JP6874465B2 - Detergent composition for oil stains - Google Patents

Detergent composition for oil stains Download PDF

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JP6874465B2
JP6874465B2 JP2017062910A JP2017062910A JP6874465B2 JP 6874465 B2 JP6874465 B2 JP 6874465B2 JP 2017062910 A JP2017062910 A JP 2017062910A JP 2017062910 A JP2017062910 A JP 2017062910A JP 6874465 B2 JP6874465 B2 JP 6874465B2
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稔之 森川
稔之 森川
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NOF Corp
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Description

本発明は、液体油、変性油脂、グリース等の油汚れを除去するために用いられる油汚れ用洗浄剤組成物に関する。 The present invention relates to a detergent composition for oil stains used for removing oil stains such as liquid oils, modified oils and fats, and greases.

金属加工業やめっき業における脱脂や、水処理フィルターの洗浄など、油汚れの除去を目的とした洗浄は広く行われており、被洗浄物の材質は金属やセラミック、プラスチック、ガラス等、多岐に渡る。また、除去の対象となる油においても、液体油、変性油脂、グリース等、性状は様々である。
このような油汚れの洗浄剤として、例えば特許文献1には炭素数1〜6のアルキル基を有する非イオン界面活性剤、アニオン界面活性剤、炭化水素、水を含む組成物が開示され、特許文献2には炭素数3〜9の分岐鎖アルキル基を有する非イオン界面活性剤、炭素数1〜9の直鎖アルキル基を有する非イオン界面活性剤、アニオン界面活性剤、炭化水素、水を含む組成物が開示されている。
しかしながら、これらの組成物では、洗浄性は高いものの、洗浄時に泡立ってしまい、洗浄装置の排水処理に負荷をかけることがある。
Cleaning for the purpose of removing oil stains, such as degreasing in the metal processing industry and plating industry, and cleaning of water treatment filters, is widely performed, and the material to be cleaned is various, such as metal, ceramic, plastic, and glass. Cross. Further, the oil to be removed also has various properties such as liquid oil, modified oil and fat, and grease.
As a cleaning agent for such oil stains, for example, Patent Document 1 discloses a composition containing a nonionic surfactant having an alkyl group having 1 to 6 carbon atoms, an anionic surfactant, a hydrocarbon, and water. Document 2 describes a nonionic surfactant having a branched alkyl group having 3 to 9 carbon atoms, a nonionic surfactant having a linear alkyl group having 1 to 9 carbon atoms, an anionic surfactant, a hydrocarbon, and water. The composition comprising is disclosed.
However, although these compositions have high detergency, they may foam during cleaning, which may impose a load on the wastewater treatment of the cleaning apparatus.

また、特許文献3には炭素数8〜10の分岐鎖アルキル基を有する非イオン界面活性剤、有機溶剤、水を含む組成物が開示されている。
しかしながら、本組成物では、有機溶剤の効果も相まって変性油の汚れ除去には優れるものの、洗浄液中への油の分散性に劣り、洗浄装置の液面接触部や被洗浄物に汚れが再度付着することがある。
Further, Patent Document 3 discloses a composition containing a nonionic surfactant having a branched chain alkyl group having 8 to 10 carbon atoms, an organic solvent, and water.
However, although this composition is excellent in removing stains on the modified oil due to the effect of the organic solvent, the dispersibility of the oil in the cleaning liquid is inferior, and the stains reattach to the liquid surface contact portion of the cleaning device and the object to be cleaned. I have something to do.

さらに特許文献4には、オキシエチレン基やオキシプロピレン基を有する非イオン界面活性剤とアニオン界面活性剤を含む組成物が開示されている。
しかしながら、本組成物では、液体油の洗浄には優れるものの、高粘性油分に対して洗浄効果を発揮するためには50℃以上の高温が必要であり、50℃未満においては、高粘性油分の除去効果が低いことがあり、また細部の洗浄に対しても洗浄効果が低いことがある。さらに、洗浄液中への油の分散性に劣り、洗浄装置の液面接触部に汚れが再度付着することがある。
このように、低泡性を示しつつ、洗浄液への油分の分散性を高めることで被洗浄物や洗浄装置などへの油分の再付着を防止し、高粘性油分に対しても洗浄性を発揮することができる油汚れ用洗浄剤組成物が求められている。
Further, Patent Document 4 discloses a composition containing a nonionic surfactant having an oxyethylene group or an oxypropylene group and an anionic surfactant.
However, although this composition is excellent for cleaning liquid oils, a high temperature of 50 ° C. or higher is required to exert a cleaning effect on highly viscous oils, and below 50 ° C., the highly viscous oils are present. The removal effect may be low, and the cleaning effect may be low even for cleaning details. Further, the dispersibility of the oil in the cleaning liquid is poor, and dirt may reattach to the liquid surface contact portion of the cleaning device.
In this way, while exhibiting low foaming properties, by improving the dispersibility of the oil content in the cleaning liquid, it is possible to prevent the oil content from reattaching to the object to be cleaned or the cleaning device, and it also exhibits cleaning property against highly viscous oil content. There is a need for a cleaning agent composition for oil stains that can be used.

特開2008−140855号公報Japanese Unexamined Patent Publication No. 2008-140855 特開平11−323382号公報Japanese Unexamined Patent Publication No. 11-3233382 特開2008−111140号公報Japanese Unexamined Patent Publication No. 2008-111140 特開平8−73890号公報Japanese Unexamined Patent Publication No. 8-73890

本発明が解決しようとする課題は、油汚れの洗浄に用いられる洗浄剤組成物であって、泡立ちを抑制することで排水処理の負荷を低減し、油分の分散性を高めることで洗浄装置などへの油分の再付着を防止し、高粘性油分に対しても高い洗浄性を有する油汚れ用洗浄剤組成物を提供することである。 The problem to be solved by the present invention is a cleaning agent composition used for cleaning oil stains, such as a cleaning device by suppressing foaming to reduce the load of wastewater treatment and increasing the dispersibility of oil content. It is an object of the present invention to provide a cleaning agent composition for oil stains, which prevents reattachment of oil to a high-viscosity oil and has high detergency even for highly viscous oil.

上記課題を解決するため、本発明者が鋭意検討した結果、分岐鎖アルキル基を有する非イオン界面活性剤と、HLB(親水親油バランス)の異なる2種類の非イオン界面活性剤とを組み合わせて用いることによって、泡立ちを抑制することで排水処理の負荷を低減し、油分の分散性を高めることで洗浄装置などへの油分の再付着を防止し、高粘性油分に対しても高い洗浄性を有する油汚れ用洗浄剤組成物が得られることを見出し、本発明の完成に至ったものである。 As a result of diligent studies by the present inventor in order to solve the above problems, a nonionic surfactant having a branched alkyl group and two types of nonionic surfactants having different HLBs (hydrophilic lipophilic balance) are combined. By using it, the load of wastewater treatment is reduced by suppressing foaming, the reattachment of oil to cleaning equipment is prevented by increasing the dispersibility of oil, and high detergency is achieved even for highly viscous oil. It has been found that a cleaning agent composition for oil stains can be obtained, and the present invention has been completed.

すなわち本発明は、洗浄剤組成物全量に対して、(A)式(1)で示されるHLBが5〜15の化合物を70〜90質量%、(B)式(2)で示されるHLBが3〜6の化合物を5〜15質量%、および(C)式(3)で示されるHLBが14〜18の化合物を5〜15質量%含有し、前記洗浄剤組成物の5質量%水溶液のpHが6〜8である油汚れ用洗浄剤組成物である。 That is, in the present invention, the compound having an HLB of 5 to 15 represented by the formula (A) (1) is 70 to 90% by mass, and the HLB represented by the formula (B) (2) is 70 to 90% by mass based on the total amount of the detergent composition. 5 to 15% by mass of the compounds of 3 to 6 and 5 to 15% by mass of the compound having an HLB of 14 to 18 represented by the formula (3) in (C), and the 5% by mass aqueous solution of the detergent composition. A detergent composition for oil stains having a pH of 6 to 8.

−O−(AO)a−H ・・・(1)
(式(1)中、Rは炭素数8〜10の分岐鎖アルキル基、AOは炭素数2〜3のオキシアルキレン基を示し、aはオキシアルキレン基の平均付加モル数でありa=4〜11であり、かつ、平均付加モル数が4以上のオキシエチレン基を少なくとも有する。)
R 1- O- (A 1 O) a-H ... (1)
(In the formula (1), R 1 represents a branched alkyl group having 8 to 10 carbon atoms, A 1 O represents an oxyalkylene group having 2 to 3 carbon atoms, and a is the average number of moles of oxyalkylene groups added. = 4-11 der is, and that an average addition mole number Yusuke least four or more oxyethylene groups.)

−O−(AO)b−H ・・・(2)
(式(2)中、Rは炭素数12〜14の分鎖アルキル基または炭素数18の直鎖アルケニル基、AOは炭素数2〜3のオキシアルキレン基を示し、bはオキシアルキレン基の平均付加モル数でありb=2〜8である。)
R 2- O- (A 2 O) b-H ... (2)
(In the formula (2), R 2 is branch Kusaria alkyl group or a straight Kusaria alkenyl group, A 2 O 18 carbon atoms of 12 to 14 carbon atoms represents an oxyalkylene group having 2 to 3 carbon atoms, b Is the average number of moles of oxyalkylene groups added, and b = 2-8 .)

−O−(EO)c−H ・・・(3)
(式(3)中、Rは炭素数12〜18の直鎖アルキル基を示し、EOはオキシエチレン基、cはオキシエチレン基の平均付加モル数でありc=15〜30である。)
R 3- O- (EO) c-H ... (3)
(In formula (3), R 3 represents a straight Kusaria alkyl group from 12 to 18 carbon atoms, EO is an oxyethylene group, c is a c = 15 to 30 is the average addition mole number of oxyethylene groups. )

本発明の油汚れ用洗浄剤組成物は、油汚れの洗浄時に用いられる洗浄剤組成物であって、泡立ちを抑制することで排水処理の負荷を低減し、油分の分散性を高めることで洗浄装置などへの油分の再付着を防止し、高粘性油分に対しても高い洗浄性を示すという効果を奏する。 The cleaning agent composition for oil stains of the present invention is a cleaning agent composition used for cleaning oil stains, and reduces the load of wastewater treatment by suppressing foaming and enhances the dispersibility of oil for cleaning. It has the effect of preventing the reattachment of oil to equipment and the like, and exhibiting high detergency even for highly viscous oil.

以下、本発明の実施形態を説明する。
本発明の油汚れ用洗浄剤組成物(以下、単に「洗浄剤組成物」ともいう。)は、成分(A)、(B)、(C)を含有し、各成分(A)〜(C)の合計は100質量%である。以下、各成分について説明する。
Hereinafter, embodiments of the present invention will be described.
The cleaning agent composition for oil stains of the present invention (hereinafter, also simply referred to as "cleaning agent composition") contains components (A), (B), and (C), and each component (A) to (C). ) Is 100% by mass. Hereinafter, each component will be described.

〔成分(A)〕
成分(A)は下記の式(1)で示される化合物であり、成分(A)として式(1)で示される化合物を1種または2種以上用いることができる。式(1)で示される化合物を用いることにより、浸透性を向上させ、高粘性油分に対して高い洗浄性を示すとともに、低泡性を向上させることができる。
[Component (A)]
The component (A) is a compound represented by the following formula (1), and one or more compounds represented by the formula (1) can be used as the component (A). By using the compound represented by the formula (1), it is possible to improve the permeability, show high detergency against highly viscous oil, and improve low foaming property.

−O−(AO)a−H ・・・(1) R 1- O- (A 1 O) a-H ... (1)

式(1)中のRは、炭素数6〜10の分岐鎖アルキル基を示し、例えば、イソオクチル基、2−エチルヘキシル基、イソノニル基、3,5,5−トリメチルヘキシル基、イソデシル基等が挙げられる。特に炭素数8〜9の分岐鎖アルキル基が好ましい。Rの炭素数が小さすぎる場合や、大きすぎる場合、浸透性に劣り、高粘性油分に対する洗浄性が低下することがある。 R 1 in the formula (1) represents a branched chain alkyl group having 6 to 10 carbon atoms, for example, an isooctyl group, a 2-ethylhexyl group, an isononyl group, a 3,5,5-trimethylhexyl group, an isodecyl group and the like. Can be mentioned. Particularly, a branched chain alkyl group having 8 to 9 carbon atoms is preferable. If the carbon number of R 1 is too small or too large, the permeability may be poor and the detergency for highly viscous oil may be lowered.

Oは炭素数2〜3のオキシアルキレン基を示し、aはオキシアルキレン基の平均付加モル数でありa=2〜15である。このポリオキシアルキレン鎖は同一のオキシアルキレン基が単独で付加して形成されていても良く、2種のオキシアルキレン基が混合して付加して形成されていても良い。特に、オキシエチレン基が単独で付加している化合物と、オキシエチレン基とオキシプロピレン基の2種が混合付加している化合物との2種類を少なくとも組み合わせることが好ましい。さらに、オキシエチレン基とオキシプロピレン基の混合付加化合物の付加形態がR−O−EO−PO−Hの順にブロック付加していることが特に好ましい。
また、オキシエチレン基が単独で付加している化合物においてはa=2〜6が好ましく、オキシエチレン基とオキシプロピレン基の混合付加化合物においてはa=5〜10が好ましい。
さらに、オキシエチレン基とオキシプロピレン基の混合付加化合物において、オキシエチレン基の平均付加モル数をa’、オキシプロピレン基の平均付加モル数をa’’とした場合、a’/a’’が0.5〜1.5であることが特に好ましい。これらの範囲の化合物を選択することで、浸透性をさらに高め、高粘性油分に対してより優れた洗浄性を達成するとともに、低泡性により優れた組成物を得ることができる。
A 1 O represents an oxyalkylene group having 2 to 3 carbon atoms, and a is the average number of moles of oxyalkylene groups added, and a = 2 to 15. This polyoxyalkylene chain may be formed by adding the same oxyalkylene group alone, or may be formed by adding two kinds of oxyalkylene groups in a mixed manner. In particular, it is preferable to combine at least two types of a compound to which an oxyethylene group is added alone and a compound to which two types of an oxyethylene group and an oxypropylene group are mixed and added. Furthermore, it is particularly preferable that the form of addition of mixed addition compounds of oxyethylene groups and oxypropylene groups are block addition in the order of R 1 -O-EO-PO- H.
Further, a = 2 to 6 is preferable for the compound to which the oxyethylene group is added alone, and a = 5 to 10 is preferable for the mixed addition compound of the oxyethylene group and the oxypropylene group.
Further, in the mixed addition compound of oxyethylene group and oxypropylene group, when the average number of moles of oxyethylene group added is a'and the average number of moles of oxypropylene group added is a'', a'/ a'' is obtained. It is particularly preferably 0.5 to 1.5. By selecting a compound in these ranges, it is possible to further enhance the permeability, achieve better detergency against highly viscous oils, and obtain a composition having better low foaming properties.

なお、成分(A)のHLBに規定はないが、好ましくはHLBが4〜13である。 The HLB of the component (A) is not specified, but the HLB is preferably 4 to 13.

本発明の洗浄剤組成物における成分(A)の含有量は、70〜90質量%であり、好ましくは75〜85質量%である。成分(A)の含有量が少なすぎる場合、浸透性や低泡性に劣ることがあり、(A)成分の含有量が多すぎる場合、油分の分散性に劣り、被洗浄物や洗浄装置などに汚れが再度付着することがある。 The content of the component (A) in the detergent composition of the present invention is 70 to 90% by mass, preferably 75 to 85% by mass. If the content of the component (A) is too small, the permeability and low foaming property may be inferior, and if the content of the component (A) is too large, the dispersibility of the oil content is poor, and the object to be cleaned, the cleaning device, etc. Dirt may reattach to.

〔成分(B)〕
成分(B)は下記の式(2)で示される化合物であり、成分(B)として式(2)で示される化合物を1種または2種以上用いることができる。式(2)で示される化合物を用いることにより、油分の分散性を向上させ、被洗浄物や洗浄装置などへの汚れの再付着を防止することができる。
[Component (B)]
The component (B) is a compound represented by the following formula (2), and one or more compounds represented by the formula (2) can be used as the component (B). By using the compound represented by the formula (2), the dispersibility of the oil content can be improved, and the reattachment of dirt to the object to be cleaned, the cleaning device, or the like can be prevented.

−O−(AO)b−H ・・・(2) R 2- O- (A 2 O) b-H ... (2)

式(2)中のRは、炭素数12〜20の直鎖もしくは分岐鎖のアルキル基または炭素数12〜20の直鎖もしくは分岐鎖のアルケニル基を示し、好ましくは炭素数12〜14のアルキル基または炭素数12〜14のアルケニル基である。
の炭素数が小さすぎる場合、油分の分散性に劣り、被洗浄物や洗浄装置などに汚れが再度付着することがある。一方、Rの炭素数が大きすぎる場合、水に対する相溶性が低下するので、洗浄性が低下することがある。
R 2 in the formula (2) represents a linear or branched alkyl group having 12 to 20 carbon atoms or a linear or branched alkenyl group having 12 to 20 carbon atoms, preferably having 12 to 14 carbon atoms. It is an alkyl group or an alkenyl group having 12 to 14 carbon atoms.
If the carbon number of R 2 is too small, the dispersibility of the oil content is poor, and dirt may reattach to the object to be cleaned, the cleaning device, and the like. On the other hand, if the carbon number of R 2 is too large, the compatibility with water is lowered, so that the detergency may be lowered.

Oは炭素数2〜3のオキシアルキレン基を示し、bはオキシアルキレン基の平均付加モル数でありb=1〜20である。bが2以上の場合、ポリオキシアルキレン鎖は同一のオキシアルキレン基が単独で付加していても、2種の異なるオキシアルキレン基が混合して付加していても良い。好ましくは、オキシエチレン基とオキシプロピレン基の2種が混合付加している化合物であり、特に好ましくは、オキシエチレン基とオキシプロピレン基の混合付加形態がR−O−PO−EO−Hの順にブロック付加している化合物である。
さらに、オキシエチレン基とオキシプロピレン基の混合付加化合物において、オキシエチレン基の平均付加モル数をb’、オキシプロピレン基の平均付加モル数をb’’とした場合、b’/b’’が0.5〜0.8であることが特に好ましい。
A 2 O represents an oxyalkylene group having 2 to 3 carbon atoms, b is the average number of moles of oxyalkylene groups added, and b = 1 to 20. When b is 2 or more, the same oxyalkylene group may be added alone to the polyoxyalkylene chain, or two different oxyalkylene groups may be added in a mixed manner. Preferably, a compound of two oxyethylene groups and oxypropylene groups are mixed addition, particularly preferably, a mixed addition form of oxyethylene groups and oxypropylene groups in R 2 -O-PO-EO- H It is a compound in which blocks are added in order.
Further, in the mixed addition compound of the oxyethylene group and the oxypropylene group, when the average number of added moles of the oxyethylene group is b'and the average number of added moles of the oxypropylene group is b'', b'/ b'' is obtained. It is particularly preferably 0.5 to 0.8.

上記の式(2)で示される化合物はHLBが3〜6である。HLBが低すぎる場合、水に対する相溶性が低下するので、洗浄性が低下することがある。なお、オキシアルキレン基の平均付加モル数bを適宜設定することによりHLBが3〜6になるように調整することができる。 The compound represented by the above formula (2) has an HLB of 3 to 6. If the HLB is too low, the compatibility with water will be reduced and the detergency may be reduced. The HLB can be adjusted to 3 to 6 by appropriately setting the average number of moles b of the oxyalkylene group added.

本発明の洗浄剤組成物における成分(B)の含有量は、5〜15質量%であり、好ましくは7〜13質量%である。成分(B)の含有量が少なすぎる場合、油分の分散性に劣り、被洗浄物や洗浄装置などに汚れが再度付着することがある。一方、成分(B)の含有量が多すぎる場合、水に対する相溶性が低下するので、洗浄性が低下することがある。 The content of the component (B) in the detergent composition of the present invention is 5 to 15% by mass, preferably 7 to 13% by mass. If the content of the component (B) is too small, the dispersibility of the oil content is poor, and stains may reattach to the object to be cleaned, the cleaning device, and the like. On the other hand, if the content of the component (B) is too large, the compatibility with water is lowered, so that the detergency may be lowered.

〔成分(C)〕
成分(C)は下記の式(3)で示される化合物であり、成分(C)として式(3)で示される化合物を1種または2種以上用いることができる。式(3)で示される化合物を用いることにより、油分の分散性を向上させ、被洗浄物や洗浄装置などへの汚れの再付着を防止することができる。
[Component (C)]
The component (C) is a compound represented by the following formula (3), and one or more compounds represented by the formula (3) can be used as the component (C). By using the compound represented by the formula (3), the dispersibility of the oil content can be improved, and the reattachment of dirt to the object to be cleaned, the cleaning device, or the like can be prevented.

−O−(EO)c−H ・・・(3) R 3- O- (EO) c-H ... (3)

式(3)中のRは、炭素数12〜20の直鎖もしくは分岐鎖のアルキル基または炭素数12〜20の直鎖もしくは分岐鎖のアルケニル基を示し、好ましくは炭素数12〜14のアルキル基または炭素数12〜14のアルケニル基である。
の炭素数が小さすぎる場合、油分の分散性に劣り、被洗浄物や洗浄装置などに汚れが再度付着することがある。一方、Rの炭素数が大きすぎる場合、水に対する相溶性が低下するので洗浄性が低下することがある。
R 3 in the formula (3) represents a linear or branched alkyl group having 12 to 20 carbon atoms or a linear or branched alkenyl group having 12 to 20 carbon atoms, preferably having 12 to 14 carbon atoms. It is an alkyl group or an alkenyl group having 12 to 14 carbon atoms.
If the carbon number of R 3 is too small, the dispersibility of the oil content is poor, and dirt may reattach to the object to be cleaned, the cleaning device, and the like. On the other hand, when the number of carbon atoms of R 3 is too large, compatibility with water may be reduced cleanability because reduced.

cはオキシエチレン基の平均付加モル数であり、c=11〜50であり、好ましくはc=15〜40であり、特に好ましくはc=15〜30である。 c is the average number of moles of oxyethylene groups added, c = 11 to 50, preferably c = 15 to 40, and particularly preferably c = 15 to 30.

上記の式(3)で示される化合物はHLBが14〜18である。HLBが高すぎる場合、親水性が強くなることで浸透性や低泡性に劣ることがある。なお、オキシエチレン基の平均付加モル数cを適宜設定することによりHLBが14〜18になるように調整することができる。 The compound represented by the above formula (3) has an HLB of 14 to 18. If the HLB is too high, the hydrophilicity may be increased, resulting in poor permeability and low foaming property. The HLB can be adjusted to be 14 to 18 by appropriately setting the average number of moles of oxyethylene groups added.

本発明の洗浄剤組成物における成分(C)の含有量は、5〜15質量%であり、特に7〜13質量%が好ましい。成分(C)の含有量が少なすぎる場合、油分の分散性に劣り、被洗浄物や洗浄装置などに汚れが再度付着することがある。一方、成分(C)の含有量が多すぎる場合、浸透性や低泡性に劣ることがある。 The content of the component (C) in the detergent composition of the present invention is 5 to 15% by mass, particularly preferably 7 to 13% by mass. If the content of the component (C) is too small, the dispersibility of the oil content is poor, and dirt may reattach to the object to be cleaned, the cleaning device, and the like. On the other hand, if the content of the component (C) is too large, the permeability and low foaming property may be inferior.

本発明の油汚れ用洗浄剤組成物は、通常、水に溶解させた水溶液として用いられる。油汚れに対する洗浄性、分散性を示すためには、成分(A)、(B)、(C)を含有する本発明の洗浄剤組成物を、好ましくは0.1質量%以上、特に好ましくは0.5〜2.5質量%含有する水溶液であることが好ましい。
なお、水としては、例えば、上水や水道水、イオン交換水、精製水などを使用することができる。また、本発明の油汚れ用洗浄剤組成物を含有する水溶液を以下、油汚れ用洗浄液ともいう。
The cleaning agent composition for oil stains of the present invention is usually used as an aqueous solution dissolved in water. In order to exhibit detergency and dispersibility against oil stains, the detergent composition of the present invention containing the components (A), (B) and (C) is preferably 0.1% by mass or more, particularly preferably 0.1% by mass or more. It is preferably an aqueous solution containing 0.5 to 2.5% by mass.
As the water, for example, tap water, tap water, ion-exchanged water, purified water and the like can be used. Further, the aqueous solution containing the oil stain cleaning agent composition of the present invention is also hereinafter referred to as an oil stain cleaning liquid.

また、本発明の油汚れ用洗浄剤組成物を5質量%含有する水溶液の室温におけるpHは6〜8が好ましい。pHが低すぎる場合、耐酸性に劣る材質に損傷を与えるおそれがあり、pHが高すぎる場合、成分(A)および成分(B)の水に対する相溶性が低下するために洗浄性が低下することがある。 Further, the pH of the aqueous solution containing 5% by mass of the cleaning agent composition for oil stains of the present invention at room temperature is preferably 6 to 8. If the pH is too low, the material with poor acid resistance may be damaged, and if the pH is too high, the compatibility of the components (A) and (B) with water decreases, resulting in a decrease in detergency. There is.

本発明の油汚れ用洗浄液は、保存安定性を向上させるために、水溶性溶剤を含有していても良い。水溶性溶剤としては、例えば、3−メトキシ−1−ブタノール、3−メトキシ−3−メチル−1−ブタノール等のアルコール系溶剤;エチレングリコール、プロピレングリコール、ポリオキシエチレンポリオキシプロピレングリコール等のグリコール系溶剤;エチレングリコールモノブチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル等のグリコールエーテル系溶剤;等が挙げられ、これらの1種または2種以上が用いられる。水溶性溶剤としてはグリコール系溶剤が好ましく、プロピレングリコール、ポリオキシエチレンポリオキシプロピレングリコールが特に好ましい。
本発明の油汚れ用洗浄液が水溶性溶剤を含有する場合における水溶性溶剤の含有量は、油汚れ用洗浄液中、5〜20質量%が好ましい。
The cleaning liquid for oil stains of the present invention may contain a water-soluble solvent in order to improve storage stability. Examples of the water-soluble solvent include alcohol solvents such as 3-methoxy-1-butanol and 3-methoxy-3-methyl-1-butanol; and glycol-based solvents such as ethylene glycol, propylene glycol and polyoxyethylene polyoxypropylene glycol. Solvents; glycol ether-based solvents such as ethylene glycol monobutyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether; and the like, and one or more of these are used. As the water-soluble solvent, a glycol-based solvent is preferable, and propylene glycol and polyoxyethylene polyoxypropylene glycol are particularly preferable.
When the cleaning liquid for oil stains of the present invention contains a water-soluble solvent, the content of the water-soluble solvent is preferably 5 to 20% by mass in the cleaning liquid for oil stains.

本発明の油汚れ用洗浄液はキレート剤を含有していても良い。キレート剤としては、例えば、エチレンジアミンテトラ酢酸、シュウ酸、マロン酸、コハク酸、アジピン酸、フタル酸、クエン酸、マレイン酸、ケイ酸、グルコン酸、フマル酸、イミノジ酢酸等およびこれらの塩が挙げられ、これらの1種または2種以上が用いられる。キレート剤としては、エチレンジアミンテトラ酢酸、クエン酸およびこれらの塩が好ましい。
本発明の油汚れ用洗浄液がキレート剤を含有する場合におけるキレート剤の含有量は、油汚れ用洗浄液中、1〜10質量%が好ましい。
The cleaning liquid for oil stains of the present invention may contain a chelating agent. Examples of the chelating agent include ethylenediaminetetraacetic acid, oxalic acid, malonic acid, succinic acid, adipic acid, phthalic acid, citric acid, maleic acid, silicic acid, gluconic acid, fumaric acid, iminodiacetic acid and salts thereof. And one or more of these are used. As the chelating agent, ethylenediaminetetraacetic acid, citric acid and salts thereof are preferable.
When the cleaning liquid for oil stains of the present invention contains a chelating agent, the content of the chelating agent is preferably 1 to 10% by mass in the cleaning liquid for oil stains.

本発明の油汚れ用洗浄液は、保存安定性を向上させるために、抗菌剤を含有していても良い。抗菌剤としては、例えば、安息香酸およびその塩、ウンデシレン酸およびその塩、ポリリジン、塩化ベンザルコニウム等が挙げられ、これらの1種または2種以上が用いられる。
本発明の油汚れ用洗浄液が抗菌剤を含有する場合における抗菌剤の含有量は、油汚れ用洗浄液中、0.01〜0.10質量%が好ましい。
The cleaning liquid for oil stains of the present invention may contain an antibacterial agent in order to improve storage stability. Examples of the antibacterial agent include benzoic acid and its salt, undecylenic acid and its salt, polylysine, benzalkonium chloride and the like, and one or more of these are used.
When the cleaning liquid for oil stains of the present invention contains an antibacterial agent, the content of the antibacterial agent is preferably 0.01 to 0.10% by mass in the cleaning liquid for oil stains.

本発明の油汚れ用洗浄剤組成物は、被洗浄物に付着した油汚れの洗浄剤として機能する。被洗浄物としては、例えば、金属、セラミック、プラスチック、ガラス等が挙げられる。 The oil stain cleaning agent composition of the present invention functions as a cleaning agent for oil stains adhering to the object to be cleaned. Examples of the object to be cleaned include metal, ceramic, plastic, glass and the like.

以下、実施例および比較例を挙げて本発明をさらに具体的に説明する。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

<油汚れ用洗浄剤組成物の調製>
表1、表2、表3に示す成分(A)、(B)、(C)を表4、表5に示す割合で混合して、油汚れ用洗浄剤組成物を調製した。なお、水希釈品のpHについては、成分(A)、(B)、(C)の合計含有量が5質量%の水溶液で室温において測定し、いずれの組成物もpH=7であることを確認した。
<Preparation of detergent composition for oil stains>
The components (A), (B), and (C) shown in Tables 1, 2, and 3 were mixed at the ratios shown in Tables 4 and 5 to prepare a detergent composition for oil stains. The pH of the water-diluted product was measured at room temperature with an aqueous solution containing 5% by mass of the total contents of the components (A), (B) and (C), and all the compositions had a pH of 7. confirmed.

Figure 0006874465
Figure 0006874465

Figure 0006874465
Figure 0006874465

Figure 0006874465
Figure 0006874465

<油汚れ用洗浄剤組成物の評価>
実施例と比較例について、下記の各試験を行った。結果を表4、表5に示す。
<Evaluation of cleaning agent composition for oil stains>
The following tests were carried out for Examples and Comparative Examples. The results are shown in Tables 4 and 5.

(1)分散性の評価(液体油分)
成分(A)、(B)、(C)の合計含有量が0.5質量%となるように水を加えた油汚れ用洗浄液49.5gに液体油としてA重油0.5gを加え、25℃下、2分間撹拌した。静置5分後、A重油の分散状態を観察した。
(評価基準)
◎:分層なし
○:若干の分層あり
×:分層あり
(1) Evaluation of dispersibility (liquid oil content)
To 49.5 g of a cleaning solution for oil stains to which water was added so that the total content of the components (A), (B), and (C) was 0.5% by mass, 0.5 g of heavy fuel oil A was added as a liquid oil, and 25 The mixture was stirred at ° C. for 2 minutes. After 5 minutes of standing, the dispersed state of heavy fuel oil A was observed.
(Evaluation criteria)
⊚: No stratification ○: Some stratification Yes ×: With stratification

(2)洗浄性の評価(高粘性油分)
高真空用シリコーングリース(東レ・ダウコーニング社製)を約0.1g塗布したステンレスの試験片を、成分(A)、(B)、(C)の合計含有量が2.5質量%となるように水を加えた油汚れ用洗浄液に浸漬し、40℃下、30分間超音波洗浄した。洗浄後、試験片からのグリースの剥離率を観察した。
(評価基準)
◎:剥離率100%
○:剥離率80%以上100%未満
×:剥離率80%未満
(2) Evaluation of detergency (highly viscous oil content)
A stainless steel test piece coated with approximately 0.1 g of silicone grease for high vacuum (manufactured by Toray Dow Corning) has a total content of components (A), (B), and (C) of 2.5% by mass. It was immersed in a cleaning solution for oil stains to which water was added, and ultrasonically cleaned at 40 ° C. for 30 minutes. After cleaning, the peeling rate of grease from the test piece was observed.
(Evaluation criteria)
⊚: Peeling rate 100%
◯: Peeling rate 80% or more and less than 100% ×: Peeling rate less than 80%

(3)洗浄性の評価(高粘性油分・細部汚れ)
アスファルトをトルエンに溶解させた溶液に100メッシュの金網を浸漬し、余分な液をろ紙に染み込ませて除き、送風乾燥でトルエンを除いた試験片を準備した。この試験片を、成分(A)、(B)、(C)の合計含有量が0.5質量%となるように水を加えた油汚れ用洗浄液に浸漬し、40℃下、20分間超音波洗浄した。洗浄後、試験片からのアスファルトの剥離率および試験片へのアスファルトの再付着を観察した。
(評価基準)
[洗浄性]
◎:剥離率100%
○:剥離率80%以上100%未満
×:剥離率80%未満
[再付着]
○:再付着なし
×:再付着あり
(3) Evaluation of detergency (highly viscous oil and detailed stains)
A 100-mesh wire mesh was immersed in a solution of asphalt dissolved in toluene, excess liquid was soaked in filter paper to remove it, and a test piece from which toluene was removed was prepared by blast drying. This test piece was immersed in a cleaning solution for oil stains to which water was added so that the total content of the components (A), (B), and (C) was 0.5% by mass, and the test piece was immersed at 40 ° C. for more than 20 minutes. It was ultrasonically cleaned. After cleaning, the peeling rate of asphalt from the test piece and the reattachment of asphalt to the test piece were observed.
(Evaluation criteria)
[Cleanability]
⊚: Peeling rate 100%
◯: Peeling rate 80% or more and less than 100% ×: Peeling rate less than 80% [reattachment]
○: No reattachment ×: With reattachment

(4)低泡性の評価
成分(A)、(B)、(C)の合計含有量が0.5質量%となるように水を加えた油汚れ用洗浄液に関して、JIS K3362の手順に則り、40℃における滴下直後の液面からの泡高さを測定した。
(評価基準)
◎:100mm未満
○:100mm以上、120mm未満
×:120mm以上
(4) Evaluation of low foam property Regarding the cleaning liquid for oil stains to which water was added so that the total content of the components (A), (B), and (C) was 0.5% by mass, the procedure of JIS K3362 was followed. , The bubble height from the liquid surface immediately after dropping at 40 ° C. was measured.
(Evaluation criteria)
⊚: less than 100 mm ○: 100 mm or more, less than 120 mm ×: 120 mm or more

Figure 0006874465
Figure 0006874465

Figure 0006874465
Figure 0006874465

実施例1〜7は、いずれも洗浄性、油分の分散性、低泡性が良好であった。
一方、比較例1では、成分(A)の含有量が少ないために浸透性が低下し、洗浄性が不十分であり、低泡性も不十分であった。
比較例2では、成分(C)が含まれていないので、細部汚れに対する洗浄性が不十分であり、油分の分散性が不十分であるため汚れの再付着が認められた。
比較例3では、成分(B)が含まれていないので、細部汚れに対する洗浄性と油分の分散性が不十分であった。
比較例4では、成分(A)のアルキル基の炭素数が本発明の規定範囲外であるので、洗浄性、油分の分散性、および低泡性が不十分であった。
比較例5では、成分(B)のHLBが本発明の規定範囲外である成分(A−6)を用いているので、低泡性および細部汚れに対する洗浄性が不十分であった。また、油分の分散性が不十分であるため汚れの再付着が認められた。
比較例6では、成分(A)のオキシアルキレン基の平均付加モル数が本発明の規定範囲外であるので、洗浄性、油分の分散性、および低泡性が不十分であった。
比較例7では、成分(C)のアルキル基の炭素数が本発明の規定範囲外である成分(A−7)を用いているので、低泡性が不十分であり、また油分の分散性が不充分であるため汚れの再付着が認められた。
In Examples 1 to 7, the detergency, oil content dispersibility, and low foaming property were all good.
On the other hand, in Comparative Example 1, since the content of the component (A) was small, the permeability was lowered, the detergency was insufficient, and the low foaming property was also insufficient.
In Comparative Example 2, since the component (C) was not contained, the detergency against fine stains was insufficient, and the dispersibility of the oil content was insufficient, so that the stains were reattached.
In Comparative Example 3, since the component (B) was not contained, the detergency and oil dispersibility against fine stains were insufficient.
In Comparative Example 4, since the number of carbon atoms of the alkyl group of the component (A) was out of the specified range of the present invention, the detergency, the dispersibility of the oil content, and the low foaming property were insufficient.
In Comparative Example 5, since the HLB of the component (B) uses the component (A-6) which is outside the specified range of the present invention, the low foaming property and the detergency against fine stains were insufficient. In addition, reattachment of dirt was observed due to insufficient dispersibility of the oil content.
In Comparative Example 6, since the average number of moles of the oxyalkylene group of the component (A) was outside the specified range of the present invention, the detergency, the dispersibility of the oil content, and the low foaming property were insufficient.
In Comparative Example 7, since the component (A-7) in which the carbon number of the alkyl group of the component (C) is outside the specified range of the present invention is used, the low foaming property is insufficient and the dispersibility of the oil content is insufficient. However, reattachment of dirt was observed.

Claims (1)

洗浄剤組成物全量に対して、(A)式(1)で示されるHLBが5〜15の化合物を70〜90質量%、(B)式(2)で示されるHLBが3〜6の化合物を5〜15質量%、および(C)式(3)で示されるHLBが14〜18の化合物を5〜15質量%含有し、前記洗浄剤組成物の5質量%水溶液のpHが6〜8である油汚れ用洗浄剤組成物。

−O−(AO)a−H ・・・(1)
(式(1)中、Rは炭素数8〜10の分岐鎖アルキル基、AOは炭素数2〜3のオキシアルキレン基を示し、aはオキシアルキレン基の平均付加モル数でありa=4〜11であり、かつ、平均付加モル数が4以上のオキシエチレン基を少なくとも有する。)

−O−(AO)b−H ・・・(2)
(式(2)中、Rは炭素数12〜14の分岐鎖アルキル基または炭素数18の直鎖アルケニル基、AOは炭素数2〜3のオキシアルキレン基を示し、bはオキシアルキレン基の平均付加モル数でありb=2〜8である。)

−O−(EO)c−H ・・・(3)
(式(3)中、Rは炭素数12〜18の直鎖アルキル基を示し、EOはオキシエチレン基、cはオキシエチレン基の平均付加モル数でありc=15〜30である。)
70 to 90% by mass of the compound having an HLB of 5 to 15 represented by the formula (A) and the compound having an HLB of 3 to 6 represented by the formula (2) with respect to the total amount of the detergent composition. 5 to 15% by mass, and 5 to 15% by mass of a compound having an HLB of 14 to 18 represented by the formula (3) in (C), and the pH of the 5% by mass aqueous solution of the detergent composition is 6 to 8. Detergent composition for oil stains.

R 1- O- (A 1 O) a-H ... (1)
(In the formula (1), R 1 represents a branched alkyl group having 8 to 10 carbon atoms, A 1 O represents an oxyalkylene group having 2 to 3 carbon atoms, and a is the average number of moles of oxyalkylene groups added. = 4-11 der is, and that an average addition mole number Yusuke least four or more oxyethylene groups.)

R 2- O- (A 2 O) b-H ... (2)
In formula (2), R 2 represents a branched chain alkyl group having 12 to 14 carbon atoms or a linear alkenyl group having 18 carbon atoms, A 2 O represents an oxyalkylene group having 2 to 3 carbon atoms, and b represents an oxyalkylene group. The average number of added moles of the group, b = 2-8.)

R 3- O- (EO) c-H ... (3)
(In the formula (3), R 3 represents a linear alkyl group having 12 to 18 carbon atoms, EO is an oxyethylene group, c is the average number of moles of oxyethylene groups added, and c = 15 to 30.)
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