201016839 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種液體洗淨劑組成物之發明，特別是 有關一種適於在自動食器洗淨機中使用之液體洗淨劑組成 物之發明。 【先前技術】 使用於將食器洗淨時之液體洗淨劑組成物已進行過各 種研究，例如：用以提高洗淨力之研究（專利文獻1及2)、 ❿用以提高所調配之酵素之儲存安定性之研究（專利文獻3)。 專利文獻1及2對提高酵素之儲存安定性及用以提高 使用性之增黏效果方面並未進行任何研究。專利文獻3雖 已研究關於酵素之儲存安定性，但並未對增黏效果進行任 何研究。 [專利文獻1]日本特開2007-23268號公報 [專利文獻2]日本特開2003-277800號公報 [專利文獻3]日本特開2006-257435號公報 ◎ 【發明内容】 (發明欲解決的課題） 然而，上述專利文獻中所記載之液體洗淨劑組成物並 非同時達成提高為了提高洗淨力所調配之酵素之儲存安定 性、得到用以提高使用性之一定的黏度、具有優良的洗淨 力、保存後仍保持透明的外觀者。 因此，本發明之課題為提供一種提高酵素之儲存安定 性、且具有使用性良好的適當範圍之黏度、並具有優良的 3 321459 201016839 洗淨力、並且保存後仍保持透明的外觀之自動食器洗淨機 用液體洗淨劑組成物。 (解決課題的手段） 本發明人等致力進行研究後之結果發現，經由將山梨 糖醇與特定多元醇組合，並且使其含於含有非交聯型聚羧 酸或其鹽與酵素之自動食器洗淨機用液體洗淨劑組成物 中，即可同時解決上述課題，遂完成本發明。 換言之，本發明提供一種自動食器洗淨機用液體洗淨 劑組成物，係含有： (A) 非交聯型聚羧酸或其鹽； (B) 山梨糖醇； (C) 從由丙二醇、甘油、葡萄糖、甘露醇及烷基葡萄糖苷所 成群組中選出之1種以上；以及 (D) 酵素， 相對於組成物之全質量， (A) 為4至20質量％、 (B) + (C)為25至70質量％，且 (B)/(C)之質量比例在2至10之範圍。 本發明另外提供一種自動食器洗淨機用液體洗淨劑組 成物，係含有： (a) (曱基）丙烯酸/順丁烯二酸共聚物之鹽； (b) 山梨糖醇； (cl)2-乙基己基葡萄糖苷； (c2)從由丙二醇及甘油所成群組中選出之1種以上；以及 4 321459 201016839 ⑷殿粉麵料及/衫白 相對於組成物之全質量， ’' (a) 為4至20質量％、201016839 VI. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a liquid detergent composition, and more particularly to an invention of a liquid detergent composition suitable for use in an automatic food washer. . [Prior Art] Various studies have been conducted on the liquid detergent composition used for washing the food, for example, studies for improving the detergency (Patent Documents 1 and 2), and for improving the enzymes to be formulated. Research on storage stability (Patent Document 3). Patent Documents 1 and 2 did not conduct any research on improving the storage stability of the enzyme and the viscosity-increasing effect for improving the usability. Although Patent Document 3 has studied the storage stability of the enzyme, it has not conducted any research on the viscosity-increasing effect. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-277800 (Patent Document 3) JP-A-2006-257435 (Patent Document) However, the liquid detergent composition described in the above-mentioned patent document does not simultaneously achieve an improvement in the storage stability of the enzyme formulated to improve the detergency, a certain viscosity for improving the usability, and an excellent cleaning. Force, the appearance that remains transparent after storage. Therefore, an object of the present invention is to provide an automatic food-washing machine which has improved storage stability of an enzyme, has a suitable range of good viscosity, and has an excellent 3321459 201016839 detergency and remains transparent after storage. Liquid machine liquid detergent composition. (Means for Solving the Problems) As a result of research conducted by the present inventors, it has been found that sorbitol is combined with a specific polyol and contained in an automatic food container containing a non-crosslinked polycarboxylic acid or a salt thereof and an enzyme. In the liquid detergent composition for a washing machine, the above problems can be simultaneously solved, and the present invention has been completed. In other words, the present invention provides a liquid detergent composition for an automatic food processor, comprising: (A) a non-crosslinked polycarboxylic acid or a salt thereof; (B) sorbitol; (C) from propylene glycol, One or more selected from the group consisting of glycerin, glucose, mannitol, and alkyl glucoside; and (D) an enzyme, (A) 4 to 20% by mass, (B) + relative to the total mass of the composition (C) is 25 to 70% by mass, and the mass ratio of (B)/(C) is in the range of 2 to 10. The present invention further provides a liquid detergent composition for an automatic food processor, comprising: (a) a salt of a (mercapto)acrylic acid/maleic acid copolymer; (b) sorbitol; (cl) 2-ethylhexyl glucoside; (c2) one or more selected from the group consisting of propylene glycol and glycerin; and 4 321459 201016839 (4) The total mass of the powdered fabric and/or white relative to the composition, '' (a ) is 4 to 20% by mass,
Cb) + CCi+C2)為 25 至 70 質量 (b) /(chC2)之質量比例在从 (發明的效果） 之範圍。 #由本發明可彳τ到提高酵素之 + 用性良好的適當範圍之黏度、並=疋性、且具有使 ❹保存後仍保持透明的外觀之新顆自動食二 淨劑組成物。本發明之組成物’特別是對茶垢之洗=洗 玻璃陰影之洗淨力、澱粉污垢之洗淨力、蛋白、 Π = 並且，本發明之洗淨劑組成 糸統整體之水刀量，而使酵素更安定。本發明之址成物之 :显安定性也優良。根據本發明’當本發明 特性香料時，可提高其保存安定性。成物4 Q 【實施方式】 ((A)成分） ⑴成分為非交聯型聚鞭酸或其鹽。經由調配（ 分’即可提高液體洗淨劑組成物之黏度，因而提高使用性。 茶垢洗淨力、破璃陰影洗淨力、_亏 力、蛋白質料洗淨力。特別是對於茶垢之洗淨效 果向。 藉 本發明中所使用 由凝膠滲透層析>去 <(Α)#父聯型高分子聚羧酸（鹽）以 所測得之重量平均分子量為〗，〇〇〇以 321459 5 201016839 上為佳、以在1，500至·，〇〇〇之範圍較佳、以在2, _ 至100,刪之範圍更佳、以在1〇, _幻〇〇, _之範圍特 佳、以在40, 000至60, 000之範圍尤佳。由於若重量平均 分子量為1，000以上，則做為玻璃陰影洗淨劑之性能提 高，若為200, 000以下，則可抑制液體洗淨劑組成物黏度 的過度增加，故較佳。 ，本發明中所使用之⑴非交聯型高分子聚竣酸（鹽）可 為具有叛基之單體之均聚物’也可為具有幾基之單體、與 具有叛基之2種以上之其他單體或不具有緩基之2種以上❹ 之其他單體之共聚物。均聚物可舉例如：聚（甲基）丙烯酸 或其鹽、聚巴豆酸或其鹽、聚伊康酸或其鹽等。具有綾基 單體/、具有緩基之2種以上之其他單體之共聚物可舉例 如.（甲基）丙烯酸-順丁烯二酸共聚物或其鹽、（曱基）丙烯 酉文巴豆酸共聚物或其鹽。具有羧基之單體與不具有羧基之 2種以上之其他單體之共聚物可舉例如：乙烯-順丁烯二酸 /、聚物或其鹽、曱基丙烯酸_丙烯酸乙酯共聚物或其鹽。 較佳可舉例如：（甲基）丙烯酸/順丁烯二酸共聚物或其 烯；興丁缔一酸共聚物或其鹽。以（曱基）丙稀酸/順 烯&共聚物或其鹽為佳。以丙烯酸/順丁烯二酸共聚物 :鹽較佳。以丙烯酸/順丁烯二酸共聚物之鹽更佳。特別 β /、聚a比（莫耳比）為75/25至50/50且重量平均分 為1萬至10萬（特別是4萬至6萬）之丙烯酸/順丁烯 、=八聚物或其鹽尤佳。鹽可舉例如：鈉鹽、鉀鹽等。（Α) 成刀係可單獨使用非交聯型高分子聚羧酸（鹽）或併用2種 321459 6 201016839 以上。 本發明中所使用之（A)成分可予以合成，也可使用市場 上可取得者。市場上可取得者可舉例如：日本觸媒（股）製 之AQUALIC TL400(丙烯酸/順丁烯二酸共聚物，重量平均 分子量：50000、黏度：約2000mPa/s(溫度：23°C，濃度： 40%))、BASF公司製之Sokalan CP7及CP5(皆為丙稀酸/ 順丁烯二酸共聚物，CP7之重量平均分子量：50000、黏度： 約1500mPa/s(溫度：23°C，濃度：40%)，CP5之重量平均 ®分子量：70000、黏度：約2000mPa/s(溫度：23°C，濃度： 40%))等。 再者’非交聯型聚羧酸或其鹽之黏度可使用例如轉子 為No· 1至4之BL型黏度測定機，於25°C、轉子之轉速為 6至60rpm、測定時間20至120秒之條件下進行測定。 ((B)成分） (B)成分為山梨糖醇。經由調配（b)成分，即可提高本 ©發明之組成物的黏度，因而提高使用性。並提高酵素之儲 存安定性、由酵素所得之洗淨力（特別是長期保存後之由酵 素所得之洗淨力）、及低溫安定性。除此之外，也有助於組 成物保存後保持透明的外觀。Cb) + CCi + C2) is a mass ratio of 25 to 70 mass (b) / (chC2) in the range from (the effect of the invention). # A new automatic detergent composition which can be used in the present invention to increase the viscosity of the proper range of the enzyme, and to have an ambiguous property and to maintain a transparent appearance after storage. The composition of the present invention 'especially the washing of tea scale = the washing power of the glass washing shadow, the washing power of the starch stain, the protein, the Π = and the detergent of the present invention constitutes the overall water knife amount, And make the enzyme more stable. The site of the present invention is also excellent in apparent stability. According to the present invention, when the perfume of the present invention is characterized, its preservation stability can be improved. Product 4 Q [Embodiment] (Component (A)) The component (1) is a non-crosslinked polyphthoke acid or a salt thereof. By adjusting the distribution, the viscosity of the liquid detergent composition can be improved, thereby improving the usability. The tea stain cleaning power, the glass shading cleaning power, the deficiency, the protein material washing power, especially for the tea scale. The cleaning effect is as follows: by the gel permeation chromatography used in the present invention><(Α)# parent-linked high molecular polycarboxylic acid (salt), the measured weight average molecular weight is 〇, 〇 〇〇 is preferred on 321459 5 201016839, in the range of 1,500 to 〇〇〇, 〇〇〇 is better, in the range of 2, _ to 100, the scope is better, in 1〇, _ 〇〇, The range of _ is particularly good, and it is particularly preferably in the range of 40,000 to 6,000. Since the weight average molecular weight is 1,000 or more, the performance as a glass shading detergent is improved, and if it is 200,000 or less, It is preferable to suppress excessive increase in viscosity of the liquid detergent composition. (1) The non-crosslinked polymer polycapric acid (salt) used in the present invention may be a homopolymer of a monomer having a repellent group. 'It can also be a monomer having several groups, two or more other monomers having a rebel group, or two or more types having no slow group. A copolymer of another monomer, for example, poly(meth)acrylic acid or a salt thereof, polycrotonic acid or a salt thereof, polyiconic acid or a salt thereof, etc., having a mercapto group/having a slow group The copolymer of two or more other monomers may, for example, be a (meth)acrylic acid-maleic acid copolymer or a salt thereof, a (fluorenyl) propylene crotonic acid copolymer or a salt thereof. The copolymer of the body and the other monomer having two or more kinds of carboxyl groups may, for example, be ethylene-maleic acid/polymer or a salt thereof, or a methacrylic acid-ethyl acrylate copolymer or a salt thereof. For example, a (meth)acrylic acid/maleic acid copolymer or an alkene thereof; a chitosan acid copolymer or a salt thereof, and a (mercapto)acrylic acid/cisene copolymer; or a salt thereof Preferably, the acrylic acid/maleic acid copolymer: salt is preferred. The salt of the acrylic acid/maleic acid copolymer is more preferable. The specific β /, poly a ratio (mole ratio) is 75/25 to 50/50 and an average weight of 10,000 to 100,000 (especially 40,000 to 60,000) of acrylic acid/cisene, = octamer or a salt thereof is preferred. A sodium salt, a potassium salt, etc. (Α) A non-crosslinking type high molecular weight polycarboxylic acid (salt) may be used alone or two types of 321459 6 201016839 may be used in combination. The component (A) used in the present invention may be synthesized. A commercially available one can also be used. For example, AQUALIC TL400 (acrylic acid/maleic acid copolymer) manufactured by Nippon Shokubai Co., Ltd., weight average molecular weight: 50,000, viscosity: about 2000 mPa /s (temperature: 23 ° C, concentration: 40%)), Sokalan CP7 and CP5 manufactured by BASF (all are acrylic acid / maleic acid copolymer, CP7 weight average molecular weight: 50000, viscosity: about 1500 mPa/s (temperature: 23 ° C, concentration: 40%), weight average of CP5® molecular weight: 70,000, viscosity: about 2000 mPa/s (temperature: 23 ° C, concentration: 40%), and the like. Further, the viscosity of the non-crosslinked polycarboxylic acid or a salt thereof can be, for example, a BL type viscosity measuring machine having a rotor No. 1 to 4, a rotation speed of 6 to 60 rpm at 25 ° C, and a measurement time of 20 to 120. The measurement was carried out under the conditions of seconds. (Component (B)) The component (B) is sorbitol. By blending the component (b), the viscosity of the composition of the present invention can be improved, thereby improving the usability. It also improves the storage stability of the enzyme, the detergency obtained from the enzyme (especially the detergency obtained from the enzyme after long-term storage), and the low temperature stability. In addition to this, it also helps to maintain a transparent appearance after the composition is preserved.
所使用之（B)成分可予以合成，也可使用市場上可取得 者。市場上可取得者可舉例如：R0QUETTE公司製之NE0S0RB 7〇/〇2β、三菱商事 Foodtech 公司製之 Sorbit D-70、SANEIThe component (B) used can be synthesized or used in the market. For example, R0QUETTE's NE0S0RB 7〇/〇2β, Mitsubishi Corporation Foodtech's Sorbit D-70, SANEI
糖化公司製之Sorbit A0-T、日研化成公司製之Sorbitol S 等。 7 321459 201016839 ((c)成分） (C)成分係從由丙二醇、甘油、葡萄糖、甘露醇及烧基 葡萄糖苷所成群組中選出之1種以上。 經由調配（C)成分，而發揮提高本發明之組成物中所含 之酵素之儲存安定性之機能。並且，也有助於保持組成物 之透明的外觀、提高酵素之儲存安定性。丙二醇、甘油、 葡萄糖及甘露醇，其中尤其是丙二醇、甘油，係有助於提 高本發明之組成物中所含之酵素之儲存安定性、組成物保 存後保持透明的外觀。 (C)以烷基葡萄糖苷與從由丙二醇、甘油、葡萄糖及甘 露醇所成群組中選出之1種以上之混合物為佳。 (C)以烷基葡萄糖苷與從由丙二醇及甘油所成群組中 選出之1種以上之混合物更佳。 前述烷基葡萄糖苷宜使用下述式（1)所示之化合物： R'COR^xGy (1) (式中，R1為碳數2至10，較佳為4至10，更佳為4至8) 之直鏈或分支（較佳為直鏈）之烷基或烯基， R2為碳數2至4，較佳為2至3之直鏈或分支之伸烷 基， G為源自碳數5或6之還原醣之殘基，以源自葡萄糖 之殘基為佳， X之平均值為0至5，以0至2為佳、以0較佳，y之 平均值為1. 0至4. 2，以1. 0至3. 0為佳、以1. 0(亦即單 _ )較佳）。 8 321459 201016839 前述烧基葡萄糖苦以2一乙基己基葡萄糖苦特佳。 (C)以（cl)2-乙基己基葡萄糖芽與（⑵從由丙二醇及 甘油所成群組中選出之！種以上之混合物更特佳。 (C) 成力可^以合成，也可使用市場上可取得者。2_ 乙基己基葡萄糖苦之市售品可例舉如· Ll〇N似^公司製 之AG6202。甘油之市售品可例舉如：阪本藥品工業公司製 之濃甘油、日本油脂公司製之日本藥典濃甘油。市售之丙 二醇可例舉如：旭玻璃公司製之丙二醇、昭和電工公司製 ❹之丙二醇、ADEKA公司製之丙二醇。 特別是，在本發明中，經由併用前述（A)成分、（B)成 分及（C)成分（其中尤其是（cl)成分及（c2)成分），而在（D) 成分調配系統中，與單獨使用此等成分時相比，可相乘地 得到提高使用性之適當黏度及優良的洗淨力、以及有助於 提高酵素之儲存安定性、及於組成物保存後保持透明的外 觀。此外，經由併用前述（A)成分、（B)成分及（c)成分（其 ❹中尤其是（cl)成分及（C2)成分），即可安定地調配香料。 ((D)成分） (D) 成分為酵素。經由調配酵素，可提高被洗物之污垢 洗淨月b力’特別是提高去除附著於食器之澱粉污垢及蛋白 質污垢的能力。 酵素可含有1種以上’以調配從由澱粉分解酵素及蛋 白質分解酵素所成群組中選出之1種以上之酵素較佳。 酵素以調配從由殿粉酶及蛋白酶所成群級中選出之1 種以上為佳。以併用澱粉酶與蛋白酶特佳。 321459 9 201016839 殿粉酶可舉例如：Termamyl Ultra 300L(Novozymes 公司製）、Termamyl 300L Type DX(Novozymes 公司製）、 Stainzyme 12L(Novozymes 公司製）、Stainzyme Plus 12L (Novozymes 公司製）、Duramyl 300L Type DX(Novozymes 公司製）等。 蛋白酶可舉例如：Everlase 16L Type DX(Novozymes 公司製）、Savinase Ultra 16XL(Novozymes 公司製）、 PURAFECT PRIME 4000LCGENENCOR 公司製）、PURAFECT OX4000L(GENENCOR 公司製）、PROPERASE L(GENENC0R 公司 ❹ 製）、Alcalase Ultra 2. 5L(Novozymes 公司製）、Alcalase 2.5L Type DX(Novozymes 公司製）等。 (香料組成物） 本發明之組成物可另外含有香料組成物。本發明之組 成物中可使用之香料組成物可舉例如選自下列組群之香料 組成物：乙酸2-甲基丁酯、乙酸苯甲酯、乙酸丁酯、丁酸 丁酯、莰烯（camphene)、癸醛、二氫月桂烯醇 參 (dihydromyrcenol)、2-乙基丁酸乙酯、香葉醛 (geranial)、香葉醇（geraniol)、乙酸香葉酯（geranyi acetate)、乙酸己酯、己基肉桂醛、柳酸己酯、L-香芹酮 (carvone)、檸檬烯、沉香醇（linalool)、L-薄荷醇、月桂 烯（myrcene)、辛醛、萜品油烯（terpinolene)、α -蒎烯（α -pinene)及α -萜品醇（a -terpineol)。以含有此等香料全 部之香料組成物為佳。 (其他成分） 10 321459 201016839 本發明之自動食器洗淨機用液體洗淨劑I且成物可調配 水做為其他成分。再者，本發明之組成物中之水分含量係 指組成物中之總水分含量。亦即，係指為取得組成物之平 衡而調配之水量、與將原料調配成溶液時之該溶液中之水 量合計而得之量。 本發明之組成物可復含有一般自動食器洗淨機用液體 洗淨劑組成物中所含之成分。特別是以含有非離子性界面 活性劑、陽離子性界面活性劑、防腐劑為佳。 ❹ 非離子性界面活性劑可舉例如：下列式（2)所示之聚氧 伸乙基聚氧伸喊絲_。本發明德成物㈣含有非 離子性界面活㈣丨畴高油污洗淨力、組成物之經時安 性’故較佳。Sorbit A0-T manufactured by Saccharification Co., Ltd., and Sorbitol S manufactured by Nikken Chemical Co., Ltd. 7 321459 201016839 (Component (c)) The component (C) is one or more selected from the group consisting of propylene glycol, glycerin, glucose, mannitol, and glucosinolate. By blending the component (C), the function of improving the storage stability of the enzyme contained in the composition of the present invention is exhibited. Moreover, it also contributes to maintaining the transparent appearance of the composition and improving the storage stability of the enzyme. Propylene glycol, glycerin, glucose, and mannitol, among them, propylene glycol and glycerin, are particularly useful for improving the storage stability of the enzyme contained in the composition of the present invention and maintaining a transparent appearance after the composition is preserved. (C) It is preferred that the alkyl glucoside is a mixture of one or more selected from the group consisting of propylene glycol, glycerin, glucose and mannitol. (C) It is more preferred that the alkyl glucoside is a mixture of one or more selected from the group consisting of propylene glycol and glycerin. The above alkyl glucoside is preferably a compound represented by the following formula (1): R'COR^xGy (1) (wherein R1 is a carbon number of 2 to 10, preferably 4 to 10, more preferably 4 to 8) a linear or branched (preferably linear) alkyl or alkenyl group, R2 is a linear or branched alkyl group having 2 to 4 carbon atoms, preferably 2 to 3, and G is derived from carbon. The residue of the reducing sugar of 5 or 6 is preferably a residue derived from glucose, and the average value of X is 0 to 5, preferably 0 to 2, preferably 0, and the average value of y is 1.0. Preferably, it is 1. 0 to 3.0, preferably 1.0 (ie, single_). 8 321459 201016839 The aforementioned calcined glucose is particularly preferred as 2-ethylhexylglucose. (C) It is more preferable to use (cl) 2-ethylhexyl glucose bud and (2) a mixture selected from the group consisting of propylene glycol and glycerin. (C) It can be synthesized or The product which is commercially available is exemplified by the product of the company, which is exemplified by the company. Japanese Pharmacopoeia glycerin, which is manufactured by Nippon Oil & Fat Co., Ltd., such as propylene glycol manufactured by Asahi Glass Co., Ltd., propylene glycol manufactured by Showa Denko Co., Ltd., and propylene glycol manufactured by ADEKA Co., Ltd. In particular, in the present invention, The components (A), (B), and (C) (particularly (cl) and (c2)) are used in combination with the component (D), and when these components are used alone. It is possible to multiply the appropriate viscosity for improving usability, excellent detergency, and to improve the storage stability of the enzyme and to maintain a transparent appearance after storage of the composition. Further, by using the above-mentioned (A) component in combination , (B) component and (c) component (its In the sputum, the (cl) component and the (C2) component can be formulated in a stable manner. ((D) component) (D) The component is an enzyme. By mixing the enzyme, the dirt of the laundry can be improved. In particular, it is capable of improving the ability to remove starch stains and protein stains attached to the food. The enzyme may contain one or more kinds of enzymes selected from the group consisting of amylolytic enzymes and proteolytic enzymes. The enzyme is preferably one or more selected from the group consisting of phosphatase and protease, and is preferably used in combination with amylase and protease. 321459 9 201016839 For example, Termamyl Ultra 300L (manufactured by Novozymes Co., Ltd.) ), Termamyl 300L Type DX (manufactured by Novozymes Co., Ltd.), Stainzyme 12L (manufactured by Novozymes Co., Ltd.), Stainzyme Plus 12L (manufactured by Novozymes Co., Ltd.), Duramyl 300L Type DX (manufactured by Novozymes Co., Ltd.), etc. The protease may, for example, be Everlase 16L Type DX ( It is manufactured by Novozymes Co., Ltd., Savinase Ultra 16XL (manufactured by Novozymes Co., Ltd.), PURAFECT PRIME 4000 LCGENENCOR Co., Ltd., PURAFECT OX4000L (manufactured by GENENCOR Co., Ltd.), PROPERASE L (manufactured by GENENC0R Co., Ltd.), Alcalase Ultra 2. 5L (manufactured by Novozymes Co., Ltd.), Alcalase 2.5L Type DX (manufactured by Novozymes Co., Ltd.), and the like. (Perfume Composition) The composition of the present invention may additionally contain a fragrance composition. The perfume composition which can be used in the composition of the present invention may, for example, be a perfume composition selected from the group consisting of 2-methylbutyl acetate, benzyl acetate, butyl acetate, butyl butyrate, and decene ( Camphene), furfural, dihydromyrcenol, ethyl 2-ethylbutyrate, geranial, geraniol, geranyi acetate, acetic acid Ester, hexyl cinnamaldehyde, hexyl hexanoate, L-carvone, limonene, linalool, L-menthol, myrcene, octanal, terpinolene,蒎-pinene (α-pinene) and α-terpineol (a-terpineol). It is preferred to use a perfume composition containing all of these fragrances. (Other Ingredients) 10 321459 201016839 The liquid detergent I for the automatic food purifier of the present invention is provided with water as an additional component. Further, the moisture content in the composition of the present invention means the total moisture content in the composition. That is, it means the amount of water which is prepared in order to obtain a balance of the composition, and the amount of water in the solution when the raw material is formulated into a solution. The composition of the present invention may contain the components contained in the liquid detergent composition for general automatic food cleaners. In particular, it is preferred to contain a nonionic surfactant, a cationic surfactant, and a preservative. ❹ The nonionic surfactant may, for example, be a polyoxyalkylene group represented by the following formula (2). The invention (4) of the present invention preferably contains a nonionic interface (4) high oil cleaning power and a time stability of the composition.
Rl-0-(E0)p(P0)q-H (2) R1為碳數8至20，較佳為8至16之疏水基，可為直 鍵或支鏈。疏水基可舉例如：以高級醇、高級脂肪酸二 ❹級脂肪釀胺做為原料者。表示環氧㈣基，P〇表示^ 丙烧基。p及q為環氧乙烧基及環氧丙烧基之平均加成莫 耳數i p及q分別在！至6之範圍。若 泡增加，會有斟& & a '』起 +自動&器洗淨乾燥機造成負擔且降低洗淨 力之虞。此夕K，4 ^ 右q超過6，則有時組成物之經時安定性 f良此外’ ？與Q之合計以3至1G為佳。若p與q之合 ::未達3 ’則在油污洗淨效果之觀點上稍微不良，此外， 右超過H) ’則會發生起泡增加、或組成物之經時安定性不 良之情形’故不佳。非離子性界面活性劑以式⑵之聚氧伸 321459 11 201016839 乙基聚氧伸丙基烧基謎特佳。 下述式（3)所示之化合 陽離子性界面活性劑可舉例如： 物等。 1 ⑶ 式中，L及L分別獨立地表示碳數丨至2〇,較佳為碳 數10至18之直鏈或支鏈之錄或稀基、長鏈羥基炫基、 曱山苯基、苯基、苯甲基中之任—者。^、h中之一者為 石反數10至18之直鏈或支鏈之烷基或烯基， 或甲苯基之組合特佳。E0表示環氧乙燒基。m及n為環& 乙烷基之平均加成莫耳數，分別獨立地表示〇以上之整 數。此外，ιη + η為10以上，且以1〇至5〇為佳。若m + n 為10以上，料更加提高對茶垢污垢之洗淨力。r為陰離 子，可舉例如：氯離子、溴離子、碘離子等鹵素原子離子； 或通式FWK惟，R4為碳數丨至3之烷基，以甲基為佳）所 示之離子等。 陽離子性界面活性劑以式（3)所示之化合物為佳，以氯 化5^氧伸乙基（15)院基甲基按較佳。 〃 本發明之組成物中可使用之防腐劑可舉例如：2_溴_2— 硝基-1, 3-丙二醇、異噻唑酮（is〇thiaz〇1〇ne)等。 其他成分可舉例如：乙醇等溶劑類、無機金屬鹽、植 物萃取物、抗菌/殺菌劑、除臭劑、安定劑、增黏劑、離子 性界面活性劑、高分子、無機鹽類等一般自動食器洗淨機 用液體洗淨劑組成物中所含之物質。 321459 12 201016839 (調配量） 相對於組成物之全質量，本發明 &月之紐成物传含有CA)4 至20質量％，而以8至18質量％為佳、丨”係3有⑷4 以1〇至14質量％ 較佳。令（A)成分之含量為4質量卜 ' 茶垢洗淨力及玻璃陰影洗淨力，且^ ㈣充分的 度。令含量為20質量%以下，即可將0 :提鬲組成物之黏 將衾且成物之黏度控制在 使用性良好的適度範圍，且可提高酵素之儲存;二:制= ❹ 存後仍可保持組成物之透明的外觀。 =子文疋 保 相對於組成物之全質量，本發明 4贫明之組成物以含有（B)2〇 至6〇質量％為佳，而以30至55質 含有αυπ 貝董<較佳、以32至50 質置％更佳。令（Β)成分之含量為2〇暂θ π π質以上，即有助於 提高組成物之黏度，且可提高酵素之儲存安隸、保存後 仍可保持組成物之透明的外觀。令含㈣55質量㈣下， =將組成物之黏度控制在使用性良好的適度的範圍，並 k南低溫安定性。 ❿㈣於組成物之全質量，本發明之組成物以含有 (C)4·5至12質量％為佳，而以5至8質量％較佳。 田使用（cl)及/或（C2)做為（c)時，相對於組成物之全 質量’以含有⑻0.5至5質量％為佳，而以〇.7至3質量 %較佳。以含有（C2)4至11質量％為佳，而以4至7質量％ 較佳。令⑻為0. 5質量％以上，即可提高酵素之儲存安定 =、保存後仍可保持組成物之透明的外觀。令（⑴為5質 里/〇以下’即可提间酵素之錯存安定性、保存後仍可保持組 成物之透明的外㉟。令（⑵為4質量％以上，即可提高酵素 321459 201016839 之錯存女^V保存後仍可保持組成物之透明的外觀。令 (c2)為11貝量％以下，保存後仍可保持組成物之透明的外 觀。Rl-0-(E0)p(P0)q-H (2) R1 is a hydrophobic group having a carbon number of 8 to 20, preferably 8 to 16, which may be a straight bond or a branched chain. The hydrophobic group may, for example, be a higher alcohol or a higher fatty acid diterpenoid fatty amine as a raw material. Represents an epoxy (tetra) group, and P 〇 represents a propyl group. p and q are the average addition moles of epoxy Ethylene and Ethylene propylene groups i p and q respectively! To the extent of 6. If the bubble is increased, there will be a burden between the && a && a > + automatic & On the eve of K, 4 ^ and the right q is more than 6, sometimes the composition of the time stability is good. It is preferably 3 to 1G in total with Q. If the combination of p and q: is less than 3', it is slightly inferior in terms of the effect of cleaning the oil. In addition, if the right exceeds H) 'the foaming will increase, or the stability of the composition may be poor." It is not good. The nonionic surfactant is a polyoxygen extension of the formula (2). 321459 11 201016839 Ethyl polyoxyl extended propyl group is particularly good. The compounding cationic surfactant represented by the following formula (3) may, for example, be an object or the like. 1 (3) wherein L and L each independently represent a carbon number of 丨 to 2 〇, preferably a linear or branched carbon or a branched chain, a long-chain hydroxy hydrazone, or an anthracene phenyl group. Any of the phenyl and benzyl groups. One of ^, h is a linear or branched alkyl or alkenyl group having a reverse number of 10 to 18, or a combination of tolyl groups. E0 represents an epoxy group. m and n are the average addition moles of the ring & ethane group, which independently represent the integer above 〇. Further, ιη + η is 10 or more, and preferably 1 〇 to 5 。. If m + n is 10 or more, the material is more improved in the cleaning power of the tea scale dirt. r is an anion, and examples thereof include a halogen atom such as a chloride ion, a bromide ion or an iodide ion; or an ion represented by the formula FWK, wherein R4 is an alkyl group having a carbon number of 丨 to 3 and preferably a methyl group. The cationic surfactant is preferably a compound represented by the formula (3), and it is preferred to chlorinate the ethyl group (15). The preservative which can be used in the composition of the present invention may, for example, be 2-bromo-2-nitro-1, 3-propanediol or isothiazolone (is〇thiaz〇1〇ne). Other components include, for example, solvents such as ethanol, inorganic metal salts, plant extracts, antibacterial/bactericides, deodorants, stabilizers, tackifiers, ionic surfactants, polymers, inorganic salts, and the like. The substance contained in the liquid detergent composition for the food washer. 321459 12 201016839 (mixing amount) The present invention & month of the present invention contains CA) 4 to 20% by mass, and 8 to 18% by mass, preferably 丨"3 (4) 4 with respect to the total mass of the composition. It is preferably from 1 to 14% by mass, and the content of the component (A) is 4 masses of 'tea scale cleaning power and glass shading detergency, and ^ (4) sufficient degree. The content is 20% by mass or less, that is, 0: The viscosity of the composition can be controlled, and the viscosity of the product can be controlled to a moderate range of good use, and the storage of the enzyme can be improved; Secondly, the transparent appearance of the composition can be maintained after the storage. = The sub-document ensures that the composition of the present invention is preferably (B) 2 〇 to 6 〇 by mass, and 30 to 55 υ υ 贝 & & & & 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳It is better to use 32% to 50%. The content of (Β) component is 2〇 θθ π π or more, which helps to increase the viscosity of the composition, and can improve the storage and storage of the enzyme. Keep the transparent appearance of the composition. Let (4) 55 mass (four), = control the viscosity of the composition to a moderate degree of good use.围, and k South low temperature stability. 四 (4) In the total mass of the composition, the composition of the present invention preferably contains (C) 4 · 5 to 12% by mass, and preferably 5 to 8 % by mass. When cl) and/or (C2) is (c), it is preferably 0.5 to 5% by mass based on (8), and preferably 〇7 to 3% by mass, based on the total mass of the composition. C2) 4 to 11% by mass is preferred, and 4 to 7% by mass is preferred. If (8) is 0.5% by mass or more, the storage stability of the enzyme can be improved = and the transparent appearance of the composition can be maintained after storage. Let ((1) be 5 里 / 〇 ' 即可 即可 即可 提 提 酵 酵 酵 酵 酵 酵 酵 酵 酵 酵 酵 酵 酵 酵 酵 酵 酵 酵 酵 酵 酵 酵 酵 酵 酵 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 In 201016839, the female VV can maintain the transparent appearance of the composition after storage. Let (c2) be 11% by volume or less, and the transparent appearance of the composition can be maintained after storage.
並且’相對於組成物之全質量，本發明之洗淨組成物 係含有（B)及（C)合計為25至70質量％，且以3〇至6〇質量 0/〇為佳、以30至5〇質量％較佳、以40至50質量％更佳。藉 由使（B)成分及（C)成分之合計量成為25質量％以上，即可 在使用性上具有良好的適當黏度、提高酵素之儲存安定 性、保存後仍可保持透明外觀之組成物。令合計量為7〇 Q 質量％以下時，可提高使用性之適當黏度，並提高低溫安定 性。當使用（cl)及（c2)之組合做為（C)時’（cl)與（c2)之人 計調配量以4至12質量％為佳、以5至8質量％較佳。 此外’本發明之洗淨劑組成物中所調配之（B)成分及（c) 成分係以使（B)/(C)之質量比例成為在2至1 〇之範圍（較佳 在4至9之範圍）之方式調配。令質量比例在上述範圍，可 得到具有用以提高使用性之適當黏度及優良的洗淨力、提 高酵素之儲存安定性、洗淨劑組成物不會變濁或分離、保 參 存後仍可保持透明外觀之組成物。 (D)成分之酵素以調配0.05至10質量％為佳、以〇 ^ 至5質量％較佳、以o.i至1質量％更佳。令此合計含i為 〇. 05%質量％至1〇質量％之範圍，可提高洗淨性能。 … 在組成中，澱粉分解酵素以調配0· 〇〇6至3〇單位 /g(U/g)為佳、以0.012至15單位/g(u/g)較佳、以〇 至3單位/g(|j/g)更佳。使其含量在此範圍，可提高對爽於 321459 14 201016839 污垢之洗淨性能。 在組成中，蛋白質分解酵素以調配0. 00125至400單 位/g(U/g)為佳、以0.0025至200單位/g(U/g)較佳、以 0. 0025至40單位/g(U/g)更佳。使其含量在此範圍，可提 高對蛋白質污垢之洗淨性能。 相對於組成物之總質量，水以調配65質量％以下為 佳、以60質量％以下較佳、以55質量％以下更佳，具體而 言可在40至50質量％之範圍調配。若超過65質量％，則有 © 時會降低酵素之儲存安定性。 相對於組成物之總質量，香料組成物以在0.01至〇. 1 質量％之範圍調配為佳、以在0. 03至0. 1質量％之範圍調配 較佳。 相對於組成物之總質量，非離子性界面活性劑以在 0. 01至0. 1質量％之範圍調配為佳、以在0. 05至0. 1質量 %之範圍調配較佳。 φ 相對於組成物之總質量，陽離子性界面活性劑以在 0. 1至1. 0質量％之範圍調配為佳、以在0. 5至1.0質量％ 之範圍調配較佳。 相對於組成物之總質量，防腐劑以在0. 001至0. 01 質量％之範圍調配為佳、以在0. 005至0. 01質量％之範圍調 配較佳。 (本發明之組成物之製造方法） 本發明之組成物之製造方法並無特別限制，可使用習 知製造液體洗淨劑組成物時所用之任何方法。例如以下述 15 321459 201016839 方法為佳：調配（A)至（c)成分及其他成分，並使用汕 劑將pH調整成任何pH，例如6至8之間，然後再_ _ i 成分。 D』（D) (本發明之組成物之物性） 本發明之組成物之pH以在6至8之範圍為佳。因入 pH在6至8之範圍時，可提咼叙製等食器之洗淨性， 提高酵素之儲存安定性。pH可使用pH調整劑（例如：〒: 化鈉、硫酸）進行調整。 ’氧氣 本發明之組成物之黏度以在1〇〇至2〇〇〇mPa.s之 為佳、以在200至l000mPa.s之範圍較佳。在此範園，已六 易計量組成物且容易將組成物投入自動食^洗淨機中，= 使用性良好的適當黏度範圍。黏度可使用例如轉子為N疋 至4之BL型黏度測定機，並在25t，轉子之轉速為至1 60rpni、測定時間20至12〇秒之條件下進行測定。 以下，藉由實施例更詳細說明本發明。再者，以下 貫她例¥然不對本發明之範圍做任何限制。 (實施例） 實施例、比較例中所使用之各成分係下述者。 ((A)成分） •順丁烯二酸丙埽酸聚合物（AqUALIC TL400 : B 士 媒），有效成分：40%，水分：60%，重量平均分早县 50000 量： •順丁烯二酸丙埽酸聚合物（S〇kalan CP7 : BASF)，有效 成分：92% ’水分：8%，重量平均分子量：50000 16 321459 201016839 •順丁烯二酸丙烯酸聚合物（Sokalan CP5 : BASF)，有效 成分：92% ’水分：8% ’重量平均分子量：70000 ((B)成分） •山梨糖醇（NEOSORB 70/02B : R0QUETTE公司），有效成 分：70%，水分：30% ((C)成分） 春2-乙基己基葡萄糖苷（AG6202，LION AKZ0)，有效成分： 65%，水分：35% © •甘油（濃甘油，阪本藥品工業（股）），有效成分：100% •丙二醇（旭玻璃（股）），有效成分：100% ((D)成分） 籲澱粉酶（Termamyl Ultra 300L，Novozymes 公司），100% 產品之調配力價為300KNU(L)/g •蛋白酶（Savinase Ultra 16XL，Novozymes 公司），100% 產品之調配力價為16KNPU-S/g φ ♦香料組成物 乙酸2-曱基丁酯：1%、乙酸苯甲酯：1%、乙酸丁酯：2%、 丁酸丁酯：0. 5%、莰烯：0. 5%、癸醛：0. 5%、二氩月桂烯 醇：2%、2-乙基丁酸乙酯：1%、香葉醛：3%、香葉醇：6%、 乙酸香葉酯·· 4%、乙酸己酯：2%、己基肉桂醛：2%、柳酸 己酯：3%、L-香芹酮：1%、檸檬烯：55%、沉香醇：8%、L-薄荷醇：3. 5%、月桂烯：0. 5%、辛醛：0. 5%、萜品油烯： 1%、α-蒎烯：1%、α-萜品醇：1%(各香料後之「％」表示 以此等之總量為基準之比例） 17 321459 201016839 (任意成分） _ CnH2n+1〇(EO)3(PO)3H(n=12/13 混合物（質量比 65/35)， 有效成分：96. 5%，水分 3. 5%，Neodo卜23(Shell 製， 分支率20%之醇）之平均E03P03莫耳加成物。合成係按 照曰本特開2007-23268號公報之段落0063之記载進 行） _氣化聚氧伸乙基（15)烷基曱基銨（（EsocardC/25，LION AKZO) ’有效成分：95%，水分：2%) * 2->臭-2~硝基-1，3-丙二醇（（Protectol BN，BASF 公司 製）’有效成分：99%以上） •異噻唑_溶液（（KATHON CG :羅門哈斯製），有效成分： 1. 5% ’ 鎂鹽：23%，水：75. 5%) •氫氧化鈉或硫酸（pH調整劑）：適量 •精製水··餘量 將上述所示之（A)至（C)成分及任意成分混合，並使用 pH調整劑將該混合物之PH調整成7. 3後，加入（D)成分再 予以混合，並加入精製水取得平衡，藉此得到實施例及比 較例之自動食器洗淨機用液體洗淨劑組成物。各成分之量 如表1及表2所記載，所示之量為純成分之量。pH係在25 t：使用玻璃電極進行測定。藉由下述各測試評估所製得之 組成物。結果如表1及表2所示。 《評估方法》 < 1.組成物之黏度之測定方法> (測定條件）BL型黏度測定機（DIGITAL VISMETRON VDA) 321459 18 201016839 測定溫度：25°C，轉速：6至60rpm，測定時間：20至120 秒，轉子：No. 1至4 <2.使用性之評估方法> 將各組成物80mL裝入100mL玻璃燒杯中，在25°C恆 溫槽中將組成物之溫度調整成25°C後，請5名測試員將組 成物6g投入10mL燒杯中，並藉由下述基準評估使用性。 溶液容易投入，也容易調節投入液量 3點 溶液容易投入，稍微難調節投入液量 2點 ❹ 溶液難投入，也難調節投入液量 1點 算出5人之評分之平均值，按照下述設定評估結果。 評估基準：〇至◎為合格範圍 ◎:平均分數為2. 8以上 〇：平均分數為2. 6以上未達2. 8 △:平均分數為2.0以上未達2. 6 X :平均分數未達2. 0 ©<3.觀察在40°C保存後之外觀> 將各組成物80mL裝入PS11之瓶（100mL)中，以肉眼觀 察在40°C保存1個月後之外觀，並藉由下述基準進行評估。 〇：透明 △:稍微混濁 X ·混濁 <4.洗淨力評估方法> (4. 1 由酵素所得之洗淨力之評估方法） 藉由下述之評估方法，評估將各組成物保存前與保存 19 321459 201016839 後（保存條件：室溫，保存6個月）之洗淨力。 (4.1.1澱粉污垢洗淨力） 使用將佐藤食品工業（股）製「佐藤的飯」5g (直控115_，高度50咖)後放置於阶、_H布^ 整晚（24小時），然後以此進行洗淨評估。食器洗淨^ =Natlonal公司製之Np_4〇SX2，選擇標準程序將爆使 藉由下述基準評估洗淨後之碗之狀態。 / 。 評估基準：〇至◎為合格範圍 ◎:污垢已良好地脫落 〇：污垢已脫落 △:污垢大致有脫落 x:污垢完全未脫落 (4. 1.2 蛋白質污垢洗淨力） 將蛋/水= 1/9均勻攪拌後注入1〇〇乩燒杯中，使用蒸 飯機蒸20㈣°之後’將燒杯内之溶液倒掉，並使用乾燥 後之燒杯進行洗淨評估。食器洗淨機係使用Nati〇nal公司 ‘之NP-40SX2，選擇標準程序將燒杯洗淨。藉由下述基準 評估洗淨後之燒杯之狀態。 評估基準：〇至◎為合格範圍 ◎:污垢已良好地脫落 〇：污垢已脫落 △:污垢大致有脫落 x :污垢完全未脫落 (4. 2 茶垢洗淨力之評估法） 321459 20 201016839 將喝完紅茶後放置於25°C、50%RH條件下5天之附有 紅茶茶垢之咖啡杯（内徑70mm，高度70mm)3個裝填至自動 食器洗淨乾燥機「松下電器產業（股）製，機種NP-40SX2」 Λ 中，使用所調製之組成物6g進行標準程序洗淨後，依照下 述評估基準對完成狀態進行感觀評估。 評估基準： ◎:污垢完全無殘留，也無粗糙等不協調感 〇：無法以肉眼辨識污垢殘留，但觸摸時有些許粗糙等 ©不協調感 △:可以肉眼辨識些許污垢殘留 X:污垢未脫落 (4. 3 玻璃陰影洗淨力之評估法） 將玻璃杯（上徑63mm，下徑53腿，高度100mm)裝填至 自動食器洗淨乾燥機中，並將碳酸鈉1. 2g裝入機内後，使 用30度硬水進行洗淨至洗滌之全步驟，而得到經白化之杯 @子，將該杯子裝填至自動食器洗淨乾燥機「松下電器產業 (股）製，機種NP-40SX2」中，並使用所調製之組成物6g 進行標準程序洗淨後，依照下述評估基準對完成狀態進行 感觀評估。 評估基準： ◎:白化物完全無殘留，也無粗糙等不協調感 〇：一部分可辨識白化物些微殘留 △:可以肉眼辨識些許白化物殘留，整體上已失去透明 感 21 321459 201016839 X :白化物未脫落 <5.低溫安定性評估> 將各組成物80mL裝入PS11之瓶（100mL)中，以肉眼觀 察在-5°C保存1個月後之外觀，並藉由下述基準進行評估。 〇：透明 △:混濁 X :有析出物 22 321459 201016839 表1 οΟ 5 埃 «Β： CO Ο g d o' ΙΟ r^ o 5 O 策 _ k 8 r» Φ as eo ο €·> kA 〇 ο 〇 9 〇 〇 ο ο 〇 Μ Μ V s. o 5 tf> S <·* o g m « >w 錐 S — C4 » «· 卜 «·> o m o ο 〇 〇 〇 〇 ο ο 〇 ΟΙ — Ο «Μ» g s 5 in 1^; g 1 <w 锖 »w k δ «*» «Μ «4 9 卜· er> ia β» «V o ο 〇 Ο 〇 〇 ο ο 〇 Ο Μ 幸 in — g o 5 in o g S； 〇 _ 请 _ 錐 δ s CSI s Q 卜 t>> s •M o ο Θ 〇 〇 〇 ο ο 〇 σ> €4 ψ^> 智 i d v> e w s w p m 请 m 逛 s ·» 10 «4 «» 苈 ID iri c» s 0 ο 〇 〇 〇 0 ο ο 〇 βο CD «5 Ο W s d 〇· tn o' S ·» § m « «Ν 錐 δ δ 9 <9 i o ο 〇 〇 〇 ο ο ο 〇 卜 «0 ο s o 4» 5 p «Mr s m m 傘 8 — 穿 黉 萃 o ο 〇 〇 〇 〇 ο ο 〇 «» Μ Κ ΙΟ g o 5 u> oa o Ξ G> m 臂 m S 釋 Μ Μ 产 w CJ <e o 卜 W «1 o ο & Θ 0 0 0 ο 〇 ιο «si «·* ft 1ί> 1 § P 〇 g 〇 m 領 *w 傘 8 t·» 穿 Γ4 » CM Φ o o ο 〇 〇 〇 〇 0 ο 〇 寸 Μ m Μ Μ 卜 «Μ» 1 5 tn o* % m 请 Φ4 # S η Μ 穿 J? S CO G ο e e 〇 b ο ο 〇 η C4 η eo ir> «1·· 〇 w 〇· u> r^ § *<· § _ 帮 _ 錐 8 9 «4 •9"· m «e t«> tf> M o ο 〇 〇 〇 〇 ο ο 〇 Μ Μ ▼-· Λ «0 CM •0» o d 1C ci g 9 m 帮 m 傘 S s> 94 mmm 80 3 CO S 聲 Θ ο d 〇 〇 〇 ο ❹ 〇 Μ Ο u> — s o 5 ΙΛ 1 »·- g m m m 傘 s 产 Μ JJ S 5 in o ο ο 〇 〇 〇 ο ο 〇 /-S Ο I 6- Ρ W 審 « 龙 « Λ * h 竇 £ Λ ι # « « '1 « h /^\ § α 1 ¥ * 款 m « Ί « Η* 靛 « 寐 -5 % 霣 « ϋ co 、1 * /-N Ο 〇 CO tet 亡 ο •Mi 1 ί i 靼 m | 60 α> CO § •-H > # 窠 Φ 翥 玆 ί： 拿 «ί 垅 6- s WH s-> 0 拿 Δ2 « M e TO 4 苷 d, 1 * ώ 唉 轶 Ψ «fe /-N Μ 蠏 c £ 4M 霣 s * g. m «V； 言 •w 余 ί w m Φ v Φ <-Ν g. _ 如 /^, 3 十 £ m s w X • ea 3 « ii 匿 HC 專 维 Ρ * Ifc 鉬 典 SC » Φ « « 年 « « sc «ΐ *φ η 掩 />>> βς 隳 W «! 炻 珐 «ί 维 5 Φ 嗜 m § % 23 321459 201016839 表2 ο N % 1 0.05 1 ο 1 0-75 1 g 5 Ο m « \Λ±Λ s «D cw ψ^· s 1 CS s 〇 K o ο < < o ο ο m M <««· s 1 0.05 1 ο 1 078 1 LmJ 2 m 膂 1 1 8 Μ 9 LjmJ V» s 〇 X o ο <1 < o ο ο to ο — 窝 i 0.09 1 1 0-7S 1 Γα〇Π 1 001 1 _ « ί餘*Ί s w cv 7 w 巧 $ < K o ο o o o ο ο r- 严 £ csa ΙΟ 0.05 1 d ί 0-75 1 I 〇.〇1_1 1 m « ί 1 s ew 5 «D 0» Γ» I X o o ο o o o ο X Φ C4 ΙΑ <*· 1 0.05 1 1 075 1 ί_. 0.0t .」 Lp-〇iJ m « L餘量1 s s Μ •ψ^ 卜 IA r> s < X o ο <1 < o ο ο in s Κ» 1 0.05 1 5 丨 〇,75 —J 1 ig o l J 1餘量」 8 94 «Ο 曾· 卜 m δ P4 o 〇 X X X X o ο ο CM κ> ! 0Ό5 1 d 1 m 1 I o 丨適* 1 1餘f 1 s Μ 1 U> < X o ο < < o ο ο C*3 u> 5 ΙΟ 0.05 1 5 0.75 1 〇·〇ι 1 p e \Λ*\ ί 1 8 <» Μ> 5 ，· 卜 卜· 1 3600 K X o ο < <3 o ο ο CXI tf> R 40 - 1 0加1 5 丨 0.75 J Loou 丨 0.01 1 1財1 L餘量1 8 S 9 C9 ID < o o ο o • ό X X ο <〇 «· to 0.05 1 5 1 0-75.1 1 1 丨適董1 1龟量J S in Ο VQ 卜 C> < o o ο o o X X ο g 3 卜 9 ? s-** « Μ « sr « >1 * Η 寄 項丁烯二酸丙烯酸共聚物(Sokalan CP5) | β t « St « 11 * h 山梨螗醇 I 寒 霣 m n3 Ο 晒 CS3 丙二酵 1 甘油 1 Λ粉峰(Ternaniyl Ultra 300L) | 曰 GO •Η οβ α> § •*-1 > ed CO w 鬵 # w ¢: 9ί 螬 〇 «ί 氯化聚氡伸己基（15)妮基T基銥 1 2-溴-2-蜗基-〖，3-丙二if 1 異嚏喳明溶液 pll«壑«(氫氧化鋼或硫酸） 精製水 1 合计Hit X) 1水分含量 1(A)成分之含董（質董X) (B) + (C)之含量（貿量X) 1 (bv(c)之 ir* 比 ! 1 « 典 1使用性 f 串 P # w 女 I M粉污垢 1 蛋白R污垢 1 戮粉汚垢 璀 你 1茶垢洗淨力 爸 iS 染 霣 w ϊ 9 «Μ 举 Ρ 7 蝉 t 1(B)成分 1 (w成分 保存觫 1 e s i 1 (A)成分 (C)成分 < * Pt S s ? i t t Ik 24 321459 201016839 如表1及表2所示，在本發明之範圍中之洗淨劑組成 物可達成良好的黏度範圍，藉此可達成良好的使用性。此 外，不僅在保存前顯示良好的洗淨性，在保存後也顯示優 鏞 良的洗淨性，可確認本發明之液體洗淨劑組成物具有優良 的酵素之儲存安定性。相對於此，關於超出本發明之範圍 外之比較例，因黏度過度地降低或升高，而造成使用性不 良。此外，也可確認其酵素之保存安定性降低。 【圖式簡單說明】無 © 【主要元件符號說明】無 ❹ 25 321459And 'with respect to the total mass of the composition, the cleaning composition of the present invention contains (B) and (C) in a total amount of 25 to 70% by mass, and preferably 3 to 6 〇 mass 0 / 、, and 30 It is preferably from 5% by mass to more preferably from 40 to 50% by mass. When the total amount of the component (B) and the component (C) is 25% by mass or more, it is possible to have a suitable viscosity in terms of usability, improve the storage stability of the enzyme, and maintain a transparent appearance after storage. . When the total amount is 7 〇 Q mass% or less, the appropriate viscosity for usability can be improved and the low temperature stability can be improved. When the combination of (cl) and (c2) is used as (C), the blending amount of '(cl) and (c2) is preferably 4 to 12% by mass, and preferably 5 to 8% by mass. Further, the component (B) and the component (c) to be blended in the detergent composition of the present invention are such that the mass ratio of (B)/(C) is in the range of 2 to 1 Torr (preferably 4 to 9 range)). When the mass ratio is in the above range, it is possible to obtain an appropriate viscosity for improving usability, excellent detergency, improved storage stability of the enzyme, no turbidity or separation of the detergent composition, and preservation after storage. A composition that maintains a transparent appearance. The enzyme of the component (D) is preferably 0.05 to 10% by mass, more preferably 〇^ to 5% by mass, even more preferably 0.1% by mass to 1% by mass. Let this total include i in the range of 5%. 05% by mass to 1% by mass to improve the cleaning performance. In the composition, the amylolytic enzyme is preferably formulated in an amount of from 0.6 to 3 units/g (U/g), preferably from 0.012 to 15 units/g (u/g), and in an amount of up to 3 units/ g(|j/g) is better. The content of this is in this range, which can improve the cleaning performance of the dirt on 321459 14 201016839. In the composition, the proteolytic enzyme is preferably 0. 00125 to 400 units / g (U / g), preferably 0.0025 to 200 units / g (U / g), preferably 0. 0025 to 40 units / g ( U/g) is better. By making it in this range, the cleaning performance against protein soil can be improved. The water is preferably blended in an amount of 65 mass% or less, more preferably 60 mass% or less, more preferably 55 mass% or less, and particularly preferably 40 to 50 mass%, based on the total mass of the composition. If it exceeds 65 mass%, there is a decrease in the storage stability of the enzyme when there is ©.至优选的质量优选的优选。 Preferably, the blending composition is preferably in the range of from 0.01 to 0.1% by mass, preferably from 0. 03 to 0.1% by mass. The mass ratio of the composition is preferably in the range of from 0.05 to 0.1% by mass, preferably from 0. 01 to 0.1% by mass, based on the total mass of the composition.至优选为优选的范围之间。 Preferably φ is preferably in the range of from 0.1 to 1.0% by mass, preferably from 0.5 to 1.0% by mass. 005质量质量优选范围内优选优选的范围内的范围内的范围内的范围内的范围内。 Preferably, the preservative is preferably in the range of from 0.0001 to 0.01% by mass. (Manufacturing method of the composition of the present invention) The method for producing the composition of the present invention is not particularly limited, and any method used in the conventional production of the liquid detergent composition can be used. For example, the following 15 321459 201016839 method is preferred: the components (A) to (c) and other ingredients are formulated, and the pH is adjusted to any pH using a tanning agent, for example, between 6 and 8, and then the _ _ i component. D"(D) (physical properties of the composition of the present invention) The pH of the composition of the present invention is preferably in the range of 6 to 8. When the pH is in the range of 6 to 8, the detergent of the food can be improved and the storage stability of the enzyme can be improved. The pH can be adjusted using a pH adjuster (for example: hydrazine: sodium, sulfuric acid). 'Oxygen The viscosity of the composition of the present invention is preferably from 1 Torr to 2 Å mPa.s, preferably from 200 to 1000 mPa.s. In this garden, it is easy to measure the composition and it is easy to put the composition into the automatic food washing machine, and the appropriate viscosity range is good. The viscosity can be measured, for example, by a BL type viscosity measuring machine having a rotor of N 疋 to 4, and at 25 t, the rotation speed of the rotor is up to 1 60 rpni, and the measurement time is 20 to 12 sec. Hereinafter, the present invention will be described in more detail by way of examples. Furthermore, the following examples are not intended to limit the scope of the invention. (Example) Each component used in the examples and comparative examples is as follows. ((A) component) • Maleic acid propionic acid polymer (AqUALIC TL400: B), active ingredient: 40%, moisture: 60%, weight average, early county, 50000 Quantity: • Butene Acid propionic acid polymer (S〇kalan CP7: BASF), active ingredient: 92% 'moisture: 8%, weight average molecular weight: 50000 16 321459 201016839 • maleic acid acrylic acid polymer (Sokalan CP5: BASF), Active ingredient: 92% 'Moisture: 8%' Weight average molecular weight: 70,000 ((B) ingredients) • Sorbitol (NEOSORB 70/02B: R0QUETTE), active ingredient: 70%, moisture: 30% ((C) Ingredients) Spring 2-ethylhexyl glucoside (AG6202, LION AKZ0), active ingredient: 65%, moisture: 35% © • Glycerin (concentrated glycerin, Sakamoto Pharmaceutical Co., Ltd.), active ingredient: 100% • Propylene glycol ( Asahi Glass Co., Ltd., active ingredient: 100% ((D) ingredient) Amylase (Termamyl Ultra 300L, Novozymes), 100% product price is 300KNU(L)/g • Protease (Savinase Ultra 16XL) , Novozymes), 100% of the product's blending power price is 16KNPU-S/g φ ♦ The composition of the material is 2-mercaptobutyl acetate: 1%, benzyl acetate: 1%, butyl acetate: 2%, butyl butyrate: 0.5%, decene: 0.5%, furfural: 0. 5%, diargonyl enol: 2%, ethyl 2-ethylbutyrate: 1%, geranyl aldehyde: 3%, geraniol: 6%, geranyl acetate · 4%, acetic acid Hexyl ester: 2%, hexyl cinnamaldehyde: 2%, hexyl hexanoate: 3%, L-carvone: 1%, limonene: 55%, linalool: 8%, L-menthol: 3. 5% , myrcene: 0.5%, octanal: 0.5%, terpinolene: 1%, α-pinene: 1%, α-terpineol: 1% ("%" after each fragrance) The ratio based on the total amount of such) 17 321459 201016839 (optional component) _ CnH2n+1〇(EO)3(PO)3H(n=12/13 mixture (mass ratio 65/35), active ingredient: 96 5%, moisture 3.5%, Neodo Bu 23 (Shell, 20% alcohol) average E03P03 molar addition. The synthesis is in accordance with paragraph 0063 of 曰本特开2007-23268 Carrying out _ gasification polyoxyl extended ethyl (15) alkyl decyl ammonium ((EsocardC / 25, LION AKZO) 'active ingredient: 95%, moisture: 2%) * 2-> odor-2 ~ nitrate Base-1,3- Glycol ((Protectol BN, manufactured by BASF)' active ingredient: 99% or more) • Isothiazole_solution ((KATHON CG: manufactured by Rohm and Haas), active ingredient: 1. 5% 'Magnesium salt: 23%, water :75. 5%) • Sodium hydroxide or sulfuric acid (pH adjuster): Appropriate amount • Purified water·· balance The ingredients (A) to (C) shown above and optional ingredients are mixed and used as a pH adjuster. After the pH of the mixture was adjusted to 7.3, the component (D) was added and mixed, and purified water was added thereto to obtain a balance, whereby the liquid detergent composition for the automatic food processor of the examples and the comparative examples was obtained. The amount of each component is as shown in Tables 1 and 2, and the amount shown is the amount of the pure component. The pH was measured at 25 t using a glass electrode. The compositions prepared were evaluated by the following tests. The results are shown in Tables 1 and 2. <<Evaluation method>> < 1. Method for measuring viscosity of composition> (Measurement condition) BL type viscosity measuring machine (DIGITAL VISMETRON VDA) 321459 18 201016839 Measurement temperature: 25 ° C, rotation speed: 6 to 60 rpm, measurement time: 20 to 120 seconds, rotor: No. 1 to 4 < 2. Evaluation method of usability> 80 mL of each composition was placed in a 100 mL glass beaker, and the temperature of the composition was adjusted to 25 in a 25 ° C thermostatic bath. After the °C, 5 testers were asked to put 6 g of the composition into a 10 mL beaker, and the usability was evaluated by the following criteria. The solution is easy to put in, and it is easy to adjust the amount of the input solution. It is easy to put in the solution at 3 o'clock. It is difficult to adjust the amount of the input solution to 2 o'clock. It is difficult to input the solution. It is also difficult to adjust the amount of the input solution to calculate the average value of the score of 5 people. evaluation result. Evaluation criteria: 〇 to ◎ is the qualified range ◎: the average score is 2. 8 or more 平均: the average score is 2. 6 or less up to 2. 8 △: the average score is 2.0 or more and less than 2. 6 X: the average score is not up to 2. 0 © <3. Observation of appearance after storage at 40 ° C> 80 mL of each composition was placed in a bottle (100 mL) of PS11, and the appearance after storage at 40 ° C for one month was visually observed, and The evaluation was performed by the following criteria. 〇:transparent △: slightly turbid X·turbidity<4. Detergency evaluation method> (4.1. Evaluation method of detergency by enzyme) The composition was evaluated by the following evaluation method. Before and after the preservation of 19 321459 201016839 (storage conditions: room temperature, stored for 6 months) the detergency. (4.1.1 Washing power of the starchy soil) 5g (Direct control 115_, height 50 coffee) made by Sato Food Industry Co., Ltd., placed in the order, _H cloth ^ night (24 hours), then This is used for washing evaluation. The food is washed ^ = Np_4〇SX2 manufactured by Natlonal Co., Ltd., and the standard procedure is selected to explode. The state of the washed bowl is evaluated by the following criteria. / . Evaluation criteria: 〇 to ◎ is the qualified range ◎: The dirt has fallen off well 〇: The dirt has fallen off △: The dirt is almost detached x: The dirt is not falling off at all (4. 1.2 Protein dirt washing power) Egg/water = 1/ 9 Evenly stir and inject into a 1 〇〇乩 beaker, steam 20 (four) ° using a rice cooker, then 'pour the solution in the beaker and use a dried beaker for washing evaluation. The food washing machine uses the Nati〇nal ‘NP-40SX2, and the standard procedure is used to wash the beaker. The state of the washed beaker was evaluated by the following criteria. Evaluation criteria: 〇 to ◎ is the qualified range ◎: The dirt has fallen off well 〇: The dirt has fallen off △: The dirt is almost detached x: The dirt is not falling off at all (4.2. Evaluation method of the cleaning ability of the tea scale) 321459 20 201016839 After drinking black tea, place it at 25 ° C, 50% RH for 5 days with a black coffee tea stained coffee cup (inner diameter 70mm, height 70mm) 3 pieces to the automatic food washing and drying machine "Panasonic Electric Industry Co., Ltd. In the system, NP-40SX2" ,, after the standard procedure was used to clean the prepared composition 6g, the sensory evaluation was performed on the completion state according to the following evaluation criteria. Evaluation criteria: ◎: The dirt is completely free of residue, and there is no rough and other uncoordinated feelings: the dirt residue cannot be recognized by the naked eye, but it is slightly rough when touched. © Uncoordinated feeling △: Some dirt can be recognized by the naked eye X: The dirt does not fall off (3. 3 glass shadow cleaning power evaluation method) The glass cup (upper diameter 63mm, lower diameter 53 legs, height 100mm) was loaded into the automatic food washing and drying machine, and sodium carbonate 1. 2g was loaded into the machine , using 30-degree hard water for washing to the whole step of washing, and obtaining a whiteened cup@子, the cup is filled into an automatic food washing and drying machine "Panasonic Electric Industrial Co., Ltd., model NP-40SX2", After the standard procedure was washed using the prepared composition 6g, the completion state was visually evaluated in accordance with the following evaluation criteria. Evaluation criteria: ◎: The white matter is completely free of residue, and there is no rough and other uncoordinated feeling: some of the recognizable white matter is slightly residual △: some white residue can be recognized by the naked eye, and the transparency has been lost as a whole. 21 321459 201016839 X : Whitening [Non-falling <5. Evaluation of low-temperature stability] 80 mL of each composition was placed in a bottle (100 mL) of PS11, and the appearance after storage at -5 ° C for one month was visually observed, and was carried out by the following criteria. Evaluation. 〇:transparent △: turbidity X: precipitated 22 321459 201016839 Table 1 οΟ 5 埃«Β: CO Ο gdo' ΙΟ r^ o 5 O _ k 8 r» Φ as eo ο €·> kA 〇ο 〇 9 〇〇ο ο 〇Μ Μ V s. o 5 tf> S <·* ogm « >w cone S — C4 » «· 卜«·> omo ο 〇〇〇〇ο ο 〇ΟΙ — Ο « Μ» gs 5 in 1^; g 1 <w 锖»wk δ «*» «Μ «4 9 卜 er> ia β» «V o ο 〇Ο 〇〇ο ο 〇Ο Μ 幸幸 in — go 5 In og S; 〇_ please_ cone δ s CSI s Q 卜 t>> s •M o ο Θ 〇〇〇ο ο 〇σ> €4 ψ^> wise id v> ewswpm please m s ·» 10 «4 «» 苈ID iri c» s 0 ο 〇〇〇0 ο ο 〇βο CD «5 Ο W sd 〇· tn o' S ·» § m « «Ν cone δ δ 9 <9 io ο 〇 〇〇ο ο ο 〇 « «0 ο so 4» 5 p «Mr smm umbrella 8 — wear o 黉 o ο 〇〇〇〇ο ο 〇 «» Μ Κ ΙΟ go 5 u> oa o Ξ G> m arm m S 释Μ Μ production w CJ <eo 卜W «1 o ο & Θ 0 0 0 ο 〇ιο «si «·* ft 1ί> 1 § P 〇g 〇m collar *w umbrella 8 t·» Γ 4 » CM Φ oo ο 〇〇〇〇0 ο 〇 inchΜ m Μ Μ 卜 «Μ» 1 5 tn o* % m Please Φ4 # S η Μ wear J? S CO G ο ee 〇b ο ο 〇η C4 η eo ir> «1·· 〇w 〇· u> r^ § *<· § _ _ _ cone 8 9 «4 •9"· m «et«>tf> M o ο 〇〇〇〇ο ο 〇Μ Μ ▼-· Λ «0 CM • 0» od 1C ci g 9 m 帮 m Umbrella S s> 94 mmm 80 3 CO S sonar ο d 〇〇〇ο ❹ 〇Μ Ο u> — so 5 ΙΛ 1 »·- gmmm Umbrella s Μ JJ S 5 In o ο ο 〇〇〇ο ο 〇/-S Ο I 6- Ρ W trial « dragon « Λ * h sin £ Λ ι # « « '1 « h /^\ § α 1 ¥ * m « Ί « Η* 靛« 寐-5 % 霣« ϋ co , 1 * /-N Ο 〇CO tet οο •Mi 1 ί i 靼m | 60 α> CO § •-H ># 窠Φ 翥兹ί: Take «ί 垅6- s WH s-> 0 Take Δ2 « M e TO 4 glucoside d, 1 * ώ 唉轶Ψ «fe /-N Μ 蠏c £ 4M 霣s * g. m «V; w 余ί wm Φ v Φ <-Ν g. _ 如/^, 3 十 £ msw X • ea 3 « ii HC HC Ρ * Ifc Molybdenum SC » Φ « « Year « « sc «ΐ *φ η / />>> βς 隳W «! 炻珐«ί维 5 Φ 嗜m § % 23 321459 201016839 Table 2 ο N % 1 0.05 1 ο 1 0-75 1 g 5 Ο m « \Λ± Λ s «D cw ψ^· s 1 CS s 〇K o ο << o ο ο m M <««· s 1 0.05 1 ο 1 078 1 LmJ 2 m 膂1 1 8 Μ 9 LjmJ V» s 〇X o ο <1 < o ο ο to ο — 窝 i 0.09 1 1 0-7S 1 Γα〇Π 1 001 1 _ « ί余*Ί sw cv 7 w 巧$ < K o ο ooo ο ο r- 严 £ csa ΙΟ 0.05 1 d ί 0-75 1 I 〇.〇1_1 1 m « ί 1 s ew 5 «D 0» Γ» IX oo ο ooo ο X Φ C4 ΙΑ <*· 1 0.05 1 1 075 1 ί_. 0.0t ." Lp-〇iJ m « L margin 1 ss Μ •ψ^ IA r> s < X o ο <1 < o ο ο in s Κ» 1 0.05 1 5丨〇,75 —J 1 ig ol J 1 balance” 8 94 «Ο 曾·卜m δ P4 o 〇XXXX o ο ο CM κ> ! 0Ό5 1 d 1 m 1 I o丨适* 1 1 remainder f 1 s Μ 1 U>< X o ο << o ο ο C*3 u> 5 ΙΟ 0.05 1 5 0.75 1 〇·〇ι 1 pe \Λ*\ ί 1 8 <» Μ> 5 ,· 卜 · 1 3600 KX o ο <<3 o ο ο CXI tf> R 40 - 1 0 plus 1 5 丨 0.75 J Loou 丨 0.01 1 1 财 1 L balance 1 8 S 9 C9 ID < oo ο o • ό XX ο <〇«· to 0.05 1 5 1 0-75.1 1 1 丨适董1 1 Turtle JS in Ο VQ 卜 C>< oo ο oo XX ο g 3 卜 9 ? s-** « Μ « sr « >1 * 寄 丁烯 丁烯 丁烯 丁烯 丁烯 S (Sokalan CP5) | β t « St « 11 * h sorbitol I 霣 m n3 Ο drying CS3 propylene glycol 1 glycerol 1 T powder peak (Ternaniyl Ultra 300L) | 曰GO •Η οβ α> § •*-1 > ed CO w 鬵# w ¢: 9ί 螬〇«ί chlorinated 氡 己 己15) Nikki T-based 铱1 2-bromo-2-volvary--, 3-propanedi-if 1 isoindole solution pll«壑« (hydroxide or sulfuric acid) refined water 1 total Hit X) 1 moisture Content 1 (A) contains Dong (quality Dong X) (B) + (C) content (trade volume X) 1 (bv (c) ir* ratio! 1 « Code 1 usability f string P # w Female IM powder dirt 1 Protein R dirt 1 戮 powder dirt 璀 you 1 tea scale cleaning power dad iS dye 霣 w ϊ 9 «Μ Ρ Ρ 7 蝉t 1 (B) ingredient 1 (w ingredient preservation 觫 1 Esi 1 (A) component (C) component < * Pt S s ? itt Ik 24 321459 201016839 As shown in Table 1 and Table 2, the detergent composition in the scope of the present invention can achieve a good viscosity range, Thereby good usability can be achieved. Further, not only the good detergency was exhibited before storage, but also the detergency of the liquid detergent after the storage was observed, and it was confirmed that the liquid detergent composition of the present invention has excellent storage stability of the enzyme. On the other hand, in the comparative example which is outside the range of the present invention, the viscosity is excessively lowered or increased, resulting in poor usability. In addition, it is also confirmed that the preservation stability of the enzyme is lowered. [Simple diagram description] None © [Main component symbol description] None ❹ 25 321459