JP2019035099A - Concentrated liquid detergent composition for automatic dishwasher and method for cleaning tableware by automatic dishwasher - Google Patents
Concentrated liquid detergent composition for automatic dishwasher and method for cleaning tableware by automatic dishwasher Download PDFInfo
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- JP2019035099A JP2019035099A JP2018221234A JP2018221234A JP2019035099A JP 2019035099 A JP2019035099 A JP 2019035099A JP 2018221234 A JP2018221234 A JP 2018221234A JP 2018221234 A JP2018221234 A JP 2018221234A JP 2019035099 A JP2019035099 A JP 2019035099A
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- Prior art keywords
- cleaning
- component
- automatic dishwasher
- acid
- mass
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- 239000007788 liquid Substances 0.000 title claims abstract description 183
- 238000004140 cleaning Methods 0.000 title claims abstract description 148
- 239000000203 mixture Substances 0.000 title claims abstract description 87
- 239000003599 detergent Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- -1 alkali metal salt Chemical class 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 40
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- 229910052783 alkali metal Inorganic materials 0.000 claims description 18
- 238000004851 dishwashing Methods 0.000 claims description 18
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- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 8
- 235000013922 glutamic acid Nutrition 0.000 claims description 8
- 239000004220 glutamic acid Substances 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims description 7
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052751 metal Inorganic materials 0.000 claims description 3
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Landscapes
- Washing And Drying Of Tableware (AREA)
- Detergent Compositions (AREA)
Abstract
Description
本発明は、自動食器洗浄機用濃縮液体洗浄剤組成物、特に業務用の自動食器洗浄機用として好適な自動食器洗浄機用濃縮液体洗浄剤組成物に関する。また本発明はこの自動食器洗浄機用濃縮液体洗浄剤組成物を用いた食器類の洗浄方法に関する。 The present invention relates to a concentrated liquid detergent composition for an automatic dishwasher, and more particularly to a concentrated liquid detergent composition for an automatic dishwasher suitable for a commercial automatic dishwasher. The present invention also relates to a dishwashing method using the concentrated liquid detergent composition for an automatic dishwasher.
近年、食器類の洗浄に自動食器洗浄機が広く利用されるようになっており、ホテル、レストラン、給食会社、病院、会社の食堂等においても、使用後の食器を効率よく洗浄するために、また近年の衛生意識の向上から業務用の自動食器洗浄機が広く用いられている。 In recent years, automatic dishwashers have been widely used to wash dishes, and in order to efficiently wash used dishes in hotels, restaurants, lunch companies, hospitals, company cafeterias, etc. Moreover, automatic dishwashers for business use are widely used for the recent hygiene awareness improvement.
自動食器洗浄機、特に業務用の自動食器洗浄機により食器類を洗浄する場合、所定濃度に調製した洗浄液を洗浄液タンク内で加熱保持し、次いで洗浄液タンク内の洗浄液をノズルから洗浄機庫内に一定量を噴射して洗浄機庫内の食器類を洗浄した後、すすぎ液を洗浄機のノズルから一定量噴射してすすぎを行い、乾燥するという工程を経て洗浄が行われる。自動食器洗浄機用の洗浄剤としては、従来、液状、粒状、粉末状、固体状のものが用いられており、液状のものはポンプ等による供給が容易であり、粉末状、粒状、固形状のものは高濃度で少容積化が可能であるという利点を有する。 When washing dishes with an automatic dishwasher, especially an automatic dishwasher for business use, the cleaning liquid prepared to a predetermined concentration is heated and held in the cleaning liquid tank, and then the cleaning liquid in the cleaning liquid tank is transferred from the nozzle into the cleaning machine cabinet. After a certain amount is jetted to wash the dishes in the washing machine cabinet, a certain amount of rinsing liquid is jetted from the nozzle of the washing machine to perform rinsing and drying. As cleaning agents for automatic dishwashers, liquid, granular, powder, and solid substances have been used in the past, and liquid substances can be easily supplied by a pump, etc., and are powdery, granular, and solid substances. Have the advantage that the volume can be reduced at a high concentration.
自動食器洗浄機用の洗浄剤として、アルカリ金属水酸化物、腐食防止剤、界面活性剤を含む洗浄剤組成物と、水及びキレート化酸を含むすすぎ溶液とからなるもの（特許文献１）、アルカリ金属水酸化物、オルソケイ酸塩、メタケイ酸ナトリウムを必須成分とするもの（特許文献２）、アルカリ剤２０〜６０重量％含むアルカリ液体洗浄剤組成物中にホスホノブタントリカルボン酸あるいはその塩を配合した高濃度アルカリ液体洗浄剤組成物（特許文献３）、グルタミン酸系、アスパラギン酸系、ポリアスパラギン酸系、イミノジコハク酸系、イミノジ酢酸系の生分解性金属イオン封鎖剤を含み、固形分濃度を６０〜７６重量％とした液体洗浄剤組成物（特許文献４）、水酸化ナトリウム及び水酸化カリウムを合計で３０〜４０重量％、ケイ酸ナトリウムを２〜８重量％、水溶性高分子キレート形成剤２〜７重量％含み、水酸化ナトリウム及び水酸化カリウムと、ケイ酸ナトリウムの合計の割合、ケイ酸ナトリウムと水溶性高分子キレート形成剤とが特定の割合となるようにした液体洗剤（特許文献５）、アルカリ剤０．５〜３０重量％、金属イオン捕捉能を有するポリアクリル酸又はマレイン酸系高分子物質０．５〜３０重量％、漂白剤０．１〜１０重量％を含有する洗浄剤（特許文献６）、ポリオキシアルキレンエーテル型非イオン界面活性剤０．１〜３重量％、その他の非イオン界面活性剤を、ポリオキシアルキレンエーテル型非イオン界面活性剤との合計量の２０重量％以下含む液体洗浄剤（特許文献７）、水酸化ナトリウム、水酸化カリウム、珪酸塩の少なくとも１種を１０〜５０質量％、３−ヒドロキシ−２，２′−イミノジコハク酸あるいはその塩を１０〜５０質量％、カルボキシル基含有水溶性ポリマーを０．５〜１０質量％含む洗浄剤（特許文献８）、ポリオキシアルキレンアルキルエーテル化合物を１〜２０質量％、アルカリ化合物２〜６０質量％含有し、ポリオキシアルキレンアルキルエーテル化合物に対するアルカリ化合物の割合を、２〜６となるようにした洗浄剤（特許文献９）が知られている。また特許文献１０には、ポリオキシアルキレンアルキルエーテル化合物用いて節水型食器洗浄機で洗浄する方法が記載されている。 As a cleaning agent for an automatic dishwasher, a cleaning agent composition containing an alkali metal hydroxide, a corrosion inhibitor and a surfactant, and a rinsing solution containing water and a chelating acid (Patent Document 1), Phosphonobutane tricarboxylic acid or a salt thereof is contained in an alkaline liquid detergent composition containing alkali metal hydroxide, orthosilicate, sodium metasilicate as an essential component (Patent Document 2), and alkali liquid detergent composition containing 20 to 60% by weight of alkali agent. Contains a blended high-concentration alkaline liquid detergent composition (Patent Document 3), glutamic acid-based, aspartic acid-based, polyaspartic acid-based, iminodisuccinic acid-based, iminodiacetic acid-based biodegradable sequestering agent, and has a solid content concentration 60 to 76% by weight of liquid detergent composition (Patent Document 4), 30 to 40% by weight in total of sodium hydroxide and potassium hydroxide, Contains 2 to 8% by weight of sodium, 2 to 7% by weight of water-soluble polymer chelate-forming agent, total proportion of sodium hydroxide and potassium hydroxide and sodium silicate, sodium silicate and water-soluble polymer chelate-forming agent And a liquid detergent (Patent Document 5) in which a specific ratio is obtained, an alkali agent of 0.5 to 30% by weight, and a polyacrylic acid or maleic acid polymer material having a metal ion scavenging ability of 0.5 to 30% by weight %, A detergent containing 0.1 to 10% by weight of bleach (Patent Document 6), a polyoxyalkylene ether type nonionic surfactant 0.1 to 3% by weight, other nonionic surfactants, At least one of a liquid detergent (Patent Document 7), sodium hydroxide, potassium hydroxide, and silicate containing 20% by weight or less of the total amount with the oxyalkylene ether type nonionic surfactant A detergent containing 0 to 50% by mass, 10 to 50% by mass of 3-hydroxy-2,2′-iminodisuccinic acid or a salt thereof, and 0.5 to 10% by mass of a carboxyl group-containing water-soluble polymer (Patent Document 8), A cleaning agent containing 1 to 20% by mass of a polyoxyalkylene alkyl ether compound and 2 to 60% by mass of an alkali compound so that the ratio of the alkali compound to the polyoxyalkylene alkyl ether compound is 2 to 6 (Patent Document 9) )It has been known. Patent Document 10 describes a method of washing with a water-saving dishwasher using a polyoxyalkylene alkyl ether compound.
特許文献１、２に記載されている洗浄剤は、固体状又は粉末状であるため水又は湯を噴射して溶解させて調製した洗浄液を洗浄液タンクに供給し、洗浄液タンク内の洗浄液濃度が低下すると固体状又は粉末状洗浄剤を水又は湯で溶解して洗浄液タンクに供給するということを繰り返す。しかしながら複数の成分を含む固体状又は粉末状の洗浄剤は、配合された各成分が必ずしも均一分布しているとは言えないため、洗浄液中の成分濃度にバラつきが生じやすいという問題があった。特許文献３、４に記載されている洗浄剤は液状であるためポンプ供給が容易であり、また各成分濃度は常に均一に保たれるが、洗浄力を高めるためにアルカリ剤を高濃度で配合しており、洗浄液タンク内で加熱保持されている間に空気中の二酸化炭素を吸収して不溶性塩が生成され、これが洗浄機庫内にスケールとして付着残存する虞があり、特に洗浄液を加熱保持している洗浄液タンク内の電熱線（ヒーター部分）でのスケールが生じやすく、アルカリ金属水酸化物やケイ酸ナトリウム等のアルカリ剤を多量に含有する特許文献５記載の洗浄剤もスケールが生じやすいという問題があった。 Since the cleaning agents described in Patent Documents 1 and 2 are solid or powdery, the cleaning liquid prepared by jetting water or hot water to dissolve is supplied to the cleaning liquid tank, and the concentration of the cleaning liquid in the cleaning liquid tank decreases. Then, the solid or powdery cleaning agent is dissolved in water or hot water and supplied to the cleaning liquid tank. However, a solid or powdery cleaning agent containing a plurality of components has a problem in that the concentration of components in the cleaning liquid tends to vary because the blended components are not necessarily uniformly distributed. Since the cleaning agents described in Patent Documents 3 and 4 are in a liquid state, pump supply is easy, and the concentration of each component is always kept uniform, but an alkaline agent is blended at a high concentration to enhance cleaning power. Insoluble salt is generated by absorbing carbon dioxide in the air while it is heated and held in the cleaning liquid tank, and there is a possibility that it will remain as a scale in the cleaning machine cabinet. A scale is easily generated on the heating wire (heater portion) in the cleaning liquid tank, and the cleaning agent described in Patent Document 5 containing a large amount of alkali agent such as alkali metal hydroxide or sodium silicate is also likely to generate scale. There was a problem.
更に特許文献６に記載の洗浄剤は、洗浄機タンク内の汚れによって塩素が失活し茶渋等の汚れ除去に十分な作用を発揮できない虞があり、スケール付着の抑制効果も十分ではなかった。また特許文献７記載の洗浄剤は繰り返し洗浄した際に食器に茶渋汚れが蓄積していくのを防止することを目的としているが、食器に茶渋汚れが付着してしまうと除去が困難であり、またスケール付着抑制効果も不十分であった。特許文献８記載の洗浄剤は、スケールの付着を抑制することを目的としているが、金属イオン封鎖性能が不十分であり、洗浄機庫内にスケールを生じやすいという問題があった。また特許文献９、１０に記載の洗浄剤は、すすぎ水の量の少ない節水型自動食器洗浄機で洗浄した場合でもウォータースポットが生じにくいことを目的としているが、洗浄剤成分を残留させるため汚れの多い条件下では食器類に曇を生じ易いという問題があった。 Furthermore, the cleaning agent described in Patent Document 6 has a possibility that chlorine is deactivated by dirt in the washing machine tank, and there is a possibility that it cannot exert a sufficient action for removing dirt such as tea astringency, and the effect of suppressing scale adhesion is not sufficient. In addition, the cleaning agent described in Patent Document 7 is intended to prevent the accumulation of tea astringent stains on the tableware when repeatedly washed, but is difficult to remove if the tea astringent stains adhere to the tableware, Moreover, the scale adhesion inhibitory effect was also inadequate. The cleaning agent described in Patent Document 8 is intended to suppress the adhesion of scale, but has a problem that the metal ion sequestering performance is insufficient and scale is likely to be generated in the cleaning machine cabinet. The detergents described in Patent Documents 9 and 10 are intended to prevent water spots even when washed with a water-saving automatic dishwasher with a small amount of rinse water. There is a problem that the tableware tends to be fogged under the conditions with a large amount of water.
自動食器洗浄機では、洗浄液タンク内の洗浄液を洗浄機庫内の食器類に噴射して洗浄した後、洗浄後の洗浄液と、洗浄工程後のすすぎ工程で用いたすすぎ水とが洗浄液タンクで混合され、汚れを含んだ所定量以上の混合液を洗浄液タンクからオーバーフローして排水し、残りの混合液（排水とともに排出された残りの汚れを含む）の洗浄成分濃度を調整して再度洗浄に使用している。自動食器洗浄機として、近年、食器類洗浄後のすすぎ工程におけるすすぎ水量を減少させた節水型自動食器洗浄機が普及しているが、すすぎ水量の少ない節水型自動食器洗浄機では、洗浄後のオーバーフロー量も少ないため、洗浄液タンク内の汚れ負荷が著しく増加する。このため食器類の再汚染や洗浄機庫内にスケールやバイオフィルムが生じやすいという問題があった。また、すすぎ水が少ないため食器類に洗浄剤が残留しやすいという問題があった。 In an automatic dishwasher, the cleaning liquid in the cleaning liquid tank is sprayed onto the dishes in the cleaning machine cabinet for cleaning, and then the cleaning liquid after cleaning and the rinse water used in the rinsing process after the cleaning process are mixed in the cleaning liquid tank. Overflowing and draining a liquid mixture containing a certain amount of dirt from the washing liquid tank, adjusting the concentration of the washing components in the remaining liquid mixture (including the remaining dirt discharged together with the wastewater) and using it again for washing doing. In recent years, water-saving automatic dishwashers that reduce the amount of rinsing water in the rinsing process after dishwashing have become widespread as automatic dishwashers. However, in water-saving automatic dishwashers that have a small amount of rinse water, Since the overflow amount is also small, the dirt load in the cleaning liquid tank is remarkably increased. For this reason, there existed a problem that scale and a biofilm were easy to produce in the recontamination of tableware and a washing machine cabinet. Moreover, since there was little rinse water, there existed a problem that a cleaning agent remained easily in tableware.
本発明は、上記従来技術の問題を解決するためになされたもので、低濃度で優れた洗浄性を有し、節水型自動食器洗浄機で洗浄した場合でも、食器類への汚れの再付着や茶渋、スケール、バイオフィルムの発生が少なく、すすぎ性に優れるため食器類に洗浄剤の残留がないコンパクトで作業性の高い自動食器洗浄機用濃縮液体洗浄剤組成物を提供することを目的とする。また本発明はこの濃縮液体洗浄剤組成物を用いた自動食器洗浄機による食器類の洗浄方法を提供することを目的とする。 The present invention has been made in order to solve the above-described problems of the prior art, and has excellent cleaning properties at a low concentration. Even when washed with a water-saving automatic dishwasher, the stain reattaches to the dishes. An object of the present invention is to provide a concentrated liquid detergent composition for an automatic dishwasher that is compact and highly workable, with little generation of detergent, tea astringency, scale, biofilm, and excellent rinsing performance, so that no detergent remains on the dishes. To do. Another object of the present invention is to provide a dishwashing method using an automatic dishwashing machine using the concentrated liquid detergent composition.
上記課題を解決するために、本発明者等は鋭意検討した結果、（Ａ）成分としてアルカリ剤、（Ｂ）成分として金属イオン封鎖剤、（Ｃ）成分としてポリカルボン酸型ポリマー又はその塩を特定の割合で含有し、（Ａ）成分と（Ｂ）成分とが特定の比率となるようにした濃縮液体洗浄剤組成物が、上記従来の課題を解決できることを見出し、本発明を完成するに至った。 In order to solve the above-mentioned problems, the present inventors have intensively studied and as a result, (A) an alkali agent as a component, (B) a sequestering agent as a component, and (C) a polycarboxylic acid type polymer or a salt thereof as a component. In order to complete the present invention, it has been found that a concentrated liquid detergent composition that is contained at a specific ratio and has a specific ratio of the component (A) and the component (B) can solve the above conventional problems. It came.
即ち本発明は、
（１）（Ａ）成分としてアルカリ剤３〜２５質量％、
（Ｂ）成分としてエチレンジアミン四酢酸及びそのアルカリ金属塩、ニトリロ三酢酸及びそのアルカリ金属塩、メチルグリシン二酢酸及びそのアルカリ金属塩、グルタミン酸二酢酸及びそのアルカリ金属塩より選ばれた少なくとも１種の金属イオン封鎖剤１０〜３５質量％、
（Ｃ）成分としてポリカルボン酸型ポリマー又はその塩０．１〜１０質量％、
（Ｄ）成分として水、
を含有し、（Ａ）成分と（Ｂ）成分の合計の割合、（Ａ）＋（Ｂ）＝３３〜６０質量％であり、かつ、（Ａ）成分と（Ｂ）成分の質量比が、（Ａ）／（Ｂ）＝１〜１．２５であることを特徴とする自動食器洗浄機用濃縮液体洗浄剤組成物、
（２）金属イオン封鎖剤が、ｐＨ９〜１１の何れかのｐＨにおいて、Ｃａ（II)に対する安定度定数が５．０以上のものである上記（１）記載の自動食器洗浄機用濃縮液体洗浄剤組成物、
（３）ポリカルボン酸型ポリマーが、ポリアクリル酸又はその塩、ポリメタクリル酸又はその塩、ポリマレイン酸又はその塩、アクリル酸−マレイン酸共重合体又はその塩、オレフィン−マレイン酸共重合体又はその塩、アクリル酸−スルホン酸共重合体又はその塩より選ばれた少なくとも１種である上記（１）又は（２）記載の自動食器洗浄機用濃縮液体洗浄剤組成物、
（４）（Ｂ）成分と（Ｃ）成分の質量比が、（Ｂ）／（Ｃ）＝１〜３５０である上記（１）〜（３）のいずれかに記載の自動食器洗浄機用濃縮液体洗浄剤組成物、
（５）上記（１）〜（４）のいずれかに記載の自動食器洗浄機用濃縮液体洗浄剤組成物を自動食器洗浄機の洗浄液タンクに供給し、自動食器洗浄機用濃縮液体洗浄剤組成物の（Ｂ）成分の濃度として０．００３〜０．１質量％に希釈した洗浄液を自動食器洗浄機の洗浄液タンク内で加熱保持する工程、洗浄液タンク内の洗浄液を洗浄機庫内に噴射して洗浄機庫内の食器類を洗浄する工程、すすぎ液を洗浄機庫内に噴射して食器類をすすぐ工程、とからなることを特徴とする自動食器洗浄機による食器類の洗浄方法、
（６）上記（１）〜（４）のいずれかに記載の自動食器洗浄機用濃縮液体洗浄剤組成物を自動食器洗浄機の洗浄液タンクに供給し、自動食器洗浄機用濃縮液体洗浄剤組成物を、０．０３〜０．１５質量％に希釈した洗浄液を自動食器洗浄機の洗浄液タンク内で加熱保持する工程、洗浄液タンク内の洗浄液を洗浄機庫内に噴射して洗浄機庫内の食器類を洗浄する工程、すすぎ液を洗浄機庫内に噴射して食器類をすすぐ工程、とからなることを特徴とする自動食器洗浄機による食器類の洗浄方法、
（７）濃縮液体洗浄剤組成物をペリスタルティックポンプで洗浄液タンクに供給する上記（５）又は（６）記載の自動食器洗浄機による食器類の洗浄方法、
（８）前記すすぎ液を洗浄機の平面積２５００ｃｍ２ 当たり、１Ｌ〜３Ｌ噴射して食器類をすすぐ上記（５）〜（７）のいずれかに記載の自動食器洗浄機による食器類の洗浄方法、
を要旨とするものである。
That is, the present invention
(1) Alkaline agent 3-25% by mass as component (A),
(B) at least one metal selected from ethylenediaminetetraacetic acid and its alkali metal salt, nitrilotriacetic acid and its alkali metal salt, methylglycine diacetic acid and its alkali metal salt, glutamic acid diacetic acid and its alkali metal salt as component (B) 10-35% by mass of ion sequestering agent,
(C) 0.1-10% by mass of a polycarboxylic acid type polymer or a salt thereof as a component,
(D) Water as a component,
The total ratio of the component (A) and the component (B), (A) + (B) = 33 to 60% by mass, and the mass ratio of the component (A) to the component (B) is (A) / (B) = 1-1.25, concentrated liquid detergent composition for automatic dishwasher,
(2) The concentrated liquid washing for automatic dishwashing machine according to the above (1), wherein the sequestering agent has a stability constant of 5.0 or more with respect to Ca (II) at any pH of 9-11. Agent composition,
(3) The polycarboxylic acid type polymer is polyacrylic acid or a salt thereof, polymethacrylic acid or a salt thereof, polymaleic acid or a salt thereof, an acrylic acid-maleic acid copolymer or a salt thereof, an olefin-maleic acid copolymer or The concentrated liquid detergent composition for an automatic dishwasher according to the above (1) or (2), which is at least one selected from a salt thereof, an acrylic acid-sulfonic acid copolymer or a salt thereof,
(4) Concentration for automatic dishwasher in any one of said (1)-(3) whose mass ratio of (B) component and (C) component is (B) / (C) = 1-350. Liquid detergent composition,
(5) Concentrating liquid detergent composition for automatic dishwashers by supplying the concentrated liquid detergent composition for automatic dishwashers according to any of (1) to (4) above to a washing liquid tank of an automatic dishwasher The step of heating and holding the cleaning liquid diluted to 0.003 to 0.1% by mass as the concentration of the component (B) of the product in the cleaning liquid tank of the automatic dishwashing machine, spraying the cleaning liquid in the cleaning liquid tank into the cleaning machine cabinet Cleaning the dishes in the washing machine cabinet, and rinsing the tableware by spraying a rinsing liquid into the washing machine cabinet.
(6) Supplying the concentrated liquid detergent composition for automatic dishwashers according to any one of the above (1) to (4) to the washing liquid tank of the automatic dishwasher, and the concentrated liquid detergent composition for automatic dishwashers The step of heating and holding the cleaning liquid diluted from 0.03 to 0.15 mass% in the cleaning liquid tank of the automatic dishwashing machine, and spraying the cleaning liquid in the cleaning liquid tank into the cleaning machine cabinet A method for washing dishes with an automatic dishwasher, characterized by comprising a step of washing dishes, a step of rinsing dishes by spraying a rinsing liquid into the washing machine cabinet,
(7) A method for cleaning dishes using the automatic dishwasher according to (5) or (6) above, wherein the concentrated liquid cleaning composition is supplied to a cleaning liquid tank by a peristaltic pump.
(8) The method for washing dishes with the automatic dishwasher according to any one of (5) to (7) above, wherein the rinse liquid is sprayed by 1 L to 3 L per 2500 cm 2 of a flat area of the washing machine to rinse the dishes. ,
Is a summary.
本発明の自動食器用濃縮液体洗浄剤組成物は、低濃度で使用した場合でも汚れに優れた洗浄性を有し、茶渋等の付着抑制性や洗浄性を有し、スケール付着抑制性、バイオフィルム抑制性に優れる。また、すすぎ水量を少なくし、汚れの負荷が大きくなるような節水型自動食器洗浄機で洗浄した場合でも、すすぎ性に優れるため、食器類への汚れの再付着やスケール、バイオフィルムの発生が少なく、すすぎ性に優れるため、食器類への洗浄剤成分の付着残留が少ない等の効果を有する。本発明の自動食器洗浄機用濃縮液体洗浄剤組成物は安定性に優れ、冬季の低温下及び夏季の高温下においても保存中に析出物の発生や分離等が生じる虞がない。また本発明の自動食器洗浄機用濃縮液体洗浄剤組成物は高濃度に濃縮することによりコンパクトな容器に保存でき、洗浄剤組成物の補充・交換頻度も少なくて済むため、効率よくかつ良好に食器類の洗浄を行うことができる等の効果を奏する。 The concentrated liquid detergent composition for automatic tableware of the present invention has an excellent cleaning property against dirt even when used at a low concentration, has an adhesion inhibitory property and a cleaning property such as tea astringency, scale adhesion inhibitory property, bio Excellent film suppression. In addition, even when washed with a water-saving automatic dishwasher that reduces the amount of rinse water and increases the load of dirt, it is excellent in rinsing performance, so that it does not reattach dirt to dishes, scales, or biofilms. Since it is small and excellent in rinsing properties, it has effects such as little adhesion of the detergent component to the tableware. The concentrated liquid detergent composition for an automatic dishwasher of the present invention is excellent in stability, and there is no possibility of generation or separation of precipitates during storage even at low temperatures in winter and high temperatures in summer. In addition, the concentrated liquid detergent composition for automatic dishwashers of the present invention can be stored in a compact container by concentrating to a high concentration, and the frequency of replenishment and replacement of the detergent composition can be reduced. There are effects such as washing of dishes.
本発明の自動食器洗浄機用濃縮液体洗浄剤組成物は、従来品の２倍以上に濃縮された濃縮液体洗浄剤組成物であり、本発明の濃縮液体洗浄剤組成物における（Ａ）成分であるアルカリ剤としては、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩、珪酸ナトリウム、珪酸カリウム、珪酸リチウム等のアルカリ金属珪酸塩等が挙げられる。アルカリ剤は単独または混合して用いることができるが、これらのうち水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、オルソ珪酸ナトリウム、オルソ珪酸カリウム、メタ珪酸ナトリウム、３号珪酸ナトリウム、日本化学工業社製の商品名：Ａ珪酸カリウム（純分４０％）（モル比ＳｉＯ２：Ｋ２Ｏ＝３：１）が洗浄性とコストの理由で好ましい。本発明の濃縮液体洗浄剤組成物は、アルカリ剤を３〜２５質量％含有するが、５〜２４．５質量％含有することが好ましく、７〜２４質量％含有することがより好ましい。アルカリ剤が３質量％未満では洗浄力不足となり、２５質量％を超えるとすすぎ性不良、貯蔵安定性不良、スケール付着抑制性不良となる。 The concentrated liquid detergent composition for an automatic dishwasher according to the present invention is a concentrated liquid detergent composition concentrated twice or more of the conventional product, and is a component (A) in the concentrated liquid detergent composition of the present invention. Examples of the alkali agent include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal silicates such as sodium silicate, potassium silicate, and lithium silicate. It is done. Alkaline agents can be used alone or in combination. Of these, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium orthosilicate, potassium orthosilicate, sodium metasilicate, No. 3, sodium silicate, Nippon Chemical Product name: A potassium silicate (pure content 40%) (molar ratio SiO 2 : K 2 O = 3: 1) is preferred for reasons of detergency and cost. Although the concentrated liquid cleaning composition of this invention contains 3-25 mass% of alkaline agents, it is preferable to contain 5-24.5 mass%, and it is more preferable to contain 7-24 mass%. If the alkali agent is less than 3% by mass, the detergency is insufficient, and if it exceeds 25% by mass, the rinsing property is poor, the storage stability is poor, and the scale adhesion control property is poor.
（Ｂ）成分の金属イオン封鎖剤としては、グルタミン酸二酢酸、トリポリリン酸、アスパラギン酸二酢酸、エチレンジアミン四酢酸、ニトリロ三酢酸、ジエチレントリアミン五酢酸、メチルグリシン二酢酸、３−ヒドロキシ−２，２′−イミノジコハク酸、ヒドロキシエチルイミノ二酢酸、イミノ二酢酸、クエン酸、エチレンジアミンジマロン酸、イミノジコハク酸、エチレンジアミンジコハク酸、酒石酸、グルコン酸やオルトリン酸、ピロリン酸、ヘキサメタリン酸、ヒドロキシエチレンジアミン三酢酸、トリエチレンテトラアミン六酢酸、ジヒドロキシエチルグリシン、β-アラニン二酢酸、セリン二酢酸、グリコール酸、乳酸、クエン酸、リンゴ酸や、これらのアルカリ金属塩、アンモニウム塩、モノエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン等のアルカノールアミン塩が挙げられる。これらのうちｐＨ９〜１１の範囲のいずれかのｐＨにおいて、Ｃａ（II)に対する安定度定数が５．０以上のものが好ましく、ｐＨ＝１０〜１１の範囲のいずれかのｐＨにおいてＣａ（II)に対する安定度定数が５．５以上のものがより好ましい。Ｃａ（II)に対する安定度定数とは、錯体の安定度を示す尺度であり、Ｃａ（II)水和イオン：Ｍ、その濃度を[Ｍ]、金属イオン封鎖剤：Ｌ、その濃度を[Ｌ]、金属イオン封鎖剤のモル数：ｎ、Ｃａ(II)水和イオン：Ｍと、金属イオン封鎖剤：Ｌとから形成される錯体：ＭＬｎ、その濃度を[ＭＬｎ]とした時、下記式（１）より錯体が生成するときの平衡定数：Ｋｎを求め、この平衡定数より下記式（２）より安定度定数：βを求めることができる。 (B) Component sequestering agents include glutamic acid diacetic acid, tripolyphosphoric acid, aspartic acid diacetic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, methylglycine diacetic acid, 3-hydroxy-2,2'- Iminodisuccinic acid, hydroxyethyliminodiacetic acid, iminodiacetic acid, citric acid, ethylenediaminedimalonic acid, iminodisuccinic acid, ethylenediaminedisuccinic acid, tartaric acid, gluconic acid or orthophosphoric acid, pyrophosphoric acid, hexametaphosphoric acid, hydroxyethylenediaminetriacetic acid, triethylene Tetraamine hexaacetic acid, dihydroxyethyl glycine, β-alanine diacetic acid, serine diacetic acid, glycolic acid, lactic acid, citric acid, malic acid and their alkali metal salts, ammonium salts, monoethanolamine, triethanol Min include alkanolamine salts such as monoisopropanolamine. Among these, at any pH in the range of pH 9-11, the stability constant for Ca (II) is preferably 5.0 or more, and at any pH in the range of pH = 10-11, Ca (II) It is more preferable that the stability constant with respect to is 5.5 or more. The stability constant for Ca (II) is a measure of the stability of the complex. Ca (II) hydrated ion: M, its concentration is [M], sequestering agent: L, its concentration is [L ], Number of moles of sequestering agent: n, Ca (II) hydrated ion: M, sequestering agent: complex formed with L: MLn, and when its concentration is [MLn], From (1), the equilibrium constant when the complex is formed: Kn can be obtained, and from this equilibrium constant, the stability constant: β can be obtained from the following formula (2).
（数１）
Ｋｎ＝[ＭＬｎ]／[Ｍ][Ｌ]ｎ （１）
(Equation 1)
Kn = [MLn] / [M] [L] n (1)
（数２）
β＝ｌｏｇＫｎ （２）
(Equation 2)
β = log Kn (2)
ｐＨ９〜１１の範囲のいずれかのｐＨにおいて、Ｃａ（II)に対する安定度定数が５．０以上の金属イオン封鎖剤としては、例えばグルタミン酸二酢酸及びその塩（ｐＨ＝９．０でのＣａ(II)に対する安定度定数＝５．６、ｐＨ＝１０．０でのＣａ(II)に対する安定度定数＝６．２、ｐＨ＝１１でのＣａ(II)に対する安定度定数＝６．４）、トリポリリン酸及びその塩（ｐＨ＝１０．５でのＣａ(II)に対する安定度定数＝５．７）、アスパラギン酸二酢酸及びその塩（ｐＨ＝１０．５でのＣａ(II)に対する安定度定数＝５．８）、エチレンジアミン四酢酸及びその塩（ｐＨ＝９でのＣａ(II)に対する安定度定数＝９．６、ｐＨ＝１０でのＣａ(II)に対する安定度定数＝１０．４、ｐＨ＝１１でのＣａ(II)に対する安定度定数＝１０．８）、ニトリロ三酢酸及びその塩（ｐＨ＝９でのＣａ(II)に対する安定度定数＝５．８、ｐＨ＝１０でのＣａ(II)に対する安定度定数＝６．４、ｐＨ＝１１でのＣａ(II)に対する安定度定数＝６．５）、ジエチレントリアミン五酢酸及びその塩（ｐＨ＝９でのＣａ(II)に対する安定度定数＝９．０、ｐＨ＝１０でのＣａ(II)に対する安定度定数＝１０．０、ｐＨ＝１１でのＣａ(II)に対する安定度定数＝１０．６）、メチルグリシン二酢酸及びその塩（ｐＨ＝９でのＣａ(II)に対する安定度定数＝５．６、ｐＨ＝１０でのＣａ(II)に対する安定度定数＝６．４、ｐＨ＝１１でのＣａ(II)に対する安定度定数＝６．９）等が挙げられる。これらのなかでもグルタミン酸二酢酸及びそのアルカリ金属塩、トリポリリン酸及びそのアルカリ金属塩、エチレンジアミン四酢酸及びそのアルカリ金属塩、ニトリロ三酢酸及びそのアルカリ金属塩、メチルグリシン二酢酸及びそのアルカリ金属塩が好ましく、特にエチレンジアミン四酢酸及びそのアルカリ金属塩、ニトリロ三酢酸及びそのアルカリ金属塩、メチルグリシン二酢酸及びそのアルカリ金属塩、グルタミン酸二酢酸及びそのアルカリ金属塩が好ましい。これらの金属イオン封鎖剤は、単独又は２種類以上組み合わせて用いることができる。（Ｂ）成分の金属イオン封鎖剤は、濃縮液体洗浄剤組成物中に１０〜３５質量％含有されるが、１２〜３３質量％が好ましく、１５〜３０質量％がより好ましい。金属イオン封鎖剤が１０質量％未満ではスケール付着抑制性不良、茶渋洗浄性不良、バイオフィルム抑制性不良となり、３５質量％を超えると貯蔵安定性不良となる。 As a sequestering agent having a stability constant with respect to Ca (II) of 5.0 or more at any pH in the range of pH 9 to 11, for example, glutamic acid diacetic acid and its salt (Ca (pH = 9.0) Stability constant for II) = 5.6, stability constant for Ca (II) at pH = 10.0 = 6.2, stability constant for Ca (II) at pH = 11 = 6.4), Tripolyphosphoric acid and its salt (stability constant for Ca (II) at pH = 10.5 = 5.7), aspartic acid diacetic acid and its salt (stability constant for Ca (II) at pH = 10.5) = 5.8), ethylenediaminetetraacetic acid and its salts (stability constant for Ca (II) at pH = 9 = 9.6, stability constant for Ca (II) at pH = 10 = 10.4, pH = Stability constant for Ca (II) at 11 = 10.8), nitrilotriacetic acid And its salts (stability constant for Ca (II) at pH = 9 = 5.8, stability constant for Ca (II) at pH = 10 = stability for Ca (II) at pH = 11 (Frequency constant = 6.5), diethylenetriaminepentaacetic acid and its salts (stability constant for Ca (II) at pH = 9 = 9.0, stability constant for Ca (II) at pH = 10 = 10.0 , Stability constant for Ca (II) at pH = 11 = 10.6), methylglycine diacetic acid and its salts (stability constant for Ca (II) at pH = 9 = 5.6, pH = 10) Stability constant for Ca (II) = 6.4, stability constant for Ca (II) at pH = 11 = 6.9), and the like. Of these, glutamic acid diacetic acid and its alkali metal salt, tripolyphosphoric acid and its alkali metal salt, ethylenediaminetetraacetic acid and its alkali metal salt, nitrilotriacetic acid and its alkali metal salt, methylglycine diacetic acid and its alkali metal salt are preferred. In particular, ethylenediaminetetraacetic acid and its alkali metal salt, nitrilotriacetic acid and its alkali metal salt, methylglycine diacetic acid and its alkali metal salt, glutamic acid diacetic acid and its alkali metal salt are preferred. These sequestering agents can be used alone or in combination of two or more. The sequestering agent (B) component is contained in the concentrated liquid detergent composition in an amount of 10 to 35% by mass, preferably 12 to 33% by mass, and more preferably 15 to 30% by mass. If the sequestering agent is less than 10% by mass, the adhesion to scales is poor, the tea astringency is poor, and the biofilm is inadequate, and if it exceeds 35% by mass, the storage stability is poor.
（Ｃ）成分のポリカルボン酸型ポリマー又はその塩としては、ポリアクリル酸、ポリメタクリル酸、ポリマレイン酸、ポリイタコン酸、アクリル酸−メタクリル酸共重合体、アクリル酸−マレイン酸共重合体、オレフィン−マレイン酸共重合体、アクリル酸−スルホン酸共重合体、無水マレイン酸−スチレン共重合体、無水マレイン酸−エチレン共重合体、無水マレイン酸−酢酸ビニル共重合体、無水マレイン酸−アクリル酸エステル共重合体等や、これらの塩が挙げられるが、ポリアクリル酸又はその塩、ポリマレイン酸又はその塩、アクリル酸−メタクリル酸共重合体、アクリル酸−マレイン酸共重合体、オレフィン−マレイン酸共重合体、アクリル酸−スルホン酸共重合体が好ましい。これらのポリカルボン酸型ポリマー又はその塩は、単独で用いても２種類以上組み合わせて用いても良い。アクリル酸型共重合体、マレイン酸型共重合体、メタクリル酸型共重合体等の共重合体としては、アミド結合を含まないものが好ましい。ポリアクリル酸の重量平均分子量は５００〜２０，０００が好ましく、特に好ましくは１５００〜１５，０００である。重量平均分子量が５００未満であると、スケール付着抑制性の点で好ましくなく、２０,０００を超えると貯蔵安定性の点で好ましくない。（Ｃ）成分のポリカルボン酸型ポリマー又はその塩は、本発明の濃縮液体洗浄剤組成物中に０．１〜１０質量％含有されるが、０．３〜８質量％が好ましく、０．５〜５質量％がより好ましい。（Ｃ）成分が０．１質量％未満ではすすぎ水で薄められた洗浄機庫内のスケール付着抑制性不良となり、１０質量％を超えると高温の貯蔵安定性不良となる。 (C) Component polycarboxylic acid type polymer or salt thereof includes polyacrylic acid, polymethacrylic acid, polymaleic acid, polyitaconic acid, acrylic acid-methacrylic acid copolymer, acrylic acid-maleic acid copolymer, olefin- Maleic acid copolymer, acrylic acid-sulfonic acid copolymer, maleic anhydride-styrene copolymer, maleic anhydride-ethylene copolymer, maleic anhydride-vinyl acetate copolymer, maleic anhydride-acrylic acid ester Examples thereof include copolymers and salts thereof, but polyacrylic acid or a salt thereof, polymaleic acid or a salt thereof, an acrylic acid-methacrylic acid copolymer, an acrylic acid-maleic acid copolymer, an olefin-maleic acid copolymer. A polymer and an acrylic acid-sulfonic acid copolymer are preferable. These polycarboxylic acid type polymers or salts thereof may be used alone or in combination of two or more. As a copolymer such as an acrylic acid type copolymer, a maleic acid type copolymer, and a methacrylic acid type copolymer, those containing no amide bond are preferable. The weight average molecular weight of polyacrylic acid is preferably 500 to 20,000, particularly preferably 1500 to 15,000. When the weight average molecular weight is less than 500, it is not preferable from the viewpoint of scale adhesion inhibition, and when it exceeds 20,000, it is not preferable from the viewpoint of storage stability. The polycarboxylic acid type polymer of component (C) or a salt thereof is contained in the concentrated liquid detergent composition of the present invention in an amount of 0.1 to 10% by mass, preferably 0.3 to 8% by mass, and 5-5 mass% is more preferable. If the component (C) is less than 0.1% by mass, the scale adhesion suppression in the washing machine diluted with rinsing water will be poor, and if it exceeds 10% by mass, the storage stability at high temperatures will be poor.
（Ｄ）成分の水としては、特に限定はなく、イオン交換水、軟水、純水、水道水などが挙げられ、自動食器洗浄機用濃縮液体洗浄剤組成物の安定性の観点から、イオン交換水又は純水が好ましい。 (D) Component water is not particularly limited, and examples include ion-exchanged water, soft water, pure water, and tap water. From the viewpoint of the stability of the concentrated liquid detergent composition for automatic dishwashers, ion exchange is possible. Water or pure water is preferred.
本発明の濃縮液体洗浄剤組成物中における上記（Ａ）成分と（Ｂ）成分の合計の割合、（Ａ）＋（Ｂ）＝１３．０〜６０質量％であるが、（Ａ）＋（Ｂ）＝１５〜５５質量％が好ましく、２０〜５０質量％がより好ましい。また（Ａ）成分と（Ｂ）成分の質量比は、（Ａ）／（Ｂ）＝０．１〜１．２５であるが、０．１３〜１．１５が好ましく、０．１５〜０．９５がより好ましい。（Ａ）＋（Ｂ）が１３．０質量％未満であると、洗浄性不良、スケール付着抑制性不良、バイオフィルム抑制性不良となり、６０質量％を超えると貯蔵安定性不良となる。また（Ａ）／（Ｂ）が０．１未満であると、洗浄性不良となり、１．２５を超えるとスケール付着抑制性不良となる。 The total ratio of the component (A) and the component (B) in the concentrated liquid cleaning composition of the present invention, (A) + (B) = 13.0-60% by mass, (A) + ( B) = 15-55 mass% is preferable, and 20-50 mass% is more preferable. Moreover, although mass ratio of (A) component and (B) component is (A) / (B) = 0.1-1.25, 0.13-1.15 are preferable and 0.15-0.3. 95 is more preferable. When (A) + (B) is less than 13.0% by mass, the cleaning property is poor, the scale adhesion suppression property is poor, and the biofilm suppression property is poor, and when it exceeds 60% by mass, the storage stability is poor. Further, when (A) / (B) is less than 0.1, the cleaning property is poor, and when it exceeds 1.25, the scale adhesion suppressing property is poor.
本発明の濃縮液体洗浄剤組成物は、（Ｂ）成分と（Ｃ）成分の質量比が、（Ｂ）／（Ｃ）＝１〜３５０であることが好ましいが、１．５〜１１０が好ましく、３〜６０がより好ましい。（Ｂ）／（Ｃ）＝１〜３５０となるように（Ｂ）成分と（Ｃ）成分を含有していると、ガラス製食器に対する腐食防止性が向上する。 In the concentrated liquid detergent composition of the present invention, the mass ratio of the component (B) and the component (C) is preferably (B) / (C) = 1 to 350, but preferably 1.5 to 110. 3 to 60 are more preferable. When the component (B) and the component (C) are contained so that (B) / (C) = 1 to 350, the corrosion resistance to glass tableware is improved.
本発明の濃縮液体洗浄剤組成物には、必要に応じて非イオン界面活性剤、次亜塩素酸塩、除菌剤、消泡剤、増粘剤、ハイドロトロープ剤、酵素、色素、香料等を本発明の効果を損なわない範囲で適宜配合することができる。非イオン界面活性剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンポリオキシプロピレンアルキルエーテル（エチレンオキシドとプロピレンオキシドはランダム、ブロックの何れでもよい）等のポリオキシアルキレンアルキルエーテル、ポリオキシエチレンアルケニルエーテル、ポリオキシエチレンポリオキシプロピレンアルケニルエーテル（エチレンオキシドとプロピレンオキシドはランダム、ブロックの何れでもよい）等のポリオキシアルキレンアルケニルエーテル、ポリエチレングリコールプロピレンオキシド付加物、ポリプロピレングリコールエチレンオキシド付加物、グリセリン脂肪酸エステル又はそのエチレンオキシド付加物、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、アルキルポリグルコシド、脂肪酸モノエタノールアミド又はそのエチレンオキシド付加物、脂肪酸−Ｎ−メチルモノエタノールアミド又はそのエチレンオキシド付加物、脂肪酸ジエタノールアミド又はそのエチレンオキサイド付加物、ショ糖脂肪酸エステル、アルキル（ポリ）グリセリンエーテル、ポリグリセリン脂肪酸エステル、ポリエチレングリコール脂肪酸エステル、脂肪酸メチルエステルエトキシレート、Ｎ−長鎖アルキルジメチルアミンオキシド等が挙げられる。 The concentrated liquid detergent composition of the present invention includes a nonionic surfactant, a hypochlorite, a disinfectant, an antifoaming agent, a thickener, a hydrotrope, an enzyme, a dye, a fragrance and the like as necessary. Can be appropriately blended within a range not impairing the effects of the present invention. Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers (ethylene oxide and propylene oxide may be random or block), polyoxyalkylene alkyl ethers, polyoxyethylene alkenyl ethers, Polyoxyalkylene alkenyl ether such as polyoxyethylene polyoxypropylene alkenyl ether (ethylene oxide and propylene oxide may be either random or block), polyethylene glycol propylene oxide adduct, polypropylene glycol ethylene oxide adduct, glycerin fatty acid ester or ethylene oxide addition thereof , Sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester Alkyl polyglucoside, fatty acid monoethanolamide or its ethylene oxide adduct, fatty acid-N-methyl monoethanolamide or its ethylene oxide adduct, fatty acid diethanolamide or its ethylene oxide adduct, sucrose fatty acid ester, alkyl (poly) glycerin ether, Examples thereof include polyglycerin fatty acid ester, polyethylene glycol fatty acid ester, fatty acid methyl ester ethoxylate, and N-long chain alkyldimethylamine oxide.
上記除菌剤としては、例えば、チアゾリン類、ヒダントイン類や、ヨード−２−プロピニルブチルカーバメイト、イソプロピルメチルフェノール、ヘキサクロロフェン、イルガサン、トリクロサン等が挙げられる。チアゾリン類としては、５−クロロ−２−メチル−４−イソチアゾリン−３−オン、２−メチル−４−イソチアゾリン−３−オン、イソチアゾリン−３−オン、１，２−ベンズイソチアゾリン−３−オン、Ｎ−ｎ−ブチル−ベンズイソチアゾリン−３−オン等が挙げられる。ヒダントイン類としては、１，３−ジメチロール−５，５−ジメチルヒダントイン、１又は３−モノメチロール−５，５−ジメチルヒダントイン、ジメチルヒダントイン、１、３−ジクロロ−５，５−ジメチルヒダントイン、１、３−ジクロロエチルメチルヒダントイン等が挙げられる。 Examples of the disinfectant include thiazolines, hydantoins, iodo-2-propynylbutyl carbamate, isopropylmethylphenol, hexachlorophene, irgasan, triclosan and the like. Thiazolines include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, isothiazoline-3-one, 1,2-benzisothiazolin-3-one, Nn-butyl-benzisothiazolin-3-one and the like. Hydantoins include 1,3-dimethylol-5,5-dimethylhydantoin, 1 or 3-monomethylol-5,5-dimethylhydantoin, dimethylhydantoin, 1,3-dichloro-5,5-dimethylhydantoin, 1, Examples include 3-dichloroethylmethylhydantoin.
また消泡剤としてはシリコーンオイル、ポリプロピレングリコール、ポリブチレングリコール、ポリエチレングリコールポリプロピレングリコール共重合体、グリセリン脂肪酸エステル等が挙げられる。増粘剤としては、平均分子量２００〜６，０００のポリエチレングリコール、エチレングリコール、１，３−ブチレングリコール、還元でんぷん糖化物等の多価アルコール、ポリビニルアルコール、ポリビニルピロリドン、ヒドロキシエチルセルロース、ヒドロキシプロピルメチルセルロース等のセルロース誘導体、アクリル酸系ポリマー等が挙げられる。ハイドロトロープ剤としては、２−エチルヘキサン酸及び／又はその塩、カプリル酸及び／又はその塩、アルケニルスルホコハク酸及び／又はその塩、メタキシレンスルホン酸及び／又はその塩、アルキル（Ｃ６〜１０）グルコシド、オクチルアミンオキシド、デシルジメチルアミンオキシド等が挙げられる。酵素としては、リパーゼ、アルカリアミラーゼ、アミラーゼ、セルラーゼ、プロテアーゼ、プルラナーゼ等が挙げられる。色素としては例えば、天然色素、合成色素、これらの混合物が挙げられる。香料としては例えば、天然香料、合成香料、これらの調合香料等が挙げられる。 Examples of the antifoaming agent include silicone oil, polypropylene glycol, polybutylene glycol, polyethylene glycol polypropylene glycol copolymer, and glycerin fatty acid ester. Examples of the thickener include polyethylene glycol having an average molecular weight of 200 to 6,000, ethylene glycol, 1,3-butylene glycol, polyvalent alcohol such as reduced starch saccharified product, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxyethyl cellulose, hydroxypropyl methylcellulose, etc. Cellulose derivatives, acrylic acid polymers, and the like. Examples of the hydrotrope include 2-ethylhexanoic acid and / or its salt, caprylic acid and / or its salt, alkenylsulfosuccinic acid and / or its salt, metaxylenesulfonic acid and / or its salt, alkyl (C6-10) Examples include glucoside, octylamine oxide, and decyldimethylamine oxide. Examples of the enzyme include lipase, alkaline amylase, amylase, cellulase, protease, pullulanase and the like. Examples of the dye include natural dyes, synthetic dyes, and mixtures thereof. Examples of the fragrances include natural fragrances, synthetic fragrances, and blended fragrances thereof.
自動食器洗浄機用濃縮液体洗浄剤組成物により食器類の洗浄を行う場合、本発明の自動食器洗浄機用濃縮液体洗浄剤組成物の（Ｂ）成分の濃度を０．００３〜０．１質量％に希釈して調製した洗浄液を用いる。好ましくは（Ｂ）成分の濃度を０．００５〜０．０８質量％、より好ましくは（Ｂ）成分の濃度を０．００８〜０．０５質量％に希釈して調製した洗浄液を用いる。濃縮液体洗浄剤組成物はポンプ等により洗浄液タンクに供給され、洗浄液タンク内に供給される水（通常は温水）と混合されて（Ｂ）成分の濃度を０．００３〜０．１質量％の濃度に希釈された洗浄液が、洗浄液タンク内で加熱保持される。次いで洗浄液は、洗浄液タンク内からポンプ等によりノズルから洗浄機庫内の食器類に噴射して食器類を洗浄する。食器類に噴射された洗浄液は、洗浄液タンクに回収される。次いですすぎ液を、ノズルより洗浄機庫内の食器類に噴射してすすぎを行う。すすぎ後のすすぎ液は洗浄液タンクに流入し、洗浄液タンク内の洗浄液濃度は低下するが、濃縮液体洗浄剤組成物を洗浄液タンクに供給して洗浄液濃度を調整する。 When washing dishes with the concentrated liquid detergent composition for an automatic dishwasher, the concentration of the component (B) in the concentrated liquid detergent composition for an automatic dishwasher of the present invention is 0.003 to 0.1 mass. Use a cleaning solution prepared by diluting to a concentration of 1%. Preferably, a cleaning liquid prepared by diluting the concentration of the component (B) to 0.005 to 0.08 mass%, more preferably, the concentration of the component (B) to 0.008 to 0.05 mass% is used. The concentrated liquid cleaning composition is supplied to the cleaning liquid tank by a pump or the like and mixed with water (usually warm water) supplied into the cleaning liquid tank, so that the concentration of the component (B) is 0.003 to 0.1% by mass. The cleaning liquid diluted to the concentration is heated and held in the cleaning liquid tank. Next, the cleaning liquid is sprayed from the cleaning liquid tank through the nozzle to the tableware in the cleaning machine cabinet to wash the tableware. The cleaning liquid sprayed on the tableware is collected in the cleaning liquid tank. Next, rinsing is performed by spraying the rinsing liquid from the nozzle onto the dishes in the washing machine cabinet. The rinse liquid after rinsing flows into the cleaning liquid tank, and the concentration of the cleaning liquid in the cleaning liquid tank decreases, but the concentration of the cleaning liquid is adjusted by supplying the concentrated liquid cleaning composition to the cleaning liquid tank.
自動食器洗浄機用濃縮液体洗浄剤組成物により食器類の洗浄を行う場合、本発明の自動食器洗浄機用濃縮液体洗浄剤組成物を０．０３〜０．１５質量％に希釈することで、（Ｂ）成分の濃度が０．００３〜０．１質量％の洗浄液として調製することができる。好ましくは０．０４〜０．１２質量％、より好ましくは０．０５〜０．０９質量％に希釈して調製した洗浄液を用いる。濃縮液体洗浄剤組成物はポンプ等により洗浄液タンクに供給され、洗浄液タンク内に供給される水（通常は温水）と混合されて（Ｂ）成分の濃度を０．００３〜０．１質量％の濃度に希釈された洗浄液が、洗浄液タンク内で加熱保持される。次いで洗浄液は、洗浄液タンク内からポンプ等によりノズルから洗浄機庫内の食器類に噴射して食器類を洗浄する。食器類に噴射された洗浄液は、洗浄液タンクに回収される。次いですすぎ液を、ノズルより洗浄機庫内の食器類に噴射してすすぎを行う。すすぎ後のすすぎ液は洗浄液タンクに流入し、洗浄液タンク内の洗浄液濃度は低下するが、濃縮液体洗浄剤組成物を洗浄液タンクに供給して洗浄液濃度を調整する。 When washing dishes with a concentrated liquid detergent composition for an automatic dishwasher, by diluting the concentrated liquid detergent composition for an automatic dishwasher of the present invention to 0.03 to 0.15% by mass, (B) It can prepare as a washing | cleaning liquid whose density | concentration of a component is 0.003-0.1 mass%. Preferably, a cleaning solution prepared by diluting to 0.04 to 0.12% by mass, more preferably 0.05 to 0.09% by mass is used. The concentrated liquid cleaning composition is supplied to the cleaning liquid tank by a pump or the like and mixed with water (usually warm water) supplied into the cleaning liquid tank, so that the concentration of the component (B) is 0.003 to 0.1% by mass. The cleaning liquid diluted to the concentration is heated and held in the cleaning liquid tank. Next, the cleaning liquid is sprayed from the cleaning liquid tank through the nozzle to the tableware in the cleaning machine cabinet to wash the tableware. The cleaning liquid sprayed on the tableware is collected in the cleaning liquid tank. Next, rinsing is performed by spraying the rinsing liquid from the nozzle onto the dishes in the washing machine cabinet. The rinse liquid after rinsing flows into the cleaning liquid tank, and the concentration of the cleaning liquid in the cleaning liquid tank decreases, but the concentration of the cleaning liquid is adjusted by supplying the concentrated liquid cleaning composition to the cleaning liquid tank.
濃縮液体洗浄剤組成物を所定濃度に希釈調製した洗浄液は、洗浄液タンク内で通常、４０〜７０℃で保持される。洗浄液は洗浄機庫内の食器類に対し、３０〜１２０秒噴射される。すすぎ液としては通常、水道水が用いられるがリンス剤を用いても用いなくても良い。すすぎ液は、洗浄機の食器設置平面積２５００ｃｍ２当たり１Ｌ〜３Ｌが好ましい。またすすぎ液の温度は４０℃以上、９５℃以下が好ましく、より好ましくは６０℃以上、９０℃以下である。すすぎ液の水道水としては、例えば、東京都荒川区の水道水（ｐＨ＝７．６、総アルカリ度（炭酸カルシウム換算として）４０．５ｍｇ／Ｌ、ドイツ硬度８．１°ＤＨ（そのうち、カルシウム硬度６．３°ＤＨ、マグネシウム硬度２．１°ＤＨ）、塩化物イオン２１．９ｍｇ／Ｌ、ナトリウム及びその化合物１３ｍｇ／Ｌ、硝酸態窒素及び亜硝酸態窒素１．１ｍｇ／Ｌ、フッ素及びその化合物０．０９ｍｇ／Ｌ、ホウ素及びその化合物０．０４ｍｇ／Ｌ、総トリハロメタン０．０１４ｍｇ／Ｌ、残留塩素０．４ｍｇ／Ｌ、有機物（全有機炭素量）０．５ｍｇ／Ｌ）が挙げられる。濃縮液体洗浄剤組成物を洗浄液タンクに供給するためのポンプとしては、ペリスタルティックポンプが好ましい。本発明の濃縮洗浄剤組成物は高濃度に濃縮されており、洗浄液タンクへの１回の供給量は少量であるため、供給量の僅かな誤差によって洗浄液濃度のバラツキが大きくなる虞があるが、ペリスタルティックポンプは少量の洗浄剤組成物を正確に供給することができる。ペリスタティックポンプから洗浄剤組成物を供給する際のチューブ径は１．０〜５．０ｍｍ（内径）が標準的であるが、好ましくは２．０〜４．５ｍｍ（内径）であり、より好ましくは２．５〜４．０ｍｍ（内径）とすると少量の洗浄剤組成物を安定的に供給でき、洗浄液濃度の調整がより容易となる。従来の濃縮液体洗浄剤組成物は、低温環境下で濃縮液体洗浄剤組成物を保管する容器内や供給ポンプ内等で析出物が生じ易く、ペリスタルティックポンプで供給した場合、その析出物が供給チューブ内等で目詰まりを起こし易いが、本発明の濃縮液体洗浄剤組成物は、濃縮液体洗浄剤保管容器内やチューブ内で析出が生じたり目詰りを生じる虞がない。 The cleaning liquid prepared by diluting the concentrated liquid cleaning composition to a predetermined concentration is usually kept at 40 to 70 ° C. in the cleaning liquid tank. The cleaning liquid is sprayed for 30 to 120 seconds to the dishes in the cleaning machine cabinet. As the rinsing liquid, tap water is usually used, but a rinsing agent may or may not be used. The rinsing liquid is preferably 1 L to 3 L per 2500 cm 2 of the dish installation flat area of the washing machine. The temperature of the rinsing liquid is preferably 40 ° C. or higher and 95 ° C. or lower, more preferably 60 ° C. or higher and 90 ° C. or lower. As the rinsing liquid tap water, for example, tap water in Arakawa-ku, Tokyo (pH = 7.6, total alkalinity (calculated in terms of calcium carbonate) 40.5 mg / L, German hardness 8.1 ° DH (of which calcium Hardness 6.3 ° DH, magnesium hardness 2.1 ° DH), chloride ion 21.9 mg / L, sodium and its compound 13 mg / L, nitrate nitrogen and nitrite nitrogen 1.1 mg / L, fluorine and its Compound 0.09 mg / L, boron and its compound 0.04 mg / L, total trihalomethane 0.014 mg / L, residual chlorine 0.4 mg / L, organic matter (total organic carbon content) 0.5 mg / L). As a pump for supplying the concentrated liquid cleaning composition to the cleaning liquid tank, a peristaltic pump is preferable. Since the concentrated cleaning composition of the present invention is concentrated at a high concentration and the amount of supply to the cleaning solution tank is small, there is a possibility that the variation in the concentration of the cleaning solution may increase due to a slight error in the supply amount. The peristaltic pump can accurately supply a small amount of the cleaning composition. The tube diameter when supplying the cleaning composition from the peristatic pump is typically 1.0 to 5.0 mm (inner diameter), preferably 2.0 to 4.5 mm (inner diameter), more preferably. Is 2.5 to 4.0 mm (inner diameter), a small amount of the cleaning composition can be stably supplied, and the adjustment of the concentration of the cleaning solution becomes easier. In conventional concentrated liquid detergent compositions, precipitates are likely to occur in containers or supply pumps that store concentrated liquid detergent compositions in a low-temperature environment. When supplied with a peristaltic pump, the precipitates are supplied. Although clogging is likely to occur in a tube or the like, the concentrated liquid detergent composition of the present invention has no risk of causing precipitation or clogging in a concentrated liquid detergent storage container or in a tube.
本発明の自動食器洗浄機用濃縮液体洗浄剤組成物は、油脂、蛋白質、でんぷん等、あらゆる汚れに対して優れた洗浄性能を示し、アルミ製、ステンレス製、銀製等の金属製、メラミン製、プラスチック製、ガラス製、磁器、漆器、陶磁器などあらゆる素材の食器等の洗浄用途に適し、家庭用自動食器洗浄機、業務用自動食器洗浄機の洗浄剤として用いることができるが、ホテル、レストラン、学校、病院、飲食店、給食会社、会社の食堂等において使用される業務用の自動食器洗浄機に好適に用いることができる。特に、すすぎ液の使用量の少ない節水型の業務用自動食器洗浄機用として好適である。 The concentrated liquid detergent composition for automatic dishwashing machine of the present invention exhibits excellent cleaning performance against all kinds of dirt such as fats and oils, proteins, starch, etc., made of metal such as aluminum, stainless steel, silver, melamine, Suitable for cleaning dishes such as plastic, glass, porcelain, lacquerware, ceramics, etc., and can be used as a cleaning agent for household automatic dishwashers and commercial automatic dishwashers. It can be suitably used for commercial automatic dishwashers used in schools, hospitals, restaurants, catering companies, company cafeterias and the like. In particular, it is suitable for a water-saving business automatic dishwasher with a small amount of rinsing liquid used.
以下、本発明を実施例と比較例により具体的に説明する。実施例、比較例において配合に用いた（Ａ）〜（Ｃ）成分を下記に示す。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The components (A) to (C) used for blending in Examples and Comparative Examples are shown below.
（Ａ）成分
Ａ−１：水酸化カリウム 商品名：フレーク苛性カリ、東亞合成社製
Ａ−２：水酸化ナトリウム 商品名：粒状苛性ソーダ、旭硝子社製
Ａ−３：炭酸カリウム 商品名：炭酸カリウム、旭硝子社製
Ａ−４：珪酸ナトリウム（モル比ＳｉＯ２：Ｎａ２Ｏ＝１：１） 商品名：無水メタ珪酸ナトリウム（純分９５％）、日本化学工業社製
Ａ−５：珪酸カリウム（モル比ＳｉＯ２：Ｋ２Ｏ＝３：１） 商品名：Ａ珪酸カリ（純分４０％）、日本化学工業社製
(A) Component A-1: Potassium hydroxide Product name: Flakes caustic potash, manufactured by Toagosei Co., Ltd. A-2: Sodium hydroxide Product name: Granular caustic soda, manufactured by Asahi Glass Co., Ltd. A-3: Potassium carbonate Product names: Potassium carbonate, Asahi Glass A-4: Sodium silicate (Molar ratio SiO 2 : Na 2 O = 1: 1) Product name: Anhydrous sodium metasilicate (pure content 95%), Nippon Chemical Industry Co., Ltd. A-5: Potassium silicate (Molar ratio) SiO 2 : K 2 O = 3: 1) Product name: A potassium silicate (pure content 40%), manufactured by Nippon Chemical Industry Co., Ltd.
（Ｂ）成分
Ｂ−１：ニトリロ三酢酸ナトリウム塩 商品名：Ｔｒｉｌｏｎ Ａ９２Ｒ、ＢＡＳＦ社製Ｂ−２：エチレンジアミン四酢酸ナトリウム塩 商品名：ディゾルビンＮＡ、アクゾノーベル社製
Ｂ−３：グルタミン酸二酢酸ナトリウム塩 商品名：ディゾルビンＧＬ−４７−Ｓ、アクゾノーベル社製
Ｂ−４：メチルグリシン二酢酸ナトリウム塩 商品名：Ｔｒｉｌｏｎ Ｍ Ｐｏｗｄｅｒ、ＢＡＳＦ社製
Ｂ−５：３-ヒドロキシ−２,２’−イミノジコハク酸四ナトリウム塩 商品名：ＨＩＤＳ、純分５０％、日本触媒社製
(B) Component B-1: Sodium nitrilotriacetate Product name: Trilon A92R, BASF B-2: Ethylenediaminetetraacetate sodium salt Product name: Dissolvin NA, Akzo Nobel B-3: Glutamic acid diacetate sodium salt Product name: Dissolvin GL-47-S, Akzo Nobel B-4: Methylglycine diacetate sodium salt Product name: Trilon M Powder, BASF B-5: 3-hydroxy-2,2'-iminodisuccinic acid tetra Sodium salt Product name: HIDS, 50% pure, manufactured by Nippon Shokubai Co., Ltd.
（Ｃ）成分
Ｃ−１：ポリアクリル酸ナトリウム：重量平均分子量が４０００ 商品名：Ｓｏｋａｌａｎ ＰＡ２５ＣＬ（純分４５％）、ＢＡＳＦ社製
Ｃ−２：ポリマレイン酸ナトリウム：ポリマレイン酸（重量平均分子量が５００、 商品名：Ｂｅｌｃｌｅｎｅ ２００ＬＡ（純分５０％）、ＢＷＡ社製）を水酸化ナトリウムで中和して使用
Ｃ−３：ポリアクリル酸マレイン酸共重合体ナトリウム塩：重量平均分子量が１００００ 商品名：アクアリック ＴＬ２１３（純分３６％）、日本触媒社製
Ｃ−４：ポリアクリル酸マレイン酸共重合体ナトリウム塩：重量平均分子量が１９００ 商品名：ＡＣＵＳＯＬ ４２５Ｎ（純分５０％）、ロームアンドハース社製
Ｃ−５：ポリアクリル酸マレイン酸共重合体ナトリウム塩：重量平均分子量が７００００ 商品名：Ｓｏｋａｌａｎ ＣＰ５（純分４０％）、ＢＡＳＦ社製
(C) Component C-1: Sodium polyacrylate: weight average molecular weight 4000 Product name: Sokalan PA25CL (pure 45%), BASF C-2: sodium polymaleate: polymaleic acid (weight average molecular weight 500, Product name: Belclene 200LA (50% pure), manufactured by BWA) neutralized with sodium hydroxide and used C-3: Polyacrylic acid maleic acid copolymer sodium salt: Weight average molecular weight is 10,000 Product name: Aqua Rick TL213 (36% pure), Nippon Shokubai Co., Ltd. C-4: Polyacrylic acid maleic acid copolymer sodium salt: 1900 weight average molecular weight Product name: ACUSOL 425N (50% pure), manufactured by Rohm and Haas C-5: Polyacrylic acid maleic acid copolymer sodium salt: weight average molecular weight is 70000 Name: Sokalan CP5 (purity 40%), manufactured by BASF
Ｄ−１：イオン交換水 D-1: Ion exchange water
その他成分
１：次亜塩素酸ナトリウム 商品名：次亜塩素酸ソーダ（有効塩素濃度として１２％）、昭和電工社製
２：ポリオキシアルキレンアルキルエーテル：Ｒ−Ｏ−(ＥＯ)a−(ＰＯ)b−Ｈ （３）（式中、Ｒは炭素数１２〜１４の２級アルキル基、a=７．０、b＝８．５を示す） 商品名：ソフタノールＥＰ７０８５、日本触媒社製
Other components 1: Sodium hypochlorite Product name: Sodium hypochlorite (effective chlorine concentration: 12%), Showa Denko KK 2: Polyoxyalkylene alkyl ether: R—O— (EO) a— (PO) b-H (3) (wherein R represents a secondary alkyl group having 12 to 14 carbon atoms, a = 7.0, b = 8.5) Product name: Softanol EP7085, manufactured by Nippon Shokubai Co., Ltd.
実施例１〜２０、比較例１〜１４
表１〜４に示す配合に基づき自動食器洗浄機用の濃縮液体洗浄剤組成物を調製した。各濃縮液体洗浄剤組成物を用い、自動食器洗浄機（ホシザキ電気製自動食器洗浄機：ＪＷＥ−６８０ＡＪ）により下記試験を行った。結果を表１〜４に示す。尚、表中における実施例および比較例の各成分の配合割合は純分の質量％を表す。
Examples 1-20, Comparative Examples 1-14
Concentrated liquid detergent compositions for automatic dishwashers were prepared based on the formulations shown in Tables 1-4. Each concentrated liquid detergent composition was used, and the following test was performed with an automatic dishwasher (automatic dishwasher manufactured by Hoshizaki Electric Co., Ltd .: JWE-680AJ). The results are shown in Tables 1-4. In addition, the mixture ratio of each component of the Example in a table | surface and a comparative example represents the mass% of a pure part.
（１）洗浄性
＜被洗浄物＞
直径２０ｃｍのガラス皿にマヨネーズ２ｇを均一に塗布し、室温で乾燥させた汚染皿を被洗浄物とした。
＜試験方法＞
濃縮液体洗浄剤組成物の濃度を０．０５質量％、０．０７質量％に希釈した洗浄液を洗浄機の洗浄液タンクに貯留して６６℃で保持し、洗浄ラックに汚染皿５枚を設置し、以下の条件で洗浄、すすぎを行った。濃縮液体洗浄剤組成物の希釈水、すすぎ水は塩化カルシウムを用いて硬度３°ＤＨに調製した人工硬水を用いた。
＜洗浄条件＞
洗浄温度：６６℃
洗浄時間：４１秒
すすぎ温度：８２℃
すすぎ時間：６秒
＜洗浄性評価＞
洗浄、すすぎ後の皿を室温で乾燥後、暗室において蛍光灯光を照射、反射させて汚れの残存状況を目視判定により以下の基準で評価した。
◎：清浄な皿と比較して差がない。
○：うすい曇りのみが認められる。
△：スポットのみが認められる。
×：曇りとスポットが認められる。
とし、△、○、◎を実用性のあるものとして判定した。
(1) Detergency <object to be cleaned>
A contaminated dish obtained by uniformly applying 2 g of mayonnaise to a glass dish having a diameter of 20 cm and drying at room temperature was used as an object to be cleaned.
<Test method>
The cleaning liquid diluted to a concentration of 0.05% by mass and 0.07% by mass in the concentrated liquid cleaning composition is stored in the cleaning liquid tank of the cleaning machine and held at 66 ° C., and 5 contamination dishes are installed in the cleaning rack. Washing and rinsing were performed under the following conditions. As the diluting water and rinsing water of the concentrated liquid detergent composition, artificial hard water prepared to a hardness of 3 ° DH using calcium chloride was used.
<Cleaning conditions>
Washing temperature: 66 ° C
Cleaning time: 41 seconds Rinsing temperature: 82 ° C
Rinsing time: 6 seconds <detergency evaluation>
The dish after washing and rinsing was dried at room temperature, and then the fluorescent lamp light was irradiated and reflected in the dark room, and the remaining state of the soil was evaluated by visual judgment based on the following criteria.
(Double-circle): There is no difference compared with a clean dish.
○: Only light cloudiness is recognized.
(Triangle | delta): Only a spot is recognized.
X: Cloudiness and spots are recognized.
And Δ, ○, and ◎ were determined to be practical.
（２）すすぎ性
濃度が高い洗浄液を用いた場合のすすぎ性を試験した。
＜被洗浄物＞
清浄な茶碗を被洗浄物とした。
＜試験方法＞
濃縮液体洗浄剤組成物の濃度を０．１５質量％に希釈した洗浄液を洗浄機の洗浄タンクに貯留して６６℃で保持し、洗浄ラックに茶碗を糸尻が上になるように５個設置し、以下の条件で洗浄、すすぎを行った。濃縮液体洗浄剤組成物の希釈水、すすぎ水は塩化カルシウムを用いて硬度３°ＤＨに調製した人工硬水用いた。
＜洗浄条件＞
洗浄温度：６６℃
洗浄時間：４１秒
すすぎ温度：８２℃
すすぎ時間：６秒
＜すすぎ性評価＞
洗浄、すすぎ後の茶碗の糸尻に残留している水にフェノールフタレイン液を滴下しアルカリ剤の残留による変色反応を目視判定し、以下の基準で評価した。
◎：全く変色反応が認められない。
○：ほとんど変色反応が認められない。
△：僅かな変色反応が認められる。
×：顕著な変色反応が認められる。
とし、△、○、◎を実用性のあるものとして判定した。
(2) Rinsing property The rinsing property when a cleaning solution having a high concentration was used was tested.
<To be cleaned>
A clean tea bowl was used as an object to be cleaned.
<Test method>
The cleaning liquid diluted to a concentration of 0.15% by mass of the concentrated liquid cleaning composition is stored in the cleaning tank of the cleaning machine and held at 66 ° C., and five teacups are installed in the cleaning rack so that the thread end is on the top. Then, washing and rinsing were performed under the following conditions. Artificial hard water prepared to a hardness of 3 ° DH using calcium chloride was used as dilution water and rinse water of the concentrated liquid cleaning composition.
<Cleaning conditions>
Washing temperature: 66 ° C
Cleaning time: 41 seconds Rinsing temperature: 82 ° C
Rinse time: 6 seconds <Rinse evaluation>
A phenolphthalein solution was dropped into the water remaining on the thread tail of the teacup after washing and rinsing, and the color change reaction due to the remaining alkali agent was visually determined and evaluated according to the following criteria.
(Double-circle): A discoloration reaction is not recognized at all.
○: Almost no discoloration reaction is observed.
Δ: Slight discoloration reaction is observed.
X: Remarkable discoloration reaction is recognized.
And Δ, ○, and ◎ were determined to be practical.
（３）茶渋洗浄性試験
＜被洗浄物＞
清浄なプラスチックカップを被洗浄物とした。
＜試験方法＞
濃縮液体洗浄剤組成物の濃度を０．０５質量％、０．０７質量％に希釈した洗浄液を洗浄機の洗浄液タンクに貯留して６６℃で保持し、食器洗浄機の洗浄ラックにプラスチックカップ５個を設置し、以下の条件で、茶渋汚れ付着／インターバル／洗浄／すすぎ／インターバルの工程を１００サイクル繰り返し行った。濃縮液体洗浄剤組成物の希釈水、すすぎ水は塩化カルシウムを用いて硬度６°ＤＨに調製した人工硬水を用いた。
＜洗浄条件＞
茶渋汚れ付着：５秒
インターバル：３０秒
洗浄温度：６６℃
洗浄時間：４１秒
すすぎ温度：８２℃
すすぎ時間：６秒
インターバル：５秒
＜茶渋汚れ付着＞
煮出した紅茶（紅茶葉２．５ｇ、水１００ｍｌ）をプラスチックカップに１８０ｍｌ注ぎ、直ちに廃棄して、所定位置に設置した。煮出した紅茶の水は、塩化カルシウムを用いて硬度１０°ＤＨに調製した人工硬水用いた。
＜茶渋洗浄性評価＞
洗浄工程１００サイクル後の、プラスチックカップへの茶渋付着状態を目視判定し、以下の基準で評価した。
◎：茶渋の付着が認められない。
○：茶渋の付着がほとんど認められない。
△：茶渋の付着が認められる。
×：茶渋の付着が著しい。
とし、△、○、◎を実用性のあるものとして判定した。
(3) Tea astringency washability test <object to be washed>
A clean plastic cup was the object to be cleaned.
<Test method>
The cleaning liquid diluted to a concentration of 0.05% by mass and 0.07% by mass of the concentrated liquid cleaning composition is stored in the cleaning liquid tank of the cleaning machine and held at 66 ° C., and the plastic cup 5 is stored in the cleaning rack of the dishwasher. The process was repeated for 100 cycles under the following conditions under the following conditions: adhesion of tea astringent stain / interval / cleaning / rinsing / interval. Artificial hard water prepared to have a hardness of 6 ° DH using calcium chloride was used as dilution water and rinse water of the concentrated liquid detergent composition.
<Cleaning conditions>
Adhering tea astringency: 5 seconds Interval: 30 seconds Cleaning temperature: 66 ° C
Cleaning time: 41 seconds Rinsing temperature: 82 ° C
Rinse time: 6 seconds Interval: 5 seconds
Boiled black tea (2.5 g of tea leaves, 100 ml of water) was poured into a plastic cup, 180 ml, immediately discarded, and placed in place. Artificial hard water prepared to a hardness of 10 ° DH using calcium chloride was used as the tea water.
<Evaluation of tea washing ability>
The state of tea astringent adhesion to the plastic cup after 100 cycles of the washing process was visually determined and evaluated according to the following criteria.
A: Adherence of tea astringency is not recognized.
○: Adherence of tea astringency is hardly recognized.
Δ: Adherence of tea astringent is recognized.
X: Adherence of tea astringent is remarkable.
And Δ, ○, and ◎ were determined to be practical.
（４）スケール付着抑制性試験
スケール付着抑制性試験−１
食器洗浄機の洗浄液タンク内の電熱線（ヒーター部分）および壁面へのスケール付着抑制性を、洗浄液タンク内と同様の擬似的条件下で試験した。
＜試験方法＞
塩化カルシウムで硬度６°ＤＨに調製した人工硬水より濃縮液体洗浄剤組成物の濃度を０．０５質量％、０．０７質量％に希釈した洗浄液を作成し、この洗浄液中にＳＵＳ３０４製のテスト板（２．５ｃｍ×７．５ｃｍ）を浸漬させ、８０℃で２４時間保持した。その後テスト板を取り出してイオン交換水ですすぎ、乾燥後、テスト板のスケール付着量を目視判定し、以下の基準により評価した。
＜評価基準＞
◎：スケールの付着が全く認められなかった。
○：スケールの付着がほとんど認められなかった。
△：スケールの付着が認められた。
×：著しいスケールの付着が認められた。
とし、△、○、◎を実用性のあるものとして判定した。
(4) Scale adhesion inhibition test Scale adhesion inhibition test-1
Inhibition of scale adhesion to the heating wire (heater part) and the wall surface in the washing liquid tank of the dishwasher was tested under the same pseudo condition as in the washing liquid tank.
<Test method>
A cleaning liquid is prepared by diluting the concentration of the concentrated liquid cleaning composition from artificial hard water prepared with calcium chloride to a hardness of 6 ° DH to 0.05% by mass and 0.07% by mass. In this cleaning liquid, a test plate made of SUS304 is prepared. (2.5 cm × 7.5 cm) was immersed and held at 80 ° C. for 24 hours. Thereafter, the test plate was taken out, rinsed with ion-exchanged water, and after drying, the amount of scale attached to the test plate was visually judged and evaluated according to the following criteria.
<Evaluation criteria>
A: No adhesion of scale was observed.
○: Almost no adhesion of scale was observed.
(Triangle | delta): The adhesion of the scale was recognized.
X: Significant scale adhesion was observed.
And Δ, ○, and ◎ were determined to be practical.
スケール付着抑制性試験−２
食器洗浄機庫内の壁面（洗浄液タンク内は除く）の洗浄液がすすぎ水で薄まった条件でのスケール付着抑制性を、以下の方法で試験した。
＜試験方法＞
洗浄ラックに２５０ｍｌのグラス３６個を設置し、塩化カルシウムで硬度１０°ＤＨに調製した人工硬水より濃縮液体洗浄剤組成物の濃度を０．０５質量％、０．０７質量％に希釈した洗浄液により下記条件で洗浄／すすぎ／インターバルを２００サイクル繰り返した後、洗浄機庫内のスケール付着量を目視判定し、以下の基準で評価した。
＜洗浄条件＞
洗浄温度：６６℃
洗浄時間：４１秒
すすぎ温度：８２℃
すすぎ時間：６秒
インターバル：５秒
＜評価基準＞
◎：スケールの付着が全く認められなかった。
○：スケールの付着がほとんど認められなかった。
△：スケールの付着が認められた。
×：著しいスケールの付着が認められた。
とし、△、○、◎を実用性のあるものとして判定した。
Scale adhesion inhibition test-2
The scale adhesion inhibitory property under the condition that the cleaning liquid on the wall surface in the dishwasher cabinet (excluding the cleaning liquid tank) was diluted with rinse water was tested by the following method.
<Test method>
36 glasses of 250 ml are installed in the washing rack, and the concentration of the concentrated liquid detergent composition is 0.05 mass% and 0.07 mass% diluted with artificial hard water prepared with calcium chloride to a hardness of 10 ° DH. After repeating 200 cycles of washing / rinsing / interval under the following conditions, the amount of scale adhesion in the washing machine cabinet was visually judged and evaluated according to the following criteria.
<Cleaning conditions>
Washing temperature: 66 ° C
Cleaning time: 41 seconds Rinsing temperature: 82 ° C
Rinse time: 6 seconds Interval: 5 seconds <Evaluation criteria>
A: No adhesion of scale was observed.
○: Almost no adhesion of scale was observed.
(Triangle | delta): The adhesion of the scale was recognized.
X: Significant scale adhesion was observed.
And Δ, ○, and ◎ were determined to be practical.
＜スケール付着抑制性総合評価＞
スケール付着抑制性試験−１、スケール付着抑制性試験−２の両試験の結果より、以下の基準で評価した。
◎：１および２の両試験でスケールの付着が全く認められなかった。
○：１および２のどちらかの試験でスケールの付着がほとんど認められなかった。
△：１および２のどちらかの試験でスケールの付着が認められた。
×：１および２のどちらかの試験で著しいスケールの付着が認められた。
とし、△、○、◎を実用性のあるものとして判定した。
<Comprehensive evaluation of scale adhesion inhibition>
From the results of both the scale adhesion inhibition test-1 and the scale adhesion inhibition test-2, the following criteria were used for evaluation.
A: No scale adhesion was observed in both the tests 1 and 2.
○ Scale adhesion was hardly observed in either of the tests 1 and 2.
Δ: Scale adhesion was observed in either test: 1 or 2.
X: Significant scale adhesion was observed in either test: 1 or 2.
And Δ, ○, and ◎ were determined to be practical.
（５）バイオフィルム防止性試験
＜試験方法＞
各濃縮液体洗浄剤組成物５ｇを滅菌済みのミューラーヒントン培地〔日本ベクトン・ディッキンソン株式会社製〕に添加して全量を１００ｇにして、各濃縮液体洗浄剤組成物の５質量％コンク溶液を調製した。本コンク溶液を更に滅菌済みミューラーヒントン培地を用いて濃縮液体洗浄剤組成物の濃度として０．１質量％となるように希釈調製し、それぞれ２４穴マイクロプレート〔旭テクノグラス株式会社製〕に２ｍＬ量りとった。また、汚れ成分として、３質量％ウシアルブミンをコンク溶液として調製し、２４穴マイクロプレートに０．３質量％となるように添加した。
緑膿菌（Pseudomonas aeruginosa ＮＢＲＣ１３２７５）、クレブシェラ菌（Klebsiella pneumoniae ＡＴＣＣ１３８８３）をそれぞれＬＢ培地〔日本ベクトン・ディッキンソン株式会社製〕を用いて、３７℃で１８時間前培養して増殖した菌液を、ピペットマンを用いて当該マイクロプレート内の試験溶液に１０μｌ接種した。これを３７℃で４８時間培養後に培養液を廃棄し、滅菌精製水２ｍＬで各ウェル内を５回洗浄した。マイクロプレート壁に付着したバイオフィルムを０．１質量％クリスタルバイオレット液で染色し、滅菌水ですすいだ後、バイオフィルムの形成状態を目視判断し、バイオフィルム抑制性を以下の基準で評価した。
＜評価基準＞
１点：バイオフィルムがプレート壁面の０〜２０％未満を覆う状態。
２点：バイオフィルムがプレート壁面の２０％以上４０％未満を覆う状態。
３点：バイオフィルムがプレート壁面の４０％以上６０％未満を覆う状態。
４点：バイオフィルムがプレート壁面の６０％以上を覆う状態。
として上記各菌種についてプレート壁面の状態を点数で評価し、２菌種のプレート壁面の状態を点数の平均値を求め、以下の基準でバイオフィルム防止性を評価した。
◎：平均値が１点以上１．５点未満
○：平均値が１．５点以上２．５点未満
△：平均値が２．５点以上３．５点未満
×：平均値が３．５点以上
とし、△、○、◎を実用性のあるものとして判定した。
(5) Biofilm prevention test <Test method>
5 g of each concentrated liquid detergent composition was added to a sterilized Mueller Hinton medium (manufactured by Nippon Becton Dickinson Co., Ltd.) to make a total amount of 100 g, thereby preparing a 5% by weight concentrated solution of each concentrated liquid detergent composition. . This concentrated solution is further diluted with a sterilized Mueller Hinton medium so that the concentration of the concentrated liquid detergent composition is 0.1% by mass, and 2 mL each in a 24-well microplate (Asahi Techno Glass Co., Ltd.). Weighed. Further, 3% by weight bovine albumin was prepared as a soil solution as a conc. Solution and added to a 24-well microplate so as to be 0.3% by weight.
Using a LB medium (manufactured by Nippon Becton Dickinson Co., Ltd.) for each of Pseudomonas aeruginosa NBRC13275 and Klebsiella pneumoniae ATCC13883, the bacterial solution which had been pre-cultured for 18 hours at 37 ° C. The test solution in the microplate was used to inoculate 10 μl. After culturing at 37 ° C. for 48 hours, the culture solution was discarded, and each well was washed 5 times with 2 mL of sterilized purified water. The biofilm adhering to the microplate wall was dyed with 0.1% by mass crystal violet solution, rinsed with sterilized water, the state of biofilm formation was visually judged, and biofilm inhibition was evaluated according to the following criteria.
<Evaluation criteria>
1 point: A state in which the biofilm covers 0 to less than 20% of the plate wall surface.
2 points: A state in which the biofilm covers 20% or more and less than 40% of the plate wall surface.
3 points: A state in which the biofilm covers 40% or more and less than 60% of the plate wall surface.
4 points: A state in which the biofilm covers 60% or more of the plate wall surface.
As for each of the above bacterial species, the state of the plate wall surface was evaluated by a score, and the state of the plate wall surface of the two bacterial species was determined as an average score, and the biofilm prevention property was evaluated according to the following criteria.
A: The average value is 1 point or more and less than 1.5 points. ○: The average value is 1.5 points or more and less than 2.5 points. Δ: The average value is 2.5 points or more and less than 3.5 points. The score was 5 or more, and Δ, ○, and ◎ were judged as practical.
（６）濃縮液体洗浄剤組成物の貯蔵安定性
低温安定性
＜試験方法＞
２５０ｍｌ透明ポリプロピレン製容器に濃縮液体洗浄剤組成物を２５０ｍｌとり、蓋をして−５℃恒温槽に保管。１週間に１回揺り動かすことを繰り返し１ヶ月間行い、濃縮液体洗浄剤組成物の状態を以下の基準で評価した。
＜評価基準＞
○：析出物や凍結が見られず安定である。
×：析出物もしくは凍結が見られる。
とし、○を実用性のあるものとして判定した。
高温安定性
＜試験方法＞
２５０ｍｌ透明ポリプロピレン製容器に濃縮液体洗浄剤組成物を２５０ｍｌとり、蓋をして４０℃恒温槽に保管し静置。６ヶ月後、濃縮液体洗浄剤組成物の状態を以下の基準で評価した。
＜評価基準＞
○：析出物や濁りが見られず安定である。
△：析出物や濁りが、若干見られる。
×：析出物もしくは濁りが見られる。
とし、△、○を実用性のあるものとして判定した。
(6) Storage stability of concentrated liquid detergent composition Low temperature stability <Test method>
Take 250 ml of the concentrated liquid detergent composition in a 250 ml transparent polypropylene container, cover it and store it in a -5 ° C thermostatic bath. The shaking was repeated once a week for 1 month, and the state of the concentrated liquid detergent composition was evaluated according to the following criteria.
<Evaluation criteria>
○: Precipitates and freezing are not seen and stable.
X: Precipitation or freezing is observed.
And ○ was determined to be practical.
High temperature stability <Test method>
Take 250 ml of the concentrated liquid detergent composition in a 250 ml transparent polypropylene container, cover it and store it in a constant temperature bath at 40 ° C. After 6 months, the state of the concentrated liquid detergent composition was evaluated according to the following criteria.
<Evaluation criteria>
○: Precipitates and turbidity are not seen and stable.
Δ: Precipitates and turbidity are slightly observed.
X: Precipitation or turbidity is observed.
And Δ and ○ were determined to be practical.
Claims (8)
（Ｂ）成分としてエチレンジアミン四酢酸及びそのアルカリ金属塩、ニトリロ三酢酸及びそのアルカリ金属塩、メチルグリシン二酢酸及びそのアルカリ金属塩、グルタミン酸二酢酸及びそのアルカリ金属塩より選ばれた少なくとも１種の金属イオン封鎖剤１０〜３５質量％、
（Ｃ）成分としてポリカルボン酸型ポリマー又はその塩０．１〜１０質量％、
（Ｄ）成分として水、
を含有し、（Ａ）成分と（Ｂ）成分の合計の割合、（Ａ）＋（Ｂ）＝３３〜６０質量％であり、かつ、（Ａ）成分と（Ｂ）成分の質量比が、（Ａ）／（Ｂ）＝１〜１．２５であることを特徴とする自動食器洗浄機用濃縮液体洗浄剤組成物。 (A) Alkaline agent 3-25 mass% as a component,
(B) at least one metal selected from ethylenediaminetetraacetic acid and its alkali metal salt, nitrilotriacetic acid and its alkali metal salt, methylglycine diacetic acid and its alkali metal salt, glutamic acid diacetic acid and its alkali metal salt as component (B) 10-35% by mass of ion sequestering agent,
(C) 0.1-10% by mass of a polycarboxylic acid type polymer or a salt thereof as a component,
(D) Water as a component,
The total ratio of the component (A) and the component (B), (A) + (B) = 33 to 60% by mass, and the mass ratio of the component (A) to the component (B) is (A) / (B) = 1-1.25 A concentrated liquid detergent composition for an automatic dishwasher.
The method for washing dishes with an automatic dishwasher according to any one of claims 5 to 7, wherein the rinsing liquid is sprayed by 1 L to 3 L per 2500 cm 2 of a flat area of the washing machine to rinse dishes.
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