CN1027451C - Detergent compositions - Google Patents
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- CN1027451C CN1027451C CN 90108720 CN90108720A CN1027451C CN 1027451 C CN1027451 C CN 1027451C CN 90108720 CN90108720 CN 90108720 CN 90108720 A CN90108720 A CN 90108720A CN 1027451 C CN1027451 C CN 1027451C
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Abstract
A cleaning composition comprising at least one low molecular weight polyorganosiloxane selected from the group consisting of straight chain polydiorganosiloxane and cyclic polydiorganosiloxane. To use it as a water system cleaning agent, polyoxyalkylene group containing polyorganosiloxane, a surfactant, and water are additionally mixed. Accordingly, a cleaning effect free from environmental destruction and contamination, equivalent to flon containing cleaning agents, and satisfactorily stable in terms of dispersion as a water system cleaning agent can be obtained. In addition, to use as a dewatering cleaning agent, the low molecular weight polyorganosiloxane is additionally mixed alone or with a surfactant and/or a hydrophilic solvent. Accordingly, cleaning and water substituting properties equivalent to flon containing dewatering cleaning agents and environmental safety can be obtained.
Description
The present invention relates to a kind of cleansing compositions that replaces fluorine Lyons class organic solvent detergent.
At metal parts, electroplating part, paint parts, in various parts such as electronic unit, the semiconductor device manufacturing process, be that organic solvents such as fluorine Lyons kind solvent of representative and trichloroethane, trieline, zellon, tetracol phenixin are extensive use of as removing the smeary detergent with fluorine Lyons 113.
Above-mentioned this class organic solvent detergent also can be used as the dehydration detergent after the various parts washings.This detergent can be avoided, when hope during attached to the moisture content convection drying cleaned on the thing, must be under the high temperature (more than 100 ℃) (power loss is big) and spended time thereby production efficiency is reduced, and Yin Gaowen may bring substrate distortion (thermal expansion surpasses permissible value) and needs cooling and thermoshield space and cause the problem such as area increase that is provided with of decontaminating apparatus.
Said herein dehydration detergent, be meant by the quilt after will washing and clean thing dipping or spray, after being attached to the moisture displacement of being cleaned on the thing (water displacement), make it to wave with room temperature or the warm braw below 60 ℃ diffusing, thereby can make by clean thing exsiccant detergent.
Recently, people know that gradually the release in fluorine Lyons can damage the ozone layer, therefore human body and organic sphere are had very big influence, and plan is carried out the phase down of world scale to the use in the high fluorine Lyons 12 of ozone layer destroying coefficient and fluorine Lyons 113, completely forbids up in the future and uses.And, to chlorine class organic solvents such as trieline and zellons, also notice environmental problems such as soil that they cause and underground water, thereby strengthened their use regulation.
Under these circumstances, study destroying the existing low freon-type material of fluorine Lyons kind solvent of ozone coefficient ratio, and a part has been carried out industrial production, even but these materials neither not damage the ozone layer the alternative detergent that therefore is not regarded as fully.
Therefore, as the surrogate of above-mentioned organic solvent class detergent, begin to re-recognize the water class detergent that does not cause environmental disruption and environmental pollution, use tensio-active agent.But, only be a little less than its power of impregnation of detergent of tensio-active agent, for example, can not give full play to its clearing power to the dirt and medium viscosity to the high viscosity greasy dirt of invading the tiny position of parts.
The dirt of removing cloth with siloxane compound is on the books in the public clear 63-50463 communique of spy.This technology discloses to adopt cleans the clean composition of liquid state that the Si number that contains significant quantity in the solvent is the annular siloxane of 4-6, and the purging method of cloth.Yet, the above-mentioned liquid state that contains the silica alkyl compound is cleaned composition, be to be to clean object with cloth, therefore give no thought to cleaning of general industry goods, owing to be only to be the mixed stocker of annular siloxane or annular siloxane and organic solvent, therefore do not consider the system that makes water is cleaned simultaneously yet.And this type systematic, certainly to the dispersed extreme difference of water, even use surfactant also to be difficult to uniform mixing simultaneously, generation at once is separated, and therefore can not use as the water system detergent.
The spy opens and has recorded and narrated aerosol-type water-based cleansing composition in the clear 53-56203 communique, per molecule cooperates the chain polydimethylsiloxane that contains 2-3 Siliciumatom in this water-soluble cleansing composition, its use level is defined as 0.02～0.1(weight) %, therefore can show that abundant raising water system cleans the effect of the clean ability of composition.
Therefore, strong hope invention is a kind of can not to cause environmental problem, and has the ability of enough cleaning, and also possesses as detergent simultaneously can play one's part to the full and stable water system detergent.
On the other hand, as the surrogate of the dehydration detergent of above-mentioned organic solvent, studied the use of the lower alcohol of Virahol and so on.Yet the point of ignition of above-mentioned Virahol is 11.7 ℃, and is lower than room temperature, therefore under common working conditions usually with the danger of fire.And the intermiscibility height of Virahol and water promptly enables to keep the dewatering at initial stage, produces lysed water when using continuously and adheres to, therefore along with its dewatering of time will reduce unavoidably.From the Virahol that contains this water, remove and make with extra care so that when re-using the sizable reinvestment of needs behind the water.And therefore Virahol will use regulation to it to the toxicity height of human body.
Use point of ignition to surpass the hydrocarbon of room temperature, during higher alcohols, dewater easily, but because the volatile performance of himself is low, for example, therefore can not use as the dehydration detergent being lower than dry difficulty under 60 ℃ the low temperature.
Therefore, the object of the invention is to provide a kind of clean ability to compare U.S. with fluorine Lyons class organic solvent detergent, and is also very good as the aspects such as stability of water system, and can not destroy environment and the water system cleansing composition that causes environmental pollution.
Another object of the present invention is to provide a kind of clean ability to compare U.S. with fluorine Lyons class organic solvent detergent, the danger of almost not catching fire simultaneously and so on, and can not cause the cleansing composition of the dehydration usefulness of environmental disruption.
The feature of the present invention's cleansing composition be it contain the straight chain shape polydiorganosiloxane represented by formula I and the ring-type polydiorganosiloxane represented by formula II at least a low-molecular-weight organopolysiloxane that chooses.
(I) formula
(in the formula, R
1Represent the identical or different replacement or any monovalent organic radical of non-replacement, the integer of 1 expression 0～5).
(II) formula
(in the formula, R
1Represent the identical or different replacement or any monovalent organic radical of non-replacement, m is 3～7 integer).
Above-mentioned low-molecular-weight organopolysiloxane can be brought into play very strong power of impregnation to dirt, and if they are independent forms then demonstrate good displacement with water that it is the characteristic component among the present invention.R in above-mentioned (I) formula and (II) formula
1Be to replace or any monovalent organic radical of non-replacement, methyl for example, ethyl, propyl group, the monovalence substituted hydrocarbon radical of alkyl such as butyl and the non-substituted hydrocarbon radical of this class monovalence of phenyl, trifluoromethyl and so on etc., the R of end in the last formula I
1, also can exemplify amino, amide group, acrylate-based, sulfhedryl etc., but from keeping the stability and the volatility of system, preferably methyl.
The present invention's cleansing composition is broadly divided into water system detergent and dehydration detergent.
Lower molecular weight organopolysiloxane when using as the water system detergent, from power of impregnation and detergency viewpoint, preferably use octamethylcyclotetrasiloxane with ring texture, tetradecyl D5 and composition thereof and octamethyltrisiloxane with linear chain structure, decamethyl tetrasiloxane etc.The alkaline strong field of water system cleansing composition, from the stability of polysiloxane, the material that preferably above-mentioned (I) formula is represented with straight chain structure.
Lower molecular weight organopolysiloxane when using as the dehydration detergent from aspects such as water substituting, impregnabilities, preferably has the material of ring texture, and octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane and composition thereof are suitable for.
Below explanation with the present invention's cleansing composition the situation during as the water system detergent.
The lower molecular weight organopolysiloxane that above-mentioned (I) and (II) formula are represented, can bring into play very strong power of impregnation to dirt as mentioned above, but be insoluble to water during their Individual existences, and dispersion stabilization is poor, may cause being separated in the water, therefore, by also using the organopolysiloxane that contains polyoxy alkylidene (being the polyoxy alkylidene that in 1 molecule, has first siloxane unit shown in the formula III at least), good distribution stability can be obtained, and the strong power of impregnation of above-mentioned lower molecular weight organopolysiloxane can be given full play to dirt to water.And, also can by and tensio-active agent improve washing (-)off properties.
Formula III
(in the formula, R
2The expression alkyl or phenyl, A represents polyoxy alkylidene).
The best form that is the present invention's water system detergent is to contain the lower molecular weight organopolysiloxane that above-mentioned (I) formula and (II) formula are represented, with contain the organopolysiloxane that has the unitary polyoxy alkylidene of silicomethane oxygen shown in 1 formula III in the molecule at least, and tensio-active agent and water.
The above-mentioned organopolysiloxane that contains polyoxy alkylidene, by the polyoxy alkylidene that is bonded on the Siliciumatom water is demonstrated affinity, be to form the stable aqueous dispersion or the composition of the aqueous solution, thereby also have the effect that dirt is peeled off at the interface between the substrates such as metal of soaking into dirt and being covered by dirt, and froth breaking effect.
In that platinum is arranged is in the presence of the catalyst, will have the organopolysiloxane of hydroxyl silyl (セ De ロ シ リ Le) and the terminal poly (oxyalkylene) compound that unsaturated group arranged to carry out addition reaction and can obtain this organopolysiloxane that contains polyoxy alkylidene.
The polyoxy alkylidene of A can exemplify the monad radical that formula IV is represented in above-mentioned (III) formula.
Formula IV
(in the formula, R
3Expression is selected from the alkylidene group of carbon number 1～8, the beta-hydroxy propylidene oxyalkylene of carbon number 4～11 and the divalent radical of polymethylene oxyalkylene, R
4The alkylidene group of expression carbon number 2-4, R
5Expression is selected from the end group of hydrogen atom and any monovalent organic radical, and n represents positive integer.）
There is no particular limitation to form the siloxanes of the above-mentioned organopolysiloxane main framing that contains polyoxy alkylidene.Be combined in the organic radical on the Siliciumatom of this siloxanes, be methyl basically, and in the scope of not damaging effect of the present invention, also can be to contain ethyl, propyl group, butyl, the material of monovalence alkyl such as phenyl and trifluoromethyl and so on monovalence substituted hydrocarbon radical.
Also there is no particular limitation for the molecular weight of molecular weight and each above-mentioned polyoxy alkylidene, even should the big material of value because and use tensio-active agent, also can be fully water-soluble or can stably carry out water-dispersion.But from practicality, each molecular weight preferably about 100～5000 of polyoxy alkylidene.In the poly (oxyalkylene) chain, oxygen ethylidene part is preferably 40 moles more than the % in the whole poly (oxyalkylene).
There is no particular limitation for the amount of polyoxy alkylidene, from system stability, preferably with whole organic radical that the Siliciumatom of this organopolysiloxane combines in more than 5 moles for better.
This organopolysiloxane that contains polyoxy alkylidene can exemplify the chain polysiloxane that following formula is represented.
(in the formula, p, q, r and s represent positive integer),
And the cyclic polysiloxanes represented of following formula.
(in the formula, t, u and v represent positive integer).
Tensio-active agent is the dirt dissolving or the emulsification of will peel off by above-mentioned lower molecular weight organopolysiloxane and the organopolysiloxane that contains polyoxy alkylidene, and makes it the composition of stabilization.
This tensio-active agent according to the active chemical structure of performance, can be divided into cationic, anionic species, nonionic class, both sexes class and their complex class, and the present invention can use any class wherein.But, when considering the combined effect with the above-mentioned organopolysiloxane that contains polyoxy alkylidene, preferably use anionic species, nonionic class or both sexes class are made tensio-active agent, particularly use anionic species/nonionic class combination, or the tensio-active agent that the both sexes class/the nonionic class is combined into, can obtain the detergency that obtains by it and contain the lower molecular weight organopolysiloxane and contain the organopolysiloxane of polyoxy alkylidene and the effect that significantly multiplies each other of impregnability two aspects that obtain by above-mentioned.
In these tensio-active agents, to the present invention the most suitable be, can exemplify polyoxyalkylene alkyl ether sulfonate, anionic species tensio-active agents such as phosphoric acid ester, multivalence alcohol fatty acid ester, the polyoxy alkylidene fatty acid ester, nonionic class tensio-active agents such as poly (oxyalkylene) alkyl oxide, cationic tensio-active agents such as amphotericses such as imidazolidine derivatives, alkylamine salt, alkyl quaternary ammonium salts, other seldom exists with one matter, but can exemplify the terpene compound that extracts from natural goods and high-grade aliphatic ester etc.The synthetic compound that also can adopt the part with the chemical structure of above-mentioned all cpds to replace with fluorine atom and Siliciumatom.
Its ratio of components in the water system detergent of above-mentioned 4 kinds of compositions is not particularly limited, but preferably with respect to organopolysiloxane 100 weight parts that contain polyoxy alkylidene, with the range fit tensio-active agent of 10～1000 weight parts; Add up to 100 weight parts with respect to above-mentioned tensio-active agent and the organopolysiloxane that contains polyoxy alkylidene, cooperate the lower molecular weight organopolysiloxane by being no more than 1000 weight parts.If the use level of tensio-active agent is very few, clearing power weakens; If then power of impregnation dies down too much.If lower molecular weight organopolysiloxane use level is too much, is not easy in the system of being dispersed in, and reduces as the stability of water system composition.The proportioning of above-mentioned tensio-active agent, organopolysiloxane 100 weight parts with respect to containing polyoxy alkylidene can be 30～700 weight parts, are more preferably in 50～300 weight ranges.The better proportioning of lower molecular weight organopolysiloxane is 10～1000 weight part scopes.The use level of water in the water system detergent of above-mentioned 4 kinds of compositions, there is no particular limitation, but from the stability of detergent, account for 40(weight in whole composition) more than the % for well, 70～99.5(weight preferably) scope of %.
Contain the organopolysiloxane that has 1 unitary polyoxy alkylidene of silane oxygen shown in the above-mentioned formula III in the molecule at least, himself also can soak into above-mentioned dirt and its covering substrates such as metal the interface and have the effect that dirt is peeled off, therefore, the above-mentioned organopolysiloxane that contains polyoxy alkylidene, three kinds of composition systems of tensio-active agent and water also can be brought into play the effect of water system detergent.In such cases, can cooperate by the water system detergent proportioning of above-mentioned 4 kinds of composition systems.
The water system detergent of above-mentioned three kinds of compositions or four kinds of compositions, preferably the data of estimating under the room temperature that the canvas method records according to the impregnability of the specification JIS of Japanese Industrial Standards fabric test method regulation are below 15, below 10, below 5, design its proportioning.The washing (-)off properties of these water system detergents depends on the pH value of liquid itself, therefore preferably is adjusted in the alkaline territory.Better p H value is 8～14 scope.
The water system detergent of above-mentioned this three compositions or four-component system is organopolysiloxane, tensio-active agent and the water that contains polyoxy alkylidene with above-mentioned, and the lower molecular weight organopolysiloxane that above-mentioned (I) formula of adding as required and (II) formula are represented mixes, just stirs and can obtain.During mixing, use known diverting device just can obtain the water system detergent at an easy rate.
In the above-mentioned water system detergent, also can be according to character, quantity, the attachment state of dirt, the condition of cleaning etc., auxiliary agent and the reagent that improves the value added after cleaning as washing, also can cooperate the pH that adds in the ortho-water dissolubility detergent to adjust agent, sorbent material, solid shape saccharoid, synthetic synergistic agent, rust-preventive agent, anti-live agent etc., represent its critical positions according to purposes.
The use of the present invention's water system detergent specifically, is a metal parts to liking metal, pottery, plastics etc., surface treatment unit, electronic unit, semiconductor device, electrical component, precision optical machinery parts, optics, glass component, ceramic component etc.Widely used clean flow process concrete example, be with above-mentioned as the various parts of cleaning object, after cleaning through ultrasonic wave, mechanical stirring, spray etc., wash (pure water and ion exchanged water for well) with water, warm air drying is dewatered is general method.Compositions-treated is cleaned in the dirt that contains after cleaning, and is with behind the separation dirts such as strainer, with general draining treatment technology, can be easy to reach nuisancelessization.
The water system detergent of the invention described above, because the lower molecular weight poly (oxyalkylene) shown in formula I and (II) is to the strong power of impregnation at interface between dirt and the substrate, with the clearing power of tensio-active agent to dirt, can obtain comparing the clean effect of U.S. with previously used fluorine Lyons class, owing to and, then can obtain dispersion stabilization good in the water system with the organopolysiloxane that contains polyoxy alkylidene.Even contain the organopolysiloxane of polyoxy alkylidene, the three composition systems that tensio-active agent and water are formed owing to contain the power of impregnation of the organopolysiloxane of polyoxy alkylidene to dirt, also can obtain enough clean effects.And, owing to be water system, therefore also needn't worry environmental disruption and environmental pollution.Therefore water system detergent that we can say the present invention be have problem of environmental pollution organic solvent detergents such as fluorine Lyons class effectively substitute detergent.
Below, the situation of the cleansing composition that the present invention is described during as the dehydration detergent.
Herein, so-called dehydration detergent is to be the material of example name with representative liquid-water that available above-mentioned lower molecular weight organopolysiloxane replaces, and the present invention's the composition of cleaning can also be as replacing.Take off the liquid detergent when cleaning other liquid.Liquid as its object is insoluble or indissoluble to above-mentioned lower molecular weight organopolysiloxane preferably, and the surface tension liquid bigger than lower molecular weight organopolysiloxane.In addition, as the water of cleaning object, be to contain the various liquid that use water as dispersion medium, for example wherein dissolved the mixed solution that is mixed with alcohol and the liquid of various materials.
The lower molecular weight organopolysiloxane of above-mentioned formula I and (II) expression as previously mentioned, demonstrates good and displacement water when they are independent, wave diffusingly with the warm braw below 60 ℃, is easy to carry out drying.
As this dehydration detergent, even in fact form by above-mentioned lower molecular weight organopolysiloxane, also can obtain its effect fully, and in above-mentioned lower molecular weight organopolysiloxane matching surface promoting agent and/or hydrophilic solvent and the composition that forms can also be given good detergency, dehydration property etc.
Above-mentioned tensio-active agent is the material that can improve dehydration property and improve detergency.Be applicable to tensio-active agent of the present invention, can exemplify the polyoxy alkylidene ether sulfonate, nonionogenic tensides such as anion surfactants such as phosphoric acid ester, polyvalent ester fat acid esters, polyoxy alkylidene fatty acid ester, polyoxyalkylene alkyl ether, imidazoles drenches cats products such as amphoterics, alkylamine salt, alkyl quaternary ammonium salts such as derivative, other seldom exists with one matter, but can exemplify the terpene compound that extracts from natural goods and high-grade aliphatic ester etc.The synthetic compound that also can adopt the part with the chemical structure of above-mentioned all cpds to replace with fluorine atom and Siliciumatom.If when particularly considering the effect of the detergent that combines with the lower molecular weight organopolysiloxane, preferably use nonionogenic tenside.
The ratio of components of tensio-active agent is not particularly limited, but with respect to lower molecular weight organopolysiloxane 100 weight parts, preferably below 20 weight parts, better is no more than 3 weight parts.
Above-mentioned hydrophilic solvent can adopt the material that the lower molecular weight organopolysiloxane is had intermiscibility, particularly point of ignition the most suitable at the material more than 40 ℃.This hydrophilic solvent also can improve water substituting.
This wetting ability dissolubility, can exemplify glycol monomethyl methyl ether, ethylene glycol monomethyl ether, the glycol monomethyl propyl ether, ethylene glycol monobutyl ether, multivalence alcohol such as glycol monomethyl phenyl ether acetic ester, Diethylene Glycol single-butyl ether and derivative thereof etc., consider with the intermiscibility of low-molecular-weight organo-siloxane with to the security of human body etc., preferably the Diethylene Glycol single-butyl ether.Therefore these compounds can improve its volatility when coexisting with the lower molecular weight organopolysiloxane, only are the water displacements of this title complex, also can drying.
The combination ratio of hydrophilic solvent is not particularly limited, but with respect to lower molecular weight organopolysiloxane 100 weight parts, is below 100 weight parts, preferably 50 weight parts.
The use of above-mentioned dehydration detergent more particularly, is a metal parts to liking metal, pottery, plastics etc., surface treatment unit, electronic unit, semiconductor device, electrical component, precision optical machinery parts, optics, glass component, ceramic component etc.Widely used clean flow process when using above-mentioned dehydration detergent, specifically, generally be that above-mentioned this cleaning object thing is immersed in the present invention's the dehydration detergent, or the dehydration detergent of spraying the present invention on object, after carrying out the water displacement, use the warm braw drying.Also can and use ultrasonic wave, mechanical stirring etc. when above-mentioned dipping and spraying.
The dehydration detergent of the invention described above has very strong dehydration property, thereby can obtain clean identical with previously used fluorine Lyons class etc.The water replacement result, and erosion is extremely low, can carry out stable cleaning to various base materials.Owing to be substantially free of chlorine and this haloid element of bromine in its constituent, therefore have environmental disruption and the problem of environmental pollution that fluorine Lyons class dehydration of organic solvent detergent brings hardly.Therefore, the present invention's dewatering agent can be described as problem of environmental pollution fluorine Lyons class organic solvent detergent effectively substitute the dehydration detergent.
The accompanying drawing simple declaration.
Fig. 1 illustrates the decontaminating apparatus structure example of the dehydration detergent that uses the present invention.
Describe the present invention by the following examples in detail.
At first, just the embodiment that composition is used for the water system detergent that cleans with the present invention describes.
As the organopolysiloxane that contains polyoxy alkylidene, prepare 2 kinds (A1, A2) that following formula (V) and formula VI are represented respectively.
Secondly, with following each composition respectively in accordance with regulations the amount weigh, the polysiloxane that makes the poly (oxyalkylene) modification of (A1) shown in above (V) formula: the polysiloxane of the poly (oxyalkylene) modification of (A2) shown in above-mentioned (VI) formula: tensio-active agent sodium laurate (B1) and polyoxyethylene octyl phenyl ether (B2) (polyoxyethylene: 20 moles): the weight ratio of water is 5: 5: 4: 82, with mixing in their input vortex mixers, obtain water system cleansing composition P1 then.
The organopolysiloxane that contains polyoxy alkylidene with A1, polyoxyethylene octyl phenyl ether (B2) and water carry out quantitative weighing by the ratio of components shown in the table 1 as (B1) sodium laurate of tensio-active agent and (B2), similarly to Example 1, obtain water system and clean composition P2.
Embodiment 3-5
Select to use (A1) and the organopolysiloxane that contains poly (oxyalkylene) (A2) separately, as above-mentioned (B1) of tensio-active agent, (B2) and (B3) sulfo-succinic acid dioctyl sodium, and as the prestox tetrasiloxane (D1) and the octamethyltrisiloxane (D2) of low molecular weight polycaprolactone organo-siloxane, and water, press embodiment 1 same quadrat method, make the water system composition P3～P5 of ratio of components shown in the table 1 respectively.
Comparative Examples 1～3
Except not using the organopolysiloxane that contains polyoxy alkylidene, other is all same as the previously described embodiments, presses the ratio of components shown in the table 1, makes 3 kinds of water system cleansing compositions.
Measure all characteristic of each water system cleansing composition of embodiment 1～5 and Comparative Examples 1～3 as detergent with following method, and estimate it respectively, it the results are shown in table 1.
(1) impregnability evaluation test
Pressing canvas method/JIB method measures.The more little expression impregnability of numerical value is high more, helps cleaning of tiny position.
(2) clearing power evaluation test
Spindle oil is coated on the steel plate, made test film in 48 hours 135 ℃ of bakings.Mensuration is cleaned (ultrasonic cleansing) needed time with the grease of drying on this test film.The more little expression clearing power of numerical value is strong more.
(3) stability test
It is that the clear-glass bottle of 200ml seal it that each detergent is put into volume, and its outward appearance is observed in slow cooling to 25 ℃ after heating under 50 ℃ 6 hours.
After table 1 is seen literary composition
Can be clear that by evaluation result shown in the table 1 the present invention's water system detergent is that clearing power and power of impregnation are all very good, the purposes that can use with former fluorine Lyons kind solvent detergent, and also stability is fine, so practicality is also high.In contrast, the water system detergent of Comparative Examples is that clearing power and power of impregnation all can not satisfy.
Below, the example of the detergent that uses the present invention being cleaned concrete object is illustrated.
In the manufacturing process of liquid-crystal apparatus, liquid crystal cell is made after the high vacuum again with in the liquid crystal material sealed in unit.At this moment, the vacuum diffusion pump big with exhaust performance carries out exhaust-gas disposal, and diffusion oil slowly forms spraying and enters vacuum system, therefore needs often pump to be cleaned so that remove and deoils.
Present embodiment is the concrete example that replaces previously used three ethane detergents with the present invention's water system detergent.
That is, by to be cleaned thing be the pump parts, it is to be silicone oil F-4(SHIN-ETSU HANTOTAI chemistry (strain) system by adhering to diffusion oil) stainless steel SUS304 and go up the material formation of plating Ni.
The water system detergent that uses cooperates as follows.
Normal temperature stirs down fully ion exchanged water 80(weight) %, wherein slowly add 6(weight) % has the organopolysiloxane that contains polyoxy alkylidene of following chemical structural formula, makes the water white transparency homogeneous solution.
On the other hand, as tensio-active agent, with special non-ionic type ァ テ カ ノ-Le B-4001(rising sun electrification (strain) system) 8(weight) %, with anionic TWA-2023(one side society grease (strain) system that sulfuric ester プ Le ロ ニ ッ Network structure is arranged) 6(weight) % mixes it, its mixture added in above-mentioned water/siloxane solution.
The water system detergent that obtains thus dilutes with ion exchanged water with arbitrary proportion, is used for the detergency test of above-mentioned silicone oil F-4, can be divided into 10 times of water gaging dilutions, 1 minute at normal temperatures stirring dipping; With the dilution of 30 times of water yields, 40 ℃ were shaken dipping in following 1 minute, or 20 ℃ of 1 minute ultrasonic cleansings; 50 times of dilutions, 50 ℃ of following 1 minute ultrasonic cleansings, test-results shows fully to clean removes greasy dirt.
With the present invention than than, use do not contain the organopolysiloxane of polyoxy alkylidene in the above-mentioned cleansing composition, only for above-mentioned tensio-active agent compositional system, carry out same cleaning, even also with ultrasonic wave and 10 times of amount of dilution, surpass 10 minutes dipping down through normal temperature, can not clean and residual silicone oil.Therefore, under this concentration and identical conditions, need more than 65 ℃ the treatment time above 5 minutes.
This result represents that the present invention's the organopolysiloxane detergent that contains polyoxy alkylidene has preeminent clean effect.
Embodiment 7
The present invention's organopolysiloxane that contains polyoxy alkylidene and lower molecular weight organopolysiloxane also can improve the clean effect of commercially available water-soluble detergent greatly.
Clean foaminess that use, that contain tensio-active agent, the rust-preventing characteristic detergent Network シ Network リ-Application MS-109 aqueous solution (Sanyo changes into industry (strain) system) 65(weight as mechanical part and metal parts) among the %, sneak into polyoxy alkylidene modified polyorganosiloxane (A1) the 3(weight shown in above-mentioned (V) formula of use among the embodiment 1) % and ring-type hexamethyl cyclotrisiloxane 5(weight) %, ion exchanged water 17(weight) % is mixed with novel clean composition.
By 20 times of dilution said compositions, estimate detergency with ion exchanged water according to following method.Its result is in showing table 2.As a comparison case, 20 times of water-reducible materials have also been put down in writing about Network ミ リ-commercially available detergent of Application MS-109.
Test method
(1) detergency test-1
To go up the following dirt of immersion coating through the aluminium sheet (AC-4A) of degreasing, air-dry then it, under agitation (400rpm) is immersed in each ablution (20 times of diluents) and reached 15 seconds-1 minute.Thereupon, back under water is air-dry, is attached on the blank sheet of paper after duplicating dirt with adhesive tape, measures its reflectivity with colourimeter and obtains clean rate.
Pollutent
Ingot oil 78%
Carbon black 2%
Clean rate (%)=
R
oThe reflectivity of :=former blank sheet of paper
R
wPollution plate reflectivity after :=clean
(2) detergency test-2
Way is identical with above-mentioned detergency test 1, but pollution substance is to add carbon black 2% in water-soluble machining oil (latex system).Same as described above, obtain clean rate.
Table 2
Dipping time is cleaned rate (%)
(second) MS-109 of the present invention
30????86.5????65.2
60????100.0????67.8
30????93.8????71.0
To as the super effectiveness ablution EP-680(ィ-ピ of commercially available water system detergent-ジ セ パ Application (strain) system), latex type degreasing cleaning agent バ Application ラ ィ D-20(often coils chemical industry (strain) system), powerful special ablution ヒ カ リ ェ-ス (clear light trading (strain)) tests equally, the result is, with the present invention's organopolysiloxane that contains poly (oxyalkylene) and low-molecular-weight organopolysiloxane, can obtain especially good detergency by also.
The present invention's water system detergent also demonstrates unusual effect to the cleaning of welding agent of carrying out on the printed circuit board (PCB) using when parts are real adorns (distribution).Welding agent can be divided into rosin based and water-soluble class, cleans and rosin based is the most difficult, therefore is illustrated with regard to this type of embodiment.
As the pretreatment procedure that parts is welded on the printed circuit board (PCB), be after WW is the rosin ester coating, thereby finish distribution by 230～250 ℃ scolder bath.Confirm that through 35 ℃, 45 seconds spray Cleaning for High Capacity can be removed welding agent fully with following water system detergent.
Used in addition water system is cleaned composition and is the organopolysiloxane 2(weight that contains polyoxy alkylidene that following (VII) formula is represented) %, amphoterics セ Application カ ノ-dying of Le FM(Japan (strain) system) 3(weight) % and sodium.N-コ コ ィ Le レ メ チ ヴ リ Application is nonionogenic tenside ニ ッ コ-Le CTM-30(Japan サ-コ Network Application ト (strain) system) 5 weight %, fit in 100(weight with ion exchanged water) %.
After 10 times of amounts of rare dose of one-tenth of said composition usefulness ion exchanged water, through the cleaning accelerated ag(e)ing test of MIL-F-14256C standard (U.S.), the surface insulation impedance experiments, oil residue test etc., these tests as a result all can be satisfied.
Below, the embodiment the when cleansing composition with the present invention is used to dewater detergent describes.
Embodiment 9～17
As the lower molecular weight organopolysiloxane, prepare octamethyltrisiloxane (E1), prestox tetrasiloxane (E2) and decamethyl five siloxanes (E3); As tensio-active agent, prepare polyoxyethylene oil ether (F1) (P.O.E=6mol) and polyoxyethylene octyl phenyl ether (F2) (P.O.E=10mol) as the wetting ability dissolubility, prepare di-alcohol single-butyl ether (G1).
Select to use above-mentioned each composition, be mixed with various dehydration detergents by the ratio of components shown in the table 3.
Comparative Examples 4-8
As previously used dehydration detergent, prepare fluorine Lyons 113, methylene dichloride, Virahol and ethanol are modulated into 5 kinds of dehydration detergents by the ratio of components shown in the table 3.
Estimate the various characteristics of the dehydration detergent of embodiment 9～17 and Comparative Examples 4-8 respectively with following method.It the results are shown in table 3.
(1) dehydration property
After various base materials (stainless steel plate, pottery, polycarbonate, plating Ni steel plate) washing, be immersed in the various detergents.To the dehydration detergent of embodiment 13～15, wash with the lower molecular weight organopolysiloxane that adopts respectively again.At 50 ℃ baking oven carry out drying thereafter.Dried water stain (stain that incrustation scale causes) observed with visual or scanning electron microscope, according to following benchmark evaluation.
XX: base material is by etch, to such an extent as to can not estimate in the dehydration procedure.
X: water stain with being visually observed.
O: use visual observation less than water stain;
: do not observe water stain more than the 50 μ m with flying-spot microscope.
(2) continuously dehydrating
With stainless steel plate as base material, carry out 50 times dehydration property test after, identical with above-mentioned (1), its outward appearance is estimated.
(3) drying property
After being immersed in stainless steel plate in each detergent, dry in 50 ℃ of baking ovens, used finger touch in per 5 minutes, whether dryly see, be its time of unit record with 5 minutes.
Can be clear that by evaluation result shown in the table 3 no matter the present invention's dehydration detergent is which kind of, its dehydration property is all very good, can former use fluorine Lyons class etc. makes full use of in the purposes of organic solvent detergent.
In addition, Comparative Examples 4 and 5 use methylene dichloride and the detergent of Virahol cause rust property and erosion to metallic membrane and plastics.In contrast, the present invention's dehydration detergent, all very stable to metallic membrane and plastics, and the big pottery of surfaceness also had fill enough dehydration properties, to metal parts, electroplating part, electronic unit, semiconductor device, plastic components, ceramic component etc. also have enough reliabilities.In addition, Virahol and water have intermiscibility, therefore may cause adhering to once more on the base material water.
And, owing to be used tensio-active agent and hydrophilic solvent, then can further improve dehydration property.To industrial use is effective.
The following decontaminating apparatus example that the dehydration detergent that uses the present invention is described with reference to Fig. 1.
Decontaminating apparatus shown in Figure 1 is roughly by cleaning.Water displacement operation A and purification.Dehydration procedure B constitutes.
The 1st operation is to be cleaned.Among the water displacement operation A, the 1st ablution groove 1 and the 2nd ablution groove 2 that has settlement separate function and overflow separation function simultaneously is set and takes off liquid bath 3.Between above-mentioned the 1st ablution groove 1 and the 2nd ablution groove 2, link with delivery pipe 2a and upflow tube 2b.On the 1st ablution groove 1 and second ablution groove, also can and use ultrasonic wave as required, shake, mechanical stirring, detergent is heated, devices such as flushing.
In the above-mentioned the 1st and the 2nd ablution groove 1,2, accommodate respectively in the present invention's the dehydration detergent, in the lower molecular weight organopolysiloxane, added the detergent D1 of tensio-active agent.The detergent D1 that contains this tensio-active agent can design its proportion littler but bigger than lipid dirt than water.Therefore, by being cleaned the water Y that thing X brings into, respectively by below the settlement separate detergent D1 that in being housed in the 1st and the 2nd ablution groove, contains tensio-active agent.When being cleaned thing X and going up attaching oil lipid dirt Z, separated thereby lipid dirt Z floats over the top of the detergent D1 that contains tensio-active agent that the 1st and the 2nd ablution groove 1,2 accommodates on then.
Settlement separate water Y in the 2nd ablution groove 2 is being discharged to the 1st ablution groove 1 side off and on by delivery pipe 2a.And settlement separate water Y in the 1st ablution groove 1 arranges to following detergent regeneration sector C off and on by pipe arrangement 4.Being located at the comb 3a that takes off on the liquid bath 3 also joins with detergent regeneration sector C.
The isolating lipid of come-up pollutes Z in the 1st ablution groove 1 and the 2nd ablution groove 2, along overflow, through being located at the upflow tube 5 on the 1st ablution groove 1, is discharged to outside the system.
Be housed in the detergent D1 that contains tensio-active agent in the 1st ablution groove 1 and the 2nd ablution groove 2,, utilize strainer 6 to remove solids among the detergent D1, water particle, last dissolved substance etc. at ordinary times by strainer 6 circulations.
Purification in second operation.Among the dehydration procedure B, the 3rd ablution groove 7 and spray groove 8 are set.The below of spray groove 8 is provided with surge tank 9, between this surge tank 9 and the 3rd ablution groove 7, links with delivery pipe 9a and upflow tube 9b.The 3rd ablution groove 7 also can be as required, and with ultrasonic wave, shake, device such as mechanical stirring, detergent are heated, flushing.
In above-mentioned the 3rd ablution groove 7, accommodate the identical detergent D2 of polysiloxane composition of only being with the lower molecular weight organopolysiloxane that uses among above-mentioned the 1st operation A.It is littler than water that this detergent D2 can set its proportion, but bigger than oil dirt.Therefore, identical with the ablution groove of the 1st operation A, below detergent D2, and lipid dirt Z come-up is separated in the top of detergent D2 to water Y by settlement separate.
The settlement separate water Y that comes out is discharged into detergent regeneration sector C off and on by delivery pipe 10 in the 3rd ablution groove 7.And the isolating grease of come-up is dirt Z in the 3rd washing separator tank, is discharged to outside the system by upflow tube 11.
Being housed in the detergent D2 in the 3rd ablution groove 7, is by strainer 12 circulations usually, removes solids among the detergent D2, water particle, undissolved material etc. with this strainer 12.
Cleaned thing X and be sent to the 2nd process B in turn, after cleaning and dewater, carried out drying treatment by diagram elliptical Warm-air dryer from the 1st operation A, thus the clean operation of end.
Below the narration above-mentioned decontaminating apparatus in detergent recovery, re-use.
As mentioned above, be located at the 1st, the 2nd, the 3rd ablution groove 1,2,7 and take off delivery pipe 4,3a on the liquid bath 3,10, all be connected with detergent regeneration sector C.Be housed in detergent D1 or D2 in each ablution groove, often purify by strainer 6,12, and detergent is when seriously polluted, by each delivery pipe 4,10, with conveying pump 13 pumpings among the detergent regeneration sector C, fractionation is refining then.Stay and take off that detergent D1 also delivers to detergent regeneration sector C off and in the liquid bath 3.
Among the detergent regeneration sector C, at first carry out liquid by strainer 14 and separate with solid, solids component goes out of use, and only liquid component is sent to distiller 15.In this distiller 15, utilize each composition in the detergent, water, grease are the boiling point difference of dirt etc., separate.Remaining in moisture in the distiller 15 etc. further separates by decanting vessel 16.
In addition, because in the detergent that above-mentioned detergent device uses, detergent D1 adds surface agent to form in only for the detergent D2 of lower molecular weight poly organic silicon alkane, therefore, separation and Extraction lower molecular weight organopolysiloxane from detergent D1 and detergent D2 respectively, be detergent D2, and make detergent D2 regeneration.And the composition beyond the regeneration detergent D2, promptly tensio-active agent and moisture etc. are discarded it.
The detergent D2 of this regeneration is sent to by pipe arrangement 17 detergent D1 is supplied with in the ducon 18 of spray groove the 8, the 3rd ablution groove 7 or the 2nd ablution groove 2.
In the spray groove 8,, only spray clean with detergent D2 free from foreign meter with above-mentioned regeneration detergent D2 or by the new detergent D2 that detergent supplying tubing 19 transports.
In the ducon 18, with regeneration or new detergent D2, and the new surface active agents of being sent here by tensio-active agent supply-pipe 20 mixes, and is mixed with new detergent D1.This detergent D1 as required, supplies with the 2nd ablution groove 2.
Owing to used decontaminating apparatus with above-mentioned formation, therefore can use the present invention's dehydration detergent effectively, can give full play to the characteristic of dehydration detergent simultaneously.
As mentioned above, the present invention's cleansing composition, if use as the water system detergent, then can obtain comparing beautiful clean effect with previously used fluorine Lyons system, and for the water system that does not have environmental disruption and problem of environmental pollution, having good stability, the surrogate that therefore can be used as the organic solvent detergents such as fluorine Lyons system that bring environmental problem uses.In addition, when using as dewatering agent, then have very strong dehydration property and do not worry environmental disruption and problem of environmental pollution, therefore, the surrogate that can be used as the dehydration of organic solvent detergents such as fluorine Lyons system that bring environmental problem uses.
Table 1
Table 3
*: produce the solvent crackle.
Claims (3)
1, a kind of water system cleansing composition, it comprises:
1) at least a lower molecular weight organopolysiloxane, described lower molecular weight organopolysiloxane is selected from
The straight chain organopolysiloxane that logical formula I is represented,
(in the formula, R
1Be selected from methyl, ethyl, propyl group, butyl, phenyl, three fluoro-methyl, amino, acid amide base, acrylate-based and sulfhedryl,
The 1st, the integer of 0-5)
And be selected from the ring-type polydiorganosiloxane that logical formula II is represented,
(in the formula,
R
1Be selected from methyl, ethyl, propyl group, butyl, phenyl, three fluoro-methyl, amino, amide group, acrylate-based and sulfhedryl,
M is 3 to 7 integer),
2) contain the organopolysiloxane of polyoxy alkylidene,
Described organopolysiloxane has a silicomethane oxygen unit of being represented by (III) formula at least on a unit molecule.
(in the formula,
R
2Be selected from methyl, ethyl, propyl group, butyl, phenyl and three fluoro-methyl,
R
3Be divalent radical, it is selected from the alkylidene group that contains 1 to 8 carbon atom, the beta-hydroxy propylidene oxyalkylene that contains 4 to 11 carbon atoms and polymethylene oxyalkylene,
R
4Be the alkylidene group that contains 2 to 4 carbon atoms,
R
5Be the end group that is selected from hydrogen atom and any monovalent organic radical,
N represents positive integer.
3) tensio-active agent, and
4) water.
2, water system cleansing composition according to claim 1, wherein, with respect to above-mentioned organopolysiloxane 100 weight parts that contain polyoxy alkylidene, the scope that cooperates described tensio-active agent is in 10 to 1000 weight parts; Measure 100 weight parts with respect to above-mentioned tensio-active agent and the total that contains the organopolysiloxane of polyoxy alkylidene, the scope that cooperates described lower molecular weight organopolysiloxane or is lower than 1000 weight parts in 1000 weight parts; And water accounts for the 40%(weight of total composition) or more than.
3, water system cleansing composition according to claim 1 wherein, is used for described composition to clean at least a material of metal, pottery and plastics.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28086089 | 1989-10-26 | ||
| JP280860/89 | 1989-10-26 | ||
| JP302580/89 | 1989-11-21 | ||
| JP065842/90 | 1990-03-16 | ||
| JP6584190 | 1990-03-16 | ||
| JP065841/90 | 1990-03-16 |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94104356A Division CN1065562C (en) | 1989-10-26 | 1994-04-22 | Cleaning composition |
| CN94104357A Division CN1042353C (en) | 1989-10-26 | 1994-04-22 | Washing method using washing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1051196A CN1051196A (en) | 1991-05-08 |
| CN1027451C true CN1027451C (en) | 1995-01-18 |
Family
ID=26406994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90108720 Expired - Lifetime CN1027451C (en) | 1989-10-26 | 1990-10-25 | Detergent compositions |
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| Country | Link |
|---|---|
| CN (1) | CN1027451C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111433341A (en) * | 2017-12-05 | 2020-07-17 | 安全溶剂欧洲有限公司 | Component cleaning method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069615C (en) * | 1996-04-04 | 2001-08-15 | 西安交通大学 | Temperature stabilizing composite ferroelectric ceramics and its preparation |
| CN107530739B (en) * | 2015-03-26 | 2021-04-27 | 生命技术公司 | Method for processing semiconductor sensor array device |
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1990
- 1990-10-25 CN CN 90108720 patent/CN1027451C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111433341A (en) * | 2017-12-05 | 2020-07-17 | 安全溶剂欧洲有限公司 | Component cleaning method |
| CN111433341B (en) * | 2017-12-05 | 2021-09-14 | 安全溶剂欧洲有限公司 | Component cleaning method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1051196A (en) | 1991-05-08 |
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