CA2151848A1 - Cleaning compositions - Google Patents
Cleaning compositionsInfo
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- CA2151848A1 CA2151848A1 CA002151848A CA2151848A CA2151848A1 CA 2151848 A1 CA2151848 A1 CA 2151848A1 CA 002151848 A CA002151848 A CA 002151848A CA 2151848 A CA2151848 A CA 2151848A CA 2151848 A1 CA2151848 A1 CA 2151848A1
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- polyorganosiloxane
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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 represented by a general formula:
(see fig. I) (wherein R1 is an organic group of single valence substituted by the same or different group or unsubstituted, and 1 is an integer from 0 to 5), and cyclic polydiorganosiloxane represented by a general formula:
(see fig. II) (wherein R1 is an organic group of single valence substituted by the same or different group or unsubstituted, and m is an integer from 3 to 7). To use it as a water system cleaning agent polyoxayalkylene group containing polyorganosiloxane, a surfactant, and water are additionally mixed. Accordingly, a cleaning effect free from environmental destruction and contamination, equivalent to freon* 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 freon* containing dewatering cleaning agents and environmental safety can be obtained.
*Trademark
(see fig. I) (wherein R1 is an organic group of single valence substituted by the same or different group or unsubstituted, and 1 is an integer from 0 to 5), and cyclic polydiorganosiloxane represented by a general formula:
(see fig. II) (wherein R1 is an organic group of single valence substituted by the same or different group or unsubstituted, and m is an integer from 3 to 7). To use it as a water system cleaning agent polyoxayalkylene group containing polyorganosiloxane, a surfactant, and water are additionally mixed. Accordingly, a cleaning effect free from environmental destruction and contamination, equivalent to freon* 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 freon* containing dewatering cleaning agents and environmental safety can be obtained.
*Trademark
Description
21518~8 This is a divisional application of copen~ing application 2,034,488, filed February 18, 1991.
This invention relates to cleaning compositions which will replace cleaning agents containing an organic solvent including freon* and the like.
In manufacturing various parts such as metal parts, plated and coated parts, and electronic and semiconductor parts, freon* contAining solvents such as freon* 113, and organic solvents such as trichloroethane, trichlorethylene, tetrachloroethylene, and carbon tetrachloride are widely used as cleaning agents for eliminating oil stains and the like.
The above organic solvent containing cleaning agents are also used as dewatering cleaning agents after having washed various parts with water in order to avoid the following problems that are associated with direct drying of water present on an object to be cleaned:
(1) Heating (100~C or more) which entails energy loss;
This invention relates to cleaning compositions which will replace cleaning agents containing an organic solvent including freon* and the like.
In manufacturing various parts such as metal parts, plated and coated parts, and electronic and semiconductor parts, freon* contAining solvents such as freon* 113, and organic solvents such as trichloroethane, trichlorethylene, tetrachloroethylene, and carbon tetrachloride are widely used as cleaning agents for eliminating oil stains and the like.
The above organic solvent containing cleaning agents are also used as dewatering cleaning agents after having washed various parts with water in order to avoid the following problems that are associated with direct drying of water present on an object to be cleaned:
(1) Heating (100~C or more) which entails energy loss;
(2) Reducing in productivity due to time taken in drying;
(3) Likely deformation of the object to be cleaned due to heating (thermal eY~cion that exceeds the tolerance);
and (4) Increase in space for installing a cleaning system including a cooler and a heat shielding unit.
The term "dewatering cleaning agent" is used herein to * Trademark denote a cleaning agent into which an object to be cleaned, which has been washed with water, is immersed or with which the object is rinsed by shower thereby to have water present on the object substituted by itself and then vaporized by air at room temperature or heated to 60~C or less so that the object can be dried.
However, ever since it has been found that the destruction of the ozone layer by ~ieçhArge of freon* affects seriously the human body and the ecological system, the use of freons* such as freon* 12 and freon* 113 whose ozone destruction coefficients are high is on the gradual decline on a global scale for an eventual total ban.
Stricter regulations are imposed also on chlorine containing organic solvents such as trichloroethylene and tetrachloroethylene which are presumed to induce soil and underwater contaminations and the like.
Freons* whose ozone destruction coefficients are lower than the currently used freon* containing solvents are being developed, some of which are under fabrication on a commercial basis. However, these new developments are not so welcome because they still are destroyers of the ozone layer.
What gradually attracts attention as a replacement for the above organic solvents is a surfactant-based water system cleaning agent which is free from environmental destruction and contamination. However, cleaning agents contAining only * Trademark 21518~8 surfactants are not satisfactory in penetrability, thereby not cleaning, e.g. , stains penetrated into narrow portions and medium to high viscous, persistently sticky oil stains.
Japanese Patent Publication No. 50463/1988 discloses a method of cleaning woven materials by using silicone cont~ining compounds. According to the disclosure, a liquid cleaning composition containing an effective amount of cyclic siloxane having 4 to 6 silicon atoms is used. However, the liquid cleaning compositions including the above silicone cont~;ning compound are not suitable for use not only in general industrial products due to their being specifically prepared for woven materials, but also in systems using water (hereinafter referred to as "water system") due to their being based on a single cyclic siloxane or the mixture of a cyclic siloxane and an organic solvent. Further, such compositions are not so dispersive in water that the addition of a surfactant thereto does not assist in blending them homogeneously, thereby causing phase separation immediately.
Thus, they are not adapted for use as water system cleaning agents.
On the other hand, Japanese Patent Laid Open No.
56203/1978 recites an aerosol aqueous cleaning composition cont~ining a chain polydimethylsiloxane having 2 to 3 silicon atoms in a single molecular. Since its content is limited to about 0.02 to 0.1 wt.%, no such advantage as improving the 21~18~8 cleaning property of water system cleaning compositions is disclosed.
Under such circumstances, the development of high-performance water system cleaning agents free from environmental problems is strongly called for.
In the meantime, the use of lower alcohols such as isopropyl alcohol is under study for a new development that can replace the above-mentioned organic solvents for dewatering. However, isopropyl alcohol has a flash point of 11.7-C, which is lower than room temperature, and this involves some danger of fires under ordinary handling conditions. In addition, isopropyl alcohol is highly compatible with water, so that the initial dewatering property is ensured, but its repetitive use causes dissolved water to be present again. As a result its dewatering property will be impaired on a long-term basis. To refine isopropyl alcohol for reuse by removing water from the water containing isopropyl alcohol, a tremendous equipment investment is required. That isopropyl alcohol is toxin to the human body is another factor that tends to keep it from using.
The use of hydrocarbon and higher alcohols which have higher flash points than room temperature allows a comparatively easy removal of water, but their low volatility prevents drying themselves at low temperatures, e.g., 60~C or , less, thereby making them unsuitable for applications to dewatering cleaning agents.
The invention provides water system cleaning compositions which have cleaning capability equivalent to that of organic solvent contA; n ing cleaning agents including such as freon* and which are stable as water system cleaning agents and free from environmental destruction and contamination.
The invention also provides dewatering compositions which have the substituting and drying properties equivalent to those of organic colvent contA;ning dewatering cle~
agents, which have few risks of fires and which are free from environmental destruction.
A cleaning agent composition of the invention comprises at least one low mole~ll~r weight polyorganosiloxane selected from the group consisting of straight chain polydiorganosiloxane represented by a general formula: =
Rl ~ Rl ~ R
7 si o si R
Rl ~ Rl ,l Rl ... ... ... (I) (wherein Rl is an organic group of single valence substituted by the same or different group or unsubstituted, and 1 is an * Trademark integer from 0 to 5), and cyclic polydiorganosiloxane represented by a general formula:
~ Rl ' S si~
~ Rl m ... ~-- ... (II) (wherein Rl is an organic group of single valence substituted by the same of different group of unsubstituted, and m is an integer from 3 to 7).
Each of such low molecular weight polyorganosilQYAnes exhibits powerful penetrability to stains and satisfactory substituting property with water alone, making itself a feature component of the invention. Reference character lS in formulas tI) and (II) denotes a substituted or ~ln~llhctituted organic group of single valence including: a single-valence unsubstituted hydrocarbon group such as an alkyl group such as a methyl group, an ethyl group, a yr group, and a butyl group and a phenyl group; and a single-valence substituted ll~d G~arbon group such as atrifluoromethyl group. As the R1 which is placed at an end of formula (I), an amino group, an amide group, an acrylic acid ester group, and a mercaptan group are typical organic ~vuy-; however, the methyl group is most preferable from the viewpoint of stability, and maintAinAhility of volatility, and the like.
The cleaning compositions of the invention may roughly be classified into two yLOu~ a water system cleaning agent and a dewatering cleAn; ng agent.
For use as a water system cleaning agent, suitable low S molecular weight polyorganosiloxanes include:
octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and mixtures thereof, each having a cyclic structure; and octamethyltrisiloxane and decamethyltetrasiloxane, each having a straight chain structure, from the viewpoint of penetrability and cleaning capability. In regions where the water system cleaning composition has a strong alkaline property from the viewpoint of stability of polysiloxane, the low molecular weight polyorganosiloxane having a straight chain structure which is represented by formula (I) is preferable.
For use as a dewatering cleaning agent, low molecular weight polyorganosiloxanes having a cyclic structure are preferable from the viewpoint of substituting property with water and penetrability and the like, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and mixtures thereof are more preferable.
A case in which the cleaning compositions of the invention are used as water system cleaning agents will now be described.
Although the low molecular weight polyorganosiloxanes represented by formulas (I) and (II) exhibit powerful 215I8~8 penetrability to stains, each composition is not compatible with water singly nor is it soluble and stably dispersive in water so that it is likely to have phase separation in water.
~hat is, it is proposed to use them in combination with S polyoxyalkylene group cont~ning polyorganosiloxane having in a ~ingle molecule at least one siloxy unit represented by a general formula:
RZ
Si~
(wherein R2 is an alkyl or phenyl group and A is a polyoxyalkylene group). As a result of such use in combination, the low molecular weight polyorganosiloxanes, providing stable dispersion in water, exhibit S~LV~
penetrability to stains. In addition, the use of a surfactant in combination with the compositions may improve their cleaning property.
m us, preferable compositions for a water system cl~Anin~ agent of the invention contain the low molecular weight polyorganosiloxane represented by formula (I) or (II);
the polyoxyalkylene group containing polyorganosiloxane having at least one siloxy unit represented by formula (III) in a single molecular; a surfactant; and water.
The polyoxyalkylene group con~; n ing polyorganosiloxane exhibits affinity for water owing to its polyoxyalkylene - B -group bonded with the silicon atom, thus not only being a component for a stable water system ~persed solution or aqueous solution but also acting as an agent for eliminating stains by penetrating into the interface between the stains and a substrate which is made of, e.g., a metal and which has the stains deposited thereon, and as an antifoaming agent as well.
Such a polyoxyalkylene group cont~ining polyorganosiloxane can be prepared by hydrosilyl yLOu~
contAining polyorganosiloxane and a polyoxyalkylene com~un~
having an unsaturated group at the end to interact with each other for addition under the pres~nce of a platinum cont~ining catalyzer.
An example of the polyoxyalkylene group denoted by reference character A in formula (III) is, e.g. , a single-valence group represented by the formula:
- R3 - (-0--R4 - )~ ORS ... ... ... (IV) (wherein R3 is a two-valence group selected from the group consisting of an alkylene group having from 1 to 8 carbon atoms, a ~ ~y~roxy~ropyleneoxyalkylene group and a polymethylene oxyalkyelene group, both having from 4 to 11 carbon atoms; R4 is an alkylene group having from 2 to 4 C~rhQ~ atoms; R5 is an end group selected from a hydrogen atom and a single-valence organic group; and n is a positive integer).
_ g _ 21~18~8 Siloxane that forms a main component of the polyoxyalkylene group cont~;n;ng polyorganosiloxane is not particularly limited. The organic group that is to be bonded with the silicon atom of the siloxane is basically a methyl group, but may also contain a single-valence hydrocarbon group such as an ethyl group, a propyl group, a butyl group, a phenyl group, or a single-valence substituted hydrocarbon group such as a trifluoromethyl group as long as the advantages of the invention can remain harmless therefrom.
Also, the molecular weight of the siloxane is not particularly limited nor is that of a single polyoxyalkylene group. Although they are large values, the addition of a surfactant thereto and the like allows the composition to be made sufficiently water soluble or stably water dispersive.
However, it is practically preferable to limit the molecular weight of the single polyoxyalkylene group in the order of 100 to 5000. For a polyoxyalkylene chain, it is preferable to adjust its oxyethylene component to 40 mol % or more in the total polyoxyalkylene.
While the amount of the polyoxyalkylene group is not particularly limited, it is more preferable to limit it within 5 mol % or more of the total organic groups bonded with silicon atoms of the polyorganosiloxane from the standpoint of system stability.
Exemplary polyoxyalkylene group containing polyorganosiloxanes include:
a chain polysiloxane represented by the formula:
CH3 fH3 (CH3)3SiO-- ( SiO-)p --(SiO ~)q -- Si(CH3)3 ( CH2 ) 3--O- ( CH2cH2o ) r ( CH2 CHO ) J ~ OCH3 (wherein p, q, r, and 8 are positive integers); and a cyclic polysiloxane represented by the formula:
fH3 CH3 (sio--)e --(SiO ~)u -- ( CH2 ) 3-O- ( CH2CH2~ ) ~r H
(wherein t, u, and v are positive integers).
The surfactant serves as a component for dissolving, emulsifying, and stabilizing the stains removed by the low molecular weight polyorganosilo~Ane- or polyoxyalkylene group contA i n ing polyorganosiloYAnec.
Such surfactants can be classified by the activation chemical structure into the following types: cationic, anionic, nonionic, amphoteric, and combined types. The invention may be applied to all the above types of ~1~1848 surfactants. However, to obtain the advantage from their combination with the polyoxyalkylene group contAin;ng polyorganosiloxane, it is preferable to use anionic, nonionic, or amphoteric surfactants. Particularly, the use of the polyoxyalkylene group cont~ining polyorganosiloxane in combination with either anionic/nonionic surfactants or amphoteric/nonionic surfactants provides a remarkable synergetic effect in impro~ing the cleaning property and penetrability of the low molecular weight polyorganosiloxanes or the polyoxyalkylene group containing polyorganosiloxanes.
Exemplary suitable surfactants to be applied to the invention include: anionic surfactants such as polyoxyalkylene alkylether sulfonates and phosphoric esters;
nonionic surfactants such as polyalcohol fatty acid esters, polyoxyalkylene fatty acid esters, and polyoxyalkylene alkylethers; amphoteric surfactants such as imidazolin derivatives; and cationic surfactants such as alkylamine salts, alkyl quaternary ammonium salts. In addition thereto, terpene cont~;n;ng compounds which are rarely present in the form of a single substance and extracted from natural substAncPc as well as higher fatty acid esters may also be applied. It is also possible to use synthetic compounds in which part of the chemical structure of each compound is substituted by a fluorine or silicon atom.
While the composition ratio of the above-mentioned quaternary water system cleaning agent is not particularly 21518~8 limited, it is preferable to blend 10 to 1000 parts by weight of a surfactant to 100 parts by weight of the polyoxyalkylene group containing polyorganosiloxane, and 1000 parts by weight or less of the low molecular weight polyorganosiloxane to 100 parts by weight of a total combination of the above surfactant(s) and the polyoxyalkylene cont~;ning polyorganosiloxane. Too small an amount of the surfactant reduces the cleaning capability, while too large an amount impairs the penetratbility. Too large an amount of the low molecular weight polyorganosiloxane not only makes the system difficult to disperse but also reduces stability as a water system composition. A preferable fraction of the surfactant is 30 to 700 parts by weight, or, more preferably, 50 to 300 parts by weight, to 100 parts by weight of the polyoxyalkylene group contAining polyorganosiloxane. A more preferable fraction of the low molecular weight polyorganosiloxane is between 10 and 1000 part by weight.
While the fraction of water in the quaternary water system cleaning agent is not particularly limited either, it is preferable to have water 40 wt. % or more or, more preferably, 70 to 99.S wt. % to the total composition from a stability viewpoint.
By the way, the polyoxyalkylene group cont~in;ng polyorganosiloxane having in a single molecule at least one siloxy unit represénted by formula (III) penetrates, as described above, into the interface between the stains and the substrate made of, e.g., a metal to which the stainsadhere to "peel off" the stains. Thus, even a tertiary composition consisting of the polyoxyalkylene group cont~ining polyorganosiloxane, a surfactant, and water may serve as a viable water system cleaning agent. In this case, the fractions of the quaternary water system cleaning agent will apply to the tertiary composition.
The fractions of the tertiary or ~uaternary water system cleaning agents may be so designed that the value to be obtAin~ by a canvas method at room temperature for evaluating penetrability will be 15 or less, 10 or less, or 5 or less. For the evaluation, the canvas method specified as a fiber/textile test method by Japanese Industrial St~n~rds (JIS) is adopted. Since the cleaning property of these water system cleaning agents depends on the pH value of the solution itself, it is desirable to adjust the pH value to the alkali region. The pH value is more preferably be between 8 to 14.
The tertiary or quaternary cleaning agents can be prepared easily by blending and stirring the above-mentioned polyoxyalkylene group contAin;ng polyorganosiloxane, a surfactant, water, or further the low molecular weight polyorganosiloxane represented by formula (I) or (II), where n~ceScAry. The use of a known dispersing device will help obtain a water system cleaning agent with ease.
The water system cleaning agents such as described above may have additives to be applied to ordinary water-soluble cleaning agents such as pH modifiers, adsorbents, solid particles, synthetic builders, rust preventives, and antistatic agents mixed as cleaning assistants or post-cleaning added-value improving agents and the like, depending on the property, amount, adhering state, cleaning condition, and the like of a stain. Such an addition may play an important part depending on their application.
The water system cleaning agents of the invention may be applied to metals, ceramics, plastics, and the like. More specifically, they may be applied to metallic parts, surface treated parts, electronic and semiconductor parts, electric and precision machinery parts, optical parts, glass and ceramic parts, and the like. An exemplary general-purpose cleaning process usually involves cleaning of any of the above-described parts by such a process as ultrasonic process, mech~n;cal stirring and spraying, and thereafter, washing by water (preferably by pure water or ion-exchanged water), and is dewatered by drying the part with heated air or a like process. The cleaning composition in which the stain separated from the part is present is treated by, e.g., separating the stain through a filter or the like and thereafter by being subjected to a general waste water treatment process, thereby allowing the composition to be unhazardous and pollution-free easily.
21~1848 According to the water system cleaning agent of theinvention, the powerful penetrating property of the low molecular weight polyorganosiloxane represented by formula (I) or (II) for the interface between the stains and the substrate as well as the cl~n;ng capability of the surfactant(s) to the stains provides a cleaning performance equivalent to that of the conventionally used freon*
cont~i~ing cleaning agents. The use of the polyoxyalkylene group cont~ining polyorganosiloxane in combination with the water system cleaning agents of the invention allows satisfactory dispersing property in water. In addition, when applied as a tertiary composition consisting of the polyoxyalkylene group containing polyorganosiloxane, the surfactant, and water, the cleaning agent of the invention exhibits excellent cleaning property by the penetrating capability of the polyoxyalkylene group containing polyorganosiloxane with respect to the stain. Being a water system agent, it will bring no risk of environmental destruction and pollution. Thus, it can be said from the above that the water system cleaning agent of the invention can be an attractive replacement for cleaning agents based on organic solvents contA;n;ng freon* and other substances which have considered hazardous.
A case in which a cle~n;ng composition of the invention is used as a dewatering cleaning agent will now be described.
* Trademark Here, the term "dewatering agent" is only so named after "water", which is a typical liquid capable of being substituted by the low molecular weight polyorganosiloxanes, and the cleaning compositions of the invention may also be used as "liquid removing" agents in substituting and cleaning liquids other than water. The applicable liquids may be those which are insoluble or difficult to be dissolved in the low molecular weight polyorganosiloxanes and whose surface tensions are larger than those of the low molecular weight polyorganosiloxanes. The "water" to be cleaned may include liquids using water as a dispersion medium such as mixtures of water and alcohols and liquids in which various substances are dissolved.
The low molecular weight polyorganosiloxane represented by formula (I) or (II) can be, as described previously, substituted by water alone, thus allowing itself to be easily vaporized and dried by hot air below 60-C.
Such a dewatering cleaning agent may consist substantially of the low molecular weight polyorganosiloxane and with it a satisfactory effect can be obtained. However, its cleaning and dewatering properties and the like will be further improved by forming it into a composition having the low molecular weight polyorganosiloxane mixed with a surfactant and/or a hydrophilic solvent.
The above-mentioned surfactants contribute to improving particularly the cleaning and dewatering property, and 21 ~18~8 suitable surfactants to be applied to the invention include:
anionic surfactants such as polyoxyalkylene alkylether sulfonates and phosphoric esters; nonionic surfactants such as polyalcohol fatty acid esters, polyoxyalkylene fatty acid esters, and polyoxyalkylene alkylethers; amphoteric surfactants such as imidazolin derivatives; and cationic surfactants such as alkylamine salts, alkyl quaternary ammonium salts. In addition thereto, terpene containing compounds which are rarely present in the form of a single substance and extracted from natural substances as well as higher fatty acid esters may also be applied. It is also possible to use synthetic compounds in which part of the chemical structure of each compound is substituted by a fluorine or silicon atom. However, it is more preferable to use nonionic surfactants if the effect as a dewatering cleaning agent used in combination with the low molecular weight polyorganosiloxane is to be further improved.
While the composition ratio of the surfactant is not particularly limited, it is desirable to have 20 parts by weight or less, or, more preferably, 3 parts by weight or less, of the surfactant to 100 parts by weight of low molecular weight polyorganosiloxane.
A suitable hydrophilic solvent may be one compatible with the low molecular weight polyorganosiloxanes, and more particularly, one whose flash point is 40~C or more from the 21~1848 practical viewpoint. The hydrophilic solvent contributes to improving substituting property by water.
Suitable hydrophilic solvents include: polyalcohols and their derivatives such as ethylene glycol monomethyl ethers, ethylene glycol monoethyl ethers, ethylene glycol monopropyl ethers, ethylene glycol monobutyl ethers, ethylene glycol - monobutyl ether acetates, diethylene glycol monobutyl ethers.
Particularly preferable are diethylene glycol monobutyl ethers from the viewpoint of its compatibility with the low molecular weight polyorganosilox~nec and safety to the human body and the like. Since these compounds exhibit improved properties when coexisting with the low molecular weight polyorganosiloxanes, a composition only using this combination may allow substitution by water and drying.
While the composition ratio of the hydrophilic solvent is not particularly limited, it is preferable to have 100 parts by weight or less or, more preferably, 50 parts by weight or less of the hydrophilic solvent mixed with 100 parts by weight of the low molecular weight polyorganosiloxane.
The dewatering cleaning agents of the invention may be applied to metals, ceramics, plastics, and the like. More specifically, they may be applied to metallic parts, surface treated parts, electronic and semiconductor parts, electric and precision machinery parts, optical parts, glass and 2~ 51848 ceramic parts, and the like. An exemplary general-purpose cleaning process usually involves immersing of any of the above-described parts or spraying a dewatering cle~n;ng agent of the invention onto the part to substitute it by water and drying by blowing hot air and the like. The immersing and spraying proc~sC~c may be accompanied by an ultrasonic process and mech~n;cal stirring.
The dewatering cleaning agents of the invention, exhibiting a powerful dewatering property, can not only provide cleaning and water-substituting effects equivalent to those of conventional cleaning agents containing freon* and the like but also allow various materials to be stably cleaned with their low eroding action. In addition, cont~;n~ng no element halogen such as chlorine and bromine in general, the dewatering cleaning agents of the invention have few risk of destroying or polluting the environment. Thus, it can be said that the dewatering cleaning agents of the invention will be a viable replacement for the conventional organic solvent containing dewatering cleaning agents such as freon*, which have been imposing the environmental problems.
Fig. 1 is a diagram showing an exemplary construction of a cleaning system using a dewatering cleaning agent of the invention.
The invention will now be described with reference to examples in which a cleaning composition of the invention is applied to water system cleaning agents.
* Trademark - 20 -Example 1 Two kinds (Al and A2) of polyoxyalkylene group contAin;ng polyorganosiloxane, each represented by formula (V) and ~VI), were prepared.
Al:
CH3 fH3 (CH3)3SiO-- ( SiO-)8 --(7iO -~so Si(CH3)3 ~ CH3 ( CH2 ) ~-O- ( CH2cH2o ) 6 --(CH2CHO)6 - OCH3 ......... (V) A2:
IC~3CH3 (SiO-), --(SiO -)3 (CH2)3-O-(CH2CH20)l0 H ... ... ... (VI
Then, the polyoxyalkylene denatured silicone (Al) represented by formula (V), polyoxyalkylene denatured silicone (A2) represented by formula (VI), sodium laurate (Bl) and polyoxyethylene octylphenyl ether (B2) (20 moles of polyoxye~hylene), both serving as surfactants, and water were weighed so that their ratio by weight will be 5 : 5 : 4 : 4 :
82. Thereafter, these components were charged into a homogenizing mixer for blending to obtain a water system cleaning composition Pl.
Example 2 The polyoxyalkylene group containing polyorganosiloxane (Al), the sodium laurate (Bl) and polyoxyethylene octylphenyl ether (B2), both serving as surfactants, and water were weighed so that they satisfy the composition ratio specified in Table 1. Then, a water system cleaning composition P2 was obtained as in Example 1.
Examples 3 to 5 The polyoxyalkylene group con~ining polyorganosiloxanes (Al) and (A2), dioctyl sodium sulfosuccinate (B3) that serves as a surfactant in addition to the surfactants (Bl) and (B2), octamethyl tetrasiloxane (Dl) and octamethyl trisiloxane (D2), both as low molecular weight polyorganosiloxanes, and water were selectively mixed to prepare water system cleaning compositions P3 to P5 having composition ratios specified in Table 1 in the same manner as that in Example 1.
Comparative examples 1 to 3 Three kinds of water system cleaning compositions were prepared in a manner similar to that of each of the above examples except that no polyoxyalkylene group containing polyorganosiloxane was mixed.
The properties as a cleaning agent were evaluated as to the water system cleaning compositions of Examples 1 to 5 21~1848 and Comparative examples 1 to 3 by the following methods.
The result is also shown in Table 1.
(1) Penetration test Measurements were made based on the JIS-specified canvas method. The smaller value means better penetrating property;
i.e., the composition is more effective in cleaning smaller parts.
(2) Cleaning property test A sample is prepared by applying a spindle oil over a steel strip and h~ki ng it at 135-C for 48 hours. The property is evaluated by the time spent for cleaning the oil baked on the sample (by ultrasonic cleaning). The smaller the value is, the better the cleaning property becomes.
(3) Stability test Each composition was contained in a transparent bottle of 200 ml sealed thereafter and then heated at 50-C for 6 hours. After being gradually cooled from 50 to 25~C, its appearance in the bottle is observed.
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~1~1848 As is apparent from the result shown in Table 1, the water system cl~n;ng agent of the invention exhibits excellent cleaning capability and penetrability, attesting to its availability as a replacement for the conventional solvent based cleaning agents containing freon* and the like.
With its stability, it is considered a highly practical product. In contradistinction thereto, the water system cleaning agents according to Comparative examples were satisfactory neither in cle~ning capability nor in penetrability.
An exemplary process employed to clean a specific part using a water system cleaning agent of the invention will now be described.
Example 6 In fabricating a liquid crystal device, a liquid crystal cell is evacuated to a high vacuum degree and a liquid crystal material is sealed in a device. In this case, the evacuation is carried out by a high performance diffusion vacuum pump. Since the diffused oil enters into the vacuum system in the form of mist, the pump must be cleaned often to remove the oil.
In this example, the water system cleaning agent of the invention was used in lieu of a conventional triethane cleaning agent.
* Trademark 21~1848 A pump part made of a stainless steel SUS304 and a Ni-plated stainless steel SUS304 material having an adhesion of Silicon Oil F-4 (trademark of Shinetsu Chemical) as a diffusion oil was cleaned.
The composition ratio of the used water system cleaning agent is as shown below.
That is, in 80 wt. % of ion-eY~h~nged water being sufficiently stirred at ambient temperature, 6 ~t. % of the polyoxyalkylene group cont~i n; ng polyorganosiloxane having the following chemical structure was gradually added to obtain an achromatic translucent homogeneous solution.
(SiO ) (SiO -)6 ( CH2 ) 3--0- ( CH2CH2~ ) lS -- H
On the other hand, as a surfactant, a mixture of 8 wt.
of special nonionic Adecanol B-4001 (trademark of Ac~h;
Ele~rocl~emical) and 6 wt. ~ of anionic TWA-2023 (trademark of Ipposha Oil and Grease) of sulfuric acid ester PURLONIC
structure was added to the above water/siloxane solution.
After diluting the water system cleaning agent thus obtained was diluted by ion-exchanged water at an arbitrary ratio, Silicone Oil F-4 was cleaned using the diluted cleaning agents. As a result, the pump part was -satisfactorily cleaned: through immersion by stirring for 1 minute in a 1/10 diluted cleaning agent at ambient temperature; through immersion by oscillating for 1 minute in a 1/30 diluted cleaning agent at 40~C or through 1 minute ultrasonic cleaning at 20~C in the same cleaning agent; and through 1 minute ultrasonic cleaning in a 1/50 diluted cleaning agent at 50 C, respectively.
For comparison, the pump part was similarly cleaned with compositions containing only surfactant(s) and no polyoxyalkylene group cont~ining polyorganosiloxane.
Silicone Oil was not removed sufficiently with 10 or more minute immersion ultrasonic cleaning in a 1/10 diluted composition at ambient temperature. To remove Silicone Oil with this composition, it took more than 5 minutes at 65~C or more.
It is understood from this data that the cleaning agent that incorporates the polyoxyalkylene group containing polyorganosiloxane of the invention exhibits an outstanding cleaning property.
Example 7 The polyoxyalkylene group containing polyorganosiloxanes and the low molecular weight polyorganosiloxanes of the invention contribute to significantly improve the cleaning capability of commercially available water-soluble cleaning agents.
21518~8 An Aqueous solution of Chemiclean MS-109 (trademark of Sanyo Kasei Kogyo), which is a surfactant containing, low foaming, rust preventive cleaning agent, is typically used to clean mech~nical and metallic parts. Blending 3 wt. % of the polyoxyalkylene denatured silicon (Al) represented by formula (V) in Example 1, 5 wt. % of cyclic hexamethylcyclotrisiloxane, 17 wt. % of ion-exchanged water with 65 wt. % of the above aqueous solution, a new cleaning composition was prepared.
This new cleaning composition was 1/20 diluted by ion-exchanged water and its cleaning property was evaluated by the following method. The result is shown in Table 2. For comparison, the evaluation result of 1/20 diluted Chemiclean MS-109 was also shown.
Test Method (1) Cleaning test - 1 The following contaminants were applied to a degreased aluminum plate (AC-4A) by immersing, dried by blowing, and immersed while stirred (400 rpm) in respective cleaning agents (1/20 diluted) for 15 C~con~s to 1 minute. Then, after immersed in water, the aluminum plate was dried by blowing. Each contaminant was transferred on white paper through an adhesive tape for reflectance measurement by a colorimeter thereby to calculate the cleaning rate.
Contaminant:
Spindle oil 78%
Fatty acid ester 15%
Chlorinated paraffin 5%
Carbon black 2%
Cleaning rate (%) = Rw - Rs / Ro - Rs Ro: Reflectance of the original white paper Rs:
Reflectance of the st~nAArd contaminated plate Rw:
Reflectance of the contaminated plate after cleaned (2) Cleaning test - 2 A contaminant was prepared by adding 2% of carbon black to a water-soluble mac~linirg oil (emulsive), and the test was performed in a manner similar to that of Cleaning test - 1.
Its cleaning rate was similarly calculated.
Table 2 Immersion timeCleaning Rate (%) (second)Invention MS-109 Cleaning test - 1 15 72.4 59.0 86.5 65.2 100.0 67.8 Cleaning test - 2 15 81.7 58.0 93.8 71.0 Similar tests were conducted on EP-680 (trademark of E.P. Japan) which is a commercially available supereffective cleaning solution and water system cleaning agent; Banrise D-30 20 (trademark of Joban Chemical Industries) which is anemulsive degreased cleaning agent; and Hikari Ace (trademark of Shoko Trade) which is a powerful special cleaning agent.
As a result, these cleaning agents, when used in combination of the polyoxyalkylene group containing polyorganosiloxane and the low molecular weight polyorganosiloxane of the invention, exhibited a significantly improved cleaning property.
Example 8 The water system cleaning agent of the invention exhibits remarkable effect on cleaning of fluxes used in mounting electronic parts on printed boards. The flux comes roughly in two types: rosin cont~i n; ng and water-soluble. A
specific example of cleaning rosin cont~ini~g fluxes, which is said to be a difficult task, will now be described.
As a step prior to soldering a part on a printed board, a WW rosin ester was put on a part and immersed in a solder bath at 230 to 250~C and then the part was mounted. It was observed that the flux was completely removed when the printed board was shower-rinsed for 35~C for 45 seconds using a water system cleaning agent described below.
The water system cleaning composition used here is prepared by blending 2 wt. % of the polyoxyalkylene group containing polyorganosiloxane represented by formula (VII), 3 wt. % of Senkanol FM (trademark of Nippon Senka), which is an amphoteric surfactant, 5 wt. % of Nikkol CNT-30 (trademark of Nippon Surfactant), which is a sodium-N-COCOIL methyl taurine cont~n;ng nonionic surfactant, and A~;ng ion-eY~-h~nged water to prepare 100 wt. % of the composition.
~ CH3 (CH313SiO- (sio-)s - ~SiO -~3s - Si(CH3)3 (CH2)3-0-(CH2CH20) 6 ~
L (CH2CH0)6 - OCH3 ... ... ... (VII) c~3 When acceleration aging tests which guarantees US MIL-F-14256C ~tA~Ard~ surface insulation resistance tests, ion re~idual tests and the like were conducted on the above composition which was 1/10 diluted by ion-exchanged water, the results were satisfactory.
Examples in which cleaning compositions of the invention were applied to dewatering cleaning agents will now be described.
Examples 9 to 17 Octamethyltrisiloxane (El), octamethyltetrasiloxane (E2), and decamethylpentasiloxane (E3) were prepared as low molecular weight polyorganosilo~An~c; polyoxyethylene oleyl ether (Fl) (P.O.E. =6 moles), and polyoxyethylene octylphenyl ether (F2) (P.O.E. =10 moles) as surfactants; and diethylene glycol monobutyl ether (Gl) as a hydrophilic solvent were prepared.
-- 21 518~8 These components were selected and blended so that the composition ratio shown in Table 3 were satisfied to obtain respective dewatering cleaning agents.
Comparative examples 4 to 8 Freon* 113, methylene chloride, isopropyl alcohol, and ethanol were prepared as conventional dewatering cleaning agents to obtain 5 types of dewatering cleaning agents whose comrosition ratios were as shown in Table 3.
The properties of Examples 9 to 17 and Comparative examples 4 to 8 were evaluated by the following methods. The result is also shown in Table 3.
(1) Dewatering property Various pieces (a stainless steel strip, a ceramic piece, a polycarbonate piece, a Ni-plated steel strip) were immersed in each dewatering cleaning agent after washed by water. In examples 13 to 15, each piece was then rinsed by the low molecular weight polyorganosiloxane blended to prepare each dewatering cleaning agent. Thereafter, each piece was dried in an oven at 50~C. The water marks (a stain by impurities dissolved in water) after drying each piece was observed visibly and by a sc~nn;ng electron microscope and evaluated in accordance with the following criteria.
XX: Not evaluable due to erosion of the piece during dewatering.
* Trademark ~1 5 1848 X: Water marks were visibly observed.
o: No water marks were visibly observed.
: No water marks whose size is 50 ~m or more were observed by the sc~nn; ng electron microscope.
(2) Continuous dewatering property A continuous dewatering test with a frequency of 50 times were conducted on a stainless steel strip and the appearance of the strip was evaluated in a manner similar to that of item (1).
(3) Drying property The stainless steel strip was immersed in each dewatering cleaning agent and dried in the oven at 50~C.
During the drying process, the strip was touched by a finger to see the drying condition every 5 minutes and the time required for drying was recorded on a 5-minute basis.
o *
,, ,, , ,,, o ~ ~ X ~ ~ V
C o ~a O
X ~ ~ o ~ ~ ~ o X X X o o C~
~ ~ I ~ ~ ~ o ~ ~ ~ o X ~ X C~ U~
o c -<o ~ o ~~ ~ o ~ 9, ~ o ~ ~ ~o I I ~
.~ o ~ ~ o ~ o ~
~D ~ ~
, ~ o ~ o ~ o --l ~ x a ~~ o o I ~ ) ~ s~) G (~) ~
s o o I ~ ~ o ~ ~ ~ o ~ ~ ~ I I I I I I ~ O ~ ~ ~ ~n o ~ o~ ~ o u o P C~
O ~a P ~ o o s~
3 ~ o o o a ~ ~ ~ ~
c ~ _I t~ ~ ~ ~ ~ ~
-- C) V ~5 ~ ~ 07 ~ O ~ E3 I O ~ al :1 0 ~ ~ o o ~~'I u~ _1 u ~ ~ ~~: _I~ ~ ~ ~ ~ q) -- o S., _~o o ~
o'~ ~a o ~ J ~:
O O U~ H U~ Z ~ O --O ~ ..
O O O ~ ~ O
o~ 0 0 5~J C
V ~ ~ - 3 <D--I ~ V t~
21~18~8 As is apparent from the result shown in Table 3, the dewatering cleaning agents of the invention, exhibiting satisfactory dewatering property, can be a viable substitute for organic solvent containing freon* and the like based cleaning agents.
Dewatering cleaning agents contA i n i ng methylene chloride-or isopropyl alcohol (Comparative examples 4 and S) rust and erode metal films and plastics. In contradistinction thereto, the dewatering cleaning agents of the invention are stable to metal films and plastics and exhibit satisfactory dewatering property even to ceramics which have large surface roughnecs values, thereby ensuring their reliability when applied to parts including metal, plated, electronic, semiconductor, plastic, and ceramic parts. The dewatering 15 cleAni ng agent containing isopropyl alcohol permitted water to be dissolved therein, thereby causing water to present on the part again.
Moreover, it is understood that mixing of surfactants and hydrophilic solvents with the dewatering cleaning agents of the invention improved the dewatering property, thereby attesting to their industrial applicability.
An exemplary cleaning system using a dewatering cleaning agent of the invention will now be described with reference to Fig. 1.
* Trademark 21~1848 A cleaning system shown in Fig. 1 consists roughly of a cleaning/water-substituting process A and a rinsing/dewatering process B.
The cleaning/water-substituting process A, which is the S first process involves a first cleaning vessel 1 and a second cleaning vessel 2, each serving both as a separator through sedimentation and a separator through overflow, and a dewatering vessel 3. The first and second cleaning vessels 1 and 2 communicate with each other through a drain line 2a and an overflow line 2b. The first and second cleaning vessels 1 and 2 are operated together with ultrasonic, os¢illating, mech~nical stirring, cleaning agent heating, and brushing procecce-c and the like, if nec~-cs~ry.
The first and second cleaning vessels 1 and 2 respectively lS contain a cleaning agent Dl composed of a low molecular weight polyorganosiloxane and a surfactant, which is one of the dewatering cleaning agents of the invention. The surfactant containing cleaning agent Dl may be so prepared that its specific gravity is smaller than that of water and larger than that of an oily stain. Therefore, water Y
introduced by an object to be cleaned X is separated by being sedimentated at the bottom of the surfactant containing cleaning agent Dl that has been charged in the first and secon~ cleaning vessels 1 and 2. If an oily stain Z is present on the object X, the oily stain Z is separated by 2 1 ~ I8~ 8 floating upward in the surfactant containing cleaning agent Dl in the first and second cleaning vessels 1 and 2.
The water Y separated by being sedimentated in the second cleaning vessel 2 is intermittently discharged to the first cleaning vessel 1 through a drain line 2a while the water Y separated by being sedimentated in the first cleaning-vessel 1 is intermittently discharged to a cleaning agent recycling mech~nism C (described later) through a drain line 4. A drain-line 3a connected to the drainage vessel 3 is also connected to the cleaning agent recycling mech~nism C.
The oily stain Z separated by floating in the first and second vessels 1 and 2 is discharged outside while continuously overflown through an overflow line 5 connected to the first cleaning vessel 1.
The surfactant containing cleaning agent Dl charged in the first and second cleaning vessels 1 and 2 is continuously circulated through a filter 6 that serves to remove solid particles, H20 particles, lln~; scolved substances, and the like contained in the cleaning agent Dl.
The rinsing/dewatering process B, which is the second process, involves a third cl~n;ng vessel 7 and a shower rinse vessel 8. Below the shower rinse vessel 8 is a buffer tank 9 that communicates with the third cleaning vessel 7 through a drain line 9a and an overflow line 9b. The third cleaning vessel 7 is also operated together with ultrasonic, oscillating, me~h~nical stirring, cleaning agent heating, and brushing processes and the like, if nec~cc~ry.
The third cleaning vessel 7 contains a cleaning agent D2 consisting only of a silicone composition identical to the low molecular weight polyorganosiloxane used in the first process A. The cleaning agent D2 may be so prepared that its specific gravity is smaller than that of water and larger than that of an oily stain. Therefore, as in the first process A, water Y is separated by being sedimentated at the bottom of the cleaning agent D2 and the oily stain Z is separated by floating upward in the cleaning agent D2.
The water Y separated by being ce~;mentated in the third cleaning vessel 7 is intermittently discharged to the cleaning agent recycling merh~nism C through a drain line 10 while the oily stain Z separated by floating in the third cleaning vessel 7 is ~;~rh~rged outside through an overflow line 11.
The cleaning agent D2 charged in the third cleaning vessel 7 is continuously circulated through a filter 12 that serves to remove solid particles, H20 particles, undissolved substances, and the like contained in the cleaning agent D2.
The object to be cleaned X undergoes the first process A
and then the second process B, cleaned and dewatered, and then dried by a fan forced drier (not shown) to complete the cleaning process.
21~18~8 The cleaning agent used in the cleaning system is subjected to the following recycling process.
As described above, the drain lines 4, 3a, 10 of the first, second, and third cleaning vessels 1, 2, and 7, and the dewatering vessel 3 are connected to the cleaning agent recycling mech~nism C. The cleaning agent Dl or D2 contained-in each cleaning vessel is constantly cleaned by the filters 6 and 12. However, when heavily contaminated, the cleaning agent is illLLGduced to the cleaning agent recycling mech~n;sm C through drain lines 4 and 10 by a conveyer pump 13 for fractional distillation. The cleaning agent Dl deposited in the dewatering vessel 3 is also supplied intermittently to the cleaning agent recycling me~h~n;sm C.
At the cleaning agent recycling mec-h~n;~m C, the introduced cleaning agent is separated into liquid components and solid components by a filter 14, and only the liquid components are forwarded to a distiller 15 with the solid components being destroyed. The distiller 15 separates various components, water, oily stains in the cleaning agent utilizing the difference in their boiling points. Water and the like that remain in the distiller 15 are further separated by a decanter 16.
Since the cleaning agent Dl is an agent having a surfactant added to the cleaning agent D2 that contains only the low molecular weight polyorganosiloxane, the low molecular weight polyorganosiloxane, i.e., the cleaning agent 21~1848 D2, can be extracted from both cleaning agents Dl and D2, thereby allowing the cleaning agent D2 to be recycled. The components other than the recycled cleaning agent D2, i.e., the surfactant, water, and the like will be destroyed.
The recycled cleaning agent D2 is forwarded to a mixer 18 from which the cleaning agent Dl is supplied to the shower rinse vessel 8, the third cleaning vessel 7, or the second cleaning vessel 2 through a line 17.
In the shower rinse vessel 8, a shower rinsing process is conducted using only the recycled cle~n i ng agent D2 or a cle~ni ng agent D2 newly i,.~-olllce~ through a cleaning agent supply line 19, both being free from impurities.
The mixer 18 mixes the recycled or new cleaning agent D2 with the surfactant newly supplied from a surfactant supply line 20 to prepare a new cleaning agent Dl. The new cleaning agent Dl is supplied to the cDco~ cleaning vessel 2, if necessary.
With the cleaning system of such construction as described above, the dewatering cleaning agents of the invention can be used efficiently and effectively enjoying the advantage of excellent cleaning properties.
Industrial Applicability As described in the foregoing pages, the cleaning compositions of the invention, when used as water system cleaning agents, exhibit a cleaning effect equivalent to that of conventional freon* contAining cleaning agents and an excellent stability as a water system with no risk of environmental destruction and pollution, thereby making a viable replacement for the organic solvent based cleaning agents including freon* and the like which have environmental disadvantages. In addition, the cleaning compositions of the invention, when used as dewatering cleaning agents, provide a powerful dewatering property with no risk of environmental destruction and pollution, thereby serving a viable replacement for the organic solvent h~~~ dewatering cleaning agents including freon* and the like which have environmental disadvantages.
* trademark - 41 -
and (4) Increase in space for installing a cleaning system including a cooler and a heat shielding unit.
The term "dewatering cleaning agent" is used herein to * Trademark denote a cleaning agent into which an object to be cleaned, which has been washed with water, is immersed or with which the object is rinsed by shower thereby to have water present on the object substituted by itself and then vaporized by air at room temperature or heated to 60~C or less so that the object can be dried.
However, ever since it has been found that the destruction of the ozone layer by ~ieçhArge of freon* affects seriously the human body and the ecological system, the use of freons* such as freon* 12 and freon* 113 whose ozone destruction coefficients are high is on the gradual decline on a global scale for an eventual total ban.
Stricter regulations are imposed also on chlorine containing organic solvents such as trichloroethylene and tetrachloroethylene which are presumed to induce soil and underwater contaminations and the like.
Freons* whose ozone destruction coefficients are lower than the currently used freon* containing solvents are being developed, some of which are under fabrication on a commercial basis. However, these new developments are not so welcome because they still are destroyers of the ozone layer.
What gradually attracts attention as a replacement for the above organic solvents is a surfactant-based water system cleaning agent which is free from environmental destruction and contamination. However, cleaning agents contAining only * Trademark 21518~8 surfactants are not satisfactory in penetrability, thereby not cleaning, e.g. , stains penetrated into narrow portions and medium to high viscous, persistently sticky oil stains.
Japanese Patent Publication No. 50463/1988 discloses a method of cleaning woven materials by using silicone cont~ining compounds. According to the disclosure, a liquid cleaning composition containing an effective amount of cyclic siloxane having 4 to 6 silicon atoms is used. However, the liquid cleaning compositions including the above silicone cont~;ning compound are not suitable for use not only in general industrial products due to their being specifically prepared for woven materials, but also in systems using water (hereinafter referred to as "water system") due to their being based on a single cyclic siloxane or the mixture of a cyclic siloxane and an organic solvent. Further, such compositions are not so dispersive in water that the addition of a surfactant thereto does not assist in blending them homogeneously, thereby causing phase separation immediately.
Thus, they are not adapted for use as water system cleaning agents.
On the other hand, Japanese Patent Laid Open No.
56203/1978 recites an aerosol aqueous cleaning composition cont~ining a chain polydimethylsiloxane having 2 to 3 silicon atoms in a single molecular. Since its content is limited to about 0.02 to 0.1 wt.%, no such advantage as improving the 21~18~8 cleaning property of water system cleaning compositions is disclosed.
Under such circumstances, the development of high-performance water system cleaning agents free from environmental problems is strongly called for.
In the meantime, the use of lower alcohols such as isopropyl alcohol is under study for a new development that can replace the above-mentioned organic solvents for dewatering. However, isopropyl alcohol has a flash point of 11.7-C, which is lower than room temperature, and this involves some danger of fires under ordinary handling conditions. In addition, isopropyl alcohol is highly compatible with water, so that the initial dewatering property is ensured, but its repetitive use causes dissolved water to be present again. As a result its dewatering property will be impaired on a long-term basis. To refine isopropyl alcohol for reuse by removing water from the water containing isopropyl alcohol, a tremendous equipment investment is required. That isopropyl alcohol is toxin to the human body is another factor that tends to keep it from using.
The use of hydrocarbon and higher alcohols which have higher flash points than room temperature allows a comparatively easy removal of water, but their low volatility prevents drying themselves at low temperatures, e.g., 60~C or , less, thereby making them unsuitable for applications to dewatering cleaning agents.
The invention provides water system cleaning compositions which have cleaning capability equivalent to that of organic solvent contA; n ing cleaning agents including such as freon* and which are stable as water system cleaning agents and free from environmental destruction and contamination.
The invention also provides dewatering compositions which have the substituting and drying properties equivalent to those of organic colvent contA;ning dewatering cle~
agents, which have few risks of fires and which are free from environmental destruction.
A cleaning agent composition of the invention comprises at least one low mole~ll~r weight polyorganosiloxane selected from the group consisting of straight chain polydiorganosiloxane represented by a general formula: =
Rl ~ Rl ~ R
7 si o si R
Rl ~ Rl ,l Rl ... ... ... (I) (wherein Rl is an organic group of single valence substituted by the same or different group or unsubstituted, and 1 is an * Trademark integer from 0 to 5), and cyclic polydiorganosiloxane represented by a general formula:
~ Rl ' S si~
~ Rl m ... ~-- ... (II) (wherein Rl is an organic group of single valence substituted by the same of different group of unsubstituted, and m is an integer from 3 to 7).
Each of such low molecular weight polyorganosilQYAnes exhibits powerful penetrability to stains and satisfactory substituting property with water alone, making itself a feature component of the invention. Reference character lS in formulas tI) and (II) denotes a substituted or ~ln~llhctituted organic group of single valence including: a single-valence unsubstituted hydrocarbon group such as an alkyl group such as a methyl group, an ethyl group, a yr group, and a butyl group and a phenyl group; and a single-valence substituted ll~d G~arbon group such as atrifluoromethyl group. As the R1 which is placed at an end of formula (I), an amino group, an amide group, an acrylic acid ester group, and a mercaptan group are typical organic ~vuy-; however, the methyl group is most preferable from the viewpoint of stability, and maintAinAhility of volatility, and the like.
The cleaning compositions of the invention may roughly be classified into two yLOu~ a water system cleaning agent and a dewatering cleAn; ng agent.
For use as a water system cleaning agent, suitable low S molecular weight polyorganosiloxanes include:
octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and mixtures thereof, each having a cyclic structure; and octamethyltrisiloxane and decamethyltetrasiloxane, each having a straight chain structure, from the viewpoint of penetrability and cleaning capability. In regions where the water system cleaning composition has a strong alkaline property from the viewpoint of stability of polysiloxane, the low molecular weight polyorganosiloxane having a straight chain structure which is represented by formula (I) is preferable.
For use as a dewatering cleaning agent, low molecular weight polyorganosiloxanes having a cyclic structure are preferable from the viewpoint of substituting property with water and penetrability and the like, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and mixtures thereof are more preferable.
A case in which the cleaning compositions of the invention are used as water system cleaning agents will now be described.
Although the low molecular weight polyorganosiloxanes represented by formulas (I) and (II) exhibit powerful 215I8~8 penetrability to stains, each composition is not compatible with water singly nor is it soluble and stably dispersive in water so that it is likely to have phase separation in water.
~hat is, it is proposed to use them in combination with S polyoxyalkylene group cont~ning polyorganosiloxane having in a ~ingle molecule at least one siloxy unit represented by a general formula:
RZ
Si~
(wherein R2 is an alkyl or phenyl group and A is a polyoxyalkylene group). As a result of such use in combination, the low molecular weight polyorganosiloxanes, providing stable dispersion in water, exhibit S~LV~
penetrability to stains. In addition, the use of a surfactant in combination with the compositions may improve their cleaning property.
m us, preferable compositions for a water system cl~Anin~ agent of the invention contain the low molecular weight polyorganosiloxane represented by formula (I) or (II);
the polyoxyalkylene group containing polyorganosiloxane having at least one siloxy unit represented by formula (III) in a single molecular; a surfactant; and water.
The polyoxyalkylene group con~; n ing polyorganosiloxane exhibits affinity for water owing to its polyoxyalkylene - B -group bonded with the silicon atom, thus not only being a component for a stable water system ~persed solution or aqueous solution but also acting as an agent for eliminating stains by penetrating into the interface between the stains and a substrate which is made of, e.g., a metal and which has the stains deposited thereon, and as an antifoaming agent as well.
Such a polyoxyalkylene group cont~ining polyorganosiloxane can be prepared by hydrosilyl yLOu~
contAining polyorganosiloxane and a polyoxyalkylene com~un~
having an unsaturated group at the end to interact with each other for addition under the pres~nce of a platinum cont~ining catalyzer.
An example of the polyoxyalkylene group denoted by reference character A in formula (III) is, e.g. , a single-valence group represented by the formula:
- R3 - (-0--R4 - )~ ORS ... ... ... (IV) (wherein R3 is a two-valence group selected from the group consisting of an alkylene group having from 1 to 8 carbon atoms, a ~ ~y~roxy~ropyleneoxyalkylene group and a polymethylene oxyalkyelene group, both having from 4 to 11 carbon atoms; R4 is an alkylene group having from 2 to 4 C~rhQ~ atoms; R5 is an end group selected from a hydrogen atom and a single-valence organic group; and n is a positive integer).
_ g _ 21~18~8 Siloxane that forms a main component of the polyoxyalkylene group cont~;n;ng polyorganosiloxane is not particularly limited. The organic group that is to be bonded with the silicon atom of the siloxane is basically a methyl group, but may also contain a single-valence hydrocarbon group such as an ethyl group, a propyl group, a butyl group, a phenyl group, or a single-valence substituted hydrocarbon group such as a trifluoromethyl group as long as the advantages of the invention can remain harmless therefrom.
Also, the molecular weight of the siloxane is not particularly limited nor is that of a single polyoxyalkylene group. Although they are large values, the addition of a surfactant thereto and the like allows the composition to be made sufficiently water soluble or stably water dispersive.
However, it is practically preferable to limit the molecular weight of the single polyoxyalkylene group in the order of 100 to 5000. For a polyoxyalkylene chain, it is preferable to adjust its oxyethylene component to 40 mol % or more in the total polyoxyalkylene.
While the amount of the polyoxyalkylene group is not particularly limited, it is more preferable to limit it within 5 mol % or more of the total organic groups bonded with silicon atoms of the polyorganosiloxane from the standpoint of system stability.
Exemplary polyoxyalkylene group containing polyorganosiloxanes include:
a chain polysiloxane represented by the formula:
CH3 fH3 (CH3)3SiO-- ( SiO-)p --(SiO ~)q -- Si(CH3)3 ( CH2 ) 3--O- ( CH2cH2o ) r ( CH2 CHO ) J ~ OCH3 (wherein p, q, r, and 8 are positive integers); and a cyclic polysiloxane represented by the formula:
fH3 CH3 (sio--)e --(SiO ~)u -- ( CH2 ) 3-O- ( CH2CH2~ ) ~r H
(wherein t, u, and v are positive integers).
The surfactant serves as a component for dissolving, emulsifying, and stabilizing the stains removed by the low molecular weight polyorganosilo~Ane- or polyoxyalkylene group contA i n ing polyorganosiloYAnec.
Such surfactants can be classified by the activation chemical structure into the following types: cationic, anionic, nonionic, amphoteric, and combined types. The invention may be applied to all the above types of ~1~1848 surfactants. However, to obtain the advantage from their combination with the polyoxyalkylene group contAin;ng polyorganosiloxane, it is preferable to use anionic, nonionic, or amphoteric surfactants. Particularly, the use of the polyoxyalkylene group cont~ining polyorganosiloxane in combination with either anionic/nonionic surfactants or amphoteric/nonionic surfactants provides a remarkable synergetic effect in impro~ing the cleaning property and penetrability of the low molecular weight polyorganosiloxanes or the polyoxyalkylene group containing polyorganosiloxanes.
Exemplary suitable surfactants to be applied to the invention include: anionic surfactants such as polyoxyalkylene alkylether sulfonates and phosphoric esters;
nonionic surfactants such as polyalcohol fatty acid esters, polyoxyalkylene fatty acid esters, and polyoxyalkylene alkylethers; amphoteric surfactants such as imidazolin derivatives; and cationic surfactants such as alkylamine salts, alkyl quaternary ammonium salts. In addition thereto, terpene cont~;n;ng compounds which are rarely present in the form of a single substance and extracted from natural substAncPc as well as higher fatty acid esters may also be applied. It is also possible to use synthetic compounds in which part of the chemical structure of each compound is substituted by a fluorine or silicon atom.
While the composition ratio of the above-mentioned quaternary water system cleaning agent is not particularly 21518~8 limited, it is preferable to blend 10 to 1000 parts by weight of a surfactant to 100 parts by weight of the polyoxyalkylene group containing polyorganosiloxane, and 1000 parts by weight or less of the low molecular weight polyorganosiloxane to 100 parts by weight of a total combination of the above surfactant(s) and the polyoxyalkylene cont~;ning polyorganosiloxane. Too small an amount of the surfactant reduces the cleaning capability, while too large an amount impairs the penetratbility. Too large an amount of the low molecular weight polyorganosiloxane not only makes the system difficult to disperse but also reduces stability as a water system composition. A preferable fraction of the surfactant is 30 to 700 parts by weight, or, more preferably, 50 to 300 parts by weight, to 100 parts by weight of the polyoxyalkylene group contAining polyorganosiloxane. A more preferable fraction of the low molecular weight polyorganosiloxane is between 10 and 1000 part by weight.
While the fraction of water in the quaternary water system cleaning agent is not particularly limited either, it is preferable to have water 40 wt. % or more or, more preferably, 70 to 99.S wt. % to the total composition from a stability viewpoint.
By the way, the polyoxyalkylene group cont~in;ng polyorganosiloxane having in a single molecule at least one siloxy unit represénted by formula (III) penetrates, as described above, into the interface between the stains and the substrate made of, e.g., a metal to which the stainsadhere to "peel off" the stains. Thus, even a tertiary composition consisting of the polyoxyalkylene group cont~ining polyorganosiloxane, a surfactant, and water may serve as a viable water system cleaning agent. In this case, the fractions of the quaternary water system cleaning agent will apply to the tertiary composition.
The fractions of the tertiary or ~uaternary water system cleaning agents may be so designed that the value to be obtAin~ by a canvas method at room temperature for evaluating penetrability will be 15 or less, 10 or less, or 5 or less. For the evaluation, the canvas method specified as a fiber/textile test method by Japanese Industrial St~n~rds (JIS) is adopted. Since the cleaning property of these water system cleaning agents depends on the pH value of the solution itself, it is desirable to adjust the pH value to the alkali region. The pH value is more preferably be between 8 to 14.
The tertiary or quaternary cleaning agents can be prepared easily by blending and stirring the above-mentioned polyoxyalkylene group contAin;ng polyorganosiloxane, a surfactant, water, or further the low molecular weight polyorganosiloxane represented by formula (I) or (II), where n~ceScAry. The use of a known dispersing device will help obtain a water system cleaning agent with ease.
The water system cleaning agents such as described above may have additives to be applied to ordinary water-soluble cleaning agents such as pH modifiers, adsorbents, solid particles, synthetic builders, rust preventives, and antistatic agents mixed as cleaning assistants or post-cleaning added-value improving agents and the like, depending on the property, amount, adhering state, cleaning condition, and the like of a stain. Such an addition may play an important part depending on their application.
The water system cleaning agents of the invention may be applied to metals, ceramics, plastics, and the like. More specifically, they may be applied to metallic parts, surface treated parts, electronic and semiconductor parts, electric and precision machinery parts, optical parts, glass and ceramic parts, and the like. An exemplary general-purpose cleaning process usually involves cleaning of any of the above-described parts by such a process as ultrasonic process, mech~n;cal stirring and spraying, and thereafter, washing by water (preferably by pure water or ion-exchanged water), and is dewatered by drying the part with heated air or a like process. The cleaning composition in which the stain separated from the part is present is treated by, e.g., separating the stain through a filter or the like and thereafter by being subjected to a general waste water treatment process, thereby allowing the composition to be unhazardous and pollution-free easily.
21~1848 According to the water system cleaning agent of theinvention, the powerful penetrating property of the low molecular weight polyorganosiloxane represented by formula (I) or (II) for the interface between the stains and the substrate as well as the cl~n;ng capability of the surfactant(s) to the stains provides a cleaning performance equivalent to that of the conventionally used freon*
cont~i~ing cleaning agents. The use of the polyoxyalkylene group cont~ining polyorganosiloxane in combination with the water system cleaning agents of the invention allows satisfactory dispersing property in water. In addition, when applied as a tertiary composition consisting of the polyoxyalkylene group containing polyorganosiloxane, the surfactant, and water, the cleaning agent of the invention exhibits excellent cleaning property by the penetrating capability of the polyoxyalkylene group containing polyorganosiloxane with respect to the stain. Being a water system agent, it will bring no risk of environmental destruction and pollution. Thus, it can be said from the above that the water system cleaning agent of the invention can be an attractive replacement for cleaning agents based on organic solvents contA;n;ng freon* and other substances which have considered hazardous.
A case in which a cle~n;ng composition of the invention is used as a dewatering cleaning agent will now be described.
* Trademark Here, the term "dewatering agent" is only so named after "water", which is a typical liquid capable of being substituted by the low molecular weight polyorganosiloxanes, and the cleaning compositions of the invention may also be used as "liquid removing" agents in substituting and cleaning liquids other than water. The applicable liquids may be those which are insoluble or difficult to be dissolved in the low molecular weight polyorganosiloxanes and whose surface tensions are larger than those of the low molecular weight polyorganosiloxanes. The "water" to be cleaned may include liquids using water as a dispersion medium such as mixtures of water and alcohols and liquids in which various substances are dissolved.
The low molecular weight polyorganosiloxane represented by formula (I) or (II) can be, as described previously, substituted by water alone, thus allowing itself to be easily vaporized and dried by hot air below 60-C.
Such a dewatering cleaning agent may consist substantially of the low molecular weight polyorganosiloxane and with it a satisfactory effect can be obtained. However, its cleaning and dewatering properties and the like will be further improved by forming it into a composition having the low molecular weight polyorganosiloxane mixed with a surfactant and/or a hydrophilic solvent.
The above-mentioned surfactants contribute to improving particularly the cleaning and dewatering property, and 21 ~18~8 suitable surfactants to be applied to the invention include:
anionic surfactants such as polyoxyalkylene alkylether sulfonates and phosphoric esters; nonionic surfactants such as polyalcohol fatty acid esters, polyoxyalkylene fatty acid esters, and polyoxyalkylene alkylethers; amphoteric surfactants such as imidazolin derivatives; and cationic surfactants such as alkylamine salts, alkyl quaternary ammonium salts. In addition thereto, terpene containing compounds which are rarely present in the form of a single substance and extracted from natural substances as well as higher fatty acid esters may also be applied. It is also possible to use synthetic compounds in which part of the chemical structure of each compound is substituted by a fluorine or silicon atom. However, it is more preferable to use nonionic surfactants if the effect as a dewatering cleaning agent used in combination with the low molecular weight polyorganosiloxane is to be further improved.
While the composition ratio of the surfactant is not particularly limited, it is desirable to have 20 parts by weight or less, or, more preferably, 3 parts by weight or less, of the surfactant to 100 parts by weight of low molecular weight polyorganosiloxane.
A suitable hydrophilic solvent may be one compatible with the low molecular weight polyorganosiloxanes, and more particularly, one whose flash point is 40~C or more from the 21~1848 practical viewpoint. The hydrophilic solvent contributes to improving substituting property by water.
Suitable hydrophilic solvents include: polyalcohols and their derivatives such as ethylene glycol monomethyl ethers, ethylene glycol monoethyl ethers, ethylene glycol monopropyl ethers, ethylene glycol monobutyl ethers, ethylene glycol - monobutyl ether acetates, diethylene glycol monobutyl ethers.
Particularly preferable are diethylene glycol monobutyl ethers from the viewpoint of its compatibility with the low molecular weight polyorganosilox~nec and safety to the human body and the like. Since these compounds exhibit improved properties when coexisting with the low molecular weight polyorganosiloxanes, a composition only using this combination may allow substitution by water and drying.
While the composition ratio of the hydrophilic solvent is not particularly limited, it is preferable to have 100 parts by weight or less or, more preferably, 50 parts by weight or less of the hydrophilic solvent mixed with 100 parts by weight of the low molecular weight polyorganosiloxane.
The dewatering cleaning agents of the invention may be applied to metals, ceramics, plastics, and the like. More specifically, they may be applied to metallic parts, surface treated parts, electronic and semiconductor parts, electric and precision machinery parts, optical parts, glass and 2~ 51848 ceramic parts, and the like. An exemplary general-purpose cleaning process usually involves immersing of any of the above-described parts or spraying a dewatering cle~n;ng agent of the invention onto the part to substitute it by water and drying by blowing hot air and the like. The immersing and spraying proc~sC~c may be accompanied by an ultrasonic process and mech~n;cal stirring.
The dewatering cleaning agents of the invention, exhibiting a powerful dewatering property, can not only provide cleaning and water-substituting effects equivalent to those of conventional cleaning agents containing freon* and the like but also allow various materials to be stably cleaned with their low eroding action. In addition, cont~;n~ng no element halogen such as chlorine and bromine in general, the dewatering cleaning agents of the invention have few risk of destroying or polluting the environment. Thus, it can be said that the dewatering cleaning agents of the invention will be a viable replacement for the conventional organic solvent containing dewatering cleaning agents such as freon*, which have been imposing the environmental problems.
Fig. 1 is a diagram showing an exemplary construction of a cleaning system using a dewatering cleaning agent of the invention.
The invention will now be described with reference to examples in which a cleaning composition of the invention is applied to water system cleaning agents.
* Trademark - 20 -Example 1 Two kinds (Al and A2) of polyoxyalkylene group contAin;ng polyorganosiloxane, each represented by formula (V) and ~VI), were prepared.
Al:
CH3 fH3 (CH3)3SiO-- ( SiO-)8 --(7iO -~so Si(CH3)3 ~ CH3 ( CH2 ) ~-O- ( CH2cH2o ) 6 --(CH2CHO)6 - OCH3 ......... (V) A2:
IC~3CH3 (SiO-), --(SiO -)3 (CH2)3-O-(CH2CH20)l0 H ... ... ... (VI
Then, the polyoxyalkylene denatured silicone (Al) represented by formula (V), polyoxyalkylene denatured silicone (A2) represented by formula (VI), sodium laurate (Bl) and polyoxyethylene octylphenyl ether (B2) (20 moles of polyoxye~hylene), both serving as surfactants, and water were weighed so that their ratio by weight will be 5 : 5 : 4 : 4 :
82. Thereafter, these components were charged into a homogenizing mixer for blending to obtain a water system cleaning composition Pl.
Example 2 The polyoxyalkylene group containing polyorganosiloxane (Al), the sodium laurate (Bl) and polyoxyethylene octylphenyl ether (B2), both serving as surfactants, and water were weighed so that they satisfy the composition ratio specified in Table 1. Then, a water system cleaning composition P2 was obtained as in Example 1.
Examples 3 to 5 The polyoxyalkylene group con~ining polyorganosiloxanes (Al) and (A2), dioctyl sodium sulfosuccinate (B3) that serves as a surfactant in addition to the surfactants (Bl) and (B2), octamethyl tetrasiloxane (Dl) and octamethyl trisiloxane (D2), both as low molecular weight polyorganosiloxanes, and water were selectively mixed to prepare water system cleaning compositions P3 to P5 having composition ratios specified in Table 1 in the same manner as that in Example 1.
Comparative examples 1 to 3 Three kinds of water system cleaning compositions were prepared in a manner similar to that of each of the above examples except that no polyoxyalkylene group containing polyorganosiloxane was mixed.
The properties as a cleaning agent were evaluated as to the water system cleaning compositions of Examples 1 to 5 21~1848 and Comparative examples 1 to 3 by the following methods.
The result is also shown in Table 1.
(1) Penetration test Measurements were made based on the JIS-specified canvas method. The smaller value means better penetrating property;
i.e., the composition is more effective in cleaning smaller parts.
(2) Cleaning property test A sample is prepared by applying a spindle oil over a steel strip and h~ki ng it at 135-C for 48 hours. The property is evaluated by the time spent for cleaning the oil baked on the sample (by ultrasonic cleaning). The smaller the value is, the better the cleaning property becomes.
(3) Stability test Each composition was contained in a transparent bottle of 200 ml sealed thereafter and then heated at 50-C for 6 hours. After being gradually cooled from 50 to 25~C, its appearance in the bottle is observed.
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~1~1848 As is apparent from the result shown in Table 1, the water system cl~n;ng agent of the invention exhibits excellent cleaning capability and penetrability, attesting to its availability as a replacement for the conventional solvent based cleaning agents containing freon* and the like.
With its stability, it is considered a highly practical product. In contradistinction thereto, the water system cleaning agents according to Comparative examples were satisfactory neither in cle~ning capability nor in penetrability.
An exemplary process employed to clean a specific part using a water system cleaning agent of the invention will now be described.
Example 6 In fabricating a liquid crystal device, a liquid crystal cell is evacuated to a high vacuum degree and a liquid crystal material is sealed in a device. In this case, the evacuation is carried out by a high performance diffusion vacuum pump. Since the diffused oil enters into the vacuum system in the form of mist, the pump must be cleaned often to remove the oil.
In this example, the water system cleaning agent of the invention was used in lieu of a conventional triethane cleaning agent.
* Trademark 21~1848 A pump part made of a stainless steel SUS304 and a Ni-plated stainless steel SUS304 material having an adhesion of Silicon Oil F-4 (trademark of Shinetsu Chemical) as a diffusion oil was cleaned.
The composition ratio of the used water system cleaning agent is as shown below.
That is, in 80 wt. % of ion-eY~h~nged water being sufficiently stirred at ambient temperature, 6 ~t. % of the polyoxyalkylene group cont~i n; ng polyorganosiloxane having the following chemical structure was gradually added to obtain an achromatic translucent homogeneous solution.
(SiO ) (SiO -)6 ( CH2 ) 3--0- ( CH2CH2~ ) lS -- H
On the other hand, as a surfactant, a mixture of 8 wt.
of special nonionic Adecanol B-4001 (trademark of Ac~h;
Ele~rocl~emical) and 6 wt. ~ of anionic TWA-2023 (trademark of Ipposha Oil and Grease) of sulfuric acid ester PURLONIC
structure was added to the above water/siloxane solution.
After diluting the water system cleaning agent thus obtained was diluted by ion-exchanged water at an arbitrary ratio, Silicone Oil F-4 was cleaned using the diluted cleaning agents. As a result, the pump part was -satisfactorily cleaned: through immersion by stirring for 1 minute in a 1/10 diluted cleaning agent at ambient temperature; through immersion by oscillating for 1 minute in a 1/30 diluted cleaning agent at 40~C or through 1 minute ultrasonic cleaning at 20~C in the same cleaning agent; and through 1 minute ultrasonic cleaning in a 1/50 diluted cleaning agent at 50 C, respectively.
For comparison, the pump part was similarly cleaned with compositions containing only surfactant(s) and no polyoxyalkylene group cont~ining polyorganosiloxane.
Silicone Oil was not removed sufficiently with 10 or more minute immersion ultrasonic cleaning in a 1/10 diluted composition at ambient temperature. To remove Silicone Oil with this composition, it took more than 5 minutes at 65~C or more.
It is understood from this data that the cleaning agent that incorporates the polyoxyalkylene group containing polyorganosiloxane of the invention exhibits an outstanding cleaning property.
Example 7 The polyoxyalkylene group containing polyorganosiloxanes and the low molecular weight polyorganosiloxanes of the invention contribute to significantly improve the cleaning capability of commercially available water-soluble cleaning agents.
21518~8 An Aqueous solution of Chemiclean MS-109 (trademark of Sanyo Kasei Kogyo), which is a surfactant containing, low foaming, rust preventive cleaning agent, is typically used to clean mech~nical and metallic parts. Blending 3 wt. % of the polyoxyalkylene denatured silicon (Al) represented by formula (V) in Example 1, 5 wt. % of cyclic hexamethylcyclotrisiloxane, 17 wt. % of ion-exchanged water with 65 wt. % of the above aqueous solution, a new cleaning composition was prepared.
This new cleaning composition was 1/20 diluted by ion-exchanged water and its cleaning property was evaluated by the following method. The result is shown in Table 2. For comparison, the evaluation result of 1/20 diluted Chemiclean MS-109 was also shown.
Test Method (1) Cleaning test - 1 The following contaminants were applied to a degreased aluminum plate (AC-4A) by immersing, dried by blowing, and immersed while stirred (400 rpm) in respective cleaning agents (1/20 diluted) for 15 C~con~s to 1 minute. Then, after immersed in water, the aluminum plate was dried by blowing. Each contaminant was transferred on white paper through an adhesive tape for reflectance measurement by a colorimeter thereby to calculate the cleaning rate.
Contaminant:
Spindle oil 78%
Fatty acid ester 15%
Chlorinated paraffin 5%
Carbon black 2%
Cleaning rate (%) = Rw - Rs / Ro - Rs Ro: Reflectance of the original white paper Rs:
Reflectance of the st~nAArd contaminated plate Rw:
Reflectance of the contaminated plate after cleaned (2) Cleaning test - 2 A contaminant was prepared by adding 2% of carbon black to a water-soluble mac~linirg oil (emulsive), and the test was performed in a manner similar to that of Cleaning test - 1.
Its cleaning rate was similarly calculated.
Table 2 Immersion timeCleaning Rate (%) (second)Invention MS-109 Cleaning test - 1 15 72.4 59.0 86.5 65.2 100.0 67.8 Cleaning test - 2 15 81.7 58.0 93.8 71.0 Similar tests were conducted on EP-680 (trademark of E.P. Japan) which is a commercially available supereffective cleaning solution and water system cleaning agent; Banrise D-30 20 (trademark of Joban Chemical Industries) which is anemulsive degreased cleaning agent; and Hikari Ace (trademark of Shoko Trade) which is a powerful special cleaning agent.
As a result, these cleaning agents, when used in combination of the polyoxyalkylene group containing polyorganosiloxane and the low molecular weight polyorganosiloxane of the invention, exhibited a significantly improved cleaning property.
Example 8 The water system cleaning agent of the invention exhibits remarkable effect on cleaning of fluxes used in mounting electronic parts on printed boards. The flux comes roughly in two types: rosin cont~i n; ng and water-soluble. A
specific example of cleaning rosin cont~ini~g fluxes, which is said to be a difficult task, will now be described.
As a step prior to soldering a part on a printed board, a WW rosin ester was put on a part and immersed in a solder bath at 230 to 250~C and then the part was mounted. It was observed that the flux was completely removed when the printed board was shower-rinsed for 35~C for 45 seconds using a water system cleaning agent described below.
The water system cleaning composition used here is prepared by blending 2 wt. % of the polyoxyalkylene group containing polyorganosiloxane represented by formula (VII), 3 wt. % of Senkanol FM (trademark of Nippon Senka), which is an amphoteric surfactant, 5 wt. % of Nikkol CNT-30 (trademark of Nippon Surfactant), which is a sodium-N-COCOIL methyl taurine cont~n;ng nonionic surfactant, and A~;ng ion-eY~-h~nged water to prepare 100 wt. % of the composition.
~ CH3 (CH313SiO- (sio-)s - ~SiO -~3s - Si(CH3)3 (CH2)3-0-(CH2CH20) 6 ~
L (CH2CH0)6 - OCH3 ... ... ... (VII) c~3 When acceleration aging tests which guarantees US MIL-F-14256C ~tA~Ard~ surface insulation resistance tests, ion re~idual tests and the like were conducted on the above composition which was 1/10 diluted by ion-exchanged water, the results were satisfactory.
Examples in which cleaning compositions of the invention were applied to dewatering cleaning agents will now be described.
Examples 9 to 17 Octamethyltrisiloxane (El), octamethyltetrasiloxane (E2), and decamethylpentasiloxane (E3) were prepared as low molecular weight polyorganosilo~An~c; polyoxyethylene oleyl ether (Fl) (P.O.E. =6 moles), and polyoxyethylene octylphenyl ether (F2) (P.O.E. =10 moles) as surfactants; and diethylene glycol monobutyl ether (Gl) as a hydrophilic solvent were prepared.
-- 21 518~8 These components were selected and blended so that the composition ratio shown in Table 3 were satisfied to obtain respective dewatering cleaning agents.
Comparative examples 4 to 8 Freon* 113, methylene chloride, isopropyl alcohol, and ethanol were prepared as conventional dewatering cleaning agents to obtain 5 types of dewatering cleaning agents whose comrosition ratios were as shown in Table 3.
The properties of Examples 9 to 17 and Comparative examples 4 to 8 were evaluated by the following methods. The result is also shown in Table 3.
(1) Dewatering property Various pieces (a stainless steel strip, a ceramic piece, a polycarbonate piece, a Ni-plated steel strip) were immersed in each dewatering cleaning agent after washed by water. In examples 13 to 15, each piece was then rinsed by the low molecular weight polyorganosiloxane blended to prepare each dewatering cleaning agent. Thereafter, each piece was dried in an oven at 50~C. The water marks (a stain by impurities dissolved in water) after drying each piece was observed visibly and by a sc~nn;ng electron microscope and evaluated in accordance with the following criteria.
XX: Not evaluable due to erosion of the piece during dewatering.
* Trademark ~1 5 1848 X: Water marks were visibly observed.
o: No water marks were visibly observed.
: No water marks whose size is 50 ~m or more were observed by the sc~nn; ng electron microscope.
(2) Continuous dewatering property A continuous dewatering test with a frequency of 50 times were conducted on a stainless steel strip and the appearance of the strip was evaluated in a manner similar to that of item (1).
(3) Drying property The stainless steel strip was immersed in each dewatering cleaning agent and dried in the oven at 50~C.
During the drying process, the strip was touched by a finger to see the drying condition every 5 minutes and the time required for drying was recorded on a 5-minute basis.
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21~18~8 As is apparent from the result shown in Table 3, the dewatering cleaning agents of the invention, exhibiting satisfactory dewatering property, can be a viable substitute for organic solvent containing freon* and the like based cleaning agents.
Dewatering cleaning agents contA i n i ng methylene chloride-or isopropyl alcohol (Comparative examples 4 and S) rust and erode metal films and plastics. In contradistinction thereto, the dewatering cleaning agents of the invention are stable to metal films and plastics and exhibit satisfactory dewatering property even to ceramics which have large surface roughnecs values, thereby ensuring their reliability when applied to parts including metal, plated, electronic, semiconductor, plastic, and ceramic parts. The dewatering 15 cleAni ng agent containing isopropyl alcohol permitted water to be dissolved therein, thereby causing water to present on the part again.
Moreover, it is understood that mixing of surfactants and hydrophilic solvents with the dewatering cleaning agents of the invention improved the dewatering property, thereby attesting to their industrial applicability.
An exemplary cleaning system using a dewatering cleaning agent of the invention will now be described with reference to Fig. 1.
* Trademark 21~1848 A cleaning system shown in Fig. 1 consists roughly of a cleaning/water-substituting process A and a rinsing/dewatering process B.
The cleaning/water-substituting process A, which is the S first process involves a first cleaning vessel 1 and a second cleaning vessel 2, each serving both as a separator through sedimentation and a separator through overflow, and a dewatering vessel 3. The first and second cleaning vessels 1 and 2 communicate with each other through a drain line 2a and an overflow line 2b. The first and second cleaning vessels 1 and 2 are operated together with ultrasonic, os¢illating, mech~nical stirring, cleaning agent heating, and brushing procecce-c and the like, if nec~-cs~ry.
The first and second cleaning vessels 1 and 2 respectively lS contain a cleaning agent Dl composed of a low molecular weight polyorganosiloxane and a surfactant, which is one of the dewatering cleaning agents of the invention. The surfactant containing cleaning agent Dl may be so prepared that its specific gravity is smaller than that of water and larger than that of an oily stain. Therefore, water Y
introduced by an object to be cleaned X is separated by being sedimentated at the bottom of the surfactant containing cleaning agent Dl that has been charged in the first and secon~ cleaning vessels 1 and 2. If an oily stain Z is present on the object X, the oily stain Z is separated by 2 1 ~ I8~ 8 floating upward in the surfactant containing cleaning agent Dl in the first and second cleaning vessels 1 and 2.
The water Y separated by being sedimentated in the second cleaning vessel 2 is intermittently discharged to the first cleaning vessel 1 through a drain line 2a while the water Y separated by being sedimentated in the first cleaning-vessel 1 is intermittently discharged to a cleaning agent recycling mech~nism C (described later) through a drain line 4. A drain-line 3a connected to the drainage vessel 3 is also connected to the cleaning agent recycling mech~nism C.
The oily stain Z separated by floating in the first and second vessels 1 and 2 is discharged outside while continuously overflown through an overflow line 5 connected to the first cleaning vessel 1.
The surfactant containing cleaning agent Dl charged in the first and second cleaning vessels 1 and 2 is continuously circulated through a filter 6 that serves to remove solid particles, H20 particles, lln~; scolved substances, and the like contained in the cleaning agent Dl.
The rinsing/dewatering process B, which is the second process, involves a third cl~n;ng vessel 7 and a shower rinse vessel 8. Below the shower rinse vessel 8 is a buffer tank 9 that communicates with the third cleaning vessel 7 through a drain line 9a and an overflow line 9b. The third cleaning vessel 7 is also operated together with ultrasonic, oscillating, me~h~nical stirring, cleaning agent heating, and brushing processes and the like, if nec~cc~ry.
The third cleaning vessel 7 contains a cleaning agent D2 consisting only of a silicone composition identical to the low molecular weight polyorganosiloxane used in the first process A. The cleaning agent D2 may be so prepared that its specific gravity is smaller than that of water and larger than that of an oily stain. Therefore, as in the first process A, water Y is separated by being sedimentated at the bottom of the cleaning agent D2 and the oily stain Z is separated by floating upward in the cleaning agent D2.
The water Y separated by being ce~;mentated in the third cleaning vessel 7 is intermittently discharged to the cleaning agent recycling merh~nism C through a drain line 10 while the oily stain Z separated by floating in the third cleaning vessel 7 is ~;~rh~rged outside through an overflow line 11.
The cleaning agent D2 charged in the third cleaning vessel 7 is continuously circulated through a filter 12 that serves to remove solid particles, H20 particles, undissolved substances, and the like contained in the cleaning agent D2.
The object to be cleaned X undergoes the first process A
and then the second process B, cleaned and dewatered, and then dried by a fan forced drier (not shown) to complete the cleaning process.
21~18~8 The cleaning agent used in the cleaning system is subjected to the following recycling process.
As described above, the drain lines 4, 3a, 10 of the first, second, and third cleaning vessels 1, 2, and 7, and the dewatering vessel 3 are connected to the cleaning agent recycling mech~nism C. The cleaning agent Dl or D2 contained-in each cleaning vessel is constantly cleaned by the filters 6 and 12. However, when heavily contaminated, the cleaning agent is illLLGduced to the cleaning agent recycling mech~n;sm C through drain lines 4 and 10 by a conveyer pump 13 for fractional distillation. The cleaning agent Dl deposited in the dewatering vessel 3 is also supplied intermittently to the cleaning agent recycling me~h~n;sm C.
At the cleaning agent recycling mec-h~n;~m C, the introduced cleaning agent is separated into liquid components and solid components by a filter 14, and only the liquid components are forwarded to a distiller 15 with the solid components being destroyed. The distiller 15 separates various components, water, oily stains in the cleaning agent utilizing the difference in their boiling points. Water and the like that remain in the distiller 15 are further separated by a decanter 16.
Since the cleaning agent Dl is an agent having a surfactant added to the cleaning agent D2 that contains only the low molecular weight polyorganosiloxane, the low molecular weight polyorganosiloxane, i.e., the cleaning agent 21~1848 D2, can be extracted from both cleaning agents Dl and D2, thereby allowing the cleaning agent D2 to be recycled. The components other than the recycled cleaning agent D2, i.e., the surfactant, water, and the like will be destroyed.
The recycled cleaning agent D2 is forwarded to a mixer 18 from which the cleaning agent Dl is supplied to the shower rinse vessel 8, the third cleaning vessel 7, or the second cleaning vessel 2 through a line 17.
In the shower rinse vessel 8, a shower rinsing process is conducted using only the recycled cle~n i ng agent D2 or a cle~ni ng agent D2 newly i,.~-olllce~ through a cleaning agent supply line 19, both being free from impurities.
The mixer 18 mixes the recycled or new cleaning agent D2 with the surfactant newly supplied from a surfactant supply line 20 to prepare a new cleaning agent Dl. The new cleaning agent Dl is supplied to the cDco~ cleaning vessel 2, if necessary.
With the cleaning system of such construction as described above, the dewatering cleaning agents of the invention can be used efficiently and effectively enjoying the advantage of excellent cleaning properties.
Industrial Applicability As described in the foregoing pages, the cleaning compositions of the invention, when used as water system cleaning agents, exhibit a cleaning effect equivalent to that of conventional freon* contAining cleaning agents and an excellent stability as a water system with no risk of environmental destruction and pollution, thereby making a viable replacement for the organic solvent based cleaning agents including freon* and the like which have environmental disadvantages. In addition, the cleaning compositions of the invention, when used as dewatering cleaning agents, provide a powerful dewatering property with no risk of environmental destruction and pollution, thereby serving a viable replacement for the organic solvent h~~~ dewatering cleaning agents including freon* and the like which have environmental disadvantages.
* trademark - 41 -
Claims (18)
1. A cleaning method comprising the steps of:
a cleaning step of cleaning an object to be cleaned by use of a plurality of cleaning vessels in sequence, each of the cleaning vessels containing a water system cleaning agent, the cleaning vessels being connected with each other such that said water system cleaning agent is transmitted in sequence in the direction opposite to that in which the object is transmitted; and a re-supplying step of a recovered water system cleaning agent, wherein a cleaning waste agent is recovered from at least one cleaning vessel selected from said plurality of cleaning vessels; wherein said recovered waste cleaning agent is distilled to recover said water system cleaning agent, and wherein said recovered water system cleaning agent is re-supplied to at least one cleaning vessel selected from said plurality of cleaning vessels.
a cleaning step of cleaning an object to be cleaned by use of a plurality of cleaning vessels in sequence, each of the cleaning vessels containing a water system cleaning agent, the cleaning vessels being connected with each other such that said water system cleaning agent is transmitted in sequence in the direction opposite to that in which the object is transmitted; and a re-supplying step of a recovered water system cleaning agent, wherein a cleaning waste agent is recovered from at least one cleaning vessel selected from said plurality of cleaning vessels; wherein said recovered waste cleaning agent is distilled to recover said water system cleaning agent, and wherein said recovered water system cleaning agent is re-supplied to at least one cleaning vessel selected from said plurality of cleaning vessels.
2. A method as claimed in claim 1, wherein said water system cleaning agent comprises at least one polyorganosiloxane selected from the group consisting of a straight chain polyorganosiloxane represented by the formula:
, and a cyclic polyorganosiloxane represented by the formula:
wherein R1 in each of the above formulas is independently selected from the group consisting of methyl, ethyl, propyl, butyl, phenyl, trifluoromethyl, amino, amide, acrylic acid ester and mercaptan, 1 is an integer from 0 to 5, and m is an integer from 3 to 7.
, and a cyclic polyorganosiloxane represented by the formula:
wherein R1 in each of the above formulas is independently selected from the group consisting of methyl, ethyl, propyl, butyl, phenyl, trifluoromethyl, amino, amide, acrylic acid ester and mercaptan, 1 is an integer from 0 to 5, and m is an integer from 3 to 7.
3. A method as claimed in claim 2, wherein said water system cleaning agent further comprises a polyoxyalkylene group containing a polyorganosiloxane having a single molecule at least one siloxy unit represented by the formula:
wherein R2 is an alkyl group or a phenyl group and A is a polyoxyalkylene group; a surfactant; and water.
wherein R2 is an alkyl group or a phenyl group and A is a polyoxyalkylene group; a surfactant; and water.
4. A method as claimed in claim 1, which further comprises a step of drying the object.
5. A method as claimed in claim 4, wherein said step of drying is conducted by use of heated air or in a heated oven.
6. A method as claimed in claim 4, wherein said step of drying is connected by use of a dewatering agent, wherein said dewatering agent comprises at least one polyorganosiloxane selected from the group consisting of a straight chain polyorganosiloxane represented by the formula:
, and a cyclic polyorganosiloxane represented by the formula:
wherein R1 in each of the above formulas is independently selected from the group consisting of methyl, ethyl, propyl, butyl, phenyl, trifloromethyl, amino, amide, acrylic acid ester and mercaptan, 1 is an integer from 0 to 5, and m is an integer from 3 to 7.
, and a cyclic polyorganosiloxane represented by the formula:
wherein R1 in each of the above formulas is independently selected from the group consisting of methyl, ethyl, propyl, butyl, phenyl, trifloromethyl, amino, amide, acrylic acid ester and mercaptan, 1 is an integer from 0 to 5, and m is an integer from 3 to 7.
7. A method as claimed in claim 1, wherein the object comprises at least one part selected from the group consisting of metals, ceramics and plastics.
8. A method as claimed in claim 7, wherein the part comprises at least one selected from the group consisting of metallic parts, surface treated parts, electronic and semiconductor parts, electric and precision machinery parts, optical parts, and glass and ceramic parts.
9. A cleaning method comprising the steps of:
a cleaning step of cleaning an object to be cleaned by use of a cleaning vessel containing a water system cleaning agent;
a rinsing step of rinsing said object by use of a plurality of rinsing vessels in sequence, each of the rinsing vessels containing a water system rinsing agent, the rinsing vessels being connected with each other such that said water system rinsing agent is transmitted in sequence in the direction opposite to that in which the object is transmitted; and a re-supplying step of a recovered water system rinsing agent, wherein a rinsing waste agent is recovered from at least one rinsing vessel selected from said plurality of rinsing vessel, wherein said recovered waste rinsing agent is distilled to recover said water system rinsing agent, and wherein said recovered water system rinsing agent is re-supplied to at least one rinsing vessel selected from said plurality of rinsing vessels.
a cleaning step of cleaning an object to be cleaned by use of a cleaning vessel containing a water system cleaning agent;
a rinsing step of rinsing said object by use of a plurality of rinsing vessels in sequence, each of the rinsing vessels containing a water system rinsing agent, the rinsing vessels being connected with each other such that said water system rinsing agent is transmitted in sequence in the direction opposite to that in which the object is transmitted; and a re-supplying step of a recovered water system rinsing agent, wherein a rinsing waste agent is recovered from at least one rinsing vessel selected from said plurality of rinsing vessel, wherein said recovered waste rinsing agent is distilled to recover said water system rinsing agent, and wherein said recovered water system rinsing agent is re-supplied to at least one rinsing vessel selected from said plurality of rinsing vessels.
10. A method as claimed in claim 9, wherein said water system cleaning agent comprises at least one polyorganosiloxane selected from the group consisting of a straight chain polyorganosiloxane represented by the formula:
, and a cyclic polyorganosiloxane represented by the formula:
wherein R1 in each of the above formulas is independently selected from the group consisting of methyl, ethyl, propyl, butyl, phenyl, trifluoromethyl, amino, amide, acrylic acid ester and mercaptan, 1 is an integer from 0 to 5, and m is an integer from 3 to 7.
, and a cyclic polyorganosiloxane represented by the formula:
wherein R1 in each of the above formulas is independently selected from the group consisting of methyl, ethyl, propyl, butyl, phenyl, trifluoromethyl, amino, amide, acrylic acid ester and mercaptan, 1 is an integer from 0 to 5, and m is an integer from 3 to 7.
11. A method as claimed in claim 9, wherein said water system cleaning agent further comprises a polyoxyalkylene group containing a polyorganosiloxane having a single molecule at least one siloxy unit represented by the formula:
wherein R2 is an alkyl group or a phenyl group and A is a polyoxyalkylene group; a surfactant; and water.
wherein R2 is an alkyl group or a phenyl group and A is a polyoxyalkylene group; a surfactant; and water.
12. A method as claimed in claim 9, which further comprises a step of drying the object.
13. A method as claimed in claim 9, wherein said step of drying is conducted by use of heated air or in a heated oven.
14. A method as claimed in claim 9, wherein said step of drying is conducted by use of a dewatering agent, wherein said dewatering agent comprises at least one polyorganosiloxane selected from the group consisting of a straight chain polyorganosiloxane represented by the formula:
, and a cyclic polyorganosiloxane represented by the formula:
wherein R1 in each of the above formulas is independently selected from the group consisting of methyl, ethyl, propyl, butyl, phenyl, trifluoromethyl, amino, amide, acrylic acid ester and mercaptan, 1 is an integer from 0 to 5, and m is an integer from 3 to 7.
, and a cyclic polyorganosiloxane represented by the formula:
wherein R1 in each of the above formulas is independently selected from the group consisting of methyl, ethyl, propyl, butyl, phenyl, trifluoromethyl, amino, amide, acrylic acid ester and mercaptan, 1 is an integer from 0 to 5, and m is an integer from 3 to 7.
15. A method as claimed in claim 9, wherein the object comprises at least one part selected from the group consisting of metals, ceramics and plastics.
16. A method as claimed in claim 9, wherein the part comprises at least one selected from the group consisting of metallic parts, surface treated parts, electronic and semiconductor parts, electric and precision machinery parts, optical parts, and glass and ceramic parts.
17. A method as claimed in claim 10, wherein said polyorganosiloxane comprises said straight chain polyorganosiloxane represented by the formula:
wherein R1 and l are defined in claims 10.
wherein R1 and l are defined in claims 10.
18. A method as claimed in claim 10, wherein said polyorganosiloxane comprises said cyclic polyorganosiloxane represented by the formula:
wherein R1 and m are defined as in claim 10.
wherein R1 and m are defined as in claim 10.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1-280860 | 1989-10-26 | ||
| JP28086089 | 1989-10-26 | ||
| JP1-302580 | 1989-11-21 | ||
| JP30258089 | 1989-11-21 | ||
| JP2-065842 | 1990-03-16 | ||
| JP2-065841 | 1990-03-16 | ||
| JP6584290 | 1990-03-16 | ||
| JP6584190 | 1990-03-16 | ||
| CA002034488A CA2034488C (en) | 1989-10-26 | 1990-10-25 | Cleaning compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2151848A1 true CA2151848A1 (en) | 1991-04-27 |
Family
ID=27508424
Family Applications (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002151846A Abandoned CA2151846A1 (en) | 1989-10-26 | 1990-10-25 | Cleaning compositions |
| CA002151847A Abandoned CA2151847A1 (en) | 1989-10-26 | 1990-10-25 | Cleaning compositions |
| CA002151849A Abandoned CA2151849A1 (en) | 1989-10-26 | 1990-10-25 | Cleaning compositions |
| CA002151848A Abandoned CA2151848A1 (en) | 1989-10-26 | 1990-10-25 | Cleaning compositions |
Family Applications Before (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002151846A Abandoned CA2151846A1 (en) | 1989-10-26 | 1990-10-25 | Cleaning compositions |
| CA002151847A Abandoned CA2151847A1 (en) | 1989-10-26 | 1990-10-25 | Cleaning compositions |
| CA002151849A Abandoned CA2151849A1 (en) | 1989-10-26 | 1990-10-25 | Cleaning compositions |
Country Status (1)
| Country | Link |
|---|---|
| CA (4) | CA2151846A1 (en) |
-
1990
- 1990-10-25 CA CA002151846A patent/CA2151846A1/en not_active Abandoned
- 1990-10-25 CA CA002151847A patent/CA2151847A1/en not_active Abandoned
- 1990-10-25 CA CA002151849A patent/CA2151849A1/en not_active Abandoned
- 1990-10-25 CA CA002151848A patent/CA2151848A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| CA2151847A1 (en) | 1991-04-27 |
| CA2151849A1 (en) | 1991-04-27 |
| CA2151846A1 (en) | 1991-04-27 |
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