JP6790257B2 - 洗濯ケア組成物における青味剤としてのロイコ着色剤、その包装、キット及び方法 - Google Patents
洗濯ケア組成物における青味剤としてのロイコ着色剤、その包装、キット及び方法 Download PDFInfo
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- JP6790257B2 JP6790257B2 JP2019521683A JP2019521683A JP6790257B2 JP 6790257 B2 JP6790257 B2 JP 6790257B2 JP 2019521683 A JP2019521683 A JP 2019521683A JP 2019521683 A JP2019521683 A JP 2019521683A JP 6790257 B2 JP6790257 B2 JP 6790257B2
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- RYMZZMVNJRMUDD-HGQWONQESA-N simvastatin Chemical compound C([C@H]1[C@@H](C)C=CC2=C[C@H](C)C[C@@H]([C@H]12)OC(=O)C(C)(C)CC)C[C@@H]1C[C@@H](O)CC(=O)O1 RYMZZMVNJRMUDD-HGQWONQESA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229960002668 sodium chloride Drugs 0.000 description 1
- 229940079842 sodium cumenesulfonate Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 229940048842 sodium xylenesulfonate Drugs 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- QEKATQBVVAZOAY-UHFFFAOYSA-M sodium;4-propan-2-ylbenzenesulfonate Chemical compound [Na+].CC(C)C1=CC=C(S([O-])(=O)=O)C=C1 QEKATQBVVAZOAY-UHFFFAOYSA-M 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- LJFWQNJLLOFIJK-UHFFFAOYSA-N solvent violet 13 Chemical compound C1=CC(C)=CC=C1NC1=CC=C(O)C2=C1C(=O)C1=CC=CC=C1C2=O LJFWQNJLLOFIJK-UHFFFAOYSA-N 0.000 description 1
- 229940075554 sorbate Drugs 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- 229940061610 sulfonated phenol Drugs 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 108010038851 tannase Proteins 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- RLNWRDKVJSXXPP-UHFFFAOYSA-N tert-butyl 2-[(2-bromoanilino)methyl]piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CNC1=CC=CC=C1Br RLNWRDKVJSXXPP-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- RJSZFSOFYVMDIC-UHFFFAOYSA-N tert-butyl n,n-dimethylcarbamate Chemical compound CN(C)C(=O)OC(C)(C)C RJSZFSOFYVMDIC-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical class N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 229960004319 trichloroacetic acid Drugs 0.000 description 1
- 108010045994 tricholysine Proteins 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000012588 trypsin Substances 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 239000005418 vegetable material Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229940030186 xpect Drugs 0.000 description 1
- 229920001221 xylan Polymers 0.000 description 1
- 150000004823 xylans Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229940071104 xylenesulfonate Drugs 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- 239000002446 δ-tocopherol 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
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
-
- 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
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- 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
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
- C11D17/045—Multi-compartment
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
-
- 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
-
- 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
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/12—Soft surfaces, e.g. textile
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Description
本明細書で使用するとき、用語「アルコキシ」は、C1〜C8アルコキシ、及びブチレンオキシド、グリシドールオキシド、エチレンオキシド、又はプロピレンオキシドなどの繰り返し単位を有するポリオールのアルコキシ誘導体を含むことを意図する。
から選択される基に一致する1つ以上のロイコ化合物を含む組成物であって、
式I〜Vのその酸化形態に対する比は、少なくとも1:19、1:9、又は1:3、好ましくは少なくとも1:1、より好ましくは少なくとも3:1、最も好ましくは少なくとも9:1又は更には19:1である、組成物に関する。
洗濯ケア組成物は、いくつかの態様では、全体的に又は部分的に組み込まれ得る他の好適な補助剤を含んでもよい。補助剤は、選択ケア組成物の意図する機能に従って選択され得る。第1の組成物は添加剤を含み得る。いくつかの態様では、複数区画の単位用量物品の場合、添加剤は、第1の組成物とは別の区画に封入される、非第1(例えば第2、第3、第4等)の組成物の一部であってよい。非第1の組成物は、任意の好適な組成物であってよい。非第1の組成物は、固体、液体、分散体、ゲル、ペースト又はこれらの混合物の形態であってよい。単位用量が複数の区画を含む場合、ロイコ着色剤は、1つ、2つ、又は更には全ての区画に添加されてもよく、又は存在してもよい。一実施形態では、ロイコ着色剤をより大きな区画に添加して、より低濃度にし、それによって、潜在的な接触染色に関与するあらゆる問題を最小限に抑えることができる。他方、より小さな体積の区画内において抗酸化剤をロイコ着色剤で濃縮することにより、抗酸化剤の局所濃度を高くすることができ、それによって強化された安定性を提供することができる。したがって、当業者には理解されるように、配合者は、単位用量の所望の特性に従ってロイコ着色剤の位置及び量を選択することができる。
洗濯ケア組成物は、界面活性剤系を含み得る。洗濯ケア組成物は、洗濯ケア組成物の約1重量%〜約80重量%、又は1重量%〜約60重量%、好ましくは約5重量%〜約50重量%、より好ましくは約8重量%〜約40重量%の界面活性剤系を含み得る。
(R)(R1)(R2)(R3)N+X−
式中、Rは、直鎖又は分岐鎖、置換又は非置換C6〜18アルキル又はアルケニル部分であり、R1及びR2は、独立して、メチル又はエチル部分から選択され、R3は、ヒドロキシ、ヒドロキシメチル又はヒドロキシエチル部分であり、Xは、電荷の中性を提供するアニオンであり、好ましいアニオンとしては、ハロゲン化物、好ましくはクロリド;硫酸塩;及びスルホン酸塩が挙げられる。
ロイコ着色剤組成物中の成分の別の分類は、希釈剤及び/又は溶媒であり得る。希釈剤及び/又は溶媒の目的は、多くの場合、流動性を改善する及び/又はロイコ着色剤の粘度を低下させることであるが、これらに限定されない。多くの場合、その低コスト及び非毒性を考慮して、水が好ましい希釈剤及び/又は溶媒であるが、他の溶媒も同様に使用され得る。好ましい溶媒は、コストが低くかつ危険性が低いものである。好適な溶媒の例としては、エチレングリコール、プロピレングリコール、グリセリン、ポリエチレングリコール、ポリプロピレングリコールなどのアルコキシル化ポリマー、エチレンオキシドとプロピレンオキシドとのコポリマー、Tween 20(登録商標)、Tween 40(登録商標)、Tween 80(登録商標)など、及びこれらの組み合わせが挙げられるが、これらに限定されない。ポリマーの中でも、エチレンオキシドとプロピレンオキシドとのコポリマーが好ましい場合がある。これらポリマーは、多くの場合、水による曇点を特徴とし、これは、生成物を水から分離して、望ましくない水溶性不純物を除去するのに役立ち得る。エチレンオキシドとプロピレンオキシドとのコポリマーの例としては、BASFによるPLURONICシリーズのポリマー及びDowによるTERGITOL(商標)シリーズのポリマーが挙げられるが、これらに限定されない。ロイコ着色剤組成物が洗濯ケア組成物に組み込まれたとき、これらポリマーは、非イオン性界面活性剤としても作用し得る。
当該組成物は、追加の布地シェーディング剤を含み得る。好適な布地シェーディング剤としては、染料、染料−粘土複合体、及び顔料が挙げられる。好適な染料としては、低分子染料及び高分子染料が挙げられる。好適な小分子染料としては、ダイレクトブルー、ダイレクトレッド、ダイレクトバイオレット、アシッドブルー、アッシドレッド、アッシドバイオレット、ベーシックブルー、ベーシックバイオレット及びベーシックレッド、又はこれらの混合物の色指数(Colour Index、C.I.)分類に区分される染料からなる群から選択される小分子染料が挙げられる。好ましい染料としては、アルコキシル化アゾチオフェン、ソルベントバイオレット13、アシッドバイオレット50及びダイレクトバイオレット9が挙げられる。
本開示の洗浄組成物は、悪臭低減材料を含み得る。このような材料は、1種類以上の悪臭の知覚を減らすか、又は更には知覚しなくすることができる。これら材料は、計算された悪臭低減値(「MORV」)によって特徴付けることができ、MORVは国際公開第2016/049389号に示されている試験方法に従って計算される。
本開示の洗浄組成物は、タンニンを含み得る。タンニンは高等植物のポリフェノール二次代謝産物であり、かつタンニンはガロイル部分又はこれらの誘導体が種々のポリオール−、カテキン−及びトリテルペノイド核に結合している(ガロタンニン、エラジタンニン及び複合タンニン)ガロイルエステル並びにそれらの誘導体のいずれかである、あるいはタンニンはフラバニル間結合及び置換パターン(縮合タンニン)を備え得るオリゴマーのプロアントシアニジン及びポリマーのプロアントシアニジンである。本開示の洗浄組成物は、ガロタンニン、エラジタンニン、複合タンニン、縮合型タンニン、及びこれらの組み合わせからなる群から選択されるタンニンを含み得る。
(VI)−[(OCHR1−CHR2)a−O−OC−Ar−CO−]d
(VII)−[(OCHR3−CHR4)b−O−OC−sAr−CO−]e
(VIII)−[(OCHR5−CHR6)c−OR7]f
式中、
a、b及びcは、1〜200であり、
d、e及びfは、1〜50であり、
Arは、1,4−置換フェニレンであり、
sArは、5位がSO3Meにより置換された1,3−置換フェニレンであり、
Meは、Li、K、Mg/2、Ca/2、Al/3、アンモニウム、モノ、ジ、トリ、若しくはテトラアルキルアンモニウム(アルキル基は、C1〜C18アルキル又はC2〜C10ヒドロキシアルキルである)、又はこれらの混合物であり、
R1、R2、R3、R4、R5及びR6は、独立して、H又はC1〜C18 n−若しくはイソ−アルキルから選択され、
R7は、直鎖状若しくは分岐状C1〜C18アルキル、又は直鎖状若しくは分岐状C2〜C30アルケニル、又は5〜9つの炭素原子を有するシクロアルキル基、又はC8〜C30アリール基、又はC6〜C30アリールアルキル基である。
(I)−[(OCHR1−CHR2)a−O−OC−Ar−CO−]d
(II)−[(OCHR3−CHR4)b−O−OC−sAr−CO−]e
(III)−[(OCHR5−CHR6)c−OR7]f
式中、
a、b及びcは、1〜200であり、
d、e及びfは、1〜50であり、
Arは、1,4−置換フェニレンであり、
sArは、5位がSO3Meにより置換された1,3−置換フェニレンであり、
Meは、Li、K、Mg/2、Ca/2、Al/3、アンモニウム、モノ、ジ、トリ、若しくはテトラアルキルアンモニウム(アルキル基は、C1〜C18アルキル又はC2〜C10ヒドロキシアルキルである)、又はこれらの混合物であり、
R1、R2、R3、R4、R5及びR6は、独立して、H又はC1〜C18 n−若しくはイソ−アルキルから選択され、
R7は、直鎖状若しくは分岐状C1〜C18アルキル、又は直鎖状若しくは分岐状C2〜C30アルケニル、又は5〜9つの炭素原子を有するシクロアルキル基、又はC8〜C30アリール基、又はC6〜C30アリールアルキル基である。
(a)米国特許第6,312,936(B1)号、同第5,679,630号、同第4,760,025号、同第7,262,042号、及び国際公開第09/021867号に記載されている、バチルス・レンタス(Bacillus lentus)、バチルス・アルカロフィラス(B. alkalophilus)、バチルス・ズブチルス(B. subtilis)、バチルス・アミロリケファシエンス(B. amyloliquefaciens)、バチルス・プミルス(Bacillus pumilus)及びバチルス・ギブソニイ(Bacillus gibsonii)などのバチルス属由来のものを含むサブチリシン(EC 3.4.21.62)。
(b)国際公開第89/06270号に記載されているフサリウム属プロテアーゼ、並びに同第05/052161号及び同第05/052146号に記載されているセルロモナス属に由来するキモトリプシンプロテアーゼを含む、トリプシン(例えば、ブタ又はウシ起源)などのトリプシン型又はキモトリプシン型のプロテアーゼ。
(c)国際公開第07/044993(A2)号に記載されているバチルス・アミロリケファシエンスに由来するものを含むメタロプロテアーゼ。
(a)国際公開第94/02597号、同第94/18314号、同第96/23874号及び同第97/43424号に記載されている変異体、特に国際公開第96/23874号に配列番号2として列挙されている酵素に対して、以下の位置:15、23、105、106、124、128、133、154、156、181、188、190、197、202、208、209、243、264、304、305、391、408及び444の1つ以上が置換されている変異体。
(b)米国特許第5,856,164号、並びに国際公開第99/23211号、同第96/23873号、同第00/60060号及び同第06/002643号に記載されている変異体、特に国際公開第06/002643号に配列番号12として列挙されているAA560酵素に対して、以下の位置:
26、30、33、82、37、106、118、128、133、149、150、160、178、182、186、193、203、214、231、256、257、258、269、270、272、283、295、296、298、299、303、304、305、311、314、315、318、319、339、345、361、378、383、419、421、437、441、444、445、446、447、450、461、471、482、484の1つ以上が置換されている変異体、好ましくはD183*及びG184*の欠失も含有する変異体。
(c)国際公開第06/002643号における配列番号4、バチルス属SP722由来の野生型酵素と少なくとも90%の同一性を示す変異体、特に183及び184位に欠失を有する変異体、並びに参照によって本明細書に組み込まれる国際公開第00/60060号に記載されている変異体。
(d)バチルス属707の野生型酵素(米国特許第6,093,562号の配列番号7)と少なくとも95%の同一性を示す変異体、特に、以下の突然変異M202、M208、S255、R172、及び/又はM261の1つ以上を含むもの。好ましくは、当該アミラーゼは、M202L、M202V、M202S、M202T、M202I、M202Q、M202W、S255N及び/又はR172Qの1つ以上を含む。特に好ましいのは、M202L又はM202T突然変異を含むものである。
(e)国際公開第09/149130号に記載されている変異体、好ましくは国際公開第09/149130号において配列番号1又は配列番号2と少なくとも90%の同一性を示すもの、ゲオバチルス・ステアロフェルモフィルス(Geobacillus Stearophermophilus)に由来する野生型酵素又はその切断バージョン。
(1)光漂白剤、例えば、スルホン化亜鉛フタロシアニン、スルホン化アルミニウムフタロシアニン、キサンテン染料、チオキサントン、及びこれらの混合物。
(2)予形成過酸:好適な予形成過酸としては、予形成ペルオキシ酸又はその塩、典型的には過カルボン酸及び塩、過炭酸及び塩、過イミド酸及び塩、ペルオキシ一硫酸及び塩、例えばOxone(登録商標)、並びにこれらの混合物からなる群から選択される化合物が挙げられるが、これらに限らない。
(4)R−(C=O)−Lを有する漂白活性化剤、Rはアルキル基であり、場合により分岐しており、漂白活性化剤が疎水性である場合、6〜14個の炭素原子、又は8〜12個の炭素原子を有し、漂白活性化剤が親水性である場合、6つ未満の炭素原子又は更には4つ未満の炭素原子を有し、Lは脱離基である。好適な脱離基の例は、安息香酸及びその誘導体、特にベンゼンスルホネートである。好適な漂白活性化剤としては、ドデカノイルオキシベンゼンスルホネート、デカノイルオキシベンゼンスルホネート、デカノイルオキシ安息香酸又はその塩、3,5,5−トリメチルヘキサノイルオキシベンゼンスルホネート、テトラアセチルエチレンジアミン(TAED)及びノナノイルオキシベンゼンスルホネート(NOBS)が挙げられる。
(5)漂白触媒。本発明の組成物は、ペルオキシ酸及び/又はその塩から酸素原子を受け取って、その酸素原子を酸化可能な基質に転移させることができる1つ以上の漂白触媒を含んでいてもよい。好適な漂白触媒としては、イミニウムカチオン及びポリイオン;イミニウム双性イオン;修飾アミン;修飾アミンオキシド;N−スルホニルイミン;N−ホスホニルイミン;N−アシルイミン;チアジアゾールジオキシド;ペルフルオロイミン;環状糖ケトン及びαアミノ−ケトン並びにこれらの混合物が挙げられるが、これらに限定されない。特に好ましい一触媒は、4−(2−(2−((2−ヒドロキシフェニルメチル)メチレン)−ヒドラジニル)−2−オキソエチル)−4−メチルクロリドなどのアシルヒドラゾン型である。
(6)当該組成物は、好ましくは、触媒金属錯体を含み得る。金属含有漂白触媒の好ましい一種は、銅、鉄、チタン、ルテニウム、タングステン、モリブデン、又はマンガンのカチオンなどの、規定の漂白触媒活性の遷移金属カチオンを含む触媒系である。
当該組成物は、任意に、有機溶媒を含み得る。好適な有機溶媒としては、C4〜14エーテル及びジエーテル、グリコール、アルコキシル化グリコール、C6〜C16グリコールエーテル、アルコキシル化芳香族アルコール、芳香族アルコール、脂肪族分岐鎖アルコール、アルコキシル化脂肪族分岐鎖アルコール、アルコキシル化直鎖C1〜C5アルコール、直鎖C1〜C5アルコール、アミン、C8〜C14アルキル及びシクロアルキル炭化水素及びハロ炭化水素、並びにこれらの混合物が挙げられる。好適な有機溶媒としては、1,2−プロパンジオール、2,3ブタンジオール、エタノール、グリセロール、エトキシル化グリセロール、ジプロピレングリコール、メチルプロパンジオール及びこれらの混合物が挙げられる。また、他の低級アルコール、C1〜C4アルカノールアミン、例えば、モノエタノールアミン及びトリエタノールアミンなどを使用してもよい。溶媒系は、例えば本発明の無水固形物実施形態には存在しなくてもよいが、より典型的には、液体洗剤組成物の約0.1重量%〜約98重量%の範囲、好ましくは少なくとも約1重量%〜約50重量%、より通常は約5重量%〜約25重量%、あるいは約1重量%〜約10重量%の当該有機溶媒の濃度で存在する。これら有機溶媒は、水と共に使用されてもよく、又は水なしで使用されてもよい。
当該組成物が有機真珠光沢剤を含むとき、当該組成物の0.05重量%〜2.0重量%、好ましくは0.1重量%〜1.0重量%活性濃度で、100%活性有機真珠光沢剤が含まれる。好適な有機真珠光沢剤としては、エチレングリコールジステアレートなどのアルキレングリコールのモノエステル及び/又はジエステルが挙げられる。
別の実施形態では、当該組成物は無機真珠光沢剤を含んでもよい。当該組成物が無機真珠光沢剤を含むとき、当該組成物の0.005重量%〜1.0重量%、好ましくは0.01重量%〜0.2重量%活性濃度で、100%活性無機真珠光沢剤が含まれる。
一実施形態では、当該組成物は、約0.01重量%〜約5重量%、あるいは約0.05重量%〜約4重量%、あるいは約0.1重量%〜約3重量%の濃度で複数の懸濁粒子を更に含む。好適な懸濁粒子の例は、米国特許第7,169,741号及び米国特許公開第2005/0203213号に記載されており、それらの開示は参照により本明細書に組み込まれる。これら懸濁粒子は、液体コア又は固体コアを含み得る。これら液体コア粒子及び固体コア粒子の詳細な説明、並びに好ましい粒径、粒子形状、粒子密度、及び粒子破裂強度の説明は、米国特許出願第12/370,714号に記載されており、その開示は参照により本明細書に組み込まれる。
一実施形態では、当該組成物は、乳白剤を含んでもよい。
a)洗濯液体洗剤中のロイコ組成物が前洗浄又は主洗浄又はすすぎ工程で添加され、別個の液体又は固体の形態の酸化剤が前洗浄又は主洗浄又はすすぎ工程で添加される。
b)一方の区画にロイコ組成物及び他方に酸化組成物を含む単回使用の二区画サッシェであって、2つの成分が分離され、それぞれが前洗浄、主洗浄又はすすぎ工程に添加される。
c)2つの組成物を、例えば、布地洗浄プロセス中の任意の時点で、好ましくはすすぎサイクル中又はすすぎサイクル前、最も好ましくは洗浄サイクル中若しくは洗浄サイクル前、又は両方に布地洗濯機に添加してよい。
本明細書の試験方法で使用される布地見本は、Testfabrics,Inc.(West Pittston,PA)から入手され、100%木綿のStyle 403(2”×2”に切断)及び/又はStyle 464(4”×6”に切断)、並びに増白されていない多繊維布地、具体的にはStyle 41(5cm×10cm)である。
綿布見本(Style 403)をもぎとった後、増白剤無配合AATCC HE重質液体洗濯洗剤(水溶液中1.55g/L)で49℃にて2回洗浄することによって使用する。エタノール又は50:50のエタノール:水から選択される溶媒、好ましくはエタノールで、試験される各ロイコ着色剤の濃縮原液を調製する。
脱イオン水に増白剤無配合AATCC HE重質液体洗濯洗剤(1.55g/1.0L)を溶解させることによって、基本洗浄溶液を調製する。4枚のもぎとり綿布見本(stripped cotton swatches)を一緒に計量し、2枚の10mmのガラスマーブルと共に250mLの三角フラスコに入れる。試験される各洗浄溶液について、合計3つのこのようなフラスコを準備する。基本洗浄溶液にロイコ着色剤原液を投入して、所望の8.0×10−6Nの洗浄濃度のロイコ着色剤を含む洗浄溶液を得る。(一例として、493.65g/当量の当量を有するロイコ着色剤の4.0ppm洗浄溶液、又は757.97g/当量の当量を有するロイコ着色剤の6.0ppm洗浄液が、8.0×10−6Nロイコである洗浄溶液を提供する。)
LCE=DE*=[(L* c−L* s)2+(a* c−a* s)2+(b* c−b* s)2]1/2
式中、下付き文字c及びsは、それぞれ、対照、すなわちロイコ着色剤を含まない洗剤で洗浄された布地、及びサンプル、すなわちロイコ着色剤を含有する洗剤で洗浄された布地を指す。
脱イオン水に増白剤無配合AATCC HE重質液体洗濯洗剤(1.55g/1.0L)を溶解させることによって、基本洗浄溶液を調製する。4枚のもぎとり綿布見本(stripped cotton swatches)を一緒に計量し、2枚の10mmのガラスマーブルと共に250mLの三角フラスコに入れる。試験される各洗浄溶液について、合計3つのこのようなフラスコを準備する。
LCE=DE*=((L* c−L* s)2+(a* c−a* s)2+(b* c−b* s)2)1/2
式中、下付き文字c及びsは、それぞれ、対照、すなわちロイコ着色剤を含まない洗剤で洗浄された布地、及びサンプル、すなわちロイコ着色剤を含有する洗剤で洗浄された布地を指す。
上記の方法Iに従って処理された綿布にロイコ着色剤によってもたらされる相対色相角は、以下のように求められる。
a)各溶液からの48時間時点における12枚の見本のa*及びb*の値を平均し、以下の式を使用してΔa*及びΔb*を求める:
Δa*=a* s−a* c及びΔb*=b* s−b* c
式中、下付き文字c及びsは、それぞれ、ロイコ着色剤を含まない洗剤で洗浄された布地及びロイコ着色剤を含有する洗剤で洗浄された布地を指す。
b)Δa*及びΔb*の両方の絶対値が<0.25である場合、相対色相角(Relative Hue Angle、RHA)は計算されない。Δa*又はΔb*のいずれかの絶対値が≧0.25である場合、RHAは以下の式の1つを用いて求められる:
Δb*≧0の場合、RHA=ATAN2(Δa*,Δb*)
Δb*<0の場合、RHA=360+ATAN2(Δa*,Δb*)
ロイコ白色度改善数(LWIN)は、酸化剤を有する液体媒体中にロイコ組成物を含む洗濯ケア組成物で洗浄された織物物品(上記試験方法I.B、ΔWIサンプル)と、酸化剤を含まない液体媒体中にロイコ組成物を含む洗濯ケア組成物で洗浄した織物物品(上記試験方法I.A、ΔWI対照)と間の白色度の改善の変化を表す。
ΔWI=WI CIE洗浄後−WI CIE洗浄前
LWIN=[(ΔWIサンプル−ΔWI対照)/(ΔWI対照)]×100%
反応スキーム:
撹拌棒を備えた100mLの丸底フラスコに、トリフェニルメタン(TPM)化合物B(10g、39.1%固形分、3.27mmol)及び水(30mL)を添加し、pHをNaOHで〜10に調整した。シアン化ナトリウム(0.16g、3.27mmol)を添加し、反応混合物を3時間かけて70℃に加熱した。反応混合物を室温に冷却した。ロイコ着色剤Bを含有する褐色溶液を回収した。溶液は、10%固形分を含有していた。
7000ppmの上記溶液をAATCC洗剤に入れ、2.5gの洗剤を500mLのDI水に添加することにより、洗剤をDI水で5g/Lに希釈した。溶液の吸光度をThermo Scientific Genesys 10S UV/Vis分光光度計で測定した。595nmにおける吸光度は、0.041であると求められた。
以下は、本開示に係る洗浄組成物の例示の実施例であり、限定を意図するものではない。
これら実施例は、単位用量洗濯洗剤用の様々な処方を提供する。組成物8〜12は、1つの単位容量区画を含む。組成物を封入するために使用されるフィルムは、ポリビニルアルコール系フィルムである。
Claims (13)
- (a)少なくとも1つの洗濯ケア成分と、(b)ロイコ組成物と、(c)酸化剤と、を含む洗濯ケア組成物であって、前記ロイコ組成物及び前記酸化剤が、互いに物理的に分離されており、
前記ロイコ組成物が、
からなる群から選択される1つ以上の化合物から選択され、
式I〜Vのその酸化形態に対する比は、少なくとも1:3であり、環A、B及びCのそれぞれにおける各個々のR o 、R m 及びR p 基は、独立して、水素、重水素及びR 5 からなる群から選択され、各R 5 は、独立して、ハロゲン、ニトロ、アルキル、置換アルキル、アリール、置換アリール、アルカリル、置換アルカリル、−C(O)R 1 、−C(O)OR 1 、−C(O)O − 、−C(O)NR 1 R 2 、−OC(O)R 1 、−OC(O)OR 1 、−OC(O)NR 1 R 2 、−S(O) 2 R 1 、−S(O) 2 OR 1 、−S(O) 2 O − 、−S(O) 2 NR 1 R 2 、−NR 1 C(O)R 2 、−NR 1 C(O)OR 2 、−NR 1 C(O)SR 2 、−NR 1 C(O)NR 2 R 3 、−OR 1 、−NR 1 R 2 、−P(O) 2 R 1 、−P(O)(OR 1 ) 2 、−P(O)(OR 1 )O − 、及び−P(O)(O − ) 2 からなる群から選択され、前記3つの環A、B又はCの少なくとも1つにおけるR o 及びR m 基の少なくとも1つは、水素であり、各R p は、独立して、水素、−OR 1 及び−NR 1 R 2 から選択され、
Gは、独立して、水素、重水素、C 1 〜C 16 アルコキシド、フェノキシド、ビスフェノキシド、亜硝酸塩、ニトリル、アルキルアミン、イミダゾール、アリールアミン、ポリアルキレンオキシド、ハロゲン化物、アルキルスルフィド、アリールスルフィド、及びホスフィンオキシドからなる群から選択され、
R 1 、R 2 及びR 3 は、独立して、水素、アルキル、置換アルキル、アリール、置換アリール、アルカリル、置換アルカリル、及びR 4 からなる群から選択され、R 4 は、1つ以上の有機モノマーで構成される有機基であり、前記モノマーの分子量は28〜500の範囲であり、
e及びfは、独立して、0〜4の整数であり、
各R 20 及びR 21 は、独立して、ハロゲン、ニトロ基、アルキル基、置換アルキル基、−NC(O)OR 1 、−NC(O)SR 1 、−OR 1 、及び−NR 1 R 2 からなる群から選択され、
各R 25 は、独立して、単糖部分、二糖部分、オリゴ糖部分、多糖部分、−C(O)R 1 、−C(O)OR 1 、−C(O)NR 1 R 2 からなる群から選択され、
各R 22 及びR 23 は、独立して、水素、アルキル基、及び置換アルキル基からなる群から選択され、
R 30 は、架橋アミン部分に対してオルト又はパラに位置し、−OR 38 及び−NR 36 R 37 からなる群から選択され、各R 36 及びR 37 は、独立して、水素、アルキル基、置換アルキル基、アリール基、置換アリール基、アシル基、R 4 、−C(O)OR 1 、−C(O)R 1 、及び−C(O)NR 1 R 2 からなる群から選択され、
R 38 は、水素、アシル基、−C(O)OR 1 、−C(O)R 1 、及び−C(O)NR 1 R 2 からなる群から選択され、
g及びhは、独立して、0〜4の整数であり、
各R 31 及びR 32 は、独立して、アルキル基、置換アルキル基、アリール基、置換アリール基、アルカリル、置換アルカリル、−C(O)R 1 、−C(O)OR 1 、−C(O)O − 、−C(O)NR 1 R 2 、−OC(O)R 1 、−OC(O)OR 1 、−OC(O)NR 1 R 2 、−S(O) 2 R 1 、−S(O) 2 OR 1 、−S(O) 2 O − 、−S(O) 2 NR 1 R 2 、−NR 1 C(O)R 2 、−NR 1 C(O)OR 2 、−NR 1 C(O)SR 2 、−NR 1 C(O)NR 2 R 3 、−OR 1 、−NR 1 R 2 、−P(O) 2 R 1 、−P(O)(OR 1 ) 2 、−P(O)(OR 1 )O − 、及び−P(O)(O − ) 2 からなる群から選択され、
−NR 34 R 35 は、架橋アミン部分に対してオルト又はパラに位置し、R 34 及びR 35 は、独立して、水素、アルキル、置換アルキル、アリール、置換アリール、アルカリル、置換アルカリル、及びR 4 からなる群から選択され、
R 33 は、独立して、水素、−S(O) 2 R 1 、−C(O)N(H)R 1 、−C(O)OR 1 、及び−C(O)R 1 からなる群から選択され、gが2〜4であるとき、任意の2つの隣接するR 31 基が結合して、5員以上の縮合環を形成してもよく、前記縮合環における原子の2つ以下が窒素原子であってもよく、
X 40 は、酸素原子、硫黄原子、及びNR 45 からなる群から選択され、R 45 は、独立して、水素、重水素、アルキル、置換アルキル、アリール、置換アリール、アルカリル、置換アルカリル、−S(O) 2 OH、−S(O) 2 O − 、−C(O)OR 1 、−C(O)R 1 、及び−C(O)NR 1 R 2 からなる群から選択され、
R 40 及びR 41 は、独立して、−OR 1 及び−NR 1 R 2 からなる群から選択され、
j及びkは、独立して、0〜3の整数であり、
R 42 及びR 43 は、独立して、アルキル、置換アルキル、アリール、置換アリール、アルカリル、置換アルカリル、−S(O) 2 R 1 、−C(O)NR 1 R 2 、−NC(O)OR 1 、−NC(O)SR 1 、−C(O)OR 1 、−C(O)R 1 、−OR 1 、−NR 1 R 2 からなる群から選択され、
R 44 は、−C(O)R 1 、−C(O)NR 1 R 2 、及び−C(O)OR 1 であり、
前記化合物のいずれかに存在する任意の電荷が、好適な独立して選択される内部又は外部対イオンで平衡にされる、洗濯ケア組成物。 - 前記ロイコ組成物及び前記酸化剤が、透過性バリア及び不透過性バリアから選択されるバリアによって分離されている、請求項1に記載の洗濯ケア組成物。
- 前記透過性バリアが、送達粒子、水溶性フィルム、及びこれらの混合物からなる群から選択される、請求項2に記載の洗濯ケア組成物。
- 前記送達粒子が、ポリマー支援型送達粒子、シクロデキストリン系粒子、デンプン系粒子、ゼオライト担体粒子、無機担体粒子、ゲル系カプセル、及びこれらの混合物からなる群から選択される、請求項3に記載の洗濯ケア組成物。
- 前記ポリマー支援型送達粒子が、メラミン、ポリアクリルアミド、シリコーン、シリカ、ポリスチレン、ポリ尿素、ポリウレタン、ポリアクリレート、ポリアクリレートエステル系材料、ゼラチン、スチレンリンゴ酸無水物、ポリアミド、芳香族アルコール、ポリビニルアルコール、及びこれらの混合物からなる群から選択されるマイクロカプセル壁を含む、請求項4に記載の洗濯ケア組成物。
- 前記送達粒子が、前記ロイコ組成物を含む、請求項3〜5のいずれか一項に記載の洗濯ケア組成物。
- 前記酸化剤が、キノン、酸素同素体、過酸化物、窒素酸化物、ハロゲン、ハロゲン酸化物、ハロゲンオキシアニオン、酸化鉛(IV)、二酸化マンガン、酸化マンガン(VI)、酸化マンガン(VII)、過マンガン酸塩、三酸化クロム、重クロム酸塩、鉄(III)、メタバナジン酸塩、バナジン酸塩、ビスマス酸ナトリウム、ハロアミン、及びこれらの混合物からなる群から選択される酸化剤からなる群から選択される、請求項1〜6のいずれか一項に記載の洗濯ケア組成物。
- 前記洗濯ケア成分が、界面活性剤、ビルダー、キレート剤、移染防止剤、分散剤、酵素、酵素安定剤、触媒材料、漂白活性化剤、ポリマー分散剤、泥汚れ除去剤、再付着防止剤、増白剤、抑泡剤、染料、香料、香料送達系、構造化剤、布地柔軟剤、担体、ヒドロトロープ、加工助剤、顔料、抗酸化剤、及びこれらの混合物からなる群から選択される、請求項1〜7のいずれか一項に記載の洗濯ケア組成物。
- 3つの環A、B又はCの全てにおけるRo及びRm基の全てが水素である、請求項1〜8のいずれか一項に記載の洗濯ケア組成物。
- 3つのRp全てが−NR1R2である、請求項1〜9のいずれか一項に記載の洗濯ケア組成物。
- 織物物品を処理する方法であって、(a)請求項1〜10のいずれか一項に記載の洗濯ケア組成物を提供する工程と、(b)ロイコ着色剤組成物、洗濯ケア成分、及び酸化組成物を液体媒体に添加する工程と、(c)前記織物物品を前記液体媒体と接触するように置く工程と、(d)前記ロイコ着色剤組成物の少なくとも一部を前記酸化組成物で酸化させて、酸化ロイコ着色剤組成物にする工程と、(e)前記酸化ロイコ着色剤組成物の少なくとも一部を織物上に付着させる工程と、(f)任意にすすぐ工程と、(g)前記織物物品を乾燥させる工程と、を含む、方法。
- (a)パッケージと、(b)ロイコ着色剤を含む第1の組成物と、(c)酸化剤を含む第2の組成物と、(d)洗濯ケア成分と、を含む、パッケージ化された請求項1〜10のいずれか一項に記載の洗濯ケア組成物。
- (a)第1の組成物を含む第1のパッケージと、(b)第2の組成物を含む第2のパッケージと、(c)洗濯ケア成分と、を備えるキットであって、前記第1の組成物が、請求項12に記載のロイコ着色剤を含み、前記第2の組成物が、酸化剤を含む、キット。
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-
2017
- 2017-11-01 EP EP17804363.4A patent/EP3535362A1/en not_active Withdrawn
- 2017-11-01 US US15/800,121 patent/US20180119070A1/en not_active Abandoned
- 2017-11-01 JP JP2019521683A patent/JP6790257B2/ja active Active
- 2017-11-01 CN CN201780064199.6A patent/CN109890949B/zh active Active
- 2017-11-01 WO PCT/US2017/059428 patent/WO2018085315A1/en unknown
Also Published As
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WO2018085315A1 (en) | 2018-05-11 |
US20180119070A1 (en) | 2018-05-03 |
JP2019533058A (ja) | 2019-11-14 |
CN109890949B (zh) | 2021-10-01 |
CN109890949A (zh) | 2019-06-14 |
EP3535362A1 (en) | 2019-09-11 |
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