JP2732229B2 - Cleaning method and cleaning agent - Google Patents

Cleaning method and cleaning agent

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Publication number
JP2732229B2
JP2732229B2 JP6275714A JP27571494A JP2732229B2 JP 2732229 B2 JP2732229 B2 JP 2732229B2 JP 6275714 A JP6275714 A JP 6275714A JP 27571494 A JP27571494 A JP 27571494A JP 2732229 B2 JP2732229 B2 JP 2732229B2
Authority
JP
Japan
Prior art keywords
cleaning
organic
weight
oil phase
phase
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP6275714A
Other languages
Japanese (ja)
Other versions
JPH08108154A (en
Inventor
宏造 北澤
敦司 田村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp
Original Assignee
Kao Corp
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Filing date
Publication date
Application filed by Kao Corp filed Critical Kao Corp
Priority to JP6275714A priority Critical patent/JP2732229B2/en
Publication of JPH08108154A publication Critical patent/JPH08108154A/en
Application granted granted Critical
Publication of JP2732229B2 publication Critical patent/JP2732229B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Cleaning By Liquid Or Steam (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【産業上の利用分野】本発明は、ガラス、セラミック
ス、金属、プラスチック等の硬質表面の洗浄に用いる洗
浄剤組成物、並びに洗浄方法に関する。特に、油脂、機
械油、焼き入れ油、グリース、切削油等の加工油、ワッ
クス、液晶、フラックス、摩耗粉、切削粉等の汚れが付
着した機械部品、電気部品、電子部品、あるいは各種精
密部品やこれら部品の組立あるいは加工に使用される治
工具類等(以下、機械、精密部品類と言う)の洗浄に用
いる洗浄剤組成物、並びに洗浄方法に関し、さらに詳し
くは洗浄機の洗浄槽内に、液の上層部に洗浄剤由来の有
機物含有量が少ない水相を、液下層部に洗浄剤由来の有
機物含有量の多い油相を形成させ、被洗浄物が油相と接
触する様にして洗浄することを特徴とする洗浄方法にお
いて用いられる洗浄剤組成物、並びに洗浄方法に関す
る。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning composition used for cleaning hard surfaces such as glass, ceramics, metals and plastics, and a cleaning method. In particular, machine parts, electrical parts, electronic parts, or various precision parts to which dirt such as oils and fats, machine oil, quenching oil, grease, cutting oil, etc., wax, liquid crystal, flux, abrasion powder, cutting powder, etc. adhere. And a cleaning composition used for cleaning jigs and the like (hereinafter referred to as machines and precision parts) used for assembling or processing these parts, and a cleaning method, and more specifically, in a cleaning tank of a cleaning machine. In the upper layer of the liquid, an aqueous phase having a low content of organic substances derived from the detergent is formed, and in the lower layer of the liquid, an oil phase having a high content of organic substances derived from the detergent is formed, so that the object to be cleaned comes into contact with the oil phase. The present invention relates to a cleaning composition used in a cleaning method characterized by cleaning, and a cleaning method.

【0002】[0002]

【従来の技術および発明が解決しようとする課題】従
来、油脂、機械油、焼き入れ油、グリース、切削油等の
加工油、ワックス、液晶、フラックス、摩耗粉、切削粉
等の汚れが付着したガラス、セラミックス、金属、プラ
スチック等の硬質表面、例えば機械部品、電気部品、電
子部品、あるいは各種精密部品やこれら部品の組立ある
いは加工に使用される治工具類等の洗浄には、優れた洗
浄力と作業性を有するトリクロロエタンあるいはトリク
ロロトリフルオロエタン等のフロン系溶剤が使用されて
きた。
2. Description of the Related Art Conventionally, dirt such as oils and fats, machine oils, quenching oils, greases, processing oils such as cutting oils, waxes, liquid crystals, fluxes, abrasion powders, cutting powders and the like have adhered. Excellent cleaning power for cleaning hard surfaces such as glass, ceramics, metals, plastics, etc., for example, mechanical parts, electrical parts, electronic parts, various precision parts and jigs and tools used for assembling or processing these parts A fluorocarbon solvent such as trichloroethane or trichlorotrifluoroethane, which has good workability, has been used.

【0003】しかし、これらトリクロロエタンおよびフ
ロン系洗浄剤は、主成分である溶剤類が大気中に蒸発、
拡散することにより、オゾン層破壊等により地球環境を
損なう危険のある事が明らかとなり、その生産および使
用の全廃あるいは使用規制が検討され、または実施され
つつある。
[0003] However, these trichloroethane and chlorofluorocarbon-based cleaning agents have a problem that solvents as a main component evaporate into the atmosphere,
It has become clear that there is a risk of damaging the global environment due to depletion of the ozone layer, etc., due to its diffusion.

【0004】このような動きを受け、これらトリクロロ
エタンおよびフロン系洗浄剤に代替できる各種の代替洗
浄剤あるいは洗浄技術が提案されつつある。例えば、
ケロシン、トルエン、キシレン、石油系溶剤等の炭化水
素系溶剤やそれらに適当量の界面活性剤を加えた洗浄剤
で洗浄する方法、グリコール類や液状低粘度の非イオ
ン性界面活性剤を単独で、あるいはそれに少量の水を含
む洗浄剤濃厚液で洗浄する方法、界面活性剤やビルダ
ーを配合した洗浄剤を多量の水で希釈し使用する方法、
等が代表例として挙げられる。しかし、これらの洗浄剤
あるいは洗浄方法は、洗浄性あるいは洗浄作業環境等の
観点から見た場合、いずれも次のような課題を抱えてい
る。
In response to such a movement, various alternative cleaning agents or cleaning techniques that can be substituted for these trichloroethane and chlorofluorocarbon-based cleaning agents are being proposed. For example,
A method of washing with a hydrocarbon solvent such as kerosene, toluene, xylene, petroleum solvent or a detergent containing an appropriate amount of a surfactant added thereto, glycols or a liquid low-viscosity nonionic surfactant alone. , Or a method of washing with a detergent concentrate containing a small amount of water, a method of diluting a detergent containing a surfactant or a builder with a large amount of water,
And the like are typical examples. However, all of these cleaning agents and cleaning methods have the following problems when viewed from the viewpoint of cleanability, cleaning work environment, and the like.

【0005】例えば、前記のやで例示した炭化水素
系溶剤、グリコール類や液状低粘度の非イオン性界面活
性剤等の有機物、あるいはそれらに引火性防止のため少
量の水を含有させた洗浄液で洗浄する方法は、有機物が
連続相を形成している洗浄液での洗浄である。そして機
械油や金属加工油等の液状有機物の付着した部品からグ
リースあるいはフラックス等の粘稠あるいは固体状有機
物の付着した部品まで、広範な物性を有する有機汚れに
対し優れた洗浄性を示す。これは、有機物が連続相であ
るため、フロンやトリクロロエタンの場合と同様に有機
汚れを洗浄液中に溶解して除去するという洗浄機構を採
るためと考えられる。しかし、これらやの洗浄法は
連続相が有機物であるため、引火に伴う火災や爆発の危
険あるいは炭化水素溶剤やグリコール類等の揮発性有機
成分の蒸発に伴う作業環境悪化の危険を抱えている。ま
た、引火性を防止するため適量の水を含有する洗浄剤に
おいては、洗浄時の水分含有量を適切に管理すれば火災
の危険は無いが、水分管理のための分析機器、水分補給
設備あるいは管理のためのマンパワー等、資金と人の両
面の負担を必要とし、なおかつもう一つの課題である有
機成分の蒸発に伴う作業環境悪化の問題は、依然解決出
来ない。
[0005] For example, organic solvents such as the hydrocarbon solvents, glycols and liquid low-viscosity nonionic surfactants exemplified above, or a washing liquid containing a small amount of water to prevent flammability. The washing method is washing with a washing liquid in which an organic substance forms a continuous phase. In addition, it exhibits excellent detergency against organic dirt having a wide range of physical properties, from parts to which liquid organic substances such as machine oil and metal working oil adhere to parts to which viscous or solid organic substances such as grease or flux adhere. This is presumably because the organic substance is in a continuous phase, and thus a cleaning mechanism is employed in which organic dirt is dissolved in the cleaning liquid and removed as in the case of CFCs and trichloroethane. However, in these cleaning methods, since the continuous phase is organic, there is a risk of fire or explosion due to ignition or a deterioration of the working environment due to evaporation of volatile organic components such as hydrocarbon solvents and glycols. . In the case of cleaning agents containing an appropriate amount of water to prevent flammability, there is no danger of fire if the water content during cleaning is properly controlled, but there is no analytical equipment for water management, water supply equipment or The problem of deterioration of the working environment due to evaporation of organic components, which requires both financial and human burdens, such as manpower for management, cannot be solved yet.

【0006】一方、前記のの界面活性剤やビルダーを
配合した洗浄剤を多量の水で希釈して使用する方法は、
火災の危険や有機成分の蒸発に伴う作業環境悪化の問題
が無く、洗浄作業環境保持の観点からは好ましい洗浄方
法といえる。しかし、この方法は水が連続相を形成して
いる洗浄液で洗浄する方法であるため、やの有機汚
れを溶解除去する洗浄機構と異なり、水中の界面活性剤
が部品あるいはその上に付着している有機汚れに吸着
し、それらの界面張力を低下させ、有機汚れの自己凝集
を促進し、ローリングアップにより除去する洗浄機構を
主体としている。このため、粘稠なグリースや固体状の
汚れであるフラックスやワックス等に対する洗浄力は、
やのような溶解により洗浄する洗浄剤に比べ著しく
劣る。
On the other hand, a method of diluting a detergent containing a surfactant or a builder with a large amount of water and using the same is as follows.
Since there is no problem of fire or deterioration of the working environment due to evaporation of organic components, it can be said that this is a preferable washing method from the viewpoint of maintaining the washing work environment. However, this method is a method of washing with a washing solution in which water forms a continuous phase, so unlike a washing mechanism that dissolves and removes organic dirt, the surfactant in the water adheres to the part or on it. It mainly absorbs organic dirt, lowers their interfacial tension, promotes self-aggregation of organic dirt, and mainly removes them by rolling up. Therefore, the detergency against fluxes and waxes, which are viscous grease and solid dirt,
It is remarkably inferior to a cleaning agent that is washed by dissolution such as fog.

【0007】このため、やに例示した溶解機構によ
る洗浄剤のような各種物性の有機汚れに対する優れた洗
浄性と、に例示した水希釈型洗浄剤の有する非引火
性、低蒸発性等の優れた洗浄作業安全性、の両機能を兼
ね備えた洗浄剤および洗浄方法の出現が望まれていた。
[0007] For this reason, excellent cleaning properties against organic stains of various physical properties such as a cleaning agent by a dissolution mechanism exemplified in the above, and non-flammability, low evaporation property and the like of the water-dilutable cleaning agent exemplified in the above. It has been desired to develop a cleaning agent and a cleaning method having both functions of cleaning work safety.

【0008】かかる実情において、本出願人は、相分離
することを特徴とする洗浄剤あるいはその洗浄剤水溶液
を用い、洗浄機の洗浄槽内において、液の上層部に洗浄
剤由来の有機物含有量が液の下層部より少ない水相を、
液の下層部に洗浄剤由来の有機物含有量が液の上層部よ
り多い油相を形成させ、被洗浄物を該油相と接触するよ
うにして洗浄する工程、および該水相表面上部に設けら
れた液噴射口から水を噴射あるいは噴霧しながら被洗浄
物のすすぎ洗浄を行う工程を有することを特徴とする洗
浄方法、並びにそれに用いる洗浄剤組成物について、す
でに出願済である(特願平6−74254号)。しか
し、ここで用いられる洗浄剤組成物は、ハロゲン原子を
本質的に含まない化合物を好ましいとしているが、比重
を大きくしにくいため、水相と油相への分相に時間がか
かる等の問題があり、これらの点で改良の余地があっ
た。
Under such circumstances, the present applicant uses a cleaning agent characterized by phase separation or an aqueous solution of the cleaning agent, and in a cleaning tank of a cleaning machine, an upper layer of the liquid contains an organic matter content derived from the cleaning agent. Has less aqueous phase than the lower part of the liquid,
A step of forming an oil phase in which the organic matter content derived from the detergent is higher in the lower layer of the liquid than in the upper layer of the liquid, and washing the object to be cleaned so as to come into contact with the oil phase; and A cleaning method characterized by comprising a step of rinsing an object to be cleaned while spraying or spraying water from a liquid injection port provided, and a cleaning composition used for the method, have already been filed (Japanese Patent Application No. Hei 10-284,1992). No. 6-74254). However, although the detergent composition used here is preferably a compound essentially containing no halogen atom, it is difficult to increase the specific gravity, so that it takes time to separate the water phase and the oil phase. There was room for improvement in these respects.

【0009】従って、本発明の目的は、特に上記の洗浄
方法に用いることにより、各種物性の有機汚れに対する
優れた洗浄性が得られると共に、非引火性、低蒸発性等
の優れた洗浄作業安全性を確保できる洗浄剤組成物、並
びに洗浄方法を提供することにある。
[0009] Accordingly, an object of the present invention is to provide, in particular, by using the above-mentioned cleaning method, excellent cleaning properties against organic stains of various physical properties and excellent cleaning work safety such as nonflammability and low evaporation property. An object of the present invention is to provide a cleaning composition and a cleaning method capable of ensuring the property.

【0010】[0010]

【課題を解決するための手段】本発明者らは、かかる実
情に鑑み、鋭意研究を行った結果、上記の洗浄方法にお
いて、炭素原子と直接結合したハロゲン原子を有する有
機化合物を洗浄成分として用いると共に、相分離性能を
適宜調整することによって、上記の目的が達成できるこ
とを見いだし、本発明を完成するに至った。
Means for Solving the Problems In view of such circumstances, the present inventors have conducted intensive studies and as a result, in the above-mentioned cleaning method, an organic compound having a halogen atom directly bonded to a carbon atom is used as a cleaning component. At the same time, it has been found that the above object can be achieved by appropriately adjusting the phase separation performance, and the present invention has been completed.

【0011】即ち、本発明の要旨は、 (1) 炭素原子と直接結合したハロゲン原子を有し沸
点が1気圧において150℃以上の有機化合物を必須成
分として含む洗浄剤あるいはその洗浄剤水溶液を用い
て、洗浄機の洗浄槽内において、液の上層部に洗浄剤由
来の該有機物の含有量が液の下層部より少ない水相を、
液の下層部に洗浄剤由来の該有機物の含有量が液の上層
部より多い油相を形成させ、被洗浄物を該油相と接触す
るようにして洗浄することを特徴とする洗浄方法、 (2) 洗浄剤あるいはその洗浄剤水溶液を20〜10
0℃の温度で30分静置した時、含有される有機物の5
0重量%以上が油相を形成して水相から分離する前記
(1)記載の洗浄方法、 (3) 含有される有機物の50重量%以上99重量%
以下が油相を形成して水相から分離する前記(2)記載
の洗浄方法、 (4) 含有される有機物の80重量%以上99重量%
以下が油相を形成して水相から分離する前記(2)記載
の洗浄方法、 (5) 洗浄剤成分中に炭素原子と直接結合したハロゲ
ン原子を有し沸点が1気圧において150℃以上の有機
化合物を必須成分として含み、その洗浄剤あるいはその
洗浄剤の水溶液を20〜100℃の温度で30分静置し
たとき、液の上層部に洗浄剤由来の有機物含有量が下層
部よりも少ない水相を、液の下層部に洗浄剤由来の有機
物含有量が上層部よりも多い油相を形成するように相分
離し、かつ前記(1)〜(4)いずれか記載の洗浄方法
に使用されることを特徴とする洗浄剤組成物、 (6) 洗浄剤あるいはその洗浄剤の水溶液を20〜1
00℃の温度で30分静置した時、含有される有機物の
50重量%以上が油相を形成して水相から分離し、かつ
その油相の比重が水相の比重より大きく、そのため上層
に水相を下層に油相を形成することを特徴とする前記
(5)記載の洗浄剤組成物、 (7) 含有される有機物の50重量%以上99重量%
以下が油相を形成して水相から分離する前記(6)記載
の洗浄剤組成物、 (8) 含有される有機物の80重量%以上99重量%
以下が油相を形成して水 相から分離する前記(6)記載
の洗浄剤組成物、 (9) 洗浄剤の有機成分中に炭素原子と直接結合した
ハロゲン原子を有する有機化合物を30重量%以上含む
前記(5)〜(8)いずれか記載の洗浄剤組成物、 (10) 洗浄剤の有機成分中に、平均HLB7〜15
の非イオン界面活性剤を0.1〜30重量%含む前記
(5)〜(9)いずれか記載の洗浄剤組成物、 に関す
る。
That is, the gist of the present invention is as follows: (1) A compound having a halogen atom directly bonded to a carbon atom
Organic compounds with a temperature of 150 ° C or higher at 1 atm
Using a cleaning agent or an aqueous solution of the cleaning agent
In the washing tank of the washing machine, an aqueous phase in which the content of the organic matter derived from the detergent is lower than the lower part of the liquid in the upper part of the liquid,
A washing method characterized by forming an oil phase in which the content of the organic substance derived from the detergent in the lower layer of the liquid is higher than that of the upper layer of the liquid, and washing the object to be cleaned in contact with the oil phase; (2) Detergent or aqueous solution of the detergent for 20 to 10
When left at a temperature of 0 ° C. for 30 minutes, 5
0% by weight or more forms an oil phase and separates from the aqueous phase
( 3) The washing method according to (1), (3) 50% by weight or more and 99% by weight of the contained organic matter.
The following (2), wherein the following forms an oil phase and separates from the aqueous phase:
The method of cleaning, (4) 80 wt% to 99 wt% of the organic material contained
The following (2), wherein the following forms an oil phase and separates from the aqueous phase:
The method of cleaning, (5) halogen bonded directly to carbon atoms in the detergent component
Organic compounds having a boiling point of 150 ° C or more at 1 atm.
Contains a compound as an essential component, its cleaning agent or its
Leave the aqueous solution of the detergent at a temperature of 20-100 ° C for 30 minutes.
When the organic matter content derived from the detergent is
Part of the aqueous phase, the organic layer derived from the detergent
Phase so that the oil content is higher than that of the upper layer.
The cleaning method according to any one of (1) to (4) above,
Detergent composition characterized in that it is used in an aqueous solution of (6) detergent, or the cleaning agent 1:20
When left at a temperature of 00 ° C. for 30 minutes,
50% by weight or more forms an oil phase and separates from an aqueous phase, and
The specific gravity of the oil phase is greater than the specific gravity of the aqueous phase,
Forming an aqueous phase and an oil phase in a lower layer.
(5) The cleaning composition according to (5), (7) 50% by weight or more and 99% by weight of the contained organic matter
The following (6), wherein the following forms an oil phase and separates from the aqueous phase:
Of detergent composition, (8) 80 wt% to 99 wt% of the organic material contained
The following (6), wherein the following forms an oil phase and separates from the aqueous phase:
Detergent composition, bonded directly to a carbon atom in the organic component of (9) detergent
Contains 30% by weight or more of an organic compound having a halogen atom
The detergent composition according to any one of (5) to (8), (10) an average HLB of 7 to 15 in an organic component of the detergent.
Containing 0.1 to 30% by weight of a nonionic surfactant
(5) The cleaning composition according to any one of (9) to (9) .

【0012】本発明の洗浄剤組成物は、洗浄機の洗浄槽
内に、液の上層部に洗浄剤由来の有機物含有量が少ない
水相を、液下層部に洗浄剤由来の有機物含有量の多い油
相を形成させ、被洗浄物が油相と接触する様にして洗浄
する洗浄方法に用いることができる洗浄剤組成物であっ
て、洗浄剤成分中に炭素原子と直接結合したハロゲン原
子を有する有機化合物を必須成分として含み、その洗浄
剤あるいはその洗浄剤の水溶液を20〜100℃の温度
で30分静置したとき、液の上層部に洗浄剤由来の有機
物含有量が下層部よりも少ない水相を、液の下層部に洗
浄剤由来の有機物含有量が上層部よりも多い油相を形成
するように相分離する事を特徴とするものである。
The detergent composition of the present invention comprises, in a washing tank of a washing machine, an aqueous phase containing a small amount of organic substances derived from the detergent in the upper layer of the liquid and an organic substance content derived from the detergent in the lower layer of the liquid. A cleaning composition that can be used in a cleaning method in which a large amount of an oil phase is formed and an object to be cleaned comes into contact with the oil phase and is used for cleaning, wherein a halogen atom directly bonded to a carbon atom is contained in the cleaning component. When the detergent or an aqueous solution of the detergent is allowed to stand at a temperature of 20 to 100 ° C. for 30 minutes, the organic matter content derived from the detergent is higher in the upper layer of the liquid than in the lower layer. The method is characterized in that a small amount of an aqueous phase is phase-separated so as to form an oily phase in the lower part of the liquid, which contains more organic matter derived from the detergent than in the upper part.

【0013】本発明の洗浄剤組成物は、洗浄剤あるいは
その洗浄剤水溶液を静置した時、含有している有機物が
油相を形成して水相から分離し、かつその油相の比重が
水相の比重より大きく、そのため上層に水相を下層に油
相を形成する特性を有する有機物を含有する必要があ
る。
In the cleaning composition of the present invention, when the cleaning agent or the aqueous solution of the cleaning agent is allowed to stand, the contained organic matter forms an oil phase and separates from the aqueous phase, and the specific gravity of the oil phase is increased. It is necessary to contain an organic substance having a specific gravity higher than the specific gravity of the aqueous phase and having the property of forming an aqueous phase in the upper layer and an oil phase in the lower layer.

【0014】このような特性を有する有機物の例として
は、その分子中にフッ素、塩素、臭素あるいは沃素等の
ハロゲン原子を含む有機化合物が挙げられる。このよう
にハロゲン原子を有機分子中にその構成元素として含有
させることにより、有機分子の比重を大きくし、有機汚
れに対する洗浄能力を上げ、その含有量しだいでは、洗
浄剤単独での難燃性も付与できる。洗浄剤として用いる
ためには、過酷な洗浄条件下においてもハロゲン原子が
有機分子中から分解反応等により脱離しにくく、より安
定な結合状態で存在することが望まれ、このためにはこ
れらハロゲン原子は炭素原子と直接結合していることが
必要である。それにより各種洗浄条件下における化学的
安定性が確保できる。
Examples of the organic substance having such characteristics include an organic compound containing a halogen atom such as fluorine, chlorine, bromine or iodine in the molecule. By including halogen atoms as constituent elements in organic molecules in this way, the specific gravity of the organic molecules is increased, the cleaning ability against organic dirt is increased, and depending on the content, the flame retardancy of the cleaning agent alone is also increased. Can be granted. In order to be used as a detergent, it is desirable that halogen atoms are hardly eliminated from organic molecules by a decomposition reaction or the like even under severe washing conditions and exist in a more stable bonding state. Must be directly bonded to a carbon atom. Thereby, chemical stability under various washing conditions can be ensured.

【0015】これらの有機化合物としては、鎖状炭化水
素、芳香族もしくは脂環族の炭化水素、芳香族もしくは
脂環族の炭化水素を含む炭化水素、それらから誘導され
るアルコール、脂肪酸やアミン、それら同士の反応物で
あるエーテル、エステル、ケトンやアマイド、又それら
アルコール、脂肪酸、アミンのエチレンオキサイドやプ
ロピレンオキサイド等のアルキレンオキサイド付加物等
の炭素原子と結合した水素原子の一部もしくは全部をハ
ロゲン原子で置換した化合物が挙げられる。
Examples of these organic compounds include chain hydrocarbons, aromatic or alicyclic hydrocarbons, hydrocarbons including aromatic or alicyclic hydrocarbons, alcohols, fatty acids and amines derived therefrom, Some or all of the hydrogen atoms bonded to carbon atoms, such as ethers, esters, ketones and amides which are the reactants between them, and alkylene oxide adducts such as ethylene oxide and propylene oxide of alcohols, fatty acids and amines, are halogenated. Compounds substituted with an atom are exemplified.

【0016】鎖状炭化水素、芳香族もしくは脂環族の炭
化水素、芳香族もしくは脂環族の炭化水素を含む炭化水
素の炭素原子と結合した水素原子の一部もしくは全部を
ハロゲン原子で置換した化合物の具体例としては、クロ
ロシクロヘキサン、ジクロロベンジル、ジクロロキシレ
ン、クロロトルエン、塩素化ナフタリン、ブロムベンゼ
ン、ジブロムベンゼン、トリクロロベンゼン、フルオロ
スチレン、フルオロトルエン、1,5−ジクロロペンタ
ン、1,4−ジブロモブタン、臭化オクチル等が挙げら
れる。
Part or all of the hydrogen atoms bonded to carbon atoms of hydrocarbons, including chain hydrocarbons, aromatic or alicyclic hydrocarbons, and aromatic or alicyclic hydrocarbons, are substituted with halogen atoms. Specific examples of the compound include chlorocyclohexane, dichlorobenzyl, dichloroxylene, chlorotoluene, chlorinated naphthalene, bromobenzene, dibromobenzene, trichlorobenzene, fluorostyrene, fluorotoluene, 1,5-dichloropentane, and 1,4-dichloropentane. Dibromobutane, octyl bromide and the like.

【0017】鎖状炭化水素、芳香族もしくは脂環族の炭
化水素、芳香族もしくは脂環族の炭化水素を含む炭化水
素から誘導されるアルコール、脂肪酸、またそれら同士
の反応物であるエーテル、エステル、ケトンの具体例と
しては、クロロベンジルアルコール、2,3−ジブロモ
−1−プロパノール、フルオロフェノール、クロロフェ
ノール、ジクロロフェノール、p−クロロアセトフェノ
ン、o−ブロモ安息香酸メチル、2−ブロモイソ酪酸エ
チル、デカブロモジフェニルエーテル、α−ブロモ酪酸
等が挙げられる。
Alcohols and fatty acids derived from chain hydrocarbons, aromatic or alicyclic hydrocarbons, and hydrocarbons including aromatic or alicyclic hydrocarbons, and ethers and esters which are reactants thereof Examples of ketones include chlorobenzyl alcohol, 2,3-dibromo-1-propanol, fluorophenol, chlorophenol, dichlorophenol, p-chloroacetophenone, methyl o-bromobenzoate, ethyl 2-bromoisobutyrate, decaethyl Bromodiphenyl ether, α-bromobutyric acid and the like can be mentioned.

【0018】また、クロロベンジルアルコール、2,3
−ジブロモ−1−プロパノール、フルオロフェノール、
クロロフェノール、ジクロロフェノール等の有するOH
基にエチレンオキサイドやプロピレンオキサイドを、本
発明の洗浄剤組成物が有すべき特性を損なわない範疇で
付加重合させた化合物、等が挙げられる。
Further, chlorobenzyl alcohol, 2,3
-Dibromo-1-propanol, fluorophenol,
OH of chlorophenol, dichlorophenol, etc.
Examples thereof include compounds obtained by addition-polymerizing ethylene oxide or propylene oxide to a group within a range that does not impair the properties that the cleaning composition of the present invention should have.

【0019】これらの中で特に、R1 X(AO)n YR
2 で表される化合物が好ましく、洗浄剤組成物中にそれ
らを30重量%以上含む洗浄剤が好ましい。ここで、R
1 ;炭素数6〜18のフェノール誘導体、R2 ;水素原
子または炭素数1〜10の炭化水素基、X;エーテル
基、エステル基、アミノ基のいずれかを示し、Y;エー
テル基、エステル基のいずれかを示し、(AO);炭素
数2〜4のアルキレンオキサイド、n;(AO)の平均
付加モル数で1〜20の値を示す。前記のハロゲン原子
含有化合物は、単独でまたは2種以上併用して用いられ
る。
Among them, R 1 X (AO) n YR
Compounds represented by 2 are preferred, and detergents containing 30% by weight or more of them in the detergent composition are preferred. Where R
1 ; a phenol derivative having 6 to 18 carbon atoms; R 2 ; a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; X; an ether group, an ester group, or an amino group; Wherein (AO) is an alkylene oxide having 2 to 4 carbon atoms, and n is a value of 1 to 20 as an average addition mole number of (AO). The above halogen atom-containing compounds are used alone or in combination of two or more.

【0020】本発明の洗浄剤組成物であるハロゲン原子
含有有機化合物は、その沸点が1気圧に於いて100℃
以上であることが好ましく、より好ましくは150℃以
上である。地球環境保護あるいは作業環境を悪化させな
いという観点から見ると、洗浄あるいは乾燥工程で洗浄
剤成分が揮発するのは好ましいとはいえないからであ
る。
The halogen atom-containing organic compound which is the cleaning composition of the present invention has a boiling point of 100 ° C. at 1 atm.
Or more, more preferably 150 ° C. or more. From the viewpoint of protecting the global environment or not deteriorating the working environment, it is not preferable to volatilize the detergent component in the washing or drying step.

【0021】また、ハロゲン原子含有有機化合物の有す
る特性、つまり比重の大きな点、洗浄性に優れている
点、あるいは難燃性等の特性を、本発明の洗浄剤に充分
保持させるためには、洗浄剤の有機成分中、30重量%
以上が前述したハロゲン原子含有有機化合物であること
が好ましく、より好ましくは50〜100重量%であ
る。
In order for the cleaning agent of the present invention to sufficiently retain the properties of the halogen-containing organic compound, that is, the properties such as a large specific gravity, excellent cleaning properties, and flame retardancy, 30% by weight in organic components of detergent
The above is preferably the above-mentioned organic compound containing a halogen atom, more preferably 50 to 100% by weight.

【0022】本発明に使用される洗浄剤あるいはその洗
浄剤水溶液は、上層に水相を下層に油相を形成するよう
相分離することが必要であり、上層の水相と下層の油相
の2液層を効率よく短時間で得るために、その洗浄剤あ
るいは洗浄剤水溶液を20〜100℃の温度で30分間
静置したとき、含有している有機物の50重量%以上が
油相を形成して水相から分離し、水相下に油相を形成す
る方が良く、より好ましくは有機物の80重量%以上が
水相から分離できる洗浄剤が望ましい。有機物の分離率
が大きいほど水相中に残存する有機物が少なくなり、火
災や臭気等環境悪化要因も軽減できるため好ましいが、
さらに洗浄後のすすぎ性を考慮に入れると洗浄剤は適度
に水に溶解するほうが良く、その意味からは分離率の上
限は99.9重量%以下、特に99重量%以下が好まし
い。
The detergent used in the present invention or its aqueous solution needs to be phase-separated to form an aqueous phase in the upper layer and an oil phase in the lower layer. In order to efficiently obtain a two-liquid layer in a short time, when the detergent or the detergent aqueous solution is allowed to stand at a temperature of 20 to 100 ° C. for 30 minutes, 50% by weight or more of the contained organic matter forms an oil phase. It is preferable to separate from the aqueous phase to form an oil phase under the aqueous phase, and more preferably, a detergent capable of separating 80% by weight or more of organic substances from the aqueous phase. The larger the separation rate of organic matter, the smaller the amount of organic matter remaining in the aqueous phase, which is preferable because it can reduce environmental deterioration factors such as fire and odor.
Further, considering the rinsing properties after washing, it is better that the detergent is appropriately dissolved in water, and in that sense, the upper limit of the separation rate is preferably 99.9% by weight or less, particularly preferably 99% by weight or less.

【0023】洗浄剤の汚れに対する耐久性あるいは水に
よるリンス時のすすぎ性を向上させるため、洗浄剤の有
機成分中に、前述したハロゲン原子含有化合物以外の、
平均HLB7〜15の非イオン界面活性剤を0.1〜3
0重量%含めるとより好ましい洗浄性を得る事ができ、
さらに好ましくは1〜15重量%である。
In order to improve the durability of the cleaning agent against stains or the rinsing property when rinsing with water, the organic components of the cleaning agent include, in addition to the aforementioned halogen atom-containing compounds,
0.1 to 3 nonionic surfactants having an average HLB of 7 to 15
When 0% by weight is included, more preferable detergency can be obtained,
More preferably, it is 1 to 15% by weight.

【0024】用いられる非イオン界面活性剤としては、
例えばアルキルエーテル型、アルキルアリルエーテル型
等のエーテル型;アルキルエステル型;ポリオキシアル
キレンアルキルアミン等のアミンとの縮合型;ポリオキ
シアルキレンアルキルアマイド等のアミドとの縮合型;
ポリオキシエチレンとポリオキシプロピレンをランダム
またはブロック縮合させたプルロニックまたはテトロニ
ック型;ポリエチレンイミン系等の界面活性剤が挙げら
れる。
The nonionic surfactants used include:
For example, an ether type such as an alkyl ether type or an alkyl allyl ether type; an alkyl ester type; a condensation type with an amine such as a polyoxyalkylene alkylamine; a condensation type with an amide such as a polyoxyalkylene alkyl amide;
Pluronic or tetronic type obtained by random or block condensation of polyoxyethylene and polyoxypropylene; surfactants such as polyethyleneimine.

【0025】本発明で有機物とはTOC(Total
Organic Carbon、全有機炭素)値を有す
る化合物をいう。このTOC値は、基本的にはJIS−
K0102「工場排水試験方法」の中の「有機体炭素
(TOC)」に記載されている、燃焼−赤外線分析法に
より測定され、例えば、島津製作所製,TOC−500
を用いて測定することができる。また、洗浄剤あるいは
その洗浄剤水溶液である洗浄液中における有機物の分離
率とは、洗浄液下層部の洗浄液のTOC値を、下層部の
洗浄液のTOC値と上層部の洗浄液のTOC値の総和で
割り、その値に100を掛けた値を%で表している。
In the present invention, the organic substance is referred to as TOC (Total).
Organic Carbon (total organic carbon) value. This TOC value is basically JIS-
It is measured by the combustion-infrared analysis method described in “Organic Carbon (TOC)” in K0102 “Factory Wastewater Test Method”, and is, for example, TOC-500 manufactured by Shimadzu Corporation.
Can be measured. In addition, the separation rate of organic substances in the cleaning solution or the cleaning solution as an aqueous solution of the cleaning solution is obtained by dividing the TOC value of the cleaning solution in the lower layer of the cleaning solution by the sum of the TOC value of the cleaning solution in the lower layer and the TOC value of the cleaning solution in the upper layer. , And a value obtained by multiplying the value by 100 is represented by%.

【0026】本発明で使用する洗浄剤には、本発明の効
果を失わない範囲で、有機あるいは無機のキレート剤、
ビルダー、シリコーンオイル系の消泡剤、アミン系の防
錆剤、ジエタノールアミンやメチルジエタノールアミン
等のアルカノールアミン類、アルコール類、石油系溶剤
等を適宜配合しても良い。本発明の洗浄剤組成物は、洗
浄剤単独であるいはその水溶液として洗浄に用いられ、
単独で用いられる場合は洗浄剤組成物が予め水分を含有
しており、水溶液として用いられる場合は水分を含有し
ていないか、比較的少量の水分を含有している。
The detergent used in the present invention includes an organic or inorganic chelating agent as long as the effects of the present invention are not lost.
Builders, silicone oil-based defoamers, amine-based rust inhibitors, alkanolamines such as diethanolamine and methyldiethanolamine, alcohols, and petroleum solvents may be appropriately blended. The cleaning composition of the present invention is used for cleaning alone or as an aqueous solution thereof,
When used alone, the detergent composition contains water in advance, and when used as an aqueous solution, it contains no water or contains a relatively small amount of water.

【0027】本発明の洗浄方法は、以上の洗浄剤組成物
を用い、洗浄機の洗浄槽内に、液の上層部に洗浄剤由来
の有機物含有量が下相部よりも少ない水相を、液下層部
に洗浄剤由来の有機物含有量が上相部よりも多い油相を
形成させ、被洗浄物が油相と接触する様にして洗浄する
ことを特徴とするものである。被洗浄物である機械、精
密部品類の洗浄に当たっては、本発明の洗浄剤あるいは
その洗浄剤水溶液からなる洗浄液が、洗浄剤由来の有機
物の含有量の少ない水相を上層、洗浄剤濃厚液である油
相を下層として存在する液中に、該機械、精密部品類を
一定時間浸漬することにより行われる。この際、充分な
洗浄性を得るため、被洗浄物である機械、精密部品類は
その全体が下層の油相に接触した方が良く、油層に充分
に浸漬できればより良好な洗浄性を得ることができる。
油相は連続していても油滴状を呈していても良いが、連
続した油相を含む状態で洗浄する方が洗浄性の観点から
も、洗浄作業環境維持の観点からもより好ましい。
In the cleaning method of the present invention, the above-described cleaning composition is used, and in the cleaning tank of the cleaning machine, an aqueous phase in which the content of organic substances derived from the cleaning agent is lower than that of the lower phase in the upper layer of the liquid. An oil phase in which the content of organic substances derived from the detergent is higher in the lower layer than in the upper phase is formed, and the object to be cleaned is washed so as to come into contact with the oil phase. When cleaning the machine to be cleaned and precision parts, the cleaning liquid of the cleaning agent of the present invention or an aqueous solution of the cleaning agent is used as the upper layer of the aqueous phase containing a small amount of organic substances derived from the cleaning agent, and the cleaning agent concentrated liquid. This is carried out by immersing the machine and precision parts in a liquid having a certain oil phase as a lower layer for a certain period of time. At this time, in order to obtain sufficient cleaning properties, it is better that the entire machine or precision part to be cleaned is in contact with the lower oil phase, and if it can be sufficiently immersed in the oil layer, it will obtain better cleaning properties. Can be.
The oil phase may be continuous or oil-drop-shaped, but it is more preferable to wash in a state containing the continuous oil phase from the viewpoint of cleanability and also from the viewpoint of maintaining the cleaning work environment.

【0028】図1に本発明の洗浄方法に用いる洗浄機の
洗浄槽の概略構成図の一例を示すが、洗浄剤あるいはそ
の洗浄剤水溶液である洗浄液に、超音波照射、撹拌また
は液中噴流等の機械力または物理力を与えて洗浄すれ
ば、より良好な洗浄性を得ることができる。図1ではポ
ンプで水相および油相をそれぞれ循環させて各相内を攪
拌する例を示している。機械力等は、下層の油相が水相
である上層の表面上に現れない範囲で加えた方が、臭い
等が少なく洗浄作業環境維持には好ましい。
FIG. 1 shows an example of a schematic configuration diagram of a cleaning tank of a cleaning machine used in the cleaning method of the present invention. The cleaning agent or a cleaning solution as an aqueous solution of the cleaning agent is irradiated with ultrasonic waves, agitated or jetted in the liquid. If the cleaning is performed by applying the mechanical force or physical force described above, better cleaning properties can be obtained. FIG. 1 shows an example in which a water phase and an oil phase are respectively circulated by a pump to stir each phase. It is preferable to add the mechanical force and the like within a range in which the lower oil phase does not appear on the surface of the upper layer, which is the aqueous phase, because it has less odor and the like and is suitable for maintaining the washing work environment.

【0029】洗浄槽内における油相の深さは、洗浄効率
の観点から機械、精密部品類全体が浸漬できる深さ以上
に設定する方が好ましい。また水相の深さは、洗浄作業
環境維持の観点からは油相表面を覆う以上の深さがあれ
ば良いが、水相ですすぎを行う場合は機械、精密部品類
全体がほぼ浸漬できる以上の深さを確保する方が好まし
い。水相中に混入する油性汚れや固体汚れは、その循環
系に設置されたフィルターや油水分離装置等の各種除去
装置で除去しながら使用すれば、より良好な洗浄性が維
持でき好ましい。
The depth of the oil phase in the washing tank is preferably set to be greater than the depth at which the entire machine and precision parts can be immersed from the viewpoint of washing efficiency. The depth of the aqueous phase should be greater than the oil phase surface from the viewpoint of maintaining the washing work environment, but when rinsing with the aqueous phase, the entire machine and precision parts can be almost immersed. It is more preferable to secure the depth of the sheet. It is preferable that the oily dirt and solid dirt mixed in the aqueous phase be used while being removed while being removed by various kinds of removing devices such as a filter and an oil-water separator installed in the circulation system, since better cleaning properties can be maintained.

【0030】被洗浄物である機械、精密部品類をすすぎ
洗浄するため、洗浄槽内の水相表面上部に液噴射口(ノ
ズル)を1〜複数個、通常1〜20個設け、そこからす
すぎ水を噴射または噴霧しながら機械、精密部品類のす
すぎを行うと、水相の深さを浅くしてもすすぎが充分に
でき、その結果洗浄装置全体をより小型でコンパクトに
できる。ここで使用するすすぎ水は、純水、市水、ある
いは図1に示すような水相の循環水、水相を活性炭ある
いは膜分離等の油水分離装置または蒸気化等により再生
した水のいずれでもよい。必要に応じ、このノズルから
下層の油層をポンプにより循環しながら噴射させること
も可能である。
In order to rinse the machine and precision parts to be cleaned, one or more, usually 1 to 20, liquid injection ports (nozzles) are provided above the aqueous phase surface in the cleaning tank, and then rinsed therefrom. When rinsing machines and precision parts while spraying or spraying water, rinsing can be sufficiently performed even when the depth of the aqueous phase is shallow, and as a result, the entire cleaning device can be made smaller and more compact. The rinse water used here may be any of pure water, city water, circulating water of an aqueous phase as shown in FIG. 1, water obtained by regenerating the aqueous phase by activated carbon or an oil-water separator such as membrane separation, or vaporization. Good. If necessary, the lower oil layer can be injected from this nozzle while circulating by a pump.

【0031】これらの洗浄槽は、1槽でも、同様な洗浄
方法の洗浄槽を複数個並べて使用してもよく、また必要
に応じ、すでに公知の従来一般に行われている洗浄方法
と組み合わせて使用してもよい。また、ベルトコンベア
ー等により被洗浄物を搬送しながら被洗浄物を連続的に
洗浄するインライン方式で洗浄してもよく、バレル方式
でもよく、すでに公知の洗浄方式には全て適用可能であ
る。
One of these washing tanks may be used, or a plurality of washing tanks of the same washing method may be used side by side. If necessary, these washing tanks may be used in combination with a known washing method generally used in the prior art. May be. In addition, the object to be cleaned may be continuously washed while being conveyed by a belt conveyor or the like, and may be washed in an in-line system, a barrel system may be used, or any known cleaning system can be applied.

【0032】本発明の洗浄剤組成物、並びに洗浄方法
は、ガラス、セラミックス、金属、プラスチックス等の
硬質表面の洗浄に利用することができる。特に機械部
品、電機部品、精密部品およびその組立加工工程に使用
される治工具類等の洗浄時に特に優れた効果を有する。
ここで精密部品とは、例えば電子部品、電機部品、精密
機械部品、樹脂加工部品、光学部品等をいう。電子部品
とは、例えば電算機およびその周辺機器、家電機器、通
信機器、OA機器、その他電子応用機器等に用いられる
プリント配線基板;ICリードフレーム、抵抗器、コン
デンサー、リレー等の接点部材に用いられるフープ材;
OA機器、時計、電算機器、玩具、家電機器等に用いら
れる液晶表示器;映像・音声記録/再生部品、その関連
部品等に用いられる磁気記録部品;シリコンやセラミッ
クスのウェハ等の半導体材料;水晶振動子等の電歪用部
品;CD、PD、複写機器、光記録機器等に用いられる
光電交換部品などをいう。電磁部品とは、例えばブラ
シ、ロータ、ステータ、ハウジング等の電動機部品;販
売機や各種機器に用いられる発券用部品;販売機、キャ
ッシュディスペンサ等に用いられる貨幣検査用部品など
をいう。精密機器部品とは、例えば精密駆動機器、ビデ
オレコーダー等に用いられるベアリング;超硬チップ等
の加工用部品などをいう。樹脂加工部品とは、例えばカ
メラ、自動車等に用いられる精密樹脂加工部品などをい
う。さらに、光学部品とは、例えばカメラ、眼鏡、光学
機器等に用いられるレンズなどをいい、その他の部品と
して、例えばメガネフレーム、時計ケース、時計ベルト
等が挙げられる。機器部品とは、自動車のエンジンや駆
動部で使用されるギヤ、カムシャフトバネ、シャフト、
ベアリングなどをいう。電機部品とはビデオ等のモータ
ー類、プラスチック製品、電子銃、シャドーマスクなど
をいう。また、組立加工工程に使用される治工具類と
は、上述の各種部品例で示したような精密部品を製造、
成形、加工、組立、仕上げ等の各種工程において取り扱
う治具、工具の他、これらの精密部品を取り扱う各種機
器、その部品等をいう。
The cleaning composition and the cleaning method of the present invention can be used for cleaning hard surfaces such as glass, ceramics, metals and plastics. Particularly, it has a particularly excellent effect when cleaning machine parts, electric parts, precision parts and jigs and the like used in the assembling process.
Here, the precision parts refer to, for example, electronic parts, electric parts, precision machine parts, resin processed parts, optical parts and the like. Electronic components include, for example, printed wiring boards used in computers and their peripheral devices, home appliances, communication devices, OA devices, and other electronic devices; used in contact members such as IC lead frames, resistors, capacitors, and relays. Hoop material;
Liquid crystal display used for OA equipment, clocks, computer equipment, toys, home appliances, etc .; Magnetic recording parts used for video / audio recording / reproducing components, related components; Semiconductor materials such as silicon and ceramic wafers; Quartz Electrostrictive components such as vibrators; photoelectric exchange components used in CDs, PDs, copying machines, optical recording devices, and the like. Electromagnetic components include, for example, motor components such as brushes, rotors, stators, and housings; ticketing components used in vending machines and various devices; and currency inspection components used in vending machines, cash dispensers, and the like. Precision equipment parts include, for example, bearings used in precision drive equipment, video recorders, and the like; machining parts such as carbide chips, and the like. The resin processed parts refer to precision resin processed parts used for cameras, automobiles, and the like, for example. Further, the optical component refers to, for example, a lens used for a camera, eyeglasses, an optical device, and the like, and the other component includes, for example, an eyeglass frame, a watch case, a watch belt, and the like. Equipment parts include gears, camshaft springs, shafts, used in automobile engines and drive units.
Refers to bearings. The electric parts include motors such as video, plastic products, electron guns, shadow masks, and the like. In addition, jigs and tools used in the assembly processing process are used to manufacture precision parts as shown in the various parts examples above,
It refers to jigs and tools handled in various processes such as molding, processing, assembly, and finishing, as well as various devices and components for handling these precision components.

【0033】本発明の洗浄剤組成物、並びに洗浄方法
は、特に上述のうち、フラックスの残存したプリント配
線基板やガラス基板に付着した液晶等の洗浄時に好適な
性能を発揮するが、本発明において洗浄の対象となる機
械、精密部品類は、これらの例に限定されるものではな
く、組立加工工程において各種の加工油やフラックス等
の後工程の妨害物質、又は製品の特性を低下させる各種
の油性汚染物質が付着している一定形状の固体表面を有
する機械、精密部品類であれば、本発明の洗浄剤組成
物、並びに洗浄方法を使用することができる。これらの
汚染物質が、例えば油脂、機械油、焼入れ油、切削油、
グリース、液晶、ロジン系フラックスワックス等の、主
として有機油分の汚れである場合、本発明の洗浄剤組成
物、並びに洗浄方法の特徴が特に発揮される。さらに、
これらに金属粉、無機物粉等が混入した汚れも、有機油
分の除去と一緒に除去されるので、良好に洗浄できる。
The cleaning composition and the cleaning method of the present invention exhibit a suitable performance when cleaning liquid crystal and the like adhering to a printed wiring board or a glass substrate in which flux remains. Machines and precision parts to be cleaned are not limited to these examples, but various kinds of interfering substances such as various processing oils and fluxes in the post-process such as flux in the assembling process, or various characteristics that degrade the characteristics of products The machine composition and the cleaning method of the present invention can be used for machines and precision parts having a fixed solid surface to which oily contaminants are adhered. These contaminants include, for example, fats and oils, machine oils, quenching oils, cutting oils,
When the stain is mainly organic oil, such as grease, liquid crystal, or rosin flux wax, the characteristics of the cleaning composition and the cleaning method of the present invention are particularly exhibited. further,
Dirt mixed with metal powder, inorganic powder and the like is removed together with the removal of the organic oil, so that it can be cleaned well.

【0034】[0034]

【実施例】次に実施例および比較例を挙げて本発明を更
に詳細に説明するが、本発明はこれら実施例等により何
ら限定されるものではない。
The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

【0035】実施例1〜5、比較例1〜3 表1に示す組成の洗浄剤組成物を調製し、これらをイオ
ン交換水で有機物含有量が50重量%になるように希釈
し、その洗浄剤水溶液を10リットルの容量を有する超
音波発振装置および攪拌装置を備えた洗浄機(洗浄槽を
図1に示す)に7リットル入れ、70℃の温度で30分
間静置した。
Examples 1 to 5 and Comparative Examples 1 to 3 Detergent compositions having the compositions shown in Table 1 were prepared, and diluted with ion-exchanged water so that the organic matter content became 50% by weight. 7 liters of the aqueous solution of the agent was put into a washing machine (washing tank shown in FIG. 1) equipped with an ultrasonic oscillator having a capacity of 10 liters and a stirrer, and allowed to stand at 70 ° C. for 30 minutes.

【0036】30分静置後、洗浄槽内の洗浄液表面部及
び液下層部をサンプリングし、洗浄液中の有機物含有量
をTOC値より測定(島津製作所製,TOC−500を
使用)し、分離率を算出した。その結果を表1に示す。
After standing for 30 minutes, the surface of the cleaning liquid and the lower layer of the cleaning liquid in the cleaning tank were sampled, and the organic content of the cleaning liquid was measured from the TOC value (TOC-500, manufactured by Shimadzu Corporation). Was calculated. Table 1 shows the results.

【0037】[0037]

【表1】 [Table 1]

【0038】このとき、実施例1〜5は、70℃でいず
れも含有している有機物の50重量%以上が水溶液中か
ら分離し、上層に水相を下層に洗浄剤の濃厚液である油
相を形成することが確認された。また、20〜100℃
で温度を変えて同様に分離を観察した場合、実施例1は
40℃以上で、他は20℃以上の温度で良好な分離性を
示した。上記に伴い、洗浄液から発生する洗浄剤由来の
臭気は、分離前に比べ分離後はいずれも著しく軽減され
た。一方、比較例1,2も20〜100℃の間の一定の
温度以上で有機物の50重量%以上を水溶液中から分離
したが、上層に油相を下層に水相を形成するため、分離
後の方が強い臭気を発した。
At this time, in Examples 1-5, at 70 ° C., 50% by weight or more of the contained organic matter was separated from the aqueous solution, the upper layer was an aqueous phase, and the lower layer was an oil which was a concentrated solution of a detergent. The formation of a phase was confirmed. Moreover, 20-100 degreeC
When the separation was observed in the same manner while changing the temperature in Example 1, good separation properties were shown at a temperature of 40 ° C. or more in Example 1 and 20 ° C. or more in the other examples. Along with the above, the odor derived from the cleaning agent generated from the cleaning liquid was significantly reduced after the separation as compared with before the separation. On the other hand, in Comparative Examples 1 and 2, 50% by weight or more of the organic matter was separated from the aqueous solution at a certain temperature or higher between 20 and 100 ° C., but an oil phase was formed in the upper layer and an aqueous phase was formed in the lower layer. Had a stronger odor.

【0039】ついで、この30分間静置した後の洗浄液
で、テスト材1:ナフテン系の鉱油(40℃、350
cst)を塗布(10g/m2 )した鋼製テストピース
(10cm×15cm)、又はテスト材2:グリス塗
布(5g/m2 )した鋼製テストピース(10cm×1
5cm)を、テストピースが完全に油相に触れる状態に
しながら洗浄した。洗浄は洗浄温度50℃で0.5分間
超音波を当てながら行い、洗浄後そのテストピースを水
相部に移動して0.5分間超音波リンスし、洗浄槽から
取り出し、後80℃で15分間乾燥した。洗浄後のテス
トピースの洗浄性は、(洗浄前のテストピースの重量−
洗浄後のテストピースの重量)÷(洗浄前のテストピー
スの重量−テストピースそのものの重量)の値に100
を掛け、その値が90以上を◎、75〜89を○、60
〜74を△、60未満を×とした。その結果を表1に併
せて示す。表1より明らかなように、実施例1〜5は良
好な洗浄性を示したが、比較例1、2ではテストピース
を洗浄液から引き上げる際、表層にある油相が大量に付
着し除かれず、充分な洗浄性は得られなかった。
Then, the test liquid 1: naphthenic mineral oil (40 ° C., 350
cst) (10 g / m 2 ) applied to a steel test piece (10 cm × 15 cm) or test material 2: grease applied (5 g / m 2 ) steel test piece (10 cm × 1)
5 cm) was washed while the test piece was completely in contact with the oil phase. Washing is performed at a washing temperature of 50 ° C. while applying ultrasonic waves for 0.5 minutes. After washing, the test piece is moved to the aqueous phase, ultrasonically rinsed for 0.5 minutes, taken out of the washing tank, and then washed at 80 ° C. for 15 minutes. Dried for minutes. The cleanability of the test piece after cleaning is expressed as (weight of test piece before cleaning-
The value of the test piece after cleaning) ÷ (the weight of the test piece before cleaning−the weight of the test piece itself) is 100.
, And the value is 90 or more in 以上, 75 to 89 in ○, 60
74 = 74, and less than 60 ×. The results are shown in Table 1. As is clear from Table 1, Examples 1 to 5 showed good cleaning properties, but in Comparative Examples 1 and 2, when the test piece was pulled out of the cleaning solution, a large amount of the oil phase on the surface layer was not removed because it was attached. Sufficient detergency was not obtained.

【0040】ここで、洗浄槽から取り出した際、乾燥前
のテストピースにイオン交換水を1kg/cm2 の圧力
で液スプレーノズルを用いて、0.5分間すすぎをする
と、実施例1〜5の洗浄性は本操作を行わない場合に比
べ5〜20%上昇した。
Here, when the test piece was taken out of the cleaning tank, the test piece before drying was rinsed with ion-exchanged water at a pressure of 1 kg / cm 2 for 0.5 minute using a liquid spray nozzle. The detergency increased by 5 to 20% as compared with the case where this operation was not performed.

【0041】次いで、実施例1で得られた洗浄液を攪拌
装置で洗浄液全体が均一になるよう攪拌しながら、前述
したと同様なテストピースおよび洗浄方法で洗浄した
(比較例3)。その結果、表1が示すように、比較例3
は実施例1と同じ洗浄剤を使用したにもかかわらず、洗
浄性は低下した。
Next, the washing liquid obtained in Example 1 was washed with the same test piece and washing method as described above while stirring the washing liquid with a stirring device so that the whole washing liquid became uniform (Comparative Example 3). As a result, as shown in Table 1, Comparative Example 3
Although the same detergent was used as in Example 1, the detergency was reduced.

【0042】[0042]

【発明の効果】本発明によると、引火に伴う火災、爆発
等の危険や有機物の揮発による臭い等の作業環境の悪化
を防止でき、かつ、下層で油相をなす洗浄剤濃厚液で洗
浄できるため、液状ないし固体状を呈する各種の有機汚
れに対し高い洗浄性が確保できる。その結果、有機性汚
れと混在する摩耗粉等の無機性汚れに対しても良好な洗
浄効果を発揮させることができる。
According to the present invention, it is possible to prevent the danger of fire and explosion due to ignition and the deterioration of the working environment such as odor due to the volatilization of organic substances, and it is possible to wash with a concentrated solution of a cleaning agent forming an oil phase in the lower layer. Therefore, high cleaning properties can be ensured for various types of organic stains that are liquid or solid. As a result, a good cleaning effect can be exerted on inorganic dirt such as abrasion powder mixed with organic dirt.

【図面の簡単な説明】[Brief description of the drawings]

【図1】図1は、本発明の洗浄方法に用いる洗浄機の洗
浄槽の概略構成図の一例を示すものである。
FIG. 1 shows an example of a schematic configuration diagram of a cleaning tank of a cleaning machine used in the cleaning method of the present invention.

【符号の説明】[Explanation of symbols]

1 ワーク 2 液噴射ノズル 3 ポンプ 4 再生処理槽 5 超音波発振器 DESCRIPTION OF SYMBOLS 1 Work 2 Liquid injection nozzle 3 Pump 4 Regeneration tank 5 Ultrasonic oscillator

───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭58−166972(JP,A) 特開 平5−185045(JP,A) 特開 平6−240299(JP,A) 特開 昭61−296099(JP,A) 特開 昭57−101676(JP,A) 特開 昭48−47903(JP,A) 特開 平4−45842(JP,A) ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-58-166692 (JP, A) JP-A-5-185045 (JP, A) JP-A-6-240299 (JP, A) JP-A 61-1986 296099 (JP, A) JP-A-57-101676 (JP, A) JP-A-48-47903 (JP, A) JP-A-4-45842 (JP, A)

Claims (10)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 炭素原子と直接結合したハロゲン原子を
有し沸点が1気圧において150℃以上の有機化合物を
必須成分として含む洗浄剤あるいはその洗浄剤水溶液を
用いて、洗浄機の洗浄槽内において、液の上層部に洗浄
剤由来の該有機物の含有量が液の下層部より少ない水相
を、液の下層部に洗浄剤由来の該有機物の含有量が液の
上層部より多い油相を形成させ、被洗浄物を該油相と接
触するようにして洗浄することを特徴とする洗浄方法。
1. A halogen atom directly bonded to a carbon atom
Organic compounds having a boiling point of 150 ° C. or more at 1 atm.
Cleaner containing essential components or its aqueous solution
In the washing tank of the washing machine, the aqueous phase in which the content of the organic substance derived from the detergent is lower than that in the lower layer of the liquid in the upper layer of the liquid, and the content of the organic substance derived from the detergent in the lower layer of the liquid. Is formed by forming an oil phase more than the upper layer of the liquid, and washing the object to be cleaned so as to come into contact with the oil phase.
【請求項2】 洗浄剤あるいはその洗浄剤水溶液を20
〜100℃の温度で30分静置した時、含有される有機
物の50重量%以上が油相を形成して水相から分離する
請求項1記載の洗浄方法。
2. A cleaning agent or an aqueous solution of the cleaning agent,
Organics contained when left at a temperature of ~ 100 ° C for 30 minutes
50% by weight or more of the product forms an oil phase and separates from the aqueous phase
The cleaning method according to claim 1.
【請求項3】 含有される有機物の50重量%以上99
重量%以下が油相を形成して水相から分離する請求項2
記載の洗浄方法。
3. An organic substance contained in an amount of 50% by weight or more and 99% or more.
3. A method according to claim 2, wherein less than% by weight forms an oil phase and separates from the aqueous phase.
The cleaning method as described.
【請求項4】 含有される有機物の80重量%以上99
重量%以下が油相を形成して水相から分離する請求項2
記載の洗浄方法。
4. An organic substance contained in an amount of 80% by weight or more and 99% or more.
3. A method according to claim 2, wherein less than% by weight forms an oil phase and separates from the aqueous phase.
The cleaning method as described.
【請求項5】 洗浄剤成分中に炭素原子と直接結合した
ハロゲン原子を有し沸点が1気圧において150℃以上
の有機化合物を必須成分として含み、その洗浄剤あるい
はその洗浄剤の水溶液を20〜100℃の温度で30分
静置したとき、液の上層部に洗浄剤由来の有機物含有量
が下層部よりも少ない水相を、液の下層部に洗浄剤由来
の有機物含有量が上層部よりも多い油相を形成するよう
に相分離し、かつ請求項1〜4いずれか記載の洗浄方法
に使用されることを特徴とする洗浄剤組成物。
5. A detergent component directly bonded to a carbon atom.
Has a halogen atom and a boiling point of 150 ° C or more at 1 atm.
Organic compound as an essential component, and its cleaning agent or
For 30 minutes at a temperature of 20-100 ° C
When left at rest, the organic matter content from the detergent in the upper layer of the liquid
Contains less aqueous phase than the lower layer
To form an oil phase with higher organic matter content than the upper layer
The cleaning method according to any one of claims 1 to 4, wherein the phase is separated.
A cleaning composition characterized by being used for:
【請求項6】 洗浄剤あるいはその洗浄剤の水溶液を2
0〜100℃の温度で30分静置した時、含有される有
機物の50重量%以上が油相を形成して水相から分離
し、かつその油相の比重が水相の比重より大きく、その
ため上層に水相を下層に油相を形成することを特徴とす
る請求項5記載の洗浄剤組成物。
6. A cleaning agent or an aqueous solution of the cleaning agent,
When left at a temperature of 0 to 100 ° C for 30 minutes,
More than 50% by weight of the equipment forms an oil phase and separates from the water phase
And the specific gravity of the oil phase is greater than the specific gravity of the aqueous phase,
Therefore, it is characterized by forming an aqueous phase in the upper layer and an oil phase in the lower layer
The cleaning composition according to claim 5.
【請求項7】 含有される有機物の50重量%以上99
重量%以下が油相を形成して水相から分離する請求項6
記載の洗浄剤組成物。
7. An organic substance contained in an amount of 50% by weight or more and 99% or more.
7. A method according to claim 6, wherein less than% by weight forms an oil phase and separates from the aqueous phase.
The cleaning composition according to the above.
【請求項8】 含有される有機物の80重量%以上99
重量%以下が油相を形成して水相から分離する請求項6
記載の洗浄剤組成物。
8. An organic substance contained in an amount of 80% by weight or more and 99% or more.
7. A method according to claim 6, wherein less than% by weight forms an oil phase and separates from the aqueous phase.
The cleaning composition according to the above.
【請求項9】 洗浄剤の有機成分中に炭素原子と直接結
合したハロゲン原子を有する有機化合物を30重量%以
上含む請求項5〜8いずれか記載の洗浄剤組成物。
9. The method according to claim 9 , wherein the organic components of the cleaning agent are directly bonded to carbon atoms.
30% by weight or less of the organic compound having a combined halogen atom
The cleaning composition according to any one of claims 5 to 8, which comprises the above.
【請求項10】 洗浄剤の有機成分中に、平均HLB7
〜15の非イオン界面活性剤を0.1〜30重量%含む
請求項5〜9いずれか記載の洗浄剤組成物。
10. The composition according to claim 1 , wherein an average HLB of 7 is contained in an organic component of the detergent.
0.1 to 15% by weight of nonionic surfactant
The cleaning composition according to any one of claims 5 to 9.
JP6275714A 1994-10-13 1994-10-13 Cleaning method and cleaning agent Expired - Fee Related JP2732229B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP6275714A JP2732229B2 (en) 1994-10-13 1994-10-13 Cleaning method and cleaning agent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP6275714A JP2732229B2 (en) 1994-10-13 1994-10-13 Cleaning method and cleaning agent

Publications (2)

Publication Number Publication Date
JPH08108154A JPH08108154A (en) 1996-04-30
JP2732229B2 true JP2732229B2 (en) 1998-03-25

Family

ID=17559356

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Application Number Title Priority Date Filing Date
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Country Link
JP (1) JP2732229B2 (en)

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JP2012208993A (en) * 2011-03-30 2012-10-25 Konica Minolta Advanced Layers Inc Manufacturing method of glass substrate for magnetic disks
CN112607823A (en) * 2020-11-27 2021-04-06 三达奥克化学股份有限公司 Oil-water separation additive for industrial cleaning agent and use method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58166972A (en) * 1982-03-26 1983-10-03 新神戸電機株式会社 Washing method

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