JPH06100889A - Composition for dish washing machine - Google Patents
Composition for dish washing machineInfo
- Publication number
- JPH06100889A JPH06100889A JP5060565A JP6056593A JPH06100889A JP H06100889 A JPH06100889 A JP H06100889A JP 5060565 A JP5060565 A JP 5060565A JP 6056593 A JP6056593 A JP 6056593A JP H06100889 A JPH06100889 A JP H06100889A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- composition according
- composition
- builder
- phosphate
- 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.)
- Pending
Links
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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/32—Amides; Substituted amides
-
- 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
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- 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
- C11D3/128—Aluminium silicates, e.g. zeolites
-
- 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
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- 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
- C11D3/3719—Polyamides or polyimides
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)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、皿洗い機用組成物に関
する。特に本発明は、ポリアミノ酸を含み、リン酸塩を
含まない、改良された皿洗い機用組成物に関する。FIELD OF THE INVENTION The present invention relates to a dishwasher composition. In particular, the invention relates to improved dishwashing compositions containing polyamino acids and free of phosphate.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】皿洗い
機で主洗浄サイクル及び最終濯ぎ時に炭酸イオン種（CO
- 3）が高濃度であると、洗浄した物品（例えば、皿、ガ
ラス、カトラリーなど）及び機械部品への炭酸カルシウ
ム付着物（スケーリング）の形成が起こる。現在の無リ
ン配合物は、もともとビルダー作用が弱く、且つスケー
ル防止性が不十分であるビルダー（例えば、クエン酸
塩、炭酸塩、ゼオライト）を含んでおり、これらの製品
にスケールがつく危険性は慣用の三リン酸ナトリウムベ
ースの製品よりも高い。水道水の硬度が比較的高かった
り、機械中での軟水化が十分でないと、たちまち上記の
問題を起こしてしまう。スケール形成過程に含まれる他
のパラメーターは、温度（高温は付着を増加させる）及
びpH（pHが高いとスケール形成も増える）である。PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION In a dishwasher, carbonate ion species (CO
- 3) If it is a high concentration, the cleaned articles (e.g., dishes, glasses, formation of cutlery, etc.) and calcium carbonate deposits on the machine part (scaling) occurs. Current phosphorus-free formulations contain builders (eg, citrates, carbonates, zeolites) that are inherently weak in builder action and insufficient in scale protection, and the risk of scaling these products. Is higher than conventional sodium triphosphate based products. If the hardness of tap water is relatively high or the water softening in the machine is not sufficient, the above problems will occur immediately. Other parameters involved in the scale formation process are temperature (high temperature increases adhesion) and pH (high pH increases scale formation).
【０００３】従って、食器及び機械部品でのスケール形
成は、リン酸塩を含まない皿洗い機用製品に関しては、
特に、硬水地域で使用する場合及び/またはビルダー系
が炭酸ナトリウムを含む場合及び/または漂白剤系が過
炭酸ナトリウムを含む場合、重要な問題である。Therefore, scale formation on dishware and machine parts is associated with phosphate-free dishwasher products,
Especially when used in hard water areas and / or when the builder system comprises sodium carbonate and / or when the bleach system comprises sodium percarbonate it is a significant problem.
【０００４】[0004]
【課題を解決するための手段】式： ポリ（Ｘ）n ［式中、各Ｘは、独立してアスパラギン酸若しくはその
塩、グルタミン酸若しくはその塩、グルタミン、アスパ
ラギンまたはその混合物であり；ｎは３〜1000、好まし
くは３〜500である］のポリアミノ酸化合物は、リン酸
塩を含まない皿洗い機用組成物に、特定の臨界量で配合
する場合、及び組成物中の炭酸塩及び/または重炭酸塩
ビルダーの量が組成物の50重量%を超えない場合、スケ
ール形成防止剤として効果的に使用し得ることが知見さ
れた。## STR3 ## Formula: Poly (X) n [wherein each X is independently aspartic acid or a salt thereof, glutamic acid or a salt thereof, glutamine, asparagine or a mixture thereof; n is 3 ˜1000, preferably 3 to 500] of the polyamino acid compound, when incorporated into a phosphate-free dishwashing composition at a particular critical amount, and in the composition of carbonate and / or heavy salts. It has been found that when the amount of carbonate builder does not exceed 50% by weight of the composition, it can be effectively used as a scale inhibitor.
【０００５】従って、本発明は、配合する場合、炭酸塩
及び/または重炭酸塩ビルダーの量が組成物の50重量%を
超えない非リン酸塩ビルダーを含み且つ式： ポリ（Ｘ）n ［式中、各Ｘは、独立してアスパラギン酸若しくはその
塩、グルタミン酸若しくはその塩、グルタミン、アスパ
ラギンまたはその混合物であり；ｎは３〜1000であり、
好ましくは３〜500である］のポリアミノ酸化合物を少
なくとも１重量%以上、好ましくは少なくとも２から10
重量%以下で含み、リン酸塩を含まない皿洗い機用組成
物を提供する。Accordingly, the present invention comprises a non-phosphate builder, when formulated, wherein the amount of carbonate and / or bicarbonate builder does not exceed 50% by weight of the composition and has the formula: poly (X) n [ Wherein each X is independently aspartic acid or salt thereof, glutamic acid or salt thereof, glutamine, asparagine or mixture thereof; n is 3 to 1000,
Preferably 3 to 500], at least 1% by weight or more, preferably at least 2 to 10% by weight of the polyamino acid compound.
Disclosed is a phosphate-free dishwasher composition, which is included in an amount of not more than wt%.
【０００６】上記式に於いて、Ｘアミノ酸は、Ｘ基（即
ち、ポリアスパルテート、ポリグルタメート、ポリグル
タミン、ポリアスパラギン）のいずれからなっていても
よく、またはＸ基の種類の任意の組み合わせ［例えば、
ポリ（Asp）5（Glu）5］であってもよい。In the above formula, the X amino acid may consist of any of the X groups (ie, polyaspartate, polyglutamate, polyglutamine, polyasparagine), or any combination of X group types. For example,
Poly (Asp) 5 (Glu) 5 ].
【０００７】ビルダー物質（リン酸塩及び非リン酸塩ビ
ルダー物質）は、当業界で公知であり、種々の型の有機
及び無機化合物が文献に記載されている。これらは通
常、全種類の洗浄組成物に使用され、アルカリ性及び緩
衝能を与え、凝集を防ぎ、イオン強度を保持し、洗浄液
から汚れ由来の金属を抽出し及び/またはアルカリ土類
金属イオンを除去する。Builder materials (phosphate and non-phosphate builders) are known in the art and various types of organic and inorganic compounds have been described in the literature. They are typically used in all types of cleaning compositions to provide alkalinity and buffering capacity, prevent agglomeration, retain ionic strength, extract dirt-derived metals from cleaning solutions and / or remove alkaline earth metal ions. To do.
【０００８】本明細書中で使用する「ビルダー物質」と
いう用語は、種々の非リン酸塩ビルダー物質［例えば、
クエン酸、炭酸及び重炭酸のアルカリ金属塩；ニトリロ
三酢酸（NTA）；ジピコリン酸（DPA）；オキシジ琥珀酸
（ODS）；琥珀酸アルケニル塩（AKS）；及びゼオライ
ト］の任意の一種または混合物であってもよい。これら
は、本発明の組成物中に、５から約90重量%、好ましく
は10〜80重量%で配合し得る。The term "builder material" as used herein refers to various non-phosphate builder materials [eg,
Alkali metal salts of citric acid, carbonic acid and bicarbonate; nitrilotriacetic acid (NTA); dipicolinic acid (DPA); oxydisuccinic acid (ODS); succinic acid alkenyl salt (AKS); and zeolite] It may be. These may be incorporated in the compositions of the present invention at 5 to about 90% by weight, preferably 10-80% by weight.
【０００９】特に好ましいビルダーとしては、クエン酸
塩、琥珀酸アルケニル塩、炭酸塩、重炭酸塩、ゼオライ
ト及びその混合物が挙げられる。炭酸塩及び/または重
炭酸塩ビルダーを単独でまたは他のビルダーを組み合わ
せて使用する場合、その量は上記記載の如く組成物の50
重量%を超えるべきでないことが知見された。Particularly preferred builders include citrate, alkenyl succinate, carbonate, bicarbonate, zeolites and mixtures thereof. When the carbonate and / or bicarbonate builders are used alone or in combination with other builders, the amount is 50% of the composition as described above.
It was found that it should not exceed wt%.
【００１０】炭酸塩及び/または重炭酸塩ビルダーを０
〜40重量%の量で含む組成物が好ましい。0 carbonate and / or bicarbonate builders
Compositions containing from about 40% by weight are preferred.
【００１１】厳密には重要ではないが、洗浄力、汚れ除
去、起泡抑制及び/または濯ぎ助剤のために、界面活性
剤を配合してもよい。これらを配合する場合には、その
型及び特性に依存して約60重量%以下の量で使用し得
る。通常、適正にビルダーを配合したまたは多くビルダ
ーを配合した組成物では慣用であるが、洗浄力を促進し
且つ特に蛋白質の汚れにより生じる極端な起泡を抑制す
るために、非起泡性非イオン界面活性剤を少量0.1〜５
重量%で使用するのが好ましい。多量（即ち、５〜60重
量%）の洗浄効力の高い界面活性剤（例えば、高HLB非イ
オン界面活性剤、アニオン性硫酸塩またはスルホン酸塩
界面活性剤及び界面活性剤のアルキルポリグリコシド
種）は通常ビルダーを少量含む活性剤ベースの組成物に
使用し得る。Although not strictly critical, surfactants may be included for detergency, soil removal, foam control and / or rinsing aids. When incorporated, they may be used in amounts up to about 60% by weight, depending on their type and properties. Usually, it is customary in a composition containing a proper amount of builder or a large amount of builder, but in order to promote the detergency and suppress the extreme foaming caused by the dirt of the protein, a non-foaming nonionic 0.1-5 small amount of surfactant
It is preferably used in weight percent. Large amounts (ie 5-60% by weight) of high detergent efficacy surfactants (eg high HLB nonionic surfactants, anionic sulfate or sulfonate surfactants and surfactant alkyl polyglycoside species). Can usually be used in activator-based compositions containing small amounts of builders.
【００１２】本発明の組成物は、好ましくは皿洗い機組
成物では典型である、多段洗浄サイクル時に特定の目的
のために以下の特別の成分を１種以上含み得る。The compositions of the present invention may include one or more of the following special ingredients for particular purposes during the multi-stage wash cycle, which is typically typical of dishwasher compositions.
【００１３】珪酸アルカリ金属塩−約１〜約40重量%、
好ましくは５〜35重量%のレベルで珪酸ナトリウムを含
むのが好ましい。この物質は、洗浄成分、アルカリ源、
金属腐食防止剤及び磁器食器の艶の保護剤として使用し
得る。特に効果的な例としては、ＳiＯ2：Ｎa2Ｏのモル
比の値が約1.0〜約3.3、好ましくは約1.8〜約2.5の、通
常二珪酸ナトリウムと呼称される珪酸ナトリウムが挙げ
られる。 Alkali metal silicate- about 1 to about 40% by weight,
It is preferred to include sodium silicate at a level of preferably 5 to 35% by weight. This substance is a cleaning ingredient, an alkalinity source,
It can be used as a metal corrosion inhibitor and a gloss protector for porcelain dishes. A particularly effective example is sodium silicate, commonly referred to as sodium disilicate, having a molar ratio of SiO 2 : Na 2 O of about 1.0 to about 3.3, preferably about 1.8 to about 2.5.
【００１４】漂白剤系−配合する場合、１〜30重量%で
配合するのが好ましい。次亜塩素酸アルカリ金属塩は液
体組成物中に配合し得る。配合し得る他の塩素漂白剤と
しては、ジ-及びトリ-クロロ並びにジ-及びトリ-ブロモ
シアヌル酸のアルカリ金属塩が挙げられる。 Bleach system -When compounded, it is preferably compounded in an amount of 1 to 30% by weight. The alkali metal hypochlorite may be incorporated into the liquid composition. Other chlorine bleaching agents that may be included include di- and tri-chloro and alkali metal salts of di- and tri-bromocyanuric acid.
【００１５】好ましい漂白剤は過酸素漂白剤、例えば、
過ホウ酸ナトリウム（四若しくは一水和物）または過炭
酸ナトリウムが挙げられる。これらは低温で活性酸素種
を遊離させる漂白剤活性剤と組み合わせて使用するのが
好ましい。この型の多くの例の活性剤（漂白剤または過
酸前駆体と呼称される）は当業界で公知である。好まし
い漂白剤活性剤としては、国際出願公開（WO）第91/107
19号に記載のテトラアセチルエチレンジアミン（TAE
D）、グルコースペンタアセテート（GPA）及びモノ-長
鎖アシルテトラアセチルグルコースが挙げられるが、米
国特許第4,751,015号及び同第4,818,426号に記載の例え
ばコリンスルホフェニルカーボネート（CSPC）などの他
の活性剤も使用し得る。組成物中の過ホウ酸または過炭
酸ナトリウム及び漂白剤活性剤の量は、各々20重量%及
び10重量%を超えないのが好ましい。Preferred bleaches are peroxygen bleaches, eg
And sodium perborate (tetra or monohydrate) or sodium percarbonate. They are preferably used in combination with bleach activators which liberate reactive oxygen species at low temperatures. Many examples of activators of this type, called bleach or peracid precursors, are known in the art. Preferred bleach activators include International Application Publication (WO) 91/107
Tetraacetylethylenediamine (TAE
D), glucose pentaacetate (GPA) and mono-long chain acyl tetraacetyl glucose, but other active agents such as choline sulfophenyl carbonate (CSPC) described in US Pat. Nos. 4,751,015 and 4,818,426. Can also be used. The amounts of perboric acid or sodium percarbonate and bleach activator in the composition preferably do not exceed 20% and 10% by weight, respectively.
【００１６】もう１種の過酸素漂白剤としては、一過硫
酸カリウムが挙げられる。使用し得る過酸素漂白剤とし
ては、有機ペルオキシ酸及びその金属塩が挙げられる。
典型的なペルオキシ酸としては： （ｉ）ペルオキシ安息香酸及び環置換ペルオキシ安息香
酸（例えば、ペルオキシ-α-ナフトン酸）； （ii）脂肪族及び置換脂肪族モノペルオキシ酸（例え
ば、ペルオキシラウリン酸及びペルオキシステアリン
酸）； （iii）1,12-ジペルオキシドデカン二酸（DPDA）； （iv）1,9-ジペルオキシアゼライン酸； （ｖ）ジペルオキシブラシル酸；ジペルオキシセバシン
酸及びジペルオキシイソフタル酸； （vi）2-デシルジペルオキシブタン-1,4-二酸；及び （vii）フタロイルアミドペルオキシカプロン酸（PAP） が挙げられる。Another type of peroxygen bleaching agent is potassium monopersulfate. Peroxygen bleaches that can be used include organic peroxy acids and their metal salts.
Typical peroxy acids include: (i) peroxybenzoic acid and ring-substituted peroxybenzoic acids (eg, peroxy-α-naphthoic acid); (ii) aliphatic and substituted aliphatic monoperoxy acids (eg, peroxylauric acid and Peroxystearic acid); (iii) 1,12-diperoxidedecanedioic acid (DPDA); (iv) 1,9-diperoxyazelaic acid; (v) diperoxybrassic acid; diperoxysebacic acid and diperoxyisophthalic acid. (Vi) 2-decyldiperoxybutane-1,4-dioic acid; and (vii) phthaloylamide peroxycaproic acid (PAP).
【００１７】前記漂白剤活性剤の代わりにまたはこれら
と一緒に、漂白剤触媒（例えば、欧州特許出願公開第45
8,397号に記載のマンガン錯体並びに米国特許第5,041,2
32号及び同第5,047,163号に記載のスルホンイミン）も
添加し得る。Instead of or together with the bleach activator, a bleach catalyst (eg EP-A-45).
Manganese complexes described in 8,397 and US Pat. No. 5,041,2
No. 32 and No. 5,047,163, sulfonimines) may also be added.
【００１８】酵素−澱粉分解酵素及び蛋白質分解酵素を
通常使用する。本明細書中で使用し得る「澱粉分解酵
素」とは、細菌類または真菌類から誘導し得る。好まし
い澱粉分解酵素は、英国特許第1,296,839号に記載され
且つ製造され、バチルスリシェニホルミス（B.lichenif
ormis）NCIB 8061、NCIB 8059、ATCC 6334、ATCC 659
8、ATCC 11945、ATCC 8480及びATCC 9945A株から培養さ
れるものである。このような澱粉分解酵素の例として
は、SP-95及びTermanyl（登録商標；Novo industri A/
S，Copenhagen，Denmark製）として生産且つ流通してい
るものが挙げられる。これらの澱粉分解酵素は通常、粒
状であり、約２〜10マルトース単位/mgの酵素活性を有
し得る。これらは、本発明の組成物中、最終組成物が10
3〜106マルトース単位/kgの澱粉分解酵素活性を有する
ように配合し得る。 Enzymes -starch-degrading enzymes and proteolytic enzymes are commonly used. As used herein, a "starch-degrading enzyme" may be derived from bacteria or fungi. A preferred amylolytic enzyme is described and produced in British Patent No. 1,296,839 and is produced by B. lichenif
ormis) NCIB 8061, NCIB 8059, ATCC 6334, ATCC 659
8, ATCC 11945, ATCC 8480 and ATCC 9945A strains. Examples of such a starch-degrading enzyme include SP-95 and Termanyl (registered trademark; Novo industri A /
S, manufactured by Copenhagen, Denmark) and produced and distributed. These amylolytic enzymes are usually granular and may have an enzyme activity of about 2-10 maltose units / mg. These have a final composition of 10 in the composition of the present invention.
It may be formulated to have a starch degrading enzyme activity of 3 to 10 6 maltose units / kg.
【００１９】本明細書中で言及する「澱粉分解活性」と
いう用語は、P.Bernfeld“Method of Enzymology”,vol
Ｉ（1955）,p149に記載の方法により決定され得る。As used herein, the term "starch-degrading activity" refers to P. Bernfeld "Method of Enzymology", vol.
I (1955), p149.
【００２０】本明細書中で使用する「蛋白質分解酵素」
とは、例えば、枯草菌及びB.licheniformisの特定株か
ら得られるサブチリシンとしては、市販のサブチリシン
Maxatase（登録商標：Gist-Brocades NV,Delft,Holland
製）及びAlcalase（登録商標：NOVO Industri A/S Cope
nhagen，Denmark製）が挙げられる。特に好適な例とし
ては、pH８〜12に最大活性を有するバチルス属の株から
得られたプロテアーゼが挙げられ、Esperase及びSavbin
ase（登録商標：NOVO Industri A/S製）が市販されてい
る。これら及び類似の酵素の製造は、英国特許第1,243,
784号に記載されている。これらの酵素は通常、粒状
［例えば、マルメ、粒（prills）、T-顆粒など］であ
り、500〜1700グリシン単位/mgの酵素活性を有し得る。
蛋白質分解酵素活性は、M.L.Anson“Journal of Genera
l Physiology”Vol.22（1938）,p79に記載の方法により
決定し得る（１Anson単位/g＝733グリシン単位/mg）。“Proteolytic enzyme” as used herein
The subtilisin obtained from a specific strain of Bacillus subtilis and B. licheniformis is, for example, a commercially available subtilisin.
Maxatase (registered trademark: Gist-Brocades NV, Delft, Holland
Made) and Alcalase (registered trademark: NOVO Industri A / S Cope
nhagen, made by Denmark). Particularly preferred examples include proteases obtained from Bacillus strains that have maximum activity at pH 8 to 12, such as Esperase and Savbin.
ase (registered trademark: NOVO Industri A / S) is commercially available. The production of these and similar enzymes is described in British Patent 1,243,
No. 784. These enzymes are usually granular [eg malm, prills, T-granules, etc.] and may have an enzyme activity of 500 to 1700 glycine units / mg.
MLAnson “Journal of Genera
It can be determined by the method described in “L Physiology” Vol. 22 (1938), p79 (1 Anson unit / g = 733 glycine unit / mg).
【００２１】本発明の組成物中、蛋白質分解酵素は、最
終組成物が約106〜108グリシン単位/kgの蛋白質分解酵
素活性を有するような量で配合し得る。The proteolytic enzyme in the composition of the present invention may be incorporated in an amount such that the final composition has a proteolytic enzyme activity of about 10 6 to 10 8 glycine units / kg.
【００２２】他の酵素（例えば、脂肪分解酵素）も脂肪
除去を促進するために配合し得る。市販の脂肪分解酵素
の典型例としては、Lipase YL、Amano CE、Wallerstein
AW、Lipase My及びLipolase（Novo Ind.製）が挙げら
れる。Other enzymes, such as lipolytic enzymes, may also be included to promote fat removal. Typical examples of commercially available lipolytic enzymes include Lipase YL, Amano CE, Wallerstein
AW, Lipase My and Lipolase (manufactured by Novo Ind.) Can be mentioned.
【００２３】さらに少量で配合し得る他の任意の成分と
しては、洗浄物にフィルム及びスポット形成を減少する
ための鉱物粘土、特に層状鉱物粘土が挙げられる。通
常、特に好ましい市販の粘度製品としては、Laporte In
ductries LTD,Englandから製造且つ供給されているLapo
nite［例えば、Laponite S、Laponite XLS、Laponite R
D及びLaponite RDS（登録商標）］が挙げられる。亜鉛
塩（溶解性及び不溶性亜鉛塩の両方）もガラスの腐食を
最小にするための添加物として配合し得る。Other optional ingredients that may be incorporated in even smaller amounts include mineral clays, especially layered mineral clays, to reduce film and spot formation in the wash. Generally, a particularly preferred commercial viscous product is Laporte In
Lapo manufactured and supplied by ductries LTD, England
nite [eg Laponite S, Laponite XLS, Laponite R
D and Laponite RDS (registered trademark)]. Zinc salts (both soluble and insoluble zinc salts) may also be included as additives to minimize glass corrosion.
【００２４】圧縮粉末組成物中では実質的に可能な限り
省略するのが好ましいが、不活性粒状フィラー、特に硫
酸ナトリウムも配合してもよい。In the compressed powder composition it is preferred to omit it as substantially as possible, but inert particulate fillers, especially sodium sulphate, may also be incorporated.
【００２５】ポリアミノ酸化合物 本発明で使用するポリアミノ酸化合物としては、アスパ
ラギン酸、グルタミン酸、グルタミン若しくはアルパラ
ギンのホモポリマーまたは、前記アミノ酸の任意の組み
合わせのコポリマーが挙げられ、アミノ酸は、L、Dまた
はL/D型であってもよい。ｎは５〜150が好ましく、10〜
100がより好ましい。 Polyamino Acid Compounds The polyamino acid compounds used in the present invention include homopolymers of aspartic acid, glutamic acid, glutamine or asparagine, or copolymers of any combination of the above amino acids, where the amino acids are L, D or L. It may be / D type. n is preferably 5 to 150, and 10 to
100 is more preferable.
【００２６】好ましい化合物としては、Sigma Chem.Cor
p.及び味の素から広く市販されているポリアスパルテー
ト及びポリグルタメートが挙げられる。Cygnus-32（登
録商標）はポリアスパルテートを約40重量%含むポリア
ミノ酸製品（Cygnus Corporation、USA製）である。Preferred compounds include Sigma Chem. Cor
and polyaspartate and polyglutamate, which are widely commercially available from P. and Ajinomoto. Cygnus-32® is a polyamino acid product (Cygnus Corporation, USA) containing about 40% by weight of polyaspartate.
【００２７】本発明の他のポリアミノ酸も、他の理由に
より好ましい。Other polyamino acids of the invention are also preferred for other reasons.
【００２８】上記記載の如く、本発明で使用し得るポリ
アミノ酸化合物の量は、組成物の少なくとも１重量%以
上、好ましくは少なくとも２重量%から10重量%以下であ
るべきで、洗浄液中のポリアミノ酸濃度を約30〜300ppm
にし得る。As mentioned above, the amount of polyamino acid compound which can be used in the present invention should be at least 1% by weight or more, preferably at least 2% to 10% by weight or less of the composition, and the polyamino acid compound in the washing liquid should be at least 1% by weight. Amino acid concentration of about 30-300ppm
You can
【００２９】低濃度でも、特に炭酸塩含量が高くても、
ガラスの外観には目につく効果が得られず、10重量%以
上の高濃度では、他の望ましくない現象（即ち、ガラス
及び金属表面に炭酸カルシウムの微細結晶が付着して生
じたと考えられる薄青い膜の形成）により効果がないの
で、この範囲を固守すべきであることは非常に重要であ
る。最良の結果を得るために好ましい範囲は、組成物中
の３〜約８重量%のポリアミノ酸である。Even at low concentrations, especially high carbonate content,
There is no noticeable effect on the appearance of the glass, and at a high concentration of 10% by weight or more, another undesirable phenomenon (that is, thin crystals that are considered to have been caused by the adherence of fine calcium carbonate crystals to the glass and metal surfaces) It is very important that this range be adhered to as it is ineffective due to the formation of the blue film). A preferred range for best results is from 3 to about 8% by weight of polyamino acid in the composition.
【００３０】これらのレベルで使用する場合、本発明の
ポリアミノ酸化合物は、ガラス、皿等にできたスケール
を減らすのに効果的があり、これによりガラスの外観を
改善できる。これらはさらに、生分解性であり、金属腐
食を防止し得る。When used at these levels, the polyamino acid compounds of the present invention are effective in reducing scale build-up on glass, dishes, etc., which can improve the appearance of the glass. They are also biodegradable and can prevent metal corrosion.
【００３１】従って、本発明の範囲内に入る皿洗い機用
組成物は、以下の成分を含み得る。Accordingly, a dishwasher composition within the scope of the present invention may include the following ingredients.
【００３２】[0032]
【表１】 [Table 1]
【００３３】[0033]
【実施例】本発明を、以下の非限定的な実施例によりさ
らに説明する。The present invention is further described by the following non-limiting examples.
【００３４】実施例Ｉ及びII セットアップスケール形成実験 皿洗い機の洗浄工程の皿上へのスケール（炭酸カルシウ
ム）の付着を、小規模モデルスケール形成実験で研究し
た。このような実験に於ける洗浄サイクルを、予め秤量
したガラススライドを入れた洗浄溶液を加熱することに
より模擬実験する。９サイクルの付着実験中に於けるこ
れらのスライドの重量増は、付着スケールによるものと
みなす。主洗浄と最終濯ぎを組み合わせた実験を行っ
て、主洗浄組成物に関するスケール防御を研究した。 Examples I and II Setup Scale Formation Experiments The deposition of scale (calcium carbonate) on the dishes during the dishwasher washing process was studied in a small scale model scale formation experiment. The wash cycle in such an experiment is simulated by heating the wash solution containing a pre-weighed glass slide. The weight gain of these slides during the 9 cycle deposition experiment is considered to be due to the deposition scale. A combined main wash and final rinse experiment was conducted to study scale protection for the main wash composition.
【００３５】主洗浄/最終濯ぎ実験 ３リットルのガラスビーカーの硬水1.5リットルに、組
成物2.7gを添加した。この水は、脱ミネラル水に、塩化
カルシウム、塩化マグネシウム及び重炭酸ナトリウム
を、水全体の硬度がフランス硬度140（モル比 Ca/Mg:4/
1）で、一時的なフランス硬度232（重炭酸塩）となるよ
うな量で添加して作成した。予め秤量したガラススライ
ド（５×５×0.1cm）をこの溶液中に入れた後、温度を2
0℃から65℃に2.5℃/分の速度で上げ、65℃で12分間一
定保持した。この温度プロフィールは主洗浄サイクルを
シミュレートしており、水中に沈めた電気加熱要素とプ
ログラム可能な温度コントローラーを使用して実施し
た。このサイクルの終了時に、スライドを溶液から取り
出した。スライドを１枚このサイクル時のスケール形成
の測定用に使用し、新しいスライドと取り替えた。続い
て、残りのスライドに同一硬度の水1.5リットルを注ぐ
ことにより、最終濯ぎサイクルをシミュレートする。同
時に主洗浄液1.5ml（主洗浄から1/1000持ち越した分を
シミュレートする）を添加する。この最終濯ぎ溶液を20
℃から70℃に（2.5℃/分）で加熱し、10分間一定保持し
た。このサイクルの終了時に、再びスライド１枚を分析
用に取り出し、新しいスライドと取り替える。通常この
方法を９回繰り返した。 Main Wash / Final Rinse Experiment 2.7 g of the composition was added to 1.5 liters of hard water in a 3 liter glass beaker. This water, demineralized water, calcium chloride, magnesium chloride and sodium bicarbonate, the hardness of the entire water French hardness 1 40 (molar ratio Ca / Mg: 4 /
1) was prepared by adding in an amount such that the temporary French hardness 2 32 (bicarbonate). Place a pre-weighed glass slide (5 x 5 x 0.1 cm) in this solution and increase the temperature to 2
The temperature was raised from 0 ° C to 65 ° C at a rate of 2.5 ° C / min and kept constant at 65 ° C for 12 minutes. This temperature profile simulated the main wash cycle and was performed using an electric heating element submerged in water and a programmable temperature controller. At the end of this cycle, slides were removed from solution. One slide was used for measuring scale formation during this cycle and replaced with a new slide. The final rinse cycle is then simulated by pouring the remaining slides with 1.5 liters of water of the same hardness. At the same time, 1.5 ml of the main washing solution (simulating the amount of 1/1000 carryover from the main washing) is added. Add this final rinse solution to 20
Heated from ℃ to 70 ℃ (2.5 ℃ / min), and held constant for 10 minutes. At the end of this cycle, one slide is removed again for analysis and replaced with a new slide. This method was usually repeated 9 times.
【００３６】１）１°FH（Ca及び/またはMg）は0.1mmol
/l CaCO3と等しい。1) 1 ° FH (Ca and / or Mg) is 0.1 mmol
Equivalent to / l CaCO 3 .
【００３７】２）１°FH（HCO3 -）は0.2mmol/l NaHCO3
と等しい。[0037] 2) 1 ° FH (HCO 3 -) is 0.2 mmol / l NaHCO 3
Is equal to
【００３８】[0038]
【表２】 [Table 2]
【００３９】結果を以下の表に示す。The results are shown in the table below.
【００４０】[0040]
【表３】 [Table 3]
【００４１】上記結果は、総ての場合に於いて、スケー
ル形成は、ポリアミノ酸を配合することにより抑制され
ることを示している。上記データは、高含量の炭酸塩/
重炭酸塩ビルダーの負の効果及び、より純度の高いポリ
アスパルテート製品（Bayer）と比べての低濃度のCygnu
s-32（不純な製品）の低有効性も示している。The above results show that in all cases scale formation was suppressed by the incorporation of polyamino acids. The above data is for high content of carbonate /
Negative effect of bicarbonate builder and low concentration of Cygnu compared to more pure polyaspartate product (Bayer)
It also demonstrates the low efficacy of s-32 (impure product).
フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ１１Ｄ 3:33） (72)発明者 ルドルフ・ウイレム・ペー・フアン・ドル ネン オランダ国、3142・アー・エム・マースス ライス、ポプリーレンダル・20Continuation of the front page (51) Int.Cl. 5 Identification number Office reference number FI technical display location C11D 3:33) (72) Inventor Rudolf Willem P. Juan Dornen, 3142 A.M., The Netherlands・ Mars Rice, Poplarendal ・ 20
Claims (12)
酸塩ビルダーの量が組成物の50重量%を超えない非リン
酸塩ビルダー及び、式： ポリ（Ｘ）n ［式中、各Ｘは、独立してアスパラギン酸若しくはその
塩、グルタミン酸若しくはその塩、グルタミン、アスパ
ラギンまたはその混合物であり；ｎは３〜1000である］
のポリアミノ酸化合物を少なくとも１重量%以上約10重
量%以下含むことを特徴とするリン酸塩を含まない皿洗
い機用組成物。1. A non-phosphate builder, when incorporated, wherein the amount of carbonate and / or bicarbonate builder does not exceed 50% by weight of the composition and a formula: poly (X) n [wherein each X Are independently aspartic acid or a salt thereof, glutamic acid or a salt thereof, glutamine, asparagine or a mixture thereof; n is 3 to 1000].
A phosphate-free dishwasher composition, characterized in that it comprises at least 1% by weight and at most about 10% by weight of the polyamino acid compound of.
重量%含むことを特徴とする請求項１に記載の組成物。2. The polyamino acid compound is at least 2
A composition according to claim 1, characterized in that it comprises by weight.
%含むことを特徴とする請求項２に記載の組成物。3. The polyamino acid compound is contained in an amount of 3 to about 8 parts by weight.
The composition according to claim 2, wherein the composition comprises%.
求項１〜３のいずれか１項に記載の組成物。4. The composition according to claim 1, wherein n is 3 to 500.
求項４に記載の組成物。5. The composition according to claim 4, wherein n is 5 to 150.
求項５に記載の組成物。6. The composition according to claim 5, wherein n is 10 to 100.
塩、重炭酸塩及びゼオライト並びにその混合物からなる
群から選択される非リン酸塩ビルダーを含むことを特徴
とする請求項１〜６のいずれか１項に記載の組成物。7. A non-phosphate builder selected from the group consisting of citrates, alkenyl succinates, carbonates, bicarbonates and zeolites and mixtures thereof. The composition according to any one of claims.
０〜40重量%含むことを特徴とする請求項１〜７のいず
れか１項に記載の組成物。8. The composition according to claim 1, which contains 0 to 40% by weight of a carbonate and / or bicarbonate builder.
むことを特徴とする請求項１〜８のいずれか１項に記載
の組成物。9. A composition according to any one of claims 1 to 8 comprising 5 to about 90% by weight of non-phosphate builders.
物。10. b) 0 to 60% by weight of surfactant; c) 0 to 40% by weight of alkali metal silicate; d) 0 to 30% by weight of bleaching system; and e) further containing an enzyme as an optional component. The composition according to claim 9, characterized in that
%； ｂ）低起泡性〜非起泡性非イオン界面活性剤0.1〜５重
量%； ｃ）珪酸アルカリ金属塩１〜40重量%； ｄ）過酸素漂白剤系１〜30重量%；及び ｅ）組成物が103〜106マルトース単位/kgの澱粉分解酵
素活性と、106〜108グリシン単位/kgの蛋白質分解酵素
活性を有するような量の澱粉分解酵素及び蛋白質分解酵
素 を含むことを特徴とする請求項１０に記載の組成物。11. A) 10 to 80 weight of non-phosphate builder.
%) B) low foaming to non-foaming nonionic surfactant 0.1 to 5% by weight; c) alkali metal silicate salt 1 to 40% by weight; d) peroxygen bleaching system 1 to 30% by weight; and e) The composition comprises starch degrading enzymes and proteolytic enzymes in an amount such that they have a starch degrading enzyme activity of 10 3 to 10 6 maltose units / kg and a proteolytic enzyme activity of 10 6 to 10 8 glycine units / kg The composition according to claim 10, characterized in that
Ｎa2Ｏのモル比が約1.8〜2.5の二珪酸ナトリウムである
ことを特徴とする請求項１０または１１に記載の組成
物。12. The alkali metal silicate is, SiO 2:
Composition according to claim 10 or 11, characterized in that it is sodium disilicate with a molar ratio of Na 2 O of about 1.8 to 2.5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92200794 | 1992-03-20 | ||
| NL92200794.3 | 1992-03-20 | ||
| CA002091791A CA2091791A1 (en) | 1992-03-20 | 1993-03-17 | Machine dishwashing composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06100889A true JPH06100889A (en) | 1994-04-12 |
Family
ID=25675998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5060565A Pending JPH06100889A (en) | 1992-03-20 | 1993-03-19 | Composition for dish washing machine |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0561452A1 (en) |
| JP (1) | JPH06100889A (en) |
| AU (1) | AU3534793A (en) |
| BR (1) | BR9301245A (en) |
| CA (1) | CA2091791A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0770592A (en) * | 1993-07-08 | 1995-03-14 | Rhone Poulenc Chim | Premix for detergent composition, based on polyimide and silicate |
| JP2010507001A (en) * | 2006-10-16 | 2010-03-04 | ダニスコ・ユーエス・インク、ジェネンコー・ディビジョン | Non-phosphate dishwashing agent |
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| TW239160B (en) * | 1992-10-27 | 1995-01-21 | Procter & Gamble | |
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| DE4310995A1 (en) * | 1993-04-03 | 1994-10-06 | Basf Ag | Use of polyaspartic acid in cleaning formulations |
| US5389303A (en) * | 1993-09-10 | 1995-02-14 | Srchem Incorporated | Mixtures of polyamino acids and citrate |
| ATE188497T1 (en) * | 1993-11-02 | 2000-01-15 | Bayer Ag | METHOD FOR PRODUCING POLYMERS CONTAINING ASPARAGIC ACID |
| DE4425951A1 (en) * | 1994-07-21 | 1996-01-25 | Bayer Ag | Poly:succinimide, poly:aspartic acid and maleamic acid prepn. without extraneous additives |
| DE4342316A1 (en) * | 1993-12-11 | 1995-06-14 | Basf Ag | Use of polyaspartic acid in washing and cleaning agents |
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| US5531934A (en) * | 1994-09-12 | 1996-07-02 | Rohm & Haas Company | Method of inhibiting corrosion in aqueous systems using poly(amino acids) |
| EP0736596A1 (en) * | 1995-04-03 | 1996-10-09 | The Procter & Gamble Company | Soaker compositions |
| DE19540086A1 (en) * | 1995-10-27 | 1997-04-30 | Henkel Kgaa | Use of polymeric aminodicarboxylic acids in detergents |
| DE19825507A1 (en) * | 1998-06-02 | 1999-12-09 | Bayer Ag | Biotechnological production of polyglutamic acid |
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| DE19842053A1 (en) | 1998-09-15 | 2000-03-23 | Bayer Ag | Use of polyaspartic acids in cleaning formulations with an abrasive effect |
| AU2110500A (en) * | 1999-02-05 | 2000-08-25 | Unilever Plc | Dish washing process and compositions relating thereto |
| US6638902B2 (en) | 2001-02-01 | 2003-10-28 | Ecolab Inc. | Stable solid enzyme compositions and methods employing them |
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| RU2009137386A (en) | 2007-03-09 | 2011-04-20 | ДАНИСКО ЮЭс ИНК., ДЖЕНЕНКОР ДИВИЖН (US) | AMILASE VARIANTS OF BACILLUS ALKALYPHIC SPECIES, COMPOSITIONS CONTAINING AMILASE OPTIONS AND METHODS OF APPLICATION |
| BRPI0913367A2 (en) | 2008-06-06 | 2015-08-04 | Danisco Us Inc | Bacillus subtilis variant alpha-amylases and methods of use |
| EP2291526B1 (en) | 2008-06-06 | 2014-08-13 | Danisco US Inc. | Saccharification enzyme composition with Bacillus subtilis alpha-amylase |
| MX2010013108A (en) | 2008-06-06 | 2010-12-21 | Danisco Inc | Production of glucose from starch using alpha-amylases from bacillus subtilis. |
| DK2337837T4 (en) | 2008-09-25 | 2017-02-06 | Danisco Us Inc | ALPHA-AMYLASE MIXTURES AND PROCEDURES FOR USING IT |
| MX356389B (en) | 2009-10-23 | 2018-05-28 | Danisco Us Inc | Methods for reducing blue saccharide. |
| CA2844293A1 (en) * | 2011-10-19 | 2013-04-25 | Basf Se | Formulations, their use as or for producing dishwashing compositions and their preparation |
| RU2656214C2 (en) * | 2013-04-02 | 2018-06-01 | Басф Се | Formulations, their use as or for producing dishwashing detergents and their production |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0277498A (en) * | 1988-09-14 | 1990-03-16 | Lion Corp | Detergent composition for use in automatic dishwasher |
| EP0454126A1 (en) * | 1990-04-26 | 1991-10-30 | Rohm And Haas Company | Polyaminoacids as builders for detergent formulations |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3724460A1 (en) * | 1986-07-29 | 1988-02-04 | Lion Corp | Wetting agent composition compatible with skin |
| DE3626672A1 (en) * | 1986-08-07 | 1988-02-11 | Bayer Ag | POLYASPARAGINAMID ACID |
| FR2675153B1 (en) * | 1991-04-15 | 1994-07-22 | Rhone Poulenc Chimie | DETERGENT COMPOSITION CONTAINING A POLYIMIDE BIOPOLYMER HYDROLYSABLE IN A WASHING MEDIUM. |
-
1993
- 1993-03-09 EP EP93200670A patent/EP0561452A1/en not_active Withdrawn
- 1993-03-17 CA CA002091791A patent/CA2091791A1/en not_active Abandoned
- 1993-03-19 JP JP5060565A patent/JPH06100889A/en active Pending
- 1993-03-19 BR BR9301245A patent/BR9301245A/en not_active Application Discontinuation
- 1993-03-19 AU AU35347/93A patent/AU3534793A/en not_active Abandoned
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0277498A (en) * | 1988-09-14 | 1990-03-16 | Lion Corp | Detergent composition for use in automatic dishwasher |
| EP0454126A1 (en) * | 1990-04-26 | 1991-10-30 | Rohm And Haas Company | Polyaminoacids as builders for detergent formulations |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0770592A (en) * | 1993-07-08 | 1995-03-14 | Rhone Poulenc Chim | Premix for detergent composition, based on polyimide and silicate |
| JP2010507001A (en) * | 2006-10-16 | 2010-03-04 | ダニスコ・ユーエス・インク、ジェネンコー・ディビジョン | Non-phosphate dishwashing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0561452A1 (en) | 1993-09-22 |
| BR9301245A (en) | 1993-09-28 |
| AU3534793A (en) | 1993-09-23 |
| CA2091791A1 (en) | 1994-09-18 |
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