JP2016049477A - Cleaning rinse method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a washing and rinsing method for an article, to which a dirt such as oil or flux has attached, and a washing and rinsing method excellent in a washing performance and a rinsing performance and high in a finish quality.SOLUTION: A washing and rinsing method for an article comprises: a washing step of bringing an article having a contaminant attached thereto into contact with a nonflammable cleaner composite containing a hydrocarbon solvent and water; and a rinsing step of bringing said article washed at said washing step, into contact with a fluorine-based solvent containing hydrofluoric-ether and/or hydrofluoric-carbon.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for cleaning and rinsing articles, and in particular, for removing dirt such as oils and fats, flux, and dust adhering to articles such as electronic parts such as ICs, precision machine parts, glass substrates, and resin molded parts. It relates to a cleaning rinse method used.

  Conventionally, in various industrial fields such as automobiles, machinery, precision equipment, electricity, electronics, etc., flux, processing oil, wax, separation from electronic parts such as ICs, precision machine parts, glass substrates, resin molded parts, etc. Various cleaning agents such as chlorine-based, hydrocarbon-based, glycol ether-based, and water-based are used to remove dirt such as molds and dust. However, conventional cleaning agents have many problems in terms of harmfulness to the human body and the environment, flammability, costs required for processing, facilities, and the like.

  In order to solve these problems, a cleaning composition that is highly cleanable, does not require rinsing with pure water, can be dried as it is, and can be reused, includes water, diethylene glycol diethyl ether, and a water-soluble solvent. A non-flammable cleaning composition having a cloud point of 2 has been proposed (see, for example, Patent Document 1).

  However, when cleaning is performed using the cleaning composition described in Patent Document 1, drying is necessary, and when the solvent component or moisture remaining on the surface of the article during heat drying evaporates, There was a problem that spots occurred.

International Publication No. 2013-077383

  The present invention has been made in order to solve the above problems, and is a method of cleaning and rinsing an article on which dirt such as processing oil or flux adheres, has excellent cleaning performance and rinsing performance, and has a stain on the surface of the article after cleaning. The purpose of the present invention is to provide a cleaning and rinsing method with a high finished quality such that no rust occurs.

The cleaning and rinsing method of the present invention includes:
A cleaning step of contacting the contaminated article with a non-flammable cleaning composition comprising a hydrocarbon solvent and water;
A rinsing step in which the article cleaned in the cleaning step is brought into contact with a fluorinated solvent containing hydrofluoroether (hereinafter referred to as HFE) and / or hydrofluorocarbon (hereinafter referred to as HFC). It is characterized by that.

In the present specification, the hydrocarbon solvent is a hydrocarbon compound or a compound having a substituent containing a hetero atom in the hydrocarbon compound, and does not contain a halogen atom such as fluorine or chlorine in the molecule. It is a solvent. The fluorine-based solvent is a solvent made of a compound containing at least one fluorine atom in the hydrocarbon solvent. Thus, the hydrocarbon solvent and the fluorine solvent are used separately.
In the present specification, for halogenated hydrocarbons, the abbreviations of the compounds are shown in parentheses after the compound names. In the present specification, the abbreviations are used instead of the compound names as necessary.

  The cleaning method of the present invention is excellent in cleaning performance and rinsing performance with respect to articles with dirt such as processing oil and flux, which are handled in various industrial fields, and the finished article has water and high boiling point. Since the components of the cleaning composition do not remain, the finished quality is high. In addition, since the cleaning composition used is non-flammable, it is not necessary to take measures such as explosion-proof equipment, and the safety is excellent.

It is a figure which shows an example of the cleaning rinse apparatus used for the cleaning rinse method of this invention.

  Hereinafter, embodiments of the present invention will be described.

  The cleaning and rinsing method of the present invention includes a cleaning step in which an article to which a contaminant is attached is brought into contact with a non-flammable cleaning composition containing a hydrocarbon-based solvent and water, and the article cleaned in the cleaning step is converted into HFE and And / or a rinsing step for contacting with a fluorinated solvent containing HFC.

<Washing process>
In the cleaning process of the present invention, an article to which contaminants such as flux, processing oil, wax, mold release agent, and dust are attached is brought into contact with a non-flammable cleaning composition containing a hydrocarbon solvent and water, The contaminant adhering to the article is dissolved in the cleaning composition and removed.
Here, examples of the articles include semiconductor parts, metal parts, glass substrates, resin molded parts, and the like that are handled in various industrial fields such as automobiles, machines, precision instruments, electricity, and electronics.

(Cleaning composition)
The cleaning composition used in the cleaning process of the present invention is a non-flammable composition containing a hydrocarbon solvent and water. Note that non-flammability is determined by the Cleveland open-type flash point measurement method (JIS K 2265) where no ignition is permitted.

  Water contained in the cleaning composition has an effect of eliminating the flash point of the composition. There is no particular limitation on the type of water, but there are few impurities, and there are few effects on parts and cleaning equipment, and on the finished quality after washing and rinsing, for example, distilled water or ion-exchanged water can be preferably used. .

In the present invention, the hydrocarbon solvent contained in the cleaning composition preferably contains a water-soluble solvent at room temperature.
Moreover, the water-soluble solvent at room temperature refers to a solvent that exhibits water solubility at 5 ° C to 35 ° C. To exhibit water solubility refers to a solvent exhibiting solubility in water of 50 g / 100 g water or more.
Water-soluble solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monoisobutyl ether , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene Glycol ethers such as glycol monobutyl ether, triethylene glycol dimethyl ether, polyethylene glycol monomethyl ether, glycols such as ethylene glycol, diethylene glycol, propylene glycol, 2-methyl-2,4-pentanediol, isoprene glycol, 3-methoxy-1 -Butanol, 3-methyl- - methoxybutanol such as methoxy-1-butanol, methanol, ethanol, 1-propanol, 2-propanol, alcohols such as 1-butanol. 1 type (s) or 2 or more types can be mixed and used.

The water-soluble solvent should have a boiling point of 170 ° C. or higher and 210 ° C. or lower so that it has good detergency (oil solubility), is easy to handle, and has a sufficient drying property. Further, those having a flash point of 65 ° C. or higher are particularly preferable.
Among these water-soluble solvents, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, ethylene glycol, propylene, from the viewpoints of boiling point, detergency, and flash point. Examples include glycol, 2-methyl-2,4-pentanediol, and 3-methyl-3-methoxy-1-butanol.

The cleaning composition can contain a water-insoluble solvent in addition to the water-soluble solvent described above as a hydrocarbon solvent. That is, as the hydrocarbon solvent, a water-soluble solvent and a water-insoluble solvent can be used in combination. As the water-insoluble solvent that can be used in combination with the water-soluble solvent described above, from the viewpoint of compatibility with the water-soluble solvent, glycol ethers such as diethylene glycol dibutyl ether, diethylene glycol propyl methyl ether, diethylene glycol diisobutyl ether, dipropylene glycol diethyl ether, etc. , Aliphatic hydrocarbons such as hexane, cyclohexane, heptane, nonane, octane, decane, and undecane. Among these glycol ethers and aliphatic hydrocarbons, one kind or a mixture of two or more kinds can be used.
In addition, as the water-insoluble solvent, those having compatibility with the fluorine-based solvent are preferable from the viewpoint of enhancing the solubility of oil and improving the washing property, and rinsing properties in the rinsing step described later. From among glycol ethers, ethylene glycol dibutyl ether, diethylene glycol propyl methyl ether, diethylene glycol diisobutyl ether, and dipropylene glycol diethyl ether are preferred.

  When the hydrocarbon solvent is a solvent containing the water-soluble solvent, or when the hydrocarbon solvent is a solvent containing the water-insoluble solvent and the water-soluble solvent, from the viewpoint that the cleaning composition does not have a flash point, The moisture concentration of the cleaning composition is preferably 10% by mass or more. That is, in the detergent composition containing a hydrocarbon solvent and water, it is preferable to adjust the content ratio of the water-soluble solvent so that 10% by mass or more of water is contained in the water-soluble solvent. From the viewpoint of detergency, the water content is preferably 50% by mass or less, more preferably 30% by mass or less, based on the entire cleaning composition.

  From the viewpoint of detergency (oil solubility) and non-flammability, the content of the hydrocarbon solvent in the cleaning composition is preferably 50% by mass to 90% by mass, and the content of the water-soluble solvent Is preferably 50% by mass or more based on 100% by mass of the entire hydrocarbon solvent.

  This detergent composition may further contain other polyhydric alcohol derivatives, esters, ethers and the like within a range not impairing the performance of the present composition. In addition, antioxidants such as 2,6-di-tert-butyl-p-cresol (BHT), thymol, pyrocatechin, iron such as amino alcohols, alkylamines, benzotriazoles, benzothiazoles, copper, You may further contain corrosion inhibitors and rust preventive agents, such as zinc.

<Rinsing process>
In the rinsing step of the present invention, the article washed in the washing step (hereinafter also referred to as a washed article) is brought into contact with a fluorinated solvent. Since the surface of the cleaned article is covered with a cleaning composition containing water and a hydrocarbon-based solvent by the cleaning in the cleaning process, the cleaning composition covering the surface of the cleaned article is removed from the fluorine-based process in the rinsing process. Replace with solvent. As the fluorinated solvent, HFE and HFC, which are compounds containing no chlorine in the molecule and having a zero ozone depletion coefficient, are preferable. In the rinsing step of the present invention, it is preferable to bring the cleaned article into contact with HFE and / or HFC. .

The HFE and HFC used in the rinsing step are preferably highly compatible with the hydrocarbon solvent contained in the cleaning composition. When a fluorine-based solvent having low compatibility with the hydrocarbon solvent is used for rinsing, the hydrocarbon-based solvent covering the surface of the article cannot be sufficiently replaced with the fluorine-based solvent and removed. In this case, the rinsing defect such as the occurrence of a stain occurs due to the remaining hydrocarbon solvent.
From the viewpoint of drying properties after rinsing, HFE and HFE preferably have a boiling point of 30 to 100 ° C.

  From the above viewpoint, HFE includes 1,1,2,2-tetrafluoroethyl-1,1,1-trifluoroethyl ether (HFE-347pc-f), methyl nonafluorobutyl methyl ether (HFE-449s), and the like. Is mentioned. As HFC, 1,1,1-2,2,3,4,5,5,5-decafluoropentane (HFC-43-10mee), 1,1,1,3,3-pentafluorobutane (HFC-365mfc) and the like. Among these HFE and HFC, one type may be used, or two or more types may be mixed and used.

In the present invention, rinsing may be performed using a solvent obtained by mixing the fluorine-based solvent with another solvent.
Specific examples of the solvent (hereinafter referred to as a rinse aid) that can be mixed with the fluorine-based solvent include the following compounds.
Hydrocarbons: n-pentane, n-hexane, isohexane, n-heptane, isooctane, cyclopentane, cyclohexane, methylcyclohexane.
Lower alcohols: methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, butyl alcohol.
Ketones: acetone, methyl ethyl ketone.

  The mixing ratio of the rinsing aid is preferably less than 5% by mass with respect to the total amount (100% by mass) of the fluorinated solvent and the rinsing aid from the viewpoint of rinsing efficiency. From the viewpoint of efficiency when the fluorine-based solvent is distilled and reused, it is more preferably less than 1% by mass. Moreover, when the mixing ratio of the rinse aid is within this range, the mixed solvent does not have flammability.

  Next, the cleaning and rinsing method of the present invention will be described according to a specific procedure.

  First, in the cleaning step, an article to which contaminants such as processing oil and flux are attached is cleaned by bringing it into contact with a non-flammable cleaning composition containing water and a hydrocarbon solvent. The cleaning method is not particularly limited as long as the cleaning composition can be brought into contact with the article. For example, hand wiping cleaning, immersion cleaning, spray cleaning, jet cleaning, immersion rocking cleaning, immersion ultrasonic cleaning, and a combination of these can be employed. The cleaning conditions such as the time and frequency of contact of the article with the cleaning composition, the temperature of the cleaning composition at the time of contact, and the apparatus can be appropriately selected.

  The temperature of the cleaning composition at the time of contact with the article is preferably 0 ° C. or higher and 90 ° C. or lower, more preferably 10 ° C. or higher and 70 ° C. or lower. The contact time between the cleaning composition and the article is preferably 1 second or longer and 1 hour or shorter, more preferably 10 seconds or longer and 0.5 hours or shorter.

  Next, in the rinsing step, the cleaned article is brought into contact with HFE and / or HFC, which are fluorinated solvents, to perform rinsing. The cleaning composition adhering to the surface of the cleaned article is brought into the fluorinated solvent together with the cleaned article, but the hydrocarbon solvent in the cleaning composition is dissolved in the fluorinated solvent. Effectively removed.

  The contact between the cleaned article and the fluorinated solvent (HFE and / or HFC) is performed by immersing the cleaned article in a rinse solvent containing a fluorinated solvent, or by spraying the fluorinated solvent on the cleaned article with a spray or the like. Further, it can be carried out by a method of bringing the cleaned article into contact with the vapor of a fluorinated solvent. Here, in the method of immersing in a fluorinated solvent, the rinsing aid may be mixed in HFE and / or HFC at a ratio of less than 5% by mass, although it may be immersed in a solvent consisting of only HFE and / or HFC. It may be immersed in the solvent.

  In order to increase the efficiency of rinsing, the same rinsing method may be repeated or two or more different rinsing methods may be combined. For example, when the method of dipping in a fluorinated solvent and the method of contacting with the vapor of the fluorinated solvent are combined, the rinsing efficiency is increased. In this case, it is preferable that the cleaned article is immersed in the fluorinated solvent and then contacted with the vapor of the fluorinated solvent.

  In particular, from the viewpoint of preventing adhesion of water droplets or the like to the article, and generation of spots due to the residual hydrocarbon solvent, it is preferable to immerse in a boiling fluorine solvent. Note that the fluorinated solvent is in a boiling state when at least one of the fluorinated compounds (HFE and / or HFC) contained in the fluorinated solvent is kept at a temperature higher than the boiling point and boiled. It means being.

Since the cleaning composition in the present invention contains an organic solvent and water, in the rinsing step of removing the cleaning composition attached to the article, not only the organic solvent was removed by the above method, but also attached to the article. It is necessary to remove moisture. From the viewpoint of organic solvent removal and moisture removal, it is preferable to employ a method of immersing in a boiling fluorine-based solvent. When the cleaned article is immersed in a boiled fluorinated solvent, the water in the cleaning composition that adheres to the surface of the cleaned article and is brought into the fluorinated solvent is generated from the boiling fluorinated solvent. And / or accompanied by HFC vapor and taken out of the fluorinated solvent. As a result, water such as water droplets does not remain on the surface of the article after rinsing.
Thus, since the hydrocarbon solvent and water contained in the cleaning composition do not remain on the surface of the article after rinsing, the article treated with the fluorinated solvent can be dried without residual solvent and spots. it can.

  According to the cleaning and rinsing method of the present invention, it is possible to perform cleaning and rinsing with excellent cleaning performance and rinsing performance on an article on which dirt such as processing oil or flux adheres, and the finished quality of the article is high. In addition, since the solvent used for cleaning is non-flammable, no countermeasures such as explosion-proof equipment are required, and cleaning can be performed safely.

<Washing rinse device>
An example of a cleaning / rinsing apparatus for carrying out the cleaning / rinsing method of the present invention is shown in FIG.
A cleaning and rinsing apparatus 1 shown in FIG. 1 includes a cleaning unit 2 and a rinsing unit 3. The cleaning unit 2 has a cleaning tank 10. The rinsing unit 3 includes a rinsing immersion tank 20, a steam tank 30, a cooling coil 40 installed at the upper part of the entire tank, a liquid receiver 50 provided adjacent to the lower side of the cooling coil 40, and a liquid receiver 50 and a water separator 60 connected via a liquid recovery pipe 61.

  A cleaning composition 11 is accommodated in the cleaning tank 10. The cleaning composition 11 is a non-flammable cleaning composition containing the above hydrocarbon solvent and water. An ultrasonic oscillator 12 for applying ultrasonic vibration to the cleaning composition 11 is provided on the bottom surface of the cleaning tank 10. The installation of the ultrasonic oscillator 12 is not essential.

  A rinse solvent 21 is accommodated in the rinse dipping tank 20. The rinsing solvent 21 is a fluorinated solvent containing HFE and / or HFC. A heater 22 for heating and boiling the rinsing solvent 21 and an ultrasonic oscillator 23 for applying ultrasonic vibration to the rinsing solvent 21 are provided at the bottom of the rinsing bath 20. The installation of the ultrasonic oscillator 23 is not essential.

The steam tank 30 also contains the same rinsing solvent 21 as the rinse dipping tank 20. The rinsing bath 20 and the steam bath 30 are connected so that the liquid level of the rinsing solvent 21 stored in the rinsing bath 20 is higher than the liquid level of the rinsing solvent 21 stored in the steam bath 30; The rinse solvent 21 that is arranged and overflows in the rinse dipping tank 20 flows into the steam tank 30.
A heater 31 for generating the vapor V of the rinsing solvent 21 accommodated in the vapor tank 30 is provided on the bottom surface of the vapor tank 30.

  The cooling coil 40 is disposed above the rinsing bath 20 and the steam bath 30. A cooling medium such as cooling water flows inside the cooling coil 40, and the periphery of the cooling coil 40 is cooled to liquefy the vapor V of the rinsing solvent 21 generated in the rinsing immersion tank 20 and the steam tank 30. The cooling coil 40 prevents the vapor V of the rinsing solvent 21 from escaping from the rinsing portion 3.

  The liquid receiver 50 receives the condensate generated by the liquefaction of the vapor V of the rinsing solvent 21. And in the water separator 60, the condensate introduced from the liquid receiver 50 is left still, and it separates with specific gravity into the upper layer liquid D1 containing much water, and the lower layer liquid D2 containing little water. . The upper layer liquid D1 is discarded, and the lower layer liquid D2 is sent to the rinsing bath 20 through the recovery liquid supply pipe 62 and reused.

  In addition, in the rinse part 3, when the vapor | steam V of the rinse solvent 21 of sufficient quantity can be generated with the rinse immersion tank 20, installation of the vapor tank 30 is not essential. However, since the cleaning agent composition 11 adhered to the article from the cleaning tank 10 is brought into the rinse dipping tank 20, it is preferable to install the steam tank 30 for the purpose of removing the hydrocarbon solvent to be introduced from the rinse dipping tank 20. .

  In order to perform the cleaning and rinsing method of the present invention using such a cleaning and rinsing apparatus 1, the article 4 to which the contaminant is attached is first immersed in the cleaning composition 11 accommodated in the cleaning tank 10. At this time, by generating ultrasonic waves from the ultrasonic oscillator 12, dissolution and dispersion of contaminants on the surface of the article 4 can be promoted.

Subsequently, the cleaned article 5 pulled up from the cleaning tank 10 is immersed in a boiling rinse solvent 21 accommodated in the rinse dipping tank 20 and rinsed, and then the rinsed article (rinsed article) 6 is rinsed. It is lifted from the immersion tank 20 and moved into the steam tank 30 and exposed to the vapor V of the rinsing solvent 21 generated in the steam tank 30.
At this time, when the temperature of the rinsed article 6 is lower than the boiling point of the rinse solvent 21, the vapor V of the rinse solvent 21 condenses on the surface of the rinsed article 6 and falls as droplets. 21 is rinsed further. Further, since the rinsed article 6 is warmed by the vapor V of the rinse solvent 21, the rinse solvent 21 adhering to the surface of the rinsed article 6 is easily evaporated and can be dried in a short time.

  Since the vapor V of the rinsing solvent 21 stays in the upper part of the rinsing bath 20, the rinsed article 6 pulled up from the rinsing bath 20 is not moved into the steam bath 30 and is moved to the upper part of the rinsing bath 20. You may pull up out of the rinse immersion tank 10 as it is through the vapor | steam V retention part.

  In such a cleaning and rinsing method, in the rinsing step, the hydrocarbon solvent contained in the cleaning composition 11 attached to the cleaned article 5 and brought into the rinsing solvent 21 is fluorine fluorine contained in the rinsing solvent 21. It is dissolved in a system solvent (HFE and / or HFC) and removed from the surface of the cleaned article 5. On the other hand, water contained in the cleaning composition 11 is discharged from the liquid phase of the rinsing solvent 21 together with the vapor V of the fluorinated solvent generated from the rinsing solvent 21 in a boiling state, and guided to the upper side of the rinsing bath 20. Then, the water discharged by being led to the vapor V of the fluorinated solvent is liquefied by the cooling coil 40, phase-separated by the water separator 60 through the liquid receiver 50, and then discarded as the upper layer liquid D1.

  In this way, water and hydrocarbon solvent contained in the cleaning composition 11 do not remain on the surface of the rinsed article 6, so that there is no adhesion of water or formation of spots, and rinsing properties are good.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. Examples 1 to 18 are examples of the present invention, and Examples 19 and 20 are comparative examples. Examples 21, 23, 25, 27, 29, 31, 33, 35, and 37 are examples of the present invention, and Examples 22, 24, 26, 28, 30, 32, 34, 36, and 38 are reference examples. It is.

Examples 1-20
A 1 mm-thick SUS plate cut into 30 mm × 30 mm was used as a cleaning article, and the following cleaning rinse was performed.
In Examples 1 to 18, the cleaning article was placed on a jig, and was first cleaned by being immersed in 2 L of a cleaning composition 2 L shown in Table 1 contained in a 3 L beaker. Next, the cleaning article was taken out from the cleaning composition together with the jig, rinsed using the rinsing portion of the cleaning rinsing apparatus shown in FIG. 1, and then dried. In the rinsing step, the article after washing was dipped in a rinsing solvent (HFE or HFC) shown in Table 1 contained in a rinsing dipping bath for 1 minute, and then slowly pulled up. And it took out out of the rinse part and dried.

  In Example 19 and Example 20, after being immersed for 1 minute in 2 L of the cleaning composition shown in Table 1 contained in a 3 L beaker for cleaning, the cleaned article was taken out and dried by blowing hot air at 50 ° C. for 1 minute. did.

Here, the detergent composition and the rinsing solvent represented by trade names in Table 1 are the following solvents or solvent compositions, respectively.
(Cleaning composition)
・ HA-IS16 (manufactured by Tosoh Corporation):
A composition containing diethylene glycol diethyl ether, a water-soluble solvent and 16% by mass of water.
・ Fine Top J210 (Kuraray Co., Ltd.):
It is a composition containing 3-methyl-3-methoxy-1-butanol and water, and the water concentration is more than 15% by mass and 50% by mass or less.
-Cleaning agent composition A
A composition containing 40% by mass of diethylene glycol diethyl ether, 40% by mass of 3-methyl-3-methoxy-1-butanol, and 20% by mass of water.
(Rinse solvent)
AE-3000 (Asahi Glass Co., Ltd.): HFE-347pc-f
Novec 7100 (manufactured by Sumitomo 3M Limited): HFE-449s
・ Bertrel XF (Mitsui DuPont Fluorochemical Co., Ltd.): HFC-43-10mee
-Solcan 365 (manufactured by Nippon Solvay Co., Ltd.): HFC-365mfc

  As shown in Table 1, the rinsing solvent HFE or HFC was in a boiling state or maintained at a predetermined temperature below the boiling point of HFE or HFC. The holding temperature below the boiling point was 45 ° C. when the rinsing solvent was AE-3000 (boiling point 56 ° C.), Novec 7100 (boiling point 60 ° C.), and Vertrel XF (boiling point 55 ° C.). When the rinsing solvent was Solcan 365 (boiling point 40 ° C.), the holding temperature below the boiling point was set to 35 ° C.

The appearance of the article thus dried was observed with the naked eye and evaluated for rinse rinsability. Evaluation was performed according to the following criteria. Table 1 shows the results of evaluation of the washing and rinsing properties.
(Evaluation criteria)
○: At the time of taking out, water and hydrocarbon solvent did not remain on the surface of the article and it was dried, and no poor drying was observed on the surface of the article.
Δ: Although water and hydrocarbon-based solvent remained on the surface of the article at the time of taking out, it was dried within 60 seconds, and a slight dry spot was observed in the remaining portion.
X: Water and hydrocarbons remained on the surface of the article at the time of taking out, and drying took 1 minute or more. In addition, obvious drying defects such as spots were observed on the surface of the article after drying.

  As shown in Table 1, when the cleaning rinsing method of the examples shown in Examples 1 to 18 was performed, compared with Examples 19 and 20 which were dried with hot air without rinsing with HFE and / or HFC after cleaning. It was found that the product surface dried quickly and the finished surface quality of the article was good.

Examples 21-38
For the cleaning article, as shown in Table 2, except that the rinsing operation was repeated 30 times by immersing in a rinsing solvent in a boiling state or maintained at a predetermined temperature for 30 minutes. Washing and rinsing were performed as in 18. Then, it was slowly pulled up from the rinse solvent and dried.

  In this way, the appearance of the article taken out after repeating washing and rinsing 30 times was observed with the naked eye, and repeated washing and rinsing properties were evaluated. The evaluation of the repeated rinsing property was performed according to the same criteria as the criteria for the rinsing property. Table 2 shows the evaluation results of the repeated washing and rinsing properties.

  As shown in Table 2, in Examples 21, 23, 25, 27, 29, 31, 33, 35, and 37 in which rinsing was performed by immersing in a boiling rinse solvent, the cleaning rinse was repeated 30 times. The dried state of the article remained unchanged, and when it was taken out, there was no residue of water or hydrocarbon solvent and it was dried, and the finished quality was good. On the other hand, in Examples 22, 24, 26, 28, 30, 32, 34, 36, and 38 where rinsing was performed by immersing in a rinsing solvent having a temperature equal to or lower than the boiling point, the number of cleaning rinses was repeated up to the fourth time. There was no change in the state of the rinsing solvent, but from the fifth washing rinse, a water retention layer was observed on top of the rinsing solvent contained in the rinsing tank. As a result, after repeated washing and rinsing 30 times, moisture reattaches to the article when the article is pulled up, and does not dry even after 1 minute after removal, and there is an obvious drying defect on the article surface after drying. It was seen.

  According to the cleaning and rinsing method of the present invention, it is possible to perform cleaning and rinsing with excellent performance on an article on which dirt such as processing oil or flux adheres without paying attention to the danger of ignition and the like. Becomes higher. Therefore, it is suitable as a washing and rinsing method for removing and cleaning contaminants adhering to articles such as electronic parts, precision machine parts, glass substrates, and resin molded parts in various industrial fields.

  DESCRIPTION OF SYMBOLS 1 ... Cleaning rinse apparatus, 5 ... Washed article, 6 ... Rinsed article, 10 ... Cleaning tank, 11 ... Cleaning agent composition, 20 ... Rinsing immersion tank, 21 ... Rinsing solvent, 30 ... Steam tank, 40 ... Cooling coil 60 ... water separator, 12, 23 ... ultrasonic oscillator, 22, 31 ... heater.

Claims (9)

A cleaning step of contacting the contaminated article with a non-flammable cleaning composition comprising a hydrocarbon solvent and water;
And a rinsing step of bringing the article washed in the washing step into contact with a fluorinated solvent containing hydrofluoroether and / or hydrofluorocarbon.   The method for cleaning and rinsing an article according to claim 1, wherein the hydrocarbon solvent includes a water-soluble hydrocarbon solvent at room temperature.   The water-soluble hydrocarbon solvent is dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, ethylene glycol, propylene glycol, 2-methyl-2,4-pentanediol. The method for rinsing an article according to claim 2, wherein the article is at least one selected from the group consisting of 3-methyl-3-methoxy-1-butanol.   The method for cleaning and rinsing an article according to claim 2 or 3, wherein the hydrocarbon solvent further includes a water-insoluble hydrocarbon solvent.   5. The article according to claim 4, wherein the water-insoluble hydrocarbon solvent is at least one selected from the group consisting of ethylene glycol dibutyl ether, diethylene glycol propyl methyl ether, diethylene glycol diisobutyl ether, and dipropylene glycol diethyl ether. Cleaning rinse method.   6. The hydrofluorether according to claim 1, wherein the hydrofluoroether is 1,1,2,2-tetrafluoroethyl-1,1,1-trifluoroethyl ether and / or methyl nonafluorobutyl ether. A method of cleaning and rinsing articles.   The hydrofluorocarbon is 1,1,1,2,2,3,4,5,5,5-decafluoropentane and / or 1,1,1,3,3-pentafluorobutane. Item 6. The method for washing and rinsing an article according to any one of Items 1 to 5.   The method of cleaning and rinsing an article according to any one of claims 1 to 7, wherein, in the rinsing step, the article is immersed in the boiling fluorinated solvent.   The method for cleaning and rinsing an article according to any one of claims 1 to 8, wherein the article immersed in the fluorinated solvent in the rinsing step is further brought into contact with the vapor of the fluorinated solvent.

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