TWI613291B - Liquid detergent composition for tableware cleaning machine - Google Patents

Liquid detergent composition for tableware cleaning machine Download PDF

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TWI613291B
TWI613291B TW103140310A TW103140310A TWI613291B TW I613291 B TWI613291 B TW I613291B TW 103140310 A TW103140310 A TW 103140310A TW 103140310 A TW103140310 A TW 103140310A TW I613291 B TWI613291 B TW I613291B
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TW201527522A (en
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Nobuyuki Suzuki
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Kao Corp
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/08Silicates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2086Hydroxy carboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

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  • 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)

Description

餐具清潔機用液體清潔劑組合物 Liquid detergent composition for tableware cleaning machine

本發明係關於一種餐具清潔機用液體清潔劑組合物。尤其是關於一種較佳地用於商業用之自動餐具清潔機之餐具清潔機用液體清潔劑組合物。 The present invention relates to a liquid detergent composition for a dishwashing machine. More particularly, it relates to a liquid detergent composition for a dishwashing machine which is preferably used in a commercial automatic tableware cleaning machine.

自動清潔機係用於家庭或餐廳、茶館等之廚房中之弄髒之碟、玻璃杯、烹飪器具等餐具類之清潔、食品飲料工廠中使用之食材及製品用之塑膠容器之清潔。作為主要之對象污漬,有源自食品之蛋白質、澱粉、油脂等,該等污漬複合而附著於碟、玻璃杯、烹飪器具等餐具、塑膠容器。又,亦存在加熱調理時該等污漬發生熱改性,而成為牢固之污漬固著之情況。 The automatic cleaning machine is used for cleaning dishes such as soiled dishes, glasses, cooking utensils, etc. in kitchens such as homes, restaurants, teahouses, etc., and cleaning of food containers used in food and beverage factories and plastic containers for products. As a main target stain, there are proteins, starches, fats and the like derived from foods, and these stains are combined and adhered to dishes, plastic containers such as dishes, glasses, and cooking utensils. Moreover, there is also a case where the stains are thermally modified when heated and conditioned, and the stains are firmly fixed.

通常,利用自動清潔機之清潔係以清潔步驟、洗滌步驟之順序進行。該等步驟之所需時間於商業用途上係非常短之時間,清潔步驟為40~60秒左右,洗滌步驟為5~20秒左右。 Usually, the cleaning system using the automatic cleaning machine is carried out in the order of the cleaning step and the washing step. The time required for these steps is very short for commercial use, the cleaning step is about 40 to 60 seconds, and the washing step is about 5 to 20 seconds.

清潔時,屢次使用含有Ca離子、Mg離子等硬度成分之自來水或井水等。由水中之該等硬度成分產生之碳酸鈣、碳酸鎂、矽酸鈣、矽酸鎂等不溶於水,因此會附著於自動清潔機內之清潔液槽或自動清潔機內之側壁等,形成被稱為水垢之牢固之覆膜。附著於清潔液槽內之各部位之水垢成為引起熱交換部之熱效率降低、循環泵之阻塞、濃度感測器之誤作動等故障之原因。又,成為容易於附著於側壁之水垢上沈積有機物污漬之狀態,有產生衛生管理上之問題之可能性。 When cleaning, tap water or well water containing a hardness component such as Ca ion or Mg ion is repeatedly used. Calcium carbonate, magnesium carbonate, calcium citrate, magnesium citrate and the like which are produced by the hardness components in the water are insoluble in water, and therefore adhere to the cleaning liquid tank in the automatic cleaning machine or the side wall in the automatic cleaning machine to form a A strong film called scale. The scale adhering to each portion in the cleaning liquid tank is a cause of failure such as a decrease in thermal efficiency of the heat exchange portion, clogging of the circulation pump, and malfunction of the concentration sensor. Further, it is a state in which organic matter stains are easily deposited on the scale adhering to the side wall, and there is a possibility of causing problems in hygiene management.

為了降低Ca離子、Mg離子等硬度成分之影響,可列舉增加螯合劑之含量,但於液體清潔劑之情形時,就獲得穩定之液體組合物之方面而言,螯合劑之調配量存在限制。 In order to reduce the influence of hardness components such as Ca ions and Mg ions, the content of the chelating agent may be increased, but in the case of a liquid detergent, there is a limitation in the amount of the chelating agent in terms of obtaining a stable liquid composition.

於日本專利特表2013-518983號公報中,揭示有包含甲基甘胺酸二乙酸等螯合物成分、金屬檸檬酸鹽、金屬碳酸鹽、金屬矽酸鹽之洗劑組合物具有優異之清潔力特性、例如較先前之組合物減少碟上之膜形成及污垢。 In the Japanese Patent Publication No. 2013-518983, it is disclosed that a lotion composition comprising a chelate component such as methylglycine diacetic acid, a metal citrate, a metal carbonate or a metal citrate has excellent cleaning. Force characteristics, such as film formation and fouling on the disc, are reduced compared to previous compositions.

於日本專利特開2007-23210號公報中,揭示有含有特定量之檸檬酸鹽等螯合劑、界面活性劑、芳香族系溶解助劑,25℃之pH值為3以上且未達7,且鈉離子(Na+)與鉀離子(K+)具有特定之莫耳比的液體清潔劑組合物之低溫穩定性優異,減少噴出口之堵塞,且對硬質表面之污漬顯示優異之清潔力。 Japanese Patent Publication No. 2007-23210 discloses a chelating agent such as a specific amount of citrate, a surfactant, and an aromatic dissolution aid. The pH at 25 ° C is 3 or more and less than 7, and The liquid detergent composition having a specific molar ratio of sodium ion (Na + ) and potassium ion (K + ) is excellent in low-temperature stability, reduces clogging of the discharge port, and exhibits excellent cleaning power against stains on hard surfaces.

於國際公開2013/175659號中,揭示有以特定量比含有選自甲基甘胺酸二乙酸及其鹼金屬鹽中之1種或2種以上、選自檸檬酸及其鹼金屬鹽中之1種或2種以上、及選自特定之非離子界面活性劑中之1種或2種以上的自動餐具清潔機用清潔劑組合物即便於洗滌水之使用量較少之條件下,亦對於茶垢附著之抑制及水斑之減少顯示優異之效果。 In International Publication No. 2013/175659, it is disclosed that one or more selected from the group consisting of methylglycine diacetic acid and an alkali metal salt thereof are selected from a citric acid and an alkali metal salt thereof in a specific amount ratio. One or two or more kinds of detergent compositions for automatic dishwashing machines selected from one or more of specific nonionic surfactants, even under conditions in which the amount of washing water used is small, The suppression of the adhesion of the tea scale and the reduction of the water spots show an excellent effect.

本發明係關於一種餐具清潔機用液體清潔劑組合物,其係含有矽酸鹽者,且含有下述(A)成分、(B)成分、(C)成分及水:(A)成分:甲基甘胺酸二乙酸、麩胺酸二乙酸或其等之鹽(B)成分:檸檬酸或其鹽(C)成分:聚丙烯酸或其鹽,(A)成分之含量換算成酸為2.0質量%以上且5.0質量%以下,(B)成分之含量換算成酸為1.5質量%以上且5.4質量%以下,矽酸鹽之含量為2.5質量%以上且7.4質量%以下,且 該餐具清潔機用液體清潔劑組合物含有鉀離子且任意地含有鈉離子,鈉離子之含量[Na+]相對於鉀離子之含量[K+]之莫耳比[Na+]/[K+]為0以上且0.9以下。 The present invention relates to a liquid detergent composition for a dishwashing machine which contains a bismuth citrate and which comprises the following components (A), (B), (C) and water: (A): A Glycine diacetic acid, glutamic acid diacetic acid or the like (B) component: citric acid or a salt thereof (C) component: polyacrylic acid or a salt thereof, and the content of the component (A) is 2.0 mass in terms of acid % or more and 5.0% by mass or less, the content of the component (B) is 1.5% by mass or more and 5.4% by mass or less based on the acid, and the content of the citrate is 2.5% by mass or more and 7.4% by mass or less, and the tableware cleaning machine is used. The liquid detergent composition contains potassium ions and optionally contains sodium ions, and the molar ratio of the sodium ion content [Na + ] to the potassium ion content [K + ] is [Na + ] / [K + ] is 0 or more. Below 0.9.

又,本發明係關於一種清潔液,其係將上述本發明之餐具清潔機用液體清潔劑組合物利用水進行稀釋而成者,且清潔液中之(A)成分之含量換算成酸為0.0017質量%以上且0.017質量%以下。 Moreover, the present invention relates to a cleaning liquid obtained by diluting the liquid detergent composition for a dishwashing machine of the present invention with water, and the content of the component (A) in the cleaning liquid is converted into an acid of 0.0017. The mass% or more and 0.017% by mass or less.

又,本發明係關於一種餐具之清潔方法,其係將上述本發明之餐具清潔機用液體清潔劑組合物供給至自動餐具清潔機之清潔液槽,混合上述組合物與水,於清潔液槽中製備(A)成分之含量換算成酸為0.0017質量%以上且0.017質量%以下之清潔液,使用該清潔液清潔餐具。 Moreover, the present invention relates to a method for cleaning a dishware, which comprises supplying the liquid detergent composition for a dishwashing machine of the present invention to a cleaning liquid tank of an automatic tableware cleaning machine, mixing the composition with water, and cleaning the liquid tank. The content of the component (A) in the preparation is converted into a cleaning liquid having an acid content of 0.0017 mass% or more and 0.017 mass% or less, and the tableware is cleaned using the cleaning liquid.

先前,若附著水垢,則成為引起熱交換部之熱效率降低、循環泵之阻塞、濃度感測器之誤作動之故障及因有機物沈積所致之衛生狀態之惡化等之原因。 In the past, if scale is attached, it causes a decrease in thermal efficiency of the heat exchange unit, clogging of the circulation pump, malfunction of the concentration sensor, deterioration of the sanitary state due to deposition of organic matter, and the like.

日本專利特表2013-518983號公報之洗劑組合物雖可用作自動洗碗機用洗劑(ADD),但水垢附著抑制性並不充分。 The lotion composition of JP-A-2013-518983 can be used as an automatic dishwasher detergent (ADD), but the scale adhesion inhibiting property is not sufficient.

又,關於日本專利特開2007-23210號公報之液體清潔劑組合物用作餐具清潔機用組合物之情形時之清潔性及水垢附著抑制性未作具體揭示。 Further, the cleansing property and the scale adhesion inhibiting property in the case of using the liquid detergent composition of the Japanese Patent Laid-Open Publication No. 2007-23210 as a dishwashing machine composition are not specifically disclosed.

本發明提供一種不僅清潔性、茶垢附著抑制性、調配性及低溫保存穩定性優異,而且水垢附著抑制性優異之含有矽酸鹽之餐具清潔機用液體清潔劑組合物。 The present invention provides a liquid detergent composition for a tableware cleaning machine containing a phthalate which is excellent in not only cleanability, tea scale adhesion inhibiting property, formulation property, and low-temperature storage stability, but also excellent in scale adhesion inhibition property.

根據本發明,提供一種不僅清潔性、茶垢附著抑制性、調配性及低溫保存穩定性優異,而且水垢附著抑制性優異之含有矽酸鹽之餐具清潔機用液體清潔劑組合物。 According to the present invention, there is provided a liquid detergent composition for a tableware cleaning machine containing a phthalate which is excellent in not only cleanability, tea scale adhesion inhibiting property, blending property, and low-temperature storage stability, but also excellent in scale adhesion inhibiting property.

以下,於本說明書中,亦將「本發明之餐具清潔機用液體清潔劑組合物」稱為「本發明之液體清潔劑組合物」、「本發明之清潔劑組合物」、「液體清潔劑組合物」、或「清潔劑組合物」。 In the present specification, the "liquid detergent composition for tableware cleaning machine of the present invention" is also referred to as "the liquid detergent composition of the present invention", "the detergent composition of the present invention", and "liquid detergent". "Composition" or "detergent composition".

本發明之含有矽酸鹽之餐具清潔機用液體清潔劑組合物以特定量含有(A)成分:甲基甘胺酸二乙酸、麩胺酸二乙酸或其等之鹽、(B)成分:檸檬酸或其鹽、(C)成分:聚丙烯酸或其鹽、及水,且矽酸鹽之含量為特定量,鈉離子之含量[Na+]相對於鉀離子之含量[K+]之莫耳比[Na+]/[K+]為0以上且0.9以下,藉此不僅清潔性、茶垢附著抑制性、調配性及低溫保存穩定性優異,而且水垢附著抑制性亦優異。 The liquid detergent composition for a phthalate-containing dishwashing machine of the present invention contains the component (A) in a specific amount: methyl glycine diacetic acid, glutamic acid diacetic acid or the like thereof, and (B) component: citric acid or a salt thereof, (C) component: polyacrylic acid or a salt thereof, and water, and the content of a specific amount of silicate, the content of sodium ions [Na +] with respect to the potassium content of [K +] Mok ear than the [Na +] / [K + ] is 0 or more and 0.9 or less, whereby not only cleaning performance, tea scale adhesion-inhibiting, low-temperature deployment property and excellent storage stability, and also excellent in inhibiting scale adhesion.

本發明之含有矽酸鹽之餐具清潔機用液體清潔劑組合物之水垢附著抑制性優異。其原因並不明確,但作如下考慮。 The liquid detergent composition for a phthalate-containing dishwashing machine of the present invention is excellent in scale adhesion inhibition property. The reason is not clear, but it is considered as follows.

本發明者針對清潔液槽內及清潔機內側壁之水垢附著抑制之問題,發現如下情況。水垢包含矽酸鈣或矽酸鎂等難溶於水之矽酸鹽(以下稱為矽酸鹽水垢)、及碳酸鈣或碳酸鎂等難溶於水之碳酸鹽(以下稱為碳酸鹽水垢)。附著於清潔機內之不鏽鋼(SUS)表面之矽酸鹽水垢於SUS表面成為黏合劑,於此處附著清潔液槽內所存在之碳酸鹽水垢。因碳酸鹽水垢進行結晶成長而形成水垢。又,矽酸鹽水垢與碳酸鹽水垢形成層而附著。 The present inventors have found the following problems with respect to the problem of scale adhesion suppression in the cleaning liquid tank and the inner side wall of the cleaning machine. The scale includes a hardly soluble calcium silicate such as calcium citrate or magnesium citrate (hereinafter referred to as citrate scale), and a water-insoluble carbonate such as calcium carbonate or magnesium carbonate (hereinafter referred to as carbonate scale). . The bismuth scale adhered to the surface of the stainless steel (SUS) in the cleaning machine becomes a binder on the surface of the SUS, and the carbonate scale present in the cleaning liquid tank is attached thereto. Scale is formed by crystal growth of carbonate scale. Further, the citrate scale adheres to the carbonate scale to form a layer.

若Ca離子或Mg離子等水之硬度成分之量超過螯合劑之陽離子交換容量(CEC),則產生水垢。進而可知,殘留於清潔機內側壁之SUS表面之碳酸鹽水垢產生結晶成長,水垢成為更牢固之狀態。 If the amount of the hardness component of water such as Ca ion or Mg ion exceeds the cation exchange capacity (CEC) of the chelating agent, scale is generated. Further, it was found that the carbonate scale remaining on the SUS surface of the inner side wall of the cleaner crystallized and the scale became stronger.

由此,為了抑制水垢附著、尤其抑制碳酸鹽水垢附著,必須充分地捕捉水之硬度成分。 Therefore, in order to suppress the adhesion of scale and to particularly inhibit the adhesion of carbonate scale, it is necessary to sufficiently capture the hardness component of water.

由於矽酸根離子之單體向二聚物、多聚物進行結構變化而聚合物化,水垢變得易於附著於SUS表面。該矽酸聚合物引入Ca離子或Mg離子等二價陽離子,轉換為更複雜之三維網狀結構。轉換為網狀結構之聚合物進而作為矽酸鹽水垢固定於SUS表面。 Since the monomer of the citrate ion polymerizes to the dimer and the polymer, the scale becomes easy to adhere to the SUS surface. The phthalic acid polymer introduces a divalent cation such as a Ca ion or a Mg ion, and is converted into a more complicated three-dimensional network structure. The polymer converted into a network structure is further fixed to the SUS surface as a phthalate scale.

由於K之第一離子化能及電子親和力較Na小,因此認為抑制矽酸根離子之聚合物化。由此,於抑制矽酸鹽水垢附著時,重要的是於清潔液中存在固定量之K離子。 Since the first ionization energy and electron affinity of K are smaller than Na, it is considered that the polymerization of the citrate ion is suppressed. Thus, in order to inhibit the adhesion of citrate scale, it is important to have a fixed amount of K ions in the cleaning solution.

認為於鹼性液中,與其他有機酸不同,檸檬酸僅存在解離型,易溶解於凝膠狀態之矽酸聚合物中。由此,認為鹼性液中之檸檬酸捕捉Ca離子或Mg離子等硬度成分,有效地抑制水垢。 It is considered that, in the alkaline solution, unlike other organic acids, citric acid only has a dissociated type and is easily dissolved in a gelled state of a citric acid polymer. Therefore, it is considered that citric acid in the alkaline liquid captures hardness components such as Ca ions or Mg ions, and the scale is effectively suppressed.

又,由於K之第一離子化能及電子親和力較Na小,故而檸檬酸鉀較檸檬酸鈉略微容易解離。認為藉由該略微之差別,鉀離子較多之情形與鈉離子較多之情形相比,由解離之檸檬酸產生之水垢抑制效果更高。 Moreover, since the first ionization energy and electron affinity of K are smaller than Na, potassium citrate is slightly easier to dissociate than sodium citrate. It is considered that by this slight difference, the case where the potassium ions are large is higher than the case where the sodium ions are large, and the scale inhibition effect by the dissociated citric acid is higher.

因此,於抑制水垢附著時,重要的是捕捉硬度成分及抑制矽酸根離子之聚合物化。於本發明中,藉由組合(A)成分、(B)成分、(C)成分之特定3種化合物,且規定鈉離子之含量與鉀離子之含量之莫耳比,可抑制清潔液及矽酸聚合物中之硬度成分。藉由限定矽酸鹽之含量,且規定鈉離子之含量與鉀離子之含量之莫耳比,可抑制矽酸根離子之高分子化。其結果為,可抑制水垢附著。 Therefore, in suppressing the adhesion of scale, it is important to capture the hardness component and inhibit the polymerization of the citrate ion. In the present invention, by combining the specific three compounds of the component (A), the component (B), and the component (C), and by specifying the molar ratio of the content of the sodium ion to the content of the potassium ion, the cleaning liquid and the hydrazine can be suppressed. The hardness component of the acid polymer. By limiting the content of the citrate and specifying the molar ratio of the content of the sodium ion to the content of the potassium ion, the macromolecularization of the citrate ion can be suppressed. As a result, scale adhesion can be suppressed.

<(A)成分> <(A) component>

就水垢附著抑制性、茶垢附著抑制性之觀點而言,本發明之(A)成分係甲基甘胺酸二乙酸、麩胺酸二乙酸或其等之鹽。作為(A)成分之鹽,就獲取之容易性之觀點而言,較佳為鹼金屬鹽,更佳為鈉鹽。又,就水垢附著抑制性之進一步提高之觀點而言,更佳為鉀鹽。 The component (A) of the present invention is a salt of methylglycine diacetic acid, glutamic acid diacetic acid or the like from the viewpoint of scale adhesion inhibiting property and tea scale adhesion inhibiting property. The salt of the component (A) is preferably an alkali metal salt, more preferably a sodium salt, from the viewpoint of easiness of availability. Further, from the viewpoint of further improving the scale adhesion inhibiting property, a potassium salt is more preferable.

本發明之液體清潔劑組合物可含有1種或2種以上之(A)成分。 The liquid detergent composition of the present invention may contain one or more components (A).

關於(A)成分之含量,就水垢附著抑制性、清潔性、茶垢附著抑制性及調配性之觀點而言,於清潔劑組合物中為2.0質量%以上且5.0質量%以下。關於(A)成分之含量,就水垢附著抑制性及茶垢附著抑制性之觀點而言,於液體清潔劑組合物中,較佳為2.6質量%以上,更佳為3.3質量%以上,更佳為3.6質量%以上,更佳為4.2質量%以上,且就調配性之觀點而言,較佳為4.7質量%以下,更佳為4.0質量%以下,更佳為3.6質量%以下。又,關於(A)成分之含量,就水垢附著抑制性、茶垢附著抑制性、調配性之觀點而言,於液體清潔劑組合物中,較佳為2.6~5.0質量%,更佳為3.3~5.0質量%,更佳為3.3~4.7質量%,更佳為3.3~4.0質量%,更佳為3.3~3.6質量%。再者,(A)成分之含量均為換算成酸之值。 The content of the component (A) is 2.0% by mass or more and 5.0% by mass or less in the detergent composition from the viewpoint of scale adhesion inhibitory property, cleanability, tea scale adhesion inhibiting property, and blending property. The content of the component (A) is preferably 2.6 mass% or more, more preferably 3.3 mass% or more, more preferably in terms of scale adhesion inhibitory property and tea scale adhesion inhibitory property. The content is 3.6 mass% or more, more preferably 4.2 mass% or more, and from the viewpoint of blending property, it is preferably 4.7 mass% or less, more preferably 4.0 mass% or less, still more preferably 3.6 mass% or less. In addition, the content of the component (A) is preferably 2.6 to 5.0% by mass, more preferably 3.3, in the liquid detergent composition from the viewpoint of scale adhesion inhibitory property, tea scale adhesion inhibitory property, and formulation property. ~5.0% by mass, more preferably 3.3 to 4.7 mass%, more preferably 3.3 to 4.0 mass%, still more preferably 3.3 to 3.6 mass%. Further, the content of the component (A) is a value converted into an acid.

<(B)成分> <(B) component>

就水垢附著抑制性之觀點而言,本發明之(B)成分係檸檬酸或其鹽。作為(B)成分,就獲取之容易性及水垢附著抑制性之進一步提高之觀點而言,較佳為檸檬酸。作為(B)成分之鹽,就獲取之容易性之觀點而言,較佳為其鹼金屬鹽,更佳為鈉鹽或鉀鹽,更佳為鈉鹽。就水垢附著抑制性之進一步提高之觀點而言,更佳為鉀鹽。 The component (B) of the present invention is citric acid or a salt thereof from the viewpoint of scale adhesion inhibition. The component (B) is preferably citric acid from the viewpoint of further improvement in availability and scale adhesion inhibition. The salt of the component (B) is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt, and more preferably a sodium salt, from the viewpoint of availability. The potassium salt is more preferable from the viewpoint of further improvement in scale adhesion inhibition.

關於(B)成分之含量,就水垢附著抑制性、調配性及低溫保存穩定性之觀點而言,於清潔劑組合物中為1.5質量%以上且5.4質量%以下。關於(B)成分之含量,就水垢附著抑制性之進一步提高之觀點而言,於清潔劑組合物中,較佳為2.5質量%以上,更佳為3.0質量%以上,更佳為3.5質量%以上,更佳為4.5質量%以上,且就調配性、低溫保存穩定性之進一步提高之觀點而言,較佳為5.2質量%以下。又,關於(B)成分之含量,就水垢附著抑制性、調配性及低溫保存穩定性之觀點而言,於液體清潔劑組合物中,較佳為2.5~5.4質量%,更佳為2.5~5.2質量%,更佳為3.0~5.2質量%,更佳為3.5~5.2質量%,更 佳為4.5~5.2質量%。又,(B)成分之含量為1.5~5.4質量%,較佳為1.5~5.2質量%,更佳為1.5~4.5質量%,更佳為1.5~3.5質量%。再者,(B)成分之含量均為換算成酸之值。 The content of the component (B) is 1.5% by mass or more and 5.4% by mass or less in the detergent composition from the viewpoint of scale adhesion inhibiting property, blending property, and low-temperature storage stability. The content of the component (B) is preferably 2.5% by mass or more, more preferably 3.0% by mass or more, and still more preferably 3.5% by mass in terms of the detergent composition. The amount is more preferably 4.5% by mass or more, and is preferably 5.2% by mass or less from the viewpoint of further improvement in blending property and low-temperature storage stability. In addition, the content of the component (B) is preferably from 2.5 to 5.4% by mass, more preferably from 2.5 to 5% by mass, in terms of scale adhesion inhibitory, formulation, and low-temperature storage stability. 5.2% by mass, more preferably 3.0 to 5.2% by mass, more preferably 3.5 to 5.2% by mass, more Good is 4.5~5.2% by mass. Further, the content of the component (B) is from 1.5 to 5.4% by mass, preferably from 1.5 to 5.2% by mass, more preferably from 1.5 to 4.5% by mass, still more preferably from 1.5 to 3.5% by mass. Further, the content of the component (B) is a value converted into an acid.

關於(A)成分之換算成酸之含量相對於(B)成分之換算成酸之含量之質量比[(A)/(B)],就水垢附著抑制性、清潔性、茶垢附著抑制性及低溫保存穩定性之進一步提高之觀點而言,較佳為0.65以上,更佳為0.70以上,更佳為1.0以上,更佳為1.25以上,且就水垢附著抑制性及調配性之進一步提高之觀點而言,較佳為1.9以下,更佳為1.7以下,更佳為1.55以下。 The mass ratio of the content of the component (A) to the acid content of the component (B) is proportional to the content of the acid ([A)/(B)], and the scale adhesion inhibition property, the cleanliness property, and the tea scale adhesion inhibitory property. From the viewpoint of further improving the low-temperature storage stability, it is preferably 0.65 or more, more preferably 0.70 or more, still more preferably 1.0 or more, still more preferably 1.25 or more, and further improved in scale adhesion inhibition property and blendability. From the viewpoint, it is preferably 1.9 or less, more preferably 1.7 or less, still more preferably 1.55 or less.

<(C)成分> <(C) component>

就清潔性及水垢附著抑制性之觀點而言,本發明之(C)成分係聚丙烯酸或其鹽。作為(C)成分之鹽,就獲取之容易性之觀點而言,較佳為鹼金屬鹽,更佳為鈉鹽或鉀鹽,就水垢附著抑制性之進一步提高之觀點而言,更佳為鉀鹽。 The component (C) of the present invention is a polyacrylic acid or a salt thereof from the viewpoint of cleanability and scale adhesion inhibition. The salt of the component (C) is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt, from the viewpoint of ease of availability, and more preferably from the viewpoint of further improving the scale adhesion inhibiting property. Potassium salt.

關於(C)成分之分子量,重量平均分子量較佳為1,000以上,更佳為3,000以上,且較佳為10,000以下,更佳為8,000以下,更佳為6,000以下,更佳為5,000以下。又,根據相同之原因,(C)成分之重量平均分子量較佳為1,000~10,000,更佳為3,000~8,000,更佳為3,000~6,000,更佳為3,000~5,000。 The molecular weight of the component (C) preferably has a weight average molecular weight of 1,000 or more, more preferably 3,000 or more, and is preferably 10,000 or less, more preferably 8,000 or less, still more preferably 6,000 or less, still more preferably 5,000 or less. Further, for the same reason, the weight average molecular weight of the component (C) is preferably from 1,000 to 10,000, more preferably from 3,000 to 8,000, still more preferably from 3,000 to 6,000, still more preferably from 3,000 to 5,000.

此處,(C)成分之重量平均分子量可將乙腈與水之混合溶劑(磷酸緩衝溶液)作為展開溶劑,藉由尺寸排除層析法以聚丙烯酸為標準物質而求出。 Here, the weight average molecular weight of the component (C) can be determined by using a mixed solvent of acetonitrile and water (phosphate buffer solution) as a developing solvent and using polyacrylic acid as a standard material by size exclusion chromatography.

關於(C)成分之含量,就清潔性之進一步提高之觀點而言,於清潔劑組合物中,較佳為0.8質量%以上,更佳為1.8質量%以上,更佳為2.5質量%以上,更佳為3.5質量%以上,更佳為4.5質量%以上,且較佳為5.5質量%以下,更佳為2.8質量%以下,更佳為2.2質量%以 下。又,關於(C)成分之含量,就清潔性之進一步提高之觀點而言,於液體清潔劑組合物中,較佳為0.8~5.5質量%,更佳為1.8~5.5質量%,更佳為2.5~5.5質量%,更佳為3.5~5.5質量%,更佳為4.5~5.5質量%。又,就兼具水垢附著抑制性、低溫保存穩定性、清潔性、茶垢附著抑制性及調配性之觀點而言,於液體清潔劑組合物中,較佳為0.8~5.5質量%,更佳為0.8~2.8質量%,更佳為1.8~2.8質量%,更佳為1.8~2.2質量%。 The content of the component (C) is preferably 0.8% by mass or more, more preferably 1.8% by mass or more, and still more preferably 2.5% by mass or more, from the viewpoint of further improving the cleanability. More preferably, it is 3.5 mass% or more, more preferably 4.5 mass% or more, and is preferably 5.5 mass% or less, more preferably 2.8 mass% or less, still more preferably 2.2 mass%. under. Further, the content of the component (C) is preferably from 0.8 to 5.5% by mass, more preferably from 1.8 to 5.5% by mass, more preferably from 1.8 to 5.5% by mass, more preferably from the viewpoint of further improvement in cleanability. 2.5 to 5.5% by mass, more preferably 3.5 to 5.5% by mass, still more preferably 4.5 to 5.5% by mass. In addition, it is preferably from 0.8 to 5.5% by mass, more preferably from 0.8 to 5.5% by mass in the liquid detergent composition, from the viewpoints of scale adhesion inhibition property, low-temperature storage stability, cleanability, tea scale adhesion inhibition property, and formulation property. It is 0.8 to 2.8% by mass, more preferably 1.8 to 2.8% by mass, still more preferably 1.8 to 2.2% by mass.

關於(B)成分之換算成酸之含量相對於(C)成分之含量之質量比(B)/(C),就水垢附著抑制性、清潔性、茶垢附著抑制性、調配性及低溫保存穩定性之進一步提高之觀點而言,較佳為0.5以上,更佳為0.8以上,更佳為1.2以上,且就調配性之觀點而言,較佳為2.5以下。 The mass ratio (B)/(C) of the content of the component (B) to the content of the component (C), the scale adhesion inhibition property, the cleanliness, the tea scale adhesion inhibition property, the formulation property, and the cryopreservation From the viewpoint of further improvement of the stability, it is preferably 0.5 or more, more preferably 0.8 or more, still more preferably 1.2 or more, and from the viewpoint of blending property, it is preferably 2.5 or less.

關於(A)成分之換算成酸之含量相對於(C)成分之含量之質量比(A)/(C),就水垢附著抑制性、清潔性及茶垢附著抑制性之進一步提高之觀點而言,較佳為0.7以上,更佳為0.8以上,更佳為1.0以上,更佳為1.3以上,更佳為1.6以上,且就獲取之容易性之觀點而言,較佳為3.4以下,更佳為2.5以下。 The mass ratio (A)/(C) of the content of the component (A) to the content of the component (C) is further improved in terms of scale adhesion inhibition property, cleanability, and tea scale adhesion inhibition property. In particular, it is preferably 0.7 or more, more preferably 0.8 or more, still more preferably 1.0 or more, still more preferably 1.3 or more, still more preferably 1.6 or more, and from the viewpoint of easiness of acquisition, preferably 3.4 or less, more preferably Good is below 2.5.

本發明之液體清潔劑組合物中,關於(A)成分之換算成酸之含量、(B)成分之換算成酸之含量及(C)成分之含量之合計,就水垢附著抑制性、清潔性及茶垢附著抑制性之進一步提高之觀點而言,較佳為6.0質量%以上,更佳為7.5質量%以上,且就調配性及低溫穩定性之進一步提高之觀點而言,較佳為12.0質量%以下,更佳為10質量%以下,更佳為9質量%以下,更佳為8.5質量%以下。 In the liquid detergent composition of the present invention, the amount of the component (A) converted to the acid content, the component of the component (B) converted to the acid content, and the content of the component (C) are combined in terms of scale adhesion inhibition property and cleanability. From the viewpoint of further improving the adhesion inhibition property of the tea scale, it is preferably 6.0% by mass or more, more preferably 7.5% by mass or more, and is preferably 12.0 from the viewpoint of further improvement in blendability and low-temperature stability. The mass% or less is more preferably 10% by mass or less, more preferably 9% by mass or less, and still more preferably 8.5 mass% or less.

<水> <water>

本發明之液體清潔劑組合物含有水。 The liquid detergent composition of the present invention contains water.

<矽酸鹽> <Citrate>

就防耐酸鋁腐蝕性之觀點而言,本發明之液體清潔劑組合物含 有矽酸鹽作為鹼劑。 The liquid detergent composition of the present invention contains from the viewpoint of preventing corrosion resistance of acid aluminum There is a citrate as an alkali agent.

關於矽酸鹽之含量,就清潔性、茶垢附著抑制性、防耐酸鋁腐蝕性及水垢附著抑制性之觀點而言,於液體清潔劑組合物中為2.5質量%以上且7.4質量%以下。 The content of the bismuth salt is 2.5% by mass or more and 7.4% by mass or less in the liquid detergent composition from the viewpoints of cleanability, inhibition of the adhesion of the scale, adhesion prevention of the acid-resistant aluminum, and scale adhesion inhibition.

關於矽酸鹽之含量,就相同之觀點而言,於液體清潔劑組合物中,較佳為3質量%以上,更佳為4質量%以上,且較佳為7質量%以下,更佳為6質量%以下。 The content of the citrate is preferably 3% by mass or more, more preferably 4% by mass or more, and particularly preferably 7% by mass or less, more preferably in the liquid detergent composition. 6 mass% or less.

作為矽酸鹽,就防耐酸鋁腐蝕性、調配性及獲取之容易性之進一步提高之觀點而言,較佳為選自鹼金屬矽酸鹽中之1種或2種以上。作為鹼金屬矽酸鹽,就水垢附著抑制性、清潔性、茶垢附著抑制性、調配性、低溫保存穩定性及獲取之容易性之進一步提高之觀點而言,較佳為選自1號矽酸鹽、2號矽酸鹽、3號矽酸鹽及4號矽酸鹽中之1種或2種以上之矽酸鹽,更佳為選自1號矽酸鹽、2號矽酸鹽及3號矽酸鹽中之1種或2種以上之矽酸鹽,更佳為選自1號矽酸鹽及2號矽酸鹽中之1種或2種以上之矽酸鹽,更佳為選自1號矽酸鹽中之1種或2種以上之矽酸鹽。此處,鹼金屬矽酸鹽係由式M2O.nSiO2(M為鹼金屬,n為莫耳比SiO2/M2O)所表示,1號矽酸鹽係莫耳比n平均為1.7以上且2.3以下之矽酸鹽,2號矽酸鹽係莫耳比n平均為2.4以上且2.7以下之矽酸鹽,3號矽酸鹽係莫耳比n平均為2.8以上且3.3以下之矽酸鹽,4號矽酸鹽係莫耳比n平均為3.7以上且3.9以下之矽酸鹽。 The citrate is preferably one or more selected from the group consisting of alkali metal citrates, from the viewpoint of further improving the corrosion resistance, the formulation, and the ease of acquisition. The alkali metal silicate is preferably selected from the group consisting of No. 1 in terms of scale adhesion inhibition, cleanability, tea scale adhesion inhibition, blendability, low-temperature storage stability, and ease of acquisition. One or more of the acid salts, the No. 2 citrate, the No. 3 citrate and the No. 4 citrate, more preferably selected from the group consisting of No. 1 citrate, No. 2 citrate One or more of the citrates of the citrate No. 3, more preferably one or more citrates selected from the group consisting of citrate No. 1 and bismuth citrate No. 2, more preferably One or two or more types of citrate selected from the group consisting of citrate No. 1. Here, the alkali metal citrate is of the formula M 2 O. nSiO 2 (M is an alkali metal, n is a molar ratio of SiO 2 /M 2 O), and the No. 1 citrate is a citrate having an average molar ratio of 1.7 or more and 2.3 or less. The molar ratio of the molar ratio n is 2.4 or more and 2.7 or less. The citrate of the No. 3 citrate is an average of 2.8 or more and 3.3 or less of the citrate, and the No. 4 citrate is the molar ratio of the molar ratio n. It is a citrate of 3.7 or more and 3.9 or less.

作為矽酸鹽,就獲取之容易性之觀點而言,較佳為選自矽酸鉀及矽酸鈉中之1種或2種以上。又,作為鹼金屬矽酸鹽,較佳為選自鈉鹽及鉀鹽中之鹽。作為矽酸鹽,較佳為選自1號矽酸鈉及1號矽酸鉀中之1種或2種以上之鹼金屬矽酸鹽,就獲取之容易性之觀點而言,較佳為1號矽酸鈉。又,作為鹼金屬矽酸鹽,就水垢附著抑制性之觀點而言,較佳為1號矽酸鉀。 The citrate is preferably one or more selected from the group consisting of potassium citrate and sodium citrate from the viewpoint of easiness of availability. Further, as the alkali metal ruthenate, a salt selected from the group consisting of a sodium salt and a potassium salt is preferred. The citrate is preferably one or more alkali metal silicates selected from the group consisting of sodium citrate No. 1 and potassium citrate No. 1 and is preferably one in terms of ease of availability. Sodium citrate. Further, the alkali metal citrate is preferably potassium citrate No. 1 from the viewpoint of scale adhesion inhibition.

鹼金屬矽酸鹽係由式M2O.nSiO2(M為鹼金屬,n為莫耳比SiO2/M2O)所表示,且認為,基於該M或n之性狀之變化較複雜,因此難以抑制及去除水垢。例如,於偏矽酸鈉(於上述式中,M為鈉,n=1)之水溶液或鈉多於其之矽酸鹼性水溶液中,主要存在矽酸根離子單體,於n(莫耳比SiO2/M2O)更大之矽酸鈉水溶液中,除單體(monomer)以外,亦包含二聚物、進而包含其以上之多聚物之矽酸根離子微胞。該聚矽酸根離子微胞之比率隨著n(莫耳比SiO2/M2O)增大而增加。其結果為,可知若n(莫耳比SiO2/M2O)成為2以上,則有矽酸根離子自單體之陰離子向更複雜之聚合物結構轉換之傾向。該等矽酸聚合物配向吸附於SUS表面,與清潔中使用之水(例如自來水或地下水等)中通常存在之鈣或鎂等複合而形成水垢。認為若n成為2以上,則形成之水垢以更牢固之狀態附著。鹼金屬矽酸鹽係用於提高清潔力所較理想之成分,但有促進水垢產生之傾向。本發明之液體清潔劑組合物即便於含有對提高清潔力有效之鹼金屬矽酸鹽之情形時亦可抑制水垢。 The alkali metal silicate is of the formula M 2 O. nSiO 2 (M is an alkali metal, n is the molar ratio of SiO 2 / M 2 O) represented, and it is believed, based on the change in the M n of the trait, or more complex, it is difficult to suppress and remove scale. For example, in an aqueous solution of sodium metasilicate (in the above formula, M is sodium, n=1) or an aqueous solution of sodium citrate more than the above, mainly a citrate ion monomer is present in n (mole ratio) The SiO 2 /M 2 O) larger sodium citrate aqueous solution contains, in addition to a monomer, a dimer, and further a cerium ion microcapsule containing a polymer thereof. The ratio of the polycaprate ion micelles increases as n (mola ratio SiO 2 /M 2 O) increases. As a result, it is understood that when n (mol ratio SiO 2 /M 2 O) is 2 or more, there is a tendency for the ruthenate ion to switch from the anion of the monomer to the more complicated polymer structure. These tannic acid polymers are adsorbed on the surface of SUS, and are combined with calcium or magnesium which is usually present in water used for cleaning (for example, tap water or ground water) to form scale. It is considered that if n is 2 or more, the scale formed is adhered to a more firm state. Alkali metal citrate is a desirable component for improving cleaning power, but has a tendency to promote scale formation. The liquid detergent composition of the present invention can inhibit scale even when it contains an alkali metal silicate which is effective for improving the cleaning power.

<pH值> <pH value>

關於本發明之液體清潔劑組合物之0.2質量%水稀釋液於25℃下之pH值(JIS K 3362),就水垢附著抑制性及清潔性之進一步提高之觀點而言,較佳為9以上,更佳為9.5以上,更佳為10以上,更佳為10.5以上,且就清潔性之觀點而言,較佳為12以下,更佳為11.5以下。 The pH value (JIS K 3362) of the 0.2% by mass aqueous dilution of the liquid detergent composition of the present invention at 25 ° C is preferably 9 or more from the viewpoint of further improvement in scale adhesion inhibition property and cleanability. More preferably, it is 9.5 or more, more preferably 10 or more, still more preferably 10.5 or more, and from the viewpoint of cleanability, it is preferably 12 or less, more preferably 11.5 or less.

<其他成分> <Other ingredients>

本發明之液體清潔劑組合物較佳為含有除矽酸鹽以外之鹼劑。作為除矽酸鹽以外之鹼劑,就獲取之容易性之觀點而言,較佳為選自鹼金屬氫氧化物及鹼金屬碳酸鹽中之1種或2種以上之鹼劑。 The liquid detergent composition of the present invention preferably contains an alkali agent other than phthalate. The alkali agent other than the bismuth acid salt is preferably one or more alkali chemicals selected from the group consisting of an alkali metal hydroxide and an alkali metal carbonate from the viewpoint of easiness of availability.

作為鹼金屬氫氧化物,較佳為氫氧化鉀或氫氧化鈉,更佳為氫氧化鉀。 As the alkali metal hydroxide, potassium hydroxide or sodium hydroxide is preferred, and potassium hydroxide is more preferred.

作為鹼金屬碳酸鹽,較佳為碳酸鉀或碳酸鈉,更佳為碳酸鉀。 As the alkali metal carbonate, potassium carbonate or sodium carbonate is preferred, and potassium carbonate is more preferred.

本發明之液體清潔劑組合物可含有1種或2種以上之除矽酸鹽以外之鹼劑。 The liquid detergent composition of the present invention may contain one or more alkali agents other than decanoate.

本發明之液體清潔劑組合物中,作為鹼劑,較佳為含有選自鹼金屬氫氧化物及鹼金屬碳酸鹽中之1種或2種以上,更佳為含有選自鹼金屬氫氧化物及鹼金屬碳酸鹽中之2種以上。 In the liquid detergent composition of the present invention, the alkaline agent preferably contains one or more selected from the group consisting of an alkali metal hydroxide and an alkali metal carbonate, and more preferably contains an alkali metal hydroxide. And two or more kinds of alkali metal carbonates.

本發明之液體清潔劑組合物中,就水垢附著抑制性、清潔性、茶垢附著抑制性、調配性、低溫保存穩定性之進一步提高之觀點及獲取之容易性之觀點而言,作為除矽酸鹽以外之鹼劑,較佳為含有(1)選自鹼金屬氫氧化物中之1種或2種以上、及(2)選自鹼金屬碳酸鹽中之1種或2種以上。即,含有(1)及(2)之兩者。 The liquid detergent composition of the present invention is used as a mites for the purpose of further improving scale adhesion inhibition, cleanability, tea scale adhesion inhibition, blendability, and low-temperature storage stability, and ease of acquisition. The alkali agent other than the acid salt is preferably one or more selected from the group consisting of (1) one or more selected from the group consisting of alkali metal hydroxides, and (2) one selected from the group consisting of alkali metal carbonates. That is, both of (1) and (2) are contained.

又,本發明之液體清潔劑組合物較佳為含有選自氫氧化鉀、氫氧化鈉、碳酸鉀及碳酸鈉中之1種或2種以上,更佳為含有選自氫氧化鉀、氫氧化鈉、碳酸鉀及碳酸鈉中之2種以上。 Further, the liquid detergent composition of the present invention preferably contains one or more selected from the group consisting of potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate, and more preferably contains potassium hydroxide and hydroxide. Two or more of sodium, potassium carbonate and sodium carbonate.

又,本發明之液體清潔劑組合物中,作為鹼劑,較佳為含有選自氫氧化鉀、氫氧化鈉、碳酸鉀、及碳酸鈉中之1種或2種以上,更佳為含有選自氫氧化鉀及氫氧化鈉中之1種或2種以上以及選自碳酸鉀及碳酸鈉中之1種或2種以上。 Further, in the liquid detergent composition of the present invention, the alkaline agent preferably contains one or more selected from the group consisting of potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate, and more preferably contains the selected ones. One or two or more kinds selected from the group consisting of potassium hydroxide and sodium hydroxide, and one or more selected from the group consisting of potassium carbonate and sodium carbonate.

本發明之液體清潔劑組合物較佳為含有氫氧化鉀及碳酸鉀作為除矽酸鹽以外之鹼劑。 The liquid detergent composition of the present invention preferably contains potassium hydroxide and potassium carbonate as an alkali agent other than phthalate.

就清潔性之進一步提高之觀點而言,較佳為以本發明之液體清潔劑組合物之0.2質量%水稀釋液於25℃下之pH值成為上述範圍之方式含有鹼劑。關於鹼劑之含量,亦包含矽酸鹽之含量在內,於液體清潔劑組合物中,就清潔性之進一步提高之觀點而言,較佳為10質量%以上,更佳為15質量%以上,且就低溫保存穩定性之觀點而言,較佳為25質量%以下,更佳為20質量%以下。 In view of further improvement of the cleanability, it is preferred to contain an alkaline agent in such a manner that the pH of the 0.2% by mass aqueous dilution of the liquid detergent composition of the present invention at 25 ° C is within the above range. In the liquid detergent composition, the content of the alkalinity agent is preferably 10% by mass or more, and more preferably 15% by mass or more from the viewpoint of further improving the cleanability. In view of low-temperature storage stability, it is preferably 25% by mass or less, and more preferably 20% by mass or less.

再者,關於所有鹼劑中之矽酸鹽之比率,就防耐酸鋁腐蝕性、 茶垢附著抑制性、清潔性、調配性及低溫保存穩定性之進一步提高之觀點而言,較佳為15質量%以上,更佳為20質量%以上,更佳為25質量%以上,且就水垢附著抑制性、調配性及低溫保存穩定性之進一步提高之觀點而言,較佳為45質量%以下,更佳為40質量%以下,更佳為35質量%以下。 Furthermore, regarding the ratio of citrate in all alkaline agents, it is resistant to acid aluminum corrosion, It is preferably 15% by mass or more, more preferably 20% by mass or more, and still more preferably 25% by mass or more, from the viewpoint of further improving the scale adhesion inhibition, cleanability, blendability, and low-temperature storage stability, and more preferably From the viewpoint of further improving the scale adhesion inhibiting property, the formulation property, and the low-temperature storage stability, it is preferably 45 mass% or less, more preferably 40 mass% or less, still more preferably 3 mass% or less.

較佳為本發明之液體清潔劑組合物含有選自於具有支鏈之碳數10以上且14以下之醇依序以嵌段型鍵結有環氧乙烷及環氧丙烷之非離子界面活性劑[以下稱為非離子界面活性劑(I)]中之1種或2種以上。 Preferably, the liquid detergent composition of the present invention contains an alcohol having a carbon number of 10 or more and 14 or less having a branched chain, and the nonionic interfacial activity of ethylene oxide and propylene oxide is bonded in a block type. One or two or more of the agents (hereinafter referred to as nonionic surfactant (I)).

於非離子界面活性劑(I)中,關於環氧乙烷之平均加成莫耳數,就清潔性之進一步提高之觀點及低泡性之觀點而言,較佳為4以上,更佳為5以上,且較佳為10以下,更佳為8以下。 In the nonionic surfactant (I), the average addition mole number of ethylene oxide is preferably 4 or more, more preferably 4 or more, from the viewpoint of further improvement in cleanability and low foaming property. 5 or more, and preferably 10 or less, more preferably 8 or less.

又,於非離子界面活性劑(I)中,關於環氧丙烷之平均加成莫耳數,就清潔性之進一步提高之觀點及低泡性之觀點而言,較佳為2以上,更佳為4以上,更佳為5以上,且較佳為10以下,更佳為9以下。 Further, in the nonionic surfactant (I), the average addition mole number of propylene oxide is preferably 2 or more, and more preferably from the viewpoint of further improvement of cleanability and low foaming property. It is 4 or more, more preferably 5 or more, and is preferably 10 or less, more preferably 9 or less.

較佳為本發明之液體清潔劑組合物含有選自如下非離子界面活性劑中之1種或2種以上作為非離子界面活性劑(I),該非離子界面活性劑係於具有支鏈之碳數10以上且14以下之醇依序以嵌段型鍵結有環氧乙烷及環氧丙烷者,且環氧乙烷之平均加成莫耳數為4以上且10以下,環氧丙烷平均加成莫耳數為2以上且10以下。 Preferably, the liquid detergent composition of the present invention contains one or more selected from the group consisting of nonionic surfactants (I), which are branched carbon. The alcohol having a number of 10 or more and 14 or less is bonded with ethylene oxide and propylene oxide in a block type, and the average addition molar number of ethylene oxide is 4 or more and 10 or less, and the average propylene oxide is propylene oxide. The addition molar number is 2 or more and 10 or less.

較佳為本發明之液體清潔劑組合物含有選自如下非離子界面活性劑中之1種或2種以上作為非離子界面活性劑(I),該非離子界面活性劑係於碳數10以上、更佳為碳數12以上,且較佳為碳數14以下之二級醇依序以嵌段型鍵結有環氧乙烷及環氧丙烷者。 It is preferable that the liquid detergent composition of the present invention contains one or more selected from the group consisting of nonionic surfactants, such as a nonionic surfactant (I), having a carbon number of 10 or more. More preferably, the secondary alcohol having a carbon number of 12 or more and preferably having a carbon number of 14 or less is bonded to ethylene oxide and propylene oxide in a block type.

較佳為本發明之液體清潔劑組合物含有選自如下非離子界面活性劑中之1種或2種以上作為非離子界面活性劑(I),該非離子界面活性劑係於碳數10以上、更佳為碳數12以上,且較佳為碳數14以下之二級 醇依序以嵌段型鍵結有環氧乙烷及環氧丙烷者,且環氧乙烷之平均加成莫耳數為4以上且10以下,環氧丙烷平均加成莫耳數為2以上且10以下。 It is preferable that the liquid detergent composition of the present invention contains one or more selected from the group consisting of nonionic surfactants, such as a nonionic surfactant (I), having a carbon number of 10 or more. More preferably, it has a carbon number of 12 or more, and preferably has a carbon number of 14 or less. The alcohol is bonded with ethylene oxide and propylene oxide in a block type, and the average addition molar number of ethylene oxide is 4 or more and 10 or less, and the average molar addition of propylene oxide is 2 Above and 10 or less.

本發明之液體清潔劑組合物較佳為含有下述通式(1)所表示之非離子界面活性劑作為非離子界面活性劑(I)。 The liquid detergent composition of the present invention preferably contains a nonionic surfactant represented by the following formula (1) as the nonionic surfactant (I).

R1-O-(EO)s-(PO)t-H (1) R 1 -O-(EO) s -(PO) t -H (1)

[式中,R1表示碳數10以上且14以下之支鏈烷基、或碳數10以上且14以下之支鏈烯基,又,表示碳數10~14之支鏈烷基、或碳數10~14之支鏈烯基,EO表示伸乙氧基,PO表示伸丙氧基;s、t分別表示平均加成莫耳數,s為4以上且10以下,t為2以上且10以下,t/s為0.3以上且1.5以下,又,s=4~10,t=2~10,0.3≦(t/s)≦1.5;「(EO)s」與「(PO)t」以嵌段型鍵結] In the formula, R 1 represents a branched alkyl group having 10 or more and 14 or less carbon atoms, a branched alkenyl group having 10 or more and 14 or less carbon atoms, and a branched alkyl group having 10 to 14 carbon atoms or carbon. a branched alkenyl group of 10 to 14, EO represents an ethoxy group, PO represents a propoxy group; s and t represent an average addition molar number, s is 4 or more and 10 or less, and t is 2 or more and 10 or less, t / s is 0.3 or more and 1.5 or less, and, s = 4 ~ 10, t = 2 ~ 10,0.3 ≦ (t / s) ≦ 1.5; "(EO) s 'and' (PO) t" in Block type bond]

於通式(1)中,R1較佳為具有支鏈之碳數10以上且14以下之烷基或具有支鏈之碳數10以上且14以下之烯基,更佳為具有支鏈之碳數10以上且14以下之烷基。又,關於R1,就相同之觀點而言,較佳為碳數10以上且14以下之二級烷基或碳數10以上且14以下之二級烯基,更佳為碳數10以上且14以下之二級烷基。作為二級烷基,就相同之觀點而言,較佳為下述式所表示之基。關於通式(1)中之R1,就相同之觀點而言,較佳為該式所表示之二級烷基。 In the formula (1), R 1 is preferably an alkyl group having a branched carbon number of 10 or more and 14 or less or an alkenyl group having a branched carbon number of 10 or more and 14 or less, more preferably a branched chain. An alkyl group having 10 or more carbon atoms and 14 or less carbon atoms. Further, R 1 is preferably a secondary alkyl group having 10 or more and 14 or less carbon atoms or a secondary alkenyl group having 10 or more and 14 or less carbon atoms, more preferably 10 or more carbon atoms. A secondary alkyl group of 14 or less. As the secondary alkyl group, from the same viewpoint, it is preferably a group represented by the following formula. With respect to R 1 in the formula (1), from the same viewpoint, a secondary alkyl group represented by the formula is preferred.

Figure TWI613291BD00001
Figure TWI613291BD00001

[式中,R11、R12分別為可具有支鏈之烷基或烯基,較佳為直鏈 烷基或烯基,更佳為直鏈烷基,R11、R12之碳數之合計為9以上且13以下] Wherein R 11 and R 12 are each an alkyl group or an alkenyl group which may have a branch, preferably a linear alkyl group or an alkenyl group, more preferably a linear alkyl group, and a carbon number of R 11 and R 12 The total is 9 or more and 13 or less]

於通式(1)中,s較佳為5以上且9以下,又,t為5以上且9以下。作為通式(1)之非離子界面活性劑之具體例,就獲取之容易性之觀點而言,較佳為列舉選自聚氧乙烯(7)聚氧丙烯(8.5)-第二-十二烷基醚、聚氧乙烯(7)聚氧丙烯(8.5)-第二-十三烷基醚、聚氧乙烯(7)聚氧丙烯(8.5)-第二-十四烷基醚中之1種或2種以上。此處,()內為環氧乙烷或環氧丙烷之平均加成莫耳數。 In the general formula (1), s is preferably 5 or more and 9 or less, and further, t is 5 or more and 9 or less. Specific examples of the nonionic surfactant of the formula (1) are preferably selected from the group consisting of polyoxyethylene (7) polyoxypropylene (8.5) and second to twelve from the viewpoint of easiness of acquisition. 1 of an alkyl ether, polyoxyethylene (7) polyoxypropylene (8.5)-second-tridecyl ether, polyoxyethylene (7) polyoxypropylene (8.5)-second-tetradecyl ether Kind or more than two. Here, () is the average addition mole number of ethylene oxide or propylene oxide.

於通式(1)中,較佳為t/s為0.3以上,更佳為0.7以上,更佳為0.9以上,且較佳為1.5以下,更佳為1.3以下。 In the formula (1), t/s is preferably 0.3 or more, more preferably 0.7 or more, still more preferably 0.9 or more, and is preferably 1.5 or less, more preferably 1.3 or less.

通式(1)之化合物可藉由如下方式合成,即,於對具有碳數10以上且14以下之支鏈烷基之醇、較佳為二級醇、或具有碳數10以上且14以下之支鏈烯基之醇、較佳為二級醇加成環氧乙烷之後,加成環氧丙烷。 The compound of the formula (1) can be synthesized by using an alcohol having a branched alkyl group having 10 or more and 14 or less carbon atoms, preferably a secondary alcohol, or having a carbon number of 10 or more and 14 or less. The branched alkenyl alcohol, preferably a secondary alcohol, is added to the ethylene oxide to form propylene oxide.

通式(1)之非離子界面活性劑之重量平均分子量較佳為200以上,且較佳為5,000以下,更佳為2,000以下。又,關於通式(1)之化合物之重量平均分子量,就清潔性及低泡性之觀點而言,較佳為200~5,000,更佳為200~2,000。通式(1)之化合物可自日本觸媒股份有限公司以「Softanol」之商品名獲取。 The weight average molecular weight of the nonionic surfactant of the formula (1) is preferably 200 or more, and preferably 5,000 or less, more preferably 2,000 or less. Further, the weight average molecular weight of the compound of the formula (1) is preferably from 200 to 5,000, more preferably from 200 to 2,000, from the viewpoint of cleanability and low foaming property. The compound of the formula (1) can be obtained from Nippon Shokubai Co., Ltd. under the trade name "Softanol".

關於本發明之液體清潔劑組合物中之非離子界面活性劑(I)之含量,就清潔性、低泡性及調配性之進一步提高之觀點而言,較佳為0.3質量%以上,更佳為0.4質量%以上,且較佳為0.7質量%以下,更佳為0.6質量%以下。又,根據相同之原因,非離子界面活性劑(I)於清潔劑組合物中之含量較佳為0.3~0.7質量%,更佳為0.3~0.6質量%,更佳為0.4~0.6質量%。 The content of the nonionic surfactant (I) in the liquid detergent composition of the present invention is preferably 0.3% by mass or more, more preferably from the viewpoint of further improvement of cleanability, low foaming property and blending property. It is 0.4% by mass or more, and preferably 0.7% by mass or less, more preferably 0.6% by mass or less. Further, for the same reason, the content of the nonionic surfactant (I) in the detergent composition is preferably from 0.3 to 0.7% by mass, more preferably from 0.3 to 0.6% by mass, still more preferably from 0.4 to 0.6% by mass.

本發明之液體清潔劑組合物較佳為含有選自脂肪酸或其鹽及烯 基琥珀酸或其鹽中之1種或2種以上。 The liquid detergent composition of the present invention preferably contains a selected from a fatty acid or a salt thereof and an alkene. One or more of succinic acid or a salt thereof.

關於脂肪酸之碳數,就相同之觀點而言,較佳為6以上,更佳為8以上,且較佳為12以下,更佳為10以下。又,脂肪酸之碳數較佳為6~12,更佳為8~10。 The carbon number of the fatty acid is preferably 6 or more, more preferably 8 or more, and is preferably 12 or less, and more preferably 10 or less, from the same viewpoint. Further, the carbon number of the fatty acid is preferably from 6 to 12, more preferably from 8 to 10.

關於烯基琥珀酸之碳數,就相同之觀點而言,較佳為10以上,更佳為12以上,且較佳為16以下,更佳為14以下。又,烯基琥珀酸之碳數較佳為10~16,更佳為12~14。 The carbon number of the alkenyl succinic acid is preferably 10 or more, more preferably 12 or more, and is preferably 16 or less, and more preferably 14 or less from the same viewpoint. Further, the number of carbon atoms of the alkenyl succinic acid is preferably from 10 to 16, more preferably from 12 to 14.

作為脂肪酸或烯基琥珀酸之鹽,就獲取之容易性之觀點而言,較佳為鹼金屬鹽,更佳為鈉鹽或鉀鹽,又,就水垢附著抑制性之觀點而言,更佳為鉀鹽。 The salt of a fatty acid or an alkenyl succinic acid is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt, from the viewpoint of availability, and further preferably from the viewpoint of scale adhesion inhibition. It is a potassium salt.

於含有脂肪酸或其鹽及烯基琥珀酸或其鹽之情形時,關於脂肪酸或其鹽與烯基琥珀酸或其鹽之含量之質量比,就低泡性之觀點而言,以(脂肪酸或其鹽/(烯基琥珀酸或其鹽)計,較佳為50/50以上,更佳為60/40以上,更佳為67/33以上,且較佳為99/1以下,更佳為90/10以下,更佳為80/20以下。又,脂肪酸或其鹽與烯基琥珀酸或其鹽之含量之質量比以(脂肪酸或其鹽)/(烯基琥珀酸或其鹽)計,就相同之觀點而言,較佳為50/50~99/1,更佳為50/50~90/10,更佳為67/33~80/20。 In the case of containing a fatty acid or a salt thereof and an alkenyl succinic acid or a salt thereof, the mass ratio of the fatty acid or a salt thereof to the content of the alkenyl succinic acid or a salt thereof, in terms of low foaming property, The salt/(alkenyl succinic acid or a salt thereof) is preferably 50/50 or more, more preferably 60/40 or more, still more preferably 67/33 or more, and still more preferably 99/1 or less, more preferably 90/10 or less, more preferably 80/20 or less. Further, the mass ratio of the content of the fatty acid or its salt to the alkenyl succinic acid or its salt is (yield of a fatty acid or its salt) / (alkenyl succinic acid or its salt) From the same viewpoint, it is preferably 50/50 to 99/1, more preferably 50/50 to 90/10, and even more preferably 67/33 to 80/20.

關於脂肪酸或其鹽及烯基琥珀酸或其鹽之合計含量,於清潔劑組合物中,就低溫穩定性之觀點而言,較佳為0.5質量%以上,更佳為0.75質量%以上,且較佳為5質量%以下,更佳為3質量%以下,更佳為1.5質量%以下。 The total content of the fatty acid or a salt thereof and the alkenyl succinic acid or a salt thereof is preferably 0.5% by mass or more, and more preferably 0.75% by mass or more, from the viewpoint of low-temperature stability in the detergent composition. It is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1.5% by mass or less.

又,關於脂肪酸或其鹽及烯基琥珀酸或其鹽之合計含量,就低溫穩定性之觀點而言,於清潔劑組合物中,較佳為0.5~5質量%,更佳為0.75~3質量%,更佳為0.75~1.5質量%。 Further, the total content of the fatty acid or a salt thereof and the alkenyl succinic acid or a salt thereof is preferably from 0.5 to 5% by mass, more preferably from 0.75 to 3, in terms of low-temperature stability in the detergent composition. The mass% is more preferably 0.75 to 1.5% by mass.

再者,脂肪酸或其鹽及烯基琥珀酸或其鹽之含量均為換算成酸 之值。 Further, the content of the fatty acid or its salt and the alkenyl succinic acid or its salt are converted into an acid. The value.

於本發明之液體清潔劑組合物中,可於無損本發明之目的之範圍內調配溶劑、溶解助劑、分散劑、pH值調整劑、增黏劑、黏度調整劑、香料、著色劑、抗氧化劑、防腐劑、抑泡劑、漂白劑、漂白活化劑等成分(其中,相當於(A)~(C)成分及矽酸鹽者除外)。 In the liquid detergent composition of the present invention, the solvent, the dissolution aid, the dispersant, the pH adjuster, the tackifier, the viscosity adjuster, the fragrance, the colorant, and the anti-adhesion can be formulated within the range not impairing the object of the present invention. An oxidizing agent, a preservative, a suds suppressor, a bleaching agent, a bleach activator, and the like (excluding the components (A) to (C) and bismuth citrate).

本發明之液體清潔劑組合物之剩餘成分為水。含量若無特別說明,則為相對於包含水在內之成分之總量之質量%。 The remaining component of the liquid detergent composition of the present invention is water. The content is the mass % relative to the total amount of the components including water unless otherwise specified.

本發明之液體清潔劑組合物較佳為以上述含量調配有本發明之必需成分及任意成分之組合物。 The liquid detergent composition of the present invention is preferably a composition in which the essential components of the present invention and optional components are blended in the above amounts.

<鉀離子> <potassium ion>

就水垢附著抑制性、清潔性、茶垢附著抑制性及低溫保存穩定性之觀點而言,本發明之液體清潔劑組合物含有鉀離子。 The liquid detergent composition of the present invention contains potassium ions from the viewpoints of scale adhesion inhibition, cleanability, tea scale adhesion inhibition, and low-temperature storage stability.

鉀離子係較佳地源自(A)成分之鉀鹽、(B)成分之鉀鹽、(C)成分之鉀鹽或上述矽酸鉀或上述任意成分之鹼劑之鉀鹽者。 The potassium ion is preferably derived from the potassium salt of the component (A), the potassium salt of the component (B), the potassium salt of the component (C), or the potassium salt of the potassium citrate or the alkaline agent of any of the above components.

<鈉離子> <sodium ion>

本發明之液體清潔劑組合物能以相對於鉀離子之含量[K+]之莫耳比成為特定範圍之方式含有鈉離子。即,可任意地含有鈉離子。本發明之液體清潔劑組合物可含有鉀離子及鈉離子。 The liquid detergent composition of the present invention can contain sodium ions in such a manner that the molar ratio of the potassium ion content [K + ] becomes a specific range. That is, sodium ions can be arbitrarily contained. The liquid detergent composition of the present invention may contain potassium ions and sodium ions.

鈉離子係較佳地源自(A)成分之鈉鹽、(B)成分之鈉鹽、(C)成分之鈉鹽或上述矽酸鈉或上述任意成分之鈉鹽者。 The sodium ion is preferably derived from the sodium salt of the component (A), the sodium salt of the component (B), the sodium salt of the component (C), or the sodium salt of the above sodium citrate or any of the above components.

<莫耳比[Na+]/[K+]> <Morbi [Na + ] / [K + ]>

就水垢附著抑制性、清潔性、茶垢附著抑制性、調配性及低溫保存穩定性之觀點而言,本發明之液體清潔劑組合物之鈉離子之含量[Na+]相對於鉀離子之含量[K+]之莫耳比[Na+]/[K+]為0以上且0.9以下。 The content of the sodium ion content [Na + ] relative to the potassium ion of the liquid detergent composition of the present invention from the viewpoints of scale adhesion inhibition, cleanability, tea scale adhesion inhibition, blendability, and low-temperature storage stability [K +] the molar ratio of [Na +] / [K + ] is 0 or more and 0.9 or less.

關於鈉離子之含量[Na+]相對於鉀離子之含量[K+]之莫耳比[Na+]/[K+],就水垢附著抑制性之進一步提高及調配成分之獲取之容 易性之觀點而言,較佳為0.1以上,更佳為0.2以上,更佳為0.25以上,且就水垢附著抑制性及低溫保存穩定性之進一步提高之觀點而言,較佳為0.85以下,更佳為0.70以下,更佳為0.65以下。 Regarding the molar ratio [Na + ] of the content of sodium ions [Na + ] to the content of potassium ions [K + ] [Na + ] / [K + ], the scale adhesion inhibition property is further improved and the ease of obtaining the formulation components is obtained. In view of the above, it is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.25 or more, and from the viewpoint of further improving scale adhesion inhibition property and low-temperature storage stability, it is preferably 0.85 or less, more preferably 0.70 or less, more preferably 0.65 or less.

又,關於鈉離子之含量[Na+]相對於鉀離子之含量[K+]之莫耳比[Na+]/[K+],就水垢附著抑制性、清潔性、茶垢附著抑制性、調配性及低溫保存穩定性之觀點而言,較佳為0.1~0.9,更佳為0.2~0.85,更佳為0.25~0.70,更佳為0.25~0.65。 In addition, the molar ratio [Na + ]/[K + ] of the sodium ion content [Na + ] to the potassium ion content [K + ] is in terms of scale adhesion inhibition property, cleanliness, and tea scale adhesion inhibition property, From the viewpoint of blending property and low-temperature storage stability, it is preferably 0.1 to 0.9, more preferably 0.2 to 0.85, still more preferably 0.25 to 0.70, still more preferably 0.25 to 0.65.

關於本發明之液體清潔劑組合物中之鉀離子之含量[K+],就水垢附著抑制性、清潔性、茶垢附著抑制性、調配性、低溫保存穩定性之進一步提高之觀點及調配成分之獲取之容易性之觀點而言,較佳為1mol/L以上,更佳為1.5mol/L以上,更佳為1.8mol/L以上,且較佳為3mol/L以下,更佳為2.7mol/L以下,更佳為2.4mol/L以下。 The content of the potassium ion [K + ] in the liquid detergent composition of the present invention is a viewpoint of further improvement of scale adhesion inhibition property, cleanliness, tea scale adhesion inhibition property, blending property, and low-temperature storage stability, and a blending component. From the viewpoint of easiness of obtaining, it is preferably 1 mol/L or more, more preferably 1.5 mol/L or more, still more preferably 1.8 mol/L or more, and preferably 3 mol/L or less, more preferably 2.7 mol. Below /L, it is more preferably 2.4 mol/L or less.

關於本發明之液體清潔劑組合物中之鈉離子之含量[Na+],就水垢附著抑制性、清潔性、茶垢附著抑制性、調配性、低溫保存穩定性之進一步提高之觀點及調配成分之獲取之容易性之觀點而言,較佳為0.3mol/L以上,更佳為0.4mol/L以上,更佳為0.6mol/L以上,更佳為0.9mol/L以上,更佳為1.2mol/L以上,且較佳為3mol/L以下,更佳為2mol/L以下,更佳為1.6mol/L以下,更佳為1.3mol/L以下。 The content of the sodium ion in the liquid detergent composition of the present invention [Na + ], the viewpoint of the improvement of scale adhesion inhibition property, cleanliness, tea scale adhesion inhibition property, blending property, and low-temperature storage stability, and the blending component From the viewpoint of easiness of obtaining, it is preferably 0.3 mol/L or more, more preferably 0.4 mol/L or more, still more preferably 0.6 mol/L or more, still more preferably 0.9 mol/L or more, still more preferably 1.2. The mol/L or more is preferably 3 mol/L or less, more preferably 2 mol/L or less, still more preferably 1.6 mol/L or less, still more preferably 1.3 mol/L or less.

<清潔液> <cleaning liquid>

本發明提供一種清潔液,其係將本發明之餐具清潔機用液體清潔劑組合物利用水進行稀釋而成者,且清潔液中之(A)成分之含量換算成酸為0.0017質量%以上且0.017質量%以下。用於稀釋之水可使用德國硬度(German hardness)2°dH以上、進而3°dH以上之水。 The present invention provides a cleaning liquid obtained by diluting a liquid detergent composition for a dishwashing machine of the present invention with water, and the content of the component (A) in the cleaning liquid is 0.0017 mass% or more in terms of acid. 0.017 mass% or less. Water for dilution may be water having a German hardness of 2°dH or more and further 3°dH or more.

關於本發明之清潔液,於下述清潔方法之記載中將與稀釋倍率等對應之濃度記載於下文。再者,清潔液中之鈉離子之含量[Na+]相對於鉀離子之含量[K+]之莫耳比[Na+]/[K+]與本發明之液體清潔劑組合 物同樣地為0以上且0.9以下。 In the cleaning liquid of the present invention, the concentration corresponding to the dilution ratio or the like is described below in the description of the cleaning method described below. Further, the content of sodium ions in the cleaning solution of [Na +] with respect to the content of potassium ion [K +] The molar ratio of [Na +] / [K + ] and the liquid detergent composition of the present invention in the same manner as 0 or more and 0.9 or less.

關於本發明之清潔液中之(A)成分之含量,就水垢附著抑制性及茶垢附著抑制性之進一步提高之觀點而言,換算成酸為0.0017質量%以上,更佳為0.0065質量%以上,且為0.017質量%以下,更佳為0.0072質量%以下。 The content of the component (A) in the cleaning liquid of the present invention is 0.0017 mass% or more, and more preferably 0.0065 mass% or more, from the viewpoint of further improving scale adhesion inhibition property and tea scale adhesion inhibition property. It is 0.017% by mass or less, and more preferably 0.0072% by mass or less.

關於本發明之清潔液中之(B)成分之含量,就水垢附著抑制性之進一步提高之觀點而言,換算成酸較佳為0.00125質量%以上,更佳為0.00475質量%以上,且較佳為0.0125質量%以下,更佳為0.00525質量%以下。 The content of the component (B) in the cleaning liquid of the present invention is preferably 0.001255% by mass or more, more preferably 0.00475% by mass or more, and more preferably from the viewpoint of further improving the scale adhesion inhibiting property. It is 0.0125 mass% or less, more preferably 0.00525 mass% or less.

關於本發明之清潔液中之(C)成分之含量,就清潔性及水垢附著抑制性之進一步提高之觀點而言,較佳為0.001質量%以上,更佳為0.0038質量%以上,且就茶垢附著抑制性之進一步提高觀點而言,較佳為0.011質量%以下,更佳為0.0042質量%以下。 The content of the component (C) in the cleaning liquid of the present invention is preferably 0.001% by mass or more, more preferably 0.0038% by mass or more, from the viewpoint of further improving the cleanability and the scale adhesion inhibiting property. The viewpoint of further improving the scale adhesion inhibiting property is preferably 0.011% by mass or less, and more preferably 0.0042% by mass or less.

關於本發明之清潔液中之矽酸鹽之含量,就清潔性、茶垢附著抑制性、防耐酸鋁腐蝕性及水垢附著抑制性之進一步提高之觀點而言,較佳為0.0025質量%以上,更佳為0.0095質量%以上,且較佳為0.025質量%以下,更佳為0.0105質量%以下。 The content of the phthalate in the cleaning liquid of the present invention is preferably 0.0025% by mass or more from the viewpoint of further improving the cleanability, the adhesion inhibition property, the resistance to acid-aluminum corrosion, and the scale adhesion inhibition property. More preferably, it is 0.0095% by mass or more, and is preferably 0.025% by mass or less, more preferably 0.0105% by mass or less.

關於該等清潔液,亦可含有上述成分及其他成分,較佳之態樣亦相同。又,清潔液較佳為以上述含量調配有本發明之必需成分及任意成分之組合物。 The cleaning liquid may also contain the above components and other components, and the preferred embodiment is also the same. Further, the cleaning liquid is preferably a composition in which the essential components and optional components of the present invention are blended at the above contents.

本發明可提供如下之液體清潔劑組合物之製造方法,即,將水與(A)成分、(B)成分、(C)成分、矽酸鹽進行混合,其中,(A)成分換算成酸,以總調配成分中之比率計,較佳為0.0017質量%以上,更佳為0.0065質量%以上,且較佳為0.017質量%以下,更佳為0.0072質量%以下,(B)成分換算成酸,以總調配成分中之比率計,較佳為0.00125質 量%以上,更佳為0.00475質量%以上,且較佳為0.0125質量%以下,更佳為0.00525質量%以下,(C)成分以總調配成分中之比率計,較佳為0.001質量%以上,更佳為0.0038質量%以上,且較佳為0.011質量%以下,更佳為0.0042質量%以下,矽酸鹽以總調配成分中之比率計,較佳為0.0025質量%以上,更佳為0.0095質量%以上,且較佳為0.025質量%以下,更佳為0.0105質量%以下。 The present invention can provide a method for producing a liquid detergent composition, which comprises mixing water with (A) component, (B) component, (C) component, and silicate, wherein (A) component is converted into an acid. The ratio of the total blending component is preferably 0.0017 mass% or more, more preferably 0.0065 mass% or more, and is preferably 0.017 mass% or less, more preferably 0.0072 mass% or less, and the component (B) is converted into an acid. , based on the ratio of the total blending ingredients, preferably 0.00125 The amount is more than or equal to 0.00475% by mass, more preferably 0.0125% by mass or less, still more preferably 0.00525% by mass or less, and the component (C) is preferably 0.001% by mass or more based on the total blending component. More preferably, it is 0.0038 mass% or more, and is preferably 0.011 mass% or less, more preferably 0.0042 mass% or less, and the ceric acid salt is preferably 0.0025 mass% or more, more preferably 0.0095 mass, based on the ratio of the total compounding component. % or more, and preferably 0.025% by mass or less, more preferably 0.0105% by mass or less.

於該製造方法中,作為混合之成分,亦可使用上述成分及其他成分,較佳之態樣亦相同。又,於該製造方法中,水亦可使用德國硬度2°dH以上、進而3°dH以上之水。 In the production method, as the component to be mixed, the above components and other components may be used, and preferred embodiments are also the same. Further, in the production method, water having a German hardness of 2° dH or more and further 3° dH or more may be used as the water.

<清潔方法> <Cleaning method>

本發明之液體清潔劑組合物可較佳地用於利用餐具清潔機、進而利用商業用餐具清潔機進行之清潔。本發明之清潔液較佳為由本發明之液體清潔劑組合物製備者。於利用商業用餐具清潔機進行清潔時,本發明之液體清潔劑組合物係作為與水混合之清潔液使用。此時,該組合物係藉由供給裝置以任意固定量移送至商業用餐具清潔機內部,而維持適當之清潔液之濃度。液體狀之本發明之清潔劑組合物例如係將商業用餐具清潔機專用管直接插入至填充有該組合物之塑膠等之容器中將該組合物吸上來而進行供給。其後,清潔液被供給至商業用餐具清潔機內部。 The liquid detergent composition of the present invention can be preferably used for cleaning using a tableware cleaning machine and further using a commercial tableware cleaning machine. The cleaning liquid of the present invention is preferably prepared from the liquid detergent composition of the present invention. The liquid detergent composition of the present invention is used as a cleaning liquid mixed with water when it is cleaned by a commercial tableware cleaner. At this time, the composition is transferred to the inside of the commercial dishwashing machine by the supply device in an arbitrary fixed amount while maintaining the concentration of the appropriate cleaning liquid. In the liquid detergent composition of the present invention, for example, a special tube for a commercial tableware cleaner is directly inserted into a container of plastic or the like filled with the composition, and the composition is sucked up and supplied. Thereafter, the cleaning liquid is supplied to the inside of the commercial dish cleaning machine.

本發明之清潔液通常較佳為於自動清潔機所具備之收容盒中維持為固定之濃度而製備。 The cleaning liquid of the present invention is usually preferably prepared by maintaining a fixed concentration in a storage box provided in the automatic cleaning machine.

藉由本發明,提供一種清潔方法,其使用如下清潔液藉由自動清潔機清潔餐具,該清潔液係將本發明之液體清潔劑組合物利用水以較佳為200質量倍以上,更佳為333質量倍以上,更佳為400質量倍以 上,更佳為455質量倍以上,更佳為476質量倍以上,且就水垢附著抑制性、清潔性及茶垢附著抑制性之觀點而言,較佳為2000質量倍以下,更佳為1000質量倍以下,更佳為769質量倍以下,更佳為667質量倍以下,更佳為556質量倍以下,更佳為526質量倍以下之稀釋倍率進行稀釋而成。該清潔方法可包含將本發明之液體清潔劑組合物利用水以成為上述稀釋倍率之方式進行稀釋而製備清潔液之步驟、及使用該清潔液藉由自動清潔機清潔餐具之步驟。 According to the present invention, there is provided a cleaning method for cleaning dishes by an automatic cleaning machine using a cleaning liquid which utilizes water of the liquid detergent composition of the present invention to be preferably 200 times or more, more preferably 333. More than the mass, more preferably 400 times the mass In the above, it is more preferably 455 times by mass or more, more preferably 476 times by mass or more, and is preferably 2,000 times by mass or less, more preferably 1,000 or less, from the viewpoints of scale adhesion inhibitory property, cleanability, and tea scale adhesion inhibiting property. The mass is less than 769 mass times, more preferably 667 mass times or less, more preferably 556 mass times or less, and more preferably diluted to a dilution ratio of 526 times or less. The cleaning method may include a step of preparing a cleaning liquid by diluting the liquid detergent composition of the present invention by using water to be the above-described dilution ratio, and a step of cleaning the tableware by an automatic cleaning machine using the cleaning liquid.

關於本發明之液體清潔劑組合物之使用時之清潔液中之濃度,就水垢附著抑制性、清潔性及茶垢附著抑制性之進一步提高之觀點而言,較佳為0.05質量%以上,更佳為0.10質量%以上,更佳為0.13質量%以上,更佳為0.15質量%以上,更佳為0.18質量%以上,更佳為0.19質量%以上,且較佳為0.5質量%以下,更佳為0.30質量%以下,更佳為0.25質量%以下,更佳為0.22質量%以下,更佳為0.21質量%以下。 The concentration in the cleaning liquid at the time of use of the liquid detergent composition of the present invention is preferably 0.05% by mass or more, from the viewpoint of further improving the scale adhesion inhibiting property, the cleanability, and the tea scale adhesion inhibiting property. It is preferably 0.10% by mass or more, more preferably 0.13% by mass or more, more preferably 0.15% by mass or more, still more preferably 0.18% by mass or more, still more preferably 0.19% by mass or more, and more preferably 0.5% by mass or less, more preferably It is 0.30% by mass or less, more preferably 0.25 mass% or less, still more preferably 0.22% by mass or less, still more preferably 0.21% by mass or less.

又,本發明之清潔方法中使用之清潔液中之(A)成分之含量較佳為換算成酸為0.0017質量%以上且0.017質量%以下。 In addition, the content of the component (A) in the cleaning liquid used in the cleaning method of the present invention is preferably 0.0017 mass% or more and 0.017% mass% or less in terms of acid.

又,關於清潔時間,就清潔性之進一步提高之觀點而言,較佳為10秒以上,更佳為20秒以上,更佳為30秒以上,且就作業效率性之觀點而言,較佳為3分鐘以下,更佳為2分鐘以下,更佳為1分鐘以下。 In addition, the cleaning time is preferably 10 seconds or longer, more preferably 20 seconds or longer, more preferably 30 seconds or longer, from the viewpoint of further improvement in cleanability, and is preferable from the viewpoint of work efficiency. It is 3 minutes or less, more preferably 2 minutes or less, and still more preferably 1 minute or less.

關於清潔液之清潔溫度,就生產性及清潔性之進一步提高之觀點而言,較佳為40℃以上,更佳為50℃以上,且就清潔性之觀點而言,較佳為80℃以下,更佳為70℃以下。 The cleaning temperature of the cleaning liquid is preferably 40° C. or higher, more preferably 50° C. or higher, from the viewpoint of further improvement in productivity and cleanability, and is preferably 80° C. or less from the viewpoint of cleanability. More preferably, it is 70 ° C or less.

餐具於清潔之後,通常於同一商業用餐具清潔機中快速地利用水、溫水或熱水、例如70℃以上且90℃以下之熱水洗滌5秒以上且15秒以下。 After the tableware is cleaned, it is usually quickly washed with water, warm water or hot water, for example, hot water of 70 ° C or higher and 90 ° C or lower for 5 seconds or more and 15 seconds or less in the same commercial tableware cleaning machine.

本發明之清潔劑於使用德國硬度2°dH以上或德國硬度3°dH以上 之高硬度水作為清潔液之製備及/或洗滌水之情形時亦可發揮效果。即,於本發明之清潔方法中,可將本發明之液體清潔劑組合物與德國硬度2°dH以上或德國硬度3°dH以上之水進行混合而製備清潔液。又,本發明之清潔方法可使用德國硬度2°dH以上之水進行洗滌。 The cleaning agent of the invention has a hardness of 2°dH or more or a hardness of 3°dH or more in Germany. The high hardness water can also be used as a cleaning liquid preparation and/or washing water. That is, in the cleaning method of the present invention, the liquid detergent composition of the present invention can be mixed with water having a German hardness of 2° dH or more or a German hardness of 3° dH or more to prepare a cleaning liquid. Further, the cleaning method of the present invention can be carried out using water having a German hardness of 2 ° dH or more.

商業用餐具清潔機通常使清潔液利用泵循環而反覆使用。 Commercial tableware cleaners typically use the cleaning fluid over the pump cycle.

於藉由商業用餐具清潔機清潔餐具之情形時,因由餐具引起之清潔液之帶出或洗滌水向清潔液之收容槽之轉移(carry-over)等,而隨著清潔次數變多,清潔液之收容槽中之清潔液(即用於清潔之清潔液)之濃度降低。若清潔液之濃度降低,則以將清潔液之濃度維持為適當範圍之方式,藉由自動供給裝置將適量之液體清潔劑組合物供給至清潔液之收容槽。 In the case of cleaning the tableware by the commercial tableware cleaning machine, the cleaning liquid is brought out by the tableware or the washing water is carried-over to the storage tank of the cleaning liquid, etc., and as the number of cleaning times increases, the cleaning is performed. The concentration of the cleaning liquid (ie, the cleaning liquid used for cleaning) in the liquid storage tank is lowered. When the concentration of the cleaning liquid is lowered, an appropriate amount of the liquid detergent composition is supplied to the storage tank of the cleaning liquid by the automatic supply device so that the concentration of the cleaning liquid is maintained within an appropriate range.

作為液體清潔劑組合物之自動供給裝置,並無限定,感測清潔液之濃度,接收訊號而進行控制。液體狀之本發明之組合物係使管泵驅動而供給必需量之液體清潔劑組合物。 The automatic supply device for the liquid detergent composition is not limited, and the concentration of the cleaning liquid is sensed, and the signal is received and controlled. The liquid composition of the present invention is such that the tube pump is driven to supply the necessary amount of liquid detergent composition.

該自動供給裝置可較佳地用於1天之清潔次數非常多之商業用清潔機,若使用自動供給裝置,則具有與每次清潔時以手投入相比非常節省功夫之優點,此外,若使用自動供給裝置,則具有易於在1天中(清潔中)將清潔液之濃度維持為適當濃度範圍之優點。 The automatic feeding device can be preferably used for a commercial cleaning machine with a very large number of cleaning times per day, and if an automatic feeding device is used, it has the advantage of being labor-saving compared with the hand-input for each cleaning, and further, if The use of an automatic supply device has the advantage that it is easy to maintain the concentration of the cleaning liquid within an appropriate concentration range within one day (cleaning).

作為本發明之餐具之清潔方法,可列舉如下方法(以下稱為方法1),即,其係利用具備清潔液之收容機構、及使收容於該收容機構之清潔液與餐具接觸之機構之自動清潔機清潔餐具的餐具之清潔方法,且上述清潔液係上述本發明中之任一清潔液,使與餐具接觸後之清潔液循環至上述貯存機構中,以上述貯存機構中所收容之清潔液之導電度作為指標,供給濃厚組合物,控制清潔液之濃度。 The cleaning method of the tableware of the present invention includes the following method (hereinafter referred to as the method 1), that is, the automatic use of the storage mechanism provided with the cleaning liquid and the mechanism for contacting the cleaning liquid contained in the storage mechanism with the tableware a cleaning method for cleaning a tableware of a cleaning machine, wherein the cleaning liquid is any one of the cleaning liquids of the present invention, and the cleaning liquid after contact with the tableware is circulated to the storage mechanism, and the cleaning liquid contained in the storage mechanism is The conductivity is used as an index to supply a thick composition to control the concentration of the cleaning liquid.

一般,自動清潔機、尤其是商業用之自動清潔機具備清潔液之收容機構、及使收容於該收容機構之清潔液與餐具接觸之機構。清潔 液之收容機構有時被稱為例如清潔液盒、清潔液槽等。又,使收容於收容機構之清潔液與餐具接觸之機構可包含清潔液之搬送機構(管等)及清潔液對餐具之應用機構(噴頭等)。又,使收容於該收容機構之清潔液與餐具接觸之機構可包含用以使清潔液與餐具接觸之經劃定之空間(有時稱為清潔室等)。於方法1中,較佳為以清潔液之導電度作為指標,對收容於上述貯存機構之清潔液供給本發明之液體清潔劑組合物,以維持所設定之濃度之方式控制清潔液之濃度。 Generally, an automatic cleaning machine, in particular, an automatic cleaning machine for commercial use, has a storage mechanism for a cleaning liquid, and a mechanism for bringing the cleaning liquid contained in the storage unit into contact with the tableware. clean The liquid accommodating mechanism is sometimes referred to as, for example, a cleaning liquid tank, a cleaning liquid tank, or the like. Further, the mechanism for bringing the cleaning liquid accommodated in the storage unit into contact with the dishes may include a cleaning liquid transfer mechanism (tube or the like) and an application mechanism (a head or the like) of the cleaning liquid to the dishes. Further, the mechanism for contacting the cleaning liquid contained in the storage mechanism with the dishes may include a defined space (sometimes referred to as a clean room or the like) for bringing the cleaning liquid into contact with the dishes. In the method 1, it is preferable to supply the liquid detergent composition of the present invention to the cleaning liquid contained in the storage means by using the conductivity of the cleaning liquid as an index, and to control the concentration of the cleaning liquid so as to maintain the set concentration.

藉由本發明,提供如下餐具之清潔方法,即,將本發明之餐具清潔機用液體清潔劑組合物供給至自動餐具清潔機之清潔液槽,混合上述組合物與水,於清潔液槽中製備(A)成分之含量換算成酸為0.0017質量%以上且0.017質量%以下之清潔液,使用該清潔液清潔餐具。 According to the present invention, there is provided a cleaning method for a tableware, which comprises supplying a liquid detergent composition for a dish cleaning machine of the present invention to a cleaning liquid tank of an automatic tableware cleaning machine, mixing the composition and water, and preparing the liquid in a cleaning liquid tank. The content of the component (A) is converted into a cleaning liquid having an acid content of 0.0017 mass% or more and 0.017 mass% or less, and the tableware is cleaned using the cleaning liquid.

關於上述實施形態,本發明揭示以下之餐具清潔機用液體清潔劑組合物、清潔液、餐具之清潔方法、用途。 In the above embodiment, the present invention discloses the following liquid detergent composition for a dish cleaning machine, a cleaning liquid, a cleaning method for tableware, and use.

<項1> <item 1>

一種餐具清潔機用液體清潔劑組合物,其係含有矽酸鹽者,且含有下述(A)成分、(B)成分、(C)成分及水:(A)成分:甲基甘胺酸二乙酸、麩胺酸二乙酸或其等之鹽(B)成分:檸檬酸或其鹽(C)成分:聚丙烯酸或其鹽,(A)成分之含量換算成酸為2.0質量%以上且5.0質量%以下,(B)成分之含量換算成酸為1.5質量%以上且5.4質量%以下,矽酸鹽之含量為2.5質量%以上且7.4質量%以下,且該餐具清潔機用液體清潔劑組合物含有鉀離子且任意地含有鈉離子,鈉離子之含量[Na+]相對於鉀離子之含量[K+]之莫耳比[Na+]/[K+] 為0以上且0.9以下。 A liquid detergent composition for a dishwashing machine comprising a bismuth citrate and comprising the following components (A), (B), (C) and water: (A) component: methylglycine Diacetic acid, glutamic acid diacetic acid or the like (B) component: citric acid or a salt thereof (C) component: polyacrylic acid or a salt thereof, and the content of the component (A) is 2.0% by mass or more in terms of acid. 5% by mass or less, the content of the component (B) is 1.5% by mass or more and 5.4% by mass or less, and the content of the citrate is 2.5% by mass or more and 7.4% by mass or less, and the liquid detergent combination for the dishwashing machine contains potassium ions and optionally containing sodium ions, the content of sodium ions [Na +] with respect to the content of potassium ion [K +] the molar ratio of [Na +] / [K + ] is 0 or more and 0.9 or less.

<項2> <item 2>

如<項1>記載之餐具清潔機用清潔劑組合物,其中(A)成分之換算成酸之含量相對於(B)成分之換算成酸之含量之質量比(A)/(B)為0.65以上且1.9以下。 The detergent composition for dishwashing machine according to <1>, wherein the mass ratio (A)/(B) of the component (A) to the acid content of the component (B) is 0.65 or more and 1.9 or less.

<項3> <item 3>

如<項1>或<項2>中任一項記載之餐具清潔機用液體清潔劑組合物,其中(B)成分之換算成酸之含量相對於(C)成分之含量之質量比(B)/(C)為0.5以上且2.5以下。 The liquid detergent composition for a dishwashing machine according to any one of the items 1 to 2, wherein the component (B) is converted into a mass ratio of the content of the acid to the content of the component (C) (B) ) / (C) is 0.5 or more and 2.5 or less.

<項4> <item 4>

如<項1>至<項3>中任一項記載之餐具清潔機用液體清潔劑組合物,其中(A)成分之換算成酸之含量相對於(C)成分之含量之質量比(A)/(C)為0.7以上且3.4以下。 The liquid detergent composition for a dishwashing machine according to any one of the items 1 to 3, wherein the component (A) is converted into a mass ratio of the content of the acid to the content of the component (C) (A) ) / (C) is 0.7 or more and 3.4 or less.

<項5> <item 5>

如<項1>至<項4>中任一項記載之餐具清潔機用液體清潔劑組合物,其中(A)成分之換算成酸之含量、(B)成分之換算成酸之含量及(C)成分之含量之合計為6.0質量%以上且12.0質量%以下。 The liquid detergent composition for a dishwashing machine according to any one of the items 1 to 4, wherein the component (A) is converted into an acid content, and the component (B) is converted into an acid content and ( The total content of the component C) is 6.0% by mass or more and 12.0% by mass or less.

<項6> <Item 6>

如<項1>至<項5>中任一項記載之餐具清潔機用液體清潔劑組合物,其中0.2質量%水稀釋液於25℃下之pH值為9以上。 The liquid detergent composition for a dishwashing machine according to any one of the items 1 to 5, wherein the pH of the 0.2% by mass aqueous dilution at 25 ° C is 9 or more.

<項7> <item 7>

如<項1>至<項6>中任一項記載之餐具清潔機用液體清潔劑組合物,其中鈉離子之含量[Na+]相對於鉀離子之含量[K+]之莫耳比[Na+]/[K+]較佳為0.1以上,更佳為0.2以上,更佳為0.25以上,且較佳為0.85以下,更佳為0.70以下,更佳為0.65以下。 The liquid detergent composition for a dishwashing machine according to any one of <1> to <6>, wherein a molar ratio of sodium ion content [Na + ] to potassium ion content [K + ] is [ Na + ] / [K + ] is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.25 or more, and is preferably 0.85 or less, more preferably 0.70 or less, still more preferably 0.65 or less.

<項8> <item 8>

如<項1>至<項7>中任一項記載之餐具清潔機用液體清潔劑組合物,其中(A)成分之含量換算成酸,於液體清潔劑組合物中較佳為2.6質量%以上,更佳為3.3質量%以上,更佳為3.6質量%以上,更佳為4.2質量%以上,且較佳為4.7質量%以下,更佳為4.0質量%以下,更佳為3.6質量%以下,又,(A)成分之含量換算成酸,於液體清潔劑組合物中較佳為2.6~5.0質量%,更佳為3.3~5.0質量%,更佳為3.3~4.7質量%,更佳為3.3~4.0質量%,更佳為3.3~3.6質量%。 The liquid detergent composition for a dishwashing machine according to any one of the above items, wherein the content of the component (A) is converted into an acid, and is preferably 2.6% by mass in the liquid detergent composition. More preferably, it is 3.3 mass% or more, more preferably 3.6 mass% or more, more preferably 4.2 mass% or more, and preferably 4.7 mass% or less, more preferably 4.0 mass% or less, still more preferably 3.6 mass% or less. Further, the content of the component (A) is preferably 2.6 to 5.0% by mass, more preferably 3.3 to 5.0% by mass, still more preferably 3.3 to 4.7% by mass, more preferably in the liquid detergent composition. 3.3 to 4.0% by mass, more preferably 3.3 to 3.6% by mass.

<項9> <item 9>

如<項1>至<項8>中任一項記載之餐具清潔機用液體清潔劑組合物,其中(B)成分之檸檬酸或其鹽之含量於清潔劑組合物中較佳為2.5質量%以上,更佳為3.0質量%以上,更佳為3.5質量%以上,更佳為4.5質量%以上,且較佳為5.2質量%以下,又,(B)成分之含量於液體清潔劑組合物中較佳為2.5~5.4質量%,更佳為2.5~5.2質量%,更佳為3.0~5.2質量%,更佳為3.5~5.2質量%,更佳為4.5~5.2質量%,又,(B)成分之含量為1.5~5.4質量%,較佳為1.5~5.2質量%,更佳為1.5~4.5質量%,更佳為1.5~3.5質量%。 The liquid detergent composition for a dishwashing machine according to any one of the above items, wherein the content of the citric acid or the salt thereof of the component (B) is preferably 2.5 in the detergent composition. More preferably, it is 3.0% by mass or more, more preferably 3.5% by mass or more, more preferably 4.5% by mass or more, and preferably 5.2% by mass or less, and further, the content of the component (B) is in the liquid detergent composition. The amount is preferably 2.5 to 5.4% by mass, more preferably 2.5 to 5.2% by mass, still more preferably 3.0 to 5.2% by mass, still more preferably 3.5 to 5.2% by mass, still more preferably 4.5 to 5.2% by mass, and further, (B) The content of the component is from 1.5 to 5.4% by mass, preferably from 1.5 to 5.2% by mass, more preferably from 1.5 to 4.5% by mass, still more preferably from 1.5 to 3.5% by mass.

<項10> <item 10>

如<項1>至<項9>中任一項記載之餐具清潔機用液體清潔劑組合物,其中(C)成分之聚丙烯酸或其鹽之含量於清潔劑組合物中較佳為0.8質量%以上,更佳為1.8質量%以上,更佳為2.5質量%以上,更佳為3.5質量%以上,更佳為4.5質量%以上,且較佳為5.5質量%以下,更佳為2.8質量%以下,更佳為2.2質量%以下,又,(C)成分之含量較佳為0.8~5.5質量%,更佳為1.8~5.5質量%,更佳為2.5~5.5質量%,更佳為3.5~5.5質量%,更佳為4.5~5.5質量%,又,(C)成分之含量較佳為0.8~5.5質量%,更佳為0.8~2.8質量%,更佳為1.8~2.8質量%,更佳為1.8~2.2質量%。 The liquid detergent composition for a dishwashing machine according to any one of the above-mentioned item, wherein the content of the polyacrylic acid or the salt thereof of the component (C) is preferably 0.8 mass in the detergent composition. More preferably, it is 1.8% by mass or more, more preferably 2.5% by mass or more, more preferably 3.5% by mass or more, still more preferably 4.5% by mass or more, and more preferably 5.5% by mass or less, still more preferably 2.8% by mass. More preferably, it is 2.2% by mass or less, and the content of the component (C) is preferably 0.8 to 5.5% by mass, more preferably 1.8 to 5.5% by mass, still more preferably 2.5 to 5.5% by mass, still more preferably 3.5 to 5% by mass. 5.5% by mass, more preferably 4.5 to 5.5% by mass, and the content of the component (C) is preferably 0.8 to 5.5% by mass, more preferably 0.8 to 2.8% by mass, still more preferably 1.8 to 2.8% by mass, more preferably It is 1.8 to 2.2% by mass.

<項11> <item 11>

如<項1>至<項10>中任一項記載之餐具清潔機用液體清潔劑組合物,其中(A)成分之換算成酸之含量、(B)成分之換算成酸之含量及(C)成分之含量之合計更佳為6.5質量%以上,更佳為7.0質量%以上,更佳為7.5質量%以上,且較佳為12.0質量%以下,更佳為11.5質量%以下,更佳為10質量%以下,更佳為9.5質量%以下,更佳為9質量%以下,更佳為8.5質量%以下。 The liquid detergent composition for a dishwashing machine according to any one of the items 1 to 3, wherein the component (A) is converted into an acid content, and the component (B) is converted into an acid content and ( The total content of the component C) is more preferably 6.5 mass% or more, more preferably 7.0 mass% or more, still more preferably 7.5% by mass or more, and preferably 12.0 mass% or less, more preferably 11.5% by mass or less, more preferably It is 10% by mass or less, more preferably 9.5 mass% or less, still more preferably 9% by mass or less, still more preferably 8.5 mass% or less.

<項12> <item 12>

如<項1>至<項11>中任一項記載之餐具清潔機用液體清潔劑組合物,其中矽酸鹽較佳為鹼金屬矽酸鹽,又,較佳為選自1號矽酸鹽、2號矽酸鹽、3號矽酸鹽及4號矽酸鹽中之1種或2種以上之矽酸鹽,更佳為選自1號矽酸鹽、2號矽酸鹽及3號矽酸鹽中之1種或2種以上之矽酸鹽,更佳為選自1號矽酸鹽及2號矽酸鹽中之1種或2種以上之矽酸鹽,更佳為選自1號矽酸鹽中之1種或2種以上之矽酸鹽,又,矽酸鹽較佳為選自矽酸鉀及矽酸鈉中之1種或2種以上,又,較佳為選自1號矽酸鈉及1號矽酸鉀中之1種或2種以上之鹼金屬矽酸鹽,較佳為1號矽酸鈉,又,較佳為1號矽酸鉀。 The liquid detergent composition for a dishwashing machine according to any one of the preceding claims, wherein the bismuth citrate is preferably an alkali metal ruthenate, and further preferably selected from the group consisting of citric acid No. 1 One or more of the salts of the salt, the No. 2 citrate, the No. 3 citrate and the No. 4 citrate, more preferably selected from the group consisting of No. 1 citrate, No. 2 citrate and 3 One or more of the citrates of the citrate are more preferably one or more citrates selected from the group consisting of citrate No. 1 and bismuth citrate No. 2, more preferably selected And one or more of the citrates of the citrate No. 1 and the citrate are preferably one or more selected from the group consisting of potassium citrate and sodium citrate, and more preferably One or more alkali metal silicates selected from the group consisting of sodium citrate No. 1 and potassium citrate No. 1 are preferably sodium citrate No. 1, and further preferably potassium citrate No. 1.

<項13> <item 13>

如<項1>至<項12>中任一項記載之餐具清潔機用液體清潔劑組合物,其中矽酸鹽之含量於液體清潔劑組合物中較佳為3質量%以上,更佳為4質量%以上,且較佳為7質量%以下,更佳為6質量%以下。 The liquid detergent composition for a dishwashing machine according to any one of the items of the present invention, wherein the content of the ceric acid salt is preferably 3% by mass or more, more preferably 4% by mass or more, and preferably 7% by mass or less, more preferably 6% by mass or less.

<項14> <item 14>

如<項1>至<項13>中任一項記載之餐具清潔機用液體清潔劑組合物,其中作為除矽酸鹽以外之鹼劑,含有選自鹼金屬氫氧化物及鹼金屬碳酸鹽中之1種或2種以上之鹼劑,較佳為選自氫氧化鉀、氫氧 化鈉、碳酸鉀及碳酸鈉中之1種或2種以上之鹼劑,更佳為選自氫氧化鉀及氫氧化鈉中之1種或2種以上以及選自碳酸鉀及碳酸鈉中之1種或2種以上,更佳為氫氧化鉀及碳酸鉀。 The liquid detergent composition for a dishwashing machine according to any one of the items 1 to 3, wherein the alkali agent other than the bismuth acid salt is selected from the group consisting of alkali metal hydroxides and alkali metal carbonates. One or more alkaline agents, preferably selected from the group consisting of potassium hydroxide and hydrogen hydroxide One or two or more kinds of alkali chemicals of sodium, potassium carbonate and sodium carbonate are more preferably one or more selected from the group consisting of potassium hydroxide and sodium hydroxide, and selected from potassium carbonate and sodium carbonate. One type or two or more types are more preferably potassium hydroxide and potassium carbonate.

<項15> <Item 15>

如<項14>記載之餐具清潔機用液體清潔劑組合物,其中矽酸鹽及除矽酸鹽以外之鹼劑之含量之合計於液體清潔劑組合物中較佳為10質量%以上,更佳為15質量%以上,且較佳為25質量%以下,更佳為20質量%以下。 The liquid detergent composition for a dishwashing machine according to the item [1], wherein the total content of the bismuth salt and the alkali agent other than the bismuth citrate is preferably 10% by mass or more in the liquid detergent composition. It is preferably 15% by mass or more, and more preferably 25% by mass or less, and still more preferably 20% by mass or less.

<項16> <Item 16>

如<項1>至<項15>中任一項記載之餐具清潔機用液體清潔劑組合物,其中0.2質量%水稀釋液於25℃下之pH值較佳為9以上,更佳為9.5以上,更佳為10以上,更佳為10.5以上,且較佳為12以下,更佳為11.5以下。 The liquid detergent composition for a dishwashing machine according to any one of the above-mentioned items, wherein the pH of the 0.2% by mass water dilution solution at 25 ° C is preferably 9 or more, more preferably 9.5. The above is more preferably 10 or more, still more preferably 10.5 or more, and is preferably 12 or less, more preferably 11.5 or less.

<項17> <item 17>

如<項1>至<項16>中任一項記載之餐具清潔機用液體清潔劑組合物,其含有選自於具有支鏈之碳數10以上且14以下之醇依序以嵌段型鍵結有環氧乙烷及環氧丙烷的非離子界面活性劑[以下稱為非離子界面活性劑(I)]中之1種或2種以上。 The liquid detergent composition for a dishwashing machine according to any one of the above-mentioned items, wherein the alcohol-containing detergent composition having a branched carbon number of 10 or more and 14 or less has a block type. One or two or more kinds of nonionic surfactants (hereinafter referred to as nonionic surfactants (I)) of ethylene oxide and propylene oxide are bonded to each other.

<項18> <Item 18>

如<項17>記載之餐具清潔機用液體清潔劑組合物,其中非離子界面活性劑(I)之環氧乙烷之平均加成莫耳數較佳為4以上,更佳為4.5以上,更佳為5以上,且較佳為10以下,更佳為9以下,更佳為8以下。 The liquid detergent composition for a dishwashing machine according to <17>, wherein the average addition molar number of the ethylene oxide of the nonionic surfactant (I) is preferably 4 or more, more preferably 4.5 or more. More preferably, it is 5 or more, and is preferably 10 or less, more preferably 9 or less, still more preferably 8 or less.

<項19> <Item 19>

如<項17>或<項18>中任一項記載之餐具清潔機用液體清潔劑組合物,其中非離子界面活性劑(I)之環氧丙烷之平均加成莫耳數較 佳為2以上,更佳為3以上,更佳為4以上,更佳為5以上,且較佳為10以下,更佳為9.5以下,更佳為9以下。 The liquid detergent composition for a dishwashing machine according to any one of the items <1>, wherein the average addition mole number of the propylene oxide of the nonionic surfactant (I) is It is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, still more preferably 5 or more, and more preferably 10 or less, more preferably 9.5 or less, still more preferably 9 or less.

<項20> <item 20>

如<項17>至<項19>中任一項記載之餐具清潔機用液體清潔劑組合物,其中非離子界面活性劑(I)之含量於液體清潔劑組合物中較佳為0.3質量%以上,更佳為0.4質量%以上,且較佳為0.7質量%以下,更佳為0.6質量%以下,又,非離子界面活性劑之含量於液體清潔劑組合物中較佳為0.3~0.7質量%,更佳為0.3~0.6質量%,更佳為0.4~0.6質量%。 The liquid detergent composition for a dishwashing machine according to any one of the items of the present invention, wherein the content of the nonionic surfactant (I) is preferably 0.3% by mass in the liquid detergent composition. More preferably, it is 0.4% by mass or more, and preferably 0.7% by mass or less, more preferably 0.6% by mass or less, and further, the content of the nonionic surfactant is preferably 0.3 to 0.7 by mass in the liquid detergent composition. % is more preferably 0.3 to 0.6% by mass, still more preferably 0.4 to 0.6% by mass.

<項21> <Item 21>

如<項1>至<項20>中任一項記載之餐具清潔機用液體清潔劑組合物,其含有選自脂肪酸或其鹽及烯基琥珀酸或其鹽中之1種或2種以上。 The liquid detergent composition for a dishwashing machine according to any one of the above-mentioned item, which contains one or more selected from the group consisting of a fatty acid or a salt thereof and an alkenyl succinic acid or a salt thereof. .

<項22> <Item 22>

如<項21>記載之餐具清潔機用液體清潔劑組合物,其中脂肪酸之碳數較佳為6以上,更佳為8以上,且較佳為12以下,更佳為10以下,又,脂肪酸之碳數較佳為6~12,更佳為8~10。 The liquid detergent composition for a dishwashing machine according to the invention, wherein the carbon number of the fatty acid is preferably 6 or more, more preferably 8 or more, and is preferably 12 or less, more preferably 10 or less, and further, fatty acid. The carbon number is preferably from 6 to 12, more preferably from 8 to 10.

<項23> <item 23>

如<項21>或<項22>記載之餐具清潔機用液體清潔劑組合物,其中烯基琥珀酸之碳數較佳為10以上,更佳為12以上,且較佳為16以下,更佳為14以下,又,烯基琥珀酸之碳數較佳為10~16,更佳為12~14。 The liquid detergent composition for a dishwashing machine according to the invention, wherein the alkenyl succinic acid has a carbon number of preferably 10 or more, more preferably 12 or more, and preferably 16 or less. Preferably, the number of carbon atoms of the alkenyl succinic acid is from 10 to 16, more preferably from 12 to 14.

<項24> <item 24>

如<項21>至<項23>中任一項記載之餐具清潔機用液體清潔劑組合物,其含有脂肪酸或其鹽及烯基琥珀酸或其鹽,且脂肪酸或其鹽及烯基琥珀酸或其鹽之含量之質量比換算成酸,以(脂肪酸或其 鹽)/(烯基琥珀酸或其鹽)計較佳為50/50以上,更佳為60/40以上,更佳為67/33以上,且較佳為99/1以下,更佳為90/10以下,更佳為86/14以下,更佳為80/20以下,又,含有脂肪酸或其鹽及烯基琥珀酸或其鹽,且脂肪酸或其鹽與烯基琥珀酸或其鹽之含量之質量比以(脂肪酸或其鹽)/(烯基琥珀酸或其鹽)計,較佳為50/50~99/1,更佳為50/50~90/10,更佳為60/40~86/14,更佳為67/33~80/20。 A liquid detergent composition for a dishwashing machine according to any one of the above-mentioned items, comprising a fatty acid or a salt thereof, an alkenyl succinic acid or a salt thereof, and a fatty acid or a salt thereof and an alkenyl amber The mass ratio of the content of the acid or its salt is converted into an acid to (fatty acid or The salt) / (alkenyl succinic acid or a salt thereof) is preferably 50/50 or more, more preferably 60/40 or more, still more preferably 67/33 or more, and further preferably 99/1 or less, more preferably 90/. 10 or less, more preferably 86/14 or less, more preferably 80/20 or less, further containing a fatty acid or a salt thereof and an alkenyl succinic acid or a salt thereof, and a fatty acid or a salt thereof and an alkenyl succinic acid or a salt thereof The mass ratio is preferably 50/50 to 99/1, more preferably 50/50 to 90/10, still more preferably 60/40, based on (fatty acid or a salt thereof) / (alkenyl succinic acid or a salt thereof). ~86/14, more preferably 67/33~80/20.

<項25> <Item 25>

如<項21>至<項24>中任一項記載之餐具清潔機用液體清潔劑組合物,其中脂肪酸或其鹽及烯基琥珀酸或其鹽之合計含量換算成酸,較佳為0.5質量%以上,更佳為0.75質量%以上,且較佳為5質量%以下,更佳為3質量%以下,更佳為1.5質量%以下,又,脂肪酸或其鹽及烯基琥珀酸或其鹽之合計含量換算成酸,較佳為0.5~5質量%,更佳為0.75~3質量%,更佳為0.75~1.5質量%。 The liquid detergent composition for a dishwashing machine according to any one of the above-mentioned items, wherein the total content of the fatty acid or a salt thereof and the alkenyl succinic acid or a salt thereof is converted into an acid, preferably 0.5. More preferably, the mass is at least 0.75% by mass, more preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1.5% by mass or less, and further, a fatty acid or a salt thereof and an alkenyl succinic acid or the same The total content of the salt is converted into an acid, preferably 0.5 to 5% by mass, more preferably 0.75 to 3% by mass, still more preferably 0.75 to 1.5% by mass.

<項26> <Item 26>

一種清潔液,其係將如<項1>至<項25>中任一項記載之餐具清潔機用液體清潔劑組合物利用水進行稀釋而成者,且清潔液中之(A)成分之含量換算成酸為0.0017質量%以上且0.017質量%以下。 A liquid detergent composition for a dishwashing machine according to any one of <1> to <25> which is diluted with water, and the component (A) in the cleaning liquid The content is converted into an acid of 0.0017% by mass or more and 0.017% by mass or less.

<項27> <item 27>

如<項26>記載之清潔液,其中清潔液中之(A)成分之含量換算成酸,較佳為0.0034質量%以上,更佳為0.0040質量%以上,更佳為0.0044質量%以上,更佳為0.0051質量%以上,更佳為0.0061質量%以上,更佳為0.0065質量%以上,且較佳為0.010質量%以下,更佳為0.0094質量%以下,更佳為0.0085質量%以下,更佳為0.0075質量%以下,更佳為0.0072質量%以下。 In the cleaning liquid according to the above item, the content of the component (A) in the cleaning liquid is preferably 0.0034% by mass or more, more preferably 0.0040% by mass or more, even more preferably 0.0044% by mass or more, more preferably converted to an acid. It is preferably 0.0051% by mass or more, more preferably 0.0061% by mass or more, still more preferably 0.0065% by mass or more, and more preferably 0.010% by mass or less, still more preferably 0.009% by mass or less, still more preferably 0.0085% by mass or less, more preferably It is 0.0075 mass% or less, more preferably 0.0072 mass% or less.

<項28> <Item 28>

如<項26>或<項27>中任一項記載之清潔液,其中清潔液中 之(B)成分之含量換算成酸,較佳為0.00125質量%以上,更佳為0.0025質量%以上,更佳為0.0030質量%以上,更佳為0.00325質量%以上,更佳為0.00375質量%以上,更佳為0.0045質量%以上,更佳為0.00475質量%以上,且較佳為0.0125質量%以下,更佳為0.011質量%以下,更佳為0.010質量%以下,更佳為0.009質量%以下,更佳為0.0075質量%以下,更佳為0.0070質量%以下,更佳為0.00625質量%以下,更佳為0.0060質量%以下,更佳為0.0055質量%以下,更佳為0.00525質量%以下。 The cleaning liquid according to any one of <26> or <27>, wherein the cleaning liquid is in the cleaning liquid The content of the component (B) is preferably 0.001255% by mass or more, more preferably 0.0025% by mass or more, even more preferably 0.0030% by mass or more, even more preferably 0.00325% by mass or more, and still more preferably 0.00375% by mass or more. More preferably, it is 0.0045 mass% or more, more preferably 0.00475 mass% or more, and is preferably 0.0125 mass% or less, more preferably 0.011 mass% or less, still more preferably 0.010 mass% or less, still more preferably 0.009 mass% or less. More preferably, it is 0.0075 mass% or less, more preferably 0.0070 mass% or less, still more preferably 0.00625 mass% or less, still more preferably 0.0060 mass% or less, still more preferably 0.0055 mass% or less, still more preferably 0.00525 mass% or less.

<項29> <Item 29>

如<項26>至<項28>中任一項記載之清潔液,其中清潔液中之(C)成分之含量較佳為0.001質量%以上,更佳為0.0016質量%以上,更佳為0.0020質量%以上,更佳為0.0026質量%以上,更佳為0.0030質量%以上,更佳為0.0036質量%以上,更佳為0.0038質量%以上,且較佳為0.011質量%以下,更佳為0.010質量%以下,更佳為0.009質量%以下,更佳為0.007質量%以下,更佳為0.005質量%以下,更佳為0.0044質量%以下,更佳為0.0042質量%以下。 The cleaning liquid according to any one of the above-mentioned items, wherein the content of the component (C) in the cleaning liquid is preferably 0.001% by mass or more, more preferably 0.0016% by mass or more, and still more preferably 0.0020%. The mass% or more is more preferably 0.0026% by mass or more, more preferably 0.0030% by mass or more, still more preferably 0.0036% by mass or more, still more preferably 0.0038% by mass or more, and still more preferably 0.011% by mass or less, still more preferably 0.010% by mass. % or less is more preferably 0.009% by mass or less, still more preferably 0.007% by mass or less, still more preferably 0.005% by mass or less, still more preferably 0.0044% by mass or less, still more preferably 0.0042% by mass or less.

<項30> <item 30>

如<項26>至<項29>中任一項記載之清潔液,其中清潔液中之矽酸鹽之含量較佳為0.0025質量%以上,更佳為0.005質量%以上,更佳為0.006質量%以上,更佳為0.0065質量%以上,更佳為0.0075質量%以上,更佳為0.0080質量%以上,更佳為0.009質量%以上,更佳為0.0095質量%以上,且較佳為0.025質量%以下,更佳為0.015質量%以下,更佳為0.014質量%以下,更佳為0.0125質量%以下,更佳為0.012質量%以下,更佳為0.0110質量%以下,更佳為0.0105質量%以下。 The cleaning liquid according to any one of the above-mentioned items, wherein the content of the ceric acid salt in the cleaning liquid is preferably 0.0025 mass% or more, more preferably 0.005 mass% or more, still more preferably 0.006 mass. More preferably, it is 0.0065 mass% or more, more preferably 0.0075 mass% or more, more preferably 0.0080 mass% or more, still more preferably 0.009 mass% or more, more preferably 0.0095% by mass or more, and preferably 0.025% by mass. The amount is more preferably 0.015% by mass or less, more preferably 0.014% by mass or less, still more preferably 0.0125% by mass or less, still more preferably 0.012% by mass or less, still more preferably 0.0110% by mass or less, still more preferably 0.0105% by mass or less.

<項31> <item 31>

一種清潔液,其係將如<項1>至<項25>中任一項記載之餐具清潔機用液體清潔劑組合物利用水以較佳為200質量倍以上、更佳為333質量倍以上、更佳為400質量倍以上、更佳為455質量倍以上、更佳為476質量倍以上、且較佳為2000質量倍以下、更佳為1000質量倍以下、更佳為769質量倍以下、更佳為667質量倍以下、更佳為556質量倍以下、更佳為526質量倍以下之稀釋倍率進行稀釋而成。 A liquid detergent composition for a dishwashing machine according to any one of the items 1 to 2, which is preferably 200 mass times or more, more preferably 333 mass times or more. More preferably, it is 400 mass times or more, more preferably 455 mass times or more, more preferably 476 mass times or more, and more preferably 2,000 mass times or less, more preferably 1000 mass times or less, and even more preferably 769 mass times or less. More preferably, it is diluted by 667 mass times or less, more preferably 556 mass times or less, more preferably 526 mass times or less.

<項32> <item 32>

一種餐具之清潔方法,其係將如<項1>至<項25>中任一項記載之餐具清潔機用液體清潔劑組合物供給至自動餐具清潔機之清潔液槽,混合上述組合物與水,於清潔液槽中製備(A)成分之含量為0.0017質量%以上且0.017質量%以下之清潔液,並使用該清潔液清潔餐具。 A cleaning method for a tableware according to any one of the items 1 to 2, wherein the liquid detergent composition for a dishwashing machine is supplied to a cleaning liquid tank of an automatic tableware cleaning machine, and the composition is mixed with Water is used to prepare a cleaning liquid having a content of the component (A) of 0.0017 mass% or more and 0.017 mass% or less in a cleaning liquid tank, and the tableware is cleaned using the cleaning liquid.

<項33> <Item 33>

如<項32>記載之餐具之清潔方法,其中清潔液中之(A)成分之含量換算成酸,較佳為0.0034質量%以上,更佳為0.0040質量%以上,更佳為0.0044質量%以上,更佳為0.0051質量%以上,更佳為0.0061質量%以上,更佳為0.0065質量%以上,且較佳為0.010質量%以下,更佳為0.0094質量%以下,更佳為0.0085質量%以下,更佳為0.0075質量%以下,更佳為0.0072質量%以下。 The cleaning method of the tableware according to the item [32], wherein the content of the component (A) in the cleaning liquid is preferably 0.0034% by mass or more, more preferably 0.0040% by mass or more, and still more preferably 0.0044% by mass or more. More preferably, it is 0.0051% by mass or more, more preferably 0.0061% by mass or more, still more preferably 0.0065% by mass or more, and more preferably 0.010% by mass or less, still more preferably 0.009% by mass or less, still more preferably 0.0085% by mass or less. More preferably, it is 0.0075 mass% or less, more preferably 0.0072 mass% or less.

<項34> <item 34>

如<項32>或<項33>中任一項記載之餐具之清潔方法,其中清潔液中之(B)成分之含量換算成酸,較佳為0.00125質量%以上,更佳為0.0025質量%以上,更佳為0.0030質量%以上,更佳為0.00325質量%以上,更佳為0.00375質量%以上,更佳為0.0045質量%以上,更佳為0.00475質量%以上,且較佳為0.0125質量%以下,更佳為0.011質量%以下,更佳為0.010質量%以下,更佳為0.009質量%以下,更佳為 0.0075質量%以下,更佳為0.0070質量%以下,更佳為0.00625質量%以下,更佳為0.0060質量%以下,更佳為0.0055質量%以下,更佳為0.00525質量%以下。 The method for cleaning a tableware according to any one of the above items, wherein the content of the component (B) in the cleaning liquid is converted into an acid, preferably 0.00125 mass% or more, more preferably 0.0025 mass%. The above is more preferably 0.0030% by mass or more, more preferably 0.00325% by mass or more, still more preferably 0.00375% by mass or more, still more preferably 0.0045% by mass or more, still more preferably 0.00475% by mass or more, and still more preferably 0.0125% by mass or less. More preferably, it is 0.011 mass% or less, more preferably 0.010 mass% or less, still more preferably 0.009 mass% or less, more preferably 0.0075 mass% or less, more preferably 0.0070 mass% or less, more preferably 0.00625 mass% or less, still more preferably 0.0060 mass% or less, still more preferably 0.0055 mass% or less, still more preferably 0.00525 mass% or less.

<項35> <Item 35>

如<項32>至<項34>中任一項記載之餐具之清潔方法,其中清潔液中之(C)成分之含量較佳為0.001質量%以上,更佳為0.0016質量%以上,更佳為0.0020質量%以上,更佳為0.0026質量%以上,更佳為0.0030質量%以上,更佳為0.0036質量%以上,更佳為0.0038質量%以上,且較佳為0.011質量%以下,更佳為0.010質量%以下,更佳為0.009質量%以下,更佳為0.007質量%以下,更佳為0.005質量%以下,更佳為0.0044質量%以下,更佳為0.0042質量%以下。 The method for cleaning a tableware according to any one of the above-mentioned items, wherein the content of the component (C) in the cleaning liquid is preferably 0.001% by mass or more, more preferably 0.0016% by mass or more, more preferably It is 0.0020% by mass or more, more preferably 0.0026% by mass or more, more preferably 0.0030% by mass or more, still more preferably 0.0036% by mass or more, still more preferably 0.0038% by mass or more, and further preferably 0.011% by mass or less, more preferably It is 0.010% by mass or less, more preferably 0.009% by mass or less, more preferably 0.007% by mass or less, still more preferably 0.005% by mass or less, still more preferably 0.0044% by mass or less, still more preferably 0.0042% by mass or less.

<項36> <Item 36>

如<項32>至<項35>中任一項記載之餐具之清潔方法,其中清潔液中之矽酸鹽之含量較佳為0.0025質量%以上,更佳為0.005質量%以上,更佳為0.006質量%以上,更佳為0.0065質量%以上,更佳為0.0075質量%以上,更佳為0.0080質量%以上,更佳為0.009質量%以上,更佳為0.0095質量%以上,且較佳為0.025質量%以下,更佳為0.015質量%以下,更佳為0.014質量%以下,更佳為0.0125質量%以下,更佳為0.012質量%以下,更佳為0.0110質量%以下,更佳為0.0105質量%以下。 The method for cleaning a tableware according to any one of the items of the present invention, wherein the content of the citrate in the cleaning liquid is preferably 0.0025 mass% or more, more preferably 0.005 mass% or more, more preferably 0.006 mass% or more, more preferably 0.0065 mass% or more, more preferably 0.0075 mass% or more, still more preferably 0.0080 mass% or more, still more preferably 0.009 mass% or more, more preferably 0.0095% by mass or more, and preferably 0.025 mass%. The mass % or less is more preferably 0.015% by mass or less, more preferably 0.014% by mass or less, still more preferably 0.0125% by mass or less, still more preferably 0.012% by mass or less, still more preferably 0.0110% by mass or less, still more preferably 0.0105% by mass. the following.

<項37> <item 37>

一種餐具之清潔方法,其係將如<項1>至<項25>中任一項記載之餐具清潔機用液體清潔劑組合物供給至自動餐具清潔機之清潔液槽,混合上述組合物與水,以較佳為200質量倍以上、更佳為333質量倍以上、更佳為400質量倍以上、更佳為455質量倍以上、更佳為476質量倍以上、且較佳為2000質量倍以下、更佳為1000質量倍以下、更 佳為769質量倍以下、更佳為667質量倍以下、更佳為556質量倍以下、更佳為526質量倍以下之稀釋倍率於清潔液槽中製備清潔液,並使用該清潔液清潔餐具。 A cleaning method for a tableware according to any one of the items 1 to 2, wherein the liquid detergent composition for a dishwashing machine is supplied to a cleaning liquid tank of an automatic tableware cleaning machine, and the composition is mixed with The water is preferably 200 mass times or more, more preferably 333 mass times or more, more preferably 400 mass times or more, still more preferably 455 mass times or more, more preferably 476 mass times or more, and more preferably 2000 mass times. The following, more preferably 1000 mass times or less, more Preferably, the cleaning liquid is prepared in the cleaning liquid tank at a dilution ratio of 769 mass times or less, more preferably 667 mass times or less, more preferably 556 mass times or less, more preferably 526 mass times or less, and the tableware is cleaned using the cleaning liquid.

<項38> <item 38>

如<項32>至<項37>中任一項記載之餐具之清潔方法,其中將上述組合物與德國硬度2°dH以上或德國硬度3°dH以上或德國硬度4°dH以上之水進行混合。 The method for cleaning a tableware according to any one of the above items, wherein the composition is made of water having a hardness of 2°dH or more or a German hardness of 3°dH or more and a German hardness of 4°dH or more. mixing.

<項39> <item 39>

一種如<項1>至<項25>中任一項記載之餐具清潔機用液體清潔劑組合物之用途,其係作為餐具清潔機用液體清潔劑之用途。 The use of the liquid detergent composition for a dishwashing machine according to any one of the items 1 to 2, which is used as a liquid detergent for a dishwashing machine.

實施例 Example

下述實施例係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者,並非用以限定本發明。 The following examples are illustrative of the practice of the invention. The examples are intended to be illustrative of the invention and are not intended to limit the invention.

關於表1~4中所記載之液體清潔劑組合物,利用下述方法評價水垢附著抑制性(1)、水垢附著抑制性(2)、水垢附著抑制性(3)、清潔性、茶垢附著抑制性、調配性及低溫保存穩定性,將結果示於表1~4。又,藉由JIS K 3362測定0.2質量%水稀釋水溶液於25℃下之pH值,記載於表1~4。 With respect to the liquid detergent composition described in Tables 1 to 4, the scale adhesion inhibitory property (1), the scale adhesion inhibitory property (2), the scale adhesion inhibitory property (3), the cleanability, and the tea scale adhesion were evaluated by the following methods. Inhibition, formulation, and low temperature storage stability, the results are shown in Tables 1-4. Further, the pH of the 0.2% by mass water-diluted aqueous solution at 25 ° C was measured by JIS K 3362, and is shown in Tables 1 to 4.

再者,實施例1~19、比較例1~18所示之調配組成之液體清潔劑組合物之製備方法如下所述。 Further, the preparation methods of the liquid detergent compositions of the blending compositions shown in Examples 1 to 19 and Comparative Examples 1 to 18 are as follows.

<液體清潔劑組合物之製備方法> <Preparation method of liquid detergent composition> 實施例1~15、比較例1、2、5、6、17 Examples 1 to 15, Comparative Examples 1, 2, 5, 6, and 17

以各成分之合計量成為500g之方式計算調配量。以下述順序向500mL燒杯中投入各組成。使用攪拌機(TOKYO DRIKAKIKAI公司製造,型號Z-2200)及攪拌翼(3片翼:直徑4cm)以轉數200(rpm/min)進行混合。再者,製備時之溫度係考慮由中和熱產生之放熱,於25℃至 35℃之範圍進行調整。 The blending amount was calculated in such a manner that the total amount of each component became 500 g. The compositions were placed in a 500 mL beaker in the following order. The mixture was mixed at a number of revolutions of 200 (rpm/min) using a stirrer (manufactured by TOKYO DRIKAKIKAI, model Z-2200) and a stirring blade (three blades: 4 cm in diameter). Furthermore, the temperature at the time of preparation considers the exotherm generated by the neutralization heat at 25 ° C to Adjust the range of 35 °C.

投入離子交換水、氫氧化鉀、辛酸(Lunac8-98)、烯基琥珀酸(Latemul DSK)、非離子界面活性劑(Softanol EP7085),並進行混合直至均勻溶解為止。其後,投入碳酸鉀、1號矽酸鈉、聚丙烯酸鈉(Sokalan PA25CL-FR),並進行混合直至均勻溶解為止。其後,投入MGDA(methyl glycine diacetic acid,甲基甘胺酸二乙酸)、檸檬酸,並進行混合直至均勻溶解為止,獲得液體清潔劑組合物。 Ion-exchanged water, potassium hydroxide, octanoic acid (Lunac 8-98), alkenyl succinic acid (Latemul DSK), and a nonionic surfactant (Softanol EP7085) were added and mixed until homogeneously dissolved. Thereafter, potassium carbonate, sodium citrate No. 1 and sodium polyacrylate (Sokalan PA25CL-FR) were added and mixed until homogeneously dissolved. Thereafter, MGDA (methyl glycine diacetic acid) and citric acid were added and mixed until homogeneously dissolved to obtain a liquid detergent composition.

實施例16、比較例3、4 Example 16, Comparative Example 3, 4

於相同之添加時期使用表中所記載之量之GLDA(glutamate diacetic acid,麩胺酸二乙酸)代替MGDA,除此以外,與實施例1同樣地製備液體清潔劑組合物。 A liquid detergent composition was prepared in the same manner as in Example 1 except that GLDA (glutamate diacetic acid) was used in the same manner as in the above-mentioned addition period instead of MGDA.

實施例17、18 Examples 17, 18

於相同之添加時期使用表中所記載之1號矽酸鈉或1號矽酸鉀代替1號矽酸鈉,除此以外,與實施例1同樣地製備液體清潔劑組合物。 A liquid detergent composition was prepared in the same manner as in Example 1 except that sodium citrate No. 1 or potassium citrate No. 1 described in the table was used instead of sodium citrate No. 1 in the same addition period.

實施例19 Example 19

於相同之添加時期使用表中所記載之聚丙烯酸鉀代替聚丙烯酸鈉,又,於相同之添加時期使用表中所記載之1號矽酸鉀代替1號矽酸鈉,除此以外,與實施例1同樣地製備液體清潔劑組合物。 In the same addition period, potassium polyacrylate described in the table was used instead of sodium polyacrylate, and in addition, potassium citrate No. 1 described in the table was used instead of sodium citrate No. 1 in the same addition period, and the same was carried out. Example 1 A liquid detergent composition was prepared in the same manner.

比較例7 Comparative Example 7

於相同之添加時期使用表中所記載之量之EDTA(ethylenediaminetetraacetic acid,乙二胺四乙酸)代替MGDA,除此以外,與實施例1同樣地製備液體清潔劑組合物。 A liquid detergent composition was prepared in the same manner as in Example 1 except that EDTA (ethylenediaminetetraacetic acid) was used instead of MGDA in the same manner.

比較例8 Comparative Example 8

除未調配檸檬酸以外,與實施例1同樣地製備液體清潔劑組合物。 A liquid detergent composition was prepared in the same manner as in Example 1 except that citric acid was not prepared.

比較例9 Comparative Example 9

於相同之添加時期使用蘋果酸代替檸檬酸,除此以外,與實施例1同樣地製備液體清潔劑組合物。 A liquid detergent composition was prepared in the same manner as in Example 1 except that malic acid was used instead of citric acid in the same addition period.

比較例10 Comparative Example 10

於相同之添加時期使用葡萄糖酸代替檸檬酸,除此以外,與實施例1同樣地製備液體清潔劑組合物。 A liquid detergent composition was prepared in the same manner as in Example 1 except that gluconic acid was used instead of citric acid in the same addition period.

比較例11 Comparative Example 11

於相同之添加時期使用琥珀酸代替檸檬酸,除此以外,與實施例1同樣地製備液體清潔劑組合物。 A liquid detergent composition was prepared in the same manner as in Example 1 except that succinic acid was used instead of citric acid in the same addition period.

比較例12 Comparative Example 12

於相同之添加時期使用表中所記載之量之檸檬酸三鈉代替檸檬酸,除此以外,與實施例1同樣地製備液體清潔劑組合物。 A liquid detergent composition was prepared in the same manner as in Example 1 except that trisodium citrate was used in place of citric acid in the same addition period.

比較例13、14 Comparative Examples 13, 14

於相同之添加時期使用表中所記載之量之氫氧化鉀或氫氧化鈉代替氫氧化鉀,除此以外,與實施例1同樣地製備液體清潔劑組合物。 A liquid detergent composition was prepared in the same manner as in Example 1 except that potassium hydroxide or sodium hydroxide in an amount described in the table was used instead of potassium hydroxide in the same addition period.

比較例15、16 Comparative Examples 15, 16

於相同之添加時期使用表中所記載之量之碳酸鉀或碳酸鈉代替碳酸鉀,除此以外,與實施例1同樣地製備液體清潔劑組合物。 A liquid detergent composition was prepared in the same manner as in Example 1 except that potassium carbonate or sodium carbonate in an amount described in the table was used instead of potassium carbonate in the same addition period.

比較例18 Comparative Example 18

除未使用聚丙烯酸鈉(Sokalan PA25CL-FR)以外,與實施例1同樣地製備液體清潔劑組合物。 A liquid detergent composition was prepared in the same manner as in Example 1 except that sodium polyacrylate (Sokalan PA25CL-FR) was not used.

以上,為了形成辛酸(Lunac8-98)、檸檬酸、蘋果酸、葡萄糖酸或琥珀酸之中和鹽,氫氧化鉀或氫氧化鈉係考慮AV當量而決定調配量。再者,組合物中之作為氫氧化鉀或氫氧化鈉之未中和量之剩餘部分全部設為4.8質量%。 As described above, in order to form a neutralizing salt of octanoic acid (Lunac8-98), citric acid, malic acid, gluconic acid or succinic acid, potassium hydroxide or sodium hydroxide determines the blending amount in consideration of the AV equivalent. Further, the remainder of the unneutralized amount of potassium hydroxide or sodium hydroxide in the composition was 4.8% by mass.

<水垢附著抑制性(1)> <scale adhesion inhibition (1)>

以由表之清潔劑組合物製備之清潔液裝滿一門型之商業用餐具清潔機(三洋電機SANYO DR53)之清潔液槽(38L)。將清潔溫度70℃、清潔時間40秒、洗滌溫度80℃、洗滌時間6秒之條件設為1週期(70秒)。實施500週期(約10小時)之連續運轉。以清潔液中之清潔劑組合物之濃度成為0.2質量%之方式,利用水將清潔劑組合物稀釋成500質量倍,從而製備清潔液。再者,該餐具清潔機係以於清潔中收容於清潔液槽之清潔液之各成分之濃度成為固定之方式進行控制。 The cleaning liquid prepared by the detergent composition of the watch is filled with a cleaning liquid tank (38L) of a commercial tableware cleaning machine (Sanyo Electric SANYO DR53). The conditions of the cleaning temperature of 70 ° C, the cleaning time of 40 seconds, the washing temperature of 80 ° C, and the washing time of 6 seconds were set to one cycle (70 seconds). Continuous operation of 500 cycles (about 10 hours) was carried out. The cleaning liquid was prepared by diluting the detergent composition to 500 times by mass with water so that the concentration of the detergent composition in the cleaning liquid became 0.2% by mass. Further, the dish cleaning machine is controlled such that the concentration of each component of the cleaning liquid contained in the cleaning liquid tank during cleaning is fixed.

又,於清潔液之製備及洗滌中使用之水中添加利用氯化鈣調整為10000°dH(德國硬度)之硬水,以上述餐具清潔機之運轉中之硬度成為1~7°dH之方式,以0.5°dH為單位進行調整。 Moreover, hard water adjusted to 10000 ° dH (German hardness) by using calcium chloride is added to water used for preparation and washing of the cleaning liquid, and the hardness in the operation of the above-mentioned dish cleaning machine is 1 to 7 ° dH, Adjusted in units of 0.5°dH.

使用各硬度之水,分別運轉500週期,運轉結束後,目視判定清潔室側壁及濾器中之水垢之附著程度。將抑制水垢附著之上限硬度作為耐硬度(°dH)記載於表中。耐硬度越高,水垢附著抑制之效果越高。 Each of the hardness waters was used for 500 cycles, and after the operation was completed, the degree of adhesion of the scale in the side walls of the clean room and the filter was visually determined. The upper limit hardness which inhibits the adhesion of scale is shown in the table as the hardness resistance (°dH). The higher the hardness resistance, the higher the effect of inhibiting scale adhesion.

此處,所謂抑制水垢附著係表示與運轉前相比,完全未發現變色或變質,具有與初期同等之光澤之狀態,或雖然略微地變色但未附著水垢,具有光澤之狀態。再者,若附著水垢,則光澤消失,成為表面粗糙之之狀態。 Here, the scale-inhibiting system has a state in which it has no discoloration or deterioration, and has a gloss equivalent to that in the initial stage, or a slight discoloration, but does not adhere to scale, and has a luster state. Further, when scale is adhered, the gloss disappears and the surface becomes rough.

再者,清潔液中之(A)成分之含量換算成酸如下。 Further, the content of the component (A) in the cleaning liquid is converted into an acid as follows.

實施例1、19:0.0046質量% Example 1, 19: 0.0046% by mass

實施例2:0.0060質量% Example 2: 0.0060% by mass

實施例3、6~18:0.0068質量% Example 3, 6~18: 0.0068 mass%

實施例4:0.0076質量% Example 4: 0.0076 mass%

實施例5:0.0090質量% Example 5: 0.0090% by mass

比較例1、3:0.0030質量% Comparative Example 1, 3: 0.0030% by mass

比較例2:0.0106質量% Comparative Example 2: 0.0106% by mass

比較例4:0.0104質量% Comparative Example 4: 0.0104% by mass

比較例5、6、8~18:0.0068質量% Comparative Example 5, 6, 8~18: 0.0068 mass%

比較例7:0質量% Comparative Example 7: 0% by mass

<水垢附著抑制性(2)> <scale adhesion inhibition (2)>

以清潔液中之清潔劑組合物之濃度成為0.15質量%之方式,利用水將清潔劑組合物稀釋成670質量倍,而製備清潔液,除此以外,與上述水垢附著抑制性(1)同樣地進行評價。 In the same manner as the above-described scale adhesion inhibitory property (1), the detergent composition was diluted to 670 times by mass with water to prepare a cleaning liquid, in a manner that the concentration of the detergent composition in the cleaning liquid was 0.15% by mass. Evaluation.

再者,清潔液中之(A)成分之含量換算成酸如下。 Further, the content of the component (A) in the cleaning liquid is converted into an acid as follows.

實施例1、19:0.00345質量% Example 1, 19: 0.00345% by mass

實施例2:0.0045質量% Example 2: 0.0045% by mass

實施例3、6~18:0.0051質量% Example 3, 6~18: 0.0051% by mass

實施例4:0.0057質量% Example 4: 0.0057% by mass

實施例5:0.00675質量% Example 5: 0.00675 mass%

比較例1、3:0.00225質量% Comparative Example 1, 3: 0.00225 mass%

比較例2:0.00795質量% Comparative Example 2: 0.00795 mass%

比較例4:0.0078質量% Comparative Example 4: 0.0078% by mass

比較例5、6、8~18:0.0051質量% Comparative Example 5, 6, 8~18: 0.0051% by mass

比較例7:0質量% Comparative Example 7: 0% by mass

<水垢附著抑制性(3)> <scale adhesion inhibition (3)>

以清潔液中之清潔劑組合物之濃度成為0.1質量%之方式,利用水將清潔劑組合物稀釋成1000質量倍,而製備清潔液,除此以外,與上述水垢附著抑制性(1)同樣地進行評價。 In the same manner as the above-described scale adhesion inhibitory property (1), the detergent composition was diluted to 1000 times by mass with water to prepare a cleaning liquid, and the concentration of the detergent composition in the cleaning liquid was 0.1% by mass. Evaluation.

再者,清潔液中之(A)成分之含量換算成酸如下。 Further, the content of the component (A) in the cleaning liquid is converted into an acid as follows.

實施例1、19:0.0023質量% Example 1, 19: 0.0023% by mass

實施例2:0.0030質量% Example 2: 0.0030% by mass

實施例3、6~18:0.0034質量% Example 3, 6~18: 0.0034% by mass

實施例4:0.0038質量% Example 4: 0.0038% by mass

實施例5:0.0045質量% Example 5: 0.0045% by mass

比較例1、3:0.0015質量% Comparative Example 1, 3: 0.0015% by mass

比較例2:0.0053質量% Comparative Example 2: 0.0053 mass%

比較例4:0.0052質量% Comparative Example 4: 0.0052% by mass

比較例5、6、8~18:0.0034質量% Comparative Example 5, 6, 8~18: 0.0034% by mass

比較例7:0質量% Comparative Example 7: 0% by mass

<清潔性> <cleanliness>

對具有內徑200mm且高度30mm之周壁之瓷碟,以中心部7cm半徑均勻地塗佈作為樣本污漬之由紅色色素著色之蛋黃2g。其後,進行80℃/30分鐘乾燥,準備4片用於評價之瓷碟。將其等設置於一門型之商業用餐具清潔機(三洋電機股份有限公司製造,SANYO DR53)。以由表之清潔劑組合物製備之清潔劑組合物濃度為0.15質量%之清潔液(其中,以德國硬度為4°dH之水進行稀釋)裝滿該清潔機之清潔液槽(38L)。於清潔溫度50、清潔時間40秒、洗滌溫度80℃、洗滌時間10秒之條件下進行清潔。再者,該餐具清潔機係以於清潔中收容於清潔液槽之清潔液之濃度成為固定之方式進行控制。取出已清潔之瓷碟之後,於調整為25℃±5℃之房間進行乾燥後,藉由圖像處理求出殘留於該瓷碟之中心部7cm半徑之樣本污漬之面積。將求出之殘留之樣本污漬之面積設為試驗後面積,又,將試驗前面積設為半徑7cm之圓之面積(塗佈有污漬之中心部之面積),藉由式[[(試驗前面積-試驗後面積)/(試驗前面積)]×100]求出清潔率(%)。將4片之平均值示於表1~4。 For a porcelain dish having a peripheral wall having an inner diameter of 200 mm and a height of 30 mm, 2 g of egg yolk colored by a red pigment as a sample stain was uniformly applied at a central portion of a radius of 7 cm. Thereafter, drying was carried out at 80 ° C / 30 minutes, and 4 pieces of porcelain plates for evaluation were prepared. They are placed in a door type commercial tableware cleaning machine (made by Sanyo Electric Co., Ltd., SANYO DR53). The cleaning liquid tank (38L) of the cleaning machine was filled with a cleaning liquid having a concentration of 0.15 mass% of the detergent composition prepared from the detergent composition of the table (wherein diluted with water having a German hardness of 4 ° dH). The cleaning was carried out under the conditions of a cleaning temperature of 50, a cleaning time of 40 seconds, a washing temperature of 80 ° C, and a washing time of 10 seconds. Further, the dish cleaner is controlled such that the concentration of the cleaning liquid accommodated in the cleaning liquid tank during cleaning is fixed. After the cleaned porcelain dish was taken out, it was dried in a room adjusted to 25 ° C ± 5 ° C, and the area of the sample stain remaining in the 7 cm radius of the center portion of the porcelain plate was determined by image processing. The area of the sample stain remaining after the determination is set as the area after the test, and the area before the test is set to the area of the circle having a radius of 7 cm (the area of the center portion to which the stain is applied), by the formula [[(before the test) Area - area after test / (area before test)] × 100] The cleaning rate (%) was determined. The average of the four pieces is shown in Tables 1 to 4.

再者,清潔液中之(A)成分之含量換算成酸,與上述水垢附著抑制性(2)相同。 In addition, the content of the component (A) in the cleaning liquid is converted into an acid, which is the same as the above-described scale adhesion inhibitory property (2).

<茶垢附著抑制性> <tea scale adhesion inhibition>

將液體清潔劑組合物投入至一門型之商業用餐具清潔機[三洋電機股份有限公司製造,SANYO DR53]。於清潔溫度60℃、清潔液中之清潔劑組合物濃度0.15質量%、清潔時間40秒、洗滌溫度80℃、洗滌時間10秒、及每洗滌1次之水量2L之條件下,使清潔機連續運轉50次。試驗時,以清潔液中之清潔劑組合物濃度無偏差之方式進行調整。調整後,茶垢附著抑制性之試驗中以如下方法進行。以自清潔開始至清潔結束,於清潔槽(38L)內存在樣本污漬(酪蛋白Ca鹽)之方式進行設定。 The liquid detergent composition was put into a commercial type tableware cleaning machine [manufactured by Sanyo Electric Co., Ltd., SANYO DR53]. The cleaning machine is continuously operated at a cleaning temperature of 60 ° C, a detergent composition concentration of 0.15 mass% in the cleaning liquid, a cleaning time of 40 seconds, a washing temperature of 80 ° C, a washing time of 10 seconds, and a water quantity of 2 L per washing. Run 50 times. During the test, the concentration of the detergent composition in the cleaning liquid was adjusted without deviation. After the adjustment, the tea scale adhesion inhibition test was carried out in the following manner. From the start of self-cleaning to the end of cleaning, set the sample stain (casein Ca salt) in the cleaning tank (38L).

(清潔條件) (cleaning conditions)

‧清潔溫度:60℃ ‧ Cleaning temperature: 60 ° C

‧清潔劑組合物濃度:0.15質量% ‧ detergent composition concentration: 0.15 mass%

‧清潔時間:40秒 ‧ Cleaning time: 40 seconds

‧洗滌溫度:80℃ ‧ Washing temperature: 80 ° C

‧洗滌時間:10秒 ‧ Washing time: 10 seconds

‧每洗滌1次之水量:2L ‧Water volume per wash: 2L

‧清潔水之硬度:德國硬度2°dH ‧The hardness of clean water: German hardness 2°dH

‧清潔液槽內之樣本污漬:酪蛋白Ca鹽 ‧Sample stains in the cleaning tank: Casein Ca salt

[對清潔液槽內投入樣本污漬之方法] [Method of putting sample stains into the cleaning tank]

作為酪蛋白Ca鹽之樣本,將白蛋白(來源於蛋,和光純藥工業股份有限公司製造:試劑)以清潔液槽內之白蛋白之濃度成為50ppm之方式,自清潔開始至結束連續地投入至清潔液槽內。 As a sample of the casein Ca salt, albumin (derived from Egg, Wako Pure Chemical Industries, Ltd.: reagent) was continuously supplied from the beginning to the end of the cleaning in such a manner that the concentration of albumin in the cleaning liquid tank became 50 ppm. Into the cleaning tank.

[茶垢附著抑制效果之評價方法] [Evaluation method of tea scale adhesion inhibition effect]

將焙茶之煮出物(對沸騰水1.8L加入10個焙茶袋泡茶,將10分鐘煮出者冷卻至室溫者)於4個三聚氰胺製杯(容量約150cc)中分別放入至8成。靜置10~20秒鐘後,廢棄焙茶,於上述清潔條件下進行清潔。將其重複進行50次(進行50次焙茶之投入、廢棄、清潔)。其後, 目視觀察外觀,以下述基準判定茶垢附著抑制效果。再者,利用各清潔劑組合物之清潔中,無法確認4個杯之間之狀態之差別。 The boiled tea boiled material (added to 1000 tea bags of boiling water to 10 liters of tea, and the boiled tea was cooled to room temperature for 10 minutes) was placed in 8 melamine cups (capacity: 150 cc). to make. After standing for 10 to 20 seconds, the roasted tea is discarded and cleaned under the above-mentioned cleaning conditions. This was repeated 50 times (50 times of baking, input, disposal, and cleaning). Thereafter, The appearance was visually observed, and the tea scale adhesion inhibiting effect was judged by the following criteria. Further, in the cleaning using the respective detergent compositions, the difference in state between the four cups could not be confirmed.

再者,清潔液中之(A)成分之含量換算成酸,與上述水垢附著抑制性(2)相同。 In addition, the content of the component (A) in the cleaning liquid is converted into an acid, which is the same as the above-described scale adhesion inhibitory property (2).

*茶垢附著抑制效果之評價基準 *Evaluation criteria for inhibition of tea scale adhesion

5:4個三聚氰胺製杯均未附著茶垢。 5: None of the 4 melamine cups were attached to the tea scale.

4:4個三聚氰胺製杯均略微地附著有茶垢。(較評價5可確認到略微之附著) 4: 4 melamine cups are slightly attached to the tea scale. (Compared with evaluation 5, it can be confirmed that it is slightly attached)

3:4個三聚氰胺製杯均發現茶色之部分附著。 3: Four cups of melamine were found to be partially attached to the brown color.

2:4個三聚氰胺製杯均發現茶垢附著。(可確認到附著多於評價3,且附著少於評價1) 2: Four melamine cups were found to adhere to the tea scale. (It can be confirmed that the adhesion is more than the evaluation 3, and the adhesion is less than the evaluation 1)

1:4個三聚氰胺製杯均發現較濃之茶垢之附著。 1:4 melamine cups were found to adhere to the thicker tea scale.

<調配性> <Materiality>

於利用上述之方法製備液體清潔劑組合物時,確認自剛將作為最終原料之MGDA、GLDA、EDTA、檸檬酸、或檸檬酸三鈉進行混合後至均勻溶解為止之時間,以如下基準評價。 When the liquid detergent composition was prepared by the above method, it was confirmed that the time until the MGDA, GLDA, EDTA, citric acid, or trisodium citrate as the final raw material was mixed until it was uniformly dissolved was evaluated on the following basis.

*調配性之評價基準 *Assessment benchmark for blending

5:最終原料混合後,於未達2分鐘時溶解。 5: After the final raw materials were mixed, they dissolved after less than 2 minutes.

4:最終原料混合後,於2分鐘以上且未達5分鐘時溶解。 4: After the final raw materials are mixed, they are dissolved in 2 minutes or more and less than 5 minutes.

3:最終原料混合後,於5分鐘以上且未達10分鐘時溶解。 3: After the final raw materials were mixed, they dissolved after 5 minutes or more and less than 10 minutes.

2:最終原料混合後,於10分鐘以上且未達20分鐘時溶解。 2: After the final raw materials were mixed, they were dissolved at 10 minutes or more and less than 20 minutes.

1:最終原料混合後,於20分鐘以上時溶解。 1: After the final raw materials are mixed, they are dissolved in 20 minutes or more.

<低溫保存穩定性> <Cryogenic storage stability>

於250ml之聚丙烯製容器中加入200ml表之液體清潔劑組合物並加以密閉,於-5℃保存10天,以下述基準評價液體之外觀狀態。 A liquid detergent composition of 200 ml of a watch was placed in a 250 ml polypropylene container and sealed, and stored at -5 ° C for 10 days, and the appearance of the liquid was evaluated on the basis of the following criteria.

(判定基準) (judgment basis)

5:均勻透明(完全未發現渾濁)。 5: Uniform and transparent (no turbidity was found at all).

4:極少地發現渾濁。 4: Very little turbidity is found.

3:略微地發現渾濁。 3: Slightly found turbid.

2:發現渾濁。 2: Found turbid.

1:發現渾濁且產生2層分離。 1: turbidity was found and two layers of separation were produced.

Figure TWI613291BD00002
Figure TWI613291BD00002
Figure TWI613291BD00003
Figure TWI613291BD00003

Figure TWI613291BD00004
Figure TWI613291BD00004
Figure TWI613291BD00005
Figure TWI613291BD00005

Figure TWI613291BD00006
Figure TWI613291BD00006
Figure TWI613291BD00007
Figure TWI613291BD00007

Figure TWI613291BD00008
Figure TWI613291BD00008
Figure TWI613291BD00009
Figure TWI613291BD00009

(註)表中之成分係以下者。再者,表中,將(A)成分之比較成分設為(A)成分,又,將(B)成分之比較成分設為(B)成分,從而方便地表示質量比。 (Note) The components in the table are the following. In the table, the comparative component of the component (A) is referred to as the component (A), and the comparative component of the component (B) is referred to as the component (B), thereby conveniently indicating the mass ratio.

<(A)成分或其比較成分> <(A) component or its comparative component>

‧MGDA:甲基甘胺酸二乙酸三鈉、「Trilon M Powder」[BASF公司製造] ‧MGDA: Trisodium methylglycine diacetate, "Trilon M Powder" [manufactured by BASF Corporation]

‧GLDA:麩胺酸二乙酸四鈉、「Dissolvine GL-PD-S」[AkzoNobel公司製造) ‧GLDA: tetrasodium glutamate diacetate, "Dissolvine GL-PD-S" [AkzoNobel)

‧EDTA:乙二胺四乙酸四鈉、「Chelest400」[Chelest股份有限公司製造] ‧EDTA: tetrasodium edetate, "Chelest400" [manufactured by Chelest Co., Ltd.]

<(B)成分或其比較成分> <(B) component or its comparative component>

‧檸檬酸:試劑(1級) ‧ Citric acid: reagent (Grade 1)

‧檸檬酸三鈉:「精製檸檬酸鈉M」(扶桑化學工業股份有限公司製造) ‧ Trisodium citrate: "Refined sodium citrate M" (manufactured by Fuso Chemical Industry Co., Ltd.)

‧蘋果酸:試劑(DL-蘋果酸)(特級) ‧ Malic acid: reagent (DL-malic acid) (special grade)

‧葡萄糖酸:試劑(50%葡萄糖酸水溶液),表中之數字表示有效成分之調配量。 ‧ Gluconic acid: Reagent (50% aqueous gluconate solution), the numbers in the table indicate the amount of active ingredient.

‧琥珀酸:試劑(特級) ‧Succinic acid: reagent (special grade)

<(C)成分> <(C) component>

‧聚丙烯酸鈉:「Sokalan PA25CL FR」[BASF JAPAN股份有限公司製造,丙烯酸均聚物之鈉鹽,重量平均分子量4,000] ‧Sodium polyacrylate: "Sokalan PA25CL FR" [manufactured by BASF JAPAN Co., Ltd., sodium salt of acrylic acid homopolymer, weight average molecular weight 4,000]

‧聚丙烯酸鉀:「Oigomer M3」[花王股份有限公司製造,丙烯酸均聚物之鉀鹽,重量平均分子量9000] ‧Polyacrylic acid potassium: "Oigomer M3" [manufactured by Kao Co., Ltd., potassium salt of acrylic acid homopolymer, weight average molecular weight 9000]

<其他成分> <Other ingredients>

‧辛酸:「Lunac8-98」[花王股份有限公司製造] ‧ bitterness: "Lunac8-98" [made by Kao Co., Ltd.]

‧烯基琥珀酸:「Latemul DSK」[花王股份有限公司製造] ‧ Alkenyl succinic acid: "Latemul DSK" [Manufactured by Kao Corporation]

‧氫氧化鉀:試劑(特級) ‧ Potassium Hydroxide: Reagent (Special)

‧氫氧化鈉:試劑(特級) ‧Sodium hydroxide: reagent (special grade)

‧碳酸鉀:試劑(特級) ‧ Potassium carbonate: reagent (special grade)

‧碳酸鈉:試劑(特級) ‧Sodium carbonate: Reagent (special grade)

‧1號矽酸鉀:日本化學工業股份有限公司製造,SiO2/K2O莫耳比=2.0~2.3[根據日本化學工業股份有限公司之說明書] ‧1 potassium citrate: manufactured by Nippon Chemical Industry Co., Ltd., SiO 2 /K 2 O molar ratio = 2.0~2.3 [according to the specifications of Nippon Chemical Industry Co., Ltd.]

‧1號矽酸鈉:日本化學工業股份有限公司製造,SiO2/Na2O莫耳比=2.0~2.3[根據日本化學工業股份有限公司之說明書] ‧1 sodium citrate: manufactured by Nippon Chemical Industry Co., Ltd., SiO 2 /Na 2 O molar ratio = 2.0~2.3 [according to the specifications of Nippon Chemical Industry Co., Ltd.]

‧非離子界面活性劑:通式(1)中之R1為碳數12~14之二級烷基,s=7.0、t=8.5之非離子界面活性劑,商品名「Softanol EP7085」(日本觸媒股份有限公司製造) ‧Nonionic surfactant: R 1 in the formula (1) is a secondary alkyl group having 12 to 14 carbon atoms, a nonionic surfactant having s=7.0 and t=8.5, and the trade name is "Softanol EP7085" (Japan) Catalyst Co., Ltd.)

由表1~表4所示之實施例與比較例之對比可知,本發明之液體清潔劑組合物不僅對含有蛋白質之污漬具有良好之清潔性及茶垢附著抑制性,調配性及低溫穩定性優異,而且具有優異之水垢附著抑制性。 From the comparison of the examples shown in Tables 1 to 4 and the comparative examples, it is understood that the liquid detergent composition of the present invention not only has good cleansing property and stain adhesion inhibition, blending property and low temperature stability for protein-containing stains. Excellent and excellent in scale adhesion inhibition.

關於實施例1~19及比較例1~18之液體清潔劑組合物,利用下述方法評價防耐酸鋁腐蝕性,結果均未觀察到損傷,具有良好之防耐酸鋁腐蝕性。 With respect to the liquid detergent compositions of Examples 1 to 19 and Comparative Examples 1 to 18, the corrosion resistance of the acid-resistant aluminum was evaluated by the following method, and as a result, no damage was observed, and the acid-resistant aluminum corrosion resistance was excellent.

<防耐酸鋁腐蝕性> <Anti-acid aluminum corrosion resistance>

於100ml玻璃製標準瓶(No.11)中,加入將液體清潔劑組合物以離子交換水稀釋成500質量倍而成之0.2質量%水稀釋清潔液30mL。於 其中將自實施了耐酸鋁加工之鋁製餐具(AIHO公司製造)切取之3cm×5cm之試驗板浸漬至長度方向之約一半,於液溫60℃保持1小時。保持後,取出試驗板,於20℃±5℃之流水中沖洗30秒鐘後,於空氣中去除水滴,於25℃±5℃進行乾燥。乾燥後,目視觀察所獲得之試驗板之外觀並評價。 To a 100 ml glass standard bottle (No. 11), 30 mL of a 0.2% by mass water-diluted cleaning liquid obtained by diluting the liquid detergent composition with ion-exchanged water to a mass of 500 times was added. to Among them, a test piece of 3 cm × 5 cm cut out from an aluminum tableware (manufactured by AIHO Co., Ltd.) which was subjected to an alumite treatment was immersed in about half of the longitudinal direction, and kept at a liquid temperature of 60 ° C for 1 hour. After the holding, the test plate was taken out, rinsed in running water at 20 ° C ± 5 ° C for 30 seconds, and the water was removed in the air and dried at 25 ° C ± 5 ° C. After drying, the appearance of the obtained test plate was visually observed and evaluated.

Claims (8)

一種餐具清潔機用液體清潔劑組合物,其係含有矽酸鹽者,且含有下述(A)成分、(B)成分、(C)成分及水:(A)成分:甲基甘胺酸二乙酸、麩胺酸二乙酸或其等之鹽(B)成分:檸檬酸或其鹽(C)成分:聚丙烯酸或其鹽,(A)成分之含量換算成酸為2.0質量%以上且5.0質量%以下,(B)成分之含量換算成酸為1.5質量%以上且5.4質量%以下,矽酸鹽之含量為2.5質量%以上且7.4質量%以下,且該餐具清潔機用液體清潔劑組合物含有鉀離子且任意地含有鈉離子,鈉離子之含量[Na+]相對於鉀離子之含量[K+]之莫耳比[Na+]/[K+]為0以上且0.9以下。 A liquid detergent composition for a dishwashing machine comprising a bismuth citrate and comprising the following components (A), (B), (C) and water: (A) component: methylglycine Diacetic acid, glutamic acid diacetic acid or the like (B) component: citric acid or a salt thereof (C) component: polyacrylic acid or a salt thereof, and the content of the component (A) is 2.0% by mass or more in terms of acid. 5% by mass or less, the content of the component (B) is 1.5% by mass or more and 5.4% by mass or less, and the content of the citrate is 2.5% by mass or more and 7.4% by mass or less, and the liquid detergent combination for the dishwashing machine contains potassium ions and optionally containing sodium ions, the content of sodium ions [Na +] with respect to the potassium content of [K +] the molar ratio of [Na +] / [K + ] is 0 or more and 0.9 or less. 如請求項1之餐具清潔機用液體清潔劑組合物,其中(A)成分之換算成酸之含量相對於(B)成分之換算成酸之含量之質量比(A)/(B)為0.65以上且1.9以下。 The liquid detergent composition for a dishwashing machine according to claim 1, wherein the mass ratio (A)/(B) of the component (A) to the acid content of the component (B) is 0.65. Above and above 1.9. 如請求項1或2之餐具清潔機用液體清潔劑組合物,其中(B)成分之換算成酸之含量相對於(C)成分之含量之質量比(B)/(C)為0.5以上且2.5以下。 The liquid detergent composition for a dishwashing machine according to claim 1 or 2, wherein the mass ratio (B)/(C) of the component (B) to the content of the component (C) is 0.5 or more and 2.5 or less. 如請求項1或2之餐具清潔機用液體清潔劑組合物,其中(A)成分之換算成酸之含量相對於(C)成分之含量之質量比(A)/(C)為0.7以上且3.4以下。 The liquid detergent composition for a dishwasher according to claim 1 or 2, wherein the mass ratio (A)/(C) of the component (A) to the content of the component (C) is 0.7 or more and 3.4 or less. 如請求項1或2之餐具清潔機用液體清潔劑組合物,其中(A)成分之換算成酸之含量、(B)成分之換算成酸之含量及(C)成分之含量之合計為6.0質量%以上且12.0質量%以下。 The liquid detergent composition for a dishwashing machine according to claim 1 or 2, wherein the total amount of the component (A) converted to the acid content, the component (B) converted to the acid content, and the (C) component is 6.0. The mass% or more and 12.0 mass% or less. 如請求項1或2之餐具清潔機用液體清潔劑組合物,其中0.2質量%水稀釋液於25℃下之pH值為9以上。 A liquid detergent composition for a dishwashing machine according to claim 1 or 2, wherein the 0.2% by mass aqueous dilution has a pH of 9 or higher at 25 °C. 一種清潔液,其係將如請求項1至6中任一項之餐具清潔機用液體清潔劑組合物利用水稀釋而成者,且清潔液中之(A)成分之含量換算成酸為0.0017質量%以上且0.017質量%以下。 A cleaning liquid obtained by diluting a liquid detergent composition for a dishwasher according to any one of claims 1 to 6 with water, and converting the content of the component (A) in the cleaning liquid into an acid of 0.0017 The mass% or more and 0.017% by mass or less. 一種餐具之清潔方法,其係將如請求項1至6中任一項之餐具清潔機用液體清潔劑組合物供給至自動餐具清潔機之清潔液槽,混合上述組合物與水,於清潔液槽中製備(A)成分之含量換算成酸為0.0017質量%以上且0.017質量%以下之清潔液,並使用該清潔液清潔餐具。 A cleaning method for a tableware, which is characterized in that the liquid detergent composition for a dishwashing machine according to any one of claims 1 to 6 is supplied to a cleaning liquid tank of an automatic tableware cleaning machine, and the composition and water are mixed with the cleaning liquid. The content of the component (A) in the tank is adjusted to a cleaning liquid having an acid content of 0.0017 mass% or more and 0.017 mass% or less, and the tableware is cleaned using the cleaning liquid.
TW103140310A 2013-11-22 2014-11-20 Liquid detergent composition for tableware cleaning machine TWI613291B (en)

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