JPWO2005033257A1 - Partial azeotropic composition - Google Patents

Abstract

Non-azeotrope comprising two or more volatile components, particularly HFC365mfc, a non-chlorine fluorine compound having a ratio of fluorine atoms to hydrogen atoms in the molecule of 2 or more, and one or more high-boiling nonvolatile components Multi-component composition that is excellent in detergency, drying properties, safety and environmental conservation, and can be suitably used as a detergent composition that can easily control component composition fluctuations over a long period of use. A composition that can.

Description

  The present invention relates to various processing oils and greases and waxes used when processing precision machine parts and optical machine parts, fluxes used when soldering electrical and electronic parts, and screens used when manufacturing substrates. Uses a composition suitably used for cleaning agents and rinsing agents, and cleaning agents and rinsing agents that are preferably used for cleaning inks and pastes adhering to the resin and resins adhering to the mixing section of the resin discharge device It relates to the cleaning method.

  Various processing oils such as cutting oil, press oil, drawing oil, heat treatment oil, rust preventive oil, lubricating oil, or greases, waxes, etc. are used when processing precision machine parts, optical machine parts, etc. However, these stains need to be finally removed, and removal with a solvent is generally performed.

  Soldering is the most commonly used method for joining electronic circuits, but rosin is used for the purpose of removing and cleaning oxides on the metal surface to be soldered, preventing reoxidation, and improving solder wettability. In general, the soldering surface is pre-treated with a flux containing as a main component. As a soldering method, after the substrate is immersed in a solution-like flux, the flux is attached to the substrate surface, and then a molten solder is supplied, or the flux and solder powder are mixed in advance to form a paste. There are methods such as heating after supplying to the place to be soldered, but in any case, flux residue causes corrosion of metal and deterioration of insulation, so remove it thoroughly after soldering There is a need.

  In recent years, the screen printing method has been widely used in the electronic industry field. These are made of silk (nylon, tetron, etc.), or a cloth (screen) woven with stainless steel wire, etc., and fixed around the circumference. The main ingredients such as polyvinyl alcohol, vinyl acetate emulsion, acrylic monomer, and diazonium are fixed on it. Apply a mixture of photosensitizers such as salts and dichromate, stir and mix emulsions by photochemical methods to close the eyes other than the required lines, and a screen with a pattern and urethane called squeegee Printing is performed using a tool with rubber attached. The screen and the squeegee that have been printed must be washed and removed from the screen and the squeegee for the purpose of storage or reuse.

  In addition, resin discharge devices are widely used for joining, filling, or sealing various electric / electronic components and the like with resins such as epoxy, urethane, silicone, and polyester. The resin used for this purpose is often a two-component type (main agent and curing agent) that crosslinks and cures at around room temperature, and the two components are automatically measured in proportion, mixed and stirred. When interrupted, it is necessary to wash the mixing part and the nozzle part in order to prevent the resin from hardening in the discharge device.

  These washing and removal have many characteristics such as nonflammability, low toxicity, and excellent solubility, so that 1,1,2-trichloro-1,2,2-trifluoroethane (hereinafter referred to as “removable”) CFC113) or a mixture of CFC113 and alcohol. However, global environmental pollution problems such as ozone depletion were pointed out for CFC113, and its production was abolished in Japan at the end of 1995. As an alternative to the CFC 113, 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 “CFC 113”) Hydrochlorofluorocarbons such as HCFC225 and 1,1-dichloro-1-fluoroethane (hereinafter referred to as HCFC141b) have been proposed, but these are also slightly depleted in the ozone layer, so in Japan in 2020 It is scheduled to be banned.

Therefore, in recent years, non-flammable fluorine-based solvents having no ozone layer destructive ability such as hydrofluorocarbons (hereinafter referred to as HFC) and hydrofluoroethers (hereinafter referred to as HFE) containing no chlorine atom have been proposed. In addition, since it does not contain chlorine atoms and has low solubility and cannot be used alone as a cleaning agent, several azeotrope-like cleaning technologies that combine a flammable solvent with high solubility in HFC or HFE have been disclosed. (Patent Document 1)
For example, Patent Document 2 discloses a cleaning agent that uses a high-boiling glycol ether in combination in order to increase the dissolving power in HFC and HFE. However, since this cleaning agent uses HFC or HFE having a boiling point of 55 ° C. or higher, the boiling steam contains a lot of high boiling glycol ethers, and the high quick-drying property inherent to HFC and HFE. Since the drying property of the object to be washed exposed to the cleaning agent vapor is reduced, the cleaning use is limited. Furthermore, since the ratio of alkyl groups having no fluorine atom is small with respect to all alkyl groups in the molecule, the solubility in dirt such as processing oil is low. For this reason, when the cleaning liquid that has been used for a long time and contaminated with dirt adheres to the object to be washed and is brought into the rinse process and the steam cleaning process, it becomes difficult to prevent the dirt from reattaching.

  Patent Document 3 discloses cleaning using glycol ethers in combination with HFC having a boiling point of 40 ° C. The HFC used in this cleaning agent has a minimum ignition energy as small as 10 mj and is insufficient in self-extinguishing properties when used in combination with flammable glycol ethers having a flash point. Furthermore, since it has a combustion range of 3.6 to 13.6% by volume, when steam cleaning is performed by heating, the effect as a nonflammable component is low.

  As described above, the conventionally known cleaning agents that combine non-flammable HFCs and HFEs with flammable solvents having high solubility are still insufficient for use as cleaning agents. Or the self-extinguishing property is insufficient, and there are many problems in using it as a cleaning agent.

  On the other hand, especially in a cleaning method using a multi-component cleaning composition containing a high-boiling component, generally the cleaning composition vapor is constantly dissipated from the opening of the cleaning apparatus during the cleaning operation. In addition, the composition of the cleaning composition fluctuates, so that 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 this problem of composition variation, attempts have been made to use various multi-component cleaning compositions that form azeotropic mixtures (Patent Document 1). However, since the components constituting the composition forming the azeotrope are limited in their types and composition ratios, the solubility of the detergent composition depending on the types of components and the composition ratios, self There was a problem that fire extinguishing properties were similarly restricted.

  As described above, as a substitute for CFC113, the cleaning agents that have been proposed so far are prohibited from being used in the future due to the problem of ozone depletion even if cleaning is possible, and the composition variation of the cleaning agent is suppressed. Therefore, even if an azeotropic mixture is used, sufficient cleaning cannot be performed due to the low detergency of the fluorinated solvent, or even if a flammable high boiling point solvent is added to the fluorinated solvent in order to increase the dissolving power. The composition of the cleaning agent fluctuates and it is impossible to maintain a certain level of cleaning agent performance, or there is a danger of ignition. Many products are required for use as cleaning agents that combine all of the various properties required for products, namely environmental safety, cleanability, drying properties, low flammability, self-extinguishing properties, low toxicity, and composition stability. Having a problem That's at present.

Special table 2003-518144 JP-A-10-212498 JP2003-129090A

  The present invention exhibits high cleaning power comparable to HCFC225 against all types of dirt in cleaning, and has low oxidative deterioration during steam cleaning at high temperatures, low toxicity, low flammability, and self-extinguishing Cleaning agent capable of easily controlling composition fluctuations even in a long-term cleaning operation, although it is a multi-component composition that is excellent in water and drying properties and is a non-azeotropic composition It aims at providing the washing | cleaning method using.

  The inventor has two or more volatile components each having excellent properties as a cleaning agent component, in particular, HFC365mfc (manufactured by Nippon Solvay Co., Ltd.) having excellent drying properties, rinsing properties, steam cleaning properties, and the like, and A non-azeotropic composition comprising HFC or HFE having excellent self-extinguishing properties, and further comprising non-volatile components, particularly glycol ethers, glycol ether acetates, and hydroxycarboxylic acid esters which are high-boiling solvents with high solubility However, it has been found that the composition of the vapor composed of a plurality of components generated at its boiling point is constant over a long period of time, and even when used for a long period of time, the liquid composition variation is small as in the azeotropic composition, and the flash point is low. It does not appear, has sufficient self-extinguishing properties, can clean all kinds of dirt, can be used as a rinsing agent or steam cleaning agent, To complete the multi-component detergent compositions which can be used continuously at high temperatures by the addition of agents.

  That is, in the first aspect of the present invention, at least two kinds of volatile components (A) having a vapor pressure at 20 ° C. larger than the reference vapor pressure Po defined by the formula (1), and the vapor pressure at 20 ° C. is higher than Po. It is a partially azeotropic composition comprising at least one kind of a small non-volatile component (B), in which the composition of the gas phase and the liquid phase at the boiling point under normal pressure satisfies the relationship of the formulas (3) and (4).

Po = Pav / 5 (1)
(Where Pav is the component average vapor pressure defined by equation (2))
Pav = (ΣPai + ΣPbj) / (na + nb) (2)
(In the formula, Pai is the vapor pressure at 20 ° C. of each volatile component (Ai) in the composition, Pbj is the vapor pressure at 20 ° C. of each nonvolatile component (Bj), and na is the volatile component (A ), Nb is the number of the non-volatile component (B) in the composition, and is an integer satisfying 2 ≦ na and 1 ≦ nb, and i and j are 1 ≦ i ≦ na and 1 ≦ j ≦, respectively. It is an integer that satisfies nb.)

(ΣBvj / ΣBoj) ≦ 0.1 (3)
(In the formula, Bvj is the weight ratio of each nonvolatile component (Bj) in the gas phase, Boj is the weight ratio of each nonvolatile component (Bj) in the partial azeotropic composition, and j is the same as in Formula (2)). is there.).

−0.1 ≦ (Avi / ΣAvi) − (Aoi / ΣAoi) ≦ 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 in formula (2).)
The second aspect of the invention is the partially azeotropic composition of Invention 1 that satisfies the relationship of the formula (5).
0.0001 ≦ (ΣBvj / ΣBj) ≦ 0.1 (5)
(In the formula, Boj, Bvj, and j are the same as in formulas (3) and (4).)
A third aspect of the invention is the partial azeotrope composition according to any one of the first and second aspects, wherein a part is vaporized and the gas phase covers the remaining liquid phase surface.

The fourth aspect of the invention is a compound in which the vapor pressure at 20 ° C. of all volatile components (A1 to Ana) in the composition is 1.33 × 10 ³ Pa or more, and 20% of all nonvolatile components (B1 to Bnb). It is a partial azeotropic composition according to any one of Inventions 1 to 3, which is a compound having a vapor pressure of less than 1.33 × 10 ³ Pa at ° C.

  A fifth aspect of the invention is the partial azeotrope composition according to any one of the inventions 1 to 4, wherein the volatile component (A) comprises a compound selected from halogenated hydrocarbons, hydrocarbons, alcohols, esters, and ketones. It is.

  A sixth aspect of the invention is the partial azeotropic composition according to the fifth aspect, wherein the volatile component (A) is composed of two or more compounds selected from halogenated hydrocarbons.

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

  In an eighth aspect of the invention, the volatile component (A) is 2H, 2H, 4H, 4H, 4H-perfluorobutane (HFC365mfc) (A1), and the ratio of the number of fluorine atoms in the volatile component molecule to the number of hydrogen atoms is 2. It is a partial azeotrope composition of the invention 7 which consists of 1 type, or 2 or more types of compounds (A2) chosen from the above non-chlorine type fluorine compounds.

  A ninth aspect of the invention is the partial azeotropic composition according to any one of the first to eighth aspects, wherein the nonvolatile component (B) is a compound selected from hydrocarbons, alcohols, and ketones.

  A tenth aspect of the present invention is the partial azeotropic composition according to any one of the first to ninth aspects, wherein the nonvolatile component (B) is composed of one or more compounds selected from the group consisting of organic compounds having an ether bond and / or an ester bond. .

  The eleventh aspect of the invention is the partial azeotrope composition of Invention 10, wherein the non-volatile component (B) comprises one or more compounds selected from the group consisting of glycol ethers, glycol ether acetates and hydroxycarboxylic acid esters. It is.

  A twelfth aspect of the invention is a part of the invention 11 wherein the nonvolatile component (B) comprises one or more compounds selected from glycol ethers and one or more compounds selected from the group consisting of glycol ether acetates and hydroxycarboxylic acid esters. An azeotropic composition.

  In a thirteenth aspect of the invention, the nonvolatile component (B) is composed of one or more compounds selected from the group consisting of compounds represented by the following general formulas (6), (7), (8), and (9). It is a partial azeotropic composition of the invention 11.

(In the formula, R ¹ represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group, or a cycloalkyl group, R ² , R ³ , and R ⁴ represent hydrogen or a methyl group, and n represents an integer of 0 or 1.)

(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 hydrogen or a methyl group, R ⁶ is an alkyl group having 3 to ⁶ carbon atoms, An alkenyl group or a cycloalkyl group, n represents an integer of 0 or 1)

(In the formula, R ¹⁰ is an alkyl group having 1 to 6 carbon atoms, an alkenyl group or a cycloalkyl group, R ¹¹ , R ¹² and R ¹³ are hydrogen or a methyl group, n is an integer of 0 to 1, and m is 1 to 4) Indicates an integer)

(In the formula, R ¹⁴ represents an alkyl group, alkenyl group or cycloalkyl group having 1 to 6 carbon atoms.)
According to a fourteenth aspect of the invention, the nonvolatile component (B) comprises one or more compounds (B1) selected from glycol ether monoalkyl ethers and one or more compounds (B2) selected from glycol ether dialkyl ethers. Partially azeotropic composition.

  The 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.

  A sixteenth aspect of the invention is the partially azeotropic composition according to the fourteenth aspect, wherein the component (B1) is a hydrophobic compound and the component (B2) is a hydrophilic compound.

  The seventeenth aspect of the present invention is the partially azeotropic composition according to the fourteenth aspect of the present invention, wherein the component (B1) and the component (B2) are both hydrophilic compounds.

  The eighteenth aspect of the invention is the partially azeotrope composition of invention 14 wherein both component (B1) and component (B2) are hydrophobic compounds.

  According to a nineteenth aspect of the invention, the component (B1) is one or two selected from 3-methoxybutanol, 3-methoxy-3-methylbutanol, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether. It is a partial azeotrope composition of the invention 14 containing a compound more than a seed | species.

  A twentieth aspect of the invention is the partial azeotrope composition according to the fourteenth aspect, wherein the component (B2) contains one or more compounds selected from diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, and dipropylene glycol dimethyl ether.

  According to a twenty-first aspect of the present invention, the nonvolatile component (B) includes one or more compounds (B1) selected from glycol ether monoalkyl ethers and one or more compounds (B3) selected from glycol ether acetates. Any partially azeotropic composition.

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

  A twenty-third aspect of the present invention is the partially azeotropic composition according to any one of the first to twenty-second aspects, which is excellent in self-extinguishing properties.

  A twenty-fourth aspect of the present invention is a cleaning agent comprising the partially azeotropic composition according to any one of the first to twenty-third aspects.

  A twenty-fifth aspect of the present invention is a vapor condensate generated by heating the partial azeotropic composition according to any of the first to twenty-third aspects.

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

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

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

  A twenty-ninth aspect of the present invention is a cleaning method using the cleaning agent of the twenty-fourth invention and the supplement for the cleaning agent of the twenty-seventh aspect.

  A thirtieth aspect of the invention is a cleaning method using the cleaning agent of the twenty-fourth invention, the rinsing agent of the twenty-sixth invention, and the supplement for the cleaning agent of the twenty-seventh invention.

  The thirty-first aspect of the invention is a finish cleaning agent having the same composition as the condensate of the twenty-fifth aspect of the invention.

In the thirty-second aspect of the invention, 2H, 2H, 4H, 4H, 4H-perfluorobutane (HFC365mfc) is used as the volatile component (A1), and the number ratio of fluorine atoms / hydrogen atoms in the molecule is 2 as the volatile component (A2). One or two or more compounds selected from the above non-chlorine fluorine compounds, and the component (B) are composed of compounds having a vapor pressure at 20 ° C. of less than 1.33 × 10 ³ a, and their weight ratio [ (A1) + (A2)] / (B) is a composition of 80/20 to 99.9 / 0.1% by weight.

  A thirty-third aspect of the invention is a rinse agent comprising the composition according to the thirty-second aspect of the invention.

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

  A thirty-fifth aspect of the present invention is a finish cleaning agent comprising the composition according to the thirty-second aspect.

It is an example of the washing | cleaning apparatus for implementing washing | cleaning using the cleaning composition of this invention, and is the washing | cleaning apparatus used in the Example. 2 is a graph showing a composition change of each component in the cleaning agent in Example 1. FIG.

Explanation of symbols

1 Washing tank 2 Rinse tank 3 Steam zone 4 Water separator 5 Ultrasonic vibrator 6 Heater 7 Cooling pipe 8 Steam flow 9 Condensate pipe 10 Condensate pipe after water separation 11 Overflow liquid flow 12 Cooling pipe 13 Washer opening

  Hereinafter, the present invention will be described in detail.

  In the present invention, cleaning is an operation that removes dirt components adhering to an object to be cleaned to a level that does not affect the next process using the cleaning composition. Means a cleaning composition. In addition, rinsing is an operation of replacing a cleaning agent containing a dirt component adhering to an object to be washed with a composition not containing a dirt component, and the rinse agent is a composition used at this time. It is. Furthermore, steam cleaning is an operation that condenses and liquefies the vapor generated from the cleaning agent or rinse agent on the surface of the object to be cleaned, thereby removing the dirt components slightly remaining on the surface of the object to be cleaned. is there. In addition, finishing cleaning is an operation that removes very slight dirt such as processing oil, flux, foreign matter, fingerprints, etc. remaining slightly on the object to be cleaned, such as cleaning before product shipment. It is a cleaning composition used at this time. Furthermore, the replenisher is a composition that is replenished into the system to replenish a portion of the cleaning composition that dissipates into the atmosphere as vapor from the scrubber system during cleaning.

  The partial azeotrope composition of the present invention is a non-azeotropic multi-component composition consisting of two or more volatile components (A) and one or more nonvolatile components (B) as a whole, 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 at the boiling point. Therefore, the composition of the cleaning composition in the cleaning tank system is obtained by using this partially azeotropic composition as a cleaning composition and using a previously prepared composition having the same composition as the vapor composition at the boiling point as a replenisher. It was found that fluctuations can be suppressed. As a result, while maintaining the excellent properties (for example, excellent drying properties) of conventional azeotropic composition-based cleaning agents, problems (for example, cleaning properties) that could not be solved by azeotropic composition-based cleaning agents It was possible to solve this problem and to maintain its excellent characteristics stably during a long washing operation. Conventionally, as such a multi-component detergent composition for stable use for a long period of time, it has been considered essential to be an azeotropic composition. However, the composition of the present invention enables a non-azeotropic composition. It has been found that the problem of composition variation of the multi-component detergent can be solved even with the azeotropic composition.

  The partially azeotropic composition of the present invention has two or more volatile components having a vapor pressure at 20 ° C. larger than the reference vapor pressure Po defined by the formulas (1) and (2), and one or more volatile components smaller than Po. It consists of a non-volatile component (B). Here, the component average vapor pressure Pav in the formula is an arithmetic average of the vapor pressure at 20 ° C. of each volatile component (Ai) and nonvolatile component (Bj) alone constituting the composition of the present invention. By using in combination the components belonging to the two groups separated by the reference vapor pressure Po as a boundary, the present invention has excellent cleaning properties, drying properties, and nonflammability, and there is little composition fluctuation during long-term cleaning operations. A boiling composition can be obtained.

  In addition, the partially azeotropic composition of the present invention is such that the composition of the gas phase generated by the composition and each nonvolatile component (Bj) in the liquid phase satisfies the relationship of formula (3) at the boiling point under normal pressure. It is. When the amount of the non-volatile component (B) present in the vapor phase is a certain amount or less, there is little composition fluctuation during the long-term washing operation, and both the excellent drying property and the washing property at the time of vapor washing are compatible. Can be obtained. The boiling point under normal pressure here can be calculated | required, for example as a gaseous-phase temperature observed in the constant temperature state which the composition of this invention reaches | attains in the reflux test mentioned later. Further, Bvj in the formula (3) can be obtained by collecting a condensate obtained by condensing the vapor phase at this time and analyzing the composition thereof.

  In a multi-component detergent composition, a non-volatile component having a high boiling point is often used for the purpose of improving soil solubility, and such a high detergency component is used as a non-volatile component (B) in a large amount even at the boiling point. Remaining in the liquid phase contributes to stably securing the high cleaning property of the cleaning agent. When it is necessary to perform steam cleaning, a constant detergency may be required for the vapor phase while maintaining good drying properties. In this case, the value of (ΣBvj / ΣBoji) is 0.0001. The non-volatile component (B) needs to be present in the vapor phase within the range of 0.1 or more and more preferably 0.001 or more and 0.05 or less.

  Further, in the partially azeotropic composition of the present invention, the composition of each volatile component (Ai) in the liquid phase and the gas phase generated by the composition satisfies the relationship of the formula (4) at the boiling point under normal pressure. The weight ratio of each volatile component (Ai) in the gas phase to the total volatile component in the gas phase, and the total amount of each volatile component (Ai) in the partially azeotropic composition at room temperature in the partially azeotropic composition at room temperature. When the difference in the weight ratio with respect to the volatile component is within ± 0.1, the composition fluctuation is small, and even if the composition itself is a non-azeotropic composition, it is actually used as a cleaning agent in the same manner as the azeotropic composition. It becomes possible to suppress composition variation. More preferably, the difference is within ± 0.07, and even more preferably within ± 0.05. In addition, Avi in Formula (4) can be calculated | required by the same method as Bvj mentioned above here.

  The components constituting this partially 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 nonvolatile components. Any compound can be used as long as it is a non-azeotropic composition comprising (B) and each component thereof satisfies the formulas (3) and (4). For example, halogenated hydrocarbons, Examples thereof include hydrocarbons, alcohols, ketones, organic compounds having an ether bond and / or an ester bond.

  Hereinafter, each compound that can be used in the partial azeotropic composition of the present invention will be exemplified in order of increasing vapor pressure at room temperature.

Examples of halogenated hydrocarbons include non-chlorine bromine compounds and non-chlorine fluorine compounds. Examples of non-chlorine bromine compounds include isopropyl bromide and propyl bromide. The non-chlorine fluorine compound is a fluorine compound in which a part of hydrogen atoms of hydrocarbons or ethers are substituted with only fluorine atoms and does not contain a chlorine atom. For example, a cyclic compound represented by the following general formula (11) HFC, chain HFC represented by formula (12), or HFE represented by formula (13), which is a compound composed of carbon atom, hydrogen atom, oxygen atom and fluorine atom, which does not contain chlorine atom, and among these compounds The combination of 2 or more types of compounds chosen can be mentioned.
_{C n H 2n-m F m} (11)
(In the formula, n and m are integers satisfying 4 ≦ n ≦ 6 and 5 ≦ m ≦ 2n−1)
_{C x H 2x + 2-y} F y (12)
(Wherein x and y represent integers of 4 ≦ x ≦ 6 and 6 ≦ y ≦ 12)
C _s F _{2s + 1} OR (13)
(Wherein 4 ≦ s ≦ 6, R is an alkyl group having 1 to 3 carbon atoms)
Specific examples of the cyclic HFC include 3H, 4H, 4H-perfluorocyclobutane, 4H, 5H, 5H-perfluorocyclopentane, 5H, 6H, 6H-nonafluorocyclohexane.

Specific examples of the chain HFC include 1H, 2H-perfluorobutane, 1H, 3H-perfluorobutane, 1H, 4H-perfluorobutane, 2H, 3H-perfluorobutane, 4H, 4H-perfluorobutane, 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, , 3H, 5H-perfluoropentane, 1H, 5H, 5H-perfluoropentane, 2H, 2H, 4H-perfluoropentane, 1H, 2H, 4H, 5H-perfluoropentane, 1H, 4H, 5H, 5H, 5H -Perfluoropentane, 1H, 2H-perfluorohexane, 2H, 3H-perfluorohexane, 2H, 4H-perfluorohexane, 2H, 5H-perfluorohexane, 3H, 4H-perfluorohexane and the like can be mentioned. .
Specific examples of HFE include methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, methyl perfluoropentyl ether, methyl perfluorocyclohexyl ether, and 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- Examples include trimethylhexane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, menthane, bicyclohexyl, cyclododecane, 2,2,4,4,6,8,8-heptamethylnonane.

Examples of alcohols include methanol, ethanol, 2-propanol, tert-butanol, 1-propanol, sec-butanol, isobutanol (vapor pressure at 20 ° C .: 1.06 × 10 ³ Pa), n-butanol. , Isoamyl alcohol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol, benzyl alcohol, furfuryl alcohol, ethylene glycol and propylene glycol.

As for ketones, acetone, methyl ethyl ketone, 3-pentanone, 2-pentanone, methyl isobutyl ketone, 2-hexanone (vapor pressure 3.99 × 10 ² Pa at 20 ° C.), methyl-n-amyl ketone, diisobutyl ketone, diacetone alcohol, Examples include holon, isophorone, cyclohexanone, and acetophenone.

  An organic compound having an ether bond is a compound containing at least one ether bond (C—O—C) in the molecular structure, and an organic compound having an ester bond is an ester bond in the molecular structure. It is a compound containing at least one (—COO—).

  As a compound which has an ether bond, the compound specified by following General formula (14) can be mentioned, for example.

Wherein R ¹⁵ and R ¹⁶ are an aliphatic compound residue or alicyclic ring having one or more selected from 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 compound residue, an aromatic compound residue and a heterocyclic compound residue, and R ^{17 to} R ²⁰ represent 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 or alicyclic compounds in which two hydroxyl groups are bonded to two different carbon atoms, in which one of the hydroxyl groups is a hydrocarbon residue. Or it is the compound substituted by the hydrocarbon residue containing an ether bond. In addition, glycol ether dialkyl ethers are aliphatic or alicyclic compounds in which two hydroxyl groups are bonded to two different carbon atoms, and both hydrogens of the two hydroxyl groups are hydrocarbon residues or It is a compound substituted with 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).

(In the formula, R ²¹ is an alkyl group having 1 to 6 carbon atoms, an alkenyl group or a cycloalkyl group, R ²² , R ²³ and R ²⁴ are hydrogen or a methyl group, n is an integer of 0 to 1, and m is 1 to 4) Indicates an integer)

(In the formula, R ²⁵ is an alkyl group, alkenyl group or cycloalkyl group having 1 to 6 carbon atoms, R ²⁶ is an alkyl group or alkenyl group having 1 to 4 carbon atoms, R ²⁷ , R ²⁸ , and R ²⁹ are hydrogen or methyl. Group, n is an integer of 0 to 1, m is an integer of 1 to 4)
In addition, glycol ethers are classified into hydrophilic glycol ethers and hydrophobic glycol ethers, and include hydrophilic glycol ether monoalkyl ethers and hydrophilic glycol ether dialkyl ethers used in the partial azeotrope composition of the present invention. Is a glycol ether that can form a uniform single liquid phase with no phase separation when mixed at 30 ° C. in a weight ratio of 60/40 glycol ether / water. Ether monoalkyl ethers and hydrophobic glycol ether dialkyl ethers are glycol ethers in which phase separation is observed when glycol ethers / water are mixed at a mass ratio of 60/40 at 30 ° C.

  Preferred hydrophilic glycol 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. Preferred hydrophobic glycol ether monoalkyl ethers and hydrophobic ethers Glycol ether dialkyl ethers are glycol ethers having a solubility in water of 60% by mass or less at 30 ° C.

In glycol ether monoalkyl ethers, for example, specific examples of hydrophilic glycol ether monoalkyl ethers include propylene glycol monomethyl ether (vapor pressure 8.91 × 10 ² Pa at 20 ° C.), 3-methoxybutanol, 3-methoxy -3-methylbutanol, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-i-propyl ether, diethylene glycol mono-n-propyl ether, tripropylene glycol monomethyl ether, diethylene glycol mono-n-butyl ether Specific examples of hydrophobic glycol ether monoalkyl ethers include propylene group Recall mono-n-butyl ether (vapor pressure 7.98 × 10 Pa at 20 ° C.), ethylene glycol mono-n-hexyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-n-propyl ether, etc. Can do.

In glycol ether dialkyl ethers, for example, specific examples of hydrophilic glycol ether dialkyl ethers include diethylene glycol dimethyl ether (vapor pressure 3.99 × 10 ² Pa at 20 ° C.), diethylene glycol diethyl ether, and the like. Examples of the glycol ether dialkyl ether include dipropylene glycol dimethyl ether (vapor pressure 6.65 × 10 Pa at 20 ° C.), diethylene glycol di-n-butyl ether, and the like.

Glycol ethers used in the partial azeotrope of the present invention include 3-methoxybutanol (vapor pressure at 20 ° C. of 1.20 × 10 ² Pa) that does not produce alkoxyacetic acid in the metabolic system in the human body, 3-methoxy- 3-methylbutanol, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-n-propyl ether and the like are preferred because of their lower toxicity.

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

(Wherein R ³⁰ is an alkyl group having 1 to 6 carbon atoms, an alkenyl group, or a cycloalkyl group, R ³¹ , R ³² , and R ³³ are hydrogen or a methyl group, n is an integer of 0 to 1, and m is 1 to 4) Indicates an integer)
Specific examples include acetates of monoalkyl ethers such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, dipropylene glycol and tripropylene glycol. be able to.

  The glycol ether acetates used in the partially azeotropic composition of the present invention include 3-methoxybutyl acetate and 3-methoxy-3-methylbutyl acetate, dipropylene glycol monomethyl ether acetate that do not produce alkoxyacetic acid in the metabolic system in the human body. Dipropylene glycol mono-n-propyl ether acetate, dipropylene glycol mono-n-butyl ether acetate and the like are preferred because of their lower toxicity.

  Examples of the compound having an ester bond include a compound represented by the following general formula (18).

(Wherein R ³⁴ and R ³⁵ are an aliphatic compound residue or alicyclic ring having one or more selected from 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 aromatic compound residue and a heterocyclic compound residue.)
Specific examples include isopropyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate (vapor pressure 1.33 × 10 ³ Pa at 20 ° C.), isoamyl acetate, methyl acetoacetate, methyl lactate, ethyl lactate, lactic acid Propyl, cyclohexyl acetate, ethyl acetoacetate, butyl lactate, 3-methyl-3-methoxybutyl acetate, dimethyl succinate, 2-ethylhexyl acetate, dipropylene glycol monomethyl ether acetate, γ-butyrolactone, dimethyl glutarate, dimethyl adipate , Dipropylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate and the like.

  Moreover, hydroxycarboxylic acid ester can be mentioned as another example of the compound which has an ester bond. Hydroxycarboxylic acid esters are ester compounds having a hydroxyl group, and are preferably specified by the following general formula (19).

(In the formula, R ³⁶ represents an alkyl group, alkenyl group or cycloalkyl group having 1 to 6 carbon atoms.)
Specific examples include glycol monoesters, lactic acid esters, malic acid esters, tartaric acid esters, citrate esters, glycerin monoesters, glycerin diesters, ricinoleic acid esters, and castor oil.

  The partial azeotropic composition of the present invention selects the non-volatile component (B) and the volatile component (A) based on the reference vapor pressure Po defined by the formulas (1) and (2) among the above components. Can be obtained by mixing at a specific ratio that satisfies the relations of the expressions (3) and (4).

  In general, a plurality of volatile components (A) having intermolecular hydrogen bond strengths close to each other may be combined with a non-volatile component (B) having significantly different intramolecular hydrogen bond strengths. it can. The hydrogen bond strength here depends on the presence and number of atoms having high electronegativity (oxygen, nitrogen, fluorine) and active hydrogen atoms (hydrogen atoms bonded to oxygen, nitrogen, etc.) in each compound. .

  For example, a combination of selecting an atom having a high electronegativity and an active hydrogen atom in the volatile component (A) and selecting a hydrocarbon having no intermolecular hydrogen bond in the nonvolatile component (B) The combination which selects the non-chlorine-type fluorine compound which contains a fluorine atom for a component (A), and selects the compound which does not contain a fluorine atom for a non-volatile component (B) can be mentioned.

  Of the above combinations, for example, a plurality of volatile components (A) themselves form an azeotropic composition, and the azeotropic properties of this composition are affected even in the presence of the non-volatile component (B). As a result, the partially azeotropic composition of the present invention can be realized.

  More specifically, the vapor pressure at 20 ° C. is close to each other, and two or more compounds constituting the azeotropic composition are volatile components (A), and the vapor pressure at 20 ° C. is sufficiently higher than these volatile components (A). One or more kinds of low compounds can be used as the nonvolatile component (B).

  In order to determine the desirable component composition of each volatile component (Ai) selected at this time, as an example, a rectification test using only the volatile component (A) in each necessary amount, for example, an equal amount was obtained. The method of measuring a condensate composition is mentioned. In this rectification test, a composition composed of a volatile component (A) with a known composition, which is put into a predetermined vessel equipped with a rectification tower, is heated to form steam once, and then cooled and condensed. The operation of returning the liquid to the original composition is continuously performed until the composition of the gas phase becomes constant. At this time, the weight ratio of each volatile component (A) is determined by measuring the liquid composition obtained by cooling and condensing the generated vapor.

  When a new composition is prepared by adding the non-volatile component (B) to the composition comprising only the volatile component (A) thus obtained, the weight of each non-volatile component (Bj) with respect to the entire composition When the proportion (Boji) is in an appropriate range that does not affect the azeotropic properties of the volatile component (A), all components in the new composition can satisfy the formulas (3) and (4). . The appropriate range of Boj can be confirmed and determined by measuring the composition of the condensate obtained by conducting a reflux test on several new compositions with different Boj.

  In this reflux test, a composition composed of a volatile component (A) and a non-volatile component (B) having a known composition that has been put into a predetermined container is heated to form a vapor once, and this is cooled and condensed to form a liquid. The operation of returning to the original composition is continuously performed until the composition of the gas phase and the liquid phase becomes constant. At this time, the cooled and condensed liquid composition of the generated vapor is measured, and it is confirmed that the content of the non-volatile component (B) in the condensed liquid is not more than a predetermined value.

  Moreover, the composition obtained by preparing a composition in which each volatile component and each non-volatile component composition were adjusted so as to satisfy the desired drying property, nonflammability, and cleanability without performing a prior reflux test. This partial azeotropic property can also be confirmed by a reflux test.

  Hereinafter, the volatile component (A) and the non-volatile component (B) of the partial azeotrope composition of the present invention that can be particularly suitably used as the cleaning composition will be described.

  In the volatile component (A) of the present invention as a cleaning composition component, at least one 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. As used herein, “non-flammable” and “no flash point” mean that the cleaning agent is recognized as having no flash point by the flash point evaluation test described in JISK2265. When such a partial azeotropic composition is used as a cleaning agent in particular, it is possible to ensure operational safety by covering the liquid phase surface with a vapor phase composed of non-flammable volatile components. Preferred non-flammable volatile components include halogenated hydrocarbons. More preferred are non-chlorine fluorine compounds and non-chlorine bromine compounds that do not have an ozone depletion coefficient. More preferred is a non-chlorine fluorine compound having a ratio of the number of fluorine atoms to the number of hydrogen atoms in the nonflammable molecule of 2 or more.

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), a chain HFC represented by (21), or ( Examples of the HFE represented by 22) include a compound containing no carbon atom, a carbon atom, a hydrogen atom, an oxygen atom and a fluorine atom, and a combination of two or more compounds selected from these.
_{C n H 2n-m F m} (20)
(In the formula, n and m represent integers satisfying 4 ≦ n ≦ 6 and (4/3) n ≦ m ≦ 2n−1).
_{C x H 2x + 2-y} F y (21)
(Wherein x and y are integers of 4 ≦ x ≦ 6, 4 (x + 1) / 3 ≦ y ≦ 2x + 1)
C _s F _{2s + 1} OC _t H _{2t + 1} (22)
(In the formula, s and t are integers satisfying (4t + 1) / 2 ≦ s ≦ 7, 1 ≦ t ≦ 3)
More specifically, for example, among the above-exemplified non-chlorine fluorine compounds, those satisfying the formulas (20) to (22) may be mentioned. Among these, a chain HFC or HFE 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 partially azeotropic composition excellent in self-extinguishing properties of the present invention. Preferred component. The self-extinguishing property referred to here is a kind of flame retardancy of a substance. Even if a substance having this property is ignited once, the flame disappears spontaneously after a certain time. Furthermore, “excelling in self-extinguishing” means that spontaneous fire extinguishing is recognized within 10 seconds after ignition in a self-extinguishing test described later.

  As a specific example of the volatile component excellent in the effect of improving the self-extinguishing property of the partial azeotropic composition of the present invention, 2H, 3H-perfluoropentane (HFC43-10mee) having no minimum ignition energy and excellent nonflammability Methyl perfluorobutyl ether, methyl perfluoroisobutyl ether and a mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether (HFE7100).

  In the cleaning composition of the present invention, one or two or more kinds of non-flammable volatile components 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. A combination of compounds can be used.

  Further, as the volatile component (A), one or more selected from non-chlorine fluorine compounds in which the ratio of the number of fluorine atoms to the number of hydrogen atoms in the molecule is 2 or more, alcohols, hydrocarbons, esters A combination of one or more selected from the group of ketones and ketones is also preferable because it simultaneously achieves excellent non-flammability, excellent self-extinguishing properties, and excellent solubility in mild soils such as low-viscosity processing oils.

  Furthermore, as the excellent volatile component (A) of the present invention, a non-chlorine fluorine compound having at least half of alkyl groups having no fluorine atom with respect to all alkyl groups in the molecule can be mentioned. These have higher solubility in processing oil and the like than other non-chlorine fluorine compounds, and as a result, have excellent rinsing properties and steam cleaning properties. Examples thereof include 2H, 2H, 4H, 4H, 4H-perfluorobutane (HFC365mfc) (A1).

  Another preferred volatile component (A) is a compound 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 amount or less, and therefore it is preferable when the drying property is particularly important in the vapor cleaning. Examples thereof include 2H, 2H, 4H, 4H, 4H-perfluorobutane (HFC365mfc) (A1) having a boiling point of 40 ° C.

  As the particularly excellent volatile component (A) as the cleaning composition component of the present invention, for example, the above-described HFC365mfc (A1) excellent in drying property and the ratio of the number of fluorine atoms in the nonflammable molecule to the number of hydrogen atoms Is a combination of two or more non-chlorine fluorine compounds (A2), improving the self-extinguishing property of component (A1) and reducing non-flammable risk when non-volatile component (B) is flammable Is preferable. In this case, more preferably, as component (A2), 2H, 3H-perfluoropentane (HFC43-10mee) is combined with either methyl perfluorobutyl ether, methyl perfluoroisobutyl ether, or a mixture of both (HFE7100). Can be used to 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 concentration of component (B) in the vapor layer. By doing so, while improving the drying property of the to-be-cleaned object after steam cleaning, the composition fluctuation | variation of the cleaning composition in use can be suppressed.

When a non-chlorine fluorine compound is used as the volatile component (A), the non-volatile component (B) is improved in cleaning power and rinsing performance against all kinds of dirt such as processing oils, greases, waxes and fluxes. Therefore, it is preferable to use a compound selected from components having a vapor pressure of less than 1.33 × 10 ³ Pa at 20 ° C., or a combination of two or more.

When the vapor pressure of the component (B) is within this range, it is easy to obtain a cleaning composition according to the present invention that is excellent in drying property, cleaning property, and non-flammability and has little composition fluctuation. Become. More preferably, the vapor pressure at 20 ° C. is 6.66 × 10 ² Pa or less, and more preferably 0.13 Pa or more and 1.33 × 10 ² Pa or less in consideration of the steam cleaning property.

  Examples of such a non-volatile component (B) include various hydrocarbons, alcohols, ketones, and organic compounds having ether bonds and / or ester bonds, which have good detergency against various types of dirt. As a more specific example, among the hydrocarbons, alcohols, ketones and the like exemplified above, compounds having the above-mentioned vapor pressure can be mentioned. Of these compounds, hydrocarbons are preferably used for cleaning processing oil, grease, wax, liquid crystal, etc., and glycol ethers, esters, ketones, especially glycol ethers are used for cleaning resins such as flux. Are particularly preferably used.

  Among the above non-volatile components (B), compounds having an ether bond and / or an ester bond are preferable. In particular, glycol ethers, glycol ether acetates and hydroxycarboxylic acid esters are flammable alcohols as other components. When using together, since the effect which suppresses the flammability is especially high, it is more preferable.

  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) are excellent in their pollution solubility. Therefore, it is used more suitably.

  As the component (B1), a compound represented by the following general formula (6) has excellent detergency particularly against various types of stains. Examples thereof include 3-methoxybutanol, 3-methoxy-3- Mention may be made of methylbutanol.

(In the formula, R ¹ represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group, or a cycloalkyl group, R ² , R ³ , and R ⁴ represent hydrogen or a methyl group, and n represents an integer of 0 or 1.)
Furthermore, as component (B1), dipropylene glycol mono-n-propyl ether and dipropylene glycol mono-n-butyl ether are particularly contaminated with amine hydrochlorides and organic acids that cause ionic residues in flux cleaning. In addition, it is excellent in detergency against dirt such as a polymerized rosin and a metal salt of rosin that are produced by a soldering process and cause white residue.

  As the component (B2), the compound represented by the following general formula (7) has particularly excellent cleaning properties against various types of dirt, and examples include diethylene glycol di-n-butyl ether. .

(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 hydrogen or a methyl group, R ⁶ is an alkyl group having 3 to ⁶ carbon atoms, An alkenyl group or a cycloalkyl group, n represents an integer of 0 or 1)
Furthermore, especially as component (B2), diethylene glycol diethyl ether and dipropylene glycol dimethyl ether are excellent in the detergency for rosin contained in the flux component.

  In the detergent composition using the partial azeotrope composition of the present invention, more preferred glycol ether monoalkyl ethers (B1) and glycol ether dialkyl ethers (B2) for various types of soils are used depending on the purpose of washing. You can choose a combination.

  For example, the combination of one of the components (B1) and (B2) being hydrophilic and the other being hydrophobic is a combination of thermosetting ink such as various types of flux cleaning and various solder resist inks applied to the substrate surface, or UV curing. Especially suitable for cleaning inks and liquid crystals, and the combination of both components being hydrophilic is an epoxy or urethane two-component liquid used for cleaning various fluxes and bonding and sealing various electrical and electronic components. It is particularly suitable for cleaning of the mixing and discharging mixer (dispenser) mixer part and nozzle part. In addition, the combination of both components being hydrophobic is a combination of various processing oils such as cutting oil, press oil, drawing oil, heat treatment oil, rust prevention oil when processing precision machinery parts and optical machine parts with low polarity. It is particularly suitable for cleaning lubricating oils, greases, waxes and liquid crystals.

  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 cleaning properties. By using the components (B1) and (B3) in combination, various processing oils used when processing precision machine parts and optical machine parts with low polarity, such as cutting oil, press oil, drawing oil, heat treatment oil, A cleaning composition suitable for cleaning rust-preventing oil, lubricating oil, etc., greases, waxes and the like can be obtained. For example, the combination of 3-methoxy-3-methylbutanol as the component (B1) and 3-methyl-3-methoxybutyl acetate as the component (B3) exhibits high process oil cleaning properties during boiling cleaning, The processing oil brought into the cleaning agent can be easily separated because of its excellent processing oil separability, and not only the life of the cleaning agent is prolonged, but also the ester odor of 3-methyl-3-methoxybutyl acetate can be suppressed. Therefore, it is preferable.

  Examples of hydroxycarboxylic acid esters used as the nonvolatile component (B) include methyl lactate, ethyl lactate, propyl lactate, butyl lactate, and pentyl lactate. Among these, particularly preferred examples include a compound containing at least one butyl group or isobutyl group as part of its molecular structure, and a compound containing a chain hydrocarbon structure having 4 to 6 carbon atoms and an oxygen atom in the molecule. Can be mentioned. For example, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl lactate, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-isobutyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono- Examples include i-butyl ether, 3-methoxybutanol, 3-methoxy-3-methylbutanol, and diethylene glycol di-n-butyl ether. These compounds not only have excellent rosin solubility in flux cleaning, but also have excellent cleaning properties against ionic substances and white residue-causing substances.

  The detergent composition comprising the partially azeotropic composition of the present invention exhibits excellent detergency against any dirt.

  In addition, as a non-volatile component (B), when rinse property is especially required for a cleaning composition, it is preferable that it is a low-viscosity component, and the viscosity in 20 degreeC has more preferable 100 cp or less, Furthermore, Preferably it is 50 cp or less.

  Furthermore, in the present invention, the non-volatile component (B) is preferably not a surfactant. Since surfactants generally have foaming properties, when cleaning is performed by boiling a detergent containing this surfactant, detergent splashes are mixed in a tank containing other liquids such as a rinse agent. As a result, the performance of the rinse agent may deteriorate. Furthermore, when it is necessary to perform steam cleaning, the vapor phase may be required to have a certain level of cleanability. In this case, the vapor phase is also non-volatile with high solubility so as not to impair the drying property. It is necessary that component (B) is present. However, surfactants are generally too low in vapor pressure and it is difficult to include such substances in the vapor phase of the cleaning agent. Furthermore, surfactants with a cleaning mechanism that removes soil by emulsifying and dispersing dirt in the liquid do not provide a sufficient effect with the amount of liquid condensed around the object to be washed in steam cleaning, but merely reduce drying properties. In particular, it is unsuitable as a non-volatile component (B) of a cleaning composition having vapor cleaning properties.

  The partially azeotropic composition of the present invention is obtained by mixing and homogenizing each volatile component (Ai) and each nonvolatile component (Bj) according to a conventional method. The weight ratio of each component is not particularly limited as long as it satisfies the formulas (3) and (4) and satisfies the required performance of the partial azeotrope composition of the present invention. The ratio (ΣAoi) / (ΣBoji) is preferably 95/5 to 10/90. When the amount ratio of both is in this range, the resulting cleaning composition can achieve both preferable cleaning properties and drying properties. More preferably, it is 20/80 to 80/20, more preferably 30/70 to 70/30, and still more preferably 40/60 to 60/40.

  In particular, HFC365mfc is used as component (A1), and one 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 molecule of 2 or more are used as component (A2). The weight ratio of the components is not particularly limited as long as the high detergency, low toxicity, low flammability, and high self-extinguishing properties that are the characteristics of the cleaning composition of the present invention are not impaired. The ratio of the component amount to the nonvolatile component amount, (Ao1 + Ao2) / (ΣBoji), is preferably 95/5 to 30/70. When the weight ratio of the component (B) is larger than 5, a more preferable effect of improving dissolving power against various types of dirt can be obtained, and when it is smaller than 70, more preferable low flammability and high self-extinguishing property can be achieved. A more preferable range is 90/10 to 40/60 in consideration of the balance between the cleaning property of the cleaning agent, low flammability and high self-extinguishing property.

  In this case, the ratio of the composition ratio of component (A1) and component (A2), and the range of Ao1 / Ao2 is preferably 97/3 to 60/40. When the weight ratio of the component (A2) is larger than 3, a more preferable self-extinguishing improvement effect is obtained, and when it is smaller than 40, more excellent excellent drying property during steam cleaning is obtained. In consideration of the balance between the self-extinguishing property of the cleaning agent and the drying property during steam cleaning, a more preferable range is 97/3 to 85/15, and a more preferable range is 95/5 to 88/12.

  Furthermore, 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 should be used as a rinse agent and a replenisher used in the cleaning step together with the same cleaning agent. Can do. The range of (Ao1 + Ao2) / (ΣBoji) in this rinse agent and replenisher is the characteristic of the rinse agent, high drying, low toxicity, low flammability, high self-extinguishing property, and suppression of composition fluctuations of the cleaning agent used together There is no particular limitation as long as the effect is not impaired, but it is preferably 98/2 to 99.9 / 0.1. When the weight ratio of the component (B) is smaller than 2, high drying property, low flammability, and high self-extinguishing property are obtained, and when it is larger than 0.1, the composition fluctuation suppressing effect of the cleaning agent used in combination is more preferable. . A more preferable range in consideration of the balance between the high drying property of the rinse agent and the effect of suppressing the composition fluctuation is 99/1 to 99.8 / 0.2.

  The ratio of the preferable composition ratio of the component (A1) and the component (A2) in the rinse agent and the replenisher is the same as the ratio in the above-described cleaning agent.

  In particular, a rinsing agent containing 2H, 2H, 4H, 4H, 4H-perfluorobutane (HFC365mfc) as component (A1) has higher processing oil solubility than rinsing agents made of other non-chlorine fluorine compounds. Therefore, even if the cleaning object with a lot of dirt accumulated by long-term use adheres to the rinsing process, it prevents re-attachment of the dirt to the object to be cleaned and has a sufficient rinsing function. It can be demonstrated. Accordingly, it is possible to reduce the frequency of replacement of the cleaning agent with a decrease in the rinse function as a guideline, and as a result, it is possible to extend the life of the cleaning agent. Furthermore, by using the component (B) in combination, it is possible to cope with a wider variety of types of dirt than when only the volatile component (A) is included.

  Further, the composition having the same composition as the rinse agent and the replenisher can be used as a finish cleaning agent. This is especially true when the cleaning method can be applied with physical forces such as rocking, ultrasonic, showering or wiping, or when the dirt to be cleaned is relatively light, such as foreign matter or low-viscosity processing oil. A cleansing agent is more preferably used because it can achieve both finish cleaning properties and drying properties.

  For example, after cleaning a printed circuit board with soldered mounting parts with the cleaning agent described in this application, partial correction may be performed by simply wiping off locally remaining flux or white residue with a cotton swab, etc. It is necessary to complete the washing with one solution. In a cleaning agent containing a large amount of non-volatile components, the non-volatile components spread between mounted parts, and it is difficult to wipe off with a rinse agent later, resulting in poor drying. On the other hand, the washability is insufficient only with a volatile component having poor solubility.

  Component (B1) when the glycol ether monoalkyl ether (B1) and the glycol ether dialkyl ether (B2) are used in combination as the nonvolatile component (B) in the partial azeotrope composition of the present invention The range of the mass ratio with respect to (B2) is more preferably 90/10 to 10/90. When the mass ratio of the component (B1) is larger than 10, more preferable rosin solubility is obtained, and when it is smaller than 90, more preferable detergency for polymerized rosin or metal salt of rosin is obtained. When considering the balance between the solubility of the cleaning agent in rosin and the detergency against dirt that causes white residue such as polymerized rosin, the range of the mass ratio of the component (B1) to the component (B2) is more preferably 80/20 to 20/80, and more preferably 70/30 to 30/70.

  In the partial azeotrope composition of the present invention, as the non-volatile component (B), the component (B1) when the glycol ether monoalkyl ether (B1) and the glycol ether acetate (B3) are used in combination. As for the range of the mass ratio with respect to a component (B3), it is more preferable that it is 90/10-10/90. When the mass ratio of the component (B1) is larger than 10, more preferable excellent metal stability and low odor are obtained, and when it is smaller than 90, more preferable detergency for various processing oils is obtained. When considering the balance between the solubility of the cleaning agent in processing oil and excellent metal stability and low odor, the range of the mass ratio of the component (B1) to the component (B3) is more preferably 80/20 to 20/80. Yes, more preferably 70/30 to 30/70.

  In the cleaning method of the present invention, the range of the mass ratio of the component (B1) to the component (B3) of the rinse agent and the replenisher and the range of the mass ratio of the component (B3) of the component (B1) are used together. Is the same as the liquid composition obtained by the reflux test. By using the same composition, when used in combination with the cleaning agent, it is possible to suppress fluctuations in the cleaning agent composition and to maintain the excellent cleaning property and self-extinguishing property of the cleaning agent.

  In the cleaning composition of the present invention, various auxiliary agents such as antioxidants, ultraviolet absorbers, surfactants, stabilizers, antifoaming agents, etc., if necessary, to the extent that the effects of the present invention are not significantly impaired. May be added as necessary. The specific example of the additive which can be added to the cleaning composition of this invention below is illustrated.

  Examples of antioxidants are shown below for each type.

  Examples of phenolic antioxidants include 1-oxy-3-methyl-4-isopropylbenzene, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butylphenol, butylhydroxyanisole, 2,6 -Di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-hydroxymethylphenol, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl- Examples thereof include compounds such as 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate.

  Examples of amine antioxidants include compounds such as diphenyl-p-phenylene-diamine, 4-amino-p-diphenylamine, and p, p'-dioctyldiphenylamine.

  Phosphorous antioxidants include phenyl isodecyl phosphite, diphenyl diisooctyl phosphite, diphenyl diisodecyl phosphite, triphenyl phosphite, trisnonyl phenyl phosphite, bis (2,4-di-tbutylphenyl) penta Mention may be made of compounds such as erythritol diphosphite.

  Examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl- Examples thereof include compounds such as 3,3′-thiodipropionic acid ester.

  Among these exemplified compounds, the effect of adding a phenolic antioxidant is large, and 2,6-di-t-butyl-p-cresol is particularly preferable. In addition, when performing steam cleaning with continuous use of the cleaning agent, at least one selected from the group of phenolic antioxidants and amine antioxidants, phosphorus antioxidants and phosphorus antioxidants By using together one or more selected from the group, it becomes possible to suppress the oxidative degradation of the cleaning agent for a long period of time.

  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, 2-hydroxy-4-methoxy- 4'-chlorobenzophenone, 2,2'-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,4-dihydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2 , 2′-dihydroxy-4,4′-dimethoxybenzophenone, benzophenones such as 4-dodecyl-2-hydroxybenzophenone, phenyl salicylate, 4-t-butylphenyl salicylate, 4-octylphenyl salicylate, bisphenol A-di-salicy Phenyl salicylates and 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α'-didimethylbenzyl) phenyl] -2H -Benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-4′-t-octylphenyl) benzotriazole, 2- (2′-hydroxy-5 ′) -Methylphenyl) benzotriazole, benzotriazo such as 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole Mention may be made of Le acids.

  When an antioxidant or an ultraviolet absorber is added to the cleaning agent, it is 1 to 1000 ppm, more preferably 10 to 1000 ppm, based on the total mass of each volatile component (Ai) and nonvolatile component (Bj).

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

  When an antioxidant or an ultraviolet absorber is added to the rinse agent of the present invention, it is preferably 1 to 1000 ppm, more preferably based on the total mass of each volatile component (Ai) and nonvolatile component (Bj) constituting the rinse agent. 10 to 1000 ppm.

  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 anionic 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 quaternary ammonium salts. Examples of nonionic surfactants include alkylphenols, ethylene oxide adducts of linear or branched aliphatic alcohols having 8 to 18 carbon atoms, and block polymers of polyethylene oxide polypropylene oxide. Examples of amphoteric surfactants include betaine type and amino acid type.

  Stabilizers used in the cleaning composition of the present invention include nitroalkanes such as nitromethane and nitroethane, epoxides such as butylene oxide, ethers such as 1,4-dioxane, amines such as triethanolamine, benzotriazole And the like.

  Examples of the antifoaming agent used in the cleaning composition of the present invention include self-emulsifying silicone, silicon, fatty acid, higher alcohol, polypropylene glycol, polyethylene glycol, and fluorine-based surfactant.

  When these surfactants, stabilizers, and antifoaming agents are added to the cleaning composition of the present invention, the total mass of each volatile component (Ai) and non-volatile component (Bj) is considered in consideration of rinsing properties. On the other hand, it is 1-1000 ppm, More preferably, it is 10-1000 ppm.

  By using the cleaning composition of the present invention, effective cleaning can be performed by the following cleaning method.

  In the cleaning method of the present invention, a rinse agent having the same composition as the vapor condensate composition, which is generated from the cleaning agent composed of the partial azeotropic composition containing the volatile component (A) and the nonvolatile component (B) of the present invention, is used. . By the cleaning method of the present invention, it is possible to realize a cleaning method that has excellent cleaning properties, quick drying of an object to be cleaned, and work safety due to self-extinguishing properties of the cleaning composition vapor.

  Moreover, in the cleaning method of the present invention, the composition of the cleaning agent is used at the same time as the amount of the cleaning composition dissipated from the cleaning device system during cleaning is reduced by using a composition having the same composition as the rinse agent as a replenisher. The fluctuation can be suppressed and the predetermined cleaning ability can be maintained for a long time. In this way, even when the azeotrope is not formed as the entire cleaning composition, it is possible to realize a cleaning method with high work stability.

  The composition of the rinse agent and the replenisher can be determined in advance by the above-described reflux test for the partially azeotropic detergent composition used as the detergent. Further, the replenisher composition can be determined by a distillation test instead of the reflux test. In the distillation test, the steam condensate generated by heating the cleaning composition is recovered as a distillate without returning to the composition, and the composition of the distillate recovered at a predetermined distillate rate is collected. By measuring, the composition of the necessary replenisher can be known. A preferable replenisher composition for suppressing the composition fluctuation of the cleaning agent is a distillate composition recovered at a distillate rate of 20% by volume or less, more preferably at a distillate rate of 10% by volume or less. The reflux test is more general than the distillation test because of its wider application range for the type of composition, but if the composition ratio of component (B) in the multi-component composition to be tested is high, the distillation test Thus, the object can be achieved more easily.

Furthermore, in the partial azeotropic composition used in the cleaning method of the present invention, HFC365mfc is used as the volatile component (A1), and the ratio of fluorine atoms in the molecule to the number of hydrogen atoms is 2 or more as the volatile component (A2). When the compound and the compound having a vapor pressure at 20 ° C. of less than 1.33 × 10 ³ Pa are used as the non-volatile component (B), the component (A2) is a cleaning composition that generates self-extinguishing vapor. When the ratio of the number of fluorine atoms to the number of hydrogen atoms in the molecule is 2 or more, the cleaning agent liquid surface with steam mainly composed of volatile components including the component (A2) generated by heating this partial azeotropic composition A highly safe cleaning method can be realized due to its excellent self-extinguishing properties. Thus, the partial azeotrope composition is excellent in the entire system by covering the upper part of the liquid surface with a vapor composition mainly composed of a volatile component having a feature (for example, excellent self-extinguishing property) generated by heating. It is also possible to have features. The cleaning device used at this time is not particularly limited as long as the above-described vapor coating can be realized. For example, one or more cleaning tanks, or one or more cleaning tanks and one or more tanks are rinsed. A washing machine including a tank is mentioned.

  In the cleaning method of the present invention, the cleaning step and the rinsing step can be combined with other cleaning methods such as dipping, spraying and showering for the purpose of improving the cleaning property and rinsing property.

The present invention will be described based on examples.

<Examples 1-5, Comparative Examples 1-4>
(1) Reflux test In order to confirm that the following cleaning agent is a partial azeotropic composition and to determine the composition of the replenisher and the rinse agent, a reflux test was performed as follows.

  As the volatile component (A) and the non-volatile component (B) satisfying the formulas (1) and (2), each component shown in Tables 1 and 2 was mixed in the composition described in the table to prepare a cleaning agent. 300 ml of the obtained cleaning agent was placed in a 500 ml eggplant type flask equipped with a reflux apparatus and refluxed for 2 hours, and then the condensate distilled off at the top was sampled and its composition was analyzed by gas chromatography. The obtained analytical values were used as the composition of the replenisher and the rinse agent. The composition analysis values at this time are shown in Tables 1 and 2.

  Since any composition of Examples 1-5 shown in Table 1 satisfy | fills Formula (3) and (4), it was confirmed that this composition is a partial azeotropic composition. On the other hand, it was confirmed that the compositions of Comparative Examples 1 to 4 shown in Table 2 did not satisfy the formula (4) and were not partially azeotropic compositions. In the compositions of Comparative Examples 1 to 4, the composition ratio of the volatile component (A) in the gas phase at the boiling point is greatly different from the composition ratio of the volatile component (A) in the composition at room temperature. Therefore, the results of Comparative Examples 1 to 4 indicate that the cleaning property exhibited by the boiling cleaning agent in the case of cleaning soils such as processing oil and flux that exhibits good solubility in the hydrocarbon and alcohol as the volatile component (A). It shows that a stable cleaning effect at the time of formulation design cannot be obtained because of the different vapor cleaning properties of the vapor phase. Moreover, since it differs from the flammability risk at the time of prescription design, it shows that the flammability risk may increase.

  Subsequently, an actual machine operation test was performed using the cleaning agents, rinsing agents, and replenishers of Examples 1 and 2, and long-term compositional stability of these cleaning agents was confirmed.

(2) Actual machine operation test 1 (composition variability 1)
A seven-day actual machine operation test was conducted by the method described below.

  The partial azeotropic composition of Example 1 was charged as a cleaning agent into the cleaning tank 1 of the cleaning apparatus shown in FIG. 1, and the rinse agent whose composition was previously determined in the rinsing tank 2 and the water separator 4 by a reflux test. Insert. The cleaning agent in the cleaning tank 1 is heated and boiled by the heater 6 to fill the steam zone 3 with the generated steam. The steam filled in the steam zone 3 is condensed and liquefied by the cooling pipe 7, and a part of the condensed liquid and the water adhering to the cooling pipe 7 are statically separated while being cooled by the cooling pipe 12 by the water separator 4. The removed condensate enters the rinsing tank 2 and finally overflows 11 and returns to the cleaning tank 1.

After the start of the test, the decrease in the cleaning composition in the system due to the dissipation of vapor from the cleaning machine opening 13 is compensated by replenishing the system with the rinse agent as a replenisher under the following operating conditions. Liquid replenishment was carried out every 2 hours. In order to investigate the composition variation of the cleaning agent during the test period, the cleaning agent in the cleaning tank 1 immediately after the replenishment of the liquid was sampled, and the composition analysis was performed by gas chromatography. Further, when the test machine was restarted after being stopped, the liquid was replenished immediately before the restart, sampling was performed, and the composition analysis was performed in the same manner. From the obtained analytical value, the detergent composition fluctuation rate was calculated by the following calculation formula.
・ Change rate of detergent composition (%)
= {(Sampling solution composition-composition before starting test) / composition before starting test} × 100
・ Operating conditions Operating time: 168 hours (running and stopping alternately)
Operation cycle During operation: 8 hours x 5 times (time when heater 6 is operating is considered as operation)
When stopped: 16 hours x 4 times, 64 hours x 1 time (the time zone when the heater 6 is stopped is considered as a stopped state)
Liquid replenishment During operation: The amount of decrease in the cleaning liquid and the rinse liquid is measured every two hours, and the amount of replenisher corresponding to the decrease is replenished to the cleaning tank 1.

At the time of stop: Before the start of operation, the decrease amount of the cleaning solution and the rinse solution is measured, and the replenisher solution corresponding to the decrease amount is supplied to the cleaning tank 1.
Washer opening During operation: Do not cover.

When stopped: Refrigerating machine with lid During operation: Operation 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 composition variation rate in the operating time zone, and FIG. 2 shows the change over time in the component composition. During the continuous operation for one week, it was confirmed that the detergent composition fluctuation rate in the cleaning tank can be stably controlled within 20%.

(3) Actual machine operation test 2 (composition variability 2)
After changing to the cleaning composition of Example 2, the frequency of liquid replenishment and sampling was changed every day, and liquid replenishment was performed immediately before restarting after stopping the test machine, and then sampling was performed. The other methods and operations were the same as in Test (2), and a 7-day actual machine test was conducted.

  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 detergent composition fluctuation rate in the cleaning tank can be stably controlled within 20%.

(4) Detergency test A test piece prepared by impregnating a 30-mesh stainless steel wire mesh (0.01 × 0.02 m) with the following metalworking oil and heating at 100 ° C. for 30 minutes was performed using the apparatus shown in FIG. The sample cleaning composition was used for cleaning under the following cleaning conditions, followed by rinsing, followed by steam cleaning using steam generated from the sample cleaning composition and drying. The state of the stainless steel wire mesh after drying was visually evaluated to determine the cleanability of the sample cleaner.

Evaluation is based on the following criteria.
◎: No processing oil left ○: Part of processing oil left ×: Processing oil left (5) Flux cleaning performance test A glass epoxy printed circuit board (35 mm × 48 mm) is immersed in a commercial flux on one side and air dried. After that, the test piece prepared by soldering at 250 ° C. is cleaned and rinsed using the sample cleaning composition under the following cleaning conditions, and then steam cleaned using the steam generated from the sample cleaning composition. And dried. The ionic residue value α (unit: μg NaCl / sqin) of the dried printed board was measured with an omega meter (600R-SC, manufactured by Alpha Metals), and the obtained measurement value was evaluated according to the following criteria to clean the sample. The flux cleaning property of the agent was determined.
A: α ≦ 7
○: 7 <α ≦ 14
×: 14 <α
-Metal processing oil used in test (4): A liquid containing 0.1% by weight of dye (Sudan) and 25% by weight of Unicut GH35 (trade name, manufactured by Nippon Petroleum Corporation) in perchlorethylene was prepared. A metal working oil for testing was used.
-Product name of flux used in test (5): JS-64ND (manufactured by Hiroki Co., Ltd.)
・ Cleaning conditions Cleaning tank: Boil cleaning for 2 minutes Rinse tank: 2-minute immersion rocking (20 times / minute, the condensate of steam obtained by heating the cleaning agent is rinsed)
Steam zone: left for 1 minute in steam obtained by heating a cleaning agent <Examples 6 to 24>
Each component was mixed with the composition of Table 5, and the target cleaning agent which has the target partial azeotropy was obtained. The above-mentioned (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 (HFC365mfc) and component (A2) a kind selected from non-chlorine fluorine compounds in which the ratio of the number of fluorine atoms in the molecule to the number of hydrogen atoms is 2 or more Alternatively, a combination of two or more compounds and a component (B) having a vapor pressure of less than 1.33 × 10 ³ Pa at 20 ° C. yielded a cleaning agent excellent in processing oil solubility and flux solubility. .

<Comparative Examples 5-7>
The same test as Example 6-24 was done about the compound of 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) dissolves in processing oil And flux solubility were insufficient.

(6) Flash point measurement In accordance with JIS K 2265, the flash point was measured with a tag sealing type up to a measurement temperature of 80 ° C, and with a Cleveland open type at a measurement temperature of 81 ° C or higher. Evaluation is based on the following criteria.
○: No flash point ×: Flash point <Examples 25 to 37>
Each component was mixed with the composition of Table 6, and the target detergent which has the target partial azeotropy was obtained. The above (6) flash point measurement was performed for each cleaning agent, and the results are summarized in Table 6. Component (A1) 2H, 2H, 4H, 4H, 4H-perfluorobutane (HFC365mfc), Component (A2) A kind selected from non-chlorine fluorine compounds in which the ratio of the number of fluorine atoms in the molecule to the number of hydrogen atoms is 2 or more Alternatively, it was confirmed that the flash point was eliminated by using two or more compounds in combination with a component (B) having a vapor pressure of less than 1.33 × 10 ³ Pa at 20 ° C.

<Comparative Examples 8-12>
The compounds shown in Table 6 were subjected to the same flash point measurement as in Examples 25-37. The results are summarized in Table 6. The flash point was confirmed for all the compounds measured.
(7) Self-extinguishing test 500 ml of sample cleaner is placed in a simple glass steam cleaner (cylindrical), heated on a hot plate, and refluxed while condensing steam in a cooling tube. After 30 minutes of reflux, after the ignition man's flame approaches the opening and ignites, the time until the flame disappears naturally (self-extinguishing time) is measured 20 times under the same conditions, and the self-extinguishing property is evaluated by the average value of 20 times. .

Evaluation criteria are based on the following criteria.
○: Fire extinguished within 10 seconds after ignition ×: Combustion and test conditions after ignition for 10 seconds or more Measurement location: In draft (no wind)
Opening area: 150 cm ² (diameter: 138 mm)
Cooling water temperature: 5 ° C
Free board ratio: 0.3
Humidity: 80%
<Examples 38 to 47>
Each component was mixed with the composition of Table 7, and the target detergent which has the target partial azeotropy was obtained. About each cleaning agent, the said (7) self-extinguishing test was done, and the result was put together in Table 7. Component (A1) 2H, 2H, 4H, 4H, 4H-perfluorobutane (HFC365mfc), Component (A2) A kind selected from non-chlorine fluorine compounds in which the ratio of the number of fluorine atoms in the molecule to the number of hydrogen atoms is 2 or more Alternatively, by using two or more compounds and component (B) a compound having a vapor pressure of less than 1.33 × 10 ³ Pa at 20 ° C., the flame naturally disappeared within 10 seconds after ignition.

<Comparative Example 13>
The compounds described in Table 7 were subjected to the same self-extinguishing test as in Examples 38 to 47. The results are summarized in Table 7. The measured 2H, 2H, 4H, 4H, 4H-perfluorobutane (HFC365mfc) continued to burn for 10 seconds or more after ignition.

(8) Dryability test In a state where 20 glass fibers (diameter: 0.17 mm, length: 100 mm) were bundled, the glass fiber was washed with the sample cleaning agent in the apparatus of FIG. 1 and then rinsed with the following rinsing agent. After that, it is washed with steam and dried. The drying property was determined by observing the state of the 20 glass fibers by visual observation after determining the drying property of the sample cleaning agent after leaving it at room temperature for 30 seconds after steam cleaning and pulling up.

Evaluation criteria are based on the following criteria.
○: 20 glass fibers are easily broken.
X: 20 glass fibers are not separated as a lump.
Test conditions Rinse agent: Steam condensate obtained by heating the cleaning agent Cleaning bath: 2 minutes boiling cleaning Rinse bath: 2-minute immersion rocking (20 times / min)
Steam zone: left for 1 minute in steam obtained by heating a cleaning agent <Examples 48 to 55>
Each component was mixed with the composition of Table 8, and the target cleaning agent which has the target partial azeotropy was obtained. The above (8) drying test was performed for each cleaning agent, and the results are summarized in Table 8. Component (A1) 2H, 2H, 4H, 4H, 4H-perfluorobutane (HFC365mfc) and component (A2) A non-chlorine fluorine compound having a ratio of the number of fluorine atoms in the molecule to the number of hydrogen atoms of 2 or more and component (B ) By using together with a compound having a vapor pressure of less than 1.33 × 10 ³ Pa at 20 ° C., it was confirmed that 20 glass fibers were easily separated after washing and had excellent drying properties.

<Comparative Examples 14-17>
The same self-extinguishing test as in Examples 48 to 55 was performed on the non-partially azeotropic composition composed of the components shown in Table 8. The results are summarized in Table 8. Component (A2) HFC having a boiling point of 55 ° C. or HFE having a boiling point of 61 ° C. and a non-chlorine fluorine compound having a ratio of fluorine atoms to hydrogen atoms in the molecule of 2 or more and (B) a vapor pressure at 20 ° C. of 1.33 When a compound of less than × 10 ³ Pa was used in combination, it was confirmed that 20 glass fibers remained in a lump after washing and had poor drying properties.

(9) Rinse property test 30 mesh stainless steel wire mesh (0.01 × 0.02m) is impregnated with metal processing oil (trade name Unicut Terrami AM30, Shin Nippon Oil Co., Ltd.) and heated at 100 ° C. for 30 minutes. A test piece was prepared. Heat a glass steam cleaner with a cooling tube containing the following cleaning composition mixed with 15% of the above processing oil on a hot plate, and immerse the previous test piece in the cleaning composition with processing oil. Then, boiling washing was performed. Subsequently, the test piece was rinsed at room temperature using each sample rinse agent, and then dried. The amount of processing oil remaining on the test piece after drying is measured using an oil content measuring device (OIL-20, manufactured by Central Science Co., Ltd.), and the obtained measurement value is evaluated according to the following criteria to rinse. Was judged.

Cleaning composition:
<1> HFC365mfc
<2> HFE7100
<3> 3-methoxy-3-methylbutanol <4> 3-methoxy-3-methylbutyl acetate Composition <1> / <2> / <3> / <4>
= 45.0 / 5.0 / 20.0 / 30.0% by mass
Evaluation is based on the following criteria.
○: Remaining processing oil amount 5 μg / cm ² or less ×: Exceeding remaining processing oil amount 5 μg / cm ²

<Examples 56 to 57>
Each component was mixed with the composition of Table 9, and the target sample rinse agent was obtained. Each sample rinse agent was subjected to the (9) rinse property test, and the results are summarized in Table 9. Component (A1) is selected from 2H, 2H, 4H, 4H, 4H-perfluorobutane (HFC365mfc), and component (A2) is selected from non-chlorine fluorine compounds in which the ratio of the number of fluorine atoms in the molecule to the number of hydrogen atoms is 2 or more The rinse agent excellent in rinse property was obtained by using together the 1 type, 2 or more types of compound, and the component (B) the compound whose vapor pressure in 20 degreeC is less than 1.33 * 10 < ³ > Pa.

<Comparative Examples 18-20>
The same tests as in Examples 56 and 57 were performed on the solvents listed in Table 9. The results are summarized in Table 9. 2H, 3H-perfluoropentane, a mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether (HFE7100), 2H, 3H-perfluoropentane and a small amount of a compound having a vapor pressure of less than 1.33 × 10 ³ Pa at 20 ° C. Rinse property was insufficient in the combination.

(10) Finish cleanability test After applying magic ink to a test piece (SUS304, 2 × 13 × 80 mm) and leaving it for 30 minutes, it was wiped 10 times with a cotton swab impregnated with a sample finish cleaning agent, and washed for 3 minutes. Left at room temperature. The state of the test piece after standing was visually evaluated to determine the finish cleaning property and drying property of the sample finish cleaning agent.

Evaluation criteria are based on the following criteria.
Finish washability ○: Wiping location, almost no ink residue ×: Wiping location, apparent ink residue drying property ○: No liquid residue on the test piece ×: Liquid residue on the test piece <Examples 58 to 61>
Each component was mixed with the composition described in Table 10 to obtain the intended finish cleaning agent. The above (10) finish detergency test was conducted for each cleaning agent, and the results are summarized in Table 10. Component (A1) 2H, 2H, 4H, 4H, 4H-perfluorobutane (HFC365mfc) and component (A2) a kind selected from non-chlorine fluorine compounds in which the ratio of the number of fluorine atoms in the molecule to the number of hydrogen atoms is 2 or more Or the cleaning agent excellent in finish washing | cleaning property and drying property was obtained by using a little amount of a 2 or more types compound and the component (B) the compound whose vapor pressure in 20 degreeC is less than 1.33 * 10 < ³ > Pa.

<Comparative Examples 21-22>
The same test as Examples 58-61 was done about the solvent of Table 10. The results are summarized in Table 10. In 2H, 3H-perfluoropentane (HFC43-10mee), a mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether (HFE7100), the finish cleaning property was insufficient.

  The present invention relates to various processing oils and greases and waxes used when processing precision machine parts and optical machine parts, fluxes used when soldering electrical and electronic parts, and screens used when manufacturing substrates. The present invention provides a cleaning agent, a rinsing agent, a cleaning agent, and a cleaning method using the rinsing agent, which are suitable for cleaning inks and pastes adhering to the resin and resins adhering to the mixing portion of the resin discharge device.

Claims (35)

At least two volatile components (A) having a vapor pressure at 20 ° C. larger than the reference vapor pressure Po defined by the formula (1), and at least one of the non-volatile components (B) having a vapor pressure at 20 ° C. smaller than Po. A partially azeotropic composition consisting of seeds, wherein the composition of the gas phase and liquid phase at the boiling point under normal pressure satisfies the relationship of formulas (3) and (4).
Po = Pav / 5 (1) (where Pav is the component average vapor pressure defined by equation (2))
Pav = (ΣPai + ΣPbj) / (na + nb) (2)
(In the formula, Pai is the vapor pressure at 20 ° C. of each volatile component (Ai) in the composition, Pbj is the vapor pressure at 20 ° C. of each nonvolatile component (Bj), and na is the volatile component (A ), Nb is the number of the non-volatile component (B) in the composition, and is an integer satisfying 2 ≦ na and 1 ≦ nb, and i and j are 1 ≦ i ≦ na and 1 ≦ j ≦, respectively. It is an integer that satisfies nb.)
(ΣBvj / ΣBoj) ≦ 0.1 (3)
(In the formula, Bvj is the weight ratio of each nonvolatile component (Bj) in the gas phase, Boj is the weight ratio of each nonvolatile component (Bj) in the partial azeotropic composition, and j is the same as in Formula (2)). is there.).
−0.1 ≦ (Avi / ΣAvi) − (Aoi / ΣAoi) ≦ 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 in formula (2).) The partial azeotrope composition of Claim 1 which satisfy | fills the relationship of Formula (5).
0.0001 ≦ (ΣBvj / ΣBj) ≦ 0.1 (5)
(In the formula, Boj, Bvj, and j are the same as in formulas (3) and (4).) The partially azeotropic composition according to any one of claims 1 and 2, wherein a part thereof is vaporized and the gas phase covers the remaining liquid phase surface. The vapor pressure at 20 ° C. of all volatile components (A1 to Ana) in the composition is 1.33 × 10 ³ Pa or more, and the vapor pressure at 20 ° C. of all nonvolatile components (B1 to Bnb) is 1. The partial azeotrope composition according to any one of claims 1 to 3, which is a compound of less than 33 x 10 ³ Pa. The partial azeotropic composition according to any one of claims 1 to 4, wherein the volatile component (A) comprises a compound selected from halogenated hydrocarbons, hydrocarbons, alcohols, esters, and ketones. The partial azeotropic composition according to claim 5, wherein the volatile component (A) comprises two or more compounds selected from halogenated hydrocarbons. The partially azeotropic composition according to claim 6, wherein the halogenated hydrocarbon is a non-chlorine fluorine compound. Volatile component (A) is 2H, 2H, 4H, 4H, 4H-perfluorobutane (HFC365mfc) (A1), and non-chlorine fluorine in which the ratio of the number of fluorine atoms to the number of hydrogen atoms in the volatile component molecule is 2 or more The partial azeotropic composition of Claim 7 which consists of 1 type, or 2 or more types of compounds (A2) chosen from a compound. The partial azeotrope composition according to any one of claims 1 to 8, wherein the non-volatile component (B) comprises a compound selected from hydrocarbons, alcohols, and ketones. The partial azeotrope composition according to any one of claims 1 to 9, wherein the nonvolatile component (B) comprises one or more compounds selected from the group consisting of organic compounds having an ether bond and / or an ester bond. The partial azeotropic composition according to claim 10, wherein the non-volatile component (B) comprises one or more compounds selected from the group consisting of glycol ethers, glycol ether acetates and hydroxycarboxylic acid esters. The partial azeotropic composition according to claim 11, wherein the nonvolatile component (B) comprises one or more compounds selected from glycol ethers and one or more compounds selected from the group consisting of glycol ether acetates and hydroxycarboxylic acid esters. 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). Boiling composition.

(In the formula, R ¹ represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group, or a cycloalkyl group, R ² , R ³ , and R ⁴ represent hydrogen or a methyl group, and n represents an integer of 0 or 1.)

(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 hydrogen or a methyl group, R ⁶ is an alkyl group having 3 to ⁶ carbon atoms, An alkenyl group or a cycloalkyl group, n represents an integer of 0 or 1)

(In the formula, R ¹⁰ is an alkyl group having 1 to 6 carbon atoms, an alkenyl group or a cycloalkyl group, R ¹¹ , R ¹² and R ¹³ are hydrogen or a methyl group, n is an integer of 0 to 1, and m is 1 to 4) Indicates an integer)

(In the formula, R ¹⁴ represents an alkyl group, alkenyl group or cycloalkyl group having 1 to 6 carbon atoms.) The partial azeotropic composition according to claim 11, wherein the nonvolatile component (B) comprises one or more compounds (B1) selected from glycol ether monoalkyl ethers and one or more compounds (B2) selected from glycol ether dialkyl ethers. . The partial azeotrope composition according to claim 14, wherein component (B1) is a hydrophilic compound and component (B2) is a hydrophobic compound. The partial azeotropic composition according to claim 14, wherein component (B1) is a hydrophobic compound and component (B2) is a hydrophilic compound. The partially azeotropic composition according to claim 14, wherein both the component (B1) and the component (B2) are hydrophilic compounds. The partially azeotropic composition according to claim 14, wherein both the component (B1) and the component (B2) are hydrophobic compounds. Component (B1) contains one or more compounds selected from 3-methoxybutanol, 3-methoxy-3-methylbutanol, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether The partially azeotropic composition of claim 14. The partial azeotropic composition of Claim 14 in which a component (B2) contains the compound of 1 type, or 2 or more types chosen from diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, and dipropylene glycol dimethyl ether. The non-volatile component (B) comprises one or more compounds (B1) selected from glycol ether monoalkyl ethers and one or more compounds (B3) selected from glycol ether acetates. Boiling composition. The partial azeotropic composition according to any one of claims 1 to 21, which has no flash point. The partial azeotropic composition according to any one of claims 1 to 22, which is excellent in self-extinguishing properties. A cleaning agent comprising the partially azeotropic composition according to claim 1. A vapor condensate generated by heating the partially azeotropic composition according to claim 1. A rinse agent having the same composition as the condensate of claim 25. A detergent replenisher having the same composition as the condensate of claim 25. A cleaning method using the cleaning agent according to claim 24 and the rinsing agent according to claim 26. A cleaning method using the cleaning agent of claim 24 and the cleaning agent replenisher of claim 27. A cleaning method using the cleaning agent of claim 24, the rinsing agent of claim 26, and the cleaning agent replenisher of claim 27. A finish cleaner having the same composition as the condensate of claim 25. 2H, 2H, 4H, 4H, 4H-perfluorobutane (HFC365mfc) (component A1), one or two or more kinds selected from non-chlorine fluorine compounds having a fluorine atom / hydrogen atom number ratio of 2 or more in the molecule The compound (component A2) contains a compound (component B) having a vapor pressure of less than 1.33 × 10 ³ Pa at 20 ° C., and its content is (A1) + (A2) / (B) = 80 / 20˜ A composition which is 99.9 / 0.1% by weight. A rinse agent comprising the composition of claim 32. A detergent replenisher comprising the composition of claim 32. A finish cleaner comprising the composition of claim 32.

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