JPH11515039A - Detergent composition comprising a clay-agglomerated polymer having a particle size of less than 250 microns - Google Patents
Detergent composition comprising a clay-agglomerated polymer having a particle size of less than 250 micronsInfo
- Publication number
- JPH11515039A JPH11515039A JP9511329A JP51132997A JPH11515039A JP H11515039 A JPH11515039 A JP H11515039A JP 9511329 A JP9511329 A JP 9511329A JP 51132997 A JP51132997 A JP 51132997A JP H11515039 A JPH11515039 A JP H11515039A
- Authority
- JP
- Japan
- Prior art keywords
- clay
- detergent composition
- particle size
- polymer
- micrometers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 38
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 239000003599 detergent Substances 0.000 title claims abstract description 25
- 239000002245 particle Substances 0.000 title claims abstract description 22
- 239000004927 clay Substances 0.000 claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 23
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 9
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 claims 1
- 150000001860 citric acid derivatives Chemical class 0.000 claims 1
- 235000021317 phosphate Nutrition 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 11
- 239000010457 zeolite Substances 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000005194 fractionation Methods 0.000 description 6
- 238000012216 screening Methods 0.000 description 6
- 229910021647 smectite Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 3
- 229910000271 hectorite Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- 230000003311 flocculating effect Effects 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- -1 volchonskoite Inorganic materials 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 102000005575 Cellulases Human genes 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000276 sauconite Inorganic materials 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 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
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3707—Polyethers, e.g. polyalkyleneoxides
-
- 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
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
(57)【要約】 本発明は、(i)軟化クレーおよび(ii)クレー凝集重合体を含んでなる顆粒状洗剤組成物、およびその組成物の製造方法に関する。この組成物は、「洗濯による軟化」製品に特に有用である。クレー凝集重合体を、顆粒状洗剤組成物に加える前に、クレー凝集重合体の少なくとも９５重量％が２５０マイクロメートル未満、好ましくは１５０マイクロメートル未満、の粒子径を有する様に、篩にかけるか、または粉砕する。 (57) [Summary] The present invention relates to a granular detergent composition comprising (i) a softened clay and (ii) a clay-agglomerated polymer, and a method for producing the composition. This composition is particularly useful for "softening by washing" products. Prior to adding the clay agglomerated polymer to the granular detergent composition, the clay agglomerated polymer is sieved such that at least 95% by weight of the clay agglomerated polymer has a particle size of less than 250 micrometers, preferably less than 150 micrometers. Or crush.
Description
【発明の詳細な説明】 粒子径２５０ミクロン未満のクレー凝集重合体を含んでなる洗剤組成物 本発明は、(i)軟化クレーおよび(ii)クレー凝集重合体を含んでなる顆粒状洗 剤組成物、およびその組成物の製造方法に関する。この組成物は、「洗濯による 軟化」製品に特に有用である。 クレー凝集重合体、例えば高い分子量を有するポリエチレンオキシド、は１０ ０％活性粉末として市販されている。 ＥＰ−Ａ ０２９９５７５号明細書（１９８９年１月１８日公開）には、軟化 性クレーおよび重合体状クレー凝集重合体を含んでなる顆粒状洗剤組成物が開示 されている。この顆粒状洗剤組成物の製造において、重合体状クレー凝集剤は様 々な方法で加えられることが記載されている。凝集剤は、噴霧乾燥前のクラッチ ャー混合物に加えるか、または水または有機溶剤に入れた溶液から顆粒状洗剤の 上に噴霧するか、または粒子の形態で顆粒状洗剤と乾燥混合することができる。 この出願は、クレー凝集重合体の好ましい粒子径を記載していない。 しかし、重合体状クレー凝集重合体を顆粒状洗剤に乾燥混合する場合、好まし くない不均質なクレー堆積物または残留物が観察される。不均質な堆積物は、ク レーの塊が布地表面上に堆積する場合に見られる。これは、クレー粒子が分散す る機会を得る前に、非常に急速に凝集する場合に引き起こされる。これによって 布地表面上に堆積するクレーの塊が形成される。残留物は、処方物中に存在する クレー凝集重合体の局所的濃度が高い場合に、水と接触してゲルを形成する時に 起こり、製品の配量が困難になり、そして衣類の上に製品が堆積する危険性が増 大する。 さらに、クレー凝集重合体は、粒子形態で取り扱う場合、取扱い上および爆発 性の問題が生じる。 発明の概要 本発明により、クレー凝集重合体を、顆粒状洗剤組成物に加える前に、クレー 凝集重合体の少なくとも９５重量％が、２５０マイクロメートル未満、好ましく は１５０マイクロメートル未満、の粒子径を有する様に、篩にかけるか、または 粉砕することにより、好ましくない不均質なクレー堆積物および残留物が避けら れる。 好ましくは、クレー凝集重合体は、平均分子量が１００，０００〜１， ０００万、より好ましくは１５０，０００〜８００，０００、であるポリエチレ ンオキシドである。 本発明の別の態様では、クレー凝集重合体を、アルミノケイ酸塩、ケイ酸塩、 炭酸塩、クエン酸塩、リン酸塩、またはそれらの混合物、からなる群から選択さ れた粉末と予備混合する工程、および続いてその予備混合物を他の洗剤成分と混 合する工程を含んでなる、顆粒状洗剤組成物の製造方法を提供する。 好ましくは、予備混合物は、１：２０〜２０：１の比でクレー凝集重合体およ びアルミノケイ酸塩からなる。 発明の詳しい説明 ＜軟化性クレー(softening clay)＞ 軟化性クレーは、未変性でも、有機物質により変性してあってもよい。有機物 質により変性してないクレーは、イオン交換能力が少なくとも５０meq/１００ｇ クレー、好ましくは少なくとも６０meq/１００ｇクレーである、膨脹可能な３層 クレー、すなわちアルミノケイ酸塩およびケイ酸マグネシウムとして説明するこ とができる。有機物質により変性したクレーを得るための出発クレーも同様に説 明することができる。クレーの説明に使用する用語「膨脹可能な」とは、層状ク レー構造が水と接触して膨潤または膨脹する能力を意味する。ここで使用する３ 層膨脹可能クレーとは、地質学的にはスメクタイトとして区分される物質である 。 スメクタイト型クレーには、外側層における特定数のケイ素−酸素原子に対する 中央層における八面体金属−酸素配置の数に基づいて大まかに区別することので きる、２つのまったく別の種類がある。クレー鉱物に関するより詳細な解説は、 H．van Olphen による「Clay Colloidal Chemistry」、第６章、特に６６〜６９ 頁、John Wiley & Sons(Interscience Publishers)，New York，1963、に記載さ れている。 スメクタイト（またはモンモリロン石）クレーの群は、下記の三八面体鉱物、 すなわちタルク、ヘクトライト、サポー石、ソーコナイト、バーミキュル石、お よび下記の二八面体鉱物、すなわちプロフィライト、モンモリロン石、 volchonskoite、およびノントロン石、を包含する。 これらの組成物に使用するクレーは、陽イオン系対イオン、例えばプロトン、 ナトリウムイオン、カリウムイオン、カルシウムイオン、およびリチウムイオン 、を含有する。優先的または独占的に吸収される陽イオンに基づいてクレーを区 別するのが一般的である。例えば、ナトリウムクレーは、吸収される陽イオンが ほとんどナトリウムであるクレーである。その様な吸収された陽イオンは、水溶 液中に存在する陽イオンとの交換反応に関与することができる。スメクタイト型 クレーが関与する代表的な交換反応は、下記の式で表される。 スメクタイトクレー(Ｎａ)+＋ＮＨ4ＯＨ ＝＞ スメクタイトクレー(ＮＨ4)+＋ ＮａＯＨ 上記の平衡反応中、当量のアンモニウムイオンが当量のナトリウムを置き換える ので、陽イオン交換能力（「塩基交換能力」と呼ばれることがある）を、クレー １００ｇあたりのミリ当量(meq/１００g)に換算して測定するのが一般的である 。クレーの陽イオン交換能力は、電気透析、アンモニウムイオンとの交換に続く 滴定、あるいはメチレンブルー法を含む、いくつかの方法により測定できるが、 これらの方法はすべてGrimshaw，「The Chemistry and Physics of Clays」，pp26 4 -265，Interscience(1971)に詳細に記載されている。クレー材料の陽イオン交換 能力は、クレーの膨脹特性、クレーの電荷にれは少なくとも部分的に格子構造に より決定される）、およびその他のファクターに関連する。クレーのイオン交換 能力は、ある種のスメクタイトクレーに対して約２meq/１００ｇカオリナイト〜 約１５０meq/１００ｇ、およびそれ以上、の範囲内で大きく変動する。 好ましいスメクタイト型クレーは、ナトリウムモンモリロン石、カリウムモン モリロン石、ナトリウムヘクトライト、およびカリウムヘクトライトである。こ こで使用するクレーは、粒子径が約１ミクロンまでである。 ここで使用するクレーはすべて、天然産でも合成品でもよい。 ＜クレー凝集重合体(clay flocculating polymer)＞ ほとんどのクレー凝集重合体は、エチレンオキシド、アクリルアミド、アクリ ル酸、メタクリル酸ジメチルアミノエチル、ビニルアルコール、ビニルピロリド ン、およびエチレンイミンの様なモノマーに由来する、かなり長鎖の重合体およ び共重合体である。グアーガムの様なガム類も好適である。 エチレンオキシド、アクリルアミド、またはアクリル酸の重合体が好ましい。 これらの重合体は、それらの分子量が１００，０００〜１，０００万の範囲内に ある場合、布地軟化性クレーの堆積を劇的に強化する。重量平均分子量が１５０ ，０００〜５００万である様な重合体が好ましい。 最も好ましい重合体は、ポリ（エチレンオキシド）である。分子量分布は、ゲ ル透過クロマトグラフィーを使用し、分子量分布が狭いポリ（エチレンオキシド ）標準に対して容易に測定することができる。 ＜製法＞ 重合体の粒子径は、標準的な粉砕操作または粒子の物理的なスクリーニングに より、小さくする。次いで原料を所望によりミキサー中で細かいアルミノケイ酸 塩（ゼオライトタイプＡ）の様な粉末と混合し、次いで完成製品工程に加える。 ゼオライトは重合体に対するキャリヤーとして作用して、完成製品製造における 分散を促進する。 粒子径を変えるための様々な種類の装置を使用して、クレー凝集重合体の平均 粒子径を２５０マイクロメートル未満に下げることができる。Russel Finexおよ びMogenson振動スクリーンの様な連続スクリーン、または連続スクレーパースク リーンである。少量には、RoTap 変形を含むバッチスクリーニング操作も適用で きる。大規模生産には、材料の細粒化および分別を同時に行う連続空気ジェット ミルも使用できる。 本発明の特別な実施態様では、重合体粒子を微粒化により処理して、平均粒子 径をさらに下げることができる。 ＜他の洗剤成分＞ 本発明の粒子状成分は、一般的に完成洗剤製品中、特に軟化性クレーを含んで なる製品中、に配合する。陰イオン系および非イオン系界面活性剤、ビルダー、 漂白剤、漂白活性剤、発泡抑制剤、酵素（例えばプロテアーゼ、アミラーゼ、セ ルラーゼ、リパーゼ）、香料光沢剤、汚れ放出性重合体の様な、他の通常の洗剤 成分を一般的に使用する。 例 これらの諸例中、他に指示がない限り、百分率はすべて重量で表示し、下記の 略号を使用した。 （ＰＥＯ（そのまま）） Union Carbide からWSRN750(商品名)として供給されるポリエチレンオキシド 重合体である。代表的な粒子径分布は以下の通りである。 ２％が７１０マイクロメートル超過、 ８％が７１０〜５００マイクロメートル、 ２０％が５００〜２５０マイクロメートル、 ３０％が２５０〜１５０マイクロメートル、 ４０％が１５０マイクロメートル未満。 （ＰＥＯ（分別）） 上記と同様であるが、１５０マイクロメートルを超える材料の９５％を、細粒 化工程により除去してある。代表的な粒子径分布は以下の通りである。 少なくとも１００％が３００マイクロメートル未満、 少なくとも９５％が１５０マイクロメートル未満、 少なくとも５０％が１０６マイクロメートル未満。 （ゼオライトＡ） Industrial Zeolite Ltd.，Thurrock，Englandから供給。代表的な平均粒子径 は２〜１０マイクロメートルである。 （軽質ソーダ灰Ａ） 低密度炭酸ナトリウム、典型的には、９７％純度の炭酸塩、平均粒子径約１０ ０マイクロメートル、通気密度平均５５０g/lである。 例１ ＰＥＯ（そのまま）の試料を、RoTap バッチスクリーニングの手順により、１ ５０マイクロメートル篩で、ＰＥＯ（分別）に処理した。得られた重合体を、小 規模フードプロセッサーで均質状態に、ＰＥＯ（分別）１部対ゼオライトＡ２部 の比で混合した。 ＰＥＯ／ゼオライトＡの予備混合物を、バッチロータリーミキサー中で、下記 の「洗濯による軟化」洗剤組成物の粒子状成分と混合した。次いで、その上に液 体成分を噴霧した。最終組成物は優れたクレー堆積および軟化特性を有する。 例１ （重量％） ＰＥＯ／ゼオライトＡ予備混合物 ０．５ 軟化性クレー １８ 陰イオン系界面活性剤凝集物 ２６ 陽イオン系界面活性剤凝集物 ６ 非イオン系界面活性剤 ３ 過炭酸ナトリウム １３ 層状ケイ酸塩／クエン酸 １２ ゼオライト ４ 漂白活性剤粒子 ４ 発泡抑制剤 ３．５ 炭酸ナトリウム、酵素、香料、汚れ放出剤、 光沢剤、およびその他の少量成分 合計で１００になる量 例２ 細粒化工程を、１５０マイクロメートル篩を装備した連続Russel Finex振動ス クリーニングシステムにＰＥＯ（そのまま）を通して行なった以外は、例１を繰 り返した。 例３ 細粒化工程で、小バッチコーヒー粉砕機でＰＥＯ（そのまま）を粉砕し、次い でRoTap バッチスクリーニングを完了した以外は、例１を繰り返した。 例４ 細粒化工程を、１５０マイクロメートルスクリーンを装備し、ロータリーブラ シを取り付けてスクリーニング効率を改良した標準的な非振動篩デッキにＰＥＯ （そのまま）を通して行なった以外は、例１を繰り返した。 例５ 細粒化工程を、１５０マイクロメートル未満の粒子だけが空気流に乗り、除去 されて集められる様に操作する標準的な空気ジェットミルにＰＥＯ（そのまま） を通して行なった以外は、例１を繰り返した。この手順は、ＰＥＯ（そのまま） の損失が無いので、大量に処理する必要がある場合に有用である。 例６ 独自の軸上で回転し、同時に混合室中を軌道を描いて旋回するスクリューを備 えた円錐形ミキサーを有するバッチvertomixer、または類似の装置中でＰＥＯ（ 分別）をゼオライトＡと混合した以外は、例４を繰り返した。 例７ 得られた予備混合物が、ＰＥＯ（分別）１部対ゼオライトＡ１部の比を有する 以外は、例６を繰り返した。 例８ 得られた予備混合物が、ＰＥＯ（分別）１部対ゼオライトＡ１０部の比を有す る以外は、例６を繰り返した。 例９ 得られた予備混合物が、ＰＥＯ（分別）１部対微細軽質ソーダ灰１０部の比を 有する以外は、例８を繰り返した。 例１０ 液体を噴霧する前に、予備混合物を連続式洗剤製造工程に直接加える以外は、 例６を繰り返した。 例１１ 液体を噴霧した後に、予備混合物を、連続製造工程で製造した洗剤の表面上に 散布した以外は、例６を繰り返した。DETAILED DESCRIPTION OF THE INVENTION A detergent composition comprising a clay-agglomerated polymer having a particle size of less than 250 microns The present invention relates to a granular detergent composition comprising (i) a softened clay and (ii) a clay-agglomerated polymer. And a method for producing the composition. This composition is particularly useful for "softening by washing" products. Clay agglomerated polymers, such as polyethylene oxide with high molecular weight, are commercially available as 100% active powder. EP-A 0 299 575 (published Jan. 18, 1989) discloses a granular detergent composition comprising a softening clay and a polymeric clay agglomerated polymer. In the manufacture of this granular detergent composition, it is described that the polymeric clay flocculant is added in various ways. The flocculant can be added to the crutcher mixture before spray drying, or sprayed onto the granular detergent from a solution in water or an organic solvent, or dry mixed with the granular detergent in the form of particles. This application does not describe the preferred particle size of the clay agglomerated polymer. However, when the polymeric clay agglomerated polymer is dry mixed with the granular detergent, undesirable heterogeneous clay deposits or residues are observed. Heterogeneous sediments are found when clay clumps accumulate on the fabric surface. This is caused when the clay particles agglomerate very quickly before they have a chance to disperse. This forms a clump of clay that accumulates on the fabric surface. Residues occur when the local concentration of clay agglomerated polymer present in the formulation is high, forming a gel upon contact with water, making product dispensing difficult and causing product The risk of deposits increases. In addition, clay-agglomerated polymers pose handling and explosive problems when handled in particulate form. SUMMARY OF THE INVENTION In accordance with the present invention, at least 95% by weight of the clay-agglomerated polymer has a particle size of less than 250 micrometers, preferably less than 150 micrometers, prior to adding the clay-agglomerated polymer to the granular detergent composition. By sieving or grinding, as is, undesirable heterogeneous clay deposits and residues are avoided. Preferably, the clay agglomerated polymer is a polyethylene oxide having an average molecular weight of 100,000 to 10 million, more preferably 150,000 to 800,000. In another aspect of the present invention, the clay agglomerated polymer is premixed with a powder selected from the group consisting of aluminosilicate, silicate, carbonate, citrate, phosphate, or mixtures thereof. A method for producing a granular detergent composition, comprising the step of: and subsequently mixing the premix with other detergent components. Preferably, the premix consists of the clay agglomerated polymer and the aluminosilicate in a ratio of 1:20 to 20: 1. DETAILED DESCRIPTION OF THE INVENTION <Softening Clay> The softening clay may be unmodified or modified with an organic substance. Clay that has not been modified by organic matter can be described as an expandable three-layer clay having an ion exchange capacity of at least 50 meq / 100 g clay, preferably at least 60 meq / 100 g clay, ie, aluminosilicate and magnesium silicate. it can. The starting clay for obtaining the clay modified by the organic substance can be described in a similar manner. The term "expandable" as used in describing clay refers to the ability of the layered clay structure to swell or expand in contact with water. The three-layer inflatable clay used herein is a substance that is geologically classified as smectite. There are two distinct types of smectite-type clays that can be broadly distinguished based on the number of octahedral metal-oxygen configurations in the central layer relative to a particular number of silicon-oxygen atoms in the outer layer. For a more detailed commentary on clay minerals, see "Clay Colloidal Chemistry" by van Olphen, Chapter 6, especially pages 66-69, John Wiley & Sons (Interscience Publishers), New York, 1963. Groups of smectite (or montmorillonite) clays include the following trioctahedral minerals: talc, hectorite, sapphoite, sauconite, vermiculite, and the following dioctahedral minerals: profilite, montmorillonite, volchonskoite, and Nontronite. The clays used in these compositions contain cationic counterions, such as protons, sodium ions, potassium ions, calcium ions, and lithium ions. It is common to distinguish clays based on cations that are preferentially or exclusively absorbed. For example, sodium clay is a clay in which the cation absorbed is mostly sodium. Such absorbed cations can participate in exchange reactions with cations present in the aqueous solution. A typical exchange reaction involving a smectite-type clay is represented by the following formula. Smectite clay (Na) + + NH 4 OH => Smectite clay (NH 4 ) + + NaOH During the above equilibrium reaction, an equivalent amount of ammonium ion displaces an equivalent amount of sodium, so that the cation exchange capacity (referred to as “base exchange capacity”) Is sometimes measured in terms of milliequivalents per 100 g of clay (meq / 100 g). The cation exchange capacity of clay can be measured by several methods, including electrodialysis, titration following exchange with ammonium ions, or the methylene blue method, all of which are described in Grimshaw, "The Chemistry and Physics of Clays". , Pp264-265, Interscience (1971). The cation exchange capacity of the clay material is related to the expansion properties of the clay, the charge transfer of the clay is determined at least in part by the lattice structure), and other factors. The ion exchange capacity of the clay varies widely from about 2 meq / 100 g kaolinite to about 150 meq / 100 g and more for certain smectite clays. Preferred smectite-type clays are sodium montmorillonite, potassium montmorillonite, sodium hectorite, and potassium hectorite. The clays used herein have a particle size of up to about 1 micron. All clays used herein may be natural or synthetic. <Clay flocculating polymer> Most clay flocculating polymers are derived from monomers such as ethylene oxide, acrylamide, acrylic acid, dimethylaminoethyl methacrylate, vinyl alcohol, vinylpyrrolidone, and ethyleneimine. Long-chain polymers and copolymers. Gums such as guar gum are also suitable. Polymers of ethylene oxide, acrylamide, or acrylic acid are preferred. These polymers dramatically enhance the deposition of fabric softening clays when their molecular weight is in the range of 100,000 to 10 million. Polymers having a weight average molecular weight of 150,000 to 5,000,000 are preferred. The most preferred polymer is poly (ethylene oxide). The molecular weight distribution can be easily measured using gel permeation chromatography against a poly (ethylene oxide) standard with a narrow molecular weight distribution. <Production Method> The particle size of the polymer is reduced by a standard pulverization operation or physical screening of particles. The raw material is then optionally mixed with a powder such as a fine aluminosilicate (zeolite type A) in a mixer and then added to the finished product process. The zeolite acts as a carrier for the polymer, facilitating dispersion in the manufacture of the finished product. Various types of equipment for varying the particle size can be used to reduce the average particle size of the clay-agglomerated polymer to less than 250 micrometers. Continuous screens, such as Russel Finex and Mogenson vibrating screens, or continuous scraper screens. For small quantities, batch screening operations involving RoTap deformation can also be applied. For large-scale production, a continuous air jet mill that simultaneously granulates and separates the material can also be used. In a particular embodiment of the present invention, the polymer particles can be treated by atomization to further reduce the average particle size. <Other Detergent Components> The particulate components of the present invention are generally incorporated into finished detergent products, particularly products containing softening clay. Anionic and nonionic surfactants, builders, bleaches, bleach activators, foam inhibitors, enzymes (eg, proteases, amylases, cellulases, lipases), fragrance brighteners, such as soil release polymers, etc. The usual detergent ingredients are commonly used. EXAMPLES In these examples, all percentages are by weight and the following abbreviations are used, unless otherwise indicated. (PEO (as is)) Polyethylene oxide polymer supplied by Union Carbide as WSRN750 (trade name). A typical particle size distribution is as follows. 2% is greater than 710 micrometers, 8% is 710-500 micrometers, 20% is 500-250 micrometers, 30% is 250-150 micrometers, and 40% is less than 150 micrometers. (PEO (fractionation)) As above, but 95% of the material over 150 micrometers has been removed by the grain refinement step. A typical particle size distribution is as follows. At least 100% less than 300 micrometers, at least 95% less than 150 micrometers, at least 50% less than 106 micrometers. (Zeolite A) Supplied from Industrial Zeolite Ltd., Thurrock, England. A typical average particle size is 2 to 10 micrometers. (Light Soda Ash A) Low density sodium carbonate, typically 97% pure carbonate, average particle size about 100 micrometers, average aeration density of 550 g / l. Example 1 A sample of PEO (as is) was processed to PEO (fractionation) on a 150 micrometer sieve by the procedure of RoTap batch screening. The resulting polymer was mixed homogeneously in a small scale food processor at a ratio of 1 part PEO (fractionation) to 2 parts zeolite A. The PEO / zeolite A premix was mixed in a batch rotary mixer with the particulate components of the "soften by washing" detergent composition described below. Next, the liquid component was sprayed thereon. The final composition has excellent clay deposition and softening properties. Example 1 (% by weight) PEO / zeolite A premix 0.5 Softening clay 18 Anionic surfactant aggregate 26 Cationic surfactant aggregate 6 Nonionic surfactant 3 Sodium percarbonate 13 Layered silica Acid salt / citric acid 12 Zeolite 4 Bleaching activator particles 4 Foaming inhibitor 3.5 Sodium carbonate, enzymes, fragrances, soil release agents, brighteners, and other small components Amounts totaling 100 Example 2 Refining process Example 1 was repeated, except that the sample was passed through PEO (as is) through a continuous Russel Finex vibration screening system equipped with a 150 micrometer sieve. Example 3 Example 1 was repeated except that the PEO (as is) was ground in a small batch coffee grinder in the refining process and then the RoTap batch screening was completed. Example 4 Example 1 was repeated except that the granulation step was performed through PEO (as is) through a standard non-vibrating sieve deck equipped with a 150 micrometer screen and fitted with a rotary brush to improve screening efficiency. Example 5 Example 1 was repeated except that the granulation step was performed through PEO (as is) through a standard air jet mill operating such that only particles smaller than 150 micrometers were entrained in the air stream and removed and collected. Repeated. This procedure is useful when large volumes need to be processed since there is no loss of PEO (as is). Example 6 Except mixing PEO (fractionation) with zeolite A in a batch vertomixer with conical mixer with screw rotating on its own axis and simultaneously orbiting in the mixing chamber, or similar equipment Repeated Example 4. Example 7 Example 6 was repeated except that the premix obtained had a ratio of 1 part PEO (fractionation) to 1 part zeolite A. Example 8 Example 6 was repeated except that the resulting premix had a ratio of 1 part PEO (fractionation) to 10 parts zeolite A. Example 9 Example 8 was repeated except that the resulting premix had a ratio of 1 part PEO (fractionated) to 10 parts fine light soda ash. Example 10 Example 6 was repeated except that the premix was added directly to the continuous detergent manufacturing process prior to spraying the liquid. Example 11 Example 6 was repeated, except that after spraying the liquid, the premix was sprayed on the surface of the detergent produced in the continuous production process.
Claims (1)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP95306121.5 | 1995-09-01 | ||
| EP95306121 | 1995-09-01 | ||
| PCT/US1996/014106 WO1997009406A1 (en) | 1995-09-01 | 1996-09-03 | Detergent composition comprising clay flocculating polymer with particle size less than 250 microns |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11515039A true JPH11515039A (en) | 1999-12-21 |
| JP3894953B2 JP3894953B2 (en) | 2007-03-22 |
Family
ID=8221310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP51132997A Expired - Fee Related JP3894953B2 (en) | 1995-09-01 | 1996-09-03 | Detergent composition comprising clay agglomerated polymer having a particle size of less than 250 microns |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0865480B1 (en) |
| JP (1) | JP3894953B2 (en) |
| CN (1) | CN1105170C (en) |
| AT (1) | ATE221570T1 (en) |
| BR (1) | BR9610465A (en) |
| DE (1) | DE69622744T2 (en) |
| DK (1) | DK0865480T3 (en) |
| ES (1) | ES2176486T3 (en) |
| MX (1) | MX9801690A (en) |
| PT (1) | PT865480E (en) |
| WO (1) | WO1997009406A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2348435A (en) * | 1999-04-01 | 2000-10-04 | Procter & Gamble | Softening compositions |
| US6881717B1 (en) | 1999-04-01 | 2005-04-19 | The Procter & Gamble Company | Fabric softening component |
| EP1561804B1 (en) * | 2004-02-03 | 2008-08-13 | The Procter & Gamble Company | A solid particulate laundry detergent composition comprising clay and polydimethysiloxane |
| ES2340276T3 (en) * | 2004-02-03 | 2010-06-01 | THE PROCTER & GAMBLE COMPANY | DETERGENT COMPOSITION FOR WASHING THE CLOTHING, SOLID IN PARTICLES, THAT INCLUDES CLAY AND POLYDIMETHYLLXAN. |
| MX2012008097A (en) | 2010-01-11 | 2012-07-30 | Kolene Corp | Metal surface scale conditioning method and apparatus thereof. |
| DE112018004365T5 (en) | 2017-09-29 | 2020-09-24 | Unilever N.V. | Laundry products |
| CN111201311A (en) | 2017-10-05 | 2020-05-26 | 荷兰联合利华有限公司 | Method and apparatus for personalized laundry |
| GB2571336A (en) | 2018-02-26 | 2019-08-28 | Unilever Plc | Methods and system for monitoring and replenishing one or more laundry components |
| US11910982B2 (en) | 2019-11-01 | 2024-02-27 | Conopco Inc. | Recyclable auto-dosing container |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3881329T3 (en) * | 1987-10-19 | 2002-05-23 | The Procter & Gamble Company, Cincinnati | Cleaning supplies. |
| US4844821A (en) * | 1988-02-10 | 1989-07-04 | The Procter & Gamble Company | Stable liquid laundry detergent/fabric conditioning composition |
| US5443750A (en) * | 1991-01-16 | 1995-08-22 | The Procter & Gamble Company | Detergent compositions with high activity cellulase and softening clays |
| CN1145095A (en) * | 1994-03-30 | 1997-03-12 | 普罗格特-甘布尔公司 | Laundry detergent bars containing fabric softening clay |
-
1996
- 1996-09-03 PT PT96929867T patent/PT865480E/en unknown
- 1996-09-03 BR BR9610465A patent/BR9610465A/en not_active IP Right Cessation
- 1996-09-03 EP EP96929867A patent/EP0865480B1/en not_active Expired - Lifetime
- 1996-09-03 JP JP51132997A patent/JP3894953B2/en not_active Expired - Fee Related
- 1996-09-03 CN CN96197708A patent/CN1105170C/en not_active Expired - Fee Related
- 1996-09-03 DK DK96929867T patent/DK0865480T3/en active
- 1996-09-03 AT AT96929867T patent/ATE221570T1/en not_active IP Right Cessation
- 1996-09-03 DE DE69622744T patent/DE69622744T2/en not_active Expired - Lifetime
- 1996-09-03 WO PCT/US1996/014106 patent/WO1997009406A1/en active IP Right Grant
- 1996-09-03 ES ES96929867T patent/ES2176486T3/en not_active Expired - Lifetime
-
1998
- 1998-03-02 MX MX9801690A patent/MX9801690A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN1105170C (en) | 2003-04-09 |
| DE69622744D1 (en) | 2002-09-05 |
| ES2176486T3 (en) | 2002-12-01 |
| CN1200142A (en) | 1998-11-25 |
| EP0865480A1 (en) | 1998-09-23 |
| DK0865480T3 (en) | 2002-09-02 |
| EP0865480B1 (en) | 2002-07-31 |
| JP3894953B2 (en) | 2007-03-22 |
| WO1997009406A1 (en) | 1997-03-13 |
| BR9610465A (en) | 1999-03-02 |
| MX9801690A (en) | 1998-08-30 |
| PT865480E (en) | 2002-11-29 |
| ATE221570T1 (en) | 2002-08-15 |
| DE69622744T2 (en) | 2003-04-03 |
| EP0865480A4 (en) | 1999-05-26 |
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