JP3002261B2 - Cleaning agent, cleaning method and cleaning device - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a cleaning agent, a cleaning method and a cleaning apparatus in place of a chlorofluorocarbon-based solvent and a chlorine-based solvent.

BACKGROUND ART In the manufacturing process of electronic components such as HICs, modules and mounting boards, metal thin films such as lead frames for transistors and hoop materials, bearings and precision fine components, resist agents, fluxes, solder pastes, cutting oils, firing oils, etc. Various dirts such as oils, rolling oils, press oils, punching oils, drawing oils, assembling oils, drawing oils, etc., water-based or solvent-based working oils, dust, dust and the like adhere.

For example, the manufacturing process of a printed circuit board is broadly divided into a process of manufacturing a board itself (bare board) and a process of mounting ICs and electronic components on the board. In the process of manufacturing a bare board, printing and etching operations are performed. In the mounting step, dirt, such as solder and flux, is mainly adhered during the mounting process. Particularly, the contaminants that need to be removed are the activator in the flux and organic acid salts such as CuCl ₂ and (RCOO) ₂ Cu, which are reaction products of the flux with the oxide film of the base material.
Since these are polar substances, if they remain, they absorb moisture, causing leakage, migration, a decrease in insulation resistance, corrosion of pins and wirings, and the like. In addition, in a semiconductor manufacturing process, contamination of an ionic substance is a serious problem, and is called, for example, "sodium panic". Further, in a metal-worked part, problems such as corrosion and discoloration occur due to the remaining of the stained portion as described above. For this reason, the above-mentioned contaminants need to be removed before the next step or during manufacturing.

Conventionally, as a cleaning agent for the above-described dirt component, a chlorofluorocarbon-based solvent represented by chlorofluorocarbon 113, and an organic solvent such as trichloroethane, trichloroethylene, tetrachloroethylene, and carbon tetrachloride have been widely used. But,
Recently, it has been revealed that the release of chlorofluorocarbons leads to the destruction of the ozone layer and has serious effects on human bodies and biological systems.
Etc. are in the direction of total abolition on a global scale. Also,
The use of chlorinated organic solvents such as trichlorethylene and tetrachloroethylene is also being stricter due to environmental problems such as causing pollution of soil and groundwater.

Under such circumstances, there is an urgent need to reduce the amount of the above-mentioned chlorine-based organic solvent used and to develop a substitute cleaning agent capable of completely eliminating the chlorine-based organic solvent. Alternative cleaning agents are required to have improved degreasing and drying properties, flame retardancy or nonflammability, and for example, various mixtures such as a mixture of Freon 113 with isopropyl alcohol or methyl ethyl ketone, and Freon 234 with ethanol. It has been studied to use an azeotropic composition with an aliphatic lower alcohol as described above, an alcohol such as isopropyl alcohol, a ketone such as acetone, or an ether alone.

Mixtures and azeotropic compositions of the above-mentioned chlorinated organic solvents and other organic solvents, by using an organic solvent other than the chlorinated one, can reduce the amount of the chlorinated organic solvent, but it is totally abolished. It is not possible. For example, Freon 11
Even if Flon-234, whose ozone layer depletion coefficient is smaller than that of 3, is used, the destruction of the ozone layer cannot be completely eliminated, so that the characteristics required for an alternative cleaning agent cannot be completely satisfied. On the other hand, organic solvents other than chlorine solvents, such as alcohols, ketones, and ethers, degrade the object to be cleaned such as plastics, and thus have a problem in practicality. further,
Because they are flammable, they are dangerous for storage and use, and some compounds are highly toxic to the human body.
In performing the work, there is a possibility that the work is adversely affected.

For this reason, attempts have been made to switch the washing of many industrial products to water washing, alkali washing, and solvent washing. For example, the main alternative cleaning methods currently proposed for cleaning printed circuit boards and the like include a water-based cleaning method of removing a water-soluble flux with pure water, and a quasi-water-based cleaning method of rinsing with water after removing the flux with a solvent. And a solvent-based cleaning method using an organic solvent such as a hydrocarbon-based solvent.

By the way, the water-based cleaning method and the quasi-water-based cleaning method described above are expected to have high performance in removing polar substances. However, their use is due to the adsorption or permeation of water to a glass epoxy substrate or a paper phenol substrate, etc. This causes a problem that electric resistance such as resistance is reduced. Furthermore, these precision washings have problems in drying properties and the like, and rust, discoloration, drying spots, and the like are caused, thereby causing deterioration in appearance and characteristics after drying.

In consideration of the electrical characteristics, drying characteristics, and the like after washing, washing with a non-polar solvent such as a hydrocarbon solvent is desirable. However, non-polar substances such as hydrocarbon solvents cannot be expected to be cleansable against ionic substances, polar substances, and even strong stains. In other words, the properties required for cleaning and the properties required for drying contain contradictory elements, so many industrial products are washed with water, alkali,
Attempts have been made to switch to solvent cleaning, but at present it is extremely difficult to select alternative cleaning for electronic components, precision components and the like.

As described above, in the conventional chlorofluorocarbon alternative cleaning, although water-based cleaning and quasi-water-based cleaning are expected to have high performance in removing polar substances, there is a problem that electrical characteristics and appearance and characteristics after drying are deteriorated. Had. On the other hand, cleaning with a non-polar solvent such as a hydrocarbon-based solvent has a problem that it is not possible to expect cleaning properties for ionic substances, polar substances, and even strong stains.

For this reason, a cleaning method that exhibits high detergency against various contaminants such as ionic substances and polar substances, and satisfies drying characteristics including maintenance of the appearance and characteristics of the object to be cleaned after drying. The emergence of is strongly desired.

On the other hand, silicone solvents represented by low-molecular-weight polyorganosiloxanes are nonaqueous solvents with excellent drying properties, and are highly safe for the environment and the human body.
Furthermore, since it is possible to perform precision cleaning, it is regarded as a promising alternative solvent. Table 1 shows various properties of the silicone solvent.

As shown in Table 1, alternatives to halogenated hydrocarbon solvents other than low molecular weight siloxane compounds have problems such as generation of spots at the time of drying of the object to be cleaned. Furthermore, in a cleaning system using a water-based cleaning agent, technical problems such as inexpensive drainage treatment of used water, prevention of rusting of a cleaning object, and reduction in electrical reliability have not been sufficiently solved. . On the other hand, low-molecular-weight siloxane compounds represented by low-molecular-weight polyorganosiloxane have excellent drying properties,
It is highly safe for the environment and the human body, and can be used for precision cleaning in various cleaning fields. However, since it has a flash point, it is desired to take safety measures.

On the other hand, in the case where a cleaning agent that substitutes for a chlorine-based organic solvent is used as an industrial cleaning agent, it is necessary to sufficiently consider drying, which is the final stage of cleaning. Regarding drying properties, steam drying using solvent vapor is excellent. This is because the steam drying has a high drying speed and a good finish of the object to be cleaned, thereby enabling precision cleaning. An ideal cleaning agent is one that can perform from washing to drying with one liquid, such as Freon 113 and trichloroethane, but since Freon 113 and trichloroethane etc. cause environmental destruction as described above. Research on industrial cleaning agents comprising a composition in which a nonflammable solvent which does not cause environmental destruction and has excellent drying properties and a flammable solvent is being studied.

However, perfluorocarbons and perfluoroethers, which are nonflammable solvents as described above, have low toxicity to the human body and do not contain chlorine, so there is no destruction of the ozone layer, but there is no detergency against dirt such as oils and fats, Further, even when mixed with other organic solvents, it is difficult to improve the detergency easily, even if mixed with other organic solvents, because of its poor compatibility with other organic solvents. Furthermore, not only are these expensive, but those having relatively good drying properties have a high vapor pressure, so that there is a large amount of loss of liquid due to evaporation, resulting in high costs.

As the above-mentioned cleaning composition, an azeotropic or pseudo-azeotropic composition is particularly preferable. Since the azeotropic composition does not cause fractional distillation when boiling, the flammability of the combustible solvent can be eliminated in some cases. Further, there is an advantage that the cleaning agent mixed with the dirt component can be regenerated using a steam cleaning device without causing a change in composition.

As the composition as described above, for example, JP-A-6-71
No. 238 describes a homogeneous mixed composition liquid in which perfluorocarbons or perfluorinated ethers are mixed with hexamethyldisiloxane. However, when a high degree of detergency is required, the mixed composition liquid has insufficient degreasing power, and further improvement is required so that washing and drying can be performed in one liquid.

On the other hand, as an azeotropic or azeotropic composition, for example, Japanese Patent Application Laid-Open No. 6-509836 discloses 2-trifluoromethyl-1,1,1,1.
An azeotrope-like composition of 2-tetrafluorobutane and methanol, ethanol or isopropanol is disclosed in JP-A-5-339275 and JP-A-6-88098, and hexamethyldisiloxane and methanol, 2-propanol or An azeotropic or pseudo-azeotropic composition consisting of ethanol is described.

However, the azeotropic or pseudo-azeotropic compositions described above are:
Both use a highly hydrophilic polar solvent such as methanol, ethanol, and isopropanol, so when a high degree of cleanability is required, the cleanability against oily stains may be insufficient and continuous When the washing is continued, there is a problem that moisture is easily contained during use as a detergent, thereby causing stains on the article to be washed, and rust easily occurring when the article to be washed is metal.
Furthermore, the above-mentioned azeotropic or pseudo-azeotropic composition has been desired to further improve incombustibility and drying property.

As described above, in a conventional cleaning agent composed of an azeotropic or pseudo-azeotropic composition that can replace a chlorine-based organic solvent, a cleaning agent capable of satisfying both degreasing and drying properties has not been obtained. In addition, the flame retardancy and the non-flammability of the cleaning agent were insufficient.

Because of this, without destruction of the ozone layer or deterioration of the plastic, etc., it is possible to carry out the washing to the drying with a single solution like Freon 113, 1,1,1-trichloroethane, and the like, and There is a strong demand for an azeotropic or pseudo-azeotropic composition capable of minimizing a change in composition during use, making the composition flame-retardant or non-flammable, and a detergent containing these as an active ingredient.

By the way, as one of the conventional methods of using a halogenated hydrocarbon solvent, there is "water drainage drying" for the purpose of drying without stains after a plating step or after using an aqueous cleaning agent. At present, alcohol, especially IPA (isopropyl alcohol) is being used for such applications, but drying heat is likely to occur due to large heat of evaporation.
In addition, there is a problem that dry spots become more remarkable due to moisture absorption from the air.

In addition, alcohol such as IPA azeotropes with water, so it cannot be separated and regenerated by distillation, and it must be disposable. Since the speed is slow, there is a problem that hot air drying is required in some cases even after steam cleaning.

As a method for solving the above-mentioned problem, draining and washing with a mixed system of perfluorohexane and trifluoroethanol has been proposed. However, since this mixed system contains non-hydrophilic perfluorohexane, drainage is poor. There is a problem that. In the first place, because perfluorohexane and trifluoroethanol are not compatible in the liquid state, liquid management is difficult, and
Since the condensed liquid leaks unevenly to the surface of the object to be dried, there is a problem that drying spots are easily generated.

It has been attempted to use trifluoroethanol as a degreasing detergent, but since it has a very strong polarity due to the electric suction effect of the trifluoro group, it has poor dissolving power for fats and oils and rosin. Is not suitable.

The present invention has been made to address such problems, and as a first object, in cleaning electronic components such as printed circuit boards and mounted components, or metal components, etc.
A cleaning method in which the removability and drying properties of various dirt components are comparable to the cleaning method using a chlorofluorocarbon-based solvent or a chlorine-based solvent,
A cleaning agent and a cleaning device are provided.

A second object of the present invention is to provide a cleaning method and a cleaning apparatus which enable a low molecular weight siloxane compound having flammability to be used completely and effectively.

The third object is to exhibit high detergency and excellent cleaning quality against various stains without causing destruction of the ozone layer and deterioration of plastics, and at the same time, have an excellent drying speed and minimize composition change during use. It is another object of the present invention to provide a detergent containing an azeotropic or pseudo-azeotropic composition that can be made flame-retardant or non-flammable, or that can suppress the entry of moisture.

A fourth object of the present invention is to provide a draining / drying method and a draining / drying apparatus which are equivalent to the draining / drying using a CFC-based or chlorine-based solvent, and which can obtain a drying quality and a drying property that do not leave stains or the like after drying at a drying speed comparable to that of the draining / drying. It is in.

DISCLOSURE OF THE INVENTION The first cleaning method of the present invention includes a step of cleaning an object to be cleaned with a polar cleaning agent having a solubility parameter of 9 or more or a dielectric constant of 4 or more, A cleaning mixture of a polar cleaning agent and a cleaning agent having a solubility parameter of less than 9 and a dielectric constant of less than 4, comprising at least one step selected from a rinsing step and a drying step of the object to be cleaned. Features.

The dirt targeted in the present invention is generally related to dirt requiring cleaning such as machine oil, grease, wax, and flux, and a material having such dirt attached or a material having at least a portion in contact with the dirt is used. According to the present invention, an object to be cleaned is provided. The material of the object to be cleaned is not particularly limited, and examples thereof include metals, semimetals, ceramics, and plastic materials. For example, metals and semi-metals include iron, aluminum, silicon, copper, stainless steel, etc., ceramics include silicon nitride, silicon carbide, aluminum oxide, glass, porcelain, etc., and plastics include polyamide, polyimide, epoxy, polyolefin, and polyester. , An acrylic resin and the like, and a composite material thereof may be used. Specific examples include electronic parts such as printed circuit boards and mounting parts, electric parts, semiconductor parts, liquid crystal parts, metal parts, surface treatment parts, precision equipment parts, optical parts, glass parts, ceramic parts, plastic parts and the like.

Note that, in this specification, washing refers to minimizing or removing the concentration of dirt attached to an object to be washed. Rinsing refers to minimizing or removing the concentration of the cleaning agent attached to the object to be cleaned. Further, drying refers to evaporating or removing a cleaning agent or a rinsing agent from an object to be cleaned. Examples of the drying method include natural drying, vacuum drying, hot air drying, steam drying, and a method of replacing the solvent with a solvent having a higher vapor pressure.

 The cleaning agent used in the first cleaning method will be described.

The polar detergent used in the first cleaning method refers to a detergent comprising organic molecules. Factors related to organicity include solubility parameters (hereinafter, referred to as δ), dielectric constant, dipole moment, molecular polarizability, dissociation constant, molecular refractive index, and the like. In the present invention, if the δ value is 9 or more or the dielectric constant is 4 or more, it can be used as a polar detergent. Also,
Preferably, the dipole moment is in the range 1-5D. The range of 1 to 1.5D is a boundary area.

The solubility parameter δ according to the present invention is defined by the following equation (1).

δ = (ΔE / V) ^1/2 (1) where ΔE is the molecular cohesion energy (cal / mol),
V indicates a molecular volume (ml / mol). That is, δ corresponds to the square root of the cohesive energy density.

When the volume does not change due to mixing, the heat of dissolution ΔHm when mixing and dissolving the components 1 and 2 is JHHildebrand
Is represented by the following equation (2).

ΔHm = Vm (δ ₁ −δ ₂ ) ² · φ ₁ · φ ₂ (2) where Vm is the total volume (ml) of the mixture, φ is the volume fraction, and subscripts 1 and 2 are the component 1 Component 2 is each represented.
Equation (2), as the heat of dissolution ΔHm decreases the difference between the components 1 and 2 [delta] ₁ and [delta] ₂ is small, so that excellent compatibility. For example, in the cleaning agent and the cleaning method of the present invention, when the difference in δ between the soil component and the detergent component is 3 or less, the soil component can be sufficiently dissolved and removed.

The solubility parameter δ can be determined by using any one of the latent heat of vaporization method and the molecular attraction constant method. There is no particular limitation on the method of measuring δ, as long as the δ value obtained by any method satisfies the conditions of the present invention. Generally, for substances whose boiling point can be measured, use the value determined by the latent heat of vaporization method.For substances whose boiling point cannot be measured or are difficult to measure, and for substances whose chemical structural formulas are known, use the molecular attraction constant method. Use values.

In the latent heat of evaporation method, ΔH is obtained from the following equation (3), ΔE is obtained from (4) based on this value, and δ is obtained from equation (5) derived from equation (1). This method can calculate δ most directly and accurately.

ΔH ₂₅ = 23.7Tb + 0.020Tb ² −2950 (3) ΔE = ΔH-RT (4) δ = (ΔE / V) ^1/2 = ｛(d / M) ΔE｝ ^1/2 ( 5) where Tb is the boiling point (K) and R is the gas constant (1986cal /
mol), T is absolute temperature (K), d is density (g / ml)
And M represents the molecular weight (g / mol).

For example, in the case of liquid paraffin, which is an example of the base oil of machine tool oil, if the main component is C ₁₀ H ₂₂ , M = 142.2
9. Since Tb = 200 ° C. (= 478 K) and d = 0.896 (g / ml), ΔH ₂₅ = 23.7 × 473 + 0.020 × 473 ² −2950 = 12192.5 ΔE = 121919−1.986 × 298 = 11600.7 δ = ｛ (0.896 / 142.29) x 11600.7 / ^1/2 = 8.55.

In the case of the solubility parameter (δ _C ) of a compound containing a hydrogen bond, the following correction value is added to the thus obtained δ value,
That is, alcohols; δ _C = δ + 1.4, esters;
δ _C = δ + 0.6, obtained by adding ketones; δ _C = δ + 0.5. When the boiling point is 373K or more, no correction is required.

The molecular attraction constant method is a method of obtaining δ from the characteristic value of each functional group (atom or atomic group) constituting a molecule of a compound, that is, the total of the molecular attraction (G) and the molecular volume,
This is useful for obtaining a δ value of a resin or the like which is unlikely to evaporate unlike solvents. Δ according to the molecular attraction constant method is obtained by the equation (6).

δ = ΣG / V = d · ΣG / M (6) where G corresponds to the product of molecular cohesion energy and molecular volume (molecular volume cohesion energy), and the G value is published by Small et al. . For example, in the case of sulfur of a sulfurized oil and fat used as an example of an extreme pressure agent for machine tool oil, M = 32.0
7, d = 2.07 (g / ml), G value by Small is 225
[(Cal-ml) ^1/2 / mol], so that δ = 2.07 × 225 / 32.07 = 14.5.

Furthermore, [delta] _m of the mixture, generally as a weighted average value for the molar fraction of [delta] of each component is calculated by equation (7).

δ _m = ΣX _i δ _i (7) where the subscript i represents the i component. For example, in the case of a sulfurized fat containing 0.43 mol of liquid paraffin as a base oil and 1 mol of sulfur, δ _m = {(1 / (1 + 0.43)} × 14.5 + {0.43 / (1 + 0.43)} × 8.58 = 12.7.

A preferred polar detergent in the present invention has a δ value of 9 to 14.
Or a dielectric constant of 4 to 45. Here, the dielectric constant is a value at 25 ° C. Particularly, the polar detergent used for removing the activator component of the flux and extreme pressure additives such as processing oil and cutting oil has a δ value in the range of 9 to 14 or a dielectric constant of 4 or more.
It is sufficient if it is in the range of ~ 45, more preferably the δ value is 10 ~ 13
Or the dielectric constant ranges from 10 to 30. If the polar cleaning agent has a δ value of 9 or more or a dielectric constant of 4 or more, it is possible to simultaneously remove ionic substances from flux, processing oil, and cutting oil and remove nonionic oily substances. When the δ value is 14 or less or the dielectric constant is 45 or less, the δ value in the mixed cleaning agent used as the rinsing agent or the vapor cleaning agent is 9 or less.
Since the compatibility with the detergent component having a dielectric constant of less than 4 and a dielectric constant of less than 4 can be kept good, the effect of removing the polar detergent in the rinsing step or the steam drying step can be sufficiently imparted.

Examples of polar detergents having a δ value of 9 to 14 or a dielectric constant of 4 to 45 include alcohols, glycols, phenols, ketones, fatty acids and acid anhydrides, esters, and amines. Amides, quaternary ammonium salts, nitriles, morpholines, sulfoxides,
Examples include those containing at least one component selected from sultones, phosphoric acids, and derivatives thereof, N-methyl-2-pyrrolidone, and the like.

Specifically, as alcohols, methanol, ethanol, propanol, normal hexanol, 3,5,5-
Trimethylhexanol, 2-ethylhexanol, normal octanol, normal butanol, cyclohexanol, benzyl alcohol, propylene glycol monoethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether and derivatives thereof as glycols, and orthocresol as phenols, Meta-cresol, para-cresol and its derivatives as heketones acetophenone, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone and its derivatives,
Acetic acid as fatty acids and acid anhydrides, acetic anhydride and derivatives thereof, methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, methyl lactate, diethyl oxalate and derivatives thereof as esters, ethylamine, N, N as amines −
Dimethylnitroamine and its derivatives as amides
N, N-dimethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N-ethylacetamide and derivatives thereof, tetraethylammonium and derivatives thereof as quaternary ammonium salts, isobutylnitrile and nitriles as nitrites Pionitrile, acetonitrile and its derivatives, ethylmorpholine, N-acetylmorpholine and N-formylmorpholine and its derivatives as morpholines, dimethylsulfoxide and its derivatives as sulfoxides, and propanesultone and its derivatives as sultones, phosphoric acid Triethyl phosphates,
Examples thereof include tributyl phosphate and derivatives thereof.
These can be used alone or in combination. However, it is preferable to use polar cleaning agents that react with each other, such as acetic anhydride and amines, alone.

The solubility parameter used in the first cleaning method is 9
Examples of the cleaning agent having a lower dielectric constant and a dielectric constant of less than 4 include at least one selected from low molecular siloxanes, hydrocarbons, fluorocarbons, ethers, and acetals.

The low-molecular-weight siloxanes have the general formula: (Wherein R is the same or different, substituted or unsubstituted 1
A linear organic polysiloxane and a derivative thereof represented by the following general formula: (Wherein R is the same or different, substituted or unsubstituted 1
At least one selected from a cyclic polyorganosiloxane represented by the following formula: and a derivative thereof.

The R group in the above formulas (i) and (ii) is a substituted or unsubstituted monovalent organic group, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, or a phenyl group. And a monovalent substituted hydrocarbon group such as a trifluoromethyl group, a 3,3,3-trifluoropropyl group, etc., and a terminal group in the above formula (i). R groups further include an amino group, an amide group,
An acrylate group, a mercaptan group and the like are exemplified, and a methyl group is most preferred from the viewpoint of stability of the system, maintenance of volatility and the like. Specific examples of the low-molecular siloxanes include, for example, hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane.

Examples of the hydrocarbons include normal and aliphatic hydrocarbon compounds such as isoparaffin and olefin, and alicyclic hydrocarbon compounds such as cycloparaffin and cycloolefin.

Further, examples of the fluorocarbons include perfluorocarbons, hydrofluorocarbons, hydrochlorofluorocarbons, fluoroiodide carbons, hydrofluoroethers, and fluoroalcohols, and particularly those having flame retardancy or nonflammability are preferred. It is. The hydrochlorofluorocarbons preferably have an extremely low ozone depletion potential.

Examples of the perfluorocarbons, e.g. general formula: (wherein, n represents an integer of 4~12) C _n F _{2n + 2} represented or perfluoroalkanes are in, Or perfluoropolyether represented by (C ₄ F ₉ )
_{3 N, (C 5 F 11} ) 3 N, (C 2 F 5) 3 N, (C 2 F 5) (C 3 F 8) NF,
(CF ₃ ) ₂ NC ₂ F ₅ , (CF ₃ ) ₂ NC ₂ F ₄ Br, (CF ₃ ) ₂ NCF = CF ₂ ,
(CF ₃ ) ₂ NCF ₂ CF ₂ H, (CF ₃ ) ₂ NCF ₂ CF ₃ , C ₅ F ₁₀ NC ₂ F ₅ , OC ₄
Examples thereof include perfluoroamine which generates a trifluoro radical such as F ₈ NCF ₂ Br, and perfluoromorpholine. Further, a perfluoroether compound represented by the general formula: (C _x F _{2x + 1} ) ₂ O (x represents an integer of 1 to 7) can be used, and more specifically, (CF ₃ CF ₂ ) ₂ O is mentioned. be able to.

The perfluorocarbons, general _{formula: C p H q F 2p +} 2-q, C p H q F 2p-q, C p H q F 2p-2-q (p is 1 to 10, q is 1 Can be used, and more specifically, C ₅ H ₁ F
_{11, C 5 H 2 F 10} , C 5 H 3 F 9, C 4 H 3 F 7, C 6 H 2 F 12 , and the like. As fluoroiodide carbons,
For example, CF ₃ CF ₂ CF ₂ I, CH ₂ FI, CF ₃ CF ₂ CF ₂ CF ₂ I, CF ₂ I ₂ , CF ₃
(CF ₂ ) ₄ I and the like. As the hydrofluoroethers of the general _{formula: (C t H 2t + 1} -u F u -) - O - (- C v H 2v + 1-w F w) (t, u, v and w are A compound represented by any integer, preferably u = 2t + 1, w = 0) can be used, and more specifically, C ₃ F ₇
OCH ₃ , C ₄ F ₉ OCH ₃ , C ₅ F ₁₁ OCH ₃ , C ₃ F ₇ OC ₂ H ₅ , C ₄ F ₉ OC ₂ H ₅ , C
₅ F ₁₁ OC ₂ H _{5 and the} like. When the hydrofluoroether is used as a mixed detergent mixed with a polar detergent, it has a feature that the degree of freedom of solubility with the polar detergent is high and the mixed detergent is easily adjusted.

Further, ethers as detergents having a solubility parameter of less than 9 and a dielectric constant of less than 4 include di-n-
Examples of propyl ether and its derivatives, and examples of acetals include methylal and its derivatives. Among these, the solubility parameter is less than 9 and the dielectric constant is 4
As a detergent less than, preferably low molecular siloxanes,
Hydrocarbons and fluorocarbons are used.

The above-mentioned low molecular siloxanes, hydrocarbons, fluorocarbons, ethers, acetals and the like can be used alone or in combination as a detergent having a solubility parameter of less than 9 and a dielectric constant of less than 4. Table 2 shows examples of polar detergents having a solubility parameter of 9 or more or a dielectric constant of 4 or more, and Table 3 shows examples of detergents having a solubility parameter of less than 9 and a dielectric constant of less than 4, their δ values and dielectric constants. Shown together with the modulus and dipole moment. The dielectric constant is a value at 25 ° C. except for the substances shown in the lower columns of Tables 2 and 3.

In the first cleaning method, the step of cleaning the object to be cleaned is performed using the above-described polar cleaning agent. Therefore, it is possible to satisfactorily remove various stains including ionic substances, polar substances, and non-ionic oily substances.

In the first cleaning method, after the above-described cleaning step, the above-mentioned polar cleaning agent and a cleaning agent having a solubility parameter of less than 9 and a dielectric constant of less than 4, that is, a nonpolar or low-polarity cleaning agent (hereinafter, referred to as a cleaning agent) Rinsing process (rinse process) with a cleaning agent mixed with non-polar cleaning agent)
And at least one step selected from a drying step (drying step). Note that the rinsing step and the drying step may be performed continuously after the cleaning step using a polar detergent, or one of the rinsing step and the drying step may be omitted.

Further, the mixed detergent used in the rinsing step and / or the drying step is characterized by being nonflammable or nonflammable. Here, the nonflammability and the flame retardancy are defined as follows based on the evaluation result of the flammability.

That is, the flammability of each mixed detergent is determined by JIS-K-2265
The flash point is measured with a tag closed flash point measuring instrument and a Cleveland open flash point measuring instrument in accordance with the above. As a result, in both the closed tag type and the Cleveland open type, it is difficult to determine the non-flammable one in which the flash point cannot be measured, and it is difficult to determine the one in which the flash point cannot be measured in either the closed tag type or the Cleveland open type. Defined as flammable.

By using the above-mentioned mixed cleaning agent of the polar cleaning agent and the non-polar cleaning agent as a rinsing agent or a steam drying agent, the liquid replacement and the drying effect of the rinsing agent or the steam cleaning agent of the polar cleaning agent brought in from the cleaning process. In addition, the solubility of the dirt component in the polar cleaning agent can be imparted at the same time, so that it is possible to perform excellent precision cleaning that satisfies both the drying characteristics and the dirt-removing property.

Here, the polar cleaning agent used in the rinsing step and the drying step does not necessarily have to have the same components as the polar cleaning agent used in the cleaning step. It is preferable to use a polar cleaning agent having a relatively higher vapor pressure than the cleaning agent, and it is more preferable that the boiling point be lower than the boiling point of the non-polar cleaning agent.

In the mixture of the non-polar detergent and the polar detergent, the polar detergent is preferably compatible with the non-polar detergent. For example, fluorocarbons, which are non-polar detergents, are not compatible with polar detergents, while low molecular weight polyorganosiloxanes, which are also non-polar detergents, are compatible with most polar detergents. On the other hand, fluorocarbons and low-molecular-weight polyorganosiloxanes are compatible at an arbitrary addition ratio. Therefore, by adding an appropriate amount of a polar detergent to the two-component nonpolar detergent, uniform mixing without phase separation can be achieved. A cleaning agent is obtained.

Further, the mixed detergent is preferably an azeotropic composition or a pseudo-azeotropic composition. The development of azeotropic properties is found by appropriate choice of the type and mixing ratio of the polar detergent. Here, the azeotropic composition is a mixture in which the liquid phase composition and the gas phase composition match and can be distilled without changing the composition,
In addition, although the azeotropic composition system is not formed, when the boiling curve and the condensation curve are close to each other in the boiling point diagram represented by the temperature-composition, when the volatility of each component is close, the boiling point of each component is A phenomenon in which the composition of the liquid phase and the composition of the gas phase are close to each other, such as when they are close to each other, is called pseudo-azeotropic, and a mixture that forms such pseudo-azeotropic is called a pseudo-azeotropic composition. .

In the mixed cleaning agent used in the first cleaning method, the amount of the polar cleaning agent varies depending on whether it is used in the rinsing step or the drying step, but may be any necessary amount that does not impair the drying property. The content is preferably in the range of 0.1 to 30% by weight based on the total amount of the detergent. The amount of polar detergent
When the content is in the range of 0.1 to 30% by weight, the stain component in the polar cleaning agent brought in from the cleaning step can be more smoothly removed without impairing the drying property. A particularly preferred range is 1 to
It is in the range of 20% by weight.

The mixed detergent used in the rinsing step and the drying step, particularly the mixed detergent used in the drying step, preferably has nonflammability or flame retardancy. Non-combustibility and flame retardancy can be imparted by using a non-combustible or flame-retardant fluorocarbon as a main component of the mixed detergent. Furthermore, even when a low molecular weight polyorganosiloxane having flammability is used, it is difficult to use the mixed cleaning agent used in the rinsing step and the drying step by using it as a mixed system with a flame-retardant or non-flammable fluorocarbon. Flammable or non-flammable properties can be imparted.

The drying step in the first cleaning method is not particularly limited, and includes a method using steam drying, hot air drying, vacuum drying, or natural drying, and can be used as needed or combined depending on the shape of parts. . In particular, when precision cleaning properties are required, it is preferable to perform steam drying having a relatively excellent finish, and it is preferable to use the above-described mixed cleaning agent for the steam drying. As the non-polar cleaning agent in the mixed cleaning agent used as the steam drying agent, one containing a fluorocarbon as a main component is preferable for precision cleaning. Furthermore, when a fluorocarbon and a low molecular weight polyorganosiloxane are used in combination, excellent compatibility with a polar detergent is obtained, so that excellent dry finish can be obtained.

As described above, when the fluorocarbons are used in combination with the low molecular weight polyorganosiloxanes, the mixing ratio of the fluorocarbons is 10 to 10,000 parts by weight with respect to 100 parts by weight of the low molecular weight polyorganosiloxanes. It is preferable to be within the range. By blending the fluorocarbons in an amount of 10 parts by weight or more based on 100 parts by weight of the low-molecular siloxane compound, flame retardancy or nonflammability can be imparted. By blending in the range of parts by weight, phase separation between the fluorocarbons and the polar detergent can be prevented.

In the above-described first cleaning method, first, an object to be cleaned is cleaned with a polar cleaning agent, and then, a rinsing step with a mixed cleaning agent containing a non-polar or lower-polarity cleaning agent (non-polar cleaning agent) as a main component is performed. Since the drying step is performed, it is possible to achieve both cleanability (e.g., dirt removal property) and dryness in general cleaning including precision cleaning of electronic components and the like.

In using the first cleaning method, the number of cleaning tanks and rinsing tanks and the like can be arbitrarily set according to the amount and type of dirt adhering to the object to be cleaned, and are not particularly limited. In addition, the rinsing unit and the drying unit can be used as various types of cleaning devices, for example, they can be arranged as needed.

Further, in the cleaning apparatus to which the first cleaning method is applied,
It is preferable that the cleaning agent used in the washing means, the rinsing means and the drying means is recycled by distillation and regeneration. In particular, when the washing tank and the rinsing tank are composed of a plurality of tanks, they can be connected in a cascade (overflow) system. Therefore, by regenerating the contaminated liquid by the distillation apparatus, and returning to the final washing tank and the rinsing tank again, The liquid life can be extended. This makes it possible to significantly reduce running costs. When the detergent component is a mixture of a plurality of components, the boiling points of the components are preferably as close as possible, and the boiling point of the detergent component used in the cleaning step is preferably 373 K or less from the stability of the composition ratio. preferable.

The second method of cleaning of the present invention, the solubility parameter of 9 or more, or a step of dielectric constant washing the washing object four or more polar detergents, formula _{C t F u OC v H 2v} + 1 ( wherein , T, u, v represent arbitrary integers) with a cleaning agent containing hydrofluoroether as an active ingredient, and at least one step selected from a rinsing step and a drying step of the object to be cleaned. It is characterized by having.

In the rinsing step and / or the drying step, as shown in the first cleaning method, it is preferable to use a mixed detergent, but instead of the mixed detergent, a detergent containing hydrofluoroether as an active ingredient may be used. . Hydrofluoroether is preferable because it has a high degree of freedom in combination with a polar cleaning agent used in the preceding washing step, and provides good washing properties. Specific examples of hydrofluoroethers include C ₃ F ₇ OCH ₃ , C ₄ F ₉ OCH ₃ , C ₅ F ₁₁ OCH ₃ , C ₃ F ₇ OC _{2
H 5, C 4 F 9 OC} 2 H 5, C 5 F 11 OC 2 H 5 and the like are exemplified, among others C ₅ F ₁₁
OCH ₃ and C ₅ F ₁₁ OC ₂ H ₅ are preferably used. In this case, it is preferable to use a mixture of hydrofluoroethers alone or a mixture of hydrofluoroethers and hydrocarbons or low molecular weight polyorganosiloxanes,
10-100% by weight of hydrofluoroethers, especially 50
It is preferable to use it so that it may be 100100% by weight. Note that the polar cleaning agent used in the first cleaning method can be used.

The third cleaning method of the present invention uses a cleaning agent containing a low-molecular-weight siloxane compound and at least one selected from fluorocarbons and a polar cleaning agent having a solubility parameter of 9 or more or a dielectric constant of 4 or more. And performing at least one step selected from a washing step, a rinsing step, and a drying step.

In addition, the fourth cleaning method of the present invention includes a cleaning step using a cleaning agent containing a low-molecular siloxane compound, a fluorocarbon, and a polar cleaning agent having a solubility parameter of 9 or more or a dielectric constant of 4 or more, A rinsing step and a drying step are performed.

Soil to be treated in the third and fourth cleaning methods, object to be cleaned, definition of cleaning easy rinsing and drying, definition of solubility parameter and dielectric constant, suitable polar cleaning agent, type of low molecular siloxane compound and fluorocarbon, etc. Is the first
Are the same as those described in the washing method.

The components in the cleaning agents used in the third and fourth cleaning methods, that is, the fluorocarbons, the low molecular weight siloxane compound, and the polar cleaning agent having a solubility parameter of 9 or more or a dielectric constant of 4 or more are as shown below, respectively. Role.

That is, fluorocarbons are generally nonflammable liquids and have low latent heat of vaporization, so they are particularly suitable for use as a steam cleaner during drying, but do not show solubility of dirt components such as processing oils and fluxes. On the other hand, a polar detergent having a solubility parameter of 9 or more or a dielectric constant of 4 or more is incompatible with fluorocarbons, that is, excellent in dissolving dirt components, but is apt to cause stains and liquid residues when dried. On the other hand, the low-molecular-weight siloxane compound has compatibility with both the fluorocarbons and the polar detergent, and also has excellent drying properties. Therefore, by mixing a low-molecular siloxane compound with a fluorocarbon and a polar detergent, a detergent that does not phase-separate and makes use of the advantages of each, that is, a detergent that satisfies both the soil removal property and the drying property. It is possible to obtain. As described above, since the cleaning agent of the present invention achieves both the property of removing dirt and the property of drying, it can be used in any of the cleaning step, the rinsing step, and the drying step.

In the cleaning agents of the third and fourth cleaning methods, the amount of the polar cleaning agent having a solubility parameter of 9 or more or a dielectric constant of 4 or more differs depending on whether it is used in the washing step, the rinsing step or the drying step. However, the content is preferably in the range of 0.1 to 30% by weight based on the total amount of the detergent. In particular, when used in a rinsing step or a drying step, the amount may be a necessary amount that does not impair the drying property, and is 0.1 to 30% by weight.
Within this range, the dirt components brought in from the washing step can be more smoothly removed without impairing the drying property. A particularly preferred range is from 1 to 20% by weight.

The mixing ratio of the fluorocarbons varies depending on whether it is used in the washing step, the rinsing step or the drying step, but it is preferably in the range of 10 to 10,000 parts by weight with respect to 100 parts by weight of the low-molecular siloxane compound. . By blending the fluorocarbons at 10,000 parts by weight or less, preferably at 5,000 parts by weight or less with respect to 100 parts by weight of the low-molecular siloxane compound, phase separation between the fluorocarbons and the polar detergent can be prevented. Further, 10 to 10 parts by weight of low-molecular siloxane compound fluorocarbons
Sufficient drying property can be obtained by blending in at least part by weight. Furthermore, by using a flame-retardant or non-flammable fluorocarbon, despite using a low molecular weight siloxane compound having flammability,
For example, a flame retardant or non-flammable property can be imparted to a cleaning agent used in a rinsing step or a drying step. In particular, in order to impart nonflammability, it is more preferable to mix the fluorocarbons in an amount of 400 parts by weight or more based on 100 parts by weight of the low molecular weight siloxane compound.

Further, the cleaning agent of the present invention is preferably an azeotropic composition or a pseudo-azeotropic composition. The development of azeotropic properties is found by appropriate choice of the type and mixing ratio of the polar detergent.

In the third cleaning method, at least one step selected from a cleaning step, a rinsing step, and a drying step is performed using the above-described cleaning agent. The rinsing step and the drying step after the washing step may be performed continuously, and the rinsing step and the drying step may be omitted. In particular, by performing a series of steps of rinsing and drying using the cleaning agent of the present invention as shown in the fourth cleaning method, even better cleaning can be performed. Also in this case,
Each component ratio in the detergent may be different.

The drying step in the third and fourth cleaning methods is not particularly limited, and includes a method using hot air drying, natural drying, vacuum drying, or steam drying. It is also possible to combine them. In particular, when precision cleaning is required, it is preferable to perform steam drying with relatively excellent finishability, and the cleaning agent of the present invention is also suitable for such steam drying.

In the third and fourth cleaning methods, at least one step or all steps selected from a cleaning step, a rinsing step, and a drying step are performed using a cleaning agent that satisfies both drying properties and stain removal properties. In general, such as precision cleaning of electronic parts and the like, both cleanability and dryness can be achieved.

In using the third and fourth cleaning methods, the same cleaning apparatus that can be used in the first cleaning method can be used.

In the fifth cleaning method of the present invention, a closed detergent containing a mixture of a low-molecular siloxane compound and a fluorocarbon as a main component and having nonflammability or flame retardancy is filled in a closed container, and mixed from the closed container. The cleaning is performed by spraying a cleaning agent on the object to be cleaned.

The low molecular weight siloxane compound has high solubility in fluorocarbons, and some dissolve alternately, and the low molecular weight siloxane compound itself is flammable, but chemically inert fluorocarbons, that is, nonflammable The present inventors have found that by mixing a non-flammable or flame-retardant fluorocarbon, the mixture can be rendered non-flammable or flame-retardant.

However, on the other hand, a mixture of a low-molecular siloxane compound and a fluorocarbon does not necessarily show azeotropic or pseudo-azeotropic properties depending on the combination, and when used in an open state, for example, when one component is consumed, the other component is consumed. It is more than exhaustion, and the composition ratio may change, resulting in impaired incombustibility or flame retardancy, and furthermore, detergency and the like may be reduced. In view of such a point, it has been found that a change in the composition ratio can be prevented by using a mixture of a low-molecular siloxane compound and a fluorocarbon, for example, by filling the mixture in a spray. The fifth cleaning method is based on the above findings.

Specific examples of the low-molecular siloxane compound and the fluorocarbons are the same as those described in the first cleaning method. Some fluorocarbons have no problem with respect to both environmental problems and health problems, do not burn themselves, and are effective in blocking oxygen in the atmosphere. Thus, in the cleaning method of the present invention, a low-molecular-weight siloxane compound is dissolved, and a non-flammable or flame-retardant fluorocarbon is selected, and a mixed cleaning agent mainly containing a mixture of this and a low-molecular-weight siloxane compound is used. Is used. Such a mixed cleaning agent can be used as a nonflammable or flame-retardant cleaning agent.

The mixing ratio of the fluorocarbons in the mixed detergent is as follows:
Depending on the intended use, low molecular weight siloxane compounds
It is preferable that the amount be in the range of 10 to 10,000 parts by weight based on 100 parts by weight. By blending the fluorocarbons in an amount of 100 parts by weight or more with respect to 100 parts by weight of the low-molecular-weight siloxane compound, it is possible to impart flame retardancy or nonflammability to the mixed detergent. The mixing ratio of the fluorocarbons is more preferably in the range of 20 to 5,000 parts by weight based on 100 parts by weight of the low molecular weight siloxane compound.

Further, the mixed detergent used in the present invention may be one containing a mixture of the above-described low-molecular siloxane compound and fluorocarbon as a main component, and is not limited to the above-described mixture alone, and may further include a polar solvent and a hydrocarbon. A mixture of other solvents such as a system solvent, an ether-based solvent, and an acetal-based solvent, or a mixture of various additives such as a surfactant and a hydrophilic solvent may be used.

In the fifth cleaning method, the mixed detergent as described above is filled in a closed container such as a spray can and stored and used. Specifically, the mixed detergent is applied from the closed container to the object to be cleaned. This is done by spraying.

As described above, by storing and using the mixed detergent in a closed container such as a spray can, it is possible to prevent a change in the composition ratio of the mixture of the low-molecular siloxane compound and the fluorocarbon in the mixed detergent. Because you can
It is possible to maintain the non-flammable or non-flammable properties of the mixed detergent, the cleaning performance, and the like for a long period of time.

The sixth cleaning method of the present invention drains and dries an object using a liquid having compatibility with water, having no azeotropic property with water, and having a heat of evaporation of 100 cal / g or less. It is characterized by the following.

We found that the heat of evaporation of trifluoroethanol was 84
Cal / g is extremely small, and trifluoroethanol has compatibility with water but does not show azeotropic properties with water, and it has been found that such trifluoroethanol exerts a great effect on draining and drying, It has been found that not only trifluoroethanol but also liquids having similar properties exert a great effect on draining and drying. The sixth cleaning method is based on such knowledge.

The liquid used as the draining liquid in the present invention has compatibility with water and does not exhibit azeotropic property with water. By having such properties, it is possible to easily separate and regenerate from water by, for example, a distillation operation after obtaining a good water displacement effect. Accordingly, it is possible to prevent the occurrence of dry spots or the like due to water, and it is possible to extend the life of the liquid and significantly reduce the running cost.

Further, the liquid used as the draining dry liquid in the sixth cleaning method has an evaporation heat of 100 cal / g or less, and by having such an evaporation heat, it can absorb moisture from the air or the like when volatilizing after water replacement. Therefore, a very good dry surface, that is, draining dry quality can be obtained without generating dry spots or the like.

As a typical example of a liquid satisfying the above properties,
Trifluoroethanol. Trifluoroethanol (CF ₃ CH ₂ OH; boiling point = 347K, flash point = 303K)
As described above, it is completely compatible with water, does not azeotrope with water, and has a very low heat of evaporation of 84 cal / g, and also has a low surface tension and wets uniformly on the surface of the object to be drained and dried. Therefore, it has characteristics such as obtaining a good drying speed and drying quality. In addition, by using the drained dry solution of trifluoroethanol alone, there is no need to perform troublesome liquid management and the like. Trifluoroethanol is particularly effective for draining and drying lenses and glasses, which are particularly difficult to clean.

In the sixth cleaning method, it is preferable to use a drained dry solution of trifluoroethanol alone as described above. However, in order to impart noncombustibility or flame retardancy to trifluoroethanol, it is preferable to use fluorocarbons in a dissolvable range. Is also effective. Here, fluorocarbons that can be dissolved in trifluoroethanol include: Examples thereof include perfluorocarbons, hydrofluorocarbons, and hydrofluoroethers used in the first cleaning method.

The draining drying referred to in the sixth cleaning method is, for example, immersing the object in the draining liquid as described above, spraying the draining liquid on the object, or exposing the object to vapor of the draining liquid. Means to replace the water present on the surface of the object with the draining dry liquid (water replacement) and then at least dry naturally. In addition to this, warm air drying, vacuum drying, steam drying, etc. It is also possible to use them together. In this case, as the steam drying liquid, a draining drying liquid itself such as trifluoroethanol or a mixture of trifluoroethanol and a perfluorocarbon, a hydrofluorocarbon, a hydrofluoroether, or the like, which can be dissolved, can be used. Alternatively, if the draining liquid is a mixture of trifluoroethanol alone or a perfluorocarbon that can be dissolved with it, a hydrofluorocarbon, a mixture of hydrofluoroethers and the like, a perfluorocarbon that can be dissolved with trifluoroethanol as described above, Hydrofluorocarbons and the like can be used. Furthermore, a low molecular siloxane compound can be used as a vapor drying liquid.

Here, suitable low molecular weight siloxanes that can be used for steam drying have the general formula: Or And a polyorganosiloxane represented by Here, R represents the same or different substituted or unsubstituted monovalent organic groups. More specifically, hexamethyldisiloxane (MM), octamethyltrisiloxane (MD
M), decamethyltetrasiloxane (MD2M), dodecamethylpentanesiloxane (MD3M), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6) and the like. it can.

According to the draining drying method which is the sixth cleaning method, not only the water displacement operation (immersion, rocking, stirring, ultrasonic wave, spray) but also the drying operation (hot air drying, spin drying, steam drying,
(Dry pulling, vacuum drying, etc.), it is possible to effectively use a draining dry liquid made of trifluoroethanol or the like.

The cleaning agent of the present invention is characterized by containing a low molecular siloxane compound, a fluorocarbon and at least two selected from polar cleaning agents having a solubility parameter of 9 or more or a dielectric constant of 4 or more. Here, as the low-molecular siloxane compound, fluorocarbons, and polar detergent, those described in the first to fifth cleaning methods described above can be used.

Among such cleaning agents of the present invention, the cleaning agent containing an azeotropic composition and a pseudo-azeotropic composition exhibiting particularly high detergency and excellent drying characteristics as an active ingredient will be described below.

The cleaning agent containing the first azeotropic composition and the pseudo-azeotropic composition as active ingredients is an azeotropic composition comprising hexamethyldisiloxane, tert-butanol, and a perfluorocarbon represented by perfluorohexane (C ₆ F ₁₄ ). It is characterized by containing a composition or a pseudo-azeotropic composition as an active ingredient.

The cleaning agent containing the second azeotropic composition and the pseudo-azeotropic composition as active ingredients is an azeotropic composition composed of hexamethyldisiloxane, isopropyl acetate, and perfluorocarbon represented by perfluorohexane (C ₆ F ₁₄ ). Alternatively, it is characterized by containing a pseudo-azeotropic composition as an active ingredient.

The composition ratio of each component in the azeotropic composition and the pseudo-azeotropic composition (hereinafter, abbreviated as the first azeotropic composition and the pseudo-azeotropic composition), which are the active ingredients of the first detergent, is hexamethyl disiloxane 2-20 wt%, perfluorocarbon expressed by tert- butanol 2-20% by weight, and C ₆ F ₁₄ 60 to 96
The azeotropic composition or the pseudo-azeotropic composition having an azeotropic temperature of 321 to 326 K (760 mmHg) in such a constitutional ratio is obtained. The specific composition ratio of the azeotropic composition can vary depending on conditions.
In addition, the pseudo-azeotropic composition is a composition containing one or more components in excess of the azeotropic composition as long as the characteristics of the azeotropic composition are not substantially impaired. Thus, it exhibits substantially the same characteristics as the above-mentioned azeotropic composition.

The azeotropic property is exhibited when the boiling point of the mixture is lower or higher than the specific boiling point of each component. Therefore, in order to obtain an azeotropic composition, it is often impossible to obtain the azeotropic composition simply by mixing the components. If the boiling point of the mixture is lower than the intrinsic boiling point of each component, the mixture is mixed at an arbitrary ratio. The obtained liquid can be distilled, and the fraction can be repeatedly distilled, or can be obtained by rectification with a number of stages. The azeotropic composition (mixture) thus obtained is characterized in that no substantial change in the composition of the fraction is observed even when distillation is repeated under a constant pressure. The pseudo-azeotropic composition can be obtained in the same manner.

In the first azeotropic composition and the pseudo-azeotropic composition, tert.
-Butanol has high polarity and shows high dissolving power for fats and oils, but good permeation cannot be obtained by itself due to its large surface tension of 20.7 dyn / cm (293K). In addition, depending on the type of plastic to be cleaned and the conditions of use, solvent attack (phenomenon of cracking or cracking of the plastic by contact with the solvent) may occur.

Hexamethyldisiloxane has a surface tension of 15.9 dyn / cm
(293K) and excellent permeability, but the Kauributanol value (KB value) is 15 and the detergency is weak, but there is almost no risk of deteriorating the object to be cleaned such as plastic. Furthermore, hexamethyldisiloxane, optionally compatible with any of perfluorocarbon represented by tert- butanol and C ₆ F _14. On the other hand, tert-butanol and
Although C ₆ F ₁₄ hardly dissolves in each other, the addition of hexamethyldisiloxane makes the three components compatible with each other to form a uniform composition. That is,
Hexamethyldisiloxane functions as a compatibilizer for the other two components. The effect of hexamethyldisiloxane as a compatibilizer greatly differs depending on the type of polar solvent, and tert-butanol of the present invention has a C ₆ F by adding hexamethyldisiloxane compared to lower alcohols such as methanol and ethanol. The solubility in perfluorocarbon represented by ₁₄ is significantly improved.

The perfluorocarbon represented by C ₆ F ₁₄ has no detergency and is not suitable for a detergent alone, but has a latent heat of vaporization of about 21 cal / g and tert-butanol (about 131 cal / g).
g) and hexamethyldisiloxane (about 50 cal / g). In addition, since perfluorocarbon is a nonflammable liquid, when mixed with flammable liquids tert-butanol and hexamethyldisiloxane, it raises the flash point compared to those alone or as a mixture, and becomes flame retardant. And, in some cases, non-flammable.

The first azeotropic composition and the pseudo-azeotropic composition are the above-mentioned hexamethyldisiloxane, tert-butanol, and a perfluorocarbon represented by C ₆ F ₁₄ as an azeotropic composition or a pseudo-azeotropic composition. Thus, the characteristics of each of these components are derived. That is, the azeotropic composition and the pseudo-azeotropic composition have high solubility in fats and oils and the like by tert-butanol, excellent permeability by hexamethyldisiloxane, and excellent by perfluorocarbon represented by C ₆ F _14. The composition has both the drying characteristics and the drying characteristics, and can be said to be a composition suitable for a cleaning agent in which washing and drying are performed in one liquid. That is, as a cleaning agent that performs from washing to drying in one liquid, while having degreasing and drying properties, there is no substantial change in liquid composition during use,
An important requirement is that it can be regenerated by distillation or the like. This cleaning agent is 321-32 at 760 mmHg.
Since it has an azeotropic property at a temperature of 66 K, there is no substantial change in liquid composition during use, and it can be regenerated by distillation or the like. Therefore, for example, a cleaning agent capable of performing one step from washing to drying can be obtained.

The composition ratio of each component in the azeotropic composition and the pseudo-azeotropic composition (hereinafter, abbreviated as the second azeotropic composition and the pseudo-azeotropic composition), which are the active ingredients of the second detergent, is as follows: Hexamethyldisiloxane 2-20% by weight, isopropyl acetate 2
It is preferably in the range of 2020% by weight and 60-96% by weight of a perfluorocarbon represented by C ₆ F ₁₄ . With such a constitutional ratio, an azeotropic composition or a pseudo-azeotropic composition having an azeotropic temperature of 323 to 328 K (760 mmHg) can be obtained. The specific composition ratio of the azeotropic composition can vary depending on conditions. The second azeotropic composition and the pseudo-azeotropic composition are also the first azeotropic composition.
Can be obtained in the same manner as the azeotropic composition and the pseudo-azeotropic composition.

In the second azeotropic composition and the pseudo-azeotropic composition, isopropyl acetate has a strong polarity and a high dissolving power for fats and oils, but has a large surface tension of 22.1 dyn / cm (295 K). Good penetration is not obtained by itself. Further, solvent attack may occur depending on the type of plastic to be cleaned and the usage conditions. C ₆ F
_The perfluorocarbon represented by ₁₄ is as described above, and has a latent heat of vaporization of about 21 cal / g and isopropyl acetate (about 77 cal
/ g) and hexamethyldisiloxane (about 50 cal / g), so that they have excellent drying characteristics. In addition, the perfluorocarbon represented by C ₆ F ₁₄ is mixed with flammable liquids such as isopropyl acetate and hexamethyldisiloxane to increase the flash point compared to those alone or as a mixture to make them flame-retardant. It can be made non-flammable in some cases.

Hexamethyldisiloxane has the characteristics described above and is arbitrarily compatible with both isopropyl acetate and a perfluorocarbon represented by C ₆ F ₁₄ . On the other hand, isopropyl acetate and C ₆ F ₁₄ hardly dissolve in each other, but by adding hexamethyldisiloxane, the three components can be compatibilized to obtain a uniform composition. That is, hexamethyldisiloxane functions as a compatibilizer for the other two components. The effect of hexamethyldisiloxane as a compatibilizer greatly differs depending on the type of polar solvent, and isopropyl acetate of the present invention is obtained by adding hexamethyldisiloxane as compared with lower alcohols such as methanol and ethanol.
The solubility in perfluorocarbon represented by C ₆ F ₁₄ is significantly improved.

The cleaning compositions of the present invention by a hexamethyldisiloxane azeotropic composition and a perfluorocarbon represented by isopropyl acetate and C ₆ F ₁₄ or near azeotropic compositions described above, each of these components The features are derived. That is, the cleaning composition containing the second azeotropic composition and the pseudo-azeotropic composition as active ingredients has high solubility in oils and fats by isopropyl acetate, excellent permeability by hexamethyldisiloxane, and excellent C ₆ F _{It has the} excellent drying characteristics of the perfluorocarbon represented by ₁₄ , and can be said to be a composition suitable for a cleaning agent in which washing and drying are performed in one liquid.

As described above, since the cleaning agent of the present invention achieves both the removal property of the stain and the drying property, it can be used as a cleaning agent that carries out from washing to drying with one liquid, and also includes a washing step and a rinsing step. It can be used alone in any of the steps and the drying step. Further, since the cleaning agent of the present invention does not contain a chlorine-based organic solvent as a basic component, it does not cause destruction of the ozone layer, and as described in detail in the description of the azeotropic composition and the pseudo-azeotropic composition, The composition change during use can be suppressed as much as possible, and the composition can be made flame-retardant or even non-flammable.

The third azeotropic composition and detergent to a near-azeotropic composition as an active ingredient, the co consisting help Le Oro carbon represented by hexamethyldisiloxane, tert- butanol and perfluoroheptane (C ₇ F ₁₆₎ It is characterized by containing a boiling composition or a pseudo-azeotropic composition as an active ingredient.

The cleaning agent containing the fourth azeotropic composition and the pseudo-azeotropic composition as an active ingredient is an azeotropic composition comprising hexamethyldisiloxane, isopropyl acetate, and a perfluorocarbon represented by perfluoroheptane (C ₇ F ₁₆ ). Alternatively, it is characterized by containing a pseudo-azeotropic composition as an active ingredient.

The constituent ratio of each component in the azeotropic composition and the pseudo-azeotropic composition (hereinafter, abbreviated as the third azeotropic composition and the pseudo-azeotropic composition) which are the active ingredients of the third detergent is hexamethyl disiloxane 5-25%, perfluorocarbon expressed by tert- butanol 5-25% by weight and C ₇ F ₁₆ 60 to 9
It is preferably in the range of 0% by weight, and an azeotropic composition or a pseudo-azeotropic composition having an azeotropic temperature of 337 to 344 K (760 mmHg) in such a constitutional ratio is obtained. The specific composition ratio of the azeotropic composition can vary depending on conditions. In addition, the pseudo-azeotropic composition is a composition containing one or more components in excess of the azeotropic composition as long as the characteristics of the azeotropic composition are not substantially impaired. Thus, it exhibits substantially the same characteristics as the above-mentioned azeotropic composition.

The third azeotropic composition and the pseudo-azeotropic composition can be obtained by a multi-stage rectification method or the like, similarly to the first and second azeotropic compositions and the pseudo-azeotropic composition.

In a third azeotropic composition and azeotrope-like compositions, hexamethyldisiloxane, tert- butanol optionally compatible at room temperature and, optionally 308K or more perfluorocarbon expressed by C ₇ F ₁₆ Compatible with. On the other hand, tert- butanol and C ₇ F ₁₆ hardly Tokeawa each other and, by the addition of hexamethyldisiloxane, the three components were compatibilized during heating can be a homogeneous composition. That is, hexamethyldisiloxane functions as a compatibilizer for the other two components. The effect of hexamethyldisiloxane as a compatibilizer greatly differs depending on the type of polar solvent, and the tert-butanol of the present invention has a higher C ₇ F by adding hexamethyldisiloxane than a lower alcohol such as methanol or ethanol. The solubility in perfluorocarbon represented by ₁₆ is significantly improved.

Perfluorocarbon represented by C ₇ F ₁₆ has no detergency and is not suitable for a detergent alone, but has a latent heat of vaporization of about 21 cal / g and tert-butanol (about 131 cal / g).
g) and hexamethyldisiloxane (about 50 cal / g). In addition, since perfluorocarbon is a nonflammable liquid, when mixed with flammable liquids tert-butanol and hexamethyldisiloxane, it raises the flash point compared to those alone or as a mixture, and becomes flame retardant. And, in some cases, non-flammable.

The third azeotropic composition and the pseudo-azeotropic composition are the above-mentioned hexamethyldisiloxane, tert-butanol, and a perfluorocarbon represented by C ₇ F ₁₆ as an azeotropic composition or a pseudo-azeotropic composition. Thus, the characteristics of each of these components are derived. That is, the azeotropic composition and azeotrope-like composition has a high dissolving power for oils and fats by tert- butanol, and excellent permeability due hexamethyldisiloxane, excellent by perfluorocarbon expressed by C ₇ F ₁₆ The composition has both the drying characteristics and the drying characteristics, and can be said to be a composition suitable for a cleaning agent in which washing and drying are performed in one liquid.

Further, the constituent ratio of each component in the azeotropic composition and the pseudo-azeotropic composition (hereinafter, abbreviated as the fourth azeotropic composition and the pseudo-azeotropic composition), which are the active ingredients of the fourth cleaning agent, is as follows: 5 to 25% by weight of hexamethyldisiloxane, 5 of isopropyl acetate
Is preferably in the range perfluorocarbon 50-90% by weight expressed as 25% by weight and C ₇ F _16, the azeotropic temperature in such a composition ratio azeotropic composition 337~345K (760mmHg) or A pseudo-azeotropic composition is obtained. The specific composition ratio of the azeotropic composition can vary depending on conditions. The fourth azeotropic composition and the pseudo-azeotropic composition are also the third azeotropic composition.
Can be obtained in the same manner as the azeotropic composition and the pseudo-azeotropic composition.

In the fourth and pseudo-azeotropic compositions, C ₇
By perfluorocarbon represented mixed with isopropyl acetate and hexamethyldisiloxane a flammable liquid F _16, as compared with their single or mixtures can be flame retarded by increasing the flash point, further In some cases, it can be made nonflammable.

Furthermore, hexamethyldisiloxane, and having the characteristics as described above, the isopropyl acetate arbitrarily miscible at room temperature, 3 and perfluorocarbon expressed by C ₇ F ₁₆
Compatible arbitrarily above 08K. Meanwhile, isopropyl acetate and C
_{Although it} hardly dissolves with ₇ F ₁₆ , the addition of hexamethyldisiloxane allows the three components to be compatibilized during heating, resulting in a uniform composition. That is, hexamethyldisiloxane functions as a compatibilizer for the other two components. Effect as the compatibilizer of hexamethyldisiloxane, varies greatly depending on the kind of polar solvent, isopropyl acetate of the present invention is compared with lower alcohol such as methanol or ethanol, C ₇ F ₁₆ by addition of hexamethyldisiloxane The solubility in perfluorocarbon represented by the formula (1) is remarkably improved.

The cleaning composition of the present invention comprises the above-mentioned hexamethyldisiloxane, isopropyl acetate, and a perfluorocarbon represented by C ₇ F ₁₆ as an azeotropic composition or a pseudo-azeotropic composition. The features are derived. That is, the second azeotropic composition and the pseudo-azeotropic composition have high solubility in oils and fats by isopropyl acetate, excellent permeability by hexamethyldisiloxane, and perfluorocarbon represented by C ₇ F _16. It has excellent drying characteristics, and can be said to be a composition suitable for a cleaning agent in which washing and drying are performed in one liquid.

As described above, since the cleaning agent of the present invention achieves both the removal property of the stain and the drying property, it can be used as a cleaning agent that carries out from washing to drying with one liquid, and also includes a washing step and a rinsing step. It can be used alone in any of the steps and the drying step. Further, since the cleaning agent of the present invention does not contain a chlorine-based organic solvent as a basic component, it does not cause ozone destruction, and is in use as described in detail in the description of the azeotropic composition and the pseudo-azeotropic composition. Can be suppressed as much as possible, and the composition can be made flame-retardant or even non-flammable.

The non-combustible detergent containing the fifth azeotropic composition and the pseudo-azeotropic composition as active ingredients is hexamethyldisiloxane, tert-
It is characterized by containing an azeotropic composition or a pseudo-azeotropic composition comprising a perfluorocarbon represented by butanol and perfluoromorpholine as an active ingredient.

The non-flammable detergent containing the sixth azeotropic composition and the pseudo-azeotropic composition as an active ingredient is an azeotropic composition or pseudo-azeotropic composition comprising hexamesyldisiloxane, isopropyl acetate and perfluorocarbon represented by perfluoromorpholine. It is characterized in that the composition is contained as an active ingredient.

Perfluoromorpholine used in azeotropic compositions and pseudo-azeotropic compositions as fifth and sixth active ingredients (hereinafter abbreviated as fifth and sixth azeotropic compositions and pseudo-azeotropic compositions) Is preferably perfluoro-N-alkylmorpholine. Further perfluoro -N- methylmorpholine is preferably represented by the chemical formula C ₅ F ₁₁ NO.

The constituent ratio of each component in the fifth azeotropic composition and the pseudo-azeotropic composition is 1 to 20% by weight of hexamethyl thidioxane,
It is preferably in the range of 1 to 20% by weight of tert-butanol and 60 to 98% by weight of perfluoromorpholine, and the azeotropic temperature is 313 to 322K (760 mmHg) in such a constitutional ratio.
Or a pseudo-azeotropic composition is obtained. The specific composition ratio of the azeotropic composition can vary depending on conditions. In addition, the pseudo-azeotropic composition is a composition containing one or more components in excess of the azeotropic composition as long as the characteristics of the azeotropic composition are not substantially impaired. Thus, it exhibits substantially the same characteristics as the above-mentioned azeotropic composition.

The fifth azeotropic composition and the pseudo-azeotropic composition can be obtained by a multi-stage rectification method or the like, like the first azeotropic composition and the pseudo-azeotropic composition.

In the fifth azeotropic composition and the pseudo-azeotropic composition, perfluoromorpholine has no detergency and therefore has a latent heat of vaporization of about 21 cal / g, which is not suitable as a detergent, and tert-butanol (about 131 cal / g) and Methyldisiloxane (about 50ca
l / g), so it has a much higher drying speed. Further, since perfluoromorpholine is a nonflammable liquid, mixing with a flammable liquid makes it possible to raise the flash point and make it more nonflammable than when only a flammable liquid is used.

Further, hexamethyldisiloxane is optionally compatible with any of tert- butanol and perfluoro morpholine (C ₅ F ₁₁ NO). On the other hand, tert-butanol and perfluoromorpholine hardly dissolve in each other. Therefore, by blending hexamethyldisiloxane, the three components can be compatibilized and a uniform composition can be obtained. That is, hexamethyldisiloxane acts as a "compatibilizer" of the other two components. The effect of hexamethyldisiloxane as a "compatibilizer" varies greatly depending on the polar solvent, and tert-butanol is more soluble in perfluoromorpholine by adding hexamethyldisiloxane than lower alcohols such as methanol and ethanol. Is remarkably excellent. Fifth
The azeotropic composition and pseudo-azeotropic composition of (1) draw out their advantages by blending hexamethyldisiloxane, tert-butanol, and perfluoromorpholine.

The composition ratio of each component in the sixth azeotropic composition and the pseudo-azeotropic composition is 1 to 20% by weight of hexamethyldisiloxane,
Preferably, it is in the range of 1 to 20% by weight of isopropyl acetate and 60 to 98% by weight of perfluoromorpholine, and the azeotropic temperature is 315 to 322K (760 mmHg) in such a constitutional ratio.
Or a pseudo-azeotropic composition is obtained. The specific composition ratio of the azeotropic composition can vary depending on conditions. In addition, the pseudo-azeotropic composition is a composition containing one or more components in excess of the azeotropic composition as long as the characteristics of the azeotropic composition are not substantially impaired. Thus, it exhibits substantially the same characteristics as the above-mentioned azeotropic composition.

The sixth azeotropic composition and the pseudo-azeotropic composition can be obtained by a multi-stage rectification method or the like, like the first azeotropic composition and the pseudo-azeotropic composition.

In the sixth azeotropic composition and the pseudo-azeotropic composition, by blending perfluoromorpholine, which is a nonflammable liquid, the flash point can be raised and further made nonflammable as compared with the case where only the flammable liquid is used. Will be possible.

Hexamethyldisiloxane is arbitrarily compatible with both isopropyl acetate and perfluoromorpholine (C ₅ F ₁₁ NO). On the other hand, isopropyl acetate and perfluoromorpholine hardly dissolve in each other. Therefore, by blending hexamethyldisiloxane, the three components can be compatibilized and a uniform composition can be obtained. That is, hexamethyldisiloxane acts as a "compatibilizer" of the other two components. The effect of hexamethyldisiloxane as a "compatibilizing agent" varies greatly depending on the polar solvent, and isopropyl acetate has a higher solubility in perfluoromorpholine than hexamethyldisiloxane compared to lower alcohols such as methanol and ethanol. It will be significantly better. Sixth
The azeotropic composition and the pseudo-azeotropic composition of (1) draw out their advantages by blending hexamethyldisiloxane, isopropyl acetate and perfluoromorpholine.

The first to sixth cleaning agents according to the present invention may be those containing the above-described azeotropic composition or pseudo-azeotropic composition of the present invention as an active ingredient. Or not only the pseudo-azeotropic composition of the detergent alone, as long as it does not impair the detergency and drying properties, for example, further mixing and using other detergent components or azeotropic stabilizers Can be.

For example, other perfluorocarbons such as C ₆ F ₁₄ , C
₇ F ₁₆ , C ₈ F ₁₈ , perfluoromorpholine and the like can be used in combination, and further, fluorocarbons such as hydrofluorocarbon and hydrochlorofluorocarbon can be used in combination. In addition, other alcohols, ketones, tert-butanol and isopropyl acetate
Ethers, esters, amines, hydrocarbon compounds and the like can be used in combination.

Stabilizers that can be added to the first to sixth detergents of the present invention in order to suppress the decomposition of detergent components due to ultraviolet rays or the like include, for example, epoxides such as glycidol and cyclohexene oxide, 1,4-dioxane, Examples thereof include ethers such as 1,3,5-trioxane, unsaturated hydrocarbons such as 1-pentene and 1-hexene, and acrylates such as methyl acrylate and ethyl acrylate. These stabilizers are 0.1 to 5% by weight based on the total weight of the detergent.
It is preferable to add them at a ratio of about. The above-mentioned stabilizers can be added alone or in combination of two or more.

The cleaning agent of the present invention is applicable to various objects to be cleaned, and the material of the object to be cleaned is not particularly limited, and examples thereof include metals, metalloids, ceramics, and plastic materials. For example, metals and semi-metals include iron, aluminum, silicon, copper, stainless steel, etc., ceramics include silicon nitride, silicon carbide, aluminum oxide, glass, porcelain, etc., and plastics include polyamide, polyimide, epoxy, polyolefin, and polyester. , An acrylic resin and the like, and a composite material thereof may be used. Specific examples include electronic parts such as printed circuit boards and mounting parts, electric parts, semiconductor parts, metal parts, surface treatment parts, precision equipment parts, optical parts, glass parts, ceramic parts, plastic parts, and the like.

The cleaning agent containing the seventh azeotropic composition and the pseudo-azeotropic composition as an active ingredient contains, as an active ingredient, an azeotropic composition or a pseudo-azeotropic composition composed of hexamethyldisiloxane and tert-butanol. It is characterized by.

The cleaning agent containing an eighth azeotropic composition or a pseudo-azeotropic composition as an active ingredient contains an azeotropic composition or a pseudo-azeotropic composition composed of hexamethyldisiloxane and isopropyl acetate as an active ingredient. Features.

The composition ratio of each component in the azeotropic composition and the pseudo-azeotropic composition (hereinafter, abbreviated as the seventh azeotropic composition and the pseudo-azeotropic composition), which are the active ingredients of the seventh detergent, is hexamethyl 44 to 50% by weight of disiloxane and 50 to 50% of tert-butanol
It is preferably in the range of 56% by weight, and an azeotropic composition or a pseudo-azeotropic composition having an azeotropic temperature of 350 to 355 K (760 mmHg) in such a constitutional ratio is obtained. The specific composition ratio of the azeotropic composition can vary depending on conditions. The seventh azeotropic composition and the pseudo-azeotropic composition can be obtained by a multi-stage rectification method or the like, like the first azeotropic composition and the pseudo-azeotropic composition.

In the seventh azeotropic composition and the pseudo-azeotropic composition, hexamethyldisiloxane is arbitrarily compatible with tert-butanol at room temperature, so that a uniform composition can be obtained.

The seventh azeotropic composition and the pseudo-azeotropic composition were each characterized by using the above-mentioned hexamethyldisiloxane and tert-butanol as the azeotropic composition or the pseudo-azeotropic composition, respectively. Things. That is, the seventh azeotropic composition and the pseudo-azeotropic composition have both high dissolving power of tert-butanol for fats and oils, excellent permeability with hexamethyldisiloxane and a good drying rate, It can be said that the composition is suitable for a cleaning agent because it is little mixed and does not deteriorate the plastic.

The constituent ratio of each component in the azeotropic composition and the pseudo-azeotropic composition (hereinafter, abbreviated as the first azeotropic composition and the pseudo-azeotropic composition), which are the active ingredients of the eighth cleaning agent, is as follows: It is preferably in the range of 40 to 46% by weight of hexamesyldisiloxane and 54 to 60% by weight of isopropyl acetate. In such a constitutional ratio, an azeotropic composition or azeotropic composition having an azeotropic temperature of 355 to 358 K (760 mmHg). A composition is obtained. The specific composition ratio of the azeotropic composition can vary depending on conditions. The eighth azeotropic composition and the pseudo-azeotropic composition are also the first azeotropic composition.
Can be obtained in the same manner as the azeotropic composition and the pseudo-azeotropic composition.

In the eighth azeotropic composition and the pseudo-azeotropic composition, hexamethyldisiloxane is arbitrarily compatible with isopropyl acetate at room temperature, so that a uniform composition can be obtained.
By making the above-mentioned hexamethyldisiloxane and isopropyl acetate into an azeotropic composition or a pseudo-azeotropic composition, characteristics of each of these components are derived. That is, the eighth azeotropic composition and the pseudo-azeotropic composition have high solubility in oils and fats with isopropyl acetate, excellent permeability with hexamethyldisiloxane and a good drying rate, and also contain water. It can be said that the composition is suitable for a detergent because it has a low content and does not deteriorate the plastic. Therefore, by using such an azeotropic composition or a pseudo-azeotropic composition as a cleaning active ingredient, there is no substantial change in the liquid composition during use, and the degreasing property, cleaning quality, drying speed, regenerating ability, etc. An excellent cleaning agent and a cleaning agent capable of performing from washing to drying with one liquid can be obtained.

The seventh and eighth detergents may contain the azeotropic composition or the pseudo-azeotropic composition as described above as an active ingredient, and the azeotropic composition or the pseudo-azeotropic composition of the present invention may be used. The cleaning agent is not limited to a single cleaning agent, and other cleaning components, an azeotropic stabilizer, and the like can be further mixed and used as long as the cleaning performance and the drying performance are not impaired. For example, tert-butanol or isopropyl acetate can be used in combination with other alcohols, ketones, ethers, esters, amines, hydrocarbon compounds and the like.

Further, as the stabilizer that can be added to the seventh and eighth cleaning agents, the stabilizers described in the above first to sixth embodiments can be used. Further, the present invention can be applied to the various objects to be cleaned described in the first to sixth cleaning agents.

The cleaning agent containing the ninth azeotropic composition and the pseudo-azeotropic composition as an active ingredient is an azeotropic composition or pseudo-azeotropic composition comprising a fluorocarbon and a polar cleaning agent having a solubility parameter of 9 or more or a dielectric constant of 4 or more. It is characterized by containing an azeotropic composition as an active ingredient. Suitable azeotropic composition and azeotrope-like compositions, C ₄ F ₉ OCH ₃ is 95 to 90 wt% and methanol 5-10% by weight, C ₄ F ₉ OCH ₃ is 94 to 89 wt% and methanol Or 6-11% by weight of IPA, 87-8 of C ₄ F ₉ OCH ₃
1% by weight and 13-19% by weight of methyl ethyl ketone, C ₄ F
₉ OCH ₃ is 71 to 64 wt% and ethyl formate 29-36 wt%
Can be mentioned.

Further, as the stabilizer which can be added to the ninth detergent, the stabilizers described in the above first to sixth can be used. Further, the present invention can be applied to the various objects to be cleaned described in the first to sixth cleaning agents.

As described above, the cleaning agent containing the first to ninth azeotropic compositions and the pseudo-azeotropic compositions as active ingredients has been described. For example, it can be used as an azeotropic composition or a pseudo-azeotropic composition by itself for applications such as paint solvents, reagents, and various solvents.

The weight ratios used in the above-described first to ninth cleaning agents indicate the mixing ratios determined from the peak areas of the components obtained by analyzing the mixed composition by gas chromatography. The gas chromatography was measured under the following conditions. Equipment: Shimadzu GD-14
A (Detector TC-D), Column: SUS 2m × 3φ, GL Science Chromosolve Co., Ltd. WAWDMCS mesh 60/80, Filler: Silicon SE-30 10%, Injection temperature: 250
° C, TC-D temperature: 250 ° C, initial temperature: 50 ° C, initial holding time:
0 min., Heating rate: 10 ° C./min., Final temperature: 250 ° C., final holding time: 0 min., CURRENT: 100 mA, carrier gas and flow rate: He, 49 ml / min., ATTENUATION: 64.

 Next, a cleaning apparatus according to the present invention will be described.

The first cleaning device is a mixed cleaning agent in which a non-flammable or flame-retardant fluorocarbon is mixed with a cleaning agent containing a low-molecular siloxane compound, and at least one selected from cleaning, rinsing, and steam drying of an object to be cleaned. It is characterized in that it comprises a cleaning device main body for performing one, and a composition control mechanism for controlling a composition ratio of the low-molecular siloxane compound and fluorocarbons in the mixed cleaning agent.

As the low-molecular siloxane compound and fluorocarbon used in the first cleaning device, the same low-molecular siloxane compound and fluorocarbon described in the first cleaning method can be used. Further, the detergent containing the low-molecular siloxane compound used in the present invention is not limited to the above-described detergent of the low-molecular siloxane compound alone, and the low-molecular siloxane compound and a polar solvent, a hydrocarbon solvent, an ether solvent, an acetal solvent. It may be a mixture of other solvents such as a solvent, or a detergent containing various additives such as a surfactant and a hydrophilic solvent.

The low-molecular-weight siloxane compound as described above has a flash point, and when a cleaning agent containing such a low-molecular-weight siloxane compound is used, safety measures including prevention, suppression, or digestion of fire are required. Here, Table 4 shows the flash point and boiling point of typical low molecular weight siloxane compounds.

Here, in order to combust a combustible solvent, a combustible substance (combustible), oxygen (oxidant, etc.), and a heat source (ignition energy) are required, and these are called three elements of combustion. In order to burn, it is necessary that these three elements be present at the same time, and if even one of these elements is missing, combustion does not take place and its continuation is impossible.

When the flammable liquid starts burning, it may be caused by ignition or by ignition. Ignition is a phenomenon in which when a flammable liquid is heated while giving a small spark to its surface, the heat source emits a flame and starts burning. This occurs when flammable gas (vapor) is generated from the liquid surface by heating and the mixture composition with oxygen reaches the lower limit concentration of the combustion range, and the lowest temperature at which ignition occurs is defined as the flash temperature or flash point. That. Ignition is a phenomenon in which even if there is no heat source, the oxidizing heat causes a flame to start burning by itself, and the lowest temperature is called the ignition temperature or ignition point. Therefore, in order to use a flammable solvent safely, it is necessary to satisfy at least one of the following three conditions.

(1) Use a solvent whose vapor concentration is below the lower limit of the combustion range and do not heat it above the flash point.

(2) Prevent generation of heat sources (for example, electric spark, friction, etc.).

(3) Block oxygen.

Furthermore, (4) safety measures are further improved by taking measures against digestion.

Prevention or extinguishing of the flammable solvent as described above is also effective in that the flammable solvent can be used safely,
In the present invention, a non-flammable or flame-retardant fluorocarbon is mixed with a detergent containing a low molecular weight siloxane compound to impart non-flammability or flame retardancy to the detergent (mixed detergent) itself. It enables safe use of flammable low molecular weight siloxane compounds.

That is, some fluorocarbons have no problem with respect to both environmental problems and health problems, do not burn themselves, and are effective in blocking oxygen in the atmosphere. Therefore, when using the low-molecular-weight siloxane compound, a fluorocarbon that dissolves the low-molecular-weight siloxane compound and is nonflammable or flame-retardant is selected, mixed with a cleaning agent containing the low-molecular-weight siloxane compound, and mixed and washed. Used as an agent. Such mixed detergents can be used as non-flammable or non-flammable detergents.

The mixing ratio of the non-combustible or flame-retardant fluorocarbons in the above mixed detergent varies depending on whether it is used for washing, rinsing or steam drying, but it is 10 to 10,000 per 100 parts by weight of the low-molecular siloxane compound. It is preferred to be in the range of parts by weight. By blending fluorocarbons in an amount of 10 parts by weight or more based on 100 parts by weight of the low-molecular siloxane compound, it is possible to impart flame retardancy or nonflammability to the mixed detergent. The mixing ratio of the fluorocarbons is 20 to 500 parts by weight per 100 parts by weight of the low-molecular siloxane compound.
It is more preferable that the content be in the range of 0 parts by weight.

Fluorocarbons having various boiling points can be obtained depending on the molecular structure, but fluorocarbons used in the present invention basically have a boiling point not higher than the operating temperature of a detergent containing a low-molecular siloxane compound. preferable. However, in consideration of the consumption due to the volatilization of the fluorocarbons, those having a boiling point substantially equal to the use temperature of the low-molecular siloxane compound may be practically used.

By the way, in the mixture of the low-molecular siloxane compound and the fluorocarbon as described above, the consumption of one component becomes larger than the consumption of the other component depending on the use conditions and the like, and the composition ratio changes, resulting in non-combustibility or difficulty. Flammability may be impaired. Therefore, the cleaning apparatus of the present invention has a composition control mechanism for controlling the composition ratio of the low-molecular siloxane compound and the fluorocarbon in the mixed cleaning agent.

In order to control the composition ratio between the low-molecular siloxane compound and the fluorocarbon, it is necessary to measure the composition ratio of the low-molecular siloxane compound and the fluorocarbon in the mixed detergent continuously or intermittently. When the composition ratio deviates from the predetermined range, the non-combustibility or the flame retardancy can be constantly maintained by additionally supplying the insufficient component.

Here, the specific gravity, refractive index, boiling point or condensation point of the mixture of the low-molecular siloxane compound and the fluorocarbon are
Since the composition ratio changes according to the composition ratio, the composition ratio between the low-molecular siloxane compound and the fluorocarbon can be easily measured. The Si—O bond, which is the skeleton of the chemical structure of the low-molecular-weight siloxane compound, has a unique infrared absorption having a very high absorbance at 1100 cm ⁻¹ .
Therefore, by measuring the degree of infrared absorption based on the Si-O bond in the vapor of the mixed detergent, the vapor concentration of the low-molecular siloxane compound can be measured. The composition ratio can be controlled. The measurement of siloxane concentration
Using a dispersive or non-dispersive infrared spectrophotometer, it can be easily measured by an internal standard method or a calibration curve method, and the result can be easily fed back to the cleaning agent supply means.

That is, the composition ratio control mechanism in the first cleaning device includes, for example, means for measuring the composition ratio of the low-molecular siloxane compound and the fluorocarbon in the mixed cleaning agent, and low-molecular siloxane in accordance with the measurement result by the composition ratio measurement means. Means for supplying the compound or fluorocarbon into the mixed detergent. As the composition ratio measuring means, other than using an infrared spectrophotometer, means for measuring at least one selected from the specific gravity, refractive index, boiling point and freezing point of the mixed detergent is exemplified.

Table 5 shows the specific gravity, refractive index, and boiling point of hexamethyldisiloxane as an example of the low-molecular siloxane compound, and Table 5 shows the specific gravity, refractive index, and boiling point of perfluorocarbon C ₆ F ₁₄ as an example of fluorocarbons. FIG. 9 shows how the boiling point and the condensation point of the mixture of the low-molecular siloxane compound and the fluorocarbon change according to the composition ratio, and FIG. 10 shows how the specific gravity of the mixture changes according to the composition ratio.
FIG. 11 shows how the refractive index of the mixture changes according to the composition ratio.

As is clear from FIGS. 9, 10 and 11, by measuring the specific gravity, refractive index, boiling point or condensation point of the mixture of the low molecular weight siloxane compound and the fluorocarbon, the composition ratio can be easily grasped. it can.

As described above, when configuring a cleaning device using a low-molecular siloxane compound having a flash point as a cleaning agent, by mixing non-flammable or flame-retardant fluorocarbons with the low-molecular siloxane compound, Non-flammable or flame-retardant properties can be imparted to the cleaning agent itself, and safety can be ensured. Further, by providing a mechanism for controlling the composition ratio of the low-molecular siloxane compound and the fluorocarbon, the certainty of ensuring the safety is improved, and the low-molecular siloxane compound can be used effectively.

The cleaning apparatus of the present invention further enhances safety by using safety measures such as general fire prevention / suppression means or fire extinguishing means based on the above four conditions (1) to (4). Can be enhanced.

The second cleaning device is a cleaning device using a cleaning agent containing a low-molecular-weight siloxane compound. The low-molecular-weight siloxane compound generated from the cleaning agent is based on infrared absorption of Si—O bonds of the low-molecular-weight siloxane compound. And a means for measuring the vapor concentration of the gas. Further, it is characterized by comprising a temperature adjusting means for the cleaning agent.

The third cleaning device is a cleaning device using a cleaning agent containing a low-molecular-weight siloxane compound, and is selected from inside the cleaning device, around the cleaning device, inside the device constituting the cleaning device, and around the constituent devices. At least one of them is filled or arranged with a nonflammable or nonflammable fluorocarbon gas or liquid.

The fourth cleaning device is a cleaning device using a cleaning agent containing a low-molecular-weight siloxane compound, and a non-combustible or non-flammable fluorocarbon gas or liquid digestive agent is added to at least a part of the cleaning device. It is characterized by having means for jetting. Further, it is characterized in that it comprises at least one selected from a flame detecting means, a temperature detecting means and a pressure detecting means for driving the digestive spraying means.

The second to fourth cleaning apparatuses are cleaning apparatuses that use a cleaning agent containing a low-molecular-weight siloxane compound. The cleaning agent mentioned here minimizes the concentration of a dirt component adhering to an object to be cleaned. The cleaning agent used for removal, the rinse agent used for minimizing or removing the concentration of the cleaning agent adhering to the object to be cleaned, and the cleaning agent and the rinsing agent are evaporated or removed from the object to be cleaned. It contains a steam cleaner used for removal.

As the low molecular siloxane compound used in the second to fourth cleaning apparatuses, the same low molecular siloxane compound as described in the first cleaning method can be used.

Further, the cleaning agent used in the present invention is not limited to the cleaning agent of the low-molecular siloxane compound alone, and may be a mixture of the low-molecular siloxane compound with another solvent such as a polar solvent, a hydrocarbon solvent, an ether solvent, or an acetal solvent. It may be a detergent or a detergent containing various additives such as a surfactant and a hydrophilic solvent. In particular, the present invention is effective when a cleaning agent containing a low molecular weight siloxane compound as a main component is used.

The low-molecular-weight siloxane compound as described above has a flash point as shown in Table 4, and when a cleaning agent containing such a low-molecular-weight siloxane compound is used, the prevention, suppression, or digestion of a fire, etc. The above four safety measures including the above are required.

First, in order to use the solvent below its flash point based on the first condition, it is sufficient to control the temperature of the solvent. However, simply controlling the temperature of the low-molecular siloxane compound is not sufficient, and it is necessary to control the vapor concentration of the low-molecular siloxane compound outside the combustion range. Here, the structure of the low molecular weight siloxane compound Si—O
The bond has a very high specific absorbance of 1100 cm ^-1
Exists. Therefore, by measuring the degree of infrared absorption based on this Si—O bond, the vapor concentration of the low molecular siloxane compound can be measured.

The second cleaning device has a wavelength of 1100 based on the Si—O bond.
A means for measuring the vapor concentration of the low-molecular-weight siloxane compound according to the degree of infrared absorption of cm ^-1 is provided. The vapor concentration of the siloxane compound can be controlled with high accuracy outside the combustion range. further,
By using the oxygen concentration measuring means together with the vapor concentration measuring means of the low-molecular siloxane compound having a high detection sensitivity, the detergent containing the flammable low-molecular siloxane compound can be used more safely outside the combustion range. It becomes possible. Further, since the low-molecular-weight siloxane compound has a small specific heat, for example, by using fuzzy control or the like, the low-molecular-weight siloxane compound can be easily washed at the flash point or lower.

Next, in order to prevent the generation of a heat source based on the second condition, the work site using the cleaning agent is strictly prohibited from fire,
In addition, it is common to use a non-contact relay for the electrical equipment mounted on the cleaning device, or to use a motor or the like with a pressure-resistant explosion-proof specification. It cannot be prevented. Also, in order to shut off oxygen based on the third condition, a method of filling an inert gas such as nitrogen or argon is generally known. Other inert gases include helium, neon, and krypton. ,
Xenon, radon and the like are also used. However, since these conventional inert gases have a low gas density and are easily diffused and leaked, they are extremely uneconomical and, at the same time, the inside of the cleaning device provided with airtightness is in an excess pressure state, that is, the inert gas constantly. Need to be supplied.

The present inventors have conducted intensive studies, and as a result, low-molecular-weight siloxane compounds have been converted into fluorocarbons such as perfluorocarbons, hydrofluorocarbons, hydrochlorofluorocarbons, fluoroiodide carbons, fluoroalcohols, and hydrofluoroethers. It showed high solubility for some, and some were found to be mutually soluble. Since the liquids and gases of the above fluorocarbons are generally nonflammable or nonflammable, the nonflammable or nonflammable fluorocarbons are formed inside or around the cleaning device or inside or around the devices constituting the cleaning device. By filling or disposing the gas or liquid, the cleaning agent or its vapor can be cut off from the heat source, and oxygen can be cut off.

The third cleaning device is based on the above knowledge, and is provided with at least one of a nonflammable or non-flammable material selected from the inside of the cleaning device, the periphery of the cleaning device, the inside of the device constituting the cleaning device, and the periphery of the component device. It is filled or arranged with a flame-retardant fluorocarbon gas or liquid. Here, the cleaning device includes various peripheral devices,
Therefore, the constituent devices of the cleaning device include not only main devices such as a cleaning tank and a drying device but also peripheral devices such as a liquid regenerating device, electric devices such as control devices and driving devices.
The devices described below include a cleaning device and its constituent devices.

By filling a non-combustible or non-combustible fluorocarbon, for example, a gas, into a heat source generator such as an electric device, generation of a heat source can be prevented. In addition, the infiltration of oxygen into the cleaning device is prevented by filling the inside or the surroundings of the cleaning device or the components of the cleaning device with or around a nonflammable or flame-retardant fluorocarbon, for example. And the vapor concentration of the low-molecular siloxane compound inside the apparatus can be easily reduced to a value outside the combustion limit. Since fluorocarbons have a high vapor pressure and are easily vaporized, the above effects can be obtained by arranging them inside or around the apparatus. The liquid can be made non-combustible or flame-retardant by absorbing the liquid, and the cleaning device can be used more safely.

When the inside of the apparatus is made to be in an excess pressure state with fluorocarbons, the fluorocarbons have a high vapor density and are difficult to diffuse, so they are less consumed due to leakage and are economical. Invasion of oxygen from the atmosphere can be effectively prevented.

In the above description, a case in which a gas of fluorocarbons is mainly used has been described. For example, a nonflammable or flame-retardant liquid of fluorocarbons is filled around various constituent devices including a cleaning tank. Alternatively, the low-molecular-weight siloxane compound can be shielded from a heat source and oxygen by being immersed in a flame-retardant fluorocarbon liquid. The third cleaning device includes such a form. It is also possible to use a conventionally used inert gas together.

As the non-combustible or non-flammable fluorocarbons used in the third cleaning device, the same fluorocarbons as those described in the first cleaning method can be used.

Regarding the fourth condition, cooling fire hydrants, suffocation hydrants, removal fire extinguishing methods, dilution fire extinguishing methods, and the like are generally known as fire extinguishing means. For example, the nitrogen fire extinguishing method uses an inert gas such as carbon dioxide having a higher vapor density than oxygen. It is a method of extinguishing fire by directly covering the surface of the combustion material and cutting off the supply of oxygen.However, as described above, since the low-molecular siloxane compound has high solubility in fluorocarbons, the liquid or gas of fluorocarbons Suitable as a fire extinguisher.

The fourth cleaning device is provided with means for injecting a fire extinguishing agent composed of a nonflammable or flame-retardant fluorocarbon gas or liquid as described above to at least a part of the cleaning device. Since low molecular weight siloxane compounds and fluorocarbons exhibit high solubility, the use of a non-flammable or flame-retardant fluorocarbon gas or liquid fire extinguisher can stop the chain reaction of combustion or reduce flammability. It can be easily extinguished outside the flammable limit of the vapor of the low molecular weight siloxane compound and the oxygen can be extinguished to extinguish the fire. Further, since the vapor density is higher than that of a conventional inert gas such as carbon dioxide, oxygen can be more effectively cut off. Further, since the low molecular siloxane compound and the fluorocarbon show high solubility, the liquid itself of the fluorocarbon can be used as a fire extinguishing agent, and this makes it possible to obtain a more effective fire extinguishing means.

As the non-combustible or non-flammable fluorocarbons used as a fire extinguishing agent, the same fluorocarbons as those exemplified in the third cleaning apparatus can be used. In particular, fluorocarbons capable of generating a trifluoro radical having a high fire extinguishing effect are used. It is suitable.

The fifth cleaning device relates to a draining / drying device suitable for the sixth cleaning method, has compatibility with water, has no azeotropic property with water, and has an evaporation heat of 100 cal / g or less. Characterized in that it has a draining / drying means using the above liquid.

This draining / drying apparatus has a draining / drying means using a draining / drying liquid such as trifluoroethanol, and further, means for removing water or a dirt component mixed constantly or intermittently from the draining / drying liquid, For example, it is preferable to have a distillation means. The distillation means may be provided with a decompression means such as an aspirator. Thus, by providing the water removing means, it is possible to perform the most effective draining and drying without drying spots.

According to the draining drying method and the draining drying apparatus of the present invention, not only the water displacement operation (immersion, rocking, stirring, ultrasonic wave, spray) but also the drying operation (hot air drying, spin drying,
It is possible to effectively use a draining dry liquid made of trifluoroethanol or the like, including steam drying, lifting drying, and vacuum drying.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view schematically showing a configuration of a drainer / dryer according to one embodiment of the present invention.

FIG. 2 is a diagram schematically showing a configuration of a drainer / dryer according to another embodiment of the present invention.

FIG. 3 is an example of a calibration curve used for quantifying the blending ratio of the azeotropic composition.

FIG. 4 is an infrared chart of the low molecular weight siloxane compound.

FIG. 5 is a diagram schematically showing a configuration of a cleaning apparatus according to one embodiment of the present invention.

FIG. 6 is a diagram schematically showing a configuration of a cleaning apparatus according to another embodiment of the present invention.

FIG. 7 is a view showing a modified example of the cleaning tank and the like in the cleaning apparatus shown in FIG.

FIG. 8 is a view showing another modified example of the cleaning apparatus shown in FIG. 6 such as a cleaning tank.

FIG. 9 is a diagram showing how the boiling point and the condensation point of a mixture of a low-molecular siloxane compound and a fluorocarbon change according to the composition ratio.

FIG. 10 is a diagram showing how the specific gravity of a mixture of a low-molecular siloxane compound and a fluorocarbon changes according to the composition ratio.

FIG. 11 is a diagram showing how the refractive index of a mixture of a low-molecular siloxane compound and a fluorocarbon changes according to the composition.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples.

Examples 1 to 34 First, specific examples of the mixed cleaning agent used in the rinsing step and the drying step in the first cleaning method and the results of evaluating the characteristics thereof will be described.

Perfluorocarbons (C ₆
And F _14), along with providing a hexamethyldisiloxane as the low molecular weight siloxane compound, they are mixed in the range of the mixing ratio (weight ratio) 85 / 15-30 / 70, as shown in Tables 7 and 8, they Was mixed with the polar detergents shown in Tables 7 and 8, and mixed detergents were respectively prepared.

The solubility and flammability of the contaminated components of each of the thus obtained mixed detergents was evaluated as follows. First, liquid paraffin (viscosity: 30 cSt (298 K)) as a base oil for soiling substances
, A chlorinated paraffin (manufactured by Ajinomoto Co.) as an extreme pressure agent, and a flux SR-210 (low residue type) (trade name, manufactured by Senju Metal) as a flux. 5% by weight
Was added to 200 g of the mixed detergent, and the solubility was examined by silent observation of the state thereafter. The evaluation of solubility was defined as follows, and is shown in Tables 7 and 8 as evaluation results.

[Soil solubility] ：: Completely dissolved within 30 seconds after addition ○: Completely dissolved within 30 to 60 seconds after addition △: Dissolved within 60 seconds or longer after addition ×: Does not dissolve stains The flammability of the cleaning agent was evaluated by measuring the flash point in accordance with JIS-K-2265 with a tag-closed flash point measuring device and a Cleveland open type flash point measuring device. Nonflammability and flame retardancy as flammability evaluation results were defined as follows, and are shown in Tables 7 and 8 as evaluation results, respectively.

[Measurement of flash point] Non-flammable: The flash point cannot be measured in both the closed tag type and the Cleveland open type.

Flame retardant: Any of the closed tag type and the open type of Cleveland whose flash point cannot be measured.

Examples 35 to 39 and Comparative Examples 1 to 3 Next, specific examples of the first cleaning method and evaluation results thereof will be described.

Flux CRV-5V on comb-shaped substrate (JIS-Z-3197 type 2)
After applying a fluxer (RA type; trade name, manufactured by Tamura Kaken), the solvent was removed at a preheating temperature of 373 to 393K, and further baked at 503 to 533K for 30 seconds. Using this comb-shaped substrate as an evaluation sample, the flux cleaning of the comb-shaped substrate was performed at a cleaning temperature of 313 K, an ultrasonic output of 400 W / 28 kHz, and a cleaning time of 5 minutes using the cleaning agent, rinsing agent and steam cleaning agent shown in Table 9.
After performing the rinsing under the conditions of 2 tanks and a rinsing time of 5 minutes-2 tanks, steam drying (hot air drying only in Comparative Example 1) was performed.

After the washing, the ion residue, the insulation resistance, the white residue, and the drying time were measured to evaluate the washing property and the drying property. Further, the flammability of each steam cleaning agent was evaluated in the same manner as in Example 1. Table 10 shows the results of these evaluations.

As is clear from the evaluation results shown in Table 10, according to the cleaning using the cleaning agent of the present invention, compared with the cleaning according to the comparative example, the amount of ion residues is small, the insulation resistance value is high, there is no white residue, Further, it can be seen that the drying time is short, and excellent cleaning properties and drying properties are obtained.

Examples 40 to 46 and Comparative Examples 4 to 6 Spindle oil was applied on a steel plate having a size of 30 mm x 30 mm x 1 mmt.
3 g was applied and baked in a heating furnace at 423 K for 48 hours to prepare a test piece. The cleaning of the oils and fats adhered to this test piece (ultrasonic cleaning) and subsequent rinsing and drying were performed using the cleaning agents, rinsing agents and steam cleaning agents shown in Table 11, or
The test was performed under the drying conditions shown in 11, and the residual oil content and the drying time of the test piece after washing were measured. As for the residual oil content, the test piece after washing was immersed in 150 ml of carbon tetrachloride, and the residual oil content was extracted by applying ultrasonic waves. The extract was measured with an oil concentration meter (OCMA-220, manufactured by Horiba, Ltd.) to determine the amount of residual oil. In addition, the flammability of each steam cleaning agent (an example in which drying other than steam drying was performed was a rinsing agent) was evaluated in the same manner as in Example 1. Table 12 shows the results of these evaluations.

Examples 47 to 50 Evaluation results in the second cleaning method will be described together with the cleaning agent of the present invention.

The test piece used in Example 40 was used as a test piece for evaluation, and was cleaned under the same conditions and method as in Example 40, except for using a cleaning agent, a rinsing agent, and a steam drying agent shown in Table 11,
Rinsing and steam drying were performed to evaluate the cleaning property. Table 12 shows the evaluation results.

As described above, according to the cleaning agent of the present invention, the first and second cleaning methods, it is possible to obtain the removability of various kinds of dirt components comparable to a chlorofluorocarbon-based solvent or a chlorofluorocarbon-based solvent, and to obtain a good drying property. Is obtained. Therefore, it is possible to provide a cleaning method suitable for cleaning electronic components such as printed circuit boards and mounted components, metal components, and the like, instead of the cleaning method using a chlorofluorocarbon-based solvent or a chlorine-based solvent.

Examples 51 to 84 Next, examples of the third and fourth cleaning methods will be described together with the cleaning agent of the present invention.

First, perfluorocarbon (C ₆ F ₁₄ ) was prepared as fluorocarbons, and hexamethyldisiloxane was prepared as a low molecular weight siloxane compound.
As shown in Table 2, mixing was carried out at a mixing ratio (weight ratio) of 85/15 to 30/70, and the polar detergents shown in Tables 13 and 14 were added thereto to prepare respective detergents.

The solubility and flammability of the contaminant components of each cleaning agent thus obtained were evaluated under the same conditions and method as in Example 1. The evaluation results are shown in Tables 13 and 14, respectively.

Examples 85-91 and Comparative Examples 7-12 The comb-shaped substrates used in Example 35 were prepared as evaluation samples, and the cleaning agents of Examples 85-91 shown in Table 15 and Table 16 were prepared.
Using the cleaning agents of Comparative Examples 7 to 12 shown in Table 3, washing and rinsing were performed under the same conditions as in Example 35, and Tables 15 and 16 were used.
Drying was performed under the conditions shown in In the example in which the drying was performed by steam drying, a cleaning agent having the same composition as the cleaning agent used in the cleaning step and the rinsing step was used as the steam cleaning agent. In addition, in Comparative Examples 11 and 12, cleaning to drying were similarly performed using the cleaning agent, the rinsing agent, and the steam cleaning agent shown in Table 16, respectively.

After the above washing, the ion residue, the insulation resistance and the white residue were measured to evaluate the washing property. Further, the flammability of each cleaning agent was evaluated in the same manner as in Example 1. Table 17 shows the results of these evaluations.

As is clear from the evaluation results shown in Table 17, according to the cleaning using the cleaning agent of the present invention, compared to the cleaning according to the comparative example, the amount of ion residues is small, the insulation resistance value is high, and there is no white residue. It can be seen that good cleaning and drying properties can be obtained.

Examples 92 to 106 and Comparative Examples 13 to 16 Spindle oil was applied on a steel plate having a size of 30 mm × 30 mm × 1 mmt.
3 g was applied and baked in a heating furnace at 423 K for 48 hours to prepare a test piece. The cleaning (ultrasonic cleaning) of the oils and fats adhering to this test piece was performed using the cleaning agents of Examples 92 to 106 shown in Table 18 and the same cleaning agents as Comparative Examples 7 to 10 shown in Table 16 (Comparative Example 13).
To 16), and the residual oil content of the test piece after washing was measured. As for the residual oil content, the test piece after washing was immersed in 150 ml of carbon tetrachloride, and the residual oil content was extracted by applying ultrasonic waves. The extract was analyzed using an oil concentration meter (OCMA-22, manufactured by Horiba, Ltd.)
0) and the residual oil content was determined. Further, the flammability of each cleaning agent was evaluated in the same manner as in Example 51. Table 19 shows the results of these evaluations.

As described above, according to the cleaning agent of the present invention and the cleaning agents of the third and fourth cleaning methods, the removability and the drying property of various kinds of dirt components comparable to the chlorofluorocarbon-based solvent and the chlorine-based solvent can be obtained. . Therefore, it is possible to provide a cleaning agent that can be widely used from easy cleaning to drying. Further, by using such a cleaning agent, a cleaning method suitable for cleaning electronic parts such as printed circuit boards and mounted parts, metal parts, and the like instead of the cleaning method using a chlorofluorocarbon-based solvent or a chlorine-based solvent is provided. It becomes possible.

Example 107 Next, an example of the fifth cleaning method will be described together with the cleaning agent of the present invention.

First, hexamethyldisiloxane was prepared as a low molecular siloxane compound, and perfluorohexane was prepared as fluorocarbons. Then, 30 parts by weight of the above hexamethyldisiloxane and 70 parts by weight of perfluorohexane were mixed to prepare a mixed detergent.

The flash point of this mixed cleaning agent was evaluated by measuring the flash point in accordance with JIS-K-2265 with a tag closed flash point measuring device and a Cleveland open type flash point measuring device. The flash point could not be measured in any of the Cleveland open type).

Next, the mixed cleaning agent was filled in a spray can using carbon dioxide as a propellant while preventing a change in the composition ratio of the mixed cleaning agent. On the other hand, a stainless steel test panel coated with a silicone press oil YF33 (trade name, manufactured by Toshiba Silicone Co., Ltd.) is prepared as an object to be cleaned, and cleaning is performed by spraying a mixed cleaning agent from the spray can on the stainless steel test panel. Was.

Before and after the washing, the amount of oil (residual oil after washing) was quantified using an oil content meter (manufactured by HORIBA, Ltd., OCMA220), and the cleaning performance was evaluated by observing the appearance. . Table 20 shows the results of quantification of these oils and the results of appearance observation.

As is clear from Table 20, it was confirmed that a good cleaning property was obtained by spraying a mixed cleaning agent of a low-molecular siloxane compound and a fluorocarbon from a spray can. In addition, after the spray can filled with the mixed detergent was stored for a long period of time, the performance of the mixed detergent was evaluated. As a result, it was confirmed that neither the cleanability nor the flammability (non-combustibility) did not change.

Example 108 First, octamethyltrisiloxane was used as a low-molecular siloxane compound, and C ₅ F ₁₁ NO was used as fluorocarbons.
And isopropanol as another component.
Then, 10 parts by weight of the above octamethyltrisiloxane and C ₅
80 parts by weight of F ₁₁ NO and 10 parts by weight of isopropanol were mixed to prepare a mixed detergent.

The flash point of this mixed cleaning agent was evaluated by measuring the flash point with a tag closed type flash meter and a Cleveland open type flash point meter in accordance with JIS-K-2265. The flash point could not be measured in any of the open types.)

Next, while preventing the composition ratio change of the mixed cleaning agent, N ₂
It was filled in a spray can using gas as a propellant. On the other hand, a copper test panel to which isostearic acid as an oil agent was applied was prepared as an object to be cleaned, and cleaning was performed by spraying a mixed cleaning agent onto the copper test panel from the spray can.

Before and after the washing, the amount of oil (residual oil after washing) was quantified using an oil content meter (manufactured by HORIBA, Ltd., OCMA220), and the cleaning performance was evaluated by observing the appearance. . Table 21 shows the quantitative results and the appearance observation results of these oil components.

As is clear from Table 21, it was confirmed that a good cleaning property was obtained by spraying a mixed detergent of a low molecular weight siloxane compound, a fluorocarbon and isopropanol from a spray can. In addition, after the spray can filled with the mixed detergent was stored for a long time, the performance of the mixed detergent was evaluated.
It was confirmed that both did not change.

As described above, according to the fifth cleaning method, a non-flammable or flame-retardant mixed cleaning agent is added to a low-molecular siloxane compound by mixing it with a fluorocarbon in a closed container for storage and use. Therefore, the non-flammability or flame retardant properties of the mixed detergent and the cleaning performance are not impaired, so that the mixed detergent containing the low molecular weight siloxane compound can be used safely and effectively for a long period of time.

Example 109 and Comparative Examples 17 and 18 Next, an example of the sixth cleaning method will be described together with the cleaning agent of the present invention.

The glass lens after polishing and washing was immersed in trifluoroethanol to remove attached pure water. After this, 5mm / mi
The lens was dried while being lifted at a lifting speed of n. After the draining and drying, the moisture removal rate was determined according to the following method, and the dried state (surface state and presence or absence of dried spots) was visually observed and observed with a scanning electron microscope to perform an appearance inspection after drying. Table 22 shows the evaluation results.

To determine the water removal rate, first, the lens after draining and drying with trifluoroethanol is dissolved in dehydrated ethanol to dissolve the remaining water, and this water is quantified (Ag) by the Karl Fischer method. Similarly, the water content of the lens that does not perform the determination (Bg),
From these, it was determined according to the following equation.

Water removal rate (%) = {(BA) / B} × 100 Further, as a comparative example with the present invention, CFC113 / surfactant system was used for the same drainage and drying target (glass lens) as in Example 1. (0.5 parts by weight of nonionic surfactant) and draining with CFC113 (Comparative Example 17), and
Draining and drying by IPA (Comparative Example 18) was performed. afterwards,
In the same manner as in Example 109, the calculation of the water removal rate and the appearance inspection after drying were performed. Table 22 shows the results.

Example 110 and Comparative Examples 19 and 20 A sixth cleaning method will be described together with a fifth cleaning apparatus.

First, an apparatus having a configuration shown in FIG. 1 was prepared as a drainer / dryer according to one embodiment of the present invention. The draining / drying apparatus shown in FIG. 1 includes a washing step A having two washing tanks 101 and 101, and a draining / drying liquid 10 comprising trifluoroethanol.
2 is accommodated, and trifluoroethanol 102 is
Is heated and vaporized to obtain trifluoroethanol 102
And a draining / drying step B having a draining / drying tank 104 for generating steam 102a. The drainage drying liquid 102 in the draining drying tank 104 is sent to the still 105 every hour, where the water is removed by a distillation operation to regenerate the water, and then sent to the draining drying tank 104 as steam 102a. Used.
In the draining / drying apparatus shown in FIG. 1, water replacement and drying are performed by the steam of the draining / drying liquid 102 made of trifluoroethanol.

Using the drainer / dryer shown in FIG. 1 described above, the glass filter (10 sheets / basket) after chrome plating, which is the target for drainage / drying 106, is washed with water A and drained and dried B.
Was repeated 100 times. In the same manner as in Example 109, the 100th drained and dried product was subjected to the calculation of the water removal rate and the appearance inspection after drying. Table 23 shows the evaluation results.

Further, as a comparative example with the present invention, except that a mixed solution of perfluorohexane and trifluoroethanol was used as the draining drying liquid, the draining drying apparatus shown in FIG. Wash and drain the glass filter after the same chrome plating treatment.
This was performed 0 times consecutively (Comparative Example 19). Further, in the same manner except that IPA was used as the draining drying liquid, washing and draining and drying of the glass filter after the chromium plating treatment were continuously performed 100 times (Comparative Example 20). In the same manner, the water removal rate was calculated and the appearance of the dried product was inspected in the same manner as in Example 109 for the dried product after the 100th drainage. Table 23 shows the evaluation results.

As is clear from Table 23, according to Example 110 in which trifluoroethanol was used as the draining liquid, the water removal rate and the drying quality were both excellent after 100 times of drying and drying, whereas perfluorohexane was used. In Comparative Example 19 using a mixture of trifluoroethanol and trifluoroethanol, not only the drying quality was reduced, but also the water removal rate was reduced, and in Comparative Example 20 using IPA, the occurrence of dry spots was observed. A decrease in drying quality was observed. This is considered to be because water could not be removed from the IPA, water accumulated in the IPA, and high heat of evaporation of the IPA.

Examples 111 to 114 and Comparative Examples 21 and 22 As a drainer / dryer according to another embodiment of the present invention, an apparatus shown in FIG. 2 was prepared. The draining and drying apparatus shown in FIG. 2 includes a washing step A having two washing tanks 201, 201,
A draining step having two immersion draining tanks 207 and 207 containing a draining drying liquid 202 made of trifluoroethanol, and immersing the object 206 to be dried in the draining drying liquid 202 for draining (water replacement). C and a draining drying liquid 202 made of trifluoroethanol, and a steam drying step having a steam drying tank 208 for generating a vapor 202a of the trifluoroethanol 202 by heating and evaporating the trifluoroethanol 202 with the heater 203. D. Draining drying liquid 202 in immersion draining tank 207 and steam drying tank 208
Are continuously sent to the still 205, where the water is removed and regenerated by the distillation operation.
It is sent into 208 and used as steam 202a.

Using the draining / drying apparatus shown in FIG. 2, washing A, draining C, and steam drying D of the polished polygon mirror (30 pieces / basket) were continuously performed 300 times. In addition,
The steam drying time was 5 minutes. In the same manner as in Example 109, the water-dried product after the 300th drying was subjected to the calculation of the water removal rate and the appearance inspection after the drying. Further, in FIG. 2, trifluoroethanol is steam-dried C and hydrofluoroether is dried D (Example 112), and a mixture of trifluoroethanol and hydrofluoroether is steam-dried D and hydrofluoroether is steam-dried D (Example 112). Example
113), trifluoroethanol was used for draining C and steam drying was used for D, and hexamethyldisiloxane was used for D (Example 114). Draining and drying were performed in the same manner as in Example 109. Table 24 shows the evaluation results.

As a comparative example with the present invention, CFC1 was used as a drainage liquid.
13 / surfactant system (0.5 parts by weight of nonionic surfactant) and the same procedure as in Example 111 was carried out except that CFC113 was used as the steam drying liquid. Washing, draining and steam drying of the same polygon mirror after polishing were continuously performed 300 times. It was repeatedly drained and dried (Comparative Example 21). Further, in the same manner as above except that IPA was used as a draining drying liquid, washing, draining and steam drying of the polished polygon mirror were continuously performed 300 times (Comparative Example 22). Similarly for these, 30
In the same manner as in Example 1, the 0th drained and dried product was subjected to calculation of a water removal rate and an appearance inspection after drying. Table 24 shows the evaluation results.

As is clear from Table 24, according to Example 111 using trifluoroethanol as the draining liquid and the drying liquid, the water removal rate and the drying quality were both excellent after 300 times of drying and drying, In Comparative Example 22 using IPA, a decrease in drying quality due to generation of dry spots was visually observed.

As in Example 114, when hexamethyldisiloxane is used for steam drying D, the hexamethyldisiloxane has a co-melting point at which the two phases can be completely compatible with trifluoroethanol at a temperature higher than trifluoroethanol. In order to separate at room temperature, the drainage drying liquid 202 in the steam drying tank 208 is cooled in another tank, and trifluoroethanol is separated from hexamethyldisiloxane by specific gravity separation, and trifluoroethanol is recovered. If necessary, water may be removed by the still 205 to recycle. The hexamethyldisiloxane separated at the same time can be reused as it is or, if necessary, purified by a still. For separation of trifluoroethanol and hexamethyldisiloxane, a filter may be used in addition to the specific gravity separation. Of course, separation by distillation is preferable. As described above, the draining dry liquid (trifluoroethanol) in the immersion draining tank 207 is reused after removing water with the still 205, and the draining dry liquid (hexamethyldisiloxane) in the steam drying tank 208 is used in this tank. Alternatively, the configuration may be such that trifluoroethanol is separated by specific gravity in another tank and reused, and the separated trifluoroethanol is sent to the immersion draining tank 207 or the still 205.

As described above, according to the draining / drying method and the draining / drying apparatus according to the sixth cleaning method, good draining / drying properties can be obtained, and water can be easily separated by, for example, a distillation operation. It is possible to achieve both good drainage drying quality without stains and reduction in drainage drying cost. Therefore, it is possible to provide the draining drying which can achieve a drying speed and a drying quality comparable to or higher than the draining drying using a CFC-based or chlorine-based solvent.

Example 115, Comparative Examples 23 to 27 A cleaning agent containing the azeotropic or pseudo-azeotropic composition of the present invention as an active ingredient and its detergency will be described.

First, commercially available hexamethyldisiloxane TSF451-0.65
The (99%) product name, Toshiba Silicone Co., Ltd. (purity), tert-butanol and C ₆ F ₁₄ at perfluorocarbon PF-5060 (trade name, manufactured by Sumitomo 3M Co., Ltd.) represented by,
Put into a distillation flask at a volume ratio of 1: 1: 1 and add 30 theoretical plates.
Distillation was carried out under normal pressure using a rectification column of the stage. This distillation gave an azeotropic distillate at 321-326K. The composition comprising this azeotropic distillate was used as a detergent.

The azeotropic distillate was analyzed by gas chromatography, and the actual blending ratio was determined from the obtained peak area ratio. As a result, 5.7% by weight of hexamethyldisiloxane was obtained.
t- butanol 5.0 wt%, C ₆ F ₁₄ was 89.3 wt%. The gas chromatography was performed under the following conditions.

(Gas chromatography conditions) Apparatus: Shimadzu GD-14A (TC-D), Column: SUS
2m x 3mmφ (GL Science Chromosolve Co., Ltd. WAWDMC
S, mesh 60/80), filler: Silicone SE-30 10%, injection temperature: 523K, TC-D temperature: 523K, initial temperature: 323K, initial holding temperature: 0min, heating rate: 10K / min, final Temperature: 523K, final retention time: 0min, CURRENT: 100mA, FR CR
He: 40 ml, ATTENUATION: 64 The method of measuring the mixing ratio from the peak area ratio of gas chromatography will be described in detail below.

3 and perfluorocarbon which the composition is represented by the hexamethyldisiloxane and tert- butanol C ₆ F ₁₄
When it is an azeotrope composed of components, n-hexane is selected as a standard material for gas chromatography analysis, and a three-component mixture 10.3
A mixture of 33 g and 2.0704 g of n-hexane was analyzed by gas chromatography. By analysis, the peak area ratio of each component was as follows: hexamethyldisiloxane: 7.635% tert-butanol: 7.795% perfluorocarbon: 49.848% n-hexane: 34.322%. When the obtained peak area is corrected by total 100%, hexamethyldisiloxane: 7.67% tert-butanol: 7.83% perfluorocarbon: 50.04% n-hexane: 34.46%

Next, the mixing ratio was changed for each component of the three-component mixture and the standard component, n-hexane, and the mixing ratio (% by weight (wt%)) was determined by performing gas chromatography analysis.
The relationship with the peak area (%) (calibration curve) was examined. FIG. 3 shows a calibration curve of each component. Note that the calibration curve of isopropyl acetate relates to Example 116.

In the case of hexamethylcidyloxane and n-hexane, the peak area (%) is hexamethylenedisiloxane: n-hexane = 7.67: 34.46. Therefore, the peak area (%) of n-hexane in these two components is (34.46). /(34.46 + 7.67)) x 100 = 81.48%. When this value is introduced into the calibration curve of hexamethyl thidioxane shown in FIG. 3, the actual blending amount is 78.0 wt%, so the amount x (g) of hexamethyl thidioxane is 2.0704 / (2.0704 + x) × From 100 = 78.0, x becomes 0.5839 g, so that the blending ratio (% by weight) of hexamethylsidioxane is (0.5839 / 10.333) × 100 = 5.7 wt%. By the same method, the mixing ratio of tert-butanol was 5.0 wt%, and the mixing ratio of perfluorocarbon was 89.3 w
t%.

In addition, all the compositions in this specification show the mixture ratio which analyzed the mixed composition by the gas chromatography on the said conditions and quantified from the peak area of the obtained component.

Using the cleaning agent thus obtained, copper metal parts
20P (envelope parts) machine oil G-6040 (trade name,
What was immersed in Nippon Kogyo Oil) was washed as an object to be washed, and the condition after the washing was evaluated. The washing was performed according to the following procedure. That is, first, the object to be cleaned is washed at about 303K while irradiating ultrasonic waves in the first cleaning tank containing the cleaning agent, and then at room temperature in the second cleaning tank containing the cleaning agent having the same composition. The cleaning and rinsing were performed again while irradiating ultrasonic waves in the above, and finally the object to be cleaned was dried by exposing the cleaning agent having the same composition to the boiling generated by heating and boiling in the third cleaning tank.

In the above step, the finish after washing is visually observed and observed with a microscope, and the sample after washing is optionally added to
The oil was sampled and the remaining oil was extracted with 300 ml of carbon tetrachloride and quantified using a Horiba oil concentration meter OCMA-220. In addition, one clean metal part was immersed in a 313K cleaning agent, taken out and air-dried, and the time until the part was completely dried was measured. Further, the flash point of the detergent was measured by the Cleveland open method. Table 25 shows the measurement results together with the ozone depletion potential.

Further, as a comparative example with the present invention, a detergent containing only tert-butanol (Comparative Example 23), hexamethyl thidioxane TS
Using the detergent of F451-0.65 alone (Comparative Example 24), the detergent of perfluorocarbon PF-5060 alone (Comparative Example 25), and the detergent consisting of 1,1,1-trichloroethane (Comparative Example 26), Washing was carried out in the same manner as in the examples, and the washability was evaluated, and the drying time and flash point were measured in the same manner. In addition, the residual oil content in the case of not washing (Comparative Example 27) was measured. The results are shown in Table 25.

As is clear from the measurement results shown in Table 25,
It can be seen that the cleaning agent of No. 115 is excellent in detergency (degreasing property) and shows excellent drying property equal to or more than 1,1,1-trichloroethane. In addition, the flammability is tert-
The flash point was higher than that of butanol or hexamethyldisiloxane, and it was confirmed that flame retardancy could be achieved.

Example 116, Comparative Example 28 First, commercially available hexamethyldisiloxane TSF451-0.65
(Trade name, Toshiba Silicone Co., Ltd. (purity: 99% or higher)), perfluorocarbon represented by isopropyl acetate and C ₆ F ₁₄ PF-5060 (trade name, Sumitomo 3M Co., Ltd.),
Put into a distillation flask at a volume ratio of 1: 1: 1 and add 30 theoretical plates.
Distillation was carried out under a vapor pressure using a rectification column of a stage. This distillation gave an azeotropic distillate at 323-328K. The composition comprising this azeotropic distillate was used as a detergent.

The azeotropic distillate was analyzed by gas chromatography, and the actual compounding ratio was determined from the obtained peak area ratio. Hexamethyldisiloxane was 4.9% by weight, isopropyl acetate was 5.3% by weight, and C ₆ F ₁₄ was 89.8% by weight. The conditions for gas chromatography and the quantification method are as described above.

Using the cleaning agent thus obtained, copper metal parts
20P (envelope parts) machine oil G-6040 (trade name,
Washing was carried out using the material immersed in Nippon Kogyo Oil Co., Ltd. as an object to be washed, and the state after washing was evaluated. The washing was carried out under the same conditions as in Example 115. The finish after the washing was visually observed and observed with a microscope, and the residual oil content after the washing was measured under the same conditions as in Example 115. Further, in the same manner as in Example 115, the measurement of the drying time and the measurement of the flash point by the Cleveland open system were performed. Table 26 shows the measurement results together with the ozone depletion potential.

Further, as a comparative example with the present invention, cleaning was carried out in the same manner as in the above example using isopropyl acetate alone as a cleaning agent (Comparative Example 28), and the cleaning property was evaluated. The points were measured. The table also shows the results.
See Figure 26. In Table 26, the results of Comparative Examples 24 to 27 are also shown for comparison.

As is clear from the measurement results shown in Table 26,
It can be seen that the cleaning agent according to 116 is excellent in detergency (degreasing property) and also exhibits excellent drying properties equal to or more than 1,1,1-trichloroethane. In addition, with regard to flammability, the flash point was higher than that of isopropyl acetate or hexamethyl thidioxane, and it was confirmed that flame retardancy could be achieved.

As described above, the azeotropic composition and the pseudo-azeotropic composition of the present invention do not destroy the ozone layer and exhibit high detergency and excellent drying characteristics for various soil components.

Example 117 Distillation was carried out under the same conditions and method as in Example 115, except that the perfluorocarbon was replaced with perfluorocarbon PF-5070 represented by C ₆ F ₁₆ (trade name, manufactured by Sumitomo 3M). This gave an azeotropic distillate at 337-344K. The composition comprising this azeotropic distillate was used as a detergent.

Under the same conditions and under the same conditions as in Example 115, the actual mixing ratio of the azeotropic fraction was determined. Hexamethyldisiloxane is 1
0.6 wt%, tert-butanol 11.8 wt%, C ₇ F ₁₆ 7
7.6% by weight.

Hereinafter, a method of quantifying the blending ratio from the peak area ratio of gas chromatography will be described in detail.

3 and perfluorocarbon which the composition is represented by the hexamethyldisiloxane and tert- butanol C ₇ F ₁₆
When it is an azeotrope composed of components, n-hexane is selected as a standard substance for gas chromatography analysis, and a ternary mixed solution 10.0
A mixture of 084 g and 2.0074 g of n-hexane was analyzed by gas chromatography. By analysis, the peak area ratio of each component was as follows: hexamethyldisiloxane: 12.408% tert-butanol: 15.795% perfluorocarbon: 41.628% n-hexane: 30.101% When the obtained peak area is corrected by total 100%, hexamethyldisiloxane: 12.42% tert-butanol: 15.81% perfluorocarbon: 41.66% n-hexane: 30.12%

Next, using the calibration curve shown in FIG. 3, the respective proportions were quantified in the same manner as in Example 115, and the above results were obtained.

Using the cleaning agent thus obtained, washing, rinsing, drying and evaluation were performed under the same conditions and methods as in Example 115. The results are shown in Table 27 together with the ozone depletion potential. Table 27 also shows the comparative examples obtained in Example 115.

As is clear from the measurement results shown in Table 27,
It can be seen that the cleaning agent 117 has excellent detergency (degreasing property) and exhibits excellent drying properties equal to or higher than that of 1,1,1-trichloroethane. In addition, the flammability is tert-
The flash point was higher than that of butanol and hexamethyl thidioxane, and it was confirmed that flame retardancy could be achieved.

Example 118 First, commercially available hexamethylcidyloxane TSF451-0.65
(Trade name, Toshiba Silicone Co., Ltd. (purity: 99% or higher)), perfluorocarbons PF-5070 represented by isopropyl acetate and C ₇ F ₁₆ (trade name, manufactured by Sumitomo 3M Ltd.),
Put into a distillation flask at a volume ratio of 1: 1: 1 and add 30 theoretical plates.
Distillation was carried out under a vapor pressure using a rectification column of a stage. This distillation gave an azeotropic distillate at 337-345K. The composition comprising this azeotropic distillate was used as a detergent.

The azeotropic distillate was analyzed by gas chromatography, and the actual compounding ratio was determined from the obtained peak area ratio. Hexamethyldisiloxane was 10.5% by weight, isopropyl acetate was 10.7% by weight, and C ₇ F ₁₆ was It was 78.8% by weight. The conditions for gas chromatography are as described above.

Using the cleaning agent thus obtained, copper metal parts
20P (envelope parts) machine oil G-6040 (trade name,
Washing was carried out using the material immersed in Nippon Kogyo Oil Co., Ltd. as an object to be washed, and the state after washing was evaluated. The washing was carried out under the same conditions as in Example 115. The finish after the washing was visually observed and observed with a microscope, and the residual oil content after the washing was measured under the same conditions as in Example 115. Further, in the same manner as in Example 115, the measurement of the drying time and the measurement of the flash point by the Cleveland open system were performed. Table 28 shows the measurement results together with the ozone depletion potential.

 Table 28 also shows the results of Comparative Examples with the present invention.

As is clear from the measurement results shown in Table 28,
It can be seen that the cleaning agent No. 118 is excellent in detergency (degreasing property) and shows excellent drying property equal to or more than 1,1,1-trichloroethane. In addition, with regard to flammability, the flash point was higher than that of isopropyl acetate or hexamethyl thidioxane, and it was confirmed that flame retardancy could be achieved.

As described above, the azeotropic composition and the pseudo-azeotropic composition of the present invention do not destroy the ozone layer and exhibit high detergency and excellent drying characteristics for various soil components.

Example 119, Comparative Examples 29 to 33 Example 115 except that perfluorocarbon was replaced with perfluoromorpholine (trade name: PF-5052, manufactured by Sumitomo 3M).
Distillation was carried out using the same composition as in Example 115 and under the same conditions and method as in Example 115, and an azeotropic distillate was obtained at 313 to 322K. The composition comprising this azeotropic distillate was used as a detergent.

Under the same conditions and under the same conditions as in Example 115, the actual mixing ratio of the azeotropic fraction was determined.

Hexamethyldisiloxane was 5.4% by weight, tert-butanol was 5.2% by weight, and perfluoromorpholine was 89.4% by weight.

Apply spindle oil on a steel plate and heat in a 150 ° C heating furnace for 48 hours.
A test piece was prepared by baking for a period of time and used as an object to be cleaned.
Cleaning (ultrasonic cleaning) of the oils and fats attached to the test piece was performed using the above-described cleaning agent, and evaluation was performed after the cleaning. As a cleaning method, the cleaning composition is filled in a first tank, the object to be cleaned is washed at about 30 ° C. while irradiating ultrasonic waves, and then the cleaning is performed at room temperature in a second cleaning tank containing a cleaning agent having the same composition. Washing / rinsing was performed again while irradiating a sound wave. Finally, the cleaning agent having the same composition was heated and boiled in the third cleaning bath, and the object to be cleaned was exposed to steam generated and dried. The finish after washing was observed with a microscope, and the amount of residual oil was also measured. The amount of residual oil was determined by extracting the remaining oil from the washed sample with 300 ml of carbon tetrachloride for 15 minutes and then using a Horiba oil concentration meter OCMA-
Quantification using 220. In addition, as a comparative example, cleaning and drying were performed by the same procedure using only the components of the cleaning agent, and comparative evaluation was performed. The flash point of each cleaning agent was measured by a Cleveland open system. The results are shown in Table 29.

From the results in Table 29, the cleaning agent according to Example 119 has no residual in appearance after cleaning, has excellent drying properties, has a very small residual oil content, is nonflammable, and has no destruction of the ozone layer. It can be seen that it is.

Example 120, Comparative Example 34 Using the same composition as in Example 119 except that tert-butanol was replaced with isopropyl acetate, distillation was performed under the same conditions and method as in Example 119, and an azeotropic distillate was obtained at 315 to 322K. Obtained. The composition comprising this azeotropic distillate was used as a detergent.

Under the same conditions and under the same conditions as in Example 115, the actual mixing ratio of the azeotropic fraction was determined. Hexamethyldisiloxane is 3.
7% by weight, isopropyl acetate was 4.8% by weight, and perfluoromorpholine was 91.5% by weight.

Using the obtained detergent, the detergency was evaluated under the same conditions and method as in Example 119. The results are shown in Table 30.

From the results in Table 30, the cleaning agent according to Example 120 has no residual in appearance after cleaning, has excellent drying properties, has a very small residual oil content, is nonflammable, and has no destruction of the ozone layer. It can be seen that it is.

The cleaning agent comprising the azeotropic composition of the present invention does not destroy the ozone layer, is nonflammable, has excellent cleaning power, has a small composition change due to evaporation during use, and has an excellent drying speed.
It exhibits excellent effects when used as a cleaning agent.

Example 121, Comparative Examples 35 to 38 First, hexamethyldisiloxane having a gas chroma purity of 99.5% and tert-butanol having a gas chroma purity of 99.5% were weight ratio.
The mixture was mixed at a ratio of 1: 1. 200 g of this mixture was placed in a distillation flask, and distillation was performed under normal pressure using a rectification column having 30 theoretical plates. This distillation gave an azeotropic distillate at 350-355K. The composition comprising this azeotropic distillate was used as a detergent.

The azeotropic distillate was analyzed by gas chromatography, and the actual blending ratio was determined from the obtained peak area ratio.
-Butanol was 53% by weight. The conditions for gas chromatography were the same as in Example 115.

Table 31 shows the surface tension (298 K) and KB value of each of the detergent according to the above Example 121, its starting components, hexamethyldisiloxane and tert-butanol.

As comparative examples with the present invention, a detergent using trichloroethane (Comparative Example 35), a detergent using isopropyl alcohol (Comparative Example 36), a detergent using methanol (Comparative Example 37), and ethanol were used. Cleaning agent (Comparative Example 38)
Were prepared respectively.

Using the cleaning agents of Example 121 and Comparative Examples 35 to 38 described above, the cleaning properties, drying properties, and the like were evaluated under the following conditions.

[Cleaning evaluation 1] Glass lens, polycarbonate (P
C) and aluminum are prepared, and these are stained with a centering oil for the glass lens and polycarbonate,
Aluminum was coated with a cutting oil and washed with the following procedure. First, resin was applied while irradiating ultrasonic waves in the first cleaning tank containing the cleaning agent according to Example 121, and then degreased again while irradiating ultrasonic waves in the second cleaning tank containing the cleaning agent having the same composition. After rinsing while irradiating ultrasonic waves in a third cleaning tank containing a cleaning agent of the same composition, drying was performed with warm air of 323K or less. Further, the cleaning agents of Comparative Example 35 and Comparative Example 36 were similarly cleaned.

In order to evaluate the finished state after the above-mentioned washing step, the appearance was observed and the contact angles before dirt application and after washing were measured. Table 32 shows the results.

As is clear from Table 32, it can be seen that the cleaning agent of Example 121 provides better results than the cleaning using the conventional trichloroethane (Comparative Example 35) or isopropyl alcohol (Comparative Example 36).

[Cleaning evaluation 2] Spindle oil was applied on a steel plate and baked in a heating furnace at 423K for 48 hours to prepare a test piece, which was used as an object to be cleaned. This test piece was washed by the following procedure. First, after cleaning at room temperature while irradiating ultrasonic waves in the first cleaning tank containing the cleaning agent according to Example 121, room temperature is performed while irradiating ultrasonic waves in the second cleaning tank containing the cleaning agent having the same composition. Rinsing, and finally a third cleaning agent containing the same cleaning agent
In the cleaning tank, the object to be cleaned was dried by exposing the cleaning agent to steam generated by heating and boiling the cleaning agent. Further, the cleaning agents of Comparative Example 37 and Comparative Example 38 were similarly cleaned.

In order to evaluate the finished state after the above-mentioned washing step, the appearance was observed and the amount of residual oil was measured. The residual oil content is
Extract the residual oil with 300 ml of carbon tetrachloride after washing,
This was quantified using a Horiba oil concentration meter OCMA-220. Table 33 shows the results.

[Cleaning evaluation 3] Ten glass plates of 70 × 70 × 1 mm were put in a net basket, and these were washed with a detergent composed of 5% by weight of sodium laurate, 5% by weight of polyoxyethylene octylphenyl ether and 90% by weight of water. After that, they were rinsed with tap water and then with pure water. Cleaning agent of Example 121, Comparative Example 3
Using 1000 ml of the cleaning agent of Comparative Example 38 and 1000 ml of the cleaning agent of Comparative Example 38, the rinsed glass plate was drained and washed, then pulled up from each cleaning agent, and air-dried at room temperature. When 100 pieces of the above glass plates were drained and washed, observation of each detergent, measurement of the amount of water dissolved in each detergent, and observation of the washing quality (appearance) of the glass plate were performed. In addition,
The water content was measured by a Karl Fischer moisture meter. Table 34 shows the results.

As is clear from Table 34, the cleaning agent according to Example 121 has a small amount of water mixed therein, which can prevent the occurrence of spots.

Example 122 First, hexamethyldisiloxane having a gas chromatography purity of 99.5% and isopropyl acetate having a gas chromatography purity of 99.5% were mixed in a weight ratio.
The mixture was mixed at a ratio of 1: 1. 200 g of this mixture was placed in a distillation flask, and distillation was performed under normal pressure using a rectification column having 30 theoretical plates. This distillation gave an azeotropic distillate at 353-358K. The composition comprising this azeotropic component was used as a detergent.

The azeotropic distillate was analyzed by gas chromatography, and the actual blending ratio was determined from the obtained peak area ratio. As a result, hexamethyldisiloxane was 43% by weight and isopropyl acetate was 57% by weight. The conditions for gas chromatography are as described above.

Table 35 shows the surface tension (298K) and the KB value of each of the detergent according to Example 122, hexamethyldisiloxane and isopropyl acetate which are the starting components thereof.

Using the cleaning agent of Example 122 described above, the cleaning property, the drying property, and the like were evaluated in the same manner as in Example 121.

[Cleaning evaluation 1] Example 1 was performed under the same conditions as in cleaning evaluation 1 in Example 121.
Glass lenses, polycarbonate (PC), and aluminum were cleaned using 22 cleaning agents, and their finished states were evaluated. Table 36 shows the results of the external appearance observation and the results of the measurement of the contact angles before and after the dirt application and cleaning. Table 36 also shows the results of the cleaning agents of Comparative Examples 35 and 36 for reference.

As is clear from Table 36, it can be seen that the cleaning agent of Example 122 provides better results than the cleaning using the conventional trichloroethane (Comparative Example 35) or isopropyl alcohol (Comparative Example 36).

[Cleaning evaluation 2] Example 1 was performed under the same conditions as in cleaning evaluation 2 in Example 121.
Specimens (spindle oil applied to a steel plate and baked) were cleaned using 22 cleaning agents, and their finished state was evaluated. As a result, Table 37 shows the results of appearance observation and the results of measurement of residual oil content. In Table 37, for reference,
The results of the cleaning agents of Comparative Examples 37 and 38 are also shown.

[Cleaning evaluation 3] Example 1 was performed under the same conditions as in cleaning evaluation 3 in Example 121.
Table 38 shows the state of the cleaning agent, the measurement result of the amount of water in each cleaning agent, and the observation result of the cleaning quality (appearance) of the glass plate. . Table 38 also shows the results of the cleaning agents of Comparative Examples 37 and 38 for reference.

As is clear from Table 38, the cleaning agent according to Example 122 has a small amount of water mixed therein, which can prevent the occurrence of stains.

As described above, the azeotropic composition and the pseudo-azeotropic composition of the present invention do not cause destruction of the ozone layer or deterioration of plastics, and exhibit high cleaning properties and excellent cleaning quality against various stains. In addition, the drying speed is excellent, the composition change during use or regeneration can be suppressed as much as possible, and furthermore, the mixing of moisture can be suppressed. Therefore, according to the cleaning agent of the present invention using such an azeotropic composition or a pseudo-azeotropic composition, degreasing cleaning, draining cleaning, steam cleaning and the like can be performed without destruction of the ozone layer and deterioration of plastics and the like. Can be satisfactorily carried out without generating stains, rust, etc., and furthermore, washing to drying can be carried out with one liquid. In addition, since the composition change can be suppressed as much as possible, the liquid can be easily managed, and can be easily collected and reused.

Embodiment 123 Hereinafter, an embodiment according to the first cleaning apparatus of the present invention will be described with reference to the drawings.

FIG. 5 is a diagram showing a configuration of a cleaning apparatus according to one embodiment of the present invention. The main part (apparatus main body) of the cleaning apparatus shown in FIG. 1 is roughly composed of a cleaning step A, a rinsing step B, and a drying step C. In addition, a distillation regeneration mechanism D, a composition control mechanism E, a preventive safety mechanism F, and a fire extinguishing mechanism G are attached. In addition, the step of handling the flammable solvent, that is, the cleaning step A, the rinsing step B, and the drying step C are configured to be covered with the housing 502, except for a part for taking in and out the object 501 to be cleaned. Sealing doors 503 are provided at portions where the object 501 to be cleaned is taken in and out, respectively, so that the cleaning step A, the rinsing step B, and the drying step C can be arranged in the closed part.

The cleaning tank 511 of the cleaning step A is filled with a predetermined amount of a cleaning agent 512 made of a hydrocarbon-based solvent, and by immersing the cleaning object 501 in the hydrocarbon-based cleaning agent 512, Adhered dirt components are removed. The number of cleaning tanks 511 in the cleaning step A is set according to the type and amount of dirt, as well as the cleaning time and cleaning quality.
It may be a single tank or a multi-tank. The cleaning apparatus of this embodiment has two cleaning tanks 511 and 511, and a naphthesol M is used as a hydrocarbon-based cleaning agent 512.
(Trade name, manufactured by Nippon Petrochemical Co., Ltd.).
An ultrasonic generator 513 is provided at the bottom of the cleaning tank 511 as needed.

In the rinsing tank 521 of the rinsing step B, for example, hexamethyldisiloxane, which is a low molecular siloxane compound, and perfluorocarbon PF, which is an inert fluorocarbon, are added.
A predetermined amount of a mixed cleaning agent 522 for rinsing mixed with 5060 (boiling point = 329 K; trade name, manufactured by Sumitomo 3M) is filled. In this example, hexamethyldisiloxane 30 having a flash point is used.
A mixed cleaning agent 522 for rinsing, in which 70 parts by weight of perfluorocarbon PF5060 is blended with respect to parts by weight, is used.By using perfluorocarbon as such a mixed cleaning agent 522, it is made nonflammable or flame-retardant. Nature can be secured.

The cleaning object 501 after the cleaning is immersed in the mixed cleaning agent 522 for rinsing as described above, and the cleaning component adhering to the cleaning object 501 is removed. The number of the rinsing tanks 521 in the rinsing step B is set according to the cleaning time and the cleaning quality as in the cleaning step A, and may be a single tank or a multiple tank. The cleaning apparatus of this embodiment has two rinsing tanks 521, 521.
21 are connected by an overflow pipe 524. If necessary, an ultrasonic generator 523 may be provided at the bottom of the rinsing tank 521.
Is installed.

The steam cleaning tank 531 in the drying step C is filled with a steam cleaning mixed cleaning agent 532 having the same composition as the above-mentioned rinse mixed cleaning agent.
The vaporization 532a is generated by evaporating the temperature of the 32. And the object 50 to be washed after rinsing
1 is exposed to the vapor 532a of the mixed cleaning agent 532 for steam cleaning for a predetermined time, and the vapor 532a of the steam cleaning agent 532 is condensed on the surface of the object 501 to be removed to remove the mixed cleaning agent 522 for rinsing. The heated object 501 to be cleaned is heated,
On the way up from the steam cleaning tank 531, the vapor 532 a is temporarily stopped in a cooling zone provided by a cooling pipe 534 provided to prevent volatilization, and the liquid remaining on the surface of the cleaning object 501 is cooled and completely dried. . In addition, steam cleaning tank 531
Is provided with a liquid level gauge (not shown), which monitors the amount of decrease in the mixed cleaning agent 532 for vapor cleaning due to volatilization or the like. When the amount of the mixed cleaning agent 532 for steam cleaning becomes equal to or less than a predetermined amount, for example, an alarm is issued.

On the upper inner wall surface of the rinsing tank 521 and the steam cleaning tank 531,
As described above, the cooling pipes 534 and 534 are provided, respectively. By cooling and liquefying the vapors of the mixed cleaning agent 522 for rinsing and the mixed cleaning agent 532 for vapor cleaning, these vapors are rinsed by the rinsing tank 521 and the vapor cleaning tank. 531, and furthermore, it is structured to prevent dissipation to the outside of the cleaning device.

The dirt component and the hydrocarbon-based cleaning agent 512 are brought into the mixed cleaning agent 532 for steam cleaning in the steam cleaning tank 531 via the mixed cleaning agent 522 for rinsing attached to the object 501 to be cleaned with the steam drying. Since these accumulate in the steam cleaning tank 531 and have an unfavorable effect on the generation of the steam 532a, they are configured to be sent to the distillation and regeneration mechanism D via the overflow pipe 541 together with the mixed cleaning agent 532 for steam cleaning. ing. The hydrocarbon-based cleaning agent 512 attached to the cleaning object 501 is carried into the rinsing tank 521, and contaminates and accumulates the mixed cleaning agent 522 for rinsing. Therefore, the mixed cleaning agent 522 for rinsing in the rinsing tank 521 is also configured to be sent to the distillation and regeneration mechanism D via the overflow pipe 542.

The distillation regeneration mechanism D includes a rinsing tank 521 and a steam cleaning tank 531.
, A mixed cleaning agent 522 for rinsing and a mixed cleaning agent 532 for steam cleaning, which are contaminated with a dirt component or a hydrocarbon-based cleaning agent 512.
(These are mixed detergents of the same composition)
This is to regenerate by distillation according to 3. The liquid vaporized by the still 543 is sent to the distillation washing tank 531 via the pipe 544,
Used as steam 532a. The residue from the distillation is
It is discharged out of the system through 5.

Further, the mixed cleaning agent 532 for steam cleaning purified by being cooled and condensed by the cooling pipe 534 provided on the upper inner wall surface of the distillation cleaning tank 531 is returned to the downstream rinse tank 521 via the pipe 535. It is configured to be. In this way, the mixed cleaning agent 52 for rinsing purified by cooling and condensing is used.
Rinse tank 521 with mixed cleaning agent 532 for steam cleaning having the same composition as 2
The contamination concentration of the mixed cleaning agent 522 for rinsing in the rinsing tank 521 is kept at a certain level or less. In addition, as described above, since the dirty mixed cleaning agent 522 is sent to the distillation regeneration mechanism D via the overflow pipe 542,
The material balance inside the rinsing tank 521 is kept constant.

The composition control mechanism E keeps the composition of the mixed cleaning agent 522 for rinsing and the mixed cleaning agent 532 for vapor cleaning constant, and includes a composition change monitoring unit, a component adjusting unit, and a control unit. The control unit employs a fuzzy control method as needed.

The composition change monitoring unit as a composition ratio measuring unit includes a temperature sensor 5 for measuring the condensation point of the boiling point of the mixed cleaning agent 532 for steam cleaning.
51, 552, 553 and 554. Boiling point is steam cleaning tank 5
Temperature sensor 551 installed in mixed cleaning agent 532 for steam cleaning in 31, or temperature sensor installed in still 543
Measured by 552. The condensation point is determined by the steam cleaning tank 531.
The temperature is measured by a temperature sensor 553 installed in the steam 532a of the inside or a temperature sensor 554 installed in the steam of the still 543. The cleaning apparatus of this embodiment is configured to measure the temperatures of all four points described above and, when an abnormality is detected at any one of the points, emit a signal and additionally mix the insufficient component.

The component adjustment unit has a tank 555 for storing fluorocarbons (perfluorocarbon PF5060 in this embodiment) and a tank 556 for storing a low-molecular siloxane compound (hexamethyldisiloxane in this embodiment). Valves 557, 558 are provided. Then, based on the signal from the composition change monitoring unit, the control unit based on the signal from the composition change monitoring unit, based on the signal from the composition change monitoring unit, supplies the missing component to the rinsing tank 521. To open and close.

Since the cleaning apparatus of this embodiment has the above-described composition control mechanism E, the composition ratio of the non-flammable or flame-retardant mixed cleaning agents 522 and 532 can be kept constant. Thereby, for example, it is possible to prevent one component from being consumed in a large amount and the composition ratio from being changed, thereby preventing the nonflammable or flame retardant properties from being impaired. Therefore, it becomes possible to always use the flammable low molecular weight siloxane compound completely.

In the above embodiment, the composition change monitoring unit as the composition ratio measuring unit is configured by the temperature sensors 551, 552, 553, and 554 that measure the boiling point and the condensation point of the mixed cleaning agent 532 for steam cleaning.
It can also be constituted by a sensor for measuring the specific gravity and the refractive index of the mixed detergent, and a sensor for measuring the concentration of the low-molecular siloxane compound in the vapor of the mixed detergent based on the infrared absorption of the Si-O bond. . Sensors for measuring the specific gravity and the refractive index of the mixed cleaning agent are, for example, a steam cleaning tank 531 and a rinsing tank 5.
Installed in a pipe 535 that sends the mixed cleaning agent to 21. Also, Si
The infrared absorption sensor based on the -O bond is, for example, a steam cleaning tank 53.
Install in 1. As a result, the same effect as that of the composition change monitoring unit based on the measurement of the boiling point and the condensation point can be obtained.

The preventive safety mechanism F includes a low molecular siloxane compound vapor concentration detection sensor 561, an oxygen concentration detection sensor 562, for example, an inert gas purge mechanism 563 that operates based on the detection results of these sensors 561 and 562, and a liquid leakage detection alarm generation mechanism. It has 564.

From the inert gas purge mechanism 563, an inert nitrogen gas, a fluorocarbon gas, or the like is introduced into the cleaning device to dilute the vapor concentration of the low-molecular siloxane compound and maintain the vapor concentration outside the combustion range. In addition, the inert gas purge mechanism 563 is constantly operated, and the atmosphere including the atmosphere in each of the cleaning tank 511, the rinsing tank 521, and the vapor cleaning tank 531 and the upper atmosphere thereof is pressurized (excess pressure) with the inert gas. It is also possible to operate the cleaning device with.

The preventive safety mechanism F has, in addition to the above-described devices, a not-shown liquid temperature adjustment mechanism, an automatic stop mechanism for overheating, and the like. Those having contacts are subjected to contact air purging, and motors and the like are of explosion-proof specification. Further, when a low-molecular-weight siloxane compound leaks from each of the cleaning tank 511, the rinsing tank 521, and the steam cleaning tank 531, an oil pan 565 is provided so that the liquid does not leak to the floor and spreads. The liquid leaked by the agent 566 is solidified.

The fire extinguishing mechanism G has, for example, a CO ₂ automatic fire extinguisher 571, and a flame sensor 572 and a temperature sensor 573 for driving the CO ₂ automatic fire extinguisher 571 are arranged in the cleaning device. When a fire is detected by the flame sensor 572 and the temperature sensor 573, the CO ₂ extinguishing agent is injected from each fire extinguishing nozzle 571a of the automatic fire extinguisher 571. In addition, with the operation of the automatic fire extinguisher 571, the exhaust duct 504 is stopped, and the damper 574 and the sealing door 503 in the duct 504 are configured to automatically close. Prevents intrusion into the device.

The preventive safety mechanism F and the fire extinguishing mechanism G described above prevent the fire of the low-molecular-weight siloxane compound, and even if a fire occurs, the fire is automatically extinguished. Can be used safely.

The cleaning apparatus of the above embodiment is an example in which a low-molecular siloxane compound is used in the rinsing step B and the drying step C, but the present invention is not limited to this, and the cleaning step A, the rinsing step B, and the drying step The present invention is effective even when a low molecular weight siloxane compound is used in any one step of C. Further, the present invention can be applied to a cleaning apparatus having only a rinsing step and a drying step in which a cleaning step is omitted in the case of light soiling, or a single cleaning apparatus for cleaning, rinsing or drying.

As described above, according to the cleaning apparatus of the present invention, a low molecular weight siloxane compound having a flash point is blended with a fluorocarbon to impart nonflammability or flame retardancy, and the composition ratio is controlled. Thus, the non-flammability or flame retardancy is prevented from being impaired, so that a detergent containing a low molecular weight siloxane compound can be used safely and effectively.

Embodiment 124 Next, embodiments of the second to fourth cleaning apparatuses of the present invention will be described with reference to the drawings.

FIG. 6 is a diagram showing a configuration of a cleaning apparatus according to one embodiment of the present invention. The cleaning apparatus shown in FIG. 1 roughly includes a cleaning step A, a rinsing step B, and a drying step C as main parts. In addition, a preventive safety mechanism D, a fire extinguishing mechanism E, and a distillation regeneration mechanism F are attached. Further, a step of handling a flammable low molecular weight siloxane compound, that is, a cleaning step A
In the rinsing step B and the drying step C, the whole is covered with a housing 610 to form a sealed structure, and double doors 603 and 604 are installed in a portion where the object to be cleaned 602 is taken in and out,
Thus, the process for handling the flammable low-molecular-weight siloxane compound has an airtight structure.

The cleaning tank 611 in the cleaning step A is filled with a predetermined amount of a silicone-based cleaning agent 612 containing a low-molecular-weight siloxane compound, for example, octamethylcyclotetrasiloxane as a main component. By immersing the 602, the dirt component adhering to the cleaning object 602 is removed. Cleaning tank 61 in this cleaning step A
The number of 1 is set according to the type and amount of dirt, and further, the cleaning time and the cleaning quality, and may be a single tank or a multi-tank. If necessary, an ultrasonic generator 613 is installed at the bottom of the cleaning tank 611.

The rinsing tank 621 of the rinsing step B is filled with a predetermined amount of a low-molecular-weight siloxane compound, for example, a silicone-based rinse agent 622 alone of octamethylcyclotetrasiloxane, and the silicone-based rinse agent 622 is used for cleaning after cleaning. By immersing the object 602, the object 602 to be cleaned is immersed.
The detergent component adhering to the surface is removed. The number of the rinsing tanks 621 in the rinsing step B is set according to the cleaning time, the cleaning quality, and the like, similarly to the cleaning step A, and may be a single tank or multiple tanks. If necessary, an ultrasonic generator 623 is installed at the bottom of the rinsing tank 621.

In the cleaning tank 611 and the rinsing tank 621, a liquid temperature sensor 641 is placed in the silicone-based cleaning agent 612 and the silicone-based rinsing cleaning agent 622 as a part of the preventive safety mechanism D, respectively. Then, based on the measurement results of these liquid temperature sensors 641, a silicone-based cleaning agent 612 and a silicone-based rinsing
Is always kept below its flash point. The silicone-based cleaning agent 612 and the silicone-based cleaning agent 622 are circulated by motors 615 and 625 via filters 614 and 624, respectively.

The steam cleaning tank 631 in the drying step C is filled with a steam cleaning agent 632 made of a low-molecular siloxane compound, for example, hexamethyldisiloxane, and is heated and vaporized by the heater 633. The steam cleaner 632 is configured to generate steam 632a. And
The object to be cleaned 602 after rinsing is exposed to the vapor 632a of the vapor cleaning agent 632 for a predetermined time, and the surface of the object to be cleaned 602 is exposed to the vapor cleaning agent 632.
632a of dew condensation and silicone rinse agent 622
Is removed, and the object to be cleaned 602 is heated and dried by the latent heat of condensation.

Cooling pipes 616, 626, and 636 are provided on the upper inner wall surfaces of the cleaning tank 611, the rinsing tank 621, and the steam cleaning tank 631, respectively, to cool and liquefy the vapor of the low-molecular siloxane compound,
The structure is such that this vapor is prevented from dissipating outside the cleaning device.

The preventive safety mechanism D uses an inert fluorocarbon gas, for example, a gas of perfluorocarbon C ₄ F _{10 to} circulate the atmosphere including the atmosphere in each of the cleaning tank 611, the rinsing tank 621, and the steam cleaning tank 631 and the atmosphere above the tank. An inert gas purge mechanism 642 for pressurizing is provided to keep the atmosphere in the apparatus outside the combustion limit of the low-molecular-weight siloxane compound and to block the intrusion of oxygen into the apparatus. Further, with the operation of the inert gas purge mechanism 642, the double doors 603, 604
Are both closed so that the outside atmosphere is shut off to prevent oxygen from entering the device.

Further, the preventive safety mechanism D has a vapor concentration sensor 643 of a low molecular siloxane compound and an oxygen concentration sensor 644, which are connected to a control unit 645 of an inert gas purge mechanism 642. The control unit 645 sounds an alarm when the vapor concentration and the oxygen concentration of the low-molecular siloxane compound are out of the control range, and further increases the amount of purge from the inert gas purge mechanism 642 to reduce the low-molecular siloxane compound. It has a function of, for example, being out of the combustion limit of steam. As a result, the concentration of the vapor concentration of the low-molecular siloxane compound outside the combustion range is maintained in the apparatus.

Such a preventive safety mechanism D makes it possible to completely use the silicone-based cleaning agent 612, the silicone-based rinsing agent 622, and the silicone-based steam cleaning agent 632. In addition, since the low-molecular-weight siloxane compound vapor concentration sensor 643 uses a sensor that measures infrared absorption based on Si-O bonds in the low-molecular-weight siloxane compound,
The vapor concentration of the low-molecular siloxane compound can be detected with high sensitivity, and further safety is ensured.

The preventive safety mechanism D has an overheating automatic stop mechanism, a liquid leakage detection alarm generation mechanism 646, and the like, in addition to the above-described devices. Are provided with a contact air purge, and the motors and the like are of explosion-proof specification. Further, when a low-molecular-weight siloxane compound leaks from each of the cleaning tank 611, the rinsing tank 621, and the steam cleaning tank 631, an oil pan 647 is provided so that the liquid does not leak to the floor and spreads. The liquid leaked by the agent 648 is solidified. Further, non-flammable or non-flammable fluorocarbons can be used as an absorbent for the low molecular weight siloxane compound instead of the oil flocculant 648.

Further, instead of the inert gas purge mechanism 642 in the preventive safety mechanism D, or the inert gas purge mechanism 642
7, a washing tank 611, a rinsing tank 621, and a tank 64 capable of sealing each of the washing tanks 631 as shown in FIG.
With a 9, a lifting mechanism of the sealed vessel 649 is provided, except when loading and unloading the cleaning object 602, fluorocarbons sealed vessel 649 nonflammable or flame-retardant, for example, liquid hydrofluorocarbons C ₅ H ₂ F ₁₀ A structure of dipping in 650 may be adopted. By adopting such a structure, the silicone-based cleaning agent 612, the silicone-based rinsing agent 622, and the silicone-based steam cleaning agent 632 can be used safely, and even if a liquid leak occurs, The molecular siloxane compound is absorbed by the fluorocarbon liquid 650 to ensure safety. Further, by making the upper structure of the fluorocarbon liquid 650 a sealed structure, the safety can be further enhanced.

Further, as shown in FIG. 8, for example, each of the cleaning tank 611, the rinsing tank 621, and the steam cleaning tank 631 has a double structure, and the non-flammable or hard-to-react between the outer tank 651 and each of the tanks 611, 621, 631. A structure in which a filler 652 made of a flammable fluorocarbon is filled may be employed. Thus, even if a liquid leak occurs, the low-molecular siloxane compound is absorbed by the filler 652 made of fluorocarbons, so that safety is ensured.

The fire extinguishing mechanism E has an automatic fire extinguisher 661 that uses a non-combustible or flame-retardant fluorocarbon, for example, a fluoroiodide carbon CF ₂ I ₂ as a fire extinguishing agent. In addition, in order to drive the automatic fire extinguisher 661, a flame sensor 662, a temperature sensor
663 and a pressure sensor 664 are located in the device. Flame sensor 662, when a fire is detected by the temperature sensor 663 and pressure sensor 664, extinguishing agent consisting of fluoro iodide carbon CF ₂ I ₂ from each extinguishing nozzle 661a of the automatic extinguisher 661 is configured to be injected ing. As the fire extinguishing agent, for example, a liquid itself of fluoroiodide carbon CF ₂ I ₂ can be used. In addition, with the operation of the automatic fire extinguisher 661, both the double doors 603 and 604 are closed to shut off the external atmosphere and prevent oxygen from entering the device, thereby reducing the fire extinguishing effect. Even better.

The fire extinguishing mechanism E as described above can effectively extinguish a fire even if a low molecular siloxane compound causes a fire. Therefore, the silicone-based cleaning agent 612, the silicone-based rinsing agent 662, and the silicone-based steam cleaning Agent 632 can be used more safely.

Meanwhile, the silicone rinse agent 622 attached to the cleaning object 602 is carried into the steam cleaning tank 631, and contaminates and accumulates the steam rinse agent 632. Therefore, the steam cleaning tank 631
Is sent to the distillation unit 672 of the distillation and regeneration mechanism F via the pipe 671 to be purified and purified. The silicone-based steam cleaning agent 632 thus regenerated is returned to the steam cleaning tank 631 via the pipe 673. In addition, the dirt and the cleaning agent that have adhered to the cleaning object 602 are separated by distillation and discarded via the pipe 674. Regarding each device of such a distillation regeneration mechanism F,
Safety can be ensured by filling with non-combustible or flame-retardant fluorocarbons.

The cleaning apparatus of the above embodiment is an example in which a low-molecular siloxane compound is used in each of the cleaning step A, the rinsing step B, and the drying step C, but the present invention is not limited to this. The present invention is effective even when a low molecular weight siloxane compound is used in any one of the step A, the rinsing step B and the drying step C. Further, the present invention can be applied to a single washing apparatus of washing, rinsing or drying, and not only washing operation (rocking, stirring, ultrasonic wave, spraying, etc.) but also drying operation (hot air drying, spin-drying). Drying, steam drying, pulling drying, vacuum drying, etc.)
And the low molecular weight siloxane compound can be used completely and efficiently.

As described above, according to the cleaning apparatus of the present invention, it is possible to completely and easily use a low-molecular-weight siloxane compound having a flash point. For example, according to the second cleaning device, the vapor concentration of the low-molecular siloxane compound can be set out of the combustion range with high accuracy, so that safety can be ensured. Further, according to the third cleaning device, it is possible to prevent the generation of heat sources such as electric sparks and to shield the low-molecular siloxane compound from oxygen, so that the cleaning operation can be performed safely. Become. Furthermore, according to the fourth cleaning device, it is possible to effectively extinguish a fire should a fire occur, so that safety can be further improved.

INDUSTRIAL APPLICABILITY As described above, the cleaning agent, the cleaning method, and the cleaning apparatus according to the present invention are alternatives to a CFC-based solvent or a chlorine-based solvent, and do not cause environmental destruction. As a cleaning method and a cleaning apparatus, it is useful for many industrial products such as electronic parts and precision parts.

──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 6-253490 (32) Priority date October 19, 1994 (Oct. 19, 1994) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 6-253491 (32) Priority date October 19, 1994 (Oct. 19, 1994) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 6-253492 (32) Priority date October 19, 1994 (Oct. 19, 1994) (33) Countries claiming priority Japan (JP) (31) Priority claim number Japanese Patent Application Hei 7-84066 ( 32) Priority date April 10, 1995 (April 10, 1995) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 7-108410 (32) Priority date 1995 May 2 (1995.5.2) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 7-108411 (32) Priority date May 2, 1995 (1995. 5.2) (33) Japan (JP) (31) Priority claim number Japanese Patent Application No. 7-108412 (32) Priority date May 2, 1995 (5.2 May 1995) (33) Priority claim country Japan (JP) (72) Inventor Nobuhiro Saito 908-10 Toriyama, Ota City, Gunma Prefecture (72) Inventor Shigeo Yamafuji 878-12-A-205, Higashi Tanaka, Gotemba City, Shizuoka Prefecture (72) Inventor Chiyuki Shimizu 126- Takaramachi, Ota City, Gunma Prefecture 1 (72) Inventor Kazunori Umehara 1-17-24 Shimotakaido, Suginami-ku, Tokyo (56) References JP-A-6-122898 (JP, A) JP-A-1-319592 (JP, A) JP-A-5 JP-A-320693 (JP, A) JP-A-61-149204 (JP, A) JP-A-4-145988 (JP, A) JP-A-6-210103 (JP, A) JP-A-3-2388072 (JP, A) JP-A-2-286794 (JP, A) JP-A-4-130197 (JP, A) JP-A-6-71103 (JP, A) JP-A-2-261900 (JP, A) JP-A-5 140591 (JP, A) JP-A-57-101676 (JP, A) Patent 2763270 (JP, B) 1) JP-B-63-50463 (JP, B2) U.S. Pat. No. 3,498,923 (US, A) West German publication 3739711 (DE, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) B08B 1/00- 11/04 C11D 1/00-1/19 C23G 1/00-5/04 H01L 21/304

Claims (48)

(57) [Claims] 1. A step of cleaning an object to be cleaned with a polar cleaning agent having a solubility parameter of 9 to 14 or a dielectric constant of 4 to 45, and a polar cleaning agent having a solubility parameter of 9 to 14 or a dielectric constant of 4 to 45. C _t F _u OC _v H _{2v + 1} (where t, u, and v represent arbitrary integers) and a mixed detergent with a detergent containing hydrofluoroether represented by the formula: A cleaning method comprising: at least one step selected from a rinsing step and a drying step. 2. A step of washing an object to be washed with a polar detergent having a solubility parameter of 9 to 14 or a dielectric constant of 4 to 45, and a general formula C _t F _u OC _v H _{2v + 1} (where t, u and v represent arbitrary integers) and a cleaning agent containing hydrofluoroether as an active ingredient, comprising at least one step selected from a rinsing step and a drying step of the object to be cleaned. A cleaning method characterized by the above-mentioned. 3. A low molecular weight siloxane compound, a fluorocarbon and a solubility parameter of 9 or more or a dielectric constant of 4 or more.
A cleaning method comprising performing a series of steps of a cleaning step, a rinsing step, and a drying step using a cleaning agent comprising an azeotropic or pseudo-azeotropic composition containing the above-described polar cleaning agent. 4. The cleaning method according to claim 3, wherein the drying step is performed by hot air drying, natural drying, vacuum drying, or steam drying. 5. After draining with a liquid having a compatibility with water, having no azeotropic property with water, and having a heat of evaporation of 100 cal / g or less, or a mixed solvent of the liquid and hydrofluoroether. Drying by steam drying with hydrofluoroether. 6. The method of draining and drying according to claim 5,
47. A draining drying method, comprising drying with a low molecular weight siloxane compound. 7. A cleaning agent comprising a low molecular siloxane compound, a fluorocarbon and a polar cleaning agent having a solubility parameter of 9 or more or a dielectric constant of 4 or more, wherein the compounding amount of the low molecular siloxane compound is 50% by weight. A cleaning agent that performs from washing to drying in one liquid, characterized by the following. 8. The cleaning agent according to claim 7, wherein the cleaning agent containing the fluorocarbons, the low-molecular siloxane compound, and the polar cleaning agent has flame retardancy or nonflammability. Agent. 9. The cleaning agent according to claim 7, wherein the cleaning agent containing the fluorocarbons, the low molecular weight siloxane compound, and the polar cleaning agent is an azeotropic or pseudo-azeotropic composition. Cleaning agent. 10. The cleaning agent according to claim 7, wherein the fluorocarbon is a perfluorocarbon,
A cleaning agent comprising at least one selected from hydrofluorocarbons, hydrochlorofluorocarbons, fluoroiodide carbons, fluoroalcohols, and hydrofluoroethers. 11. The cleaning agent according to claim 7, wherein the low molecular weight siloxane compound has a general formula: (Wherein R is the same or different, substituted or unsubstituted 1
A linear organic polysiloxane and a derivative thereof represented by the following general formula: (Wherein R is the same or different, substituted or unsubstituted 1
A cleaning agent comprising at least one low-molecular-weight polyorganosiloxane selected from the group consisting of a cyclic polyorganosiloxane represented by the following formula: and a derivative thereof. 12. The cleaning agent according to claim 7, wherein the polar cleaning agent comprises alcohols, glycols, phenols, ketones, fatty acids and acid anhydrides, esters, amines, amides, Quaternary ammonium salts, nitriles, morpholines, sulfoxides, sultones, phosphoric acids, and derivatives thereof, N-methyl-2
-A cleaning agent comprising at least one component selected from pyrrolidone. 13. The cleaning agent according to claim 7, wherein the fluorocarbon is the low-molecular siloxane compound.
It is blended in the range of 10 to 10,000 parts by weight for 100 parts by weight,
The polar detergent is contained in the range of 0.1 to 30% by weight based on the total amount of the detergent. 14. The cleaning agent according to claim 7, wherein said fluorocarbon is at least one perfluorocarbon selected from perfluorohexane, perfluoroheptane and perfluoromorpholine, and said low-molecular siloxane compound is hexamethyldisiloxane. Wherein the polar detergent is at least one polar detergent selected from tert-butanol and isopropyl acetate. 15. The cleaning agent according to claim 14, wherein an azeotropic composition or a pseudo-azeotropic composition comprising the perfluorocarbon, the hexamethyldisiloxane, and the polar cleaning agent is contained as an active ingredient. A cleaning agent characterized by the following. 16. The cleaning agent according to claim 14, wherein an azeotropic composition or a pseudo-azeotropic composition comprising said hexamethyldisiloxane and said polar cleaning agent is contained as an active ingredient. Agent. 17. The cleaning agent according to claim 14, wherein at least one perfluorocarbon selected from the group consisting of perfluorohexane and perfluoromorpholine is 60 to 96% by weight, and said hexamethyldisiloxane is 2 to 20% by weight. A cleaning agent comprising a composition in which the polar cleaning agent comprises 2 to 20% by weight as an active ingredient. 18. The cleaning agent according to claim 14, wherein said perfluoromorpholine is a perfluoroalkylmorpholine. 19. The cleaning agent according to claim 18, wherein said perfluoroalkylmorpholine is perfluoro-
A cleaning agent comprising N-methylmorpholine. 20. The cleaning composition according to claim 14, wherein said perfluoroheptane is 50 to 90% by weight, said hexamethyldisiloxane is 5 to 25% by weight, and said polar detergent is 5 to 25% by weight. A cleaning agent characterized by containing as an active ingredient. 21. The cleaning agent according to claim 7, wherein the fluorocarbon and the solubility parameter are 9 or more.
A cleaning agent comprising, as an active ingredient, an azeotropic composition or a pseudo-azeotropic composition comprising a polar cleaning agent having a dielectric constant of 4 or more. 22. The cleaning agent according to claim 7, wherein an azeotropic composition or a pseudo-azeotropic composition comprising the fluorocarbons and the low-molecular siloxane compound is contained as an active ingredient. . 23. The cleaning agent according to claim 22, wherein the fluorocarbons are perfluorocarbons,
Hydrofluorocarbons, hydrochlorofluorocarbons, fluoroiodide carbons and fluoroalcohols, at least one fluorocarbon selected from hydrofluoroethers,
The cleaning agent, wherein the low molecular siloxane compound is at least one low molecular siloxane compound selected from hexamethyldisiloxane, octamethyltrisiloxane, and octamethylcyclotetrasiloxane. 24. A cleaning tub, comprising: a rinsing tub connected to the rinsing tub; and a drying tub connected to the rinsing tub, wherein the cleaning tub, the rinsing tub and the drying tub are provided. At least one tank contains a cleaning agent containing a low-molecular siloxane compound and / or a non-combustible or flame-retardant fluorocarbon, and controls a composition ratio of the low-molecular siloxane compound and the fluorocarbon in the cleaning agent. And a composition control mechanism. 25. The cleaning apparatus according to claim 24, wherein the composition control mechanism is configured to measure a composition ratio between the low-molecular siloxane compound and fluorocarbons in the cleaning agent, and to perform measurement by the composition ratio measurement unit. A means for supplying the low-molecular siloxane compound or the fluorocarbons to the mixed cleaning agent according to the result. 26. The cleaning apparatus according to claim 24, wherein said composition ratio measuring means has means for measuring at least one selected from the specific gravity, refractive index, boiling point and condensation point of said cleaning agent. Cleaning equipment. 27. The cleaning apparatus according to claim 24, wherein the composition ratio measuring means determines the concentration of the low-molecular siloxane compound in the vapor of the cleaning agent by using an infrared ray of the Si—O bond in the low-molecular siloxane compound. A washing apparatus comprising means for measuring based on absorption. 28. The cleaning apparatus according to claim 24, further comprising a temperature adjusting means for said cleaning agent. 29. The cleaning apparatus according to claim 24, wherein the gas or liquid of the non-combustible or non-flammable fluorocarbon is used for cleaning the inside of the cleaning apparatus, the periphery of the cleaning apparatus, and the apparatus constituting the cleaning apparatus. A cleaning device characterized by being filled or arranged in at least one selected from inside and around the constituent device. 30. The cleaning apparatus according to claim 24, further comprising means for injecting a fire extinguishing agent made of a nonflammable or nonflammable fluorocarbon gas or liquid into at least a part of the cleaning apparatus. Cleaning equipment. 31. The cleaning device according to claim 24, further comprising: flame detecting means for driving the digestive spraying means;
A cleaning device comprising at least one selected from a temperature detecting means and a pressure detecting means. 32. The cleaning apparatus according to claim 24, wherein the non-flammable or non-flammable fluorocarbon is selected from perfluorocarbons, hydrofluorocarbons, hydrochlorofluorocarbons, fluoroiodide carbons, and fluoroalcohols. The cleaning device is at least one of the following. 33. A washing step wherein a washing step and / or a rinsing step and a drying step are carried out using a mixture of a low molecular weight siloxane and at least one selected from hydrofluoroethers and hydrofluorocarbons. Method. 34. A washing step, a rinsing step and / or a washing step using a mixture of a polar detergent having a solubility parameter of 9 or more or a dielectric constant of 4 or more and at least one selected from hydrofluoroether and hydrofluorocarbon. Or a cleaning method characterized by performing a drying step. 35. The cleaning method according to claim 34, wherein the mixture is an azeotropic or pseudo-azeotropic mixture, and the cleaning, rinsing, and drying steps are performed using the azeotropic or pseudo-azeotropic mixture. A cleaning method characterized by the above-mentioned. 36. The cleaning method according to claim 34, wherein a draining and drying step is performed using the mixture. 37. The cleaning method according to claim 36, wherein a draining and drying step is performed using the azeotropic or pseudo-azeotropic mixture. 38. The cleaning method according to claim 34, wherein the mixture is nonflammable or nonflammable. 39. The cleaning method according to claim 33, wherein the drying step is performed by hot air drying, natural drying, vacuum drying, or steam drying. 40. The cleaning method according to claim 33, wherein the low molecular weight siloxane compound has a general formula: (Wherein R is the same or different, substituted or unsubstituted 1
A linear organic polysiloxane and a derivative thereof represented by the following general formula: (Wherein R is the same or different, substituted or unsubstituted 1
Wherein m is an integer of 3 to 7), and at least one low molecular weight polyorganosiloxane selected from cyclic polyorganosiloxanes and derivatives thereof. 41. The cleaning method according to claim 34, wherein said polar cleaning agent comprises alcohols, glycols, phenols, ketones, fatty acids and acid anhydrides, esters, amines, amides, Quaternary ammonium salts, nitriles, morpholines, sulfoxides, sultones, phosphoric acids, and derivatives thereof, N-methyl-2
-A washing method comprising at least one component selected from pyrrolidone. 42. The cleaning agent according to claim 7, comprising 50% by weight or less of said low-molecular siloxane compound and said polar cleaning agent. 43. The cleaning agent according to claim 7, wherein the polar cleaning agent is an alcohol. 44. The cleaning agent according to claim 42, further comprising a stabilizer selected from alcohols, ketones, ethers, esters, amines and hydrocarbon compounds. 45. A detergent for washing and drying in one liquid, comprising a uniformly mixed low-molecular-weight siloxane compound of 50% by weight or less and a polar detergent. 46. The one-part cleaning agent according to claim 45, wherein the polar cleaning agent is an alcohol. 47. The one-part detergent according to claim 45, wherein the low molecular weight siloxane compound is hexamethyldisiloxane, and the polar detergent is at least one polar compound selected from tert-butanol and isopropyl acetate. A one-part cleaning agent, which is a cleaning agent. 48. The one-part cleaning agent according to claim 45, wherein the cleaning agent is an azeotropic or pseudo-azeotropic composition.