JP2017214455A - Hard surface rinsing agent - Google Patents
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本発明は、金属、セラミックス、ガラスおよびプラスチック等の硬質表面の洗浄に用いられる硬質表面用リンス剤に関する。 The present invention relates to a hard surface rinse agent used for cleaning hard surfaces of metals, ceramics, glass, plastics and the like.
金属、セラミックス、ガラスおよびプラスチック等の硬質表面の加工後には、表面に付着した金属粉や加工油等を除去するために、主に塩素系、炭化水素系および水系洗浄剤が種々の分野で工業用洗浄剤として使用されている。その中で、近年では環境への配慮、作業環境の衛生上および防災上好ましい条件を備えているとの理由から、水系洗浄剤の需要が高まっている。一方で、水系洗浄剤で溶媒として使用される水は、他の洗浄剤で用いられる溶剤や溶媒と比較して比熱が高く、さらに沸点も高いことから、乾燥に多くのエネルギーを必要とする。そこで、洗浄後の乾燥を促進させるために、リンス剤による洗浄が行われている。 After processing hard surfaces such as metals, ceramics, glass and plastics, chlorine, hydrocarbons and water cleaners are mainly used in various fields in order to remove metal powder and processing oil attached to the surface. Used as a cleaning agent. Among them, in recent years, the demand for water-based cleaning agents has been increased because of favorable conditions for environmental considerations, hygiene of work environments, and disaster prevention. On the other hand, water used as a solvent in an aqueous cleaning agent has a higher specific heat and a higher boiling point than solvents and solvents used in other cleaning agents, and therefore requires a lot of energy for drying. Therefore, in order to promote drying after cleaning, cleaning with a rinse agent is performed.
リンス剤による洗浄を行う目的は、主として、洗浄物からの水切れを向上させたり、水滴を表面に濡れ広がらせたりすることによって、洗浄物表面の乾燥を促進させることであるが、一方で、乾燥促進効果だけでなく、乾燥後の洗浄物表面の清浄性向上効果も重要な目的として挙げられる。 The purpose of cleaning with the rinse agent is mainly to improve the dryness of the surface of the cleaning object by improving water drainage from the cleaning object or spreading water droplets on the surface. Not only the promoting effect but also the effect of improving the cleanliness of the surface of the washed product after drying is an important purpose.
リンス剤による洗浄方法としては、リンス剤に硬質表面を浸漬した後に超音波やポンプにより加圧して生じた水流やバブリング等により洗浄する方法、ポンプやエアーにより加圧した水を硬質表面に当てるシャワー洗浄方法などが挙げられる。その中でもシャワー洗浄方法は、物理的な洗浄効果が見込まれるため、短時間で洗浄が可能で、作業効率が向上するといったメリットを有する。一方で、シャワー洗浄方法は、その水の勢いによってリンス剤が泡立ち、洗浄ライン上で泡がオーバーフローすることにより、作業を停止せざるを得ない状況がしばしば起こったり、泡が洗浄物に付着することでリンス性が低下したりする問題を有している。 As a cleaning method using a rinsing agent, a method in which a hard surface is immersed in a rinsing agent and then cleaned by water flow or bubbling generated by applying pressure by an ultrasonic wave or a pump, a shower in which water pressurized by a pump or air is applied to the hard surface Examples include a cleaning method. Among them, the shower cleaning method is expected to have a physical cleaning effect, and thus has a merit that it can be cleaned in a short time and work efficiency is improved. On the other hand, in the shower cleaning method, the rinse agent foams due to the momentum of the water, and the foam overflows on the cleaning line, so there are often situations where work must be stopped or the foam adheres to the cleaning object Therefore, there is a problem that the rinsing property is lowered.
従来、リンス洗浄時の泡立ちの問題を解決するために、低泡性の界面活性剤が使用されており、かかる界面活性剤として、例えば特許文献１には、直鎖脂肪族炭化水素基または分岐脂肪族炭化水素基を有する脂肪族アルコールに炭素数２〜４のアルキレンオキシドを付加した低泡性の界面活性剤が記載されている。
また、特許文献２には、リンス洗浄が不要で、高い洗浄効果とリンス効果の２つの効果を併せ持つ食器洗浄機用の洗浄剤組成物として、炭素数１０〜１６のアルコールにエチレンオキシド、プロピレンオキシドを付加した非イオン性界面活性剤化合物の組成物が開示されている。
Conventionally, a low-foaming surfactant has been used to solve the problem of foaming during rinsing, and as such surfactant, for example, Patent Document 1 discloses a linear aliphatic hydrocarbon group or a branched chain. A low-foaming surfactant in which an alkylene oxide having 2 to 4 carbon atoms is added to an aliphatic alcohol having an aliphatic hydrocarbon group is described.
Patent Document 2 discloses that a cleaning composition for a dishwasher that does not require rinsing and has both a high cleaning effect and a rinsing effect includes ethylene oxide and propylene oxide in an alcohol having 10 to 16 carbon atoms. Disclosed are compositions of added nonionic surfactant compounds.
一方で、リンス洗浄では泡立ちの問題だけでなく、洗浄物表面にウォータースポットと呼ばれる白斑やリンス剤の主成分である界面活性剤が残るといったリンス洗浄不良により、表面がべたつくといった問題も有している。従来のリンス剤による洗浄では、洗浄物表面へ界面活性剤が微量に残ることが大きな問題とならない用途に限定されたり、また、部材の耐熱性や製造コスト増加の問題を考慮した上で、乾燥温度を高温としたり乾燥時間を長くしたりすることでそのような問題に対処していた。 On the other hand, the rinse cleaning not only has the problem of foaming, but also has a problem that the surface becomes sticky due to poor rinse cleaning such as white spots called water spots and a surfactant that is the main component of the rinse agent remaining on the surface of the cleaning object. Yes. The conventional cleaning with a rinse agent is limited to applications where a trace amount of surfactant remains on the surface of the object to be cleaned, and it is dried after taking into account the problems of heat resistance of members and increase in manufacturing costs. Such problems were addressed by increasing the temperature and increasing the drying time.
しかしながら、洗浄後の部材表面に薄膜コーティングなどを行う場合には、より微量のウォータースポットや界面活性剤の残りによってハジキ等が生じ、コーティング不良が起こることが大きな問題となっている。特に近年では、コスト削減や高性能化のために、コーティング膜をより薄くする傾向にあることから、さらにコーティング不良が起き易くなっており、リンス洗浄物表面への界面活性剤残りが極めて少ないことが求められている。 However, when thin film coating or the like is performed on the surface of the member after cleaning, repellency or the like is caused by a smaller amount of water spots or the remaining of the surfactant, which causes a serious problem of coating failure. In particular, in recent years, coating films tend to be thinner to reduce costs and improve performance, making it more prone to coating defects and having very little surfactant remaining on the surface of rinsed objects. Is required.
上記の特許文献１や２に開示されているような従来の界面活性剤および洗浄剤組成物では、高温で乾燥させても、洗浄物表面にリンス剤の主成分である界面活性剤が微量に残りやすいことから、高性能化が進む部材表面へ薄膜コーティングなどを行う場合にはコーティング不良が生じやすく、また作業効率の向上を図るために洗浄スピードをさらに上昇させることによる泡立ちの増加といった問題へは対応できていない。
それらの問題を解決するために、より低泡性であり、洗浄物表面の乾燥を促し、かつ乾燥後の洗浄物表面への界面活性剤残りが極めて少ない硬質表面用リンス剤が求められている。
In the conventional surfactant and detergent composition as disclosed in Patent Documents 1 and 2 described above, even when dried at a high temperature, a small amount of the surfactant as the main component of the rinse agent is present on the surface of the wash. Since it tends to remain, coating defects are likely to occur when thin-film coating is applied to the surface of a member with higher performance, and problems such as increased foaming by further increasing the cleaning speed in order to improve work efficiency Is not available.
In order to solve these problems, there is a demand for a rinsing agent for hard surfaces that has lower foaming properties, promotes drying of the surface of the washed product, and has very little surfactant remaining on the washed product surface after drying. .
本発明は、洗浄時の泡立ち抑制に優れ、洗浄物表面の乾燥を促し、かつ乾燥後の洗浄物表面への界面活性剤残りが極めて少ない硬質表面用リンス剤を提供することを目的とする。 An object of the present invention is to provide a rinsing agent for a hard surface that is excellent in suppressing foaming at the time of cleaning, promotes drying of the surface of the cleaning object, and has very little surfactant remaining on the surface of the cleaning object after drying.
本発明者らは、上記目的を達成するために鋭意検討を重ねた結果、特定のアルコールにオキシエチレン基を特定のモル数付加した構造物と、特定のアルコールにオキシエチレン基やオキシプロピレン基を特定の割合で、かつ特定の順序で付加した構造物とを特定の割合で配合した界面活性剤組成物の水溶液が、優れた低泡性を有し、洗浄物の乾燥を促し、かつ界面活性剤の残渣が極めて少ないといった、リンス剤として優れた性能を有することを見出し、本発明の完成に至ったものである。 As a result of intensive studies to achieve the above object, the present inventors have obtained a structure in which a specific mole of an oxyethylene group is added to a specific alcohol, and an oxyethylene group or an oxypropylene group is added to the specific alcohol. An aqueous solution of a surfactant composition formulated with a specific ratio and a structure added in a specific order at a specific ratio has excellent low foaming properties, promotes drying of the washed product, and has a surface activity. The present inventors have found that it has excellent performance as a rinsing agent such that the residue of the agent is extremely small, and has completed the present invention.
すなわち本発明は、下記（Ａ）成分を５０〜９０質量％、下記（Ｂ）成分を１０〜５０質量％含有する硬質表面用リンス剤である。 That is, this invention is a rinse agent for hard surfaces containing 50-90 mass% of the following (A) component, and 10-50 mass% of the following (B) component.
（Ａ）一般式（１）で表される非イオン界面活性剤
Ｒ１Ｏ−（ＥＯ）ａ−Ｈ （１）
（式中、Ｒ１は分岐鎖を有する炭素数６〜８のアルキル基、ＥＯはオキシエチレン基、ａはオキシエチレン基の平均付加モル数で、ａ＝３〜８である。）
(A) Nonionic surfactant R < 1 > O- (EO) a-H represented by General formula (1) (1)
(In the formula, R 1 is an alkyl group having 6 to 8 carbon atoms having a branched chain, EO is an oxyethylene group, a is an average added mole number of the oxyethylene group, and a = 3 to 8)
（Ｂ）一般式（２）で表される非イオン界面活性剤
Ｒ２Ｏ−（ＥＯ）ｂ−（ＰＯ）ｃ−Ｈ （２）
（式中、Ｒ２は３〜４つの分岐鎖を有する炭素数９〜１０のアルキル基、ＥＯはオキシエチレン基、ＰＯはオキシプロピレン基であり、ＥＯおよびＰＯはブロックで付加している。ｂはオキシエチレン基の平均付加モル数で、ｂ＝２〜６であり、ｃはオキシプロピレン基の平均付加モル数で、ｃ＝２〜５であり、ｂ／ｃ＝０．５〜２．０である。）
(B) the general formula (2) nonionic surfactant R 2 O-represented by (EO) b- (PO) c -H (2)
(Wherein R 2 is an alkyl group having 9 to 10 carbon atoms having 3 to 4 branched chains, EO is an oxyethylene group, PO is an oxypropylene group, and EO and PO are added in blocks. B Is the average addition mole number of oxyethylene groups, b = 2-6, c is the average addition mole number of oxypropylene groups, c = 2-5, and b / c = 0.5-2.0. .)
本発明の硬質表面用リンス剤は、洗浄時の泡立ち抑制に優れ、洗浄物表面の乾燥を促し、かつ乾燥後の洗浄物表面への界面活性剤残りが極めて少ないので、従来技術に対して作業効率の向上や不良率の減少が可能となり、大変有用である。
なお、本発明における「硬質表面」とは、金属、セラミックス、ガラスおよびプラスチック等の材質からなる部材の表面をいい、かかる部材としては、例えば、加工部品、金属部品、光学レンズなどの光学部品、ガラス、電子部品、精密部品などが挙げられる。本発明の硬質表面用リンス剤による除去対象は、例えば、切削油や圧延油等の加工油、防錆油、潤滑油、切削金属粉、ワックス、ピッチ、フラックスなどが挙げられる。
The rinsing agent for hard surface of the present invention is excellent in suppressing foaming at the time of cleaning, promotes drying of the surface of the cleaning object, and extremely little surfactant remains on the surface of the cleaning object after drying. It is possible to improve the efficiency and reduce the defective rate, which is very useful.
The “hard surface” in the present invention refers to the surface of a member made of a material such as metal, ceramics, glass, and plastic, and examples of such a member include processed parts, metal parts, optical parts such as optical lenses, Glass, electronic parts, precision parts, etc. are mentioned. Examples of the removal object by the hard surface rinse agent of the present invention include processing oil such as cutting oil and rolling oil, rust prevention oil, lubricating oil, cutting metal powder, wax, pitch, and flux.
以下、本発明の実施形態を説明する。
本発明の硬質表面用リンス剤は、（Ａ）成分の非イオン界面活性剤と、（Ｂ）成分の非イオン界面活性剤とをそれぞれ特定の割合で含有する。各成分について以下に説明する。
Embodiments of the present invention will be described below.
The rinsing agent for hard surface of the present invention contains a nonionic surfactant as the component (A) and a nonionic surfactant as the component (B) at specific ratios. Each component will be described below.
〔（Ａ）成分の非イオン界面活性剤〕
（Ａ）成分は、下記の一般式（１）で表される非イオン界面活性剤である。
Ｒ１Ｏ−（ＥＯ）ａ−Ｈ （１）
[Nonionic surfactant of component (A)]
The component (A) is a nonionic surfactant represented by the following general formula (1).
R 1 O- (EO) a- H (1)
Ｒ１は分岐鎖を有する炭素数６〜８のアルキル基である。濡れ性および水切れの観点から、アルキル基の炭素数は、７〜８が好ましく、特に８が好ましい。
Ｒ１の炭素数が小さすぎると、洗浄物に対する濡れ性に劣ったり、水切れが遅くなったりすることがある。反対に炭素数が大きすぎると、低泡性に劣ることがある。また、Ｒ１が炭素数６〜８の直鎖状のアルキル基であると、泡膜の安定性が高くなることから、低泡性に劣ることがある。
分岐鎖としては、メチル分岐、エチル分岐、プロピル分岐およびブチル分岐が挙げられるが、濡れ性、水切れおよび低泡性の観点から、エチル分岐、プロピル分岐が好ましく、その中でもエチル分岐が特に好ましい。分岐数は１つまたは２つであれば良く、好ましくは１つである。
R 1 is a C 6-8 alkyl group having a branched chain. From the viewpoint of wettability and running out of water, the alkyl group preferably has 7 to 8 carbon atoms, particularly preferably 8 carbon atoms.
If the carbon number of R 1 is too small, the wettability with respect to the washed product may be inferior or water drainage may be delayed. On the other hand, if the carbon number is too large, the low foaming property may be inferior. In addition, when R 1 is a linear alkyl group having 6 to 8 carbon atoms, the stability of the foam film is increased, so that the low foam property may be inferior.
Examples of the branched chain include a methyl branch, an ethyl branch, a propyl branch, and a butyl branch. From the viewpoints of wettability, drainage and low foaming properties, an ethyl branch and a propyl branch are preferable, and among them, an ethyl branch is particularly preferable. The number of branches may be one or two, and is preferably one.
ＥＯはオキシエチレン基であり、ａはオキシエチレン基の平均付加モル数である。オキシエチレン基の平均付加モル数ａは３〜８であり、好ましくは３〜５である。ａが小さすぎると、水への溶解性が低下し、リンス剤が経時的に分離したり、不均一な洗浄となったりするため、リンス剤として最大限の効果を発揮できないことがある。また、ａが大きすぎると、低泡性に劣ったり、洗浄物の乾燥後に洗浄物表面の界面活性剤の残存率が上昇したりすることがある。
なお、一般式（１）で表される非イオン界面活性剤は、１種を単独で使用しても良く、２種類以上を併用しても良い。
EO is an oxyethylene group, and a is the average added mole number of the oxyethylene group. The average added mole number a of the oxyethylene group is 3 to 8, preferably 3 to 5. If a is too small, the solubility in water decreases, and the rinsing agent separates with time or becomes non-uniformly washed, so that the maximum effect as a rinsing agent may not be exhibited. On the other hand, if a is too large, the low foaming property may be inferior, or the residual ratio of the surfactant on the surface of the washed product may increase after the washed product is dried.
In addition, the nonionic surfactant represented by General formula (1) may be used individually by 1 type, and may use 2 or more types together.
〔（Ｂ）成分の非イオン界面活性剤〕
（Ｂ）成分は、下記の一般式（２）で表される非イオン界面活性剤である。
Ｒ２Ｏ−（ＥＯ）ｂ−（ＰＯ）ｃ−Ｈ （２）
[Nonionic surfactant of component (B)]
The component (B) is a nonionic surfactant represented by the following general formula (2).
R 2 O- (EO) b- ( PO) c-H (2)
Ｒ２は３〜４つの分岐鎖を有する炭素数９〜１０のアルキル基である。アルキル基の炭素数は９が好ましい。
Ｒ２の炭素数が小さすぎると、洗浄物に対する濡れ性に劣ることがある。反対に炭素数が大きすぎると、低泡性に劣ったり、洗浄物の乾燥後に洗浄物表面の界面活性剤の残存率が上昇したりすることがある。また、Ｒ２が炭素数９〜１０の直鎖状のアルキル基であると、泡膜の安定性が高くなって低泡性に劣ったり、洗浄物の乾燥後に洗浄物表面の界面活性剤の残存率が上昇したりすることがある。
分岐鎖としては、メチル分岐、エチル分岐およびプロピル分岐などが挙げられるが、分岐鎖の合計炭素数が５以上の場合、濡れ性や水切れに劣ることがあり、また分岐数が２以下の場合、低泡性に劣ったり、洗浄物の乾燥後に洗浄物表面の界面活性剤の残存率が上昇したりすることがある。以上の観点から、分岐鎖はメチル分岐が好ましい。
R 2 is a C 9-10 alkyl group having 3-4 branched chains. The alkyl group preferably has 9 carbon atoms.
If the carbon number of R 2 is too small, the wettability with respect to the washed product may be poor. On the other hand, if the number of carbon atoms is too large, the low foaming property may be inferior, or the residual rate of the surfactant on the surface of the washed product may increase after the washed product is dried. In addition, when R 2 is a linear alkyl group having 9 to 10 carbon atoms, the stability of the foam film is increased and the foam is inferior in low-foaming property. The survival rate may increase.
Examples of the branched chain include a methyl branch, an ethyl branch, and a propyl branch. When the total carbon number of the branched chain is 5 or more, the wettability and water drainage may be inferior, and when the number of branches is 2 or less, The foam may be inferior in low foaming property, or the residual rate of the surfactant on the surface of the washed product may increase after the washed product is dried. From the above viewpoint, the branched chain is preferably a methyl branch.
ＥＯはオキシエチレン基であり、ｂはオキシエチレン基の平均付加モル数である。オキシエチレン基の平均付加モル数ｂは２〜６であり、好ましくは３〜５であり、より好ましくは３〜４である。ｂが小さすぎると、水への溶解性が低下し、リンス剤が経時的に分離したり、不均一な洗浄となったりするため、水切れの悪化や洗浄物表面における界面活性剤の残存率の上昇を引き起こす原因となることがある。また、ｂが大きすぎると、洗浄物の乾燥後に洗浄物表面の界面活性剤の残存率が上昇することがある。 EO is an oxyethylene group, and b is the average added mole number of the oxyethylene group. The average addition mole number b of an oxyethylene group is 2-6, Preferably it is 3-5, More preferably, it is 3-4. If b is too small, the solubility in water decreases, and the rinsing agent separates over time or becomes non-uniform cleaning. May cause a rise. On the other hand, if b is too large, the residual ratio of the surfactant on the surface of the washed product may increase after the washed product is dried.
ＰＯはオキシプロピレン基であり、好ましくはプロピレンオキサイド由来のオキシプロピレン基（メチルオキシエチレン基）である。ｃはオキシプロピレン基の平均付加モル数で、２〜５であり、好ましくは２〜４である。ｃが小さすぎると、低泡性に劣ることがあり、ｃが大きすぎると、水への溶解性が低下し、水切れの悪化や洗浄物表面における界面活性剤の残存率の上昇を引き起こす原因となることがある。 PO is an oxypropylene group, preferably an oxypropylene group derived from propylene oxide (methyloxyethylene group). c is the average number of moles added of the oxypropylene group, and is 2 to 5, preferably 2 to 4. If c is too small, it may be inferior in low-foaming properties, and if c is too large, the solubility in water will decrease, causing the deterioration of water drainage and the increase in the residual ratio of the surfactant on the surface of the washed product. May be.
ｂ／ｃは、オキシエチレン基の平均付加モル数ｂとオキシプロピレン基の平均付加モル数ｃとの比を意味し、０．５〜２．０であり、好ましくは０．５〜１．５であり、より好ましくは０．７〜１．３である。ｂ／ｃが小さすぎる場合、水への溶解性が低下し、水切れの悪化や洗浄物表面における界面活性剤の残存率の上昇を引き起こす原因となることがある。また、ｂ／ｃが大きすぎる場合、親水性が強くなり、濡れ性や低泡性に劣り、水切れが遅くなることがある。 b / c means the ratio of the average addition mole number b of oxyethylene groups to the average addition mole number c of oxypropylene groups, and is 0.5 to 2.0, preferably 0.5 to 1.5. More preferably, it is 0.7-1.3. When b / c is too small, the solubility in water is lowered, which may cause deterioration of water drainage and increase in the residual ratio of the surfactant on the surface of the washed product. Moreover, when b / c is too large, hydrophilicity will become strong, it may be inferior to wettability and low-foaming property, and water drainage may become slow.
ＥＯおよびＰＯはブロックで付加している。互いに位置を入れ替えた場合やランダムで付加した場合には、いずれも低泡性に劣ることがある。
なお、一般式（２）で表される非イオン界面活性剤は、１種を単独で使用しても良く、２種類以上を併用しても良い。
EO and PO are added in blocks. When the positions are exchanged with each other or when the positions are added randomly, the low-foaming property may be inferior.
In addition, the nonionic surfactant represented by General formula (2) may be used individually by 1 type, and may use 2 or more types together.
本発明の硬質表面用リンス剤において、一般式（１）で表される（Ａ）成分の含有量は、５０〜９０質量％であり、好ましくは５０〜８５質量％、特に好ましくは６０〜７５質量％である。また、一般式（２）で表される（Ｂ）成分の含有量は、１０〜５０質量％であり、好ましくは１５〜５０質量％、特に好ましくは２５〜４０質量％である。
（Ａ）成分および（Ｂ）成分の各含有量が上記範囲内であることにより、２成分の界面活性剤同士がお互いに泡膜の気液界面に安定に配向することを妨げるため低泡性に優れるとともに、洗浄物への適度な濡れ性を付与できるため、洗浄物表面の水が素早くリンス剤と置換され、かつ水切れが良いため水乾きに優れ、乾燥後のウォータースポットおよび界面活性剤の残量を低減することができる。（Ａ）成分の含有量が少なすぎたり、（Ｂ）成分の含有量が多すぎたりすると、水切れが遅くなるため、ウォータースポットが生じやすくなることがある。また、（Ａ）成分の含有量が多すぎたり、（Ｂ）成分の含有量が少なすぎたりすると、低泡性に劣ることがある。
In the hard surface rinse agent of the present invention, the content of the component (A) represented by the general formula (1) is 50 to 90% by mass, preferably 50 to 85% by mass, particularly preferably 60 to 75%. % By mass. Moreover, content of (B) component represented by General formula (2) is 10-50 mass%, Preferably it is 15-50 mass%, Most preferably, it is 25-40 mass%.
Since each content of (A) component and (B) component is in the above-mentioned range, the two component surfactants are prevented from being stably aligned with each other at the gas-liquid interface of the foam film. As well as being able to impart moderate wettability to the washed product, the water on the surface of the washed product is quickly replaced with a rinse agent, and the water is well drained, so it is excellent in water drying. The remaining amount can be reduced. If the content of the component (A) is too small, or if the content of the component (B) is too large, water drainage is delayed, and a water spot is likely to occur. Moreover, when there is too much content of (A) component or there is too little content of (B) component, it may be inferior to low foaming property.
本発明の硬質表面用リンス剤は、通常、水に溶解された水溶液にて用いられる。水としては、例えば、水道水、工業用水、脱イオン水が挙げられる。
水溶液における硬質表面用リンス剤の濃度、即ち（Ａ）成分および（Ｂ）成分の合計濃度は、０．００１〜５質量％、好ましくは０．０１〜４質量％、特に好ましくは０．１〜３質量％である。なお、水溶液のリンス剤を使用する際には、さらに水の添加により濃度を調整することができる。
水溶液における本発明の硬質表面用リンス剤の濃度が低すぎると、水切れが遅くなることがあり、リンス剤としての機能が損なわれることがあり、濃度が高すぎると、泡立ちしやすくなるため低泡性に劣ることがあり、また洗浄物の乾燥後に洗浄物表面の界面活性剤の残存率が上昇することがある。
The rinsing agent for hard surface of the present invention is usually used in an aqueous solution dissolved in water. Examples of water include tap water, industrial water, and deionized water.
The concentration of the hard surface rinse agent in the aqueous solution, that is, the total concentration of the component (A) and the component (B) is 0.001 to 5% by mass, preferably 0.01 to 4% by mass, and particularly preferably 0.1 to 5% by mass. 3% by mass. In addition, when using the rinse agent of aqueous solution, a density | concentration can be adjusted by addition of water further.
If the concentration of the rinsing agent for hard surface of the present invention in an aqueous solution is too low, water drainage may be delayed, the function as a rinsing agent may be impaired, and if the concentration is too high, foaming tends to occur and low foam In some cases, the residual ratio of the surfactant on the surface of the washed product may increase after the washed product is dried.
本発明の硬質表面用リンス剤は、リンス剤として使用できる公知の添加剤を、本発明の効果を損なわない範囲内で使用目的に応じて配合することができる。例えば、エチレングリコール、プロピレングリコール、ブチレングリコール、アルキル（炭素数１〜４）ポリアルキレングリコール等のグリコール類；グリセリン、ポリグリセリン、ソルビトール等の多価アルコール類；エタノール、プロパノール、２−プロパノール、低級アルキルエトキシレート等の可溶化剤；色素、香料等を配合することができる。 The hard surface rinse agent of this invention can mix | blend the well-known additive which can be used as a rinse agent according to the intended-use within the range which does not impair the effect of this invention. For example, glycols such as ethylene glycol, propylene glycol, butylene glycol, alkyl (C1-4) polyalkylene glycol; polyhydric alcohols such as glycerin, polyglycerin, sorbitol; ethanol, propanol, 2-propanol, lower alkyl Solubilizing agents such as ethoxylates; pigments, fragrances and the like can be blended.
以下、本発明を実施例および比較例により具体的に説明する。
本発明に用いた化合物およびその合成例を以下に示す。得られた化合物は、１Ｈ−ＮＭＲ分析により、分子設計どおりのＥＯ／ＰＯ比率であることを確認した。
なお、表１および表２に合成した化合物を示す。実施例および比較例中の配合量は質量％である。
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
The compounds used in the present invention and synthesis examples thereof are shown below. The obtained compound was confirmed by 1 H-NMR analysis to have an EO / PO ratio according to the molecular design.
Tables 1 and 2 show the synthesized compounds. The compounding quantity in an Example and a comparative example is the mass%.
（化合物Ａ−１の合成）
オートクレーブに、エチレングリコールモノ−２−エチルヘキシルエーテル（商品名：キョーワノールＯＸ、ＫＨネオケム（株）製）３４８．６ｇ（２ｍｏｌ）および水酸化ナトリウム０．３ｇを仕込み、窒素置換後、撹拌しながら１１０℃に昇温した。次に滴下装置によりエチレンオキシド１７６．２ｇ（４ｍｏｌ）を約８時間かけて滴下した後、２時間反応させた。その後、オートクレーブ内から、反応物を取り出し、塩酸で中和し、含有する水分を除去するため、１２０℃、１時間、減圧処理を行い、最後に濾過により塩を除去して、４９８．０ｇの化合物Ａ−１を得た。
(Synthesis of Compound A-1)
An autoclave was charged with 348.6 g (2 mol) of ethylene glycol mono-2-ethylhexyl ether (trade name: Kyowanol OX, manufactured by KH Neochem) and 0.3 g of sodium hydroxide. The temperature was raised to ° C. Next, 176.2 g (4 mol) of ethylene oxide was added dropwise over about 8 hours using a dropping device, and then reacted for 2 hours. Thereafter, the reaction product was taken out from the autoclave, neutralized with hydrochloric acid, and subjected to reduced pressure treatment at 120 ° C. for 1 hour to remove the contained water. Finally, the salt was removed by filtration, and 498.0 g Compound A-1 was obtained.
（化合物Ａ−２〜Ａ−８の合成）
上記化合物Ａ−１の合成に準じて、表１に示す化合物Ａ−２〜Ａ−８を合成した。
なお、化合物Ａ−８の合成に際しては、イソトリデシルアルコール（製品名：エクサール１３、エクソンモービル社製）を用いた。
(Synthesis of Compounds A-2 to A-8)
Compounds A-2 to A-8 shown in Table 1 were synthesized according to the synthesis of Compound A-1.
In the synthesis of Compound A-8, isotridecyl alcohol (product name: Exal 13, manufactured by ExxonMobil) was used.
（化合物Ｂ−１の合成）
オートクレーブに、３，５，５−トリメチル−１−ヘキサノール（商品名：ノナノール、ＫＨネオケム（株）製）４３３. ０ｇ（３ｍｏｌ）および水酸化カリウム４ｇを仕込み、窒素置換後、撹拌しながら１２０℃に昇温した。次に滴下装置によりエチレンオキシド２６４ｇ（６ｍｏｌ）を約８時間かけて滴下した後、１時間反応させた。続いて滴下装置によりプロピレンオキシド５２３ｇ（９ｍｏｌ）を５時間かけて滴下した後、３時間反応させた。その後、オートクレーブ内から、反応物を取り出し、塩酸で中和し、含有する水分を除去するため、１２０℃、１時間、減圧処理を行い、最後に濾過により塩を除去して、１１６０ｇの化合物Ｂ−１を得た。
(Synthesis of Compound B-1)
An autoclave was charged with 3,5,5-trimethyl-1-hexanol (trade name: Nonanol, manufactured by KH Neochem Co., Ltd.) 433.0 g (3 mol) and 4 g of potassium hydroxide. The temperature was raised to. Next, 264 g (6 mol) of ethylene oxide was dropped over about 8 hours with a dropping device, and then reacted for 1 hour. Subsequently, 523 g (9 mol) of propylene oxide was dropped over 5 hours with a dropping device, and then reacted for 3 hours. Thereafter, the reaction product is taken out from the autoclave, neutralized with hydrochloric acid, and subjected to reduced pressure treatment at 120 ° C. for 1 hour to remove the contained water. Finally, the salt is removed by filtration, and 1160 g of Compound B -1 was obtained.
（化合物Ｂ−２〜Ｂ−９の合成）
上記化合物Ｂ−１の合成に準じて、表２に示す化合物Ｂ−２〜Ｂ−９を合成した。
なお、化合物Ｂ−９の合成に際しては、イソトリデシルアルコール（製品名：エクサール１３、エクソンモービル社製）を用いた。
(Synthesis of Compounds B-2 to B-9)
The compounds B-2 to B-9 shown in Table 2 were synthesized according to the synthesis of the compound B-1.
In the synthesis of Compound B-9, isotridecyl alcohol (product name: EXSAR 13, manufactured by ExxonMobil) was used.
〔実施例１〕
（リンス剤の調製）
ビーカーに化合物Ａ−１：０．７ｇ、化合物Ｂ−１：０．３ｇ、水道水：４９９．０ｇを秤量し、撹拌を行うことで、界面活性剤濃度０．２％のリンス剤を調製した。
調製されたリンス剤について以下の評価を行なった。
[Example 1]
(Preparation of rinse agent)
Compound A-1: 0.7 g, Compound B-1: 0.3 g, and tap water: 499.0 g were weighed into a beaker and stirred to prepare a rinse agent having a surfactant concentration of 0.2%. .
The following evaluation was performed about the prepared rinse agent.
（濡れ性の評価）
ガラス板に対する実施例１のリンス剤の接触角（測定装置：協和界面化学（株）製、Ｄｒｏｐ Ｍａｓｔｅｒシリーズ、ＤＭ−５０１）を測定した。実施例１のリンス剤を、１８Ｇのフッ素樹脂コート針を装着したガラスシリンジに充填し、液滴量を２．０μＬに調整し、着滴１秒後の接触角の測定を行った。１サンプルにつき５回の測定を行い、その平均値を接触角の値とした。なお、評価は以下の基準で行った。結果を表３に示す。実施例１のリンス剤の接触角は２９°であった。
◎（優）：接触角が３５°未満
○（良）：接触角が３５°以上、４０°以下
×（不可）：接触角が４０°超
(Evaluation of wettability)
The contact angle of the rinse agent of Example 1 with respect to the glass plate (measuring device: manufactured by Kyowa Interface Chemical Co., Ltd., Drop Master series, DM-501) was measured. The rinse agent of Example 1 was filled in a glass syringe equipped with an 18G fluororesin-coated needle, the droplet volume was adjusted to 2.0 μL, and the contact angle 1 second after the landing was measured. The measurement was performed 5 times per sample, and the average value was taken as the value of the contact angle. Evaluation was performed according to the following criteria. The results are shown in Table 3. The contact angle of the rinse agent of Example 1 was 29 °.
◎ (excellent): contact angle is less than 35 ° ○ (good): contact angle is 35 ° or more and 40 ° or less × (impossible): contact angle exceeds 40 °
（泡立ちの評価）
１０００ｍＬのトールメスシリンダーに実施例１のリンス剤：２００ｍＬを泡が立たないように加え、温度：２５℃で、ディフーザーストーンを用いてＡｉｒを２００ｍＬ／分で吹き込み、３分後の泡立ちを確認した。泡立ちの評価は、メスシリンダーのメモリを読み取り、泡の容量を測定することで行なった。なお、評価は以下の基準で行った。結果を表３に示す。実施例１のリンス剤の泡の容量は６０ｍＬであった。
◎（優）：１００ｍＬ未満
○（良）：１００ｍＬ以上、２００ｍＬ未満
×（不可）：２００ｍＬ以上
(Evaluation of foaming)
The rinse agent of Example 1: 200 mL was added to a 1000 mL tall graduated cylinder without foaming, and air was blown at 200 mL / min using a diffuser stone at a temperature of 25 ° C., and foaming after 3 minutes was confirmed. . The foaming was evaluated by reading the memory of the graduated cylinder and measuring the foam volume. Evaluation was performed according to the following criteria. The results are shown in Table 3. The volume of the rinse agent foam of Example 1 was 60 mL.
◎ (excellent): less than 100 mL ○ (good): 100 mL or more, less than 200 mL × (impossible): 200 mL or more
（水切れの評価）
ガラス板（７６ｍｍ×２６ｍｍ）の長辺を鉛直方向として、実施例１のリンス剤に３ｃｍ浸漬させた後、ゆっくりと引き上げ、ガラス板を鉛直に吊るした状態で、室温で１０分間静置し、浸漬前と１０分静置後の重量の差を測定した。ブランクとして水道水を用いた場合の測定も行い、実施例１のリンス剤とブランクの水残り量を比較し、下記式３にて水残り量の減少率を算出した。なお、評価は以下の基準で行った。結果を表３に示す。ブランクの水残り量は７０ｍｇ、実施例１のリンス剤の水残り量は１５ｍｇであり、下記式３から水残り量の減少率を算出すると７９％であった。
（式３） 水残り量の減少率（％）＝｛１−（リンス剤の水残り量）／（ブランクの水残り量）｝×１００
◎（優）：水残り量の減少率が８０％以上
○（良）：水残り量の減少率が６０％以上、８０％未満
×（不可）：水残り量の減少率が６０％未満
(Evaluation of running out of water)
With the long side of the glass plate (76 mm × 26 mm) as the vertical direction, after 3 cm immersion in the rinsing agent of Example 1, slowly lifted and left to stand at room temperature for 10 minutes with the glass plate suspended vertically. The difference in weight before immersion and after standing for 10 minutes was measured. Measurement was also performed when tap water was used as a blank, the rinse agent of Example 1 was compared with the amount of remaining water in the blank, and the rate of decrease in the amount of remaining water was calculated using Equation 3 below. Evaluation was performed according to the following criteria. The results are shown in Table 3. The amount of water remaining in the blank was 70 mg, the amount of water remaining in the rinse agent of Example 1 was 15 mg, and the rate of decrease in the amount of water remaining was calculated from the following Equation 3 to be 79%.
(Expression 3) Reduction rate of remaining amount of water (%) = {1− (remaining amount of rinsing agent) / (blank remaining amount of water)} × 100
◎ (Excellent): Reduction rate of remaining water amount is 80% or more ○ (Good): Reduction rate of remaining water amount is 60% or more and less than 80% × (Not possible): Reduction rate of remaining water amount is less than 60%
（界面活性剤の残存率の評価）
ガラス板（７６ｍｍ×２６ｍｍ）の長辺を鉛直方向として、実施例１のリンス剤に４ｃｍ浸漬させた後、ゆっくりと引き上げ、ガラス板の平面を上に向けた状態で、１５０℃の恒温槽で６０分間静置した。その後、乾燥させたガラス板に対する水道水の接触角を測定することで、ガラス板表面の界面活性剤残量を評価した。フッ素樹脂コート針１８Ｇを装着したガラスシリンジに水道水を充填し、液滴量を２．０μＬに調整し、乾燥させたガラス板に着滴１秒後の接触角の測定を行った。１サンプルにつき５回の測定を行い、その平均値を接触角の値とした。なお、ブランクとして清浄なガラス板を用いた場合の水道水の接触角も測定し、実施例１のリンス剤に浸漬後乾燥させたガラス板とブランクのガラス板に対する接触角を比較し、下記式４にて接触角の減少率を算出した。
ガラス板表面に界面活性剤が多く残っている場合、ブランクに対して水道水の接触角は減少することから、評価は以下の基準で行った。結果を表３に示す。ブランクの接触角は５８°、実施例１のリンス剤乾燥後の接触角は５７°であり、下記式３から接触角減少率を算出すると２％であった。
（式４） 接触角減少率（％）＝｛１−（リンス剤乾燥後の接触角）／（ブランクの接触角）｝×１００
◎：接触角減少率が１０％未満
○：接触角減少率が１０％以上、２０％未満
△：接触角減少率が２０％以上、３０％未満
×：接触角減少率が３０％以上
(Evaluation of residual ratio of surfactant)
After dipping 4 cm in the rinse agent of Example 1 with the long side of the glass plate (76 mm × 26 mm) as the vertical direction, it was slowly pulled up and placed in a thermostatic bath at 150 ° C. with the plane of the glass plate facing up. Let stand for 60 minutes. Then, the residual amount of surfactant on the glass plate surface was evaluated by measuring the contact angle of tap water with respect to the dried glass plate. A glass syringe equipped with a fluororesin-coated needle 18G was filled with tap water, the droplet volume was adjusted to 2.0 μL, and the contact angle was measured after 1 second on the dried glass plate. The measurement was performed 5 times per sample, and the average value was taken as the value of the contact angle. The contact angle of tap water when a clean glass plate was used as the blank was also measured, and the contact angle of the glass plate that had been dipped in the rinse agent of Example 1 and dried and the glass plate of the blank was compared. The contact angle reduction rate was calculated at 4.
When a lot of surfactant remained on the surface of the glass plate, the contact angle of tap water with respect to the blank decreased, and thus the evaluation was performed according to the following criteria. The results are shown in Table 3. The contact angle of the blank was 58 °, the contact angle after drying the rinsing agent of Example 1 was 57 °, and the contact angle reduction rate calculated from the following formula 3 was 2%.
(Formula 4) Contact angle reduction rate (%) = {1− (contact angle after rinsing agent drying) / (contact angle of blank)} × 100
◎: Contact angle reduction rate is less than 10% ○: Contact angle reduction rate is 10% or more and less than 20% △: Contact angle reduction rate is 20% or more and less than 30% ×: Contact angle reduction rate is 30% or more
〔実施例２〜８〕
上記実施例１に準じて、リンス剤を調製し評価を行った。結果を表３に示す。
[Examples 2 to 8]
In accordance with Example 1 above, a rinse agent was prepared and evaluated. The results are shown in Table 3.
〔比較例１〜１３〕
上記実施例１に準じて、リンス剤を調製し評価を行った。結果を表４および表５に示す。
[Comparative Examples 1 to 13]
In accordance with Example 1 above, a rinse agent was prepared and evaluated. The results are shown in Table 4 and Table 5.
表３の結果から、化合物Ａ−１〜Ａ−３と、化合物Ｂ−１〜Ｂ−３とを特定の割合で配合し、調製したリンス剤は、優れた濡れ性、水切れ、低泡性を示すだけでなく、洗浄乾燥後の洗浄物表面への界面活性剤の残存率が極めて低いことが分かる。 From the results shown in Table 3, the compound A-1 to A-3 and the compounds B-1 to B-3 were blended at a specific ratio, and the prepared rinse agent has excellent wettability, drainage, and low foamability. It can be seen that the residual ratio of the surfactant on the surface of the washed product after washing and drying is extremely low.
これに対して、表４および表５に示す結果から、本発明の規定範囲から外れる比較例１〜１３では本発明の効果が得られないことが分かる。
比較例１は、一般式（２）で表される化合物におけるオキシプロピレン基の付加モル数が本発明規定の範囲の下限値よりも小さく、一般式（２）におけるｂ／ａが本発明規定の範囲の上限値よりも大きいために、低泡性に劣る。
比較例２は、一般式（２）で表される化合物のオキシエチレン基の付加モル数が本発明規定の範囲の上限値よりも大きいため、界面活性剤の残存率が高くなる。
比較例３は、一般式（２）で表される化合物のアルキル基の分岐数が本発明規定の範囲の下限値よりも小さいため、濡れ性と低泡性に劣る。
比較例４は、一般式（２）で表される化合物のアルキル基が直鎖状であるために、低泡性に劣り、界面活性剤の残存率が若干高くなる。
比較例５は、一般式（２）で表される化合物のアルキル基の炭素数および分岐数が本発明規定の範囲の下限値よりも小さいため、低泡性に劣り、界面活性剤の残存率が若干高くなる。
比較例６は、一般式（２）で表される化合物のアルキル基の炭素数が本発明規定の範囲の上限値よりも大きいため、低泡性に劣り、また界面活性剤の残存率が高くなる。
On the other hand, from the results shown in Tables 4 and 5, it can be seen that the effects of the present invention cannot be obtained in Comparative Examples 1 to 13 that deviate from the specified range of the present invention.
In Comparative Example 1, the number of added oxypropylene groups in the compound represented by the general formula (2) is smaller than the lower limit of the range defined by the present invention, and b / a in the general formula (2) is defined by the present invention. Since it is larger than the upper limit of the range, it is inferior in low foaming property.
In Comparative Example 2, since the number of added oxyethylene groups of the compound represented by the general formula (2) is larger than the upper limit of the range defined in the present invention, the residual ratio of the surfactant is increased.
In Comparative Example 3, since the number of branches of the alkyl group of the compound represented by the general formula (2) is smaller than the lower limit of the range defined in the present invention, the wettability and the low foaming property are inferior.
In Comparative Example 4, since the alkyl group of the compound represented by the general formula (2) is linear, the low foaming property is inferior, and the residual ratio of the surfactant is slightly increased.
In Comparative Example 5, since the number of carbon atoms and the number of branches of the alkyl group of the compound represented by the general formula (2) are smaller than the lower limit value of the range defined in the present invention, the low foaming property is inferior, and the residual ratio of the surfactant Is slightly higher.
In Comparative Example 6, since the number of carbon atoms of the alkyl group of the compound represented by the general formula (2) is larger than the upper limit of the range specified in the present invention, the low-foaming property is poor, and the residual ratio of the surfactant is high. Become.
比較例７は、一般式（１）で表される化合物のオキシエチレン基の付加モル数が本発明規定の範囲の上限値よりも大きいため、低泡性に劣り、さらに界面活性剤の残存率が高くなる。
比較例８は、一般式（１）で表される化合物におけるアルキル基の炭素数が本発明規定の範囲の下限値よりも小さいために、濡れ性と水切れに劣る。
比較例９は、一般式（１）で表される化合物のアルキル基が直鎖状であるために、低泡性に劣り、界面活性剤の残存率が若干高くなる。
比較例１０は、一般式（１）で表される化合物のアルキル基の炭素数が本発明規定の範囲の上限値よりも大きいため、低泡性に劣る。
比較例１１は、一般式（１）で表される化合物のアルキル基の炭素数が本発明規定の範囲の上限値よりも大きく、またオキシエチレン基の付加モル数が本発明規定の範囲の上限値よりも大きいために、低泡性に劣り、さらに界面活性剤の残存率が高くなる。
In Comparative Example 7, the number of moles of oxyethylene groups added to the compound represented by the general formula (1) is larger than the upper limit of the range defined in the present invention, so that the low foaming property is inferior, and the residual ratio of the surfactant Becomes higher.
Since the carbon number of the alkyl group in the compound represented by General formula (1) is smaller than the lower limit of the range prescribed | regulated by this invention, the comparative example 8 is inferior to wettability and water drainage.
In Comparative Example 9, since the alkyl group of the compound represented by the general formula (1) is linear, it is inferior in low-foaming property, and the residual ratio of the surfactant is slightly increased.
Since the carbon number of the alkyl group of the compound represented by General formula (1) is larger than the upper limit of the range prescribed | regulated by this invention, the comparative example 10 is inferior to low-bubble property.
In Comparative Example 11, the number of carbon atoms of the alkyl group of the compound represented by the general formula (1) is larger than the upper limit of the range specified in the present invention, and the number of moles of oxyethylene group added is the upper limit of the range specified in the present invention. Since it is larger than a value, it is inferior to low-foaming property, and also the residual rate of surfactant becomes high.
比較例１２は、一般式（１）で表される（Ａ）成分の含有量が本発明規定の範囲の上限値よりも多く、一般式（２）で表される（Ｂ）成分の含有量が本発明規定の範囲の下限値よりも少ないために、濡れ性および低泡性に劣る。
比較例１３は、一般式（１）で表される（Ａ）成分の含有量が本発明規定の範囲の下限値よりも少なく、一般式（２）で表される（Ｂ）成分の含有量が本発明規定の範囲の上限値よりも多いために、水切れに劣り、界面活性剤の残存率が高くなる。
In Comparative Example 12, the content of the component (A) represented by the general formula (1) is larger than the upper limit value of the range defined by the present invention, and the content of the component (B) represented by the general formula (2) Is lower than the lower limit value of the range defined in the present invention, so that the wettability and the low foaming property are inferior.
In Comparative Example 13, the content of the component (A) represented by the general formula (1) is less than the lower limit value of the range defined in the present invention, and the content of the component (B) represented by the general formula (2) Is more than the upper limit of the range defined in the present invention, the water is inferior and the residual ratio of the surfactant is increased.
Claims (1)
（Ａ）一般式（１）で表される非イオン界面活性剤
Ｒ１Ｏ−（ＥＯ）ａ−Ｈ （１）
（式中、Ｒ１は分岐鎖を有する炭素数６〜８のアルキル基、ＥＯはオキシエチレン基、ａはオキシエチレン基の平均付加モル数で、ａ＝３〜８である。）
（Ｂ）一般式（２）で表される非イオン界面活性剤
Ｒ２Ｏ−（ＥＯ）ｂ−（ＰＯ）ｃ−Ｈ （２）
（式中、Ｒ２は３〜４つの分岐鎖を有する炭素数９〜１０のアルキル基、ＥＯはオキシエチレン基、ＰＯはオキシプロピレン基であり、ＥＯおよびＰＯはブロックで付加している。ｂはオキシエチレン基の平均付加モル数で、ｂ＝２〜６であり、ｃはオキシプロピレン基の平均付加モル数で、ｃ＝２〜５であり、ｂ／ｃ＝０．５〜２．０である。） Rinse agent for hard surface containing 50 to 90% by mass of the following component (A) and 10 to 50% by mass of the following component (B).
(A) Nonionic surfactant R < 1 > O- (EO) a-H represented by General formula (1) (1)
(In the formula, R 1 is an alkyl group having 6 to 8 carbon atoms having a branched chain, EO is an oxyethylene group, a is an average added mole number of the oxyethylene group, and a = 3 to 8)
(B) the general formula (2) nonionic surfactant R 2 O-represented by (EO) b- (PO) c -H (2)
(Wherein R 2 is an alkyl group having 9 to 10 carbon atoms having 3 to 4 branched chains, EO is an oxyethylene group, PO is an oxypropylene group, and EO and PO are added in blocks. B Is the average addition mole number of oxyethylene groups, b = 2-6, c is the average addition mole number of oxypropylene groups, c = 2-5, and b / c = 0.5-2.0. .)
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