことを知る。
全外観試験の場合には、洗濯条件は、次の通りである。
洗濯機種類：ケンモア（１７ガロン）
洗浄時間：１２分
洗浄温度：９０°Ｆ（３２．２℃）
洗浄水硬度：６グレン／ガロン
洗濯機攪拌：通常
すすぎ時間：２分
すすぎ温度：６０°Ｆ（１５．６℃）
すすぎ水硬度：６グレン／ガロン
洗浄負荷布帛含量：各種の着色ガーメントおよび布帛および白色のガーメントおよび布帛
洗浄負荷重量：５．５ポンド（２．５kg）
平均全外観試験結果を表ＤおよびＥに示す。
毛玉減少
毛玉減少試験においては、セルロース系重合体を含有しないか例IIIのセルロース系重合体の１種を含有するかのいずれかの各種の試験組成物を使用して布帛を洗浄する。次いで、試験されたガーメントおよび布帛上の毛玉の数を測定するために画像解析を使用するコンピューター支援ピリング画像解析システムを使用して、そのように洗浄された布帛を毛玉減少について等級化する。毛玉減少を次の通り計算する。毛玉減少（％）＝｛〔毛玉数（コントロール）−毛玉数（重合体）〕／毛玉数（コントロール）｝×１００％
毛玉減少試験の場合には、洗濯条件は、例IVに前記の全外観試験の場合に使用したものと同じである。
平均毛玉減少率試験結果を表ＦおよびＧに示す。
色保護
色保護試験においては、セルロース系重合体を含有しないか例IIIのセルロース系重合体の１種を含有するかのいずれかの各種の試験組成物を使用して布帛を洗浄する。次いで、そのように洗浄された布帛をハンター比色計で試験して、試験された各布帛のデルタＥ★値を求める。デルタＥ★値は、洗浄された布帛と洗浄されない布帛との間の色差（反射率強度、色相シフトなど）と定義される。
色保護試験の場合には、洗濯条件は、例IVに前記の全外観試験の場合に使用したものと同じである。
与えられる色保護の程度は、洗浄されない試料と比較してのデルタＥ★差の％に基づく。色保護を次の通り計算する。
色保護率＝｛〔ｄＥ★（コントロール）−ｄＥ★（重合体）〕／ｄＥ★（コントロール）｝×１００％
平均色保護試験結果を表ＨおよびＩに示す。
The present invention relates to either liquid or granular forms containing a particular type of modified cellulose ether material to impart appearance and integrity benefits to fabrics and fabrics laundered in the wash liquor prepared from this composition. The present invention relates to a heavy duty laundry detergent composition.
Background art
Of course, repeated cycles of using and washing fabrics and fabrics, such as worn clothing and garments, will inevitably adversely affect the appearance and integrity of the fabrics and fabric items so used and washed. It is well known that Fabrics and fabrics are worn with use over time. Fabric and fabric laundering is necessary to remove dirt and stains that accumulate in and on it during normal use. However, the washing operation itself over many cycles can worsen and contribute to degradation of the integrity and appearance of such fabrics and fabrics.
Fabric integrity and appearance degradation may appear in several ways. The short fibers are driven out of the woven / knitted fabric / fabric structure by the mechanical action of the wash. These displaced fibers can form lint, fuzz or “pills” that are visible on the surface of the fabric and reduce the appearance of the fabric's freshness. . In addition, repeated washing of fabrics and fabrics, particularly repeated washing of fabrics and fabrics with bleach-containing laundry products, may remove dye from fabrics and fabrics and results in reduced color strength and many In some cases, the hue or color change may result in a faded and worn appearance.
From the foregoing, it is clear that the tendency of laundry fabrics / fabrics that are themselves associated with fabrics and fabric fibers that are washed using such detergent products, thereby deteriorating appearance, is reduced. There is a continuing need to identify substances that can be added to laundry detergent products that would be minimized. Of course, such detergent product additive materials should be able to benefit fabric appearance and integrity without unduly hindering the laundry detergent's ability to perform the fabric cleaning function. The present invention relates to a detergent composition containing a particular type of cellulosic material that performs in this desired manner.
Disclosure of the invention
The laundry detergent composition of the present invention comprises about 1 to 80% by weight detergent surfactant, about 0.1 to 80% by weight organic or inorganic detergency builder and about 0.1 to about a specific type of modified cellulose ether fabric treating agent. Contains 8% by weight. The detergent surfactant and detergency builder material can be any of those useful in conventional laundry detergent products. The modified cellulose ether material has a molecular weight of about 10,000 to 2,000,000 and repeat substitutions corresponding to the general formulas No. I, II and III described below in the “Best Mode for Carrying Out the Invention” section. Containing an anhydroglucose unit (wherein the substituents are shown at specific positions on the repeating anhydroglucose ring to produce a substituted cellulose ether polymer, for illustrative purposes only). It should be understood that such substituents may be found on any of the carbon atoms of anhydroglucose).
One useful class of cellulose ethers consists of hydrophobically modified nonionic materials (anhydroglucose ring alkyl substitution is about 0.1-5% by weight of the cellulose ether). The ring substituent is alkoxylated in an amount of about 1-20 moles.
A second useful class of cellulose ethers consists of cationic cellulose ether materials that may have an anhydroglucose ring alkyl substitution of about 0.1 to 5% by weight of the cellulose ether. The anhydroglucose ring substituent contains about 1-20 moles of alkoxylation and about 0.005-0.5 moles of a quaternary ammonium cation moiety.
A third type of cellulose ether consists of an anionic cellulose ether material that may have an anhydroglucose ring alkyl substitution of about 0.1 to 5% by weight of the cellulose ether. Also, the anhydroglucose ring in such anionic substances has a degree of carboxymethyl substitution of about 0.05 to 2.5. Combinations of non-ion modified cellulose ether, cation modified cellulose ether and anion modified cellulose ether can also be used.
In a method aspect, the present invention provides an aqueous cleaning or treating solution in which fabrics and fabrics are prepared from effective amounts of the detergent compositions described herein, or prepared from individual components of such compositions. It relates to washing or processing in. Rinsing and drying the fabric and fabric after washing in such a cleaning solution imparts a fabric appearance benefit to the fabric and fabric article so treated. Such benefits may include improved overall appearance, reduced fuzz / fluff, fading prevention, improved wear resistance, and / or increased flexibility.
BEST MODE FOR CARRYING OUT THE INVENTION
As noted above, the laundry detergent composition of the present invention is essential to enhance the appearance and integrity of the fabric when the detergent composition is used to wash detergent surfactants, detergency builders and fabrics and fabrics. Contains some useful modified cellulose ether fabric treating agent. Each of these essential detergent composition components, as well as optional ingredients for such compositions and the use of such compositions are described in detail as follows. All percentages and ratios given are by weight unless otherwise indicated.
A)Detergent surfactant
The detergent composition of the present invention essentially comprises about 1 to 80% by weight of detergent surfactant. Preferably, such compositions comprise about 5-50% by weight of this surfactant. The detergent surfactant utilized can have an anionic surfactant, a nonionic surfactant, a zwitterionic surfactant, an amphoteric surfactant or a cationic surfactant type, or compatibility of these types It can consist of sex mixtures. Useful detergent surfactants herein include Norris U.S. Pat. No. 3,664,961, issued May 23, 1972, Laurin et al. U.S. Pat. No. 3,919, issued December 30, 1975. No. 678, U.S. Pat. No. 4,222,905 issued September 16, 1980, and U.S. Pat. No. 4,239,659 issued Mar. 16, 1980 Are listed. All of these patents are incorporated herein by reference. Of all the surfactants, anionic surfactants and nonionic surfactants are preferred.
Useful anionic surfactants can have several different types alone. For example, water soluble salts of higher fatty acids, or “soaps”, are useful anionic surfactants in the present compositions. This includes alkali metal soaps such as sodium, potassium, ammonium, and alkylol ammonium salts of higher fatty acids having from about 8 to about 24 carbon atoms, preferably from about 12 to about 18 carbon atoms. Soaps can be produced by direct saponification of fats or oils or by neutralization of free fatty acids. Particularly useful are sodium and potassium salts of a mixture of fatty acids derived from coconut oil and tallow, ie sodium or potassium tallow soap and coconut soap.
Additional non-soap anionic surfactants suitable for use herein include organic sulfuric acid reaction products having an alkyl group of about 10 to about 20 carbon atoms and a sulfonate or sulfate group in the molecular structure. Water-soluble salts of the product, preferably alkali metal salts, and ammonium salts (the term “alkyl” includes the alkyl portion of acyl groups). Examples of this class of synthetic surfactants are (a) higher alcohols (C) such as those produced by reducing sodium alkylsulfate, potassium alkylsulfate and ammonium alkylsulfate, especially glycerides of tallow or palm oil.8~ C18Obtained by sulfation of carbon atoms); (b) sodium alkylpolyethoxylate sulfate, potassium alkylpolyethoxylate sulfate and ammonium alkylpolyethoxylate sulfate, especially 10-22 alkyl groups, preferably 12-18. Having 1 to 15 carbon atoms and a polyethoxylate chain containing 1 to 15, preferably 1 to 6 ethoxylate moieties; (c) an alkyl group having a linear or branched arrangement of about 9 to Sodium alkylbenzene sulfonates and potassium alkylbenzene sulfonates having about 15 carbon atoms, such as those of the type described in US Pat. Nos. 2,220,099 and 2,477,383. Linear linear alkylbenzene sulfonate (abbreviated as C) having an average number of carbon atoms in the alkyl group of about 11-1311-13LAS) is particularly valuable.
Preferred nonionic surfactants are those of formula R1(OC2HFour)nOH (wherein R1Is CTen~ C16An alkyl group or C8~ C12An alkylphenyl group, n being from 3 to about 80). C12~ C15Condensates of about 5 to about 20 moles of ethylene oxide per mole of alcohol, for example C condensed with about 6.5 moles of ethylene oxide per mole of alcohol12~ C13Alcohol is particularly preferred.
Additional suitable nonionic surfactants include those of the formula
B)Detergency builder
The detergent composition of the present invention also essentially contains about 0.1 to 80% by weight of a detergency builder. Preferably, such compositions in liquid form will contain from about 1 to 10% by weight of the builder component. Preferably, such compositions in granular form will contain about 1 to 50% by weight of the builder component. Detergency builders are well known in the art and can comprise, for example, phosphates and various organic and inorganic phosphorus-free builders.
Water-soluble, phosphorus-free organic builders useful herein include various alkali metals, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates. Examples of polyacetate and polycarboxylate builders are sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzenepolycarboxylic acid, and citric acid. is there. Other polycarboxylates suitable for use herein include U.S. Pat. No. 4,144,226 issued March 13, 1979 to Clutchfield, and issued March 27, 1979 to Clutchfield et al. Polyacetal carboxylates described in US Pat. No. 4,246,495, both of which are hereby incorporated by reference. Particularly preferred polycarboxylate builders are oxydisuccinate and tartlets described in US Pat. No. 4,663,071 issued May 5, 1987 to Bush et al., The disclosure of which is incorporated herein by reference. An ether carboxylate builder composition comprising a combination of rate monosuccinate and tartrate disuccinate.
Examples of suitable phosphorus-free inorganic builders include silicates, aluminosilicates, borates and carbonates. Sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and SiO2Particularly preferred are silicates having a weight ratio of alkali metal oxide to about 0.5 to about 4.0, preferably about 1.0 to about 2.4. Aluminosilicates including zeolite are also preferred. Such materials and uses as detergency builders are fully discussed in US Pat. No. 4,605,509 to Kolkir et al., The disclosure of which is hereby incorporated by reference. Also, crystalline layered silicates such as those discussed in US Pat. No. 4,605,509 (incorporated herein by reference) such as Kolkir are suitable for use in the detergent compositions of the present invention. .
C)Modified cellulosic polymer
The third essential component of the detergent composition of the present invention consists of one or more modified cellulose polymers. Such materials have been found to provide a number of cosmetic benefits to fabrics and fabrics laundered in an aqueous cleaning solution prepared from a detergent composition containing such modified cellulosic materials. It was. Such fabric appearance benefits may include, for example, an improved overall appearance of the washed fabric, reduced formation of fuzz and fluff, protection against fading, improved wear resistance, and the like. The modified cellulosic polymers used in the compositions and methods of the present invention provide this with little or no appreciable loss of the cleaning performance afforded by the laundry detergent composition in which such materials are incorporated. Such a fabric appearance benefit can be provided.
The modified cellulosic polymers useful herein may have non-ionic, cationic or anionic types, or the modified cellulosic polymer component of the composition may be of these cellulosic polymer types. It may consist of a combination. The modified cellulosic polymer component of the composition will generally comprise about 0.1-8% by weight of the composition. More preferably, such modified cellulosic material will comprise about 0.5-4% by weight of the composition, most preferably about 1% -3%.
One type of modified cellulosic polymer suitable for use herein is a hydrophobically modified having a molecular weight of about 10,000 to 2,000,000, preferably about 50,000 to 1,000,000. Made of nonionic cellulose ether. The hydrophobically modified nonionic material has repeating substituted anhydroglucose units corresponding to general formula No. I as follows.
In general formula No. I, R is H and C8~ Ctwenty fourAlkyl, preferably C8~ C16Combination with alkyl. The alkyl substitution on the anhydroglucose ring of the polymer is about 0.1-5% by weight of the polymeric material, more preferably about 0.2-2% by weight. In general formula No. I, R1Is H or methyl; x is about 1-20, preferably about 1-10.
Examples of the hydrophobically modified nonionic cellulose ether of the general formula No. I include commercially available substances and substances that can be produced by ordinary chemical modification of commercially available substances. Commercially available cellulose ethers of the general formula No. I include Polysurf 67, Natrosol Plus 430 and Natrosol Plus 330 marketed by Hercules Incorporated.
Another type of modified cellulosic polymer suitable for use herein may or may not be hydrophobically modified and has a molecular weight of about 10,000 to 2,000,000, more preferably about It comprises specific cationic cellulose ethers having 10,000 to 1,000,000. These cationic substances have repeating substituted anhydroglucose units corresponding to the general formula No. II as follows.
In general formula No. II, R is H or C8~ Ctwenty fourAlkyl, preferably C8~ C16Alkyl. The alkyl substitution on the anhydroglucose ring of the polymer is about 0.1-5% by weight of the polymeric material, more preferably about 0.2-2% by weight. In general formula No. II, R2Is CH2CHOHCH2Or C8~ Ctwenty fourAlkyl, preferably C8~ C16Alkyl. RThree, RFourAnd RFiveAre each independently methyl, ethyl or phenyl. R6Is H or methyl. Further, in general formula II, x is about 1-20, preferably about 1-10; y is about 0.005-0.5, preferably about 0.005-0.1; Z is Cl-Or Br-It is.
Similarly, examples of the cationic cellulose ether of the general formula No. II include commercially available substances and substances that can be produced by ordinary chemical modification of commercially available substances. Commercially available cellulose ethers of general formula No. II include JR30M, JR400, JR125, LR400 and LK400 UCARE polymers marketed by Union Carbide Corporation. A third type of modified cellulose polymer suitable for use herein may or may not be hydrophobically modified and has a molecular weight of about 10,000 to 2,000,000, more preferably about It consists of a specific anionic cellulose ether having 50,000 to 1,000,000. These anionic substances have repetitively substituted anhydroglucose units corresponding to the general formula No. III as follows.
In general formula No. III, R is H and (a) CH2COOA and optionally (b) C2~ Ctwenty fourAlkyl, preferably C2~ C16In combination with alkyl, A is Na or K. The alkyl substitution on the anhydroglucose ring of the polymer is about 0.1-5% by weight of the polymeric material, more preferably about 0.2-2% by weight. The anionic cellulose ether also has a degree of carboxymethyl substitution of about 0.05 to 2.5, more preferably about 0.1 to 1.0.
In addition, examples of the anionic cellulose ether of the general formula No. III include commercially available substances and those that can be produced by ordinary chemical modification of commercially available substances. Commercially available cellulose ethers of general formula No. III include CMC7H, CMC99-7M, and CMC99-7L marketed by Hercules Incorporated, and CMC D72, CMC D65, and CMC marketed by Penn Carboth. DHT is mentioned.
Commercially available cellulose ether materials useful herein are themselves derived from suitable natural cellulosic sources. Such sources include, for example, cotton linters and other plant tissues. The modified cellulose ethers used in the present invention are generally all water-soluble substances. Therefore, they can be utilized in the preparation of detergent compositions in the form of aqueous solutions of such cellulosic polymers, if desired.
D)Optional detergent ingredients
In addition to the essential surfactants, builders and modified cellulose ethers described above, the detergent compositions of the present invention can include any number of additional optional ingredients. These include the usual detergent composition ingredients, such as bleach and bleach activators, enzymes and enzyme stabilizers, foam boosters or defoamers, anti-fogging and anti-corrosion agents, soil precipitation inhibitors, antifouling agents. , Fungicides, pH adjusters, non-builder alkalinity sources, chelating agents, organic and inorganic fillers, solvents, hydrotropes, optical brighteners, dyes and fragrances.
Preferred optional ingredients for incorporation into the detergent compositions of the present invention include bleaching agents such as peroxygen bleaching agents. Such peroxygen bleaches may be organic or inorganic in nature. Inorganic peroxygen bleaches are often used in conjunction with bleach activators.
Useful organic peroxygen bleaches include percarboxylic acid bleaches and their salts. Suitable examples of this type of bleaching agent include magnesium monoperoxyphthalate hexahydrate, magnesium salt of m-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxide decanedioic acid. . Such bleaching agents are disclosed in Hartman U.S. Pat. No. 4,483,781 issued Nov. 20, 1984, Banks et al. European Patent Application EP-A No. 133,354 published Feb. 20, 1985. And U.S. Pat. No. 4,412,934 to Chang et al., Issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described in US Pat. No. 4,634,551 issued Jan. 6, 1987 to Burns et al. It is done.
Inorganic peroxygen bleaches may also be used in particulate form, generally in the detergent compositions of the present invention. Inorganic bleaches are in fact preferred. Such inorganic peroxygen compounds include alkali metal perborate and percarbonate materials. For example, sodium perborate (eg, monohydrate or tetrahydrate) can be used. Suitable inorganic bleaches also include sodium carbonate or potassium carbonate hydrogen peroxide and equivalent "percarbonate" bleach, sodium pyrophosphate hydrogen peroxide, urea hydrogen peroxide, and sodium peroxide. Can be mentioned. Persulfate bleaching agents (eg, OXONE produced commercially by DuPont) can also be used. Often the inorganic peroxygen bleach will be coated with a silicate, borate, sulfate or water soluble surfactant. For example, coated percarbonate particles can be obtained from various commercial sources such as FMC, Solvay Interlocks, Tokai Denka, Degussa.
Inorganic peroxygen bleaches such as perborate, percarbonate and the like are preferably combined with a bleach activator, which in situ forms in an aqueous solution of a peroxy acid corresponding to the bleach activator (ie, fabric laundry). / When using the composition for bleaching). Various non-limiting examples of activators include U.S. Pat. No. 4,915,854 issued Apr. 10, 1990 to Mao et al. And U.S. Pat. No. 4, issued Nov. 1, 1983 to Chang et al. No. 412,934. Nonanoyloxybenzene sulfonate (NOBS) and tetraacetylethylenediamine (TAED) activators are typical and preferred. Mixtures thereof can also be used. See also the aforementioned U.S. Pat. No. 4,634,551 for other typical bleaches and activators useful herein.
Other useful amide derived bleach activators are of the formula
R1N (RFive) C (O) R2C (O) L or
R1C (O) N (RFive) R2C (O) L
(Wherein R1Is an alkyl group having from about 6 to about 12 carbon atoms and R2Is alkylene having 1 to about 6 carbon atoms and RFiveIs H or alkyl, aryl or alkaryl having from about 1 to about 10 carbon atoms, and L is a suitable leaving group. A leaving group is a group that is displaced from a bleach activator as a result of a nucleophilic attack on the bleach activator by a perhydrolyzed anion. A preferred leaving group is phenol sulfonate.
Preferred examples of the bleach activator of the above formula include (6-octaneamidocaproyl) oxybenzenesulfonate as described in the aforementioned US Pat. No. 4,634,551, (6-nonaneamidocaproyl) Oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate, and mixtures thereof.
Another class of useful bleach activators is the activity of the benzoxazine type disclosed in US Pat. No. 4,966,723 issued October 30, 1990 to Hodge et al., Incorporated herein by reference. It consists of an agent. A highly preferred activator of the benzoxazine type has the formula
Yet another class of useful bleach activators include acyl lactam activators, particularly those of the formula
If utilized, the peroxygen bleach will generally comprise about 2-30% by weight of the detergent composition of the present invention. More preferably, the peroxygen bleach will comprise about 2-20% by weight of the composition. Most preferably, the peroxygen bleach will be present in the order of about 3-15% by weight of the composition. If utilized, the bleach activator can comprise about 2-10% by weight of the detergent composition of the present invention. Often the activator is used such that the molar ratio of bleach to activator is from about 1: 1 to 10: 1, more preferably from about 1.5: 1 to 5: 1.
Another optional component that is highly preferred in the detergent composition of the present invention is a detergent enzyme component. Enzymes can be used for a variety of purposes, including removal of protein-based blots, carbohydrate-based blots, or triglyceride-based blots from substrates, prevention of escape dye migration in fabric washing, and fabric restoration. It can mix | blend with the detergent composition of invention. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as plants, animals, bacteria, fungi and yeasts. The preferred choice is influenced by factors such as stability against pH activity and / or stability optimums, thermal stability, active detergents, builders and the like. In this respect, bacterial or fungal enzymes, such as bacterial amylases and proteases, and fungal cellulases are preferred.
As used herein, “detergent enzyme” means an enzyme that has a beneficial effect in cleaning, stain removal or otherwise in a laundry detergent composition. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases, amylases and peroxidases.
The enzyme is usually formulated in an amount sufficient to provide a “cleaning effective amount” to the detergent composition. The term “cleaning effective amount” means any amount that can produce a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on a substrate such as a fabric. For practical use of currently marketed formulations, typical amounts are up to about 5 mg (by weight) of active enzyme per gram of detergent composition, more typically 0.01 mg to 3 mg. In other words, the composition will typically comprise from 0.001 to 5% by weight, preferably 0.01 to 1% by weight of a commercially available enzyme preparation. Protease enzymes are usually present in such commercial preparations in an amount sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. Higher active ingredient amounts may be desirable in highly concentrated detergent formulations.
Suitable examples of proteases are subtilisins obtained from Bacillus subtilis and certain strains of B. licheniformis. One suitable protease is Bacillus having maximum activity over the entire pH range of 8-12 developed by Danish Novo Industries A / S (hereinafter “Novo”) and marketed as Esperase®. Obtained from strains of The preparation of this and similar enzymes is described in British Patent No. 1,243,784 to Novo. Other suitable proteases include alvocalase (ALCALASE®) and sabinase (SAVINASE®) from Novo and maxatase (MAXATASE®) from the International Bio-Synthetics Incorporated of the Netherlands and 1985 Protease A as disclosed in EP 130,756A published January 9, and EP 303,761A published 28 April 1987 and EP 130 published January 9, 1985. , 756A specification, protease B is mentioned. See also high pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140A to Novo. Enzymatic detergents including proteases, one or more other enzymes, and reversible protease inhibitors are described in WO 9203529A to Novo. Other preferred proteases include those of WO 9510591A to Procter End Gambling. When desired, proteases with reduced adsorption and increased hydrolysis are available as described in WO 9507791 to Procter End Gambling. A suitable recombinant trypsin-like protease for detergents is described in WO 9455583 to Novo.
Cellulases that can be used in the present invention include both bacterial cellulases and fungal cellulases (preferably having a pH optimum of 5-10).
U.S. Pat. No. 4,435,307 issued March 6, 1984 to U.S. Pat. No. 4,435,307 to Humicola insolens or Humicola strain DSM1800 or suitable fungal cellulases from cellulase 212 producing fungi belonging to the genus Aeromonas, and marine mollusc Cellulase extracted from the liver pancreas of (Dolabella Auricula Solander) is disclosed. Suitable cellulases are also disclosed in GB 2.0755.028, GB 2.095.275 and DE-OS 2.2477.832. Carezyme (CAREZYME®) and CELLUZYME® (Novo) are particularly useful. See also WO 9117243 to Novo.
Suitable lipase enzymes for use in detergents include those produced by microorganisms of the Pseudomonas group such as Pseudomonas stutzeri ATCC 19.154 as disclosed in British Patent 1,372,034. See also the lipase in JP-A-53-20487 published on Feb. 24, 1978. This lipase is available under the trade name lipase P “Amano” or “Amano-P” from Amano Amano Pharmaceutical Co., Ltd., Nagoya, Japan. Other suitable commercially available lipases include Amano-CES, Chromobacter viscosum, such as the lipase from Chromobacter viscosum var. Lipolyticum NRRLB3673 from Toyo Shuzo Co., Ltd., Japan; S. These include Biochemical Corporation and the Chromobacter viscosum lipase from the Dutch Decointo Company and the lipase from Pseudomonas gladioli. The lipolase (LIPOLASE®) enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EP 341,947) is a preferred lipase for use herein.
The enzyme-containing composition of the present invention optionally comprises about 0.001 to about 10%, preferably about 0.005 to about 8%, most preferably about 0.01 to about 6% by weight of the enzyme stabilization system. May be included. The enzyme stabilization system can be any stabilization system that is compatible with the detergent enzyme. Such systems can be inherently provided by other formulation active ingredients, or can be added separately, for example, by the formulator or by the manufacturer of the detergent enzyme. Such stabilization systems can consist, for example, of calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof and vary depending on the type and physical form of the detergent composition. Designed to handle stabilization issues.
E)Preparation of detergent composition
The detergent composition according to the invention can be in liquid, paste or granular form. Such compositions can be prepared by combining the required concentrations of the essential and optional ingredients in a suitable order by conventional means.
A granular composition is typically obtained by, for example, combining base particulate components (eg, surfactant, builder, water, etc.) as a slurry and spray drying the resulting slurry to a small amount of residual moisture (5-12%). Prepare. The remaining dry ingredients can be mixed with the spray dried granules in a rotary mixing drum in granular powder form and liquid components (eg, organic solutions of essential cellulosic polymers, enzymes, binders and perfumes) can be obtained in the form of granules. The finished detergent composition can be prepared by spraying onto the object. The granular composition according to the invention can also be in “compact form”, ie it may have a relatively higher density than conventional granular detergents, ie 550 to 950 g / l. In such a case, the granular detergent composition according to the present invention will contain a small amount of “inorganic filler” compared to a normal granular detergent. Typical filler salts are sulfuric and chloride alkaline earth metal salts, typically sodium sulfate. “Compact” detergents typically contain 10% or less filler salt.
Liquid detergent compositions can be prepared by combining the essential and optional ingredients in the desired order to provide a composition containing the required concentration of ingredients. The liquid composition according to the present invention can also be “compact”. In such a case, the liquid detergent composition according to the present invention will contain a small amount of water compared to a normal liquid detergent.
Addition of the cellulose ether component to the liquid detergent composition of the present invention may be accomplished by simply placing the desired aqueous solution of cellulose ether in the liquid detergent. Cellulose ethers can alter the viscosity or other rheological properties of liquid detergent products. It may therefore be necessary to compensate for the rheological changes of the liquid detergent product caused by the addition of cellulose-ether by changing the type and amount of hydrotrope and / or solvent used.
F)Fabric washing method
The present invention also provides a method for washing fabrics in a manner that imparts the fabric appearance benefits provided by the cellulosic polymers used herein. Such methods utilize contacting these fabrics with an aqueous cleaning solution prepared from an effective amount of the detergent composition described above or an aqueous cleaning solution prepared from the individual components of such a composition. Although the compositions of the present invention may also be used to prepare aqueous non-stirred soaking solutions for fabric cleaning and processing, contact between the fabric and the cleaning fluid will generally occur under stirring conditions.
Agitation is preferably provided in the washing machine for good cleaning. After washing, the wet fabric is preferably dried in a conventional fabric dryer. The effective amount of liquid or granular detergent composition in the aqueous cleaning liquid in the washing machine is preferably about 500 to about 7000 ppm, more preferably about 1000 to about 3000 ppm.
G)Fabric conditioning
The modified cellulose ethers described above as components of the laundry detergent composition of the present invention are also used to treat and condition fabrics and fabrics in the absence of the surfactant and builder components of the detergent composition embodiments of the present invention. May be. Thus, for example, a fabric conditioning composition consisting solely of a modified cellulose ether or comprising an aqueous solution of a modified cellulose ether can be used during a normal home washing operation rinse cycle to provide the desired fabric appearance and integrity benefits described above. It may be added.
Example
The following examples illustrate the compositions and methods of the invention, but are not necessarily meant to limit or otherwise define the scope of the invention.
Example I
Preparation of liquid detergent test composition
Several heavy duty liquid detergent compositions containing various modified cellulosic polymers are prepared. All such liquid detergent compositions have the following basic formulation:
Preparation of granular detergent test composition
Several heavy duty granular detergent compositions containing various modified cellulosic polymers are prepared. All such granular detergent compositions have the following basic formulation:
Cellulose polymers used in test compositions
Representative modified cellulosic polymers used in the liquid and granular detergent compositions described in Examples I and II are characterized in Table C. The various substituents indicated are those from the general formulas No. I, II and III.
Example IV
Overall appearance
In the full appearance test, the fabric is washed using various test compositions that either contain no cellulosic polymer or contain one of the cellulosic polymers of Example III. The fabric so washed after 10 cycles is then comparatively graded by three judges who evaluate the overall appearance of the washed fabric. It is the judge's decision on what to evaluate unless given specific instructions to evaluate one attribute, eg color, pilling, fluff, etc.
In the full appearance test, the Scheffe scale is used to express the judge's visual acceptance.
0 = no difference
1 = I think this is better (uncertain).
2 = Know that this is a little better.
3 = Know that this is much better.
4 = I know that this is a lot better.
In the case of a full appearance test, the washing conditions are as follows.
Washing machine type: Kenmore (17 gallons)
Cleaning time: 12 minutes
Washing temperature: 90 ° F (32.2 ° C)
Washing water hardness: 6 glen / gallon
Washing machine stirring: normal
Rinse time: 2 minutes
Rinsing temperature: 60 ° F (15.6 ° C)
Rinse water hardness: 6 Glen / gallon
Wash load fabric content: various colored garments and fabrics and white garment and fabrics
Wash load weight: 5.5 pounds (2.5 kg)
The average overall appearance test results are shown in Tables D and E.
Hairball reduction
In the pill reduction test, the fabric is washed using various test compositions that either contain no cellulosic polymer or contain one of the cellulosic polymers of Example III. A computer-aided pilling image analysis system that uses image analysis to measure the number of garments and pills on the fabric is then graded for pill reduction using a computer-aided pilling image analysis system. . Calculate pill loss as follows. Reduction in pills (%) = {[number of pills (control) −number of pills (polymer)] / number of pills (control)} × 100%
In the case of the pill reduction test, the washing conditions are the same as those used in Example IV for the full appearance test described above.
Tables F and G show the average pill reduction rate test results.
Color protection
In the color protection test, the fabric is washed using various test compositions that either contain no cellulosic polymer or contain one of the cellulosic polymers of Example III. The fabrics so washed are then tested with a hunter colorimeter and the delta E of each fabric tested.★Find the value. Delta E★The value is defined as the color difference (reflectance intensity, hue shift, etc.) between the washed fabric and the unwashed fabric.
In the case of the color protection test, the washing conditions are the same as those used for the full appearance test in Example IV above.
The degree of color protection provided is Delta E compared to the unwashed sample.★Based on% difference. Color protection is calculated as follows:
Color protection rate = {[dE★(Control) -dE★(Polymer)] / dE★(Control)} × 100%
The average color protection test results are shown in Tables H and I.
Claims (5)
（Ａ）洗剤界面活性剤１〜８０重量％、
（Ｂ）有機または無機洗浄性ビルダー１〜８０重量％、
（Ｃ）分子量１０，０００〜２，０００，０００を有し且つ一般式
Ｒ1はＨまたはメチルであり；
ｘは１〜２０である〕
に対応する反復置換アンヒドログルコース単位を有する、疎水的に変性された非イオンセルロースエーテル、
からなる群から選ばれる変性セルロースエーテル布帛処理剤０．１〜８重量％、を特徴とする、洗濯洗剤組成物。Providing fabric appearance benefits selected from fuzz / fluff reduction, fading prevention, improved abrasion resistance and / or increased flexibility to fabrics and fabrics laundered in an aqueous cleaning solution prepared therefrom A builder-containing heavy duty laundry detergent composition in a liquid or granular form comprising:
(A) Detergent surfactant 1-80% by weight,
(B) 1 to 80% by weight of organic or inorganic detergency builder,
(C) having a molecular weight of 10,000 to 2,000,000 and a general formula
R 1 is H or methyl;
x is 1-20]
A hydrophobically modified nonionic cellulose ether having repeating substituted anhydroglucose units corresponding to
A laundry detergent composition comprising 0.1 to 8% by weight of a modified cellulose ether fabric treating agent selected from the group consisting of:
（Ｂ）洗浄性ビルダーが、１０〜５０重量％によって特徴づけられ且つカルボキシレート、シリケート、アルミノシリケート、カーボネート、ボレートおよびそれらの組み合わせから選ばれ、
（Ｃ）変性セルロースエーテル布帛処理剤を０．５〜４重量％含み且つ分子量１０，０００〜１，０００，０００を有する、
請求項１に記載の組成物。(A) 5 to 50% by weight of detergent surfactant, and selected from anionic surfactant materials and nonionic surfactant materials;
(B) the detergency builder is characterized by 10-50% by weight and is selected from carboxylates, silicates, aluminosilicates, carbonates, borates and combinations thereof;
(C) 0.5 to 4% by weight of a modified cellulose ether fabric treatment agent and having a molecular weight of 10,000 to 1,000,000,
The composition of claim 1.
（ｂ）アンヒドログルコース環のＲ置換はセルロースエーテルの０．２〜２重量％であり、
（ｃ）Ｒ1はＨであり、且つ
（ｄ）ｘは１〜１０である）
に対応する疎水的に変性された非イオン物質である、請求項２に記載の組成物。The modified cellulose ether fabric treating agent has the general formula No. I
(B) R substitution on the anhydroglucose ring is 0.2-2% by weight of the cellulose ether;
(C) R 1 is H and (d) x is 1 to 10)
The composition according to claim 2, which is a hydrophobically modified nonionic substance corresponding to.
（ｉｉ）アルキルポリエトキシレート硫酸ナトリウム、アルキルポリエトキシレート硫酸カリウムおよびアルキルポリエトキシレート硫酸アンモニウム（ただし、アルキル基は１０〜２２個の炭素原子を有し且つポリエトキシレート鎖は１〜１５個のエチレンオキシド部分を含有する）；
（iii）式
のポリヒドロキシ脂肪酸アミド、
（iv）式 Ｒ1（ＯＣ2Ｈ4）nＯＨ（式中、Ｒ1はＣ10〜Ｃ16アルキル基またはＣ8〜Ｃ12アルキルフェニル基であり、ｎは３〜８０である）のアルコールエトキシレート；および
（ｖ）これらの界面活性剤の組み合わせ
から選ばれる洗剤界面活性剤５〜５０重量％；および
（ｂ）カルボキシレートおよびポリカルボキシレートビルダーから選ばれる洗浄性ビルダー成分１〜１０重量％
によって特徴づけられる液体形である、請求項１に記載の組成物。(A) (i) sodium alkyl sulfate, potassium alkyl sulfate and ammonium alkyl sulfate (wherein the alkyl group has 8 to 18 carbon atoms);
(Ii) sodium alkylpolyethoxylate sulfate, potassium alkylpolyethoxylate sulfate and alkylpolyethoxylate ammonium sulfate, wherein the alkyl group has 10 to 22 carbon atoms and the polyethoxylate chain has 1 to 15 ethylene oxide. Containing a portion);
(Iii) Formula
Of polyhydroxy fatty acid amides,
(Iv) an alcohol of the formula R 1 (OC 2 H 4 ) n OH, wherein R 1 is a C 10 to C 16 alkyl group or a C 8 to C 12 alkylphenyl group, and n is 3 to 80 Ethoxylates; and (v) 5-50% by weight of a detergent surfactant selected from combinations of these surfactants; and (b) 1-10% by weight of a detergency builder component selected from carboxylates and polycarboxylate builders.
The composition of claim 1 in a liquid form characterized by:
（ii）Ｃ9〜Ｃ15アルキルベンゼンスルホン酸ナトリウムおよびＣ9〜Ｃ15アルキルベンゼンスルホン酸カリウム；
（iii）Ｃ8〜Ｃ18アルキル硫酸ナトリウムおよびＣ8〜Ｃ18アルキル硫酸カリウム；
（iv）式
のポリヒドロキシ脂肪酸アミド；および
（ｖ）これらの界面活性剤の組み合わせ
から選ばれる洗剤界面活性剤５〜５０重量％；および
（ｂ）炭酸ナトリウム、シリケート、結晶性層状シリケート、アルミノシリケート、オキシジスクシネートおよびサイトレートから選ばれる洗浄性ビルダー１〜５０重量％
によって特徴づけられる粒状の形である、請求項１に記載の組成物。(A) (i) Sodium alkylpolyethoxylate sulfate and potassium alkylpolyethoxylate sulfate (wherein the alkyl group has 10 to 22 carbon atoms and the polyethoxylate chain contains 1 to 15 ethylene oxide moieties) Do);
(Ii) C 9 ~C 15 sodium alkylbenzenesulfonate and C 9 -C 15 potassium alkylbenzene sulfonate;
(Iii) C 8 ~C 18 sodium alkyl sulfates and C 8 -C 18 alkyl potassium sulfate;
(Iv) Formula
And (v) 5 to 50% by weight of a detergent surfactant selected from combinations of these surfactants; and (b) sodium carbonate, silicate, crystalline layered silicate, aluminosilicate, oxydisucci 1-50% by weight of a detergency builder selected from nate and citrate
The composition of claim 1, wherein the composition is in the granular form characterized by:
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US3393096P | 1996-12-26 | 1996-12-26 | |
| US60/033,930 | 1996-12-26 | ||
| PCT/US1997/023771 WO1998029528A2 (en) | 1996-12-26 | 1997-12-23 | Laundry detergent compositions with cellulosic polymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001507396A JP2001507396A (en) | 2001-06-05 |
| JP4267075B2 true JP4267075B2 (en) | 2009-05-27 |
Family
ID=21873278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP53016998A Expired - Fee Related JP4267075B2 (en) | 1996-12-26 | 1997-12-23 | Laundry detergent compositions having cellulosic polymers to provide appearance and integrity benefits to fabrics washed therewith |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0948591B1 (en) |
| JP (1) | JP4267075B2 (en) |
| CN (1) | CN1213137C (en) |
| AR (1) | AR010851A1 (en) |
| AT (1) | ATE245184T1 (en) |
| BR (1) | BR9714097A (en) |
| CA (1) | CA2276188C (en) |
| DE (1) | DE69723575T2 (en) |
| ES (1) | ES2203830T3 (en) |
| WO (1) | WO1998029528A2 (en) |
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| FR2784391B1 (en) * | 1998-10-09 | 2000-12-01 | Rhodia Chimie Sa | DETERGENT OR RINSING COMPOSITION PROTECTING TEXTILE FIBERS |
| DE69926385T2 (en) * | 1998-09-30 | 2005-12-29 | Unilever N.V. | TREATMENT OF TISSUE |
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| EP1121406B1 (en) | 1998-10-13 | 2007-12-12 | The Procter & Gamble Company | Detergent compositions or components |
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-
1997
- 1997-12-23 BR BR9714097A patent/BR9714097A/en not_active IP Right Cessation
- 1997-12-23 AT AT97953405T patent/ATE245184T1/en not_active IP Right Cessation
- 1997-12-23 JP JP53016998A patent/JP4267075B2/en not_active Expired - Fee Related
- 1997-12-23 ES ES97953405T patent/ES2203830T3/en not_active Expired - Lifetime
- 1997-12-23 AR ARP970106137A patent/AR010851A1/en unknown
- 1997-12-23 CA CA002276188A patent/CA2276188C/en not_active Expired - Fee Related
- 1997-12-23 DE DE69723575T patent/DE69723575T2/en not_active Expired - Lifetime
- 1997-12-23 WO PCT/US1997/023771 patent/WO1998029528A2/en active IP Right Grant
- 1997-12-23 EP EP97953405A patent/EP0948591B1/en not_active Expired - Lifetime
- 1997-12-23 CN CN97181945.9A patent/CN1213137C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| ES2203830T3 (en) | 2004-04-16 |
| CA2276188A1 (en) | 1998-07-09 |
| JP2001507396A (en) | 2001-06-05 |
| EP0948591B1 (en) | 2003-07-16 |
| DE69723575T2 (en) | 2004-05-13 |
| WO1998029528A2 (en) | 1998-07-09 |
| CN1247558A (en) | 2000-03-15 |
| ATE245184T1 (en) | 2003-08-15 |
| AR010851A1 (en) | 2000-07-12 |
| EP0948591A2 (en) | 1999-10-13 |
| CA2276188C (en) | 2005-11-01 |
| CN1213137C (en) | 2005-08-03 |
| DE69723575D1 (en) | 2003-08-21 |
| WO1998029528A3 (en) | 1998-09-17 |
| BR9714097A (en) | 2000-03-21 |
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