JP4407636B2 - Cleaning composition and cleaning method - Google Patents

Description

The present invention relates to a cleaning composition and a cleaning method. More specifically, the present invention relates to oils, fats, greases, fluxes, waxes, metal, glass, and plastics with contaminants such as dirt and fingerprints attached to the surface. The present invention relates to a cleaning composition for cleaning articles such as, and a cleaning method using the same.
The said cleaning composition can be utilized in the washing | cleaning process included in the various components manufacturing process in fields, such as a mechanical metal industry, a precision machine industry, an optical machine industry, an electrical electronics industry, a plastics industry.

  Conventionally, solvent compositions mainly composed of chlorofluorocarbons such as trifluorotrichloroethane and chlorohydrocarbons such as 1,1,1-trichloroethane have been used as plastics products, rubber products, and electronics. It was widely used as a solvent for cleaning parts. However, since chlorofluorocarbons and chlorinated hydrocarbons containing chlorine contain chlorine, a serious disadvantage of destroying the ozone layer has been pointed out, and its production has been suspended and its use has been restricted worldwide. Yes. Under such circumstances, research and development of alternative products that do not destroy the ozone layer are actively conducted in place of conventional chlorofluorocarbons and chlorinated hydrocarbons containing chlorine.

  As such an alternative, a cleaning solvent composition that does not destroy the ozone layer without impairing the excellent detergency and other properties of chlorine-containing chlorofluorocarbons and chlorinated hydrocarbons has been proposed. That is, Patent Document 1 discloses a mixed solvent of hydrofluorocarbon and terpenes, and Patent Document 2 discloses a mixed solvent of hydrofluorocarbon and alcohols.

  However, the mixed solvent described in the above patent document has a problem that sufficient cleaning performance cannot be obtained when used for cleaning the solder paste remaining after the soldering operation (hereinafter referred to as flux cleaning). It was.

Japanese National Publication No. 6-510721 JP-A-10-316598

  SUMMARY OF THE INVENTION An object of the present invention is to provide a cleaning composition that is stable without flux of ozone layer destruction and exhibits sufficient cleaning performance in flux cleaning, and a cleaning method using the cleaning composition. is there.

  The inventors of the present invention have made extensive studies in order to achieve the above-mentioned object, and as a result, combined use of a fluorine-containing compound that does not contain a chlorine atom and at least one compound selected from geraniol and nerol makes it possible to perform flux cleaning. The present inventors have found that a detergent composition having a particularly excellent detergency can be obtained and completed the present invention.

Thus, according to the present invention, there is provided a detergent composition comprising a fluorine-containing compound not containing a chlorine atom and at least one compound selected from geraniol and nerol.
Furthermore, according to the present invention, the step of cleaning the article to which the contaminant has adhered with the above-mentioned cleaning composition, and the rinsed solvent containing 80% by weight or more of the fluorine-containing compound containing no chlorine atom in the cleaned article. There is provided a method for cleaning an article comprising a step of rinsing with a slag.

  The cleaning composition of the present invention is less susceptible to ozone layer destruction, is easy to handle, and exhibits excellent cleaning performance particularly in flux cleaning.

It is a schematic diagram of the washing | cleaning apparatus for enforcing the washing | cleaning method of this invention. DESCRIPTION OF SYMBOLS 1 Washing tank 2 Rinse tank 3 Steam generation tank 4 Cooling pipe 5 Water separator 6 Ultrasonic generator 7 Circulation pump 8 Filter 9 Heater 10 Steam 11 Steam zone 12 Distillation regeneration part 13 Distillation tower 14 Liquid management tank 15 Concentration detection means 16 Waste liquid discharge line 17 Raw material supply line

  The cleaning composition of the present invention contains a fluorine-containing compound not containing a chlorine atom (hereinafter abbreviated as “fluorinated compound A”) and at least one compound selected from geraniol and nerol. Features.

It is essential that the cleaning composition of the present invention contains at least one compound selected from geraniol and nerol. Geraniol and nerol are isomers of each other. These are known substances as a kind of monoterpene alcohol, and are commercially available. Geraniol and nerol are particularly superior in cleaning performance in flux cleaning when used in combination with the fluorine-containing compound A, compared to other monoterpene alcohols such as linalool and terpineol.
The weight ratio of geraniol and nerol in the cleaning composition of the present invention is preferably in the range of 100/0 to 10/90, particularly preferably in the range of 90/10 to 50/50, from the viewpoint of cleaning performance.

  The fluorine-containing compound A has a chemical structure in which a part of hydrogen atoms of hydrocarbons and ethers are substituted only by fluorine atoms, does not contain chlorine atoms, and consists of carbon atoms, hydrogen atoms, and fluorine atoms, Or it is a compound which consists of these atoms and oxygen atoms.

  The fluorine-containing compound A is preferably a cyclic hydrofluorocarbon specified by the following general formula (1) (hereinafter, the hydrofluorocarbon is abbreviated as “HFC”), a chain HFC specified by the formula (2), Hydrofluoroether specified by formula (3) (hereinafter, hydrofluoroether is abbreviated as “HFE”) and hydrofluoroketone specified by formula (4) (hereinafter, hydrofluoroketone is abbreviated as “HFN”). ). These fluorine-containing compounds A may be used alone or in combination of two or more compounds selected from these.

_{C n H 2n-m F m} (1)
(In the formula, n and m each represent an integer of 4 ≦ n ≦ 6, 5 ≦ m ≦ 2n−1.)
_{C x H 2x + 2-y} F y (2)
(In the formula, x and y represent integers of 4 ≦ x ≦ 6 and 6 ≦ y ≦ 2x + 1, respectively.)
_{C s H t F 2s + 1} -t OC u H v F 2u + 1-v (3)
(Wherein, s, t, u, and v represent integers of 2 ≦ s ≦ 4, 0 ≦ t ≦ 3, 1 ≦ u ≦ 3, and 0 ≦ v ≦ 3, respectively.)
C _a H _b F _{2a + 1-b} COC _c H _d F _{2c + 1-d} (4)
(Wherein, a, b, c and d represent integers of 2 ≦ a ≦ 4, 0 ≦ b ≦ 3, 1 ≦ c ≦ 3 and 0 ≦ d ≦ 3, respectively)

  Specific examples of the cyclic HFC include 3H, 4H, 4H-perfluorocyclobutane, 4H, 5H, 5H-perfluorocyclopentane, and 5H, 6H, 6H-nonafluorocyclohexane. Among these, 4H, 5H, 5H-perfluorocyclopentane is preferable from the viewpoint of cleaning performance.

Specific examples of chain HFCs include 1H, 2H, 3H, 4H-perfluorobutane, 1H, 2H-perfluorobutane, 1H, 3H-perfluorobutane, 2H, 3H-perfluorobutane, 4H, 4H-per Fluorobutane, 1H, 1H, 3H-perfluorobutane, 1H, 1H, 4H-perfluorobutane, 1H, 2H, 3H-perfluorobutane, 1H, 1H, 1H, 3H, 3H-perfluorobutane, 1H, 2H -Perfluoropentane, 1H, 4H-perfluoropentane, 2H, 3H-perfluoropentane, 2H, 4H-perfluoropentane, 2H, 5H-perfluoropentane, 1H, 2H, 3H-perfluoropentane, 1H, 3H , 5H-perfluoropentane, 1H, 5H, 5H-perfluoropentane, 2H, 2H, H-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 such a chain HFC represented by the general formula _C 6 _{HF 13} can be exemplified.

Specific examples of HFE include CHF ₂ CF ₂ OCH ₂ CF ₃ , CF ₃ CHFCF ₂ OCH ₃ , CF ₃ CF ₂ CH ₂ OCHF ₂ , CF ₃ CF ₂ CF ₂ CF ₂ OCH ₃ , (CF ₃ ) ₂ CFCF ₂ OCH ₃ , CF ₃ CHFCF ₂ CH ₂ OCHF ₂ , CF ₃ CHFCF ₂ OCH ₂ CF ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ OCH ₃ , CF ₃ CHFCF ₂ OCH ₂ CF ₂ CHF ₂ , CF ₃ CHFCF ₂ OCH ₂ CF ₂ CF ₃ , CF ₃ CHFCF ₂ OCH ₂ CF ₂ CHF ₂ , CF ₃ CF ₂ CF ₂ CF ₂ OCH ₂ CH ₃ , (CF ₃ ) ₂ CFCF ₂ OCH ₂ CH ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ OCH ₂ CH _3, and methyl perfluoro cyclohexyl Agent Or the like can be mentioned Le. Among these, from the viewpoint of cleaning performance, CHF ₂ CF ₂ OCH ₂ CF ₃ , CF ₃ CF ₂ CF ₂ CF ₂ OCH ₃ , (CF ₃ ) ₂ CFCF ₂ OCH ₃ , CF ₃ CF ₂ CF ₂ CF ₂ OCH _{2 CH 3, (CF 3) 2} CFCF 2 OCH 2 CH 3 and mixtures thereof are preferred. More preferably CF ₃ CF ₂ CF ₂ CF ₂ OCH ₃ , (CF ₃ ) ₂ CFCF ₂ OCH ₃ and mixtures thereof, CF ₃ CF ₂ CF ₂ CF ₂ OCH ₂ CH ₃ , (CF ₃ ) ₂ CFCF ₂ OCH ₂ Mention may be made of CH ₃ and mixtures thereof. Among these, CF ₃ CF ₂ CF ₂ CF ₂ OCH ₃ , (CF ₃ ) ₂ CFCF ₂ OCH ₃ and a mixture thereof are particularly preferable.

Specific examples of HFN include CF ₃ CF ₂ COCH ₃ , CHF ₂ CF ₂ COCH ₃ , CF ₃ CF ₂ CF ₂ COCH ₃ , CF ₃ CF ₂ COCH ₂ CH ₃ , CF ₃ CF ₂ CF ₂ COCH ₂ CH ₃ , ( CF ₃ ) ₂ CFCOCH ₃ , CF ₃ CF ₂ CF ₂ CF ₂ COCH ₃ , CHF ₂ CF ₂ CF ₂ CF ₂ COCH _{3 and the} like.

  Of the fluorine-containing compound A, cyclic HFC, chain HFC and HFE having high solubility in polar solvents such as alcohols, ketones, esters and glycol ethers and low global warming potential are preferably used. Among these, cyclic HFC and HFE are more preferable, and cyclic HFC is particularly preferable.

  In the cleaning composition of the present invention, the weight ratio of the total amount of geraniol and nerol and the fluorine-containing compound A is preferably in the range of 10/90 to 80/20, more preferably 20/80 to 50/50. The range is particularly preferably 25/75 to 45/55. If the total amount of geraniol and nerol is too small, the cleaning performance is inferior.On the other hand, if the total amount of geraniol and nerol is too large, the penetrability deteriorates. Inferior.

  In the cleaning composition of the present invention, the total amount of geraniol and nerol and the fluorine-containing compound A is preferably 30% by weight or more, more preferably 60% by weight or more, and 90% by weight or more. It is particularly preferred that

  If necessary, various organic solvents and additives can be added to the cleaning composition of the present invention as long as it does not deviate from the characteristic configuration of the present invention and does not impair the effects thereof. Organic solvents and additives include, for example, improved uniformity of cleaning composition, melting point drop, cleaning power adjustment, improved cleaning power by surface activation, improved storage stability and thermal stability, UV absorption There are organic solvents and additives for the purpose of imparting performance and defoaming during cleaning.

  The type of organic solvent is not particularly limited, but for example, hydrocarbons, alcohols, ethers, glycols, sulfoxides, glycol ethers, esters, ketones, amides, ureas, phenols , Nitriles, heterocyclic compounds, volatile organic silicones and chlorinated hydrocarbons. An organic solvent can be used individually or in combination of 2 or more types. The amount of the organic solvent in the cleaning composition is preferably 20% by weight or less, particularly preferably 10% by weight or less.

  Specific examples of hydrocarbons include n-pentane, n-hexane, n-heptane, isohexane, isoheptane, n-octane, isooctane, n-decane, isodecane, n-undecane, n-dodecane, n-tridecane, etc. Aliphatic hydrocarbons; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene and xylene;

  Specific examples of alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, t-butyl alcohol, n-pentyl alcohol, isopentyl alcohol, n -Hexyl alcohol, isohexyl alcohol, 2-ethylhexyl alcohol, n-octyl alcohol, etc. are mentioned.

  Specific examples of ethers include diethyl ether, dipropyl ether, diisopropyl ether, tetrahydrofuran, 1,2-dimethoxyethane, and dioxane.

  Specific examples of glycols include ethylene glycol and propylene glycol.

  Specific examples of the sulfoxides include dimethyl sulfoxide and diethyl sulfoxide.

  Specific examples of glycol ethers include 3-methyl-3-methoxybutanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.

  Specific examples of esters include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isopropyl propionate, Examples include methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, methyl valerate, and ethyl valerate.

  Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

  Specific examples of amides include N, N-dimethylformamide and N, N-dimethylacetamide.

  Specific examples of ureas include 1,3-dimethyl-2-imidazolidinone, N, N′-dimethylpropyleneurea, 1,1,3,3-tetramethylurea and the like.

  Specific examples of phenols include phenol, p-chlorophenol, o-cresol, m-cresol, and p-cresol.

  Specific examples of nitriles include acetonitrile and benzonitrile.

  Specific examples of the heterocyclic compounds include pyridine and N-methylpyrrolidone.

  Specific examples of the volatile organic silicones include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like.

  Specific examples of the chlorinated hydrocarbons include methylene chloride, dichloroethane, dichloroethylene, trichloroethylene, and perchloroethylene.

  Although it does not specifically limit about the kind as an additive, For example, surfactant, a stabilizer, antioxidant, a ultraviolet absorber, an antifoamer etc. are mentioned. An additive can be used individually or in combination of 2 or more types.

  As the surfactant, known anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants can be used. Examples of the anionic surfactant include carboxylate, sulfonate, sulfate ester salt, phosphate ester salt and the like. Examples of the cationic surfactant include salts of amines with various acids and quaternary ammonium salts. Examples of the nonionic surfactant include polyoxyethylene ether, polyoxyethylene-polyoxypropylene glycol, polyoxyethylene-polyoxypropylene alkyl ether, and fatty acid partial ester of polyhydric alcohol. Examples of amphoteric surfactants include betaines, amino organic acids, and amine salts of fatty acids. In addition, an activator containing a fluorine atom in the molecule of these compounds is also preferably used. The amount of the additive in the cleaning composition is preferably 10% by weight or less, particularly preferably 5% by weight or less.

  Specific examples of the stabilizer include aliphatic nitro compounds such as nitromethane and nitroethane; acetylene alcohols such as 3-methyl-1-butyn-3-ol and 3-methyl-1-pentyn-3-ol; glycidol , Epoxides such as methyl glycidyl ether, and ethyl glycidyl ether; ethers such as dimethoxymethane, 1,3-dimethoxyethane, 1,4-dioxane; unsaturated hydrocarbons such as hexene, heptene, cyclopentene, and cyclohexene; And unsaturated alcohols such as allyl alcohol and 1-buten-3-ol; acrylic acid esters such as methyl acrylate and ethyl acrylate; and the like. The amount of the stabilizer in the cleaning composition is preferably 10% by weight or less, particularly preferably 5% by weight or less.

  Specific examples of the antioxidant 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], And phenolic antioxidants such as octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate; Amine antioxidants such as -phenylene-diamine, 4-amino-p-diphenylamine, and p, p'-dioctyldiphenylamine; phenylisodecyl phosphite, diphenyldiisooctyl phosphite, diphenyldiisodecyl phosphite, triphenylphosphine Phosphorous antioxidants such as phyto, trisnonylphenyl phosphite, and bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite; dilauryl-3,3′-thiodipropionic acid ester, ditridecyl Sulfur-based antioxidants such as −3,3′-thiodipropionic acid ester, dimyristyl-3,3′-thiodipropionic acid ester, and distearyl-3,3′-thiodipropionic acid ester; It is done. The amount of the antioxidant in the cleaning composition is preferably 10% by weight or less, particularly preferably 5% by weight or less.

  Specific examples of the ultraviolet absorber 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 Benzophenones such as 4,4'-dimethoxybenzophenone and 4-dodecyl-2-hydroxybenzophenone; phenyl salicylate, 4-t-butylphenyl salicylate, 4-octylphenyl salicylate, bisphenol A-di-salicylate, etc. Phenyl salicylates; 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) Benzotriazoles such as benzotriazole and 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole ; And the like. The amount of the ultraviolet absorber in the cleaning composition is preferably 10% by weight or less, particularly preferably 5% by weight or less.

  Specific examples of the antifoaming agent include self-emulsifying silicone, silicon, fatty acid, higher alcohol, polypropylene glycol polyethylene glycol and fluorine-based surfactant. The amount of the antifoaming agent in the cleaning composition is preferably 10% by weight or less, particularly preferably 5% by weight or less.

Cleaning method The method for cleaning an article of the present invention comprises a step of cleaning an article to which a contaminant has adhered (hereinafter abbreviated as “cleaning step”), and the article after cleaning with fluorine-containing compound A. It has the process (henceforth a "rinsing process") rinsed with the rinse solvent containing 80 weight% or more.

(1) Cleaning process In the cleaning process, an article to which a contaminant, which is an object to be cleaned, adheres is cleaned with the cleaning composition of the present invention in a cleaning tank. In this case, it is preferable to employ a means for stirring the cleaning agent so that the cleaning agent near the surface of the object to be cleaned is always replaced and the cleaning agent is in a dynamic state. The cleaning means is not particularly limited, and any conventionally known cleaning means such as immersion cleaning, stirring cleaning, rocking cleaning, ultrasonic cleaning, jet cleaning, barrel rotation cleaning, brush cleaning, and air bubbling cleaning can be applied. . In addition, it is preferable to warm the cleaning agent composition in the cleaning tank in combination with these cleaning means. This is because the cleaning performance is improved by these cleaning means and heating.
The internal temperature of the washing tank is preferably 20 to 80 ° C, particularly preferably 30 to 60 ° C.

(2) Rinsing step After the washing step, the washed article is rinsed with a rinse solvent. The rinsing solvent is also preferably in a dynamic state as described above, but as such means, the same means as the cleaning means in the cleaning step can be used. Moreover, it is preferable from the surface of the improvement of rinse performance to heat the rinse solvent in a rinse tank. The internal temperature of the rinsing tank is preferably 10 to 80 ° C, particularly preferably 20 to 60 ° C.

  The rinse solvent used in the present invention contains 80% by weight or more of the fluorine-containing compound A, preferably 90% by weight or more, and particularly preferably 95% by weight or more. In addition, various organic solvents and additives can be added as necessary as long as they do not depart from the characteristic configuration of the present invention and do not impair the effects thereof. The organic solvent and additive may be the same as those used in the cleaning composition, but the total amount of the organic solvent and additive used is 10% by weight or less, preferably 5% by weight in the rinsing solvent. The range is as follows.

  The rinse solvent preferably forms an azeotropic composition or an azeotrope-like composition.

  By using a rinse solvent containing the fluorine-containing compound A at a high concentration in the rinse step, the rinse effect is remarkably improved. In particular, the effect is more prominent when the washed article is continuously rinsed.

  In the cleaning method of the present invention, at least one of the step of cleaning with the cleaning composition and the step of rinsing with a rinsing solvent or after the step of rinsing with a rinsing solvent is performed. Although a step of cleaning the surface of the article with the steam containing A (hereinafter, abbreviated as “steam cleaning step”) can be provided, it is preferable to provide a steam cleaning step after the rinsing step. The vapor containing the fluorine-containing compound A has a fluorine-containing compound A concentration of preferably 50% by weight or more, more preferably 90% by weight or more, and particularly preferably 95% by weight or more. By providing the steam cleaning step, the surface of the article can be finished more cleanly.

  Furthermore, in the cleaning method of the present invention, it is preferable to finally provide a drying process in which the object to be cleaned after completion of the steam cleaning process is moved to the atmosphere and dried in the atmosphere.

  Hereinafter, the cleaning method of the present invention will be described in detail based on the cleaning apparatus shown in FIG. 1, but the cleaning method of the present invention is not limited to this embodiment. The cleaning apparatus shown in FIG. 1 includes a cleaning tank 1 containing the cleaning composition of the present invention, a rinsing tank 2 containing a rinsing solvent containing 80% by weight or more of the fluorine-containing compound A, a steam generation tank 3, and mainly a fluorine-containing compound A. A steam zone 11 filled with the steam 10, a cooling pipe 4 that condenses and liquefies the steam, and a moisture separator 5 that statically separates the condensed liquid and moisture adhering to the cooling pipe 4 by specific gravity. .

  The distillation regeneration unit 12 is not necessarily installed. However, when the cleaning work is frequently performed and a large amount of objects to be cleaned is processed, the running cost of the cleaning liquid is reduced, the amount of waste is reduced, and the environmental load is thereby reduced. It is preferably installed for the purpose of illustration. The distillation regeneration unit 12 shown in FIG. 1 includes a distillation column 13 and a liquid management tank 14. The distillation regeneration unit 12 is not limited to the in-line type as shown in FIG. 1 and may be an offline type, and the distillation column 13 of the distillation regeneration unit 12 is preferably in a reduced pressure state. Further, the cleaning tank 1 and the rinsing tank 2 can each have a configuration of two or more tanks as necessary.

  Next, a series of operations from washing to drying will be described below with reference to FIG. 1. In this embodiment, (a) a washing process in which an article is placed in a dedicated basket or the like and washed in the washing tank 1, (b) (C) A rinsing step for rinsing and moving the article to the rinsing tank 2 together with the dedicated basket after the rinsing process is completed, d) After the completion of the steam cleaning process, the article consists of a drying process in which the articles are lifted together with a dedicated basket from the steam zone 11 to the atmosphere and dried in the atmosphere.

  In the (a) cleaning step, the article to which the dirt component is adhered is immersed in the cleaning tank 1 to remove the dirt component adhering to the surface of the article. In the cleaning tank 1, the cleaning liquid can be heated as necessary, or ultrasonic cleaning can be performed by the ultrasonic generator 6. A part of the cleaning liquid in the cleaning tank 1 can be taken out by the circulation pump 7 and circulated through the filter 8.

  Next, in the (b) rinsing step, the article after the cleaning process is moved to the rinsing tank 2 and immersed in the liquid and the dirt component remaining on the surface of the article and the cleaning composition attached in the cleaning tank 1 Remove. Also in the rinsing tank 2, the rinse liquid can be heated as necessary, or ultrasonic cleaning can be performed by the ultrasonic generator 6.

  In the (c) steam cleaning step, the article is moved to the steam zone 11, and the article is exposed while the steam 10 mainly composed of the fluorine-containing compound A generated from the steam generation tank 3 is filled. Steam cleaning is performed by steam condensation.

  Finally, in the (d) drying step, when the article is pulled up from the vapor zone 11 to the atmosphere, the rinse liquid slightly remaining on the surface of the article removes heat from the article heated by the steam cleaning. Evaporate and dry instantly. Thus, a series of operations from cleaning to drying is completed.

  Further, the contaminated cleaning liquid in the cleaning tank 1 is distilled and regenerated in the distillation regeneration section 12 by the distillation tower 13 having the heater 9 at the lower part, and circulates to the cleaning tank 1 via the liquid management tank 14. Here, of the contaminated soil components in the cleaning liquid, the soil components dissolved in the cleaning liquid, such as oil and fat, are concentrated by the distillation tower 13 and discharged from the waste liquid discharge line 16 to the outside of the system. On the other hand, solid components such as metal powder and resin powder that do not dissolve in the cleaning liquid among the contaminated components in the cleaning liquid are filtered and removed by the circulation pump 7 and the filter 8. Thereby, the cleanliness of the cleaning liquid in the cleaning tank 1 is always maintained.

  The distillation column 13 and the circulation pump 7 may be a continuous type that is always operated or an intermittent type that is operated only when necessary. The distillate from the top of the distillation column 13 is temporarily stored in the liquid management tank 14, monitored by the concentration detection means 15 based on data such as refractive index, and various raw materials from the raw material supply line 17 as necessary. Is newly supplied, the blending weight ratio of the cleaning composition is adjusted, and the cleaning liquid in the cleaning tank 1 can always be maintained at a constant quality. Further, by installing a stirring device in the liquid management tank 14, the cleaning composition can be uniformly mixed and supplied to the cleaning tank 1.

  Further, the cleaning liquid in the steam generation tank 3 is heated and boiled by the heater 9, rises as steam like a steam flow 10, forms a steam zone 11, and is used for steam cleaning of articles. This steam is condensed and liquefied by the cooling pipe 4, and flows into the water separator 5 by overflow together with the moisture adhering to the cooling pipe, and the upper layer moisture is separated and discharged by static separation by specific gravity. When the condensate containing the lower fluorine-containing compound A as a main component is returned to the rinsing tank 2, the rinsing liquid overflows from the rinsing tank 2 and flows back to the steam generation tank 3.

  In this way, the rinsing liquid in the rinsing tank 2 is always filled with the distilled and recovered liquid from the steam generation tank 3, so that it is always kept clean. The detergent composition (particularly a compound selected from geraniol and nerol) and the soil component adhering to the article and mixed in the rinse tank 2 are concentrated in the steam generation tank 3. The concentrated rinsing liquid in the steam generating tank 3 is usually controlled at the boiling temperature of the liquid phase, and when it reaches the concentration limit, it is discharged as a waste liquid or transferred to the distillation column 13 for distillation regeneration. Can be reused in the washing tank 1.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, the cleaning performance was evaluated according to the following criteria.

(1) Cleaning performance evaluation method The cleaning performance evaluation was performed by visually observing the presence or absence of rosin residue and white residue, and evaluated according to the following criteria.
○: Almost no residue ×: Residue on the entire surface

[Production Example 1] Manufacture of test specimen for cleaning evaluation A glass epoxy substrate (product number: FR-4-35R manufactured by Sanhayato Co., Ltd.) with double-sided copper foil is cut into a size of 50 mm x 60 mm x 1.6 mm and isopropyl Ultrasonic cleaning was performed at 40 ° C. for 10 minutes using alcohol, and air-dried at room temperature to obtain a clean state. Next, solder paste is applied to the substrate in a pattern of 4 rows of 11 mm × 44 mm × 0.3 mm, and preheated at 180 ° C. for 2 minutes on a hot plate in accordance with the melting processing conditions during lead-free soldering. Further, the mixture was heated and melted at 240 ° C. for 1 minute, and further allowed to stand for 24 hours at room temperature to prepare a test specimen for cleaning evaluation.

  Solder paste (manufactured by Senju Metal Industry Co., Ltd.) is an easy-cleaning type with a low thixotropic agent content, product number: 63-330F-40-10 (hereinafter abbreviated as “Paste A”), and a thixotropic agent. Two types of product numbers: 63-221CM5-40-10 (hereinafter abbreviated as “paste B”) were used as the hard-to-clean types with a large content.

[Production Example 2] Production of cleaning composition The cleaning compositions shown in Tables 1 and 2 were prepared by adding geraniol, other terpene alcohols or organic solvents to fluorinated compound A or hydrochlorofluorocarbon.

In Tables 1 and 2, HFE-7100 (manufactured by Sumitomo 3M Limited) is a mixture of CF ₃ CF ₂ CF ₂ CF ₂ OCH ₃ and (CF ₃ ) ₂ CFCF ₂ OCH ₃ , and HFE-7200 (Sumitomo). 3M Co., Ltd.) is a mixture of CF ₃ CF ₂ CF ₂ CF ₂ OCH ₂ CH ₃ and (CF ₃ ) ₂ CFCF ₂ OCH ₂ CH ₃ , and HFE-S7 (manufactured by Daikin Industries, Ltd.) is CHF. ₂ CF ₂ OCH ₂ CF ₃ , Bertrell XF (Mitsui DuPont Fluorochemical Co., Ltd.) is decafluoropentane, AK225AES (Asahi Glass Co., Ltd.) is an azeotropic mixture of dichloropentafluoropropane and ethanol It is a composition. HFCP represents 4H, 5H, 5H-perfluorocyclopentane (manufactured by Nippon Zeon Co., Ltd., 1,1,2,2,3,3,4-heptafluorocyclopentane).

[Examples 1 to 5 and Comparative Examples 1 to 5]
1, the cleaning composition produced in Production Example 2 was supplied to the cleaning tank 1, and the rinsing liquid shown in Table 3 was supplied to the rinsing tank 2 and the steam generation tank 3. Next, the test specimen for cleaning evaluation manufactured in Manufacturing Example 1 was immersed in the cleaning tank 1 and cleaned at 50 ° C. for 2 minutes while applying ultrasonic waves. After completion of the cleaning process, the test specimen for cleaning evaluation was manually moved from the cleaning tank 1 to the rinsing tank 2, immersed in the rinsing tank 2, and rinsed at 25 ° C. for 1 minute while applying ultrasonic waves. After completion of the rinsing process, the wafer was manually moved to the steam zone 11 and washed with steam of the rinse liquid shown in Table 3 for 1 minute, and then moved to the atmosphere and dried. Table 4 shows the results of evaluating the test specimen for cleaning evaluation after drying by the cleaning performance evaluation method described in (1) above.

  As shown in Table 4, the cleaning composition of the present invention consisting of geraniol, nerol and fluorine-containing compound A is much better than the cleaning composition consisting of linalool and fluorine-containing compound A which are other terpene alcohols. It turns out that it has performance. Moreover, the cleaning performance was superior to that of an azeotropic mixture composition of dichloropentafluoropropane and ethanol, which is a chlorine-based cleaning agent that has been conventionally used and has a strong cleaning power.

  The cleaning composition and the cleaning method of the present invention include, for example, cleaning steps included in various parts manufacturing processes in the fields of machine metal industry, metal processing industry, precision machine industry, optical machine industry, electrical / electronic industry, plastic industry, etc. Available in

  The target article to be cleaned is not particularly limited. For example, processed parts such as metal, ceramic, glass, plastic, and elastomer can be cleaned. Specific examples include automobile parts such as bumpers, gears, mission parts, and radiator parts, printed circuit boards, IC parts, lead frames, motor parts, electronic and electric parts such as capacitors, bearings, gears, engineering plastic gears, and watch parts. Precision machine parts such as camera parts and optical lenses, printing machines, printing machine blades, printing rolls, rolled products, construction machinery, glass substrates, large machine parts such as large heavy machinery parts, daily products such as tableware, and Examples include textile products.

  Contaminant types include, for example, oils such as cutting oil, quenching oil, rolling oil, lubricating oil, machine oil, pressing oil, punching oil, drawing oil, assembly oil, and drawing oil, greases, waxes, etc. Various types such as adhesives, adhesives, fats and oils, mold release agents, molding stains, and fluxes after soldering, resists, and solder pastes. The cleaning composition of the present invention has excellent cleaning performance particularly in solder paste flux cleaning.

Claims (14)

A cleaning composition comprising a fluorine-containing compound containing no chlorine atom and at least one compound selected from geraniol and nerol. The weight ratio of the total amount of geraniol and nerol and the fluorine-containing compound containing no chlorine atom is in the range of 10/90 to 80/20, and the total of geraniol and nerol and the fluorine-containing compound containing no chlorine atom The cleaning composition according to claim 1, wherein the amount is 30% by weight or more. The cleaning composition according to claim 1, wherein the fluorine-containing compound not containing a chlorine atom is at least one selected from compounds represented by the following general formulas (1) to (4).
_{C n H 2n-m F m} (1)
(In the formula, n and m each represent an integer of 4 ≦ n ≦ 6, 5 ≦ m ≦ 2n−1.)
_{C x H 2x + 2-y} F y (2)
(In the formula, x and y represent integers of 4 ≦ x ≦ 6 and 6 ≦ y ≦ 2x + 1, respectively.)
_{C s H t F 2s + 1} -t OC u H v F 2u + 1-v (3)
(Wherein, s, t, u, and v represent integers of 2 ≦ s ≦ 4, 0 ≦ t ≦ 3, 1 ≦ u ≦ 3, and 0 ≦ v ≦ 3, respectively.)
C _a H _b F _{2a + 1-b} COC _c H _d F _{2c + 1-d} (4)
(Wherein, a, b, c and d represent integers of 2 ≦ a ≦ 4, 0 ≦ b ≦ 3, 1 ≦ c ≦ 3 and 0 ≦ d ≦ 3, respectively) The fluorine-containing compound not containing a chlorine atom is CHF ₂ CF ₂ OCH ₂ CF ₃ , CF ₃ CF ₂ CF ₂ CF ₂ OCH ₃ , (CF ₃ ) ₂ CFCF ₂ OCH ₃ , CF ₃ CF ₂ CF ₂ CF ₂ OCH ₂ CH ₃ and _{(CF 3) 2 CFCF 2 OCH} 2 CH detergent composition according to claim 1 is at least one compound selected from among the _three. The fluorine-containing compound containing no chlorine atom is at least one compound selected from 3H, 4H, 4H-perfluorocyclobutane, 4H, 5H, 5H-perfluorocyclopentane, and 5H, 6H, 6H-nonafluorocyclohexane The cleaning composition according to claim 1. The cleaning composition according to claim 1, further comprising 20% by weight or less of an organic solvent. A step of cleaning an article to which a contaminant has adhered; a cleaning composition comprising a fluorine-containing compound not containing a chlorine atom and at least one compound selected from geraniol and nerol; and an article after cleaning Rinsing with a rinsing solvent containing 80% by weight or more of a fluorine-containing compound not containing a chlorine atom. The weight ratio of the total amount of geraniol and nerol contained in the cleaning composition to the fluorine-containing compound not containing chlorine atoms is in the range of 10/90 to 80/20, and geraniol and nerol and chlorine atoms are The cleaning method according to claim 7, wherein the total amount of fluorine-containing compounds not contained is 30% by weight or more. At least one of the step of washing with a cleaning composition and the step of rinsing with a rinsing solvent, or after the rinsing with a rinsing solvent, at least one of the articles with a vapor containing a fluorine-containing compound not containing a chlorine atom The washing | cleaning method of Claim 7 which has the process of wash | cleaning. The washing | cleaning method of Claim 7 which has the process of wash | cleaning articles | goods with the vapor | steam containing the fluorine-containing compound which does not contain a chlorine atom after the process rinsed with the rinse solvent. The cleaning method according to claim 7, wherein the fluorine-containing compound containing no chlorine atom is at least one selected from compounds represented by the following general formulas (1) to (4).
_{C n H 2n-m F m} (1)
(In the formula, n and m each represent an integer of 4 ≦ n ≦ 6, 5 ≦ m ≦ 2n−1.)
_{C x H 2x + 2-y} F y (2)
(In the formula, x and y represent integers of 4 ≦ x ≦ 6 and 6 ≦ y ≦ 2x + 1, respectively.)
_{C s H t F 2s + 1} -t OC u H v F 2u + 1-v (3)
(Wherein, s, t, u, and v represent integers of 2 ≦ s ≦ 4, 0 ≦ t ≦ 3, 1 ≦ u ≦ 3, and 0 ≦ v ≦ 3, respectively.)
C _a H _b F _{2a + 1-b} COC _c H _d F _{2c + 1-d} (4)
(Wherein, a, b, c and d represent integers of 2 ≦ a ≦ 4, 0 ≦ b ≦ 3, 1 ≦ c ≦ 3 and 0 ≦ d ≦ 3, respectively) The fluorine-containing compound not containing a chlorine atom is CHF ₂ CF ₂ OCH ₂ CF ₃ , CF ₃ CF ₂ CF ₂ CF ₂ OCH ₃ , (CF ₃ ) ₂ CFCF ₂ OCH ₃ , CF ₃ CF ₂ CF ₂ CF ₂ OCH ₂ CH ₃ and cleaning method according to claim _{7, (CF 3)} is at least one compound selected from among ₂ CFCF _{2 OCH 2} CH _3. The fluorine-containing compound containing no chlorine atom is at least one compound selected from 3H, 4H, 4H-perfluorocyclobutane, 4H, 5H, 5H-perfluorocyclopentane, and 5H, 6H, 6H-nonafluorocyclohexane The cleaning method according to claim 7. The cleaning method according to claim 10, further comprising a step of moving the article after the step into the atmosphere and drying in the atmosphere after the step of washing the article with the vapor containing the fluorine-containing compound not containing a chlorine atom. .

Images