201130968 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種硬質物品用洗淨機所使用之粉末洗淨 劑組合物。更詳細而言，係關於一種用以洗淨廚房之餐具 類或食品飲料加工用塑膠容器等硬質物品之自動洗淨機用 粉末洗淨劑組合物。 【先前技術】 自動洗淨機係用於家庭或餐廳、咖啡館等之廚房中之髒 的盤子、玻璃器皿、烹飪器具等餐具類之洗淨，及食品飲 料工廠所使用之食材及製品用塑膠容器之洗淨。作為主要 之對象污漬，有來自食品之蛋白質、澱粉、油脂等，該等 污潰複合而附著於盤子、玻璃器皿、烹飪器具等餐具及塑 膠容器上。另外，亦存在加熱烹調時該等污潰進行熱變 性，成為頑固污潰而固著之情況。 通常，自動洗淨機之洗淨步驟係以洗淨_洗滌之順序進 ◎ 行，該等步驟之所需時間係非常短之時間，即，洗淨步驟 為40〜60秒左右，洗滌步驟為5〜2〇秒左右。 因此，自動洗淨機用粉末洗淨劑組合物中，為於短時間 内效率良好地洗淨該等頑固污潰而調配鹼金屬之氫氧化物 等鹼劑。 另外，洗淨時經常使用含有Ca、Mg離子等硬度成分之 自來水、井水等，該等使用水中之硬度成分與來自洗劑之 碳酸根 '矽酸根及大氣中之二氧化碳反應，形成碳酸鈣、 碳酸鎂、矽酸鈣、矽酸鎂等產物。該產物因不溶於水，故 153068.doc 201130968 附著於餐具類、自動洗淨機之槽内、槽壁等，形成被稱為 。垢之頑固覆膜。其結果成為引起熱交換部之熱效率下 降循J衣栗之堵塞、濃度感測器之誤動作等故障之原因。 為避免由結垢附著引起之故障，而使用調配有結垢附著 ^抑制效果高之三聚磷酸鹽之有射自動洗淨機用粉末洗 淨劑，但三聚璘酸鹽㈣起水之優養化之物f，故就環境 適合性之觀點而言，謀求不使用其之技術之開發。 於上述背景中’有人揭示有含有丨種以上之鹼劑、具有 金屬離子捕集能之高分子物質及漂白劑之自動餐具洗淨機 用洗淨劑組合物（例如曰本專利特開平8_199194)。日本專 利特開200242627記載有水溶性聚合物及其洗淨用途。曰 本專利特開2003-27095記載有含有偏矽酸鈉、無水碳酸鈉 及螯合劑之洗劑。日本專利4038271B記載有藉由聚丙烯 酸、聚丙烯酸鹽、聚丙烯酸共聚物等來防止結垢附著。曰 本專利特表2009-500487記載有含有聚丙烯酸酯、碳酸 鹽、磷酸鹽等之洗劑。 【發明内容】 本發明係關於一種硬質物品之自動洗淨機用粉末洗淨劑 組合物’其含有（a)聚丙烯酸或其鹽[以下稱為（a)成分]、 (b) 丙稀酸與馬來酸之共聚物或其鹽[以下稱為（b)成分]、 (c) 選自由碳酸鹽及矽酸鹽所組成之群中之1種以上之鹼劑 [以下稱為（c)成分]35重量％以上、及（句有機螯合劑，並且 U)與（b)之合計量為6重量％以上，（a)/(b)(重量比）為1以 上。 153068.doc 201130968 【實施方式】 曰本專利特開平8_199194於兼具高洗淨性與高結垢附著 抑制效果之方面不充分。 =本發明中，所謂硬質物品之自動洗淨機用粉末洗淨劑 :°物係指利用自動洗淨機洗淨餐具、烹調器具、塑膠 +器等硬質物品時使用之粉末洗淨劑組合物。 a本發明提供—種硬質物品之自動洗淨機用粉末洗淨劑組 〇 ^物，其對於廚房中之髒的盤子、玻璃器皿、烹飪器具等 誉八類之洗淨、食品飲料工廠所使用之食材及製品用塑膠 今器之洗淨等’具有高結垢附著抑制效果與高洗淨性。 根據本發明，可提供一種具有高洗淨性與高結垢附著抑 制效果的硬質物品之自動洗淨機用粉末洗淨劑組合物。 <(a)成分> 本發明之自動洗淨機用粉末洗淨劑組合物含有聚丙烯酸 或其鹽作為（a)成分。聚丙烯酸或其鹽包括丙烯酸之均聚物 Ο 或其鹽。作為（a)成分，可列舉聚丙烯酸、聚丙烯酸鈉、聚 丙烯酸鉀等，較佳為聚丙烯酸鈉、聚丙烯酸鉀。本發明之 〇)成分只要為不妨礙本發明之效果之表現的程度，則可為 包含除丙烯酸以外之單體且為可與丙烯酸共聚合之單體 (其中馬來酸除外）的共聚物。作為除丙烯酸以外之單體且 為可與丙烯酸共聚合之單體（其中馬來酸除外），可列舉乙 稀基系單體、丙烯酸系單體、苯乙烯系單體等，更具體而 言可列舉甲基丙烯酸、丙烯酸甲酯、丙烯酸乙酯、甲基丙 烯酸甲酯、苯乙烯等。只要作為（4成分不會對水溶性等物 153068.doc 201130968 性或本發明之效果之表現造成不良影響，則除丙婦酸以外 之單體且為可與丙烯酸共聚合之單體(其中馬來酸除外)於 ⑷成分中之莫耳比並無限定’於⑷成分中較佳為0〜5莫耳 %，更佳為0〜3莫耳％，最佳為〇莫耳％。因此，本發明之 聚丙烯酸或其鹽亦可為於全部構成單體中以〇〜5莫耳％之 範圍包含除丙烯酸以外之單體且為可與丙烯酸共聚合之單 體（其中馬來酸除外）的聚合物或共聚物。 另外，就結垢附著抑制效果之觀點而言，成分之重量 平均分子量較佳為UOOO〜20,000，更佳為2 〇〇〇〜15 〇〇〇。 該重量平均分子量係以乙腈與水之混合溶劑（磷酸缓衝液） 為展開溶劑，利用凝膠滲透層析法，且以分子量已知之通 常市售且可獲得之作為聚合物標準試劑之聚丙烯酸（例如 Sigma-Aldrich製造之分子量標準試劑）為標準物質而求 出。 <(b)成分> 本發明之自動洗淨機用粉末洗淨劑組合物含有丙烯酸與 馬來酸之共聚物或其鹽作為（b)成分。作為（b)成分，可列 舉丙烯酸與馬來酸之共聚物、丙烯酸與馬來酸之共聚物之 鈉鹽、丙烯酸與馬來酸之共聚物之鉀鹽等，較佳為丙烯酸 與馬來酸之共聚物之鈉鹽、丙烯酸與馬來酸之共聚物之鉀 鹽。另外’（b)成分就結垢附著抑制效果之觀點而言，較佳 為丙稀酸/馬來酸之莫耳比為〇.25〜4，更佳為〇.4〜25。本 發明之（b)成分只要為不妨礙本發明之效果之表現的程度， 則可為包含除丙稀酸及馬來酸以外之單體且為可與丙烯酸 153068.doc 201130968 及/或馬來酸共聚合之單體的共聚物。作為除丙烯酸及馬 來酸以外之單體且為可與丙烯酸及/或馬來酸共聚合之單 體，可列舉乙烯基系單體、丙烯酸系單體、苯乙烯系單體 等，更具體而言可列舉子基丙浠酸、丙烯酸甲酯、丙烯酸 乙酯、甲基丙烯酸甲酯、苯乙烯等。只要作為（|^成分不會 對水溶性等物性或本發明之效果之表現造成不良影響，則 、除丙烯酸及馬來酸以外之單體且為可與丙烯酸及/或馬來 0 酸共聚合之單體於（b)成分中之莫耳比並無限定，於（b)成 分中較佳為0〜5莫耳％，更佳為〇〜3莫耳％，最佳為〇莫耳 %。因此，本發明之丙烯酸與馬來酸之共聚物或其鹽可為 於全部構成單體中以0〜5莫耳％之範圍包含除丙烯酸及馬 來酸以外之單體且為可與丙烯酸及/或馬來酸共聚合之單 體的共聚物。 〇 s 逋τ於製造⑷成分時之共聚合反應中，馬來酸係使用馬 來酸肝’因此上述莫耳比均可為基於馬來酸野之莫耳比。 另外，就結垢附著抑制效果之觀點而言，（…成分之重 、’句刀子里較佳為1,000〜100 000 ，更佳為 2’〇〇〇 9MGG。該重量平均分子量係以乙腈與水之混合溶 劑（石^酸緩衝液）為展開溶劑，利用凝勝渗透層析法，且以 分子置已知之通常市售且可獲得之作為聚合物標準試劑之 = ::Sigma_Aldrich製造之分子量標準試劑)為標 準物質而求出。 <(c)成分> 本發明之自動洗淨機 用粉末洗淨劑組合物含有選自由碳 153068.doc 201130968 酸鹽及矽酸鹽所組成之群中之1種以上之鹼劑作為（c)成 分。作為（c)成分，可列舉正矽酸鈉、正矽酸鉀、偏矽酸 鈉、偏矽酸鉀、1號矽酸鈉、1號矽酸鉀、碳酸鈉、碳酸 舒、碳酸氫鈉、碳酸氫卸等，較佳為碳酸納、碳酸卸、偏 石夕酸鈉、偏矽酸钟’就洗淨性及保存穩定性之觀點而言， 較佳為碳酸鈉、偏矽酸鈉，就結垢附著抑制效果之觀點而 s ’車父佳為偏酸納。因此於本發明中，較佳為含有酸 鹽作為（C)成分。 <(d)成分> 就結垢抑制效果優異之觀點而言，本發明之自動洗淨機 用粉末洗淨劑組合物含有有機螯合劑作為（d)成分。作為 (d)成分，可列舉：（dl)乙二胺四乙酸四鈉、曱基甘胺酸二 乙酸二鈉、L-麩胺酸二乙酸四鈉等胺基羧酸鹽，檸檬 酸三鈉、蘋果酸二鈉、酒石酸鈉等羥基羧酸鹽等；較佳為 選自由乙二胺四乙酸四鈉、甲基甘胺酸二乙酸三鈉、^麩 胺酸二乙酸四鈉及檸檬酸三鈉所組成之群中之至少1種。 <自動洗淨機用粉末洗淨劑組合物> 本發明之自動洗淨機用粉末洗淨劑組合物係含有上述 (a)〜(d)成分者，且可進一步含有其他成分。 犹、·、〇祐附者抑制效果 用粉 .« π、曰動况淨; 末洗淨劑組合物中之（a)成分之含量較佳為5重量％ . 上’更佳為6重量％以上。上限並無特別限定，就效果」 成本之觀點而言’較佳為4〇重量％以下，更佳為重t 以下’ JU圭為15重4%以下。就上述觀點而言，上述⑷力 153068.doc 201130968 分之含量較佳為5〜40重量％，更佳為6~30重量％，更佳為 6〜15重量％。 另外’就結垢附著抑制效果之觀點而言，本發明之自動 洗淨機用粉末洗淨劑組合物中之（b)成分之含量較佳為 重里更佳為1~5重量％。較佳為0.5重量％以上， 更佳為1重量％以上。上限並無特別限定，就效果與成本 之觀點而言，較佳為1〇重量％以下，更佳為5重量％以下。 〇 〇 就上述觀點而言，上述（b)成分之含量較佳為0.5〜1〇重量 4，更佳為1〜5重量％。 另外本發明之自動洗淨機用粉末洗淨劑組合物中之（c) 成刀之含置，就係賦予洗淨性之成分且洗淨性優異之觀點 •較佳為35重量％以上，就洗淨性及結垢附著抑制效 果之觀點而言，較佳為4〇〜9〇重量％，更佳為4 旦 %，更佳為40〜55重量。/ a X/°°另外，就洗淨性及結垢附著抑制 效果之觀點而言，（、忐 0/、，u )成刀中之矽酸鹽之比率較佳為2〇重量 /〇以上’更佳為25 >、 〇重夏％ ’更佳為30〜1〇〇重量％。 就結垢附著抑制效果 用粉末果之觀點而言，本發明之自動洗淨機 用杨末洗淨劑組合物巾 网 %，#枯支之（d)成分之含量較佳為1〜50重量 /〇更佳為1 〇〜40重量％。 里 另外’就結垢附著抑 « 又果之觀點而吕，本發明夕白红 洗淨機用粉末洗淨劑組 +發月之自動 量為6重量％以上 之⑷成分與(b)成分之合計 %，更佳為8〜20重量％。為7〜60重量％，更佳為8〜40重量 另外，就結垢附著抑 果之硯點而言’本發明之自動 153068.doc 201130968 洗淨機用粉末洗淨劑組合物中之⑷成分與（b)成分之重量 比以（a)/(b)計為丨以上，較佳為2以上更佳為3以上。上阳 並無特別限定，但就效果與成本之觀點而言，較佳為⑽ 下，更佳為40以下，更佳為3〇以下，更佳心以下。就上 述觀點而言’⑷狗較佳為1，，更佳為2〜40,更佳為 3〜30，更佳為3〜15。 又1土马 另外’就兼具洗淨性與結㈣著抑制絲之觀點而言， 本發明之自動洗淨機用粉末洗淨劑組合物中 (b)成分之合計量盥（c).八夕击真l )成刀之重量比以⑷/[⑷+(b)]計較佳 為0.5〜1〇，更佳為卜8，更佳為㈠。 於本發明之自動洗淨機用粉末洗淨劑組合物中，除 ⑷〜⑷成分以外，視需要可調配芒硝、界面活性劑、漂白 劑、酵素、消泡劑、防腐劑、防錄劑、殺菌劑、抗菌劑、 色素、香料、溶解助劑等。 本發月之自動洗淨機用粉末洗淨劑組合物係用於硬質物 :用自動洗淨機。此處，所謂硬質物品，包括包含具有硬 ^表面之構件作為主體，且具有適合於利用自動洗淨機之 洗淨的大小、形狀、材質之物品。另夕卜，亦部分包含軟質 二抑作為-體之硬質物品，可列舉餐具、烹調器具、塑 ，Γ等另外，自動洗淨機可適宜使用適合於該等硬質 物品之自動洗淨的^；罢 的4置。另外，作為本發明之硬質物品用 自動洗# #例如可列舉自動餐具洗淨機、塑膠容器用洗 淨機，較佳為應用於自動餐具洗淨機。 月之自動洗淨機用粉末洗淨劑組合物不含有 153068.doc -10- 201130968 含磷之化合物，可作為所謂無磷型組合物。 本發明之自動洗淨機用粉末洗淨劑組合物就洗淨性、基 材抽傷性之觀點而言，0‘丨重量％之水溶液於25C>c下之pH值 較佳為10〜13，更佳為1丨〜12。 « 實施例 礞 以下實施例對本發明之實施進行說明。實施例係對本發 明之例示進行說明，並非用以限定本發明。 ❹ 製備表1所示之調配組成之自動洗淨機用粉末洗淨劑組 s物，利用以下方法對結垢附著抑制能力、洗淨性進行評 價。將結果示於表1。 [1 ]結垢抑制能力之評價 <試驗條件> 使用洗淨機：三洋電機（股）製造之自動餐具洗淨機 (SANYO DR53)201130968 6. DISCLOSURE OF THE INVENTION: TECHNICAL FIELD The present invention relates to a powder detergent composition for use in a cleaning device for a hard article. More specifically, the present invention relates to a powder detergent composition for an automatic washing machine for washing hard objects such as kitchen utensils or plastic containers for food and beverage processing. [Prior Art] Automatic washing machine is used for washing dishes such as dishes, glassware, cooking utensils, etc. in kitchens such as homes, restaurants, cafes, etc., and plastics for foodstuffs and products used in food and beverage factories. Wash the container. As the main target stain, there are proteins, starches, fats and the like derived from foods, and these are mixed and adhered to dishes and plastic containers such as dishes, glassware, and cooking utensils. Further, in the case of heating and cooking, the stains are thermally deformed, and they are stubbornly stained and fixed. Usually, the washing step of the automatic washing machine is carried out in the order of washing and washing, and the time required for the steps is very short, that is, the washing step is about 40 to 60 seconds, and the washing step is 5 to 2 seconds or so. Therefore, in the powder detergent composition for an automatic cleaner, an alkali agent such as an alkali metal hydroxide is prepared by efficiently washing the stubborn sludge in a short period of time. In addition, tap water, well water, or the like containing a hardness component such as Ca or Mg ions is often used for washing, and the hardness component in the water is reacted with carbonate citrate from the lotion and carbon dioxide in the atmosphere to form calcium carbonate. Products such as magnesium carbonate, calcium citrate, magnesium citrate. This product is insoluble in water, so 153068.doc 201130968 is attached to the tableware, the tank of the automatic washing machine, the groove wall, etc., and is formed. Stubborn stubborn film. As a result, the thermal efficiency of the heat exchange unit is lowered, and the malfunction of the jammer of the J chestnut or the malfunction of the concentration sensor is caused. In order to avoid the failure caused by the adhesion of scale, the powder cleaning agent for the automatic cleaning machine with the tripolyphosphate which has the high effect of scaling and adhesion inhibition is used, but the trimeric cerium salt (4) is excellent in water supply. In the case of environmentally appropriate materials, the development of technologies that do not use them is sought. In the above-mentioned background, a cleansing agent composition for an automatic dishwashing machine containing an alkali agent, a polymer material having a metal ion trapping ability, and a bleaching agent is disclosed (for example, Japanese Patent Laid-Open No. Hei 8_199194) . Japanese Patent Laid-Open No. 200242627 describes water-soluble polymers and their use for washing.洗 Patent Laid-Open No. 2003-27095 describes a lotion containing sodium metasilicate, anhydrous sodium carbonate and a chelating agent. Japanese Patent No. 4038271 B describes the prevention of scale adhesion by a polyacrylic acid, a polyacrylate, a polyacrylic acid copolymer or the like.洗 Patent No. 2009-500487 describes a lotion containing a polyacrylate, a carbonate, a phosphate or the like. SUMMARY OF THE INVENTION The present invention relates to a powder detergent composition for an automatic cleaning machine for a hard article, which comprises (a) polyacrylic acid or a salt thereof (hereinafter referred to as component (a)), and (b) acrylic acid. a copolymer of maleic acid or a salt thereof (hereinafter referred to as component (b)], and (c) one or more alkali chemicals selected from the group consisting of carbonates and citrates [hereinafter referred to as (c) The component is 35% by weight or more, and (the organic chelating agent, and the total amount of U) and (b) is 6% by weight or more, and (a)/(b) (weight ratio) is 1 or more. 153068.doc 201130968 [Embodiment] The Japanese Patent Laid-Open No. Hei 8_199194 is insufficient in terms of both high detergency and high scale adhesion inhibiting effect. In the present invention, the powder detergent for automatic washing machine for hard articles refers to a powder detergent composition used for washing hard articles such as tableware, cooking utensils, and plastics with an automatic washing machine. . The present invention provides a powder detergent composition for an automatic cleaning machine for hard articles, which is used for washing, food and beverage factories of dirty dishes, glassware, cooking utensils, etc. in the kitchen. The washing of plastics and utensils for foodstuffs and products has a high scale adhesion inhibition effect and high detergency. According to the present invention, it is possible to provide a powder detergent composition for an automatic cleaner having a high-detergency and high scale adhesion inhibiting effect. <(a) Component> The powder detergent composition for an automatic cleaner of the present invention contains polyacrylic acid or a salt thereof as the component (a). The polyacrylic acid or a salt thereof includes a homopolymer of acryl hydrazine or a salt thereof. The component (a) may, for example, be polyacrylic acid, sodium polyacrylate or potassium polyacrylate, and is preferably sodium polyacrylate or potassium polyacrylate. The component of the present invention may be a copolymer containing a monomer other than acrylic acid and being a monomer copolymerizable with acrylic acid (excluding maleic acid) as long as it does not impair the performance of the effect of the present invention. Examples of the monomer other than acrylic acid and which is copolymerizable with acrylic acid (excluding maleic acid) include a vinyl monomer, an acrylic monomer, a styrene monomer, and the like, and more specifically Examples thereof include methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, and styrene. As long as the (component 4) does not adversely affect the performance of the water-soluble substance or the effect of the present invention, the monomer other than the bupropion acid is a monomer copolymerizable with the acrylic acid (the horse therein) The molar ratio of the component (4) is not limited to the component (4), and is preferably 0 to 5 mol%, more preferably 0 to 3 mol%, and most preferably 〇 mol%. The polyacrylic acid or the salt thereof of the present invention may further comprise a monomer other than acrylic acid in a range of 〇 5 5 % by mol of the constituting monomer and is a monomer copolymerizable with acrylic acid (excluding maleic acid) Further, the weight average molecular weight of the component is preferably from 00 to 20,000, more preferably from 2 to 15 Torr, from the viewpoint of the effect of inhibiting scale adhesion. A mixed solvent of acetonitrile and water (phosphate buffer) is used as a developing solvent, and gel permeation chromatography is used, and a polyacrylic acid (for example, Sigma-Aldrich) which is a commercially available and commercially available polymer reagent having a known molecular weight is known. Molecular weight standard (Part B) The powder detergent composition for an automatic cleaner of the present invention contains a copolymer of acrylic acid and maleic acid or a salt thereof as component (b). The component (b) may, for example, be a copolymer of acrylic acid and maleic acid, a sodium salt of a copolymer of acrylic acid and maleic acid, a potassium salt of a copolymer of acrylic acid and maleic acid, or the like, preferably acrylic acid and maleic acid. a sodium salt of a copolymer, a potassium salt of a copolymer of acrylic acid and maleic acid, and the '(b) component preferably has a molar ratio of acrylic acid/maleic acid from the viewpoint of the effect of inhibiting scale adhesion. 25. 25 to 4, more preferably 4. 4 to 25. The component (b) of the present invention may be a single substance other than acrylic acid and maleic acid as long as it does not impair the performance of the effect of the present invention. Copolymer which is a monomer copolymerizable with acrylic acid 153068.doc 201130968 and/or maleic acid. It is a monomer other than acrylic acid and maleic acid and is copolymerizable with acrylic acid and/or maleic acid. Examples of the monomer include a vinyl monomer, an acrylic monomer, and a styrene monomer, and more specifically Examples thereof include a subunit propionic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, styrene, etc., as long as the (|^ component does not cause deterioration in physical properties such as water solubility or effects of the present invention. The influence of the monomer other than acrylic acid and maleic acid and the monomer copolymerizable with acrylic acid and/or maleic acid in the component (b) is not limited, and the component (b) is not limited. It is preferably 0 to 5 mol%, more preferably 〇3 to 3 mol%, and most preferably 〇 mol%. Therefore, the copolymer of acrylic acid and maleic acid of the present invention or a salt thereof may be all formed. The monomer contains a monomer other than acrylic acid and maleic acid in a range of 0 to 5 mol% and is a copolymer copolymerizable with acrylic acid and/or maleic acid. In the copolymerization reaction of 〇 s 逋τ in the production of the component (4), maleic acid is used as the maleic acid. Therefore, the above molar ratio can be a molar ratio based on maleic acid. Further, from the viewpoint of the effect of suppressing scale adhesion, (the weight of the component is preferably from 1,000 to 100,000, more preferably 2' 〇〇〇 9MGG in the knives. The weight average molecular weight is acetonitrile and water. The mixed solvent (salt acid buffer) is a developing solvent, and the molecular weight standard reagent manufactured by :: Sigma_Aldrich is used as a polymer standard reagent by a known method. ) is obtained for the reference substance. <(c) component> The powder detergent composition for an automatic cleaner of the present invention contains one or more alkali chemicals selected from the group consisting of carbon 153068.doc 201130968 acid salt and bismuth acid salt ( c) ingredients. Examples of the component (c) include sodium orthosilicate, potassium orthosilicate, sodium metasilicate, potassium metasilicate, sodium citrate No. 1, potassium citrate No. 1, sodium carbonate, sodium carbonate, sodium hydrogencarbonate, The hydrogen carbonate is discharged, etc., preferably sodium carbonate, carbonic acid unloading, sodium sulphate, and bismuth citrate. From the viewpoints of detergency and storage stability, sodium carbonate and sodium metasilicate are preferred. From the viewpoint of the effect of inhibiting the adhesion of scales, the car's father is a sodium. Therefore, in the present invention, it is preferred to contain an acid salt as the component (C). <Component (d)> The powder detergent composition for automatic washing machine of the present invention contains an organic chelating agent as the component (d) from the viewpoint of excellent scale inhibiting effect. Examples of the component (d) include (dl) an aminocarboxylic acid salt such as tetrasodium ethylenediaminetetraacetate, disodium decylglycine diacetate, and tetrasodium L-glutamic acid diacetate, and trisodium citrate. a hydroxycarboxylate such as disodium malate or sodium tartrate; preferably selected from the group consisting of tetrasodium ethylenediaminetetraacetate, trisodium methylglycine diacetate, tetrasodium glutamate diacetate and citric acid At least one of the group consisting of sodium. <Powder detergent composition for automatic washing machine> The powder detergent composition for an automatic cleaner of the present invention contains the above components (a) to (d), and may further contain other components. The content of the component (a) in the final detergent composition is preferably 5% by weight. The upper part is preferably 6% by weight. the above. The upper limit is not particularly limited, and is preferably 4% by weight or less from the viewpoint of cost, and more preferably less than t. From the above viewpoints, the content of the above (4) force 153068.doc 201130968 is preferably 5 to 40% by weight, more preferably 6 to 30% by weight, still more preferably 6 to 15% by weight. Further, the content of the component (b) in the powder detergent composition for an automatic cleaner of the present invention is preferably from 1 to 5% by weight in terms of the weight of the scale adhesion prevention effect. It is preferably 0.5% by weight or more, and more preferably 1% by weight or more. The upper limit is not particularly limited, and is preferably 1% by weight or less, and more preferably 5% by weight or less from the viewpoint of effect and cost. 〇 〇 In view of the above, the content of the component (b) is preferably from 0.5 to 1% by weight, more preferably from 1 to 5% by weight. Further, (c) the inclusion of the knives in the powder detergent composition for an automatic cleaner of the present invention is a component which imparts detergency and is excellent in detergency, and is preferably 35 wt% or more. From the viewpoint of the detergency and the scale adhesion inhibiting effect, it is preferably from 4 〇 to 9 〇 by weight, more preferably from 4 dan%, still more preferably from 40 to 55 parts by weight. / a X / ° ° In addition, from the viewpoint of the cleaning property and the scale adhesion inhibiting effect, the ratio of the bismuth salt in the (, 忐0/, u) forming knives is preferably 2 〇 / 〇 or more 'More preferably 25 >, 〇重夏%' is better than 30~1〇〇% by weight. The content of the component (d) component of the automatic cleaning machine of the present invention is preferably from 1 to 50 by weight in terms of the effect of the powdery fruit. /〇 is preferably 1 〇 ~ 40% by weight. In addition, in the case of "staining adhesion", it is also a point of view. In addition, the powder detergent group + the monthly automatic amount of the invention is 6 wt% or more (4) and (b) The total % is more preferably 8 to 20% by weight. It is 7 to 60% by weight, more preferably 8 to 40% by weight. In addition, in the case of the scale adhesion inhibition effect, the component (4) in the powder detergent composition of the automatic 153068.doc 201130968 washing machine of the present invention The weight ratio of the component (b) is 丨 or more in terms of (a)/(b), preferably 2 or more, more preferably 3 or more. The upper yang is not particularly limited, but from the viewpoint of effect and cost, it is preferably (10), more preferably 40 or less, still more preferably 3 Å or less, and more preferably less. In view of the above, the (4) dog is preferably 1, more preferably 2 to 40, more preferably 3 to 30, still more preferably 3 to 15. In addition, the total amount of the component (b) in the powder detergent composition for automatic washing machine of the present invention is (a), and the total amount of the component (b) of the powder detergent composition for automatic washing machine of the present invention. The weight ratio of the Chinese yoke to the true l) is preferably 0.5 to 1 以, more preferably 卜, and even more preferably (1), in terms of (4)/[(4)+(b). In the powder detergent composition for automatic washing machine of the present invention, in addition to the components (4) to (4), Glauber's salt, a surfactant, a bleaching agent, an enzyme, an antifoaming agent, a preservative, an anti-recording agent, and the like may be optionally provided. Bactericides, antibacterial agents, pigments, perfumes, dissolution aids, etc. The powder detergent composition for automatic washing machine of this month is used for hard materials: an automatic washing machine is used. Here, the rigid article includes a member including a member having a hard surface as a main body, and an article having a size, a shape, and a material suitable for washing by an automatic washing machine. In addition, some of them include a soft one, which is a hard object such as a tableware, a cooking utensil, a plastic, a pot, etc. In addition, the automatic washing machine can be suitably used for automatic washing of such hard articles; 4 sets. Further, as the automatic washing for hard articles of the present invention, for example, an automatic dish washing machine or a plastic container washing machine can be cited, and it is preferably applied to an automatic dish washing machine. The powder detergent composition for an automatic washing machine of the month does not contain 153068.doc -10- 201130968 A compound containing phosphorus, which can be used as a so-called phosphorus-free composition. The powder detergent composition for an automatic cleaner of the present invention has a pH of preferably from 10 to 13 at 25 C>c from the viewpoint of detergency and substrate scratch resistance. More preferably, it is 1丨~12. « EXAMPLES The following examples illustrate the practice of the present invention. The examples are illustrative of the invention and are not intended to limit the invention.粉末 A powder detergent composition for an automatic cleaner having the composition shown in Table 1 was prepared, and the scale adhesion inhibiting ability and the detergency were evaluated by the following methods. The results are shown in Table 1. [1] Evaluation of scale inhibition ability <Test conditions> Using a washing machine: Sanyo Electric Co., Ltd. Automatic tableware washing machine (SANYO DR53)
洗淨溫度：60°C 〇 洗淨時間：40秒Washing temperature: 60 ° C 〇 Washing time: 40 seconds
洗滌溫度：70°C 洗務時間：5秒 洗淨濃度：0.10重量％ 使用水：6°dH硬水（利用氯化鈣進行調整） <評價方法> 將SUS304之試樣（100 mmxl30 mm)5個置於洗淨架之特 疋位置’以上述試驗條件反覆進行洗淨、洗滌、室溫下之 風乾之操作1,000次之後’基於下述評價基準對試樣之外 153068.doc 11 · 201130968 觀進行目視判定 <評價基準> 。表1係表示5個（表背）之平均值。 6 4 2 與試驗前相比較無差別，有光澤 稍支色但未附著結垢，有光澤 變色但未附著結垢，有光澤 部分附著結垢，有光澤 整體被結垢覆蓋，無光澤 1:整體被結垢覆蓋，無光澤且表面粗糙 再者’作為本發明之結垢抑制 卩此力之砰價，只要為判斷 為未附著結垢且有光澤之4分以上，則較佳。 [2]洗淨性之評價 <模型污垢之製作> 於新品之直徑20 cm之磁器製盤子的中央部，利用毛刷 將蛋黃2 g均勾地塗佈成直徑約1〇 cm之圓形，放入設為 8〇°C之電氣乾燥機中。3G分鐘後取出塗佈有蛋黃之磁器製 盤子並進行自然冷卻，將其作為模型污垢而用於洗淨性評 價。 <評價方法> 向一洋電機（股）製造之自動餐具洗淨機（SANYO DR53) 之洗淨槽（38 L)中投入表1之自動洗淨機用粉末洗淨劑組合 物3 8 g ’利用6 0 C之溫水使其溶解。於專用托架上放置塗 佈有模型污垢之磁器製盤子4個，利用6(rc之洗淨液洗淨 4 0秒之後’利用7 0 C之洗務水洗務5秒。自專用托架上取 出磁器製盤子，使用赤蘚紅色素之1重量％水溶液使其著 I53068.doc 201130968 色，基於以下所示之判定基準以目視判定對洗淨性進行坪 價。 <洗淨性之判定基準> 污凊 5 : 4個磁器製盤子之任一個均完全未看到著色痕跡， 被去除 大部 4 : 4個磁器製盤子中之任-個看到輕微之著色痕跡， 分污潰被去除 〇 3:4個磁器製盤子全部看到輕微之著色痕跡，大部分、、_ 被去除 β凊 2:4個磁器製盤子全部 王4有到者色痕跡，—丰 留 千左右之3凊幾 1 : 4個磁器製盤子全 看到著色痕跡，大部分今、主 再者，作為本發明之 刀巧〉貝殘留 去除之3分以上，則較佳。 ’、、、斷為污凊被 〇 153068.doc -13· 201130968 o T*^ ^T) 00 ο m r-H Ο (Ν ο 1 〇 〇 cn 〇 cn OO <N 〇 ^―( 1—( m (Ν in 寸 ITi (N m o m r-H 1-H 们 c5 ο 卜 ο V〇 〇\ (N r—< ϊ—( <N 寸 寸 (N oo ^Ti (N V-) o cn τ·Η iTi ο ο ί—Η ΓΟ ο Ο) (N τ—Η ι丨4 (Ν 寸 (N m (N i〇 o 1—^ m t—H 1—^ l〇 ν〇 寸 in 赛 (Ν τ-^ (Ν r*H <N 寸 <N o in CN o T—H m ^-Η ο ο 1 VO 赛 σ> CM τ—Η <N 寸 -Ο f—H 〇 T·^ m (N o 1—H m r—Η in ο ο I iTi CTs (Ν ρ·Ή ΓΛ 寸 π oo oo CN i〇 (N m 〇 1·^ 〇 m ο ο 寸 专 σ\ 寸· rn ▼—Η »—Η 寸 卜 00 (N ir> (N o m ^Τ) ο ο τ-Η 寸 Ον 一 ΓΛ 1 < 寸 oo CN wo CN o m r 1Ή ο ο 1 "'< 寸 ir> 赛 Ο) 寸 ΟΙ f—Η r—Η 寸 to ^-H (N o m t1 Ή ι〇 <Τ) ^-Η 卜 寸 vr> Ο ι Η ι Ί ^T) 寸 寸 oo (N m <N o r—^ m r-^ iri ο ο 寸 α\ (Ν Ό 寸 m (N a 0 1 Ή »—H in ο »·Η ο ^Η ί〇 〇\· <Ν 寸 (N oo CN in <N ir> o m 1—^ 1 — ο ο 寸 ^Τ) Os (Ν ι Η -Η Ό 寸 At) •K> ㈣ oo (N 00 (N a r4 P»H oo 〇 m r-H ιη ο ο 寸 iri 〇\ Ο 1 ^ «丨-4 ITi in m T—^ ά ϊ—^ <N Xi 碳酸鈉 碳酸鉀 偏矽酸鈉·無水鹽 檸檬酸三鈉 乙二胺四乙酸四鈉 甲基甘胺酸二乙酸三鈉 L-麵胺酸二乙酸四鈉 非離子界面活性劑 (3) + 〇3)(重量％) (a)/(b)(重量比） (C)之合計(重量°/〇) (c)/[(a) + (b)](重量比） (c)中之矽酸鹽之比率(重量°/〇) pH值(25t，〇·1重量％之水溶液） Jjj3 W 鹿噠(侧_%) 153068.doc -14- 201130968 • a-1 :聚丙烯酸之鈉鹽[重量平均分子量為4,000 ’ Sokalan PA25CL Granules(BASF JAPAN(股）製造）：原料資 訊來自BASF JAPAN(股）製品目錄] •b-Ι:丙烯酸/馬來酸共聚物之鈉鹽[重量平均分子量為 70,000，丙烯酸/馬來酸共聚物比=70/30，Sokalan CP5 Granules(BASF JAPAN(股）製造）：原料資訊來自BASF JAPAN(股）製品目錄] • b-2 :丙烯酸/馬來酸共聚物鹽[重量平均分子量為 5,000，Aqualic TL37(曰本觸媒（股）製造）：原料資訊來自 曰本觸媒（股）製品目錄] •非離子界面活性劑：環氧丙烷•環氧乙烷•環氧丙烷•欲段 聚合物[重量平均分子量為3,100 ’環氧丙烷/環氧乙烧比= 80/20，Pluronic RPE2520(BASF JAPAN(股）製造）：原料資 訊來自BASF JAPAN(股）製品目錄]Washing temperature: 70 ° C Washing time: 5 seconds Washing concentration: 0.10% by weight Water: 6°dH hard water (adjusted with calcium chloride) <Evaluation method> Sample of SUS304 (100 mm×l30 mm) 5 at the special position of the cleaning rack. 'After the above test conditions, the washing, washing, and air drying at room temperature are performed 1,000 times. 'Based on the following evaluation criteria, the sample is 153068.doc 11 · 201130968 The visual judgment is <evaluation criterion>. Table 1 shows the average of 5 (back). 6 4 2 Compared with before the test, there is no difference, the gloss is slightly colored but the scale is not attached, the gloss is discolored but the scale is not attached, the shiny part is adhered to the scale, the gloss is covered by the scale, and the matte is 1: The whole is covered with scale, and the surface is rough and the surface is rough. In addition, it is preferable that the scale of the present invention is not limited to 4 points or more, and it is judged that the scale is not adhered and the gloss is 4 or more. [2] Evaluation of detergency <Production of model soil> In the center of a new magnetic plate of 20 cm in diameter, a 2 g of egg yolk was coated with a brush to a circle of about 1 cm in diameter. Shape, placed in an electric dryer set to 8 ° ° C. After 3 minutes, the magnetic plate coated with egg yolk was taken out and naturally cooled, and used as a model soil for the evaluation of the detergency. <Evaluation Method> The powder detergent composition for automatic washing machine of Table 1 was put into the washing tank (38 L) of the automatic dishwashing machine (SANYO DR53) manufactured by Yiyang Electric Co., Ltd. g 'Use 60 ° C of warm water to dissolve it. Place 4 pieces of magnetic plate coated with model dirt on the special bracket, and wash it with 6 (c wash solution for 40 seconds) and wash with 7 0 C of washing water for 5 seconds. The magnetic plate was taken out, and a 1% by weight aqueous solution of erythropoic acid was used to make I53068.doc 201130968 color, and the detergency was determined by visual judgment based on the criteria shown below. > Contamination 5: None of the 4 magnet plates were completely stained, and most of them were removed: 4 of the 4 magnet plates were seen to have a slight color trace, and the stain was removed. 〇3: All of the four magnetic plates are seen with slight traces of color, most of them, _ are removed β凊2: 4 magnets, all the kings have traces of the color, and there are 3 1 : The four magnets are all visible in the coloring of the plates. Most of them are the same as the ones of the present invention. It is preferable to remove the scallops by 3 or more. 153068.doc -13· 201130968 o T*^ ^T) 00 ο m rH Ο (Ν ο 1 〇〇cn 〇cn OO <N 〇^―( 1—( m (Ν in Int ITi (N mom rH 1-H c5 ο οο V〇〇\ (N r—< ϊ—( <N inch inch (N Oo ^Ti (N V-) o cn τ·Η iTi ο ο ί—Η ο ο Ο) (N τ—Η ι丨4 (Ν m (N i〇o 1—^ mt—H 1— ^ l〇ν〇inch in the game (Ν τ-^ (Ν r*H <N inch <N o in CN o T—H m ^-Η ο ο 1 VO 赛σ> CM τ—Η <N Inch-Ο f—H 〇T·^ m (N o 1—H mr—Η in ο ο I iTi CTs (Ν ρ·Ή 寸 inch π oo oo CN i〇(N m 〇1·^ 〇m ο ο寸Special σ\ inch·rn ▼—Η »—Η 00 00 (N ir> (N om ^Τ) ο ο τ-Η 寸Ον 一ΓΛ 1 < inch oo CN wo CN omr 1Ή ο ο 1 "'< inch ir> 赛Ο) inchΟΙ f—Η r—Η inch to ^-H (N om t1 Ή ι〇<Τ) ^-Η 卜 inch vr> Ο ι Η ι Ί ^T) inch inch oo (N m <N or-^ m r-^ iri ο ο inchα\ (Ν Ό inch m (N a 0 1 Ή »—H in ο »·Η ο ^Η ί〇〇\· <Ν inch (N oo C N in <N ir> om 1—^ 1 — ο ο inch^Τ) Os (Ν ι Η -Η Ό inch At) •K> (4) oo (N 00 (N a r4 P»H oo 〇m rH ιη ο ο iri 〇 Ο Ο 1 ^ «丨-4 ITi in m T—^ ά ϊ—^ <N Xi sodium carbonate potassium carbonate sodium citrate · anhydrous salt trisodium citrate tetraacetate tetrasodium acetate Glycosyl triacetate trisodium L- face acid diacetate tetrasodium nonionic surfactant (3) + 〇 3) (% by weight) (a) / (b) (weight ratio) (C) total ( Weight ° / 〇) (c) / [(a) + (b)] (weight ratio) The ratio of citrate in the (c) (weight ° / 〇) pH (25t, 〇 · 1% by weight of the aqueous solution Jjj3 W Luhan (side _%) 153068.doc -14- 201130968 • a-1 : sodium polyacrylate [weight average molecular weight 4,000 ' Sokalan PA25CL Granules (made by BASF JAPAN): Raw material information from BASF JAPAN Product Catalogue] • b-Ι: sodium salt of acrylic acid/maleic acid copolymer [weight average molecular weight 70,000, acrylic acid/maleic acid copolymer ratio = 70/30, Sokalan CP5 Granules (BASF JAPAN) ) Manufacturing): Raw material information from BASF JAPAN products Recorded • • b-2: Acrylic/Maleic Acid Copolymer Salt [weight average molecular weight 5,000, Aqualic TL37 (manufactured by 曰本Catalyst); raw material information from 曰本Chip (stock) product catalog] Ionic surfactant: propylene oxide, ethylene oxide, propylene oxide, polymer, polymer, weight average molecular weight, 3,100 propylene oxide / epoxy bromide ratio = 80/20, Pluronic RPE2520 (BASF JAPAN) ) Manufacturing): Raw material information from BASF JAPAN (stock) product catalogue]
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