WO2005033257A1 - Partially azeotropic composition - Google Patents

Abstract

A nonazeotropic multi-component composition which comprises: two or more volatile ingredients especially comprising HFC365mfc and a chlorine-free fluorine compound in which the molecule has a ratio of the number of fluorine atoms to that of hydrogen atoms of 2 or higher; and one or more high-boiling nonvolatile ingredients. The composition is excellent in detergency, volatility, safety, and environmental preservation. It is suitable for use as a detergent composition whose compositional fluctuations can be easily controlled over long-term use.

Description

 Specification

 Partially azeotropic composition

 Technical field

 [0001] The present invention relates to various processing oils and greases and waxes used for processing precision machine parts and optical machine parts, fluxes used for soldering electric and electronic parts, and used for manufacturing substrates. Compositions and cleaning agents suitable for cleaning agents and rinsing agents, which are preferably used for cleaning inks and pastes adhering to the screen to be cleaned and resins adhering to the mixing section of the grease discharging device. The present invention relates to a cleaning method using a cleaning agent and a rinsing agent.

 Background art

 [0002] Various processing oils, such as cutting oils, press oils, drawing oils, heat treatment oils, anti-dust oils, lubricating oils, and the like, or greases, waxes, and the like when processing precision machine parts, optical machine parts, and the like. However, it is necessary to remove these contaminants eventually, and removal with a solvent is generally performed.

 [0003] Also, soldering is most commonly used as a joining method of electronic circuits. However, it is necessary to remove and clean oxides on metal surfaces to be soldered, prevent re-oxidation, and improve solder wettability. For the purpose of (1), it is usual practice to pretreat the bonding surface with a flux containing rosin as a main component. The soldering method is to apply the flux to the substrate surface by immersing the substrate in a solution-like flux, etc., then supply molten solder, or mix the flux and solder powder in advance to form a paste. There is a method of heating after supplying the soldered material to the place where soldering is to be performed, but in any case, the flux residue causes corrosion of the metal and lowers the insulation properties. Need to be removed

[0004] In recent years, the screen printing method has been widely used in the field of the electronics industry.

They are made of silk, nylon, tetron or other fiber or stainless steel wire or other fabric (screen), stretched over a frame, fixed around the circumference, and then placed on top of this, such as polyvinyl alcohol, vinyl acetate, acrylic monomer, etc. Main agent and diazo-pam salts and dichromates A mixture of photosensitive agents is applied by stirring, and an emulsion film is formed by a photochemical method.Eyes other than the required image are covered, and a pattern-formed screen and a tool equipped with urethane rubber called a squeegee are used. And printing. Printed screens and squeegees need to be washed and removed for storage and reuse.

 [0005] A resin discharge device is widely used for joining, filling or sealing various electric and electronic parts with a resin such as epoxy, urethane, silicone, and polyester. The two-component type (base agent and curing agent) that crosslinks and cures at around room temperature is often used for the resin used in this application. When the operation is interrupted, it is necessary to clean the mixing part and the nozzle part to prevent the resin from hardening in the discharge device.

 [0006] These washing and removal have many features such as nonflammability, low toxicity and excellent solubility. For example, 1,1,2-triclo mouth—1,2,2— Washed with a solvent such as trifluoroethane (hereinafter referred to as CFC113!) Or a mixture of CFC113 and alcohol. However, with regard to CFC 113, global environmental pollution problems such as depletion of the ozone layer were pointed out, and its production was abolished at the end of 1995 in Japan. As a substitute for CFC113, a mixture of 3,3-dichloro-1,1,1,2,2 pentafluoropropane and 1,3-dichloro-1,1,2,2,3 pentafluoropropane (hereinafter referred to as HCFC225) ) And 1,1-dichloro-1-fluoroethane (hereafter referred to as HCFC141b!) Have been proposed, but these also have a slight ozone layer depletion potential in Japan in 2020. Its use will be banned.

[0007] Therefore, in recent years, the ozone layer destruction ability of no-fluoride carbons (hereinafter, HFC) and no-fluoride ethers (hereinafter, HFE and な), which do not contain any chlorine atoms, has been completely reduced. Although non-flammable fluorine-based solvents have been proposed, they do not contain chlorine atoms and have low solubility, so they cannot be used alone as cleaning agents.Therefore, they have high solubility in HFCs and HFEs and are highly flammable. Technical capabilities of azeotropic cleaning agents combined with solvents S Some are disclosed. (Patent Literature 1) For example, Patent Literature 2 discloses a cleaning agent using a high boiling point glycol ether in combination with HFC or HFE in order to increase the dissolving power. However, this detergent has a boiling point of 55 The use of HFCs or HFEs at or above ° C results in the steam at the time of boiling containing a large amount of glycol ethers with high boiling points. Washing applications are limited due to reduced drying properties of the objects exposed to steam. Further, the ratio of the alkyl group having no fluorine atom to all the alkyl groups in the molecule is small, and therefore, the solubility in processing oil and the like is low. Therefore, it becomes difficult to prevent re-adhesion of dirt when the cleaning liquid that has been used for a long time and is mixed with dirt adheres to the object to be washed and is brought into the rinsing step or the steam cleaning step.

 [0008] Patent Document 3 discloses cleaning using a glycol ether in combination with HFC having a boiling point of 40 ° C. The HFC used in this cleaning agent has insufficient self-extinguishing properties to be used in combination with flammable glycol ethers having a flash point as low as lOmj. Furthermore, since it has a combustion range of 3.6-13.6% by volume, its effect as a non-combustible component is low when steam cleaning is performed by heating.

 [0009] As described above, in the conventionally known cleaning agents in which non-flammable HFCs and HFEs are combined with a flammable solvent having a high solubility, the solubility is still unsuitable for use as a cleaning agent. At present, there are many problems in using it as a cleaning agent due to insufficient or self-extinguishing properties.

 [0010] On the other hand, in particular, in a cleaning method having a multi-component cleaning composition containing a high-boiling component, vapor of the cleaning composition is generally dissipated from an opening of a cleaning apparatus during a cleaning operation. For this reason, the composition of the cleaning composition constantly fluctuates, and therefore, there is a problem that it is difficult to maintain the physical properties of the cleaning composition at the same level as at the start of cleaning. In order to solve the problem of the composition fluctuation, it has been attempted to use various multi-component cleaning compositions which form an azeotrope (Patent Document 1). However, the components of the composition that forms the azeotrope vary in their types and composition ratios, so that the solvent power of the cleaning composition depends on the type and composition ratio of the components. However, the self-extinguishing property was similarly restricted.

[0011] As described above, the cleaning agents that have been proposed as alternatives to CFC113 have been banned in the future due to the problem of depletion of the ozone layer even if cleaning is possible, or the composition of the cleaning agent may vary. Even if an azeotropic mixture is used to control Low cleaning power due to low temperature, or even if a flammable high-boiling solvent is added to a fluorine-based solvent to increase the dissolving power, the cleaning agent composition fluctuates and maintains a constant cleaning agent performance Equipment and explosion-proof construction of equipment such as washing machines due to the danger of ignition, increasing equipment costs, and various characteristics required as a substitute for CFC113, that is, At present, there are many problems in using as a detergent that has all of environmental safety, detergency, drying property, low flammability, self-extinguishing property, low toxicity and composition stability.

 [0012] Patent Document 1: Special Table 2003—518144

 Patent Document 2: JP-A-10-212498

 Patent Document 3: JP 2003-129090

 Disclosure of the invention

 [0013] The present invention exhibits a high detergency against all types of dirt in cleaning, comparable to HCFC225, and has low toxicity and low flammability with less oxidative deterioration during steam cleaning at high temperatures. Detergent that is highly volatile, has excellent self-extinguishing properties, excellent drying properties, and is a non-azeotropic composition that can easily control its composition fluctuations even during long-term cleaning operations. And a cleaning method using the cleaning agent.

 [0014] The present inventor has developed HFC365mfc (Nihon Solvay Co., Ltd.) having two or more volatile components, each having excellent properties as a detergent component, and in particular, having excellent drying properties, rinsing properties, and steam cleaning properties. )), And HFC and HFE with excellent self-extinguishing properties, and non-volatile components, especially dalicol ethers, glycol ether acetates, and hydroxycarboxylates, which are high-boiling solvents with high solubility. Non-azeotropic composition power, which is similar in power It has been found that the composition of the vapor, which is a plurality of component powers generated at its boiling point, is constant over a long period of time. With a little soothing power, no flash point appears, it has sufficient self-extinguishing properties, it can clean all dirt, it can be used as a rinsing agent and a steam cleaning agent, and by adding an antioxidant, etc. Continuously under temperature to complete the multi-component detergent compositions that can be used.

[0015] That is, the first aspect of the present invention is that the vapor pressure at 20 ° C is the reference vapor defined by the equation (1). At least two types of volatile components (A) greater than the pressure Po and at least one type of non-volatile components (B) whose vapor pressure at 20 ° C is less than Po are gas phase and liquid at the boiling point under normal pressure. This is a partial azeotropic composition in which the component composition of the phase satisfies the relationship of the formulas (3) and (4).

 [0016] Po = Pav / 5 (1)

 (Where Pav is the component average vapor pressure defined by equation (2))

 Pav = (∑ Pai + ∑ Pbj) / (na + nb) (2)

(Where Pai is the vapor pressure of each volatile component (Ai) in the composition at 20 ° C, Pbj is the vapor pressure of each volatile component (Bj) at 20 ° C, and na is the vapor pressure of each volatile component (Bj) in the composition. The number of volatile components (A), nb is the number of non-volatile components (B) in the composition, and are integers satisfying 2≤na and l≤nb, respectively, and i and j are each l≤i It is an integer satisfying ≤na and l≤j≤nb.) ₀

 [0017] (∑Bvj / ∑Boj) ≤0.1 (3)

 (Where Bvj is the weight ratio of each non-volatile component (Bj) in the gas phase, Boj is the weight ratio of each non-volatile component (Bj) in the partial azeotropic composition, and j is the same as in formula (2). is there. ).

 [0018] -0.1 ≤ (AviZ∑ Avi)-(Aoi / ∑ Aoi) ≤ 0.1 (4)

 (Avi is the weight ratio of each volatile component (Ai) in the gas phase, Aoi is the weight ratio of each volatile component (Ai) in the partial azeotropic composition, and i is the same as the formula (2).)

 A second aspect of the present invention is the partial azeotropic composition of the first aspect, which satisfies the relationship of the formula (5).

 0.0001≤ (∑ Bvj / ∑ Boj) ≤ 0.1 (5)

 (Where Boj ゝ Bvj, j is the same as in equations (3) and (4).)

 A third aspect of the invention is a partial azeotropic composition according to inventions 1 and 2V, in which a part is vaporized and the gas phase covers the remaining liquid phase surface.

A fourth aspect of the present invention is a compound having a vapor pressure of not less than 1.33 × 10 ³ Pa at 20 ° C. for all the volatile components (A1—Ana) in the composition, and all the non-volatile components (B1—Ana). Invention 13. The partial azeotropic composition according to any one of Inventions 13 to 13, which is a compound having a vapor pressure at 20 ° C. of Bnb) of less than 1.33 × 10 ³ Pa.

[0020] A fifth aspect of the present invention resides in that the volatile component (A) comprises a compound also selected from halogenated hydrocarbons, hydrocarbons, alcohols, esters, and ketones. It is a boiling composition. A sixth aspect of the present invention is the partial azeotropic composition of the fifth aspect, wherein the volatile component (A) is composed of two or more compounds selected from halogenated hydrocarbons.

A seventh aspect of the present invention is the partial azeotropic composition of the sixth aspect, wherein the halogenated hydrocarbon is a non-chlorine fluorine compound.

 An eighth aspect of the invention is that the volatile component (A) is composed of 2H, 2H, 4H, 4H, 4H-perfluorobutane (HFC365mfc) (A1) and hydrogen having the number of fluorine atoms in the volatile component molecule. Non-chlorine fluorine compound power having a ratio of 2 or more to the number of atoms The partial azeotropic composition of Invention 7, which also has one or more selected compound (A2) powers.

 A ninth aspect of the invention is the partial azeotropic composition according to any one of inventions 18 to 18, wherein the non-volatile component (B) is formed of a compound which is also selected from hydrocarbons, alcohols, and ketones.

 [0025] A tenth aspect of the present invention is the invention wherein the non-volatile component (B) comprises one or more compounds selected from the group consisting of organic compounds having an ether bond and a Z or ester bond. It is an azeotropic composition.

 An eleventh aspect of the present invention is a non-volatile component (B), a glycol ether, a glycol ether acetate, and a hydroxycarboxylic acid ester. A group consisting of one or more compounds selected from the group consisting of a part of invention 10 It is an azeotropic composition.

 [0027] A twelfth aspect of the invention is an invention in which the nonvolatile component (B) has a group strength of at least one compound selected from glycol ethers and glycol ether acetates and hydroxycarboxylates. 11 is a partial azeotropic composition.

[0028] A thirteenth aspect of the present invention is the non-volatile component (B), wherein the nonvolatile component (B) is selected from the group consisting of compounds represented by the following general formulas (6), (7), (8), and (9). A partial azeotropic composition according to invention 11, comprising the above compound. [0029] [Formula 1]

R ² R ³

 I I

R'OC (CH ₂ ) CH— OH (6)

(Wherein, R ¹ is an alkyl group having 16 carbon atoms, an alkyl group, or a cycloalkyl group,

, R ³ and R ⁴ represent hydrogen or a methyl group, and n represents an integer of 0 or 1. )

[0031] [Formula 2] c o

 I i

R ⁵ 0— (C (CH ₂ ) _n CHO) ₂ — R ⁶ (7)

 I

R ⁹

(Wherein, R ⁵ is an alkyl group having 416 carbon atoms, an alkenyl group, or a cycloalkyl group, R ^;

R ⁸ and R ⁹ represent hydrogen or a methyl group; R ⁶ represents an alkyl group having 3 to 6 carbon atoms, an alkenyl group or a cycloalkyl group; and n represents an integer of 0 or 1. )

[0033] [Formula 3]

R ^{11 12}

 I

R "0— (C (CH ₂ ) _n CHO) _m CH 8

R ¹³

(Wherein, R ¹ "is an alkyl group, alkenyl group or cycloalkyl group having 16 carbon atoms, ¹¹ , R ¹² , and R ¹³ are hydrogen or methyl groups, n is an integer of 0 to 1, and m is 11 Indicates an integer of 4) [0035] [Formula 4]

O H O

H nf,-. ^ ¹ ΐ J lf —— ¹ —— Π v .. Pv 1 Ί (9)

(Wherein, R represents an alkyl group having 16 carbon atoms, an alkenyl group or a cycloalkyl group)

 A fourteenth aspect of the present invention is a non-volatile component (B), glycol ether monoalkyl ethers, at least one selected compound (B1) and glycol ether dialkyl ethers, at least one selected compound (B2), and a part of invention 11. It is an azeotropic composition.

 A fifteenth aspect of the invention is the partial azeotropic composition of invention 14, wherein the component (B1) is a hydrophilic compound and the component (B2) is a hydrophobic compound.

 [0038] A sixteenth aspect of the invention is the partial azeotropic composition of invention 14, wherein the component (B1) is a hydrophobic compound and the component (B2) is a hydrophilic compound.

 [0039] A seventeenth aspect of the present invention is the partial azeotropic composition of invention 14, wherein the component (B1) and the component (B2) are both hydrophilic conjugates.

 An eighteenth aspect of the invention is the partial azeotropic composition of the invention 14, wherein the component (B1) and the component (B2) are both hydrophobic conjugates.

 A nineteenth aspect of the present invention is directed to a nineteenth aspect of the present invention, wherein component (B1) is one or two selected from 3-methoxybutanol, 3-methoxy-3-methylbutanol, dipropylene glycol mono-n-propyl ether, and dipropylene glycol mono-n-butyl ether. Invention 14 is an azeotropic composition containing 14 or more compounds.

[0042] The twentieth aspect of the invention is the partial azeotropic composition of invention 14, which includes one or more compounds selected from the group consisting of component (B2) force diethylene glycol getyl ether, dimethylene glycol di- _n -butyl ether, and dipropylene glycol dimethyl ether. Things.

[0043] The twenty-first aspect of the invention is a non-volatile component (B) glycol glycol monoalkyl ethers Force One or more selected compounds (B1) and glycol ether acetate are the partial azeotropic compositions of inventions 11 and 14 containing one or more selected compounds (B3).

A twenty-second aspect of the present invention is the partial azeotropic yarn composition according to any one of the twenty-first to eleventh aspects, which has no flash point.

 [0045] The twenty-third invention is the partial azeotropic composition of any one of the inventions 112, characterized by having excellent self-extinguishing properties.

 A twenty-fourth aspect of the invention is a cleaning agent which also has a partial azeotropic composition power according to any one of the first to twenty-third aspects.

[0047] A twenty-fifth aspect of the present invention is a vapor condensate generated by heating any of the partial azeotropic compositions of the present invention.

A twenty-sixth aspect of the present invention is a rinsing agent having the same composition as the condensate of the twenty-fifth aspect.

A twenty-seventh aspect of the present invention is a replenisher for a cleaning agent having the same composition as the condensate of the twenty-fifth aspect.

[0050] The twenty-eighth aspect of the invention is a cleaning method using the cleaning agent of invention 24 and the rinsing agent of invention 26.

A twenty-ninth aspect of the present invention is a cleaning method using the cleaning agent of the invention 24 and a replenisher of the cleaning agent of the invention 27.

 A thirtieth aspect of the invention is a cleaning method using the cleaning agent of the invention 24, the rinsing agent of the invention 26, and the replenisher of the cleaning agent of the invention 27.

A thirty-first aspect of the invention is a finishing detergent having the same composition as the condensate of the twenty-fifth invention.

A thirty-second aspect of the present invention is directed to a 2H, 2H, 4H, 4H, 4H-perfluorobutane (HFC365mfc) as a volatile component (A1) and a quantity ratio of fluorine atom Z hydrogen atom in a molecule as a volatile component (A2). Is a non-chlorine fluorine compound power of 2 or more.One or more selected compounds, and as the component (B), a compound having a vapor pressure at 20 ° C of less than 1.33 × 10 ³ a , Their weight ratio [(8 1) + (8 2)] 7 () is 80 / 20-99.9 / 0.1% by weight of the composition.

[0055] A thirty-third aspect of the present invention is a rinse agent comprising the composition of the thirty-second aspect of the invention.

A thirty-fourth aspect of the present invention is a replenisher for a detergent comprising the composition of the thirty-second aspect.

A thirty-fifth aspect of the invention is a finishing detergent comprising the composition of the thirty-second aspect.

 Brief Description of Drawings

FIG. 1 is an example of a cleaning apparatus for performing cleaning using the cleaning composition of the present invention. This is the cleaning device used in the examples.

 FIG. 2 is a graph showing a change in composition of each component in a cleaning agent in Example 1.

 Explanation of symbols

[0059] 1 washing tank

 2 rinse tank

 3 steam zone

 4 water separator

 5 ultrasonic transducer

 6 heater

 7 cooling pipe

 8 Steam flow

 9 Condensate piping

 10 Condensate piping after water separation

 11 Flow of overflow liquid

 12 cooling pipe

 13 Cleaning machine opening

 BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

[0061] In the present invention, washing is an operation of using a detergent composition to remove a dirt component adhering to an object to be washed to a level that does not affect the next step. "Means the detergent composition used at this time. In addition, rinsing is an operation to replace the cleaning agent containing the dirt component that adheres to the object to be washed after cleaning with a dirt component that does not contain the dirt component. Refers to the composition used. In addition, steam cleaning refers to the operation of condensing and liquefying the steam generated from a cleaning agent or rinsing agent on the surface of the object to be cleaned, thereby removing dirt components remaining on the surface of the object after cleaning. It is. In addition, finish cleaning is an operation that removes very small dirt such as processing oil, flux, foreign matter, fingerprints, etc. that are slightly left on the object to be washed, for example, cleaning before product shipment. This refers to the detergent composition used at this time. In addition, the replenisher is used for cleaning , A composition that is replenished into the system to replenish a portion of the cleaning composition that escapes to the atmosphere as vapor.

 [0062] The partial azeotropic composition of the present invention is a non-azeotropic multi-component composition comprising two or more volatile components (A) and one or more non-volatile components (B). At the boiling point under normal pressure, the composition of the volatile component (A) in the liquid phase and the composition of the volatile component (A) in the gas phase are always constant. Therefore, by using this partial azeotropic composition as a cleaning composition and using a previously prepared composition having the same composition as the vapor composition at its boiling point as a replenisher, the composition of the cleaning composition in the cleaning tank system can be improved. It has been found that fluctuation can be suppressed. As a result, while maintaining the excellent properties (for example, excellent drying properties) of conventional azeotropic composition-based detergents, there are various problems that can be solved with azeotropic composition-based detergents (for example, Etc.), and it has become possible to maintain the excellent characteristics stably during a long cleaning operation. Conventionally, such a multi-component detergent composition for long-term stable use has been considered to be essentially an azeotropic composition. Even in this case, it has been found that, similarly to the azeotropic composition, the problem of the composition fluctuation of the multi-component detergent can be solved.

 [0063] The partial azeotropic composition of the present invention has two or more volatile components whose vapor pressure at 20 ° C is higher than the reference vapor pressure Po defined by the formulas (1) and (2), and lower than Po. Consists of one or more non-volatile components (B). Here, the component average vapor pressure Pav in the formula is the arithmetic average of the vapor pressure at 20 ° C of each of the volatile component (Ai) and the non-volatile component (Bj) alone, which constitute the composition of the present invention. By using the components belonging to the two groups separated by the reference vapor pressure Po in combination, the present invention has excellent detergency, dryness, and nonflammability, and has less composition fluctuation during a long-term cleaning operation. A partial azeotropic composition can be obtained.

The partial azeotropic composition of the present invention has a composition in which the composition of each of the non-volatile components (Bj) in the gas phase and the liquid phase at the boiling point under normal pressure is represented by the formula (Bj). It satisfies the relationship of 3). When the amount of the non-volatile component (B) present in the vapor phase is less than a certain amount, the composition fluctuation during the long-term cleaning operation is small, and a multi-component composition that has both excellent drying property and cleaning property during steam cleaning. Can be obtained. The boiling point under normal pressure as referred to herein is observed, for example, in a refraction test described below, in a constant temperature state where the composition of the present invention reaches the sample. Can be obtained as a gas temperature. Bvj in equation (3) can be obtained by collecting the condensate obtained by condensing the vapor phase at this time and analyzing the composition.

 [0065] In a multi-component detergent composition, a high-boiling non-volatile component is often used for the purpose of improving soil solubility. Such a high-detergency component is used as a non-volatile component (B) at a temperature below the boiling point. However, the large amount remaining in the liquid phase contributes to ensuring the high detergency of the detergent. If steam cleaning is required, the power that may require a certain level of cleanliness in the vapor phase while maintaining good drying properties. In that case, (∑ 7∑ 0; 0 is 0. The non-volatile component (B) needs to be present in the vapor phase in the range of 0001 or more and 0.1 or less, and more preferably 0.001 or more and 0.05 or less.

 Further, at the boiling point under normal pressure, the composition of each volatile component (Ai) in the gaseous phase and the liquid phase in which the yarn azeotrope is generated at the boiling point under normal pressure is represented by the formula: Satisfies the relationship of (4). The weight ratio of each volatile component (Ai) in the gas phase to the total volatile components in the gas phase, and the partial azeotropic composition of each volatile component (Ai) at room temperature in the partial azeotropic composition at room temperature In the case where the difference in the weight ratio to the total volatile components is within ± 0.1, even if the composition itself with a small composition fluctuation is a non-azeotropic composition, it is actually the same as the azeotropic composition. In addition, it is possible to suppress composition fluctuations as a cleaning agent. More preferably, the difference is within ± 0.07, and even more preferably, it is within ± 0.05. Here, Avi in equation (4) can be obtained by the same method as Bvj described above.

 [0067] The components constituting the partial azeotropic composition include two or more volatile components (A) selected based on the reference vapor pressure Po defined by the formulas (1) and (2) and one or more volatile components (A). Any compound can be used as long as it is a non-azeotropic composition comprising the non-volatile component (B) of the formula (1), and each component satisfies the formulas (3) and (4). Examples thereof include hydrocarbons, hydrocarbons, alcohols, ketones, and organic compounds having an ether bond and a Z or ester bond.

 [0068] Hereinafter, examples of each of the compounds that can be used in the partial azeotropic composition of the present invention will be described in order of increasing the vapor pressure at room temperature.

[0069] Examples of the halogenated hydrocarbons include a chlorine-free bromine compound and a chlorine-free fluorine compound. Non-chlorine bromine compounds include isopropyl bromide and propyl bromide. And the like. Non-chlorine fluorine compounds are fluorine compounds in which some of the hydrogen atoms of hydrocarbons and ethers are replaced only by fluorine atoms and do not contain chlorine atoms. For example, they are represented by the following general formula (11). Compounds of the following formulas: cyclic HFCs represented by the formula (12), chain HFCs represented by the formula (12), or HFEs represented by the formula (13): And a combination of two or more compounds selected from the following.

C H F (11)

 n 2n— m m

 (Where n and m are integers that satisfy 4≤n≤6 and 5≤111≤211-1)

C H F (12)

 x 2x + 2-y y

 (Where x and y are integers of 4≤x≤6, 6≤y≤12)

C F OR (13)

 s 2s + l

 (In the formula, 4≤s≤6, R is an alkyl group having 1 to 3 carbon atoms)

 Specific examples of cyclic HFC include 3H, 4H, 4H-perfluorocyclobutane, 4H, 5H, 5H-perfluorocyclopentane, 5H, 6H, 6H-nonafluorocyclohexane It comes out.

Specific examples of chain HFCs are 1H, 2H-perfluorobutane, 1H, 3H-perfluorobutane, 1H, 4H-perfluorobutane, 2H, 3H-perfluorobutane, 4H, 4H- Fluorobutane, 1H, 1H, 3H—Perfluorobutane, 1H, 1H, 4H—Perfluorobutane, 1H, 2H, 3H—Perfluorobutane, 1H, 1H, 4H—Perfluorobutane, 1H, 2H, 3H, 4H—Perfluorobutane, 2H, 2H, 4H, 4H, 4H—Perfluorobutane (HFC365mfc), 1H, 2H—Perfluoropentane, 1H, 4H—Perfluoropentane, 2H, 3H —Perfluoropentane, 2H, 4H—Perfluoropentane, 2H, 5H—Perfluoropentane, 1H, 2H, 3H—Perfluoropentane, 1H, 3H, 5H—Perfluoropentane, 1H, 5H, 5H—Perfluoropentane, 2H, 2H, 4H—Perfluoropentane, 1H, 2H, 4H, 5H—Perfluoropentane, 1H, 4H, 5H, 5 H, 5H—perfluoropentane, 1H, 2H—perfluorinated hexane, 2H, 3H—perfluorinated hexane, 2H, 4H—perfluorinated hexane, 2H, 5H—perfluorinated hexane, 3H, 4H—perfluorinated hexane and the like. Specific examples of HFE include methyl perfluoroisobutyl ether, methyl perfluorobutynoleatenol, pentynoleate, methinolenophenol, hexyl ether, and methyl ethyl perfluoropentyl ether.

 Examples of the hydrocarbons include pentane, 2,2-dimethylbutane, 2,3 dimethylbutane, 2-methylpentane, hexane, heptane, isooctane, 2,2,3 trimethylpentane, 2,2 , 5-trimethylhexane, octane, nonane, decane, pendecane, dodecane, tridecane, tetradecane, pentadecane, menthane, bicyclohexyl, cyclododecane, 2,2,4,4,6,8,8-heptamethylnonane Is mentioned.

 Examples of alcohols include methanol, ethanol, 2-propanol, tert-butanol, 1-propanol, sec-butanol, isobutanol (vapor pressure at 20 ° C. 1.06 X lCTPa), n-butanol, isoamyl Alcohol, n-heptanol, n-butanol, n-nonanol, n-decanol, n-phenol, benzyl alcohol, furfuryl alcohol, ethylene glycol, propylene glycol.

[0073] Acetone The ketone, methyl E chill ketone, 3-pentanone, 2-pentanone, methyl isobutyl ketone, the 2- cyclohexanone (vapor pressure at ^{20 ° C 3. 99 X 10 2} Pa), methyl-n amino ketone, di Isobutyl ketone, diacetone alcohol, holon, isophorone, cyclohexanone, and acetophenone.

 [0074] The organic compound having an ether bond is a compound containing at least one or more ether bonds (CO-C) in the molecular structure. The organic compound having an ester bond is an organic compound having an ester bond in the molecular structure. A compound containing at least one bond (one COO—).

[0075] Examples of the compound having an ether bond include a compound specified by the following general formula (14). [0076]

R R

 1 6 (1 4)

R R 2 0

(Wherein, R ^{1 &} and R ^lb are neutral groups of an alkyl group, an alkenyl group, a cycloalkyl group, an acetyl group, a carbonyl group, a hydroxyl group, an ester bond, and an ether bond. Represents a compound residue, an alicyclic compound residue, an aromatic compound residue and a heterocyclic compound residue, and R ¹⁷ — R ^2G represents a hydrogen or an alkyl group.

 More specific examples include glycol ethers and glycol ether acetates.

First, examples of glycol ethers include glycol ether monoalkyl ethers and glycol ether dialkyl ethers. Glycol ether monoalkyl ethers are aliphatic groups in which two hydroxyl groups are bonded to two different carbon atoms by V! /, Which is one of the hydroxyl groups in alicyclic compounds. Is a compound in which the hydrogen of the hydroxyl group is replaced by a hydrocarbon residue or a hydrocarbon residue containing an ether bond. Glycol ether dialkyl ethers are two types of aliphatic groups in which two hydroxyl groups are bonded to two different carbon atoms to form an alicyclic compound. Is a compound in which all of the above hydrogens are replaced by a hydrocarbon residue or a hydrocarbon residue containing an ether bond. Examples thereof include glycol ether monoalkyl ethers represented by the following general formula (15) and glycol ether dialkyl ethers represented by the following general formula (16). [0079] [Formula 6]

R ²² R

 I

CHO

c R I I

 9 C 7

 (Wherein, R is an alkyl group having 16 to 16 carbon atoms, an alkyl group or a cycloalkyl group,

R ²³ and R ²⁴ are hydrogen or a methyl group, n is an integer of 0 to 1, and m is an integer of 14)

[0081]

R ²⁸

 I

R ^ss O CHO) _m — (16)

(Wherein, R is an alkyl group having 16 carbon atoms, an alkenyl group or a cycloalkyl group, R is an alkyl group having 14 to 14 carbon atoms or an alkenyl group, R ²⁷ , R ²⁸ , R ²⁹ is a hydrogen or methyl group, n is an integer of 0-1 and m is an integer of 1-4)

Glycol ethers are classified into hydrophilic dalicol ethers and hydrophobic glycol ethers, and hydrophilic dalicol ether monoalkyl ethers and hydrophilic glycol ether dialkyl ethers used in the partial azeotropic composition of the present invention. Glycol ethers are glycol ethers that can form a uniform single liquid phase without any phase separation when mixed with glycol ethers Z at a mass ratio of 60Z40 at 30 ° C. Hydrophobic glycol ether monoalkyl ethers and hydrophobic glycol ether dialkyl ethers are glycol ethers at 30 ° C, and glycol ethers, at which water is mixed at a mass ratio of 60Z40, phase separation is observed. Kind. [0083] Preferred! The hydrophilic dalicol ether monoalkyl ethers and hydrophilic glycol ether dialkyl ethers are glycol ethers that can be dissolved in water at an arbitrary ratio at 30 ° C. The hydrophobic glycol ether monoalkyl ethers and hydrophobic glycol ether dialkyl ethers are glycol ethers having a solubility in water at 30 ° C. of 60% by mass or less.

[0084] Contact the glycol ether monoalkyl ethers, Te, for example, specific examples of the hydrophilic glycol ether monoalkyl ether, propylene glycol monomethyl E one ether (vapor pressure at ^{20 ° C 8. 91 X 10 2} Pa) , 3-methoxybutanol, 3-methoxy-3-methylbutanol, diethylene glycol monomethinole ether, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropane i propinoleatenore, diethylene glycolone propane Examples of the hydrophobic glycol ether monoalkyl ether include, but are not limited to, nonoleate ether, tripropylene glycol monomethinole ether, and diethylene glycolone mono- _n -butynoleether. Examples thereof include propylene glycol mono-n-butyl ether (vapor pressure at 20 ° C. 7.98 X lOPa), ethylene glycol mono-n-hexyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-n-propyl ether, and the like. .

[0085] In the glycol ether dialkyl ethers, for example, specific examples of the hydrophilic glycol E one ether dialkyl ether, diethylene glycol dimethyl ether (vapor pressure at ^{20 ° C 3. 99 X 10 2} Pa), diethylene GETS chill ether Examples of the hydrophobic glycol ether dialkyl ether include dipropylene glycol dimethyl ether (vapor pressure at 20 ° C. 6.65 × 10 Pa), and ethylene glycol di- _n -butyl ether.

[0086] Glycol ethers used in the partial azeotropic composition of the present invention include 3-methoxybutanol (vapor pressure at 20 ° C 1.20 X 10 ² Pa), 3-methoxy-3-methylbutanol, dipropylene glycol dimethyl ether, dipropylene glycol monomethinole ether, dipropylene glycol mono-n-butyl ether and dipropylene glycol mono-n-propyl ether. Low toxicity is preferred.

 [0087] The glycol ether acetates are compounds obtained by acetylating glycol ethers having a hydroxyl group, and are preferably represented by the following general formula (17).

[0088]

R ^{3 1} R ^{3 2}

 I I

R. ^{3 0} 0-(C (CH ₂ ) _n CH 0)

(Wherein, R ^dU is an alkyl group having 16 carbon atoms, an alkenyl group or a cycloalkyl group, R ^dl , R ³² , and R ³³ are a hydrogen or a methyl group, n is an integer of 0 to 1, com indicates an integer of 1 to 4.) Specific examples include ethylene glycol, diethylene glycol, and triethylene glycol.

 Η

 Propylene glycol, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, monoalkyl acetates such as dipropylene glycol and tripropylene glycol, and the like.

[0090] The glycol ether acetates used in the partial azeotropic composition of the present invention include 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, and dipropylene glycol, which do not generate alkoxyacetic acid in the metabolic system of the human body. Monomethyl ether acetate, dipropylene glycol mono-n-propyl ether acetate, dipropylene glycol mono- _n -butyl ether acetate and the like are preferred because they have lower toxicity.

[0091] Examples of the compound having an ester bond include a compound represented by the following general formula (18). [0092] [Formula 9]

R

[0093] (wherein, R ^d4 and R ^{d &} represent a C ο = alkyl group, alkenyl group, cycloalkyl group, acetyl group, ο

 Neutral strength of carbonyl group, hydroxyl group, ester bond and ether bond

 R

 It represents an aliphatic compound residue, an alicyclic compound residue, an aromatic compound residue and a heterocyclic compound residue having the above. )

Isopropyl acetate Specific examples include acetic acid n-propyl, isobutyl acetate, (vapor pressure 1. 33 X 10 ³ Pa at 20 ° C), acetic acid Isoamiru acetate n- Bed chill, Aseto methyl acetate, methyl lactate, lactic Echiru lactate Propyl, cyclohexyl acetate, ethyl acetate acetate, butyl lactate, 3-methyl-3-methoxybutyl acetate, dimethyl succinate, 2-ethylhexyl acetate, dipropylene glycol monomethyl ether acetate, γ-butyrolataton, dimethyl glutarate, dimethyl adipate And dipropylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.

 [0094] Another example of the compound having an ester bond is a hydroxycarboxylic acid ester. The hydroxycarboxylic acid esters are ester compounds having a hydroxyl group, and are preferably specified by the following general formula (19).

 [0095] [Formula 10]

O H Ο

H ₃ CCH— C— OR

(In the formula, R represents an alkyl group having 16 carbon atoms, an alkyl group or a cycloalkyl group.)

Specific examples include glycol monoester, lactate ester, malate ester, and tartaric acid. Esters, citrates, glycerin monoesters, glycerin diesters, ricinoleates, castor oil and the like can be mentioned.

 [0097] In the partial azeotropic composition of the present invention, among the above components, the nonvolatile component (B) and the volatile component (A) are selected based on the reference vapor pressure Po defined by the formulas (1) and (2). However, they can be obtained by mixing them at a specific ratio that satisfies the relations of equations (3) and (4).

 [0098] In general, a plurality of volatile components (A) having close intermolecular hydrogen bond strengths in a substance and a non-volatile component (B) having remarkably different intramolecular hydrogen bond strengths in a substance. Can be combined. The hydrogen bond strength referred to here depends on the presence and number of atoms with high electronegativity (oxygen, nitrogen, fluorine) and active hydrogen atoms (hydrogen atoms bonded to oxygen, nitrogen, etc.) in each compound. I do.

 [0099] For example, if the volatile component (A) is selected from alcohols having high electronegativity! / を atoms and active hydrogen atoms, the non-volatile component (B) is a hydrocarbon having no intramolecular hydrogen bond in the substance. And a combination of selecting a non-chlorine fluorinated compound containing a fluorine atom as the volatile component (A) and selecting compounds containing no fluorine atom as the non-volatile component (B).

[0100] Among the above-mentioned combinations, for example, a plurality of volatile components (A) themselves form an azeotropic composition, and the azeotropic property of the composition depends on the presence of the non-volatile component (B). However, those which are hardly affected by the influence can realize the partial azeotropic composition of the present invention as a result.

 [0101] More specifically, two or more compounds constituting an azeotropic composition whose vapor pressures at 20 ° C are close to each other are defined as volatile components (A). It is sufficiently lower than A), and one or more compounds can be used as the non-volatile component (B).

[0102] In order to determine a desirable component composition of each volatile component (Ai) selected at this time, as an example, a rectification test using only the required amount of each volatile component (A), for example, an equal amount, was performed. And measuring the condensate composition obtained. In this rectification test, a composition consisting of a volatile component (A) with a known composition, which was put into a predetermined vessel equipped with a rectification tower, was heated! / ヽThe operation of cooling and condensing the liquid to return to the original composition is continuously performed until the composition of the gas phase becomes constant. At this time, the generated steam is cooled. By measuring the condensed liquid composition, the weight ratio of each volatile component (A) is determined.

[0103] When a new composition is prepared by adding the nonvolatile component (B) to the composition having only the volatile component (A) thus obtained, the composition of each nonvolatile component (Bj) When the weight ratio (Boj) to the whole is within an appropriate range that does not affect the azeotropic property of the volatile component (A), all components in the new composition are represented by the formulas (3) and (4). ) Can be satisfied. The appropriate range of Bo j can be confirmed and determined by performing a reflux test on some new compositions having different Bo j and measuring the composition of the condensate obtained.

[0104] In the reflux test, a composition composed of a volatile component (A) and a non-volatile component (B) having a known composition, which was put into a predetermined container, was heated! The operation of cooling and condensing the liquid into a liquid and returning it to the original composition is continuously performed until the composition of the gas phase and the liquid phase becomes constant. At this time, the composition of the liquid generated by cooling and condensing the generated vapor is measured, and it is confirmed that the content of the non-volatile component (B) in the condensed liquid is below a predetermined value.

 [0105] Further, without conducting the above-mentioned preliminary reflux test, a composition was prepared by adjusting the composition of each volatile component and each nonvolatile component satisfying the desired drying, nonflammability, and cleaning properties, The partial azeotropic property of the obtained composition can also be confirmed by a reflux test.

 [0106] The volatile component (A) and the non-volatile component (B) of the partial azeotropic composition of the present invention, which can be particularly preferably used as a detergent composition, will be described below.

[0107] In the volatile component (A) of the present invention as a cleaning composition component, at least one of the volatile components is preferably a non-flammable volatile component. By using a non-flammable volatile component, the partial azeotropic composition having no flash point of the present invention can be obtained. Here, “non-flammable” or “having no flash point” means that the cleaning agent is recognized as having no flash point by the flash point evaluation test described in JISK2265. Particularly when such a partial azeotropic composition is used as a cleaning agent, operation safety can be ensured by covering the liquid phase surface with a vapor phase comprising a non-flammable volatile component. Preferred non-flammable volatile components include halogenated hydrocarbons. More preferably, a non-chlorine fluorine compound and a non-chlorine bromine compound having no ozone layer depletion coefficient are exemplified. More preferably, a non-chlorine fluorine compound having a ratio of the number of fluorine atoms to the number of hydrogen atoms in the non-flammable molecule of 2 or more is exemplified. [0108] Examples of the non-chlorine fluorine compound having a ratio of the number of fluorine atoms to the number of hydrogen atoms in the molecule of 2 or more include a cyclic HFC represented by the following general formula (20) and a chain HFC represented by the following formula (21): Or a compound of the HFE represented by (22), which does not contain a chlorine atom, such as a carbon atom, a hydrogen atom, an oxygen atom, and a fluorine atom, and a combination of two or more compounds selected from these. Can be.

 C H F (20)

 n 2n— m m

 (Where n and m are integers that satisfy 4≤n≤6 and (4Z3) n≤m≤2n-1) C H F (21)

 2x + 2

 (Where X and y are integers of 4≤x≤6, 4 (x + l) Z3≤y≤2x + l)

 C F OC H (22)

 s 2s + l t 2t + l

 (Wherein, s and t are (4t + l) Z2≤s≤7, and represent an integer satisfying l≤t≤3) More specifically, for example, among the above-described non-chlorine fluorine compounds, Those satisfying (20)-(22) are mentioned. Among these, chain HFCs or HFEs having a ratio of the number of fluorine atoms to the number of hydrogen atoms of 3 or more can be used to obtain a partial azeotropic composition excellent in self-extinguishing properties of the present invention, It is a more preferred component. The term “self-extinguishing property” as used herein refers to a kind of flame-retardant substance. Even if a substance having this property is ignited, its flame will extinguish spontaneously after a certain period of time. Furthermore, “excellent in self-extinguishing properties” means that spontaneous extinguishing is observed within 10 seconds after ignition in the self-extinguishing test described below.

 [0109] Specific examples of the volatile component having an excellent effect of improving the self-extinguishing property of the partial azeotropic composition of the present invention include 2H, 3H-perfluoropentane (HFC43-) which has no ignition energy and has excellent nonflammability. 10mee), methyl perfluorobutyl ether, methyl perfluoroisobutyl ether and a mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether (HFE7100).

 [0110] In the cleaning composition of the present invention, as the non-flammable volatile component, one kind selected from non-chlorine fluorine compounds having a ratio of the number of fluorine atoms to the number of hydrogen atoms in the molecule of 2 or more is used. Alternatively, two or more compounds can be used in combination.

[0111] Further, as the volatile component (A), the number of hydrogen atoms of the number of fluorine atoms in these molecules is referred to. Non-flammable, even if a combination of at least one selected from non-chlorine fluorine compounds with a ratio of at least 2 and at least one selected from alcohols, hydrocarbons, esters, and ketones It is preferred because it simultaneously achieves excellent self-extinguishing properties and excellent solubility for light soils such as processing oils with low viscosity.

[0112] Further, as the excellent volatile component (A) of the present invention, a compound which is a chlorine-free fluorine compound and has at least half the number of alkyl groups having no fluorine atom with respect to all alkyl groups in the molecule is mentioned. No. These have higher solubility in processing oils and the like than other non-chlorine fluorine compounds, and as a result, have excellent rinsing properties and steam cleaning properties. For example, 2H, 2H, 4H, 4H, 4H perfluorobutane (HFC365mfc) (A1) can be mentioned.

 [0113] Other preferable volatile components (A) include compounds having a boiling point at normal pressure of 35 ° C or higher and lower than 50 ° C. Since these have a low boiling point, the amount of the non-volatile component (B) in the vapor of the cleaning agent can be suppressed to a certain level or less, so that it is preferable when dryness is particularly important in vapor cleaning. For example, 2H, 2H, 4H, 4H, 4H-perfluorobutane (HFC365mfc) (A1) having a boiling point of 0 ° C can be mentioned.

 [0114] Particularly preferred volatile components (A) as the cleaning composition components of the present invention include, for example, the above-mentioned HFC365mfc (Al) which has excellent drying properties, and hydrogen having the number of fluorine atoms in a nonflammable molecule. When a non-chlorine fluorine compound (A2) with a ratio of 2 or more to the number of atoms is used in combination, if the self-extinguishing property of component (A1) is improved and the non-volatile component (B) is flammable, the danger of ignition This is advantageous because it has the effect of reducing the In this case, 2H, 3H perfluoropentane (HFC43-lOmee) is more preferably used as the component (A2) as methyl perfluorobutyl ether, methyl perfluoroisobutyl ether, or a mixture of both.

(HFE7100) can reduce the amount of component (A2) in the cleaning composition, resulting in a decrease in the boiling point of the cleaning composition and a decrease in the vapor phase of the cleaning composition. By reducing the concentration of the component (B) in the inside, it is possible to enhance the dryness of the object to be cleaned after the steam cleaning and to suppress the composition fluctuation of the cleaning composition during use.

[0115] When a non-chlorine fluorine compound is used as the volatile component (A), the non-volatile component (B) may be used to improve the detergency against any dirt such as processing oils, greases, waxes and fluxes, and to rinse. The vapor pressure at 20 ° C is 1.33 X 10 ³ Pa It is preferable to use one kind of a compound selected from the following components or a combination of two or more kinds.

[0116] When the vapor pressure of the component (B) is within this range, it is possible to obtain the cleaning composition according to the present invention, which is excellent in drying property, cleaning property, and nonflammability, and has less composition fluctuation. Becomes easier. More preferably, the vapor pressure at 20 ° C is not more than 6. 66 X 10 ² Pa, more preferably in consideration of the vapor cleaning of 0. 13 Pa or more 1 or less 33 X 10 ² Pa.

 Examples of such a non-volatile component (B) include various hydrocarbons, alcohols, ketones and organic compounds having an ether bond and a Z or ester bond, having good detergency against various stains. Compounds can be mentioned, and more specific examples include the compounds having the above-mentioned vapor pressure among the hydrocarbons, alcohols, ketones and the like exemplified above. Among these compounds, hydrocarbons are preferably used for washing processing oils, greases, waxes, liquid crystals, etc., and glycol ethers, esters, ketones, and especially glycols are used for washing resins such as flux. Ethers are particularly preferably used.

 [0118] Among the above non-volatile components (B), compounds having an ether bond and a Z or ester bond are preferred. In particular, glycol ethers, glycol ether acetates and hydroxycarboxylic acid esters are other components. When flammable alcohols are used in combination, it is more preferable because the effect of suppressing the flammability is particularly high.

 [0119] Among these compounds, when glycol ethers are used as the non-volatile component (B), glycol ether monoalkyl ethers (B1) and glycol ether dialkyl ethers (B2) 1S It is more preferably used because of its solubility.

[0120] As the component (B1), a compound represented by the following general formula (6) has excellent detergency especially for various stains. Examples thereof include 3-methoxybutanol and 3-methoxy- 3-methylbutanol can be mentioned. [0121] [Formula 11]

[0122] (wherein, R ¹ represents an alkyl group having 16 to 16 carbon atoms, an alkenyl group, or a cycloalkyl group,, R ³ and R ⁴ represent hydrogen or a methyl group, and n represents an integer of 0 or 1. )

 Further, as component (B1), dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, and diamines such as hydrochloride and organic acid of amine which cause ionic residues in flux cleaning, It has excellent cleaning properties against stains such as polymerized rosin and metal salts of rosin, which are generated in the soldering process and cause white residue.

 As the component (B2), a compound represented by the following general formula (7) has excellent detergency especially for various stains, and examples thereof include diethylene glycol di-n-butyl ether. be able to.

 [0124] [Formula 12]

R ⁷ R ⁸

 I

R ⁶ 0— (C (CH _? ) _N CHO) R ⁶ (7)

R ⁹

[0125] (In the formula, R ⁵ is an alkyl group having 4 to 6 carbon atoms, an alkenyl group, or a cycloalkyl group, R ⁷ , R ⁸ , and R ⁹ are a hydrogen or methyl group, and R ⁶ is a carbon atom having 3 to ⁶ carbon atoms. An alkyl group, an alkyl group or a cycloalkyl group of 6, and n represents an integer of 0 or 1.)

Further, as the component (B2), diethylene glycol getyl ether and dipropylene glycol dimethyl ether have excellent detergency against rosin contained in the flux component. [0126] In the detergent composition using the partial azeotropic composition of the present invention, glycol ether monoalkyl ethers (B1) and glycol ether dialkyl are more preferable for various types of stains depending on the purpose of washing. Combinations with ethers (B2) can be selected.

 [0127] For example, a combination in which one of the components (Bl) and (B2) is hydrophilic and the other is hydrophobic can be obtained by cleaning various fluxes or heat curing various solder resist inks applied to the substrate surface. It is particularly suitable for cleaning of hydrophilic inks and UV-curable inks and liquid crystal cleaning. The combination of both components is hydrophilic, so that epoxy and epoxy used for various flux cleaning and adhesion and sealing of various electric and electronic parts can be used. It is particularly suitable for mixing and dispensing machines (dispensers) for urethane-based two-component resins and for cleaning nozzles and nozzles. When both components are hydrophobic, various processing oils such as cutting oil, press oil, drawing oil, heat treatment oil, and anti-oil oil are used when processing low-precision precision machine parts and optical machine parts. It is particularly suitable for cleaning lubricating oils, greases, waxes, liquid crystals and the like.

 [0128] In the cleaning composition of the present invention, glycol ether monoalkyl ethers (B1) can be used in combination with glycol ether acetates (B3) for the purpose of improving processing oil detergency. By using components (B1) and (B3) together, various processing oils used for processing low-polarity precision machine parts, optical machine parts, etc., such as cutting oil, press oil, drawing oil, heat treatment oil It is possible to obtain a detergent composition that is suitable for cleaning oil, lubricating oil and the like, or greases and waxes. For example, as component (B1)

 3-Methoxy-3-methylbutanol, which is used in combination with 3-methyl-3-methoxybutyl acetate as component (B3), exhibits high processing oil washability during boiling washing, while improving processing oil separation at room temperature. Because of its excellent properties, the processing oil brought into the detergent can be easily separated, and if the life of the detergent is prolonged, it will not be easy to remove, and the ester odor of 3-methyl-3-methoxybutyl acetate can be suppressed. ,.

[0129] Examples of the hydroxycarboxylic acid esters used as the nonvolatile component (B) include methyl lactate, ethyl lactate, propyl lactate, butyl lactate, and pentyl lactate. Among these, a particularly preferred example is a butyl group as a part of its molecular structure. Alternatively, a compound containing at least one or more isobutyl groups and a compound containing a chain hydrocarbon structure having 416 carbon atoms and an oxygen atom in a molecule can be given. For example, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl lactate, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether, isobutynol ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether , 3-methoxybutanol, 3-methoxy-3-methylbutanol and diethylene glycol di- _n -butyl ether. These compounds are excellent not only in rosin solubility in flux washing but also in washing properties for ionic substances and white residue-causing substances.

[0130] The cleaning composition comprising the partial azeotropic composition of the present invention exhibits excellent cleaning properties against any stains.

 [0131] The non-volatile component (B) is preferably a low-viscosity component particularly when a rinsing property is required in the detergent composition. The following is more preferred, and more preferably 50 cp or less.

 Further, in the present invention, the non-volatile component (B) is preferably not a surfactant.

 Since surfactants generally have foaming properties, when cleaning is carried out by boiling a detergent containing this surfactant, detergent droplets are mixed into a tank containing other liquids such as a rinsing agent, As a result, the performance of the rinsing agent may deteriorate. Further, when it is necessary to perform steam cleaning, the vapor phase may be required to have a certain cleaning property. In this case, the vapor phase also has a high solubility so as not to impair its drying property. The non-volatile component (B) must be present. However, surfactants generally have too low a vapor pressure, making it difficult to include such substances in the vapor phase of the detergent. Furthermore, with surfactants with a cleaning mechanism that removes dirt by emulsifying and dispersing them in the liquid, sufficient effects cannot be obtained with the amount of liquid condensed around the object to be cleaned in steam cleaning. In particular, it is unsuitable as a nonvolatile component (B) of a detergent composition having steam cleaning properties.

[0133] The partial azeotropic composition of the present invention is obtained by mixing each volatile component (Ai) and each non-volatile component (Bj) according to a conventional method, and homogenizing them. There is no particular limitation on the weight ratio of each component as long as it satisfies the formulas (3) and (4) and the performance required of the partial azeotropic composition of the present invention is satisfied. The ratio of the volatile component to the non-volatile component, (∑Aoi) / (∑Boj), is preferably 95Z5-10Z90. When the ratio of the two is within this range, the resulting detergent composition can achieve both desirable washing properties and drying properties. More preferably, it is 20Z80-80Z20, more preferably 30 / 70-70 / 30, and still more preferably, 40 / 60-60 / 40.

 In particular, HFC365mfc as the component (A1), and a non-chlorine fluorine compound having a ratio of the number of fluorine atoms to the number of hydrogen atoms in the molecule of 2 or more as the component (A2) One or more compounds selected from the group The weight ratio of each component in the case of using is not particularly limited as long as it does not impair the high detergency, low toxicity, low flammability, and high self-extinguishing properties of the detergent composition of the present invention. Although there is no limitation, it is preferable that the ratio of the volatile component amount to the nonvolatile component amount, (Aol + Ao2) Z (2Boj), be 95Z5-30Z70. When the weight ratio of the component (B) is greater than the power, a more favorable effect of improving the dissolving power for various stains can be obtained, and when it is less than 70, more favorable low flammability and high self-extinguishing properties can be achieved. A more preferable range is 90Z10-40Z60 in consideration of the balance between the cleaning properties of the detergent, low flammability and high self-extinguishing properties.

 [0135] In this case, the composition ratio of component (A1) and component (A2), and the range of AolZAo2 are preferably 97Z3-60Z40. When the weight ratio of the component (A2) is more than 3, a more favorable effect of improving the self-extinguishing property is obtained, and when it is less than 40, more excellent drying property during steam washing is obtained. Considering the balance between the self-extinguishing properties of the detergent and the drying properties during steam cleaning, a more preferred range is 97 / 3-85 / 15, and a more preferred range is 95Z5-88Z12.

[0136] Further, in this case, a composition having the same composition as the vapor phase composition obtained in the reflux test using the above-mentioned cleaning agent, together with the same cleaning agent, a rinsing agent and a replenisher used in the cleaning step It can be used as a liquid. The range of (Aol + Ao2) Z (∑Boj) in this rinse agent and replenisher is the characteristic of the rinse agent: high drying, low toxicity, low flammability, high self-extinguishing properties, and There is no particular limitation as long as the composition fluctuation suppressing effect is not impaired, but it is preferably 98 / 2-99.9 / 0.1. When the weight ratio of the component (B) is less than 2, high dryness, low flammability, and high self-extinguishing properties can be obtained. When it is larger, the composition fluctuation suppressing effect of the more preferably used cleaning agent can be obtained. In consideration of the balance between the high drying property of the rinsing agent and the effect of suppressing composition fluctuation, a more preferable range is 99 / 1-99.8 / 0.2.

 [0137] The proportions of the component (A1) and the component (A2) in the rinsing agent and the replenisher are preferably the same as those in the above-described cleaning agent.

 [0138] In particular, the rinsing agent containing 2H, 2H, 4H, 4H, 4H-perfluorobutane (HFC365 mfc) as the component (A1) is more effective than other non-chlorinated fluorine compound rinsing agents in processing oil. Has high solubility. As a result, even if a washing object containing a large amount of dirt accumulated over a long period of time is brought into the rinsing process, re-adhesion of the dirt to the washing object is suppressed, and a sufficient rinsing function is achieved. Can be demonstrated. Therefore, it is possible to reduce the frequency of replacement of the cleaning agent with the aim of reducing the rinsing function, and as a result, it is possible to extend the life of the cleaning agent. Further, by using the component (B) together, it becomes possible to cope with a wider variety of stains than when only the volatile component (A) is included.

 [0139] A composition having the same composition as the above-mentioned rinsing agent and replenisher can also be used as a finish cleaning agent. In particular, when a physical force such as rocking, ultrasonic waves, showering or wiping can be applied to the cleaning method, or when the dirt to be cleaned is relatively small, such as a foreign substance or a low-viscosity processing oil, Such a cleaning agent is more preferably used because it can achieve both the final cleaning property and the drying property.

[0140] For example, after the printed circuit board on which the mounted components are soldered is cleaned with the cleaning agent described in the present application, a locally modified flux or white residue may be simply wiped off with a cotton swab or the like to perform a partial correction. In this case, it is necessary to complete the cleaning with one solution. With a cleaning agent containing a large amount of non-volatile components, the non-volatile components spread between the mounted components, making it difficult to wipe off with a rinsing agent later, resulting in poor drying. On the other hand, only volatile components having poor solubility have insufficient cleaning properties.

[0141] In the partial azeotropic composition of the present invention, when the glycol ether monoalkyl ethers (B1) and the glycol ether dialkyl ethers (B2) are used in combination as the non-volatile component (B), The range of the mass ratio of the component (B1) to the component (B2) is more preferably 90 Z10-10Z90. When the mass ratio of component (B1) is greater than 10, In addition, more preferable rosin solubility is obtained, and when it is smaller than 90, more preferable detergency against polymerized rosin and metal salts of rosin is obtained. Considering the balance between the solubility of the detergent in rosin and the polymerization of dirt that causes white residue such as rosin, the weight ratio of component (B1) to component (B2) is more preferably 80Z20. — 20Z80, more preferably 70Z30-30Z70.

[0142] Further, in the partial azeotropic composition of the present invention, a component in the case where a glycol ether monoalkyl ether (B1) and a glycol ether acetate (B3) are used in combination as the non-volatile component (B). The mass ratio of the component (B1) to the component (B3) is more preferably 90 / 10-10Z90. When the mass ratio of the component (B1) is larger than 10, sometimes excellent and excellent metal stability and low odor are obtained, and when it is smaller than 90, more preferable detergency against various processing oils is obtained. Considering the balance between the solubility of the detergent in the processing oil and the excellent metal stability and low odor, the mass ratio of the component (B1) to the component (B3) is more preferably 80Z20-20Z80. Preferably, it is 70Z30 to 30Z70.

 [0143] In the cleaning method of the present invention, the range of the mass ratio of the component (B1) to the component (B3) and the range of the mass ratio of the component (B3) to the component (B3) constituting the rinsing agent and the replenisher are both The detergent used has the same composition as the liquid obtained by the reflux test. By using the same composition in combination with a detergent, it is possible to suppress fluctuations in the detergent composition and to maintain excellent cleaning self-extinguishing properties of the detergent.

 [0144] The cleaning composition of the present invention may contain, if necessary, various auxiliaries such as an antioxidant, an ultraviolet absorber, a surfactant, a stabilizer, and the like, to the extent that the effects of the present invention are not significantly impaired. An antifoaming agent may be added if necessary. Hereinafter, specific examples of the additives that can be added to the cleaning composition of the present invention will be exemplified.

 [0145] Examples of the antioxidant are shown below for each type.

[0146] Examples of the phenolic antioxidants include 1-oxy-3-methyl-4 isopropylbenzene, 2,4-dimethyl-6t-butylphenol, 2,6-di-tert-butylphenol, butylhydroxylinol, and 2,6-di-tert-butylphenol. p-Cresol, 2,6-di-tert-butyl-4-ethyl phenol, 2,6-di-tert-butyl-4-hydroxymethylphenol, triethylene glycol Coruvis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], And compounds such as octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) probionate.

Examples of the amine-based antioxidant include compounds such as diphenyl-p-phenylenediamine, 4-amino-p-diphenylamine, and p, p'-dioctyldiphenylamine.

[0148] Phosphorus-based antioxidants include phenylisodecyl phosphite, diphenyldiisooctylphosphite, diphenyldiisodecylphosphite, triphenylphosphite, trisno-ylphenylphosphite, and bis (2,4-dibutylbutylphosphite). -Le) pentaerythritol diphosphite and the like.

 [0149] Examples of the zeo-based antioxidants include dilauryl 3,3'thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl 3, Compounds such as 3'-thiodipropionate can be mentioned.

 [0150] Among these exemplified compounds, 2,6-di-t-butyl-p-tarezole is particularly preferred because the effect of adding the phenol-based compound is great. In the case of performing steam cleaning using the cleaning agent continuously by heating, at least one selected from the group consisting of a phenol-based antioxidant and an amine-based antioxidant, and a phosphorus-based antioxidant. The combined use of one or more selected agents and phosphorus-based antioxidants makes it possible to suppress the oxidative decomposition of the cleaning agent for a long period of time.

[0151] Examples of the ultraviolet absorber used in the cleaning composition of the present invention include 4-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, and 2-hydroxybenzophenone. 4-Methoxy-4'-benzobenzophenone, 2,2'-hydroxy-4n otatobenzobenzophenone, 2-hydroxy-4n otatobenzobenzophenone, 2,4-dihydroxybenzophenone, 5-clotophenone Benzophenones such as hydroxybenzophenone, 2,2'-dihydroxy 4,4dimethoxybenzophenone, 4-dodecyl-2-hydroxybenzophenone, phenol salicylate, 4t butyl phenol salicylate, 4 One-year-old cutil Phenyl salicylates such as phenol salicylate and bisphenol A disalicylate and 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5bis (α, α ' —Didimethylbenzyl) phenyl] — 2Η-benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-) Hydroxyphenyl) -5 benzobenzotriazole, 2- (3,5-diamyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4't-one-octylphenyl) benzotriazole Benzotriazoles such as sol, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-5'-tert-phenyl) benzotriazole Rukoto can.

[0152] In the case where an antioxidant or an ultraviolet absorber is added to the cleaning agent, the amount is preferably 1 to 1000 ppm, more preferably 10-ΙΟΟΟρ pm, based on the total mass of each volatile component (Ai) and nonvolatile component (Bj). is there.

 [0153] The melting point of the cleaning agent of the present invention is preferably 15 ° C or lower, but is more preferably 10 ° C or lower, further preferably 5 ° C or lower in consideration of use in winter.

 [0154] When an antioxidant or an ultraviolet absorber is added to the rinsing agent of the present invention, the amount of the volatile component (Ai) and the non-volatile component (Bj) constituting the rinsing agent is 1 to 11% by mass. ΙΟΟΟρρ m, more preferably 10-100 ppm.

 [0155] As the surfactant used in the cleaning composition of the present invention, an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant may be added. Examples of the a-one-based surfactant include fatty acids having 6 to 20 carbon atoms, alkali metals such as dodecylbenzenesulfonic acid, alkanolamines, and amine salts. Examples of the cationic surfactant include a quaternary ammonium salt and the like. Examples of the non-one type surfactant include an alkyl phenol, an ethylene oxide adduct of a linear or branched aliphatic alcohol having 8 to 18 carbon atoms, and a block polymer of polyethylene oxide polypropylene oxide. Examples of the amphoteric surfactant include a betaine type and an amino acid type.

[0156] Examples of the stabilizer used in the detergent composition of the present invention include nitroalkanes such as tromethane and nitroethane, epoxides such as butylene oxide, and ethers such as 1,4 dioxane. Examples thereof include amines such as ters and triethanolamine, and benzotriazoles.

[0157] Examples of the antifoaming agent used in the cleaning composition of the present invention include self-emulsifying silicones, silicones, fatty acids, higher alcohols, polypropylene glycol, polyethylene glycol, and fluorine-based surfactants.

[0158] When these surfactants, stabilizers, and antifoaming agents are added to the cleaning composition of the present invention, the volatile components (Ai) and the non-volatile components (Bj) are considered in consideration of rinsing properties. For the total mass,

1 It is 1000 ppm, more preferably 10-100 ppm.

[0159] Using the cleaning composition of the present invention, effective cleaning can be performed by the following cleaning method.

 [0160] In the cleaning method of the present invention, a resin having the same composition as the condensate of vapor generated from the cleaning agent comprising the partial azeotropic composition containing the volatile component (A) and the non-volatile component (B) of the present invention. Use a rinsing agent. According to the cleaning method of the present invention, a cleaning method can be realized which has excellent cleaning properties, quick drying of the object to be cleaned, and work safety due to the self-extinguishing property of the vapor of the cleaning composition.

 [0161] Further, in the cleaning method of the present invention, by using a composition having the same composition as the above-mentioned rinsing agent as a replenisher, it is possible to reduce the amount of the cleaning composition in which the internal force of the cleaning apparatus is also dissipated during cleaning. Occasionally, the composition fluctuation of the cleaning agent can be suppressed, and the predetermined cleaning performance can be maintained for a long time. In this way, even when an azeotropic mixture is not formed as the entire cleaning composition, a cleaning method with high work stability can be realized.

[0162] The compositions of the above-mentioned rinsing agent and replenisher can be determined by the above-mentioned reflux test on the partially azeotropic detergent composition used as a detergent. In addition, the composition of the replenisher can be determined by a distillation test, in addition to the reflux test. In the distillation test, the cooling condensate of the steam generated by heating the detergent composition is recovered as a distillate without returning to the composition, and the composition of the distillate recovered at a predetermined distillation rate is determined. The required composition of the replenisher can be known from the measurement. The composition of the replenisher is preferably U in order to suppress the composition fluctuation of the detergent, and the composition of the replenisher is a distillate composition recovered at a distillate rate of 20% by volume or less, more preferably 10% by volume or less. The reflux test is more common than the distillation test due to the broader range of composition types, but the test When the composition ratio of the component (B) in the multi-component composition is high, the purpose can be more easily achieved by a distillation test.

[0163] Further, in the partial azeotropic composition used in the cleaning method of the present invention, the volatile component (A1) is HFC365mfc, and the volatile component (A2) has a ratio of fluorine atoms to hydrogen atoms in the molecule of 2 or more. there chlorine-fluorine compound, and, if the vapor pressure definitive to 20 ° C as a non-volatile component (B) is used: 1. less than 33 X 10 ³ Pa compounds, detergents to generate steam having a self-extinguishing composition When the ratio of the number of fluorine atoms to the number of hydrogen atoms in the molecule of component (A2) is 2 or more, volatile components including component (A2) generated by heating this partial azeotropic composition are mainly used. By covering the surface of the cleaning agent liquid with the vapor as a component, its excellent self-extinguishing properties can realize a highly safe cleaning method. As described above, the partial azeotropic composition has an excellent overall system by covering the upper part of the liquid surface with a vapor composition mainly composed of volatile components having characteristics (for example, excellent self-extinguishing properties) generated by heating. Features can be provided. The cleaning device used at this time is not particularly limited as long as the above-mentioned vapor coating can be realized.For example, one or more cleaning tanks, or one or more cleaning tanks and one or more Examples include a washing machine including a rinsing tank.

 [0164] In the cleaning method of the present invention, the cleaning step and the rinsing step are performed by combining other cleaning methods such as immersion, spray, and shower for the purpose of improving the cleaning property and the rinsing property. Monkey

 Example

 [0165] The present invention will be described based on examples.

<Examples 1 to 5, Comparative Examples 1 to 4>

 (1) Reflux test

 A reflux test was conducted as follows to confirm that the following cleaning agents were partially azeotropic compositions and to determine the composition of the replenisher and the rinsing agent.

[0167] As the volatile component (A) and the nonvolatile component (B) satisfying the formulas (1) and (2), the components shown in Tables 1 and 2 were mixed with the compositions shown in the table to prepare a detergent. 300 ml of the obtained detergent was placed in a 500 ml eggplant type flask equipped with a reflux device, and after refluxing for 2 hours, the condensate distilled off at the top was sampled, and its composition was analyzed by gas chromatography. Mind received The analysis value was used as the composition of the replenisher and the rinsing agent. Tables 1 and 2 show the composition analysis values at this time.

 [0168] Since each of the compositions of Examples 1 to 5 shown in Table 1 satisfies the formulas (3) and (4), this composition may be a partially azeotropic composition. confirmed. On the other hand, it was confirmed that the composition of Comparative Examples 14 to 14 shown in Table 2 did not satisfy the formula (4) and was not a partially azeotropic composition. In the composition of Comparative Examples 14 to 14, the composition ratio of the volatile component (A) in the gas phase at the boiling point is significantly different from the composition ratio of the volatile component (A) in the composition at normal temperature. Therefore, the results of Comparative Examples 14 to 14 indicate that when cleaning against dirt such as processing oils and fluxes that exhibit good solubility in hydrocarbons and alcohols as volatile components (A), the boiling detergent This indicates that a stable cleaning effect at the time of formulation design cannot be obtained because the cleaning performance shown differs from the steam cleaning performance shown by the vapor phase. It also indicates that the risk of ignition may increase due to the difference from the risk of ignition at the time of prescription design.

 [0169] Subsequently, an actual operation test was performed using the cleaning agent of Example 2, the rinsing agent and the replenisher, and the long-term composition stability of these cleaning agents was confirmed.

 [0170] (2) Actual operation test 1 (composition variability 1)

 A 7-day actual operation test was performed by the method described below.

 [0171] The partially azeotropic composition of Example 1 was poured into the cleaning tank 1 of the cleaning apparatus shown in Fig. 1 as a cleaning agent, and the rinse tank 2 and the water separator 4 were reexamined by a reflux test. A rinse agent whose composition has been determined is added. The cleaning agent in the cleaning tank 1 is heated and boiled by the heater 6, and the generated steam is filled in the steam zone 3. The steam filled in the steam zone 3 is condensed by the cooling pipe 7, and a part of the condensate and water adhering to the cooling pipe 7 are separated by standing still while being cooled by the cooling pipe 12 by the water separator 4. Then, it enters the condensate canister 2 from which water has been removed, and finally returns to the washing tank 1 after overflowing 11.

[0172] After the start of the test, the decrease in the detergent composition in the system due to the dissipation of steam from the opening 13 of the washing machine was confirmed by replenishing the rinse agent as a replenisher into the system under the following operating conditions. Replenishment was carried out every two hours. In order to examine the composition change of the cleaning agent during the test period, the cleaning agent in the cleaning tank 1 immediately after the replenishment was sampled, and the composition was analyzed by gas chromatography. When the test machine was restarted after stopping, the liquid was replenished immediately before the restart, then sampling was performed, and the composition was analyzed in the same manner. Analysis obtained The detergent composition variation rate was calculated from the values by the following formula.

 , Detergent composition fluctuation rate (%)

 = {(Sampling solution composition-composition before test start) Z Composition before test start} X loo • Operating conditions

 Operating time: 168 hours (run and stop alternately)

 Driving cycle

 During operation: 8 hours X 5 times (time when heater 6 is activated is considered as operation) At stop: 16 hours X 4 times, 64 hours X 1 time (stop time when heater 6 is stopped) Status)

 Liquid replenishment

 During operation: Measure the reduced amount of cleaning solution and rinsing solution every 2 hours, and replenish replenisher in cleaning tank 1 in an amount corresponding to the reduced amount.

 [0173] At the time of stoppage: Before the operation is started, the amount of reduction of the cleaning liquid and the rinsing liquid is measured, and the replenisher corresponding to the reduced amount is supplied to cleaning tank 1.

 Washer opening

 During operation: Do not cover.

 [0174] When stopped: close the lid

 refrigerator

 During operation: Operate

 When stopped: Stop

 Cooling tube temperature: 10 ° C

 Heater capacity: 370w

 Free board ratio: 0.92

 Table 3 shows the change over time in the component composition and the above-mentioned composition variation rate during the operating hours, and FIG. 2 shows the change over time in the component composition. During one week of continuous operation, it was confirmed that the fluctuation rate of the detergent composition in the washing tank could be controlled stably within 20%.

(3) Operation test 2 of actual machine (composition variability 2)

Change to the detergent composition of Example 2 and increase the frequency of replenishment and sampling every day. The sampling rate was changed after replenishing the liquid just before restarting after stopping the tester. The other methods and operations were the same as in Test (2), and a 7-day actual machine test was performed.

[0176] Table 4 shows the results of the test (3) performed using the cleaning agent, the rinsing agent, and the replenisher having the composition of Example 2. During the continuous operation for one week, it was confirmed that the fluctuation rate of the cleaning agent composition in the cleaning tank could be controlled stably within 20%.

(4) Detergency test

 Impregnate a 30-mesh stainless steel wire mesh (0.01 x 0.02 m) with the following metalworking oil.

A test piece prepared by heating at 0 ° C for 30 minutes was washed in the apparatus shown in Fig. 1 using the sample detergent composition under the following washing conditions. The steam generated was washed with steam and dried. The state of the stainless steel wire mesh after drying was visually evaluated to determine the cleanability of the sample detergent.

[0178] The evaluation is based on the following criteria.

 ◎: No residual processing oil

 〇: Processing oil remains in part

 X: Processing oil remains

 (5) Flux detergency test

 A glass epoxy printed circuit board (35 mm x 48 mm) is immersed in a commercially available flux on one side, air-dried, and then soldered at 250 ° C to prepare a test piece with a sample detergent composition! After washing and rinsing with, steam washing was performed using steam generated from the sample detergent composition and dried. The ionic residue value (unit: g NaClZsqin) of the dried printed circuit board was measured with an omega meter (600R-SC, manufactured by Alpha Metals), and the obtained measured value was evaluated according to the following criteria. The flux washability of the agent was determined. ©: a≤7

 〇: 7 <α≤14

 X: 14 <a

• Metal working oil used in test (4): A liquid containing 0.1% by weight of dye (Sudan) and 25% by weight of u-cut GH35 (trade name, manufactured by Nippon Oil Co., Ltd.) in perchlorethylene. It was adjusted and used as a metal working oil for testing. 'Trade name of the flux used in test (5): JS-64ND (manufactured by Hiroki Corporation)

 • Cleaning conditions

 Cleaning tank: 2 minutes boiling cleaning

 Rinse bath: Immersion rocking for 2 minutes (20 times for Z minutes, the condensate of steam obtained by heating the cleaning agent is used as the rinse)

 Steam zone: leave for 1 minute in the steam obtained by heating the cleaning agent

 <Example 6—24>

The components having the compositions shown in Table 5 were mixed to obtain a desired detergent having partial azeotropic properties. The above (4) cleaning test and (5) flux cleaning test were performed for each cleaning agent, and the results are summarized in Table 5. Component (A1) 2H, 2H, 4H, 4H, 4H—Perfluorobutane (HFC365 mfc) and component (A2) Non-chlorine fluorine compounds with a ratio of the number of fluorine atoms to the number of hydrogen atoms in the molecule of 2 or more One or more selected compounds and component (B) Detergent with excellent processing oil solubility and flux solubility when used in combination with a compound having a vapor pressure of less than 1.33 × 10 ³ Pa at 20 ° C was gotten.

<Comparative Example 5—7>

 The same tests as in Examples 6 to 24 were performed on the compounds described in Table 5. The results are summarized in Table 5. 2H, 2H, 4H, 4H, 4H—Perfluorobutane (HFC365mfc), 2H, 3H—Perfluoropentane (HFC43-10mee), a mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether ( HFE7100) had insufficient processing oil solubility and flux solubility.

[0180] (6) Flash point measurement

 According to JIS K 2265, the flash point was measured by a closed tag type up to a measurement temperature of 80 ° C, and a Cleveland open type at a measurement temperature of 81 ° C or more. The evaluation is based on the following criteria.

 〇: No flash point

 X: With flash point

 Example 25—37>

Each component was mixed according to the composition shown in Table 6 to obtain a desired detergent having a partial azeotropic property. The above (6) flash point was measured for each cleaning agent, and the results are summarized in Table 6. component (A1) 2H, 2H, 4H, 4H, 4H—Perfluorobutane (HFC365mfc), component (A2) Non-chlorine fluorinated compound with a ratio of the number of fluorine atoms to the number of hydrogen atoms in the molecule of 2 or more One or more compounds and components selected from the following): It was confirmed that the flash point was eliminated by using a compound having a vapor pressure of less than 1.33 × 10 ³ Pa at 20 ° C. in combination.

 [0181] <Comparative Examples 8 to 12>

 The flash points of the compounds described in Table 6 were measured in the same manner as in Examples 25-37. Table 6 summarizes the results. Flash points were confirmed for all the compounds measured.

 (7) Self-extinguishing test

 500ml of sample cleaner is put into a simple glass-made steam cleaner (cylindrical shape), heated on a hot plate, and refluxed while condensing steam with a cooling pipe. After refluxing for 30 minutes, bring the flame of the ignition man close to the opening, measure the time until the flame goes out naturally (self-extinguishing time) under the same conditions 20 times under the same conditions, and evaluate the self-extinguishing property by the average value of 20 times I do.

[0182] Evaluation criteria are based on the following criteria.

 〇: Extinguish within 10 seconds after ignition

 X: Burn for 10 seconds or more after ignition

 •Test condition

 Measurement location: Draft (no wind)

Opening area: 150cm ² (diameter: 138mm)

 Cooling water temperature: 5 ° C

 Free board ratio: 0.3

 Humidity: 80%

 Example 38—47>

The components having the compositions shown in Table 7 were mixed to obtain a desired detergent having a partial azeotropic property. The above (7) Self-extinguishing test was performed for each cleaning agent, and the results are summarized in Table 7. Component (A1) 2H, 2H, 4H, 4H, 4H—Perfluorobutane (HFC365mfc), component (A2) Non-chlorine fluorine compounds with a ratio of the number of fluorine atoms to the number of hydrogen atoms in the molecule of 2 or more One or more compounds, components (B) vapor pressure at 20 ° C The flame spontaneously extinguished within 10 seconds after ignition by using a compound with a concentration of less than 1.33 X 10 ³ Pa.

[0183] <Comparative Example 13>

 The compounds listed in Table 7 were subjected to the same self-extinguishing test as in Examples 38-47. The results are summarized in Table 7. 2H, 2H, 4H, 4H, 4H-perfluorobutane (HFC

At 365mfc), it continued burning for more than 10 seconds after ignition.

(8) Drying test

 After washing 20 pieces of glass fiber (diameter: 0.17 mm, length: 100 mm) in a bundle with the apparatus shown in Fig. 1, rinse with the following rinsing agent, and then wash with steam. dry. The drying property was raised by steam washing, the force was left at room temperature for 30 seconds, and the state of the 20 glass fibers was visually evaluated to determine the drying property of the sample detergent.

[0185] The evaluation criteria are as follows.

 〇: 20 glass fibers are easily broken.

 X: 20 pieces of glass fiber do not fall apart as a lump.

 •Test condition

 Rinse agent: vapor condensate obtained by heating the cleaning agent

 Cleaning tank: 2 minutes boiling cleaning

 Rinse bath: Immersion rocking for 2 minutes (20 times for Z,)

 Steam zone: leave for 1 minute in the steam obtained by heating the cleaning agent

 <Example 48-55>

Each component was mixed with the composition shown in Table 8 to obtain a desired partial azeotropic cleaning agent. For each detergent, the above (8) drying test was performed, and the results are summarized in Table 8. Component (A1) 2H, 2H, 4H, 4H, 4H—Non-chlorinated fluorinated compound in which the ratio of the number of fluorine atoms to the number of hydrogen atoms in the perfluorobutane (HFC365mfc) and component (A2) molecules is 2 or more Product and component (B) By using a compound with a vapor pressure of less than 1.33 x 10 ³ Pa at 20 ° C, 20 glass fibers can be easily disintegrated after washing and have excellent drying properties. This was confirmed.

<Comparative Examples 14-17> The same self-extinguishing test as in Examples 48 to 55 was performed on the non-partially azeotropic composition having the component powers shown in Table 8. Table 8 summarizes the results. Component (A2) HFC with a boiling point of 55 ° C or HFE with a boiling point of 61 ° C for a non-chlorine fluorine compound with a ratio of the number of fluorine atoms to the number of hydrogen atoms in the molecule of 2 or more and (B) the vapor pressure at 20 ° C However, when a compound having a molecular weight of less than 1.33 × 10 ³ Pa was used in combination, it was confirmed that 20 glass fibers remained in a lump after washing and were inferior in drying property.

 (9) Rinse test

 A 30-mesh stainless steel wire mesh (0.01 x 0.02 m) is impregnated with metalworking oil (trade name: u-cut terami AM30, manufactured by Nippon Oil Co., Ltd.), and heated at 100 ° C for 30 minutes to prepare a test piece. It was created. Heat a glass steam cleaner with a cooling tube containing the following cleaning composition mixed with the above processing oil on a hot plate, and immerse the test piece in the cleaning oil-containing cleaning composition. As a result, boiling cleaning was performed. Next, the test piece was rinsed at room temperature using each sample rinsing agent, and then dried. The amount of processing oil remaining on the test specimen after drying was measured using an oil content measuring device (OIL-20, manufactured by Central Science Co., Ltd.), and the obtained measured value was evaluated according to the following criteria for rinsing. Sex was determined.

 [0188] Detergent composition:

 <l> HFC365mfc

 <2> HFE7100

 <3> 3-Methoxy-3-methylbutanol

 <4> 3-Methoxy-3-methylbutyl acetate

 Composition

= 45. 0/5. 0/20. 0/30. 0 wt ^_0/0

 The evaluation is based on the following criteria.

〇: Residual processing oil amount 5 / z gZcm ² or less

X: Residual processing oil amount exceeds 5 gZcm ² .

<Example 56—57>

Each component was mixed with the composition shown in Table 9 to obtain a target sample rinsing agent. each For the sample rinsing agent, the above (9) Rinsing test was conducted, and the results are summarized in Table 9. 2H, 2H, 4H, 4H, 4H—Perfluorobutane (HFC365mfc) as the component (A1), non-chlorine fluorine with a ratio of the number of fluorine atoms to the number of hydrogen atoms in the molecule of 2 or more as the component (A 2) One or more compounds selected from the compounds and component (B) a compound having a vapor pressure of less than 1.33 × 10 ³ Pa at 20 ° C. can be used in combination with a small amount of a rinsing agent having excellent rinsing properties. Obtained.

<Comparative Examples 18-20>

The same tests as in Examples 56 and 57 were performed on the solvents described in Table 9. Table 9 summarizes the results. 2H, 3H-perfluoropentane, a mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether (HFE7100), 2H, 3H-perfluoropentane and a vapor pressure of 1.33 x 10 at 20 ° C ^The rinsing properties were insufficient when a small amount of a compound less than ³ Pa was used in combination.

(10) Finish cleaning test

 A test piece (SUS304, 2 x 13 x 80 mm) was coated with magic ink and allowed to stand for 30 minutes, then wiped 10 times with a cotton swab impregnated with a sample finish cleaning agent, washed, and allowed to stand at room temperature for 3 minutes. The condition of the test piece after standing was visually evaluated, and the finish cleaning property and the drying property of the sample finishing detergent were determined.

[0192] The evaluation criteria are based on the following criteria.

 Finish washability

 〇: Wiping area, almost no ink remaining

 X: Wipe off area, clear ink remaining

 Drying

 〇: No liquid remains on the test piece

 X: Liquid remains on test piece

 <Example 58—61>

Each component was mixed with the composition shown in Table 10 to obtain the desired finishing detergent. For each cleaning agent, the above (10) Finish cleaning test was performed, and the results are summarized in Table 10. Component (A 1) 2H, 2H, 4H, 4H, 4H—Perfluorobutane (HFC365mfc) and component (A2) molecule One or more compounds selected from non-chlorine fluorinated compounds in which the ratio of the number of fluorine atoms to the number of hydrogen atoms in the compound is 2 or more, and the component (B) has a vapor pressure at 20 ° C of 1.

By using a small amount of a compound having a concentration of less than 33 × 10 ³ Pa, a detergent excellent in finish washing property and drying property was obtained.

<Comparative Examples 21 to 22>

 The same tests as in Examples 58-61 were performed on the solvents listed in Table 10. Table 10 summarizes the results. 2H, 3H-perfluoropentane (HFC43-lOmee), a mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether (HFE7100), showed insufficient finish cleaning properties.

[0194] [Table 1]

Example at the ceremony 20

 Put

 1 2 3 4 5 51+

 Weight part type Weight part weight type expression Heavy ME Person Vapor pressure

 (4) (4) (4) (4) (4) o (Pa)

Composition vapor Composition vapor Composition vapor composition Steam composition Steam composition Composition composition Composition composition Composition composition Composition (I) 2H, 2H, 4H, 4U _t 4Η-Λ ° -full; t-mouth 4.33X 10 ⁴ 44.0 88.8 0.01 40.0 80.0 0.00 30.0 64.0 0.05 35.0 72.6 0.03 45.0 88.0 -0.02 component (Product name: HFC 36 5m fc,

 Nippon Sohe Co., Ltd.)

Composition (Π) 2H, 3H-ί, ° -full. To Tin 2.35X 10 "4.8 8.1 -0.01 20.0 35.2 -0,05

 Min (Product name η'-Trel XF,

 A Aoi Mitsui EFFLO 0 Chemical Co., Ltd.)

(m) Mo-Fu) -Tel and 2.59X 10 ⁴ 1.2 2.7 0.00 10.0 19.7 0.00 15.0 26.9 -0.03 5.0 11.7 0.02

-MM li 7 'ti 1-ter mixture

(Product name: HFE7100. Sumitomo Sum ¹ Imu Co., Ltd.)

Ingredient (IV) 3 Toxin 3-; 1 til / 0.61X10 ² 20.0 0.1-20.0 0.2-25.0 0.4 1 20.0 0.3 1 20.0 0.2-B (V) 3 Toxin 3- / til t-acetate 0.53X10 ² 30.0 0,2 1 30.0 0.1-30.0 0.2 30.0 0.1-

S 'f Dt ° VJV -Luc' 舰 -Tel 0.67X10 ² 25.0 0.4-----

3.71X10 ³ 3.47X10 ³ 3.35X10 ³ 3.47X10 ³ 3.47X10 ³ Boiling point cc) 5 0 51 52 5 1 50 Formula (3) ∑B vj ΣΒ ο j 0.0.0 08 0.006 0. 0 1 6 0. 0 1 0 0.006

S8 lO / OOZd / 13d 9P .SZCCO / SOOZ OAV Comparative example for component

 Put

 Each component 1 2 3

 of

 麵 type nt> type weight part type weight 35 type

(4) (4) (4) (4)

(Pa)

Composition Is gas composition Air composition Vapor composition S Air composition Composition composition Composition composition Composition Normal hexane 1.60 + 10 ⁴ 36.0 84.7 0.14 3S.5 90.5 0.13 39.5 64.3 -0.13 39.5 90.0 0.12 min Methanol 14.0 14.1 -0.14

A Ethanol 5.85 * 10 ³ ---10,5 7.9 -0.13 10.5 33.5 0.13 10.5 8.7 0.12 Component n-Hexanol 3.72 * 10 ² 50.0 1.2-50.0 1.6

B Decane 1.46 * 10 ² 50.0 2.2 ― ― ― ―

3 butoxy - ₃ - Chill ₇ 'ethanol ^{0.67 * 10 £ - - - _} - - - - 50.0 1.3 - based on quasi-vapor pressure Po (P a) .95 * 10 3 1.48 * 10 3 1.47 * 10 3 .46 * ! 0 ³ Boiling point () 5 7 61 58 60 Equation (3) ∑ B j / ΣΒ 0 j 0. 024 0. 032 0. 044 0. 0 16

[Table 3]

Using the composition of Example 1

[0197] [Table 4] The composition of Example 2 was used.

Number of days out of service Operating composition Composition variation rate

 Hour ftS time (% by mass) (%)

 (.nr) (hr) (1) <3) (4) (5) (1) (3) (4) (5)

 0 40.0 10.0 20.0 30.0--

1 After 1 16 8 39.5 8.6 20.7 31.2 -1.3 -14.0 3.5 4.0

2 days later 3 2 1 6 39.5 8.3 21.0 31,2 -1.3, 7.0 5.0 4.0

After 3 mouth 4 8 2 4 40.7 8.1 20.4 30.8 1.8 -19.0 2.0 2.7

4 After 6 4 3 2 39.9 8.7 20.5 30.9 -0.3 -13.0 2.5 3.0

5 days later 8 0 4 0 40.4 9,0 20.2 30.4 1.0 -10.0 1.0 1.3

7 days later 1 2 8-40,7 9.3 20.0 30.0 1.8 -7.0 0.0 0.0

Component (parts by weight)

 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 5 6 7

A 2Η, 2Η, 4Η, _t 4H-,,. -7 liters 55 55 50 50 50 50 60 40 57 50 60 50 50 44 44 64 54 ― 100 I ― ― 1 (Product name: HFC ^ Smfc, manufactured by Nippon Ri Co., Ltd.)

 A-Methyl-Fluoro D-futyl I-Tel and a mixture of 10 3 2 2 2 I 1 1 2 100 min

 (Product name: HFE7100 manufactured by Sumitomo ^ -Em Co., Ltd.)

2H, SH-A ^D -Full phase tan 5 5 10 10 10 10 5 5 8 1 SS 5 5 5 8 100 (trade name: Λ '-Mitsui τ Huho, manufactured by Nuffguchi ^ Mi Co., Ltd.)

411, 5Η, 5ΙΗ. -F MD SHICK fK ¹ lantern--------------------------------

Tofu

--One---one----one--one-one one 55-Ethanol 5

 Ethylene ethylene chilleter 10

Ingredients Water 3 Cyl 3 Toxifanol 40--20 1-36-----20 20--20-1-- Q-Pink ⁺ , J Liremo / Nutirje -Tel-50-one--one-one------20 one-- π-pyrene: ha t pi j is -tel----one-15-20-----16--one--

1 Water V Pyrenk ':]-Lumono— n Pelu-te-one--20-one 20 one 10 one 10-Ϊ0--one--

B Adult Ethylene glycol 'Ril' chiller--1-20--1 1--1--1--1-- 15--20--One one 10 one

 B Sparse ethylene gel-H-fu-tea-ter 40-one-20 one-25-one--20 one-one-one--2 water Pyrene-lusi-ter-19 20 20 20 20 20

 B 3 3 Chi 3, toxicox 'tilacetate---1-1---1-1-1 1 10 1----Butyl lactate--40 1-1---1 1--10 1 -----

(4) Washability 〇 〇 〇 〇 © ◎ ◎ ◎ Θ ◎ © X X X

(5) Flux washability 〇 〇 〇 O ◎ 〇 O © O 〇 © © © © XXX

[9 挲] [6610]

S8 lO / OOZd / 13d 09 .SZCCO / SOOZ OAV

S8 lO / OOZd / 13d 39 .SZCCO / SOOZ OAV

[8 挲] [Ϊ020]

S8 lO / OOZd / 13d P9 .SZCCO / SOOZ OAV Example Comparative Example Class 48 49 50 51 52 53 54 55 14 1 5 16 17 Ingredient 2Η, 2Η, 4Η, 4Η, 4ΗPerfluorobutane 60 60 50 44 50 45 44 44 ― ―

A 1 (trade name: HFC 365m fc, 0 pcs. From f Co., Ltd.) ― ― Ingredient 2 H, 3H—Perfluoropentane 10 ― 5 5 8 5 5 5 50 50 ·· A2 (trade name:> \ ' -mx F 'Mitsui Tung' Tuff Chemical Co., Ltd.)

 Methyl Λ '^ ΜΟƒ'ΜΟί-Ter and a mixture of 10 5 1 1 1 50 δ 0 ifl-ί -ΐΜΰίη'T l-Ter

 (Product name: HFE? IOO, manufactured by Sumitomo Sri-Em Co., Ltd.)

Ingredients エ チ レ ン ethylene 'iJ M / n チ ル チ ル ェ

B 'ethylenek リ rico- お 1 chill: r-¾ 1 30----' エ チ レ ン ethylenek '' n '' チ ル ェ-テ ル テ ル テ ル-40 ―-----シ 7 'Dt' ク'-Ji totel---40 10---

3 Toxi 3 W Tahar---50 one-20 30 50 30 50 30 Bilenk 'Rico-Rushi' Chilleter-----20-20-20

3-.i-Toxi-3-tyl) Sete-T-I-----30------Butyl lactate---40------

(8) Dryness 〇 oo 〇 o O 〇 〇 XXXX

[0202] [Table 9]

 [0203] [Table 10]

Industrial applicability The present invention relates to various processing oils and greases and waxes used for processing precision machine parts and optical machine parts, fluxes used for soldering electric and electronic parts, and screens used for manufacturing substrates. Provided are a cleaning agent, a rinsing agent, a cleaning agent, and a cleaning method using the rinsing agent, which are suitable for cleaning ink and paste adhering to the oil and the oil adhering to the mixing section of the oil discharging device.

Claims

The scope of the claims

 [1] The vapor pressure at 20 ° C is higher than the reference vapor pressure Po defined by equation (1), at least two types of volatile components (A), and the non-volatile components whose vapor pressure at 20 ° C is lower than Po Partial azeotropic composition comprising at least one kind of component (B), wherein the composition of the gas phase and the liquid phase at the boiling point under normal pressure satisfies the relations of equations (3) and (4).

 Po = Pav / 5 (1) (where Pav is the component average vapor pressure defined by equation (2))

 Pav = (∑ Pai + ∑ Pbj) / (na + nb) (2)

(Where Pai is the vapor pressure of each volatile component (Ai) in the composition at 20 ° C, Pbj is the vapor pressure of each volatile component (Bj) at 20 ° C, and na is the vapor pressure of each volatile component (Bj) in the composition. The number of volatile components (A), nb is the number of non-volatile components (B) in the composition, and are integers satisfying 2≤na and l≤nb, respectively, and i and j are each l≤i It is an integer satisfying ≤na and l≤j≤nb.) ₀

 (∑Bvj / ∑Boj) ≤ 0.1 (3)

 (Where Bvj is the weight ratio of each non-volatile component (Bj) in the gas phase, Boj is the weight ratio of each non-volatile component (Bj) in the partial azeotropic composition, and j is the same as in formula (2). is there. ).

 -0.1. (AviZ∑ Avi) (Aoi / ∑ Aoi) ≤ 0.1. (4)

 (Avi is the weight ratio of each volatile component (Ai) in the gas phase, Aoi is the weight ratio of each volatile component (Ai) in the partial azeotropic composition, and i is the same as the formula (2).)

[2] The partially azeotropic yarn composition according to claim 1, which satisfies the relationship of the formula (5).

 0.0001≤ (∑ Bvj / ∑ Boj) ≤ 0.1 (5)

 (Where Boj ゝ Bvj and j are the same as in equations (3) and (4).)

[3] The partial azeotropic composition according to any one of [1] and [2], wherein a part of the azeotropic composition is vaporized and a gaseous phase covers the remaining liquid phase surface.

[4] A compound with a vapor pressure of at least 1.33 X 10 ³ Pa at 20 ° C for all volatile components (A1—Ana) in the composition, and 20 ° C for all non-volatile components (B1—Bnb) 4. The partial azeotropic composition according to claim 1, wherein the compound is a compound having a vapor pressure of less than 1.33 × 10 ³ Pa.

[5] The partial azeotropic composition according to any one of claims 14 to 14, wherein the volatile component (A) also has a compound power selected from halogenated hydrocarbons, hydrocarbons, alcohols, esters, and ketones.

[6] The partial azeotropic composition according to claim 5, wherein the volatile component (A) comprises two or more compounds also selected from the group consisting of halogenated hydrocarbons.

7. The partial azeotropic composition according to claim 6, wherein the halogenated hydrocarbon is a chlorine-free fluorine compound.

 [8] Volatile component (A) is 2H, 2H, 4H, 4H, 4H—Perfluorobutane (HFC365mfc) (

A1) and one or two or more compounds selected from non-chlorine fluorine compounds having a ratio of the number of fluorine atoms to the number of hydrogen atoms in the volatile component molecule of 2 or more. Composition.

 [9] The partial azeotropic composition according to claim 118, wherein the non-volatile component (B) comprises a compound selected from the group consisting of hydrocarbons, alcohols, and ketones.

 [10] The partial azeotropic composition according to any one of [11] to [10], wherein the non-volatile component (B) is an organic compound having an ether bond and a Z or ester bond.

 11. The partial azeotropic composition according to claim 10, comprising one or more compounds selected from the group consisting of a non-volatile component (B) power, glycol ethers, glycol ether acetates, and hydroxycarboxylic acid esters.

 [12] The non-volatile component (B) is composed of one or more compounds selected from glycol ethers and one or more compounds selected from glycol ether acetates and hydroxycarboxylates. Boiling composition.

[13] The non-volatile component (B) comprises one or more compounds selected from the group consisting of compounds represented by the following general formulas (6), (7), (8) and (9). Partially azeotropic composition.

 [Chemical 1]

R R

_{R 'O - C (CH 2} ) n CH- OH (6) (Wherein, R ¹ represents an alkyl group having 16 to 16 carbon atoms, an alkenyl group, or a cycloalkyl group, R ^: , R ³ , and R ⁴ represent hydrogen or a methyl group, and n represents an integer of 0 or 1.) )

[Formula 2]

I i

R ⁵ 0— (C (CH ₂ ) _n CHO) ₂ — R ⁶ (7)

(Wherein, R ⁵ is an alkyl group having 4 to 6 carbon atoms, an alkenyl group, or a cycloalkyl group, R ^;, R ⁸ and R ⁹ are a hydrogen or methyl group, and R ⁶ is an alkyl group having 3 to 6 carbon atoms. Group, alkenyl group or cycloalkyl group, n represents an integer of 0 or 1. Co =)

[Formula 3]

R ¹¹

CH 8)

(Wherein, R ^1U is an alkyl group having 16 carbon atoms, an alkenyl group or a cycloalkyl group, ¹ , R ¹² and R ¹³ are hydrogen or a methyl group, n is an integer of 0 to 1, and m is an integer of 1 to 4. Indicates an integer)

[Formula 4]

OH

CH C OR (9)

(Wherein, R represents an alkyl group having 16 carbon atoms, an alkyl group or a cycloalkyl group) o)

 [14] The non-volatile component (B) power Glycol ether monoalkyl ether power One or more selected compounds (B1) and glycol ether dialkyl ether power One or more selected compounds (B2) power Composition.

 [15] The partial azeotropic composition according to claim 14, wherein the component (B1) is a hydrophilic compound, and the component (B2) is a hydrophobic compound.

 [16] The partial azeotropic composition according to claim 14, wherein the component (B1) is a hydrophobic compound, and the component (B2) is a hydrophilic compound.

 [17] The partially azeotropic composition according to claim 14, wherein the component (B1) and the component (B2) are both hydrophilic conjugates.

 [18] The partially azeotropic composition according to claim 14, wherein the component (Bl) and the component (B2) are both hydrophobic conjugates.

[19] Ingredient (Bl) 1S 3-methoxybutanol, 3-methoxy-3-methylbutanol, dipropylene glycolone mono- _n- propynoleatenole, dipropylene glycolone mono- _n —butynoleate 15. The partial azeotropic composition according to claim 14, comprising the compound of the formula (1).

 [20] The partial azeotropic composition according to claim 14, wherein the component (B2) comprises one or more compounds selected from 1S diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether.

[21] The non-volatile component (B) power glycol ether monoalkyl ether power The selected one or more compounds (B1) and the glycol ether acetate power include at least one selected compound (B3). Partially azeotropic composition.

[22] The partial azeotropic composition according to any one of [11] to [21], which has no flash point.

[23] The partial azeotropic composition according to any one of [11] to [22], which is excellent in self-extinguishing properties.

[24] A cleaning agent comprising any one of the partial azeotropic compositions.

[25] A condensate of steam generated by heating any one of the partial azeotropic compositions.

[26] A rinse agent having the same composition as the condensate of claim 25.

[27] A replenisher for a detergent having the same composition as the condensate of claim 25.

[28] A cleaning method using the cleaning agent according to claim 24 and the rinsing agent according to claim 26.

[29] A cleaning method using the cleaning agent according to claim 24 and a replenisher for the cleaning agent according to claim 27.

[30] A cleaning method using the cleaning agent according to claim 24, the rinsing agent according to claim 26, and a replenisher for the cleaning agent according to claim 27.

 [31] A finish detergent having the same composition as the condensate of claim 25.

[32] 2H, 2H, 4H, 4H, 4H—Perfluorobutane (HFC365mfc) (Component A1), a non-chlorine fluorine compound whose number ratio of fluorine atom Z hydrogen atom in the molecule is 2 or more. or two or more compounds (component A2), vapor pressure at 20 ° C is contained 1. 33 X 1 0 ³ Pa than compound (component B), the content thereof (A1) + (A2) / ( B) = 80/2 0-a composition which is 99.9 / 0.1% by weight.

 [33] A rinsing agent which also has a composition power according to claim 32.

 [34] A replenisher for a detergent comprising the composition of claim 32.

 [35] A finish detergent comprising the composition of claim 32.