JPWO2015060379A1 - Recyclable industrial azeotropic cleaner, article cleaning method, industrial azeotropic cleaner regeneration method, industrial azeotropic cleaner regenerated by the regeneration method, and cleaning regenerator - Google Patents

Abstract

The object of the present invention is to remove various industrial stains attached to the article, such as solder paste, flux residue, various oils, etc., and has no flash point, and can be recycled (distilled and regenerated) under normal pressure. It is to provide a glycol-based industrial cleaner. In the present invention, general formula (1): R1-O-[-CH2-CH (X) -O] n-R2 (in formula (1), R1 and R2 are all alkyl groups having 1 to 3 carbon atoms. N represents 2 or 3, X represents hydrogen or a methyl group), a glycol solvent (A) having a boiling point of 160 to 230 ° C. under normal pressure, water (B), An azeotrope containing a tertiary amine (C) having a boiling point of 160 to 230 ° C. under normal pressure as necessary, wherein the ratio of the component (A), the component (B) and the component (C) is 5 in order. The present invention relates to a recyclable industrial azeotropic detergent characterized by containing 35 wt%, 65 to 95 wt% and 0 to 30 wt%, and having an azeotropic point of 90 to 100 ° C. under normal pressure.

Description

  The present invention relates to a recyclable industrial azeotropic cleaner, a method for cleaning an article, a method for regenerating an industrial azeotropic cleaner, an industrial azeotropic cleaner regenerated by the regeneration method, and a cleaning and industrial use of articles. The present invention relates to a cleaning and regenerating apparatus for regenerating an azeotropic cleaning agent.

  Industrial cleaners are used, for example, to clean the surfaces of various articles such as electrical equipment, electronic parts, precision equipment, metals, glass, ceramics, and resin molded products, and to increase the reliability of products.

  Among industrial cleaners, for example, flux residue cleaners are used to remove flux residues that inevitably occur after bonding electronic components to printed circuit board electrodes using solder paste, thread solder, etc. Is done.

  Among industrial detergents, for example, metal degreasing detergents are industrial oils such as lubricating oils, rust preventive oils, mineral oils, cutting oils, and processing oils attached to metal parts or products having such parts. Used to remove.

  By the way, halogenated hydrocarbon solvents such as trichloroethylene and trichlorotrifluoroethane have been used as industrial cleaners. However, as a result of the emergence of environmental problems, non-halogen type hydrocarbon cleaners, glycol cleaners, and the like have become mainstream in recent years.

  The glycol-based cleaning agent is a cleaning agent mainly composed of various glycol-based compounds, and is excellent in removability of flux, ion residue, oil attached to metal, and the like (see Patent Documents 1 and 2). Moreover, since they generally have no flash point or are very high and are non-hazardous materials, they are superior to hydrocarbon-based solvents in that an explosion-proof cleaning device is not required and in terms of odor.

  However, when an article is cleaned with a glycol-based cleaning agent, a large amount of cleaning waste liquid and rinsing waste water containing flux residue and oil are generated each time, and corresponding equipment and cost are required for the treatment. .

  In this regard, with respect to hydrocarbon-based cleaning agents, a technique has been proposed in which the composition at the time of azeotropy is specified for the purpose of recycling the waste liquid and distillation regeneration is possible. For example, Patent Document 3 describes an azeotropic mixture composed of a saturated aliphatic hydrocarbon having a predetermined boiling range and a predetermined alcohol as a hydrocarbon-based cleaning agent having sufficient cleaning power for various processing oils and fluxes. It is said that this product does not change its composition even if it is recycled, and the liquid management is easy. Patent Documents 4 and 5 also describe cleaning agents using an azeotrope composed of a predetermined hydrocarbon compound, which are excellent in industrial oil or flux detergency and can be recycled. It is said.

  On the other hand, as far as the present applicant knows, glycolic detergents are not yet known as to not only have excellent ability to remove various industrial stains such as industrial oil and flux, but also those that can be recycled.

Japanese Patent Laid-Open No. 3-152197 Japanese Patent Laid-Open No. 10-046198 JP-A-10-53797 JP 2004-307839 A JP 2008-24901 A

  The main problem of the present invention is that it is excellent in removing power of various industrial stains adhering to articles, such as solder paste, flux residue, various oils, etc., has no flash point, and can be recycled (distilled and regenerated) under normal pressure. Another object is to provide a glycol-based industrial azeotropic cleaning agent. The present invention also relates to a method for cleaning an article using a glycol-based industrial azeotropic cleaning agent, a method for regenerating the industrial azeotropic cleaning agent used for cleaning, and a cleaning and regenerating apparatus for performing the method. Is to provide.

  As a result of the study, the inventors have studied that a group of composition liquids containing a specific chemical structure of a glycol-based solvent and having a predetermined boiling point and water azeotrope under normal pressure, and the composition liquid. It was found that the ratio of the distillate obtained after azeotropic distillation and the ratio of the distillate obtained after azeotropy were almost the same. And based on the ratio of such distillate, as a result of further investigation on the cleaning agent having a composition that optimizes the removal power of various industrial stains, particularly flux residue and industrial oil, according to the cleaning agent shown below The present inventors have found that the above problems can be solved and have completed the present invention. That is, the present invention relates to the following cleaning agents and the like.

1. Formula _{^{(1): R 1 -O -}} [- CH 2 -CH (X) -O] n -R 2 ( formula (1), both ^{R 1} and ^{R 2} is an alkyl group having 1 to 3 carbon atoms N represents 2 or 3, X represents hydrogen or a methyl group), a glycol solvent (A) having a boiling point of 160 to 230 ° C. under normal pressure, water (B), And an azeotropic mixture containing a tertiary amine (C) having a boiling point of 160 to 230 ° C. under normal pressure as necessary, wherein the ratio of the component (A), the component (B) and the component (C) is 5 in this order. A recyclable industrial azeotropic cleaning agent characterized in that it contains ˜35 wt%, 65 to 95 wt%, and 0 to 30 wt%, and has an azeotropic point of 90 to 100 ° C. under normal pressure.

2. The component (C) has the general formula (2): (R ³ ) R ⁴ N—C ₂ H ₄ —OH (in the formula (2), R ³ and R ⁴ each represents an alkyl group having 1 to 3 carbon atoms. Monoamine (C1) and / or general formula (3): (R ⁵ ) R ⁶ N—C ₂ H ₄ —Y—C ₂ H ₄ —NR ⁷ (R ⁸ ) (formula) In (3), R ⁵ , R ⁶ , R ⁷ and R ⁸ each represent an alkyl group having 1 to 3 carbon atoms, and Y represents —CH ₂ —, — (CH ₂ ) ₂ —, —O—, —NH. The industrial azeotropic cleaning agent according to Item 1, which is a polyamine (C2) represented by-and -N (CH ₃ )-).

3. Item 3. The industrial azeotropic cleaning agent according to Item 1 or 2, wherein the cloud point is 30 to 90 ° C.

4). A cleaning method for an article, wherein the industrial azeotropic cleaning agent according to any one of Items 1 to 3 is brought into contact with an article to which industrial dirt is adhered.

5. Item 4. The cleaning method according to Item 4, wherein the industrial azeotropic cleaning agent is heated to a cloud point or higher.

6). Item 6. The cleaning method according to Item 4 or 5, wherein the industrial dirt is a kind selected from the group consisting of soldering flux, solder paste, flux residue, and industrial oil.

7). An industrial azeotropic mixture obtained by distilling an industrial azeotropic cleaning agent waste liquid produced after the cleaning method according to any one of Items 4 to 6 is obtained, and again obtaining an azeotropic mixture from which industrial soil components have been removed. Regeneration method of boiling detergent.

8). An industrial azeotropic cleaning agent comprising the azeotropic mixture obtained by the regeneration method according to Item 7.

9. Item 9. The industrial azeotropic cleaning agent according to Item 8, wherein the azeotropic mixture is steam.

10. A cleaning mechanism for cleaning an article to which industrial dirt has adhered using the industrial azeotropic cleaning agent according to any one of Items 1 to 3, and a regeneration mechanism for regenerating the waste liquid of the industrial azeotropic cleaning agent used in the cleaning mechanism. A supply path for supplying the waste liquid of the industrial azeotropic cleaning agent to the regeneration mechanism, and a return flow path for returning the regenerated industrial azeotropic cleaning agent to the cleaning mechanism. A cleaning and regenerating apparatus including a vaporizer that obtains an industrial azeotropic detergent from which industrial dirt has been removed by vaporizing a waste liquid of the industrial azeotropic detergent containing dirt.

  The industrial azeotropic cleaning agent of the present invention (hereinafter also simply referred to as the cleaning agent of the present invention) is excellent in removing various industrial stains such as solder paste, flux residue, industrial oil and the like. Moreover, since the cleaning agent of the present invention is an azeotropic mixture, there is almost no difference in the composition of the composition liquid before boiling and the distilled liquid after boiling. Therefore, the cleaning agent of the present invention can be regenerated by distilling the waste liquid generated after the cleaning agent is brought into contact with an article to which industrial dirt is adhered to remove the dirt component. Further, since the industrial azeotropic cleaning agent has no flash point and is a non-hazardous material, an explosion-proof cleaning device is not required. Further, since the cleaning agent is easily dried and hardly remains in the cleaned article, the step of rinsing the article with water can be omitted. Such a cleaning agent of the present invention is particularly suitable as a flux residue cleaning agent and a metal degreasing cleaner.

It is the schematic which shows 1st Embodiment of the washing | cleaning reproduction | regeneration apparatus based on this invention. It is the schematic which shows 2nd Embodiment of the washing | cleaning reproduction | regeneration apparatus which concerns on this invention.

  The cleaning agent of the present invention comprises a predetermined glycol solvent (A) (hereinafter also referred to as component (A)), water (B) (hereinafter also referred to as component (B)), and predetermined as required. And an azeotrope containing the tertiary amine (C) (hereinafter also referred to as the component (C)). In the present specification, a distillate obtained by azeotropically boiling the azeotropic mixture is also included in the “cleaning agent of the present invention”.

The component (A) is represented by the general formula (1): R ¹ —O — [— CH ₂ —CH (X) —O] _n —R ² (in the formula (1), R ¹ and R ² are both carbon atoms. 1 to 3 alkyl groups, n is 2 or 3, and X is hydrogen or a methyl group.

  Specific examples of the component (A) include, for example, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol ethyl methyl ether, diethylene glycol diethyl ether, dipropylene glycol diethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol. Isopropyl methyl ether, diethylene glycol-n-propyl methyl ether, dipropylene glycol-n-propyl methyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, tripropylene glycol ethyl methyl ether, triethylene glycol Lumpur diethyl ether, tripropylene glycol diethyl ether, triethylene glycol isopropyl methyl ether, tripropylene glycol isopropyl methyl ether, triethylene glycol -n- propyl ether, and tripropylene glycol -n- propyl methyl ether, and the like. These can be used alone or in combination of two or more. As the component (A), the cleaning agent of the present invention containing at least one member selected from the group consisting of diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol isopropyl methyl ether, and tripropylene glycol dimethyl ether is used for soiling articles, particularly solder. It is suitable for removing pastes, flux residues, and industrial oils, and also makes it easy to distill and regenerate the waste liquid that is produced after removing such dirt by the cleaning agent.

  The component (A) has a boiling point under atmospheric pressure of about 160 to 230 ° C, preferably about 170 to 220 ° C, and more preferably about 175 to 190 ° C. “Normal pressure” means standard atmospheric pressure (the same applies hereinafter).

  Examples of the component (B) include ultrapure water, pure water, purified water, distilled water, ion exchange water, and tap water.

  The component (C) is an optional component, and can be used as necessary in order to further enhance the ability to remove industrial stains, particularly flux residues, of the cleaning agent of the present invention. Moreover, since the boiling point of (C) component is 160-230 degreeC, the cleaning agent of this invention containing this azeotropes under a normal pressure. Therefore, it is possible to regenerate the cleaning agent of the present invention by azeotropically lysing the waste liquid generated after using the cleaning agent under normal pressure. From these viewpoints, the boiling point of the component (C) is preferably about 180 to 215 ° C, and more preferably about 190 to 210 ° C.

  As the component (C), various known amines can be used without particular limitation as long as they are tertiary amines having a boiling point of about 160 to 230 ° C. Specifically, the monoamine (C1) represented by the following general formula (2) from the viewpoint of the dirt removing power of the cleaning agent of the present invention and the viewpoint of regenerating the cleaning agent of the present invention by distilling the cleaning waste liquid. Polyamine (C2) (hereinafter also referred to as (C2) component) represented by the following general formula (3) (hereinafter also referred to as (C1) component) is particularly preferred. The component (C) may be either one of the component (C1) or the component (C2), or may include both components.

General formula (2) :( R ³ ) R ⁴ N—C ₂ H ₄ —OH
(In formula (2), R ³ and R ⁴ each represent an alkyl group having 1 to 3 carbon atoms.)

Formula (3): (R ⁵ ) R ⁶ N—C ₂ H ₄ —Y—C ₂ H ₄ —NR ⁷ (R ⁸ )
(In the formula ^{(3), R 5, R} 6, R 7 and ^{R 8} each represents an alkyl group having 1 to 3 carbon atoms, Y is _{-CH 2 -, - (CH 2} ) 2 -, - O-, -NH- and -N (CH ₃₎ - represents any).

  Specific examples of the component (C1) include 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, 2- (diisopropylamino) ethanol, 2- (di-n-propylamino) ethanol, and the like. It is done. These can be used alone or in combination of two or more. Among these, particularly, one selected from the group consisting of 2- (diethylamino) ethanol and 2- (diisopropylamino) ethanol is preferable from the viewpoint of the ability to remove the flux residue and the low risk of ignition. .

  Specific examples of the component (C2) include, for example, N, N, N ′, N′-tetramethylpentamethylenediamine, N, N, N ′, N′-tetraethylpentamethylenediamine, N, N, N ′, N′-tetraisopropylpentamethylenediamine, N, N, N ′, N′-tetra-n-propylpentamethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N, N ′ , N′-tetraethylhexamethylenediamine, N, N, N ′, N′-tetraisopropylhexamethylenediamine, N, N, N ′, N′-tetra-n-propylhexamethylenediamine, bis (2-dimethylamino) Ethyl) ether, bis (2-diethylaminoethyl) ether, bis (2-diisopropylaminoethyl) ether, bis (2-di-n-propyl) Pyraminoethyl) ether, 1,1,7,7-tetramethyldiethylenetriamine, 1,1,7,7-tetraethyldiethylenetriamine, 1,1,7,7-tetraisopropyldiethylenetriamine, 1,1,7,7-tetra N-propyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, 4-methyl-1,1,7,7-tetraethyldiethylenetriamine, 4-methyl-1,1,7, Examples include 7-tetraisopropyldiethylenetriamine and 4-methyl-1,1,7,7-tetra-n-propyldiethylenetriamine. These can be used alone or in combination of two or more. Among these, N, N, N ′, N′-tetramethylhexamethylenediamine and bis (2-dimethyl) are particularly preferred because of their ability to remove industrial stains, particularly flux residues, and low risk of ignition. Aminoethyl) ether and one selected from the group consisting of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine are preferred.

  The cleaning agent of the present invention is prepared by mixing the component (A), the component (B) and the component (C) used as necessary by various known means. In addition, the ratio of the component (A), the component (B) and the component (C) indicates the composition change of the cleaning agent obtained by distilling and regenerating the cleaning waste liquid in consideration of the industrial dirt removing power, the type of industrial dirt, and the like. Set for the purpose of minimizing. Specifically, the ratio of the component (A), the component (B), and the component (C) is about 5 to 35 wt%, about 65 to 95 wt%, and about 0 to 30 wt% in order, preferably 15 to 35 wt% in order. %, 65-85 wt%, and 0-15 wt%.

  In addition, when a cleaning agent does not contain (C) component, the ratio of (A) component and (B) component is specifically about 5-35 wt% and 65-95 wt% in order, Preferably it is 15 in order. ˜35 wt% and 65 to 85 wt%, most preferably about 20 to 30 wt% and about 70 to 80 wt%, respectively.

  Moreover, when a cleaning agent contains (C) component, the ratio of (A) component, (B) component, and (C) component is about 5-35 wt% in order, 65-99.99 wt%, and 0.00. About 01-30 wt%, preferably about 10-30 wt%, about 65-89.95 wt% and about 0.05-20 wt%, most preferably about 15-27.5 wt%, about 70-84.95 wt% And about 0.05 to 12.5 wt%.

  Since the cleaning agent of the present invention has each component in such a ratio, it is particularly excellent in removal of industrial dirt, particularly flux residues (particularly flux residues generated after soldering with lead-free solder paste) and various industrial oils. Moreover, the cleaning agent regenerated by distilling the waste liquid containing the dirt has the same composition ratio as the cleaning agent before cleaning.

  The cleaning agent of the present invention has an azeotropic point under normal pressure of about 90 to 100 ° C, preferably about 95 to 100 ° C, and more preferably 97 to 99 ° C.

  As the cleaning agent of the present invention, those having a cloud point are particularly preferable. In the present specification, the “cloud point” refers to a temperature at which the cleaning agent undergoes phase separation under heating and exhibits turbidity or two-layer separation. Such a cleaning agent is a homogeneous solution when stored, but becomes cloudy when used, and effectively removes industrial dirt adhering to the article. From this viewpoint, the cloud point of the cleaning agent of the present invention is usually about 30 to 90 ° C, preferably about 45 to 75 ° C, and more preferably about 55 to 65 ° C.

  Moreover, the cleaning agent of the present invention has no flash point and is a non-hazardous material.

  Moreover, you may mix | blend various well-known additives with the cleaning agent of this invention. Specific examples of additives include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, polymer surfactants, chelating agents, antioxidants, and rust inhibitors. , Sealing agent, pH adjuster, antifoaming agent and the like.

  The method for cleaning an article according to the present invention is characterized in that the industrial azeotropic cleaning agent according to the present invention is brought into contact with an article to which industrial dirt has adhered.

  The industrial dirt is not particularly limited, but representative examples include soldering flux, solder paste, flux residue, industrial oil, and cutting powder. Among these, one selected from the group consisting of soldering flux, solder paste, flux residue and industrial oil is suitable as a removal target of the cleaning agent of the present invention.

  The soldering flux is a composition used to remove the oxide film on the surface of the solder and the base material (metal electrode, etc.) and to facilitate the bonding between them. Generally, the base resin, the activator In addition, a thixotropic agent, an antioxidant, and other additives may be blended as necessary. The soldering flux is classified according to its composition into solder paste flux and non-solder paste flux such as yarn solder flux, post flux and preflux.

  Examples of the base resin include rosin base resins and non-rosin base resins. Examples of the rosin base resin include natural rosins such as gum rosin, tall oil rosin and wood rosin, purified products of the natural rosin, hydrides and disproportionation products, polymerized rosins using these as raw materials, and unsaturated acid-modified rosins. (Acrylated rosin, fumarated rosin, maleated rosin, etc.) and rosin esters and their purified products, hydrides, disproportionates, and the like. Examples of the polyhydric alcohol constituting the rosin ester include glycerin and pentaerythritol. Non-rosin base resins include, for example, epoxy resins, acrylic resins, polyimide resins, nylon resins, polyacrylonitrile resins, vinyl chloride resins, vinyl acetate resins, polyolefin resins, fluorine resins, ABS resins, isoprene rubbers, styrene butadiene rubbers. (SBR), butadiene rubber (BR), chloroprene rubber, nylon rubber, nylon elastomer, polyester elastomer and the like.

  Examples of the activator include succinic acid, adipic acid, azelaic acid, glutaric acid, sebacic acid, dodecanedioic acid, dimer acid, fumaric acid, maleic acid, itaconic acid, trans-2,3-dibromo-1,4- Butenediol, cis-2,3-dibromo-1,4-butenediol, 3-bromopropionic acid, 2-bromovaleric acid, 5-bromo-n-valeric acid, 2-bromoisovaleric acid, ethylamine bromate, Examples include diethylamine bromate, diethylamine hydrochloride, methylamine bromate and the like.

  Examples of the organic solvent include ethanol, n-propanol, isopropanol, isobutanol, butyl carbitol, hexyl diglycol, hexyl carbitol, isopropyl acetate, ethyl propionate, butyl benzoate, diethyl adipate, n-hexane, and dodecane. , Tetradecene and the like.

  Examples of the thixotropic agent include castor oil, hydrogenated castor oil, beeswax, carnauba wax, stearamide, 12-hydroxystearic acid ethylenebisamide, and the like.

  Antioxidants include pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinamide), 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-t-butyl-4-hydroxybenzyl) benzene, 2,6-di-t-butyl-p-cresol, triphenyl phosphite, triethyl phosphite, trilauryl trithiophosphato, tris (tridecyl) Phosphite etc. are mentioned.

  Examples of other additives include antifungal agents, matting agents, thickening inhibitors, and surfactants.

  Solder paste is a composition obtained by mixing a soldering flux and solder powder. Examples of the solder powder include Sn-Ag-based, Sn-Cu-based, Sn-Sb-based and Sn-Zn-based lead-free solder powders, and lead-containing solder powders containing lead as a constituent component. These solder metals are doped with one or more elements of Ag, Al, Au, Bi, Co, Cu, Fe, Ga, Ge, In, Ni, P, Pt, Sb, and Zn. It may be. The solder paste is supplied onto the electrode through a metal mask by screen printing, and after the electronic component is placed thereon, soldering is performed under heating.

  Examples of the article to which the soldering flux or solder paste is attached include a metal mask for screen printing, a squeegee, a dispensing nozzle, a syringe, and a jig for fixing a substrate.

  The flux residue is a residue that is generated after an electronic component or the like is bonded to an electrode using solder paste, yarn solder, preflux, postflux, or the like. Since this corrodes the solder metal and the base material or lowers the insulation resistance of the substrate, it must be removed by cleaning.

  Examples of the article to which the flux residue is attached include a printed circuit board, a ceramic wiring board, a semiconductor element mounting board, a wafer, a TAB tape, a lead frame, a power module, and a camera module. In addition, as for the corresponding ones, electronic parts such as ICs, capacitors, resistors, diodes, transistors, coils, and CSPs are soldered, BGA, PGA, LGA, etc. are formed, solder leveling, etc. The pretreatment may be performed.

  Examples of the industrial oil include processing oil, cutting oil, mineral oil, machine oil grease, lubricating oil, rust preventive oil, wax, pitch, paraffin, oil and fat, grease, and the like. These reduce the friction between materials and tools to prevent seizure in the fields of machining, metal processing, etc., reduce the force required for processing to make it easier to form, and prevent rust and corrosion of products. Used to Also, if industrial oil remains in a part that is scheduled to be plated, defective plating may occur, and the cleaning agent of the present invention is particularly suitable for cleaning such parts.

  Articles to which industrial oil is attached include, for example, molded parts such as bolts, nuts, ferrules, and washers, automobile parts such as engine pistons, industrial machine parts such as gears, shafts, sprockets, and chains, and HDD parts. And electronic parts such as lead frames.

  Other industrial stains include, for example, chips generated when dicing a printed circuit board, a ceramic wiring board, a semiconductor element mounting board, a cover glass, a wafer, and the like.

  The means for cleaning the article by bringing the cleaning agent of the present invention into contact with the article having industrial dirt attached thereto is not limited. Examples of the cleaning means include immersion cleaning, shower cleaning, spray cleaning, steam cleaning, ultrasonic cleaning, liquid cleaning, and the like. Medium jet cleaning, direct cleaning (Direct Pass (registered trademark)), and the like. Moreover, as a well-known washing | cleaning apparatus, Unexamined-Japanese-Patent No. 7-328565, Unexamined-Japanese-Patent No. 2000-189912, Unexamined-Japanese-Patent No. 2001-932, Unexamined-Japanese-Patent No. 2005-144441 etc. are mentioned, for example. Note that the cleaning agent of the present invention does not burn because it is a non-hazardous material, unlike hydrocarbon solvent-based cleaning agents. Therefore, explosion-proof equipment is not necessary, and it is suitable for shower cleaning and spray cleaning.

  In the case of the steam cleaning, the cleaning agent of the present invention is heated by various known means, or the vapor of the azeotrope obtained by the regeneration method described in detail below is used as a steam cleaning agent. What is necessary is just to contact the articles | goods to which dirt adhered. The contact means is not particularly limited, and examples thereof include a method of spraying a heated steam cleaning agent onto an article through an appropriate nozzle. Another example is a method of placing or suspending an article in an appropriate cleaning tower, storing a cleaning liquid in the lower part of the article, heating the cleaning liquid, and bringing the heated vapor cleaning agent into contact with the article. As the contact means, for example, the means described in Japanese Patent Application Laid-Open No. 2004-298644 and Japanese Patent Application Laid-Open No. 5-68895 can be referred to.

  Moreover, it is desirable that the cleaning agent of the present invention is heated to a temperature equal to or higher than its cloud point when it is brought into contact with an article to which industrial dirt has adhered. A cleaning agent having a cloud point or higher becomes cloudy, and industrial stains, particularly flux residues, are preferably removed. Moreover, when heating the said cleaning agent, it is desirable to use various mixing means, such as a mechanical stirrer, a magnetic stirrer, and an ultrasonic wave.

  In addition, since the cleaning agent of this invention can be volatilized easily in a drying process, it is hard to remain | survive in the articles | goods after washing | cleaning. Therefore, the rinsing step for the article can be omitted. However, if necessary, it can be rinsed with the same cleaning agent as the present invention or various known rinsing agents. Examples of the rinse agent include pure water and water such as ion exchange water; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol.

  The regeneration method according to the present invention is a fraction obtained by distilling waste liquid of industrial azeotropic cleaning agent (including waste liquid after washing and waste liquid after rinsing) generated after carrying out the washing method to remove the soil components. (Azeotrope) is obtained again.

  The means for distilling the waste liquid is not particularly limited, and various methods can be employed. Specifically, an azeotropic mixture is obtained as a distillate by distilling waste liquid with a distiller equipped with a vaporizer including a heat source such as a heater and a heat medium, and a condenser such as a condenser and a heat exchanger. be able to. In the distiller, the soil components are concentrated to form a residue, which is discarded. In order to bring the composition of the distillate closer to the azeotropic mixture, the distillation apparatus may be provided with a packing accelerator such as Raschig ring or Dixon packing, or a separation accelerator such as a bubble cap tray or demister, if necessary. . The number of theoretical plates is arbitrary and may be increased as necessary.

  The azeotrope obtained by the regeneration method is used as it is, or by appropriately blending the component (A), the component (B), and the component (C) and the additive as necessary. Can be used. That is, the cleaning agent of the present invention may contain a liquid azeotrope obtained by the regeneration method, or may contain a steam cleaning agent in which the azeotrope is a vapor.

  The ratio of the component (A), the component (B) and the component (C) in the regenerated cleaning agent is equivalent to the ratio of the cleaning agent of the present invention described above. Specifically, it is usually about 5 to 35 wt%, 65 to 95 wt%, and about 0 to 30 wt% in order, and preferably about 15 to 35 wt%, 65 to 85 wt%, and about 0 to 15 wt% in order.

  In addition, when (C) component is not contained in the said cleaning agent, the ratio of (A) component and (B) component is specifically about 5-35 wt% and 65-95 wt% in order, Preferably It is about 15-35 wt% and 65-85 wt% in order, Most preferably, it is about 20-30 wt% and about 70-80 wt% in order.

  Moreover, when (C) component is contained, it is about 5-35 wt%, about 65-94.99 wt%, and about 0.01-30 wt% in order, Preferably it is about 10-30 wt%, 65-89. About 95 wt% and about 0.05 to 20 wt%, most preferably about 15 to 27.5 wt%, about 70 to 84.95 wt%, and about 0.05 to 12.5 wt%.

  The cleaning and regenerating apparatus 1 of the present invention regenerates the waste liquid of the industrial azeotropic cleaning agent 4 used in the cleaning mechanism 2 and the cleaning mechanism 2 that cleans articles with industrial dirt attached thereto using the industrial azeotropic cleaning agent 4. And a reproducing mechanism 3 for performing the above operation. Between the cleaning mechanism 2 and the regeneration mechanism 3, the supply path 20C for supplying the waste liquid of the industrial azeotropic cleaning agent 4 to the regeneration mechanism 3 and the industrial azeotropic cleaning agent 4 regenerated by the regeneration mechanism 3 are cleaned. A return flow path 30 </ b> A that returns to the mechanism 2 is provided. The regeneration mechanism 3 includes a vaporizer 31 that obtains an industrial azeotropic cleaning agent 4 from which industrial soil (stain components) has been removed by vaporizing the waste liquid of the industrial azeotropic cleaning agent 4 containing industrial soil. Yes. Hereinafter, a specific cleaning / reproducing apparatus 1 will be described with reference to the drawings.

1st Embodiment FIG. 1: shows the washing | cleaning reproduction | regeneration apparatus 1 of 1st Embodiment. The cleaning / regenerating apparatus 1 uses an industrial azeotropic cleaning agent 4 to clean an article to which industrial dirt has adhered, and the waste liquid of the industrial azeotropic cleaning agent 4 used for cleaning the article in the cleaning mechanism 2. And a reproducing mechanism 3 for reproducing.

  The cleaning mechanism 2 performs ultrasonic cleaning. The first liquid tank 21A, the second liquid tank 21B, the third liquid tank 21C in which the industrial azeotropic cleaning agent 4 is stored, and the liquid tanks 21A, 21B, An ultrasonic transducer 22 is provided at the bottom of 21C and irradiates ultrasonic waves inside each of the liquid tanks 21A, 21B, and 21C. As the ultrasonic transducer 22, any known transducer such as a piezoelectric element or an electromagnetic transducer can be used. A heater for heating the industrial azeotropic cleaning agent 4 stored in the first liquid tank 21A to a temperature equal to or higher than the cloud point, in the first liquid tank 21A into which articles with industrial dirt attached are first charged, A heat source 23 such as a heat medium is provided. Thereby, the industrial azeotropic cleaning agent 4 heated by the heat source 23 is phase-separated and becomes white turbid, and industrial stains adhering to the article can be effectively removed.

  The industrial azeotropic cleaning agent 4 is circulated in the direction of arrow D in FIG. 1 between the first liquid tank 21A and the second liquid tank 21B and between the second liquid tank 21B and the third liquid tank 21C. A flow path 20A is provided. Further, the first liquid tank 21A is provided with an outflow path 20D through which the industrial azeotropic cleaning agent 4 flows out from the first liquid tank 21A, and the outflow path 20D passes the industrial azeotropic cleaning agent 4 into the first liquid tank. A branch path 20B for returning to 21A and a supply path 20C for supplying the industrial azeotropic cleaning agent 4 to the regeneration mechanism 3 are branched. The industrial azeotropic cleaning agent 4 heated above the cloud point is separated into two layers of a layer containing a large amount of the component (B) and a layer containing a large amount of the components (A) and (C) due to the influence of the specific gravity. However, by providing the circulation path 20B in this way, the concentration of the industrial azeotropic cleaning agent 4 heated above the cloud point can be kept uniform (suspended state).

  Valves V1 and V2 for adjusting the flow rate of the industrial azeotropic cleaning agent 4 are provided in the outflow path 20D and the circulation path 20B, respectively. The supply path 20C is also provided with a valve V3, and the inflow of the industrial azeotropic cleaning agent 4 into the regeneration mechanism 3 is controlled by opening and closing the valve V3. A pump P1 for pumping the industrial azeotropic cleaning agent 4 is connected to the outflow path 20D.

  The regeneration mechanism 3 is a vaporizer 31 that vaporizes the industrial azeotropic cleaning agent 4 containing industrial dirt, that is, the waste liquid of the industrial azeotropic cleaning agent 4 generated after the industrial azeotropic cleaning agent 4 removes the industrial dirt of the article. And a condenser 32 for condensing the industrial azeotropic cleaning agent 4 which is vaporized into steam. The vaporizer 31 and the condenser 32 constitute a distiller for distilling the industrial azeotropic cleaning agent 4.

  The vaporizer 31 has a liquid reservoir portion for storing the industrial azeotropic cleaning agent 4 at the bottom, and a heater, a heating medium, etc. for heating and vaporizing the industrial azeotropic cleaning agent 4 in the liquid storage portion. A heat source 33 is provided. Further, the vaporizer 31 includes a packing 34 such as Raschig ring and Dixon packing and a separation accelerator 35 such as a bubble cap tray and a demister in order to make the composition of the distillate after distillation closer to the azeotropic composition. Is provided. Note that the packing 34 and the separation accelerator 35 are not necessarily provided, and one or both of them may be provided as necessary. Also, the number of theoretical plates can be arbitrarily changed.

  For the condenser 32, known condensing means such as a condenser and a heat exchanger can be used. The condenser 32 is provided with a return channel 30A for returning the condensed and liquefied industrial azeotropic cleaning agent 4 to the cleaning mechanism 2, specifically, the third liquid tank 21C.

  Next, the operation of the cleaning / reproducing apparatus 1 will be described. The industrial azeotropic cleaning agent 4 is stored in each of the liquid tanks 21A, 21B, and 21C. The industrial azeotropic cleaning agent 4 in the first liquid tank 21A is heated by the heat source 23 and is in a suspended state. An article with industrial dirt attached thereto is put into the first liquid tank 21A, and the ultrasonic vibrator 22 is operated to ultrasonically clean the article. The article cleaned in the first liquid tank 21A is moved in the direction of arrow E in FIG. 1 to the second liquid tank 21B and the third liquid tank 21C in which the cleaner industrial azeotropic cleaning agent 4 is stored. The second liquid tank 21B is rinsed, and the final rinse is performed in the third liquid tank 21C. This rinsing and finishing rinsing are also performed by operating the ultrasonic transducer 22 and performing ultrasonic cleaning. In this way, articles with industrial stains are washed.

  The industrial azeotropic cleaning agent 4 constantly circulates through the first liquid tank 21A, the outflow path 20D, and the circulation path 20B by the valves V1 and V2 that are always open. When the industrial dirt contained in the industrial azeotropic cleaning agent 4 in the first liquid tank 21A is increased by washing the article to which the industrial dirt is adhered, the valve V3 is opened and the industrial azeotropic cleaning agent 4 is supplied. It is supplied to the vaporizer 31 of the regeneration mechanism 3 through the path 20C. In the vaporizer 31, the industrial azeotropic cleaning agent 4 is vaporized, and at that time, industrial dirt contained in the industrial azeotropic cleaning agent 4 is removed. The removed industrial dirt accumulates in the vaporizer 31 and is discarded. The vaporized industrial azeotropic cleaning agent 4 flows to the condenser 32 and is condensed in the condenser 32. Then, the industrial azeotropic cleaning agent 4 that has been regenerated after removing industrial dirt is returned to the third liquid tank 21C through the return flow path 30A.

  When the industrial azeotropic cleaning agent 4 flows out from the first liquid tank 21A to the regeneration mechanism 3, the industrial azeotropic cleaning agent 4 stored in the first liquid tank 21A decreases. The reduced industrial azeotropic cleaning agent 4 is supplemented from the second liquid tank 21B via the flow path 20A. Similarly, the industrial azeotropic cleaning agent 4 decreased in the second liquid tank 21B is supplemented from the third liquid tank 21C through the flow path 20A. The industrial azeotropic cleaning agent 4 decreased in the third liquid tank 21C is compensated by returning the industrial azeotropic cleaning agent 4 regenerated by the regeneration mechanism 3 through the return flow path 30A. In this way, the industrial azeotropic cleaning agent 4 is regenerated. In the process of regenerating the industrial azeotropic cleaning agent 4, industrial dirt is discarded as described above. However, the industrial azeotropic cleaning agent 4 that has been discharged and reduced at that time may be replenished separately from the outside. Good.

  In the first embodiment, ultrasonic cleaning is performed in the cleaning mechanism 2, but the means for cleaning the article is not limited to ultrasonic cleaning. For example, in the cleaning mechanism 2, the ultrasonic vibrator 22 is not used. In addition, it is possible to perform immersion cleaning in which the articles are simply immersed in the liquid tanks 21A, 21B, and 21C for cleaning. In that case, you may convect the industrial azeotropic cleaning agent stored in each liquid tank 21A, 21B, 21C using or using physical means, such as a mechanical stirrer and a magnetic stirrer. Moreover, in-liquid jet cleaning can also be performed by providing a jet spray nozzle in each of the liquid tanks 21A, 21B, and 21C instead of the ultrasonic vibrator 22. In addition, direct cleaning can be performed by replacing any one or two of the liquid tanks 21A, 21B, and 21C, or all the tanks with a cleaning tower disclosed in JP-A-7-328565.

2nd Embodiment FIG. 2: shows the washing | cleaning reproduction | regeneration apparatus 1 of 2nd Embodiment. As in the first embodiment, the cleaning / reproducing apparatus 1 includes a cleaning mechanism 2 that cleans an article to which industrial dirt has adhered using an industrial azeotropic cleaning agent 4, and an industrial product used for cleaning the article in the cleaning mechanism 2. And a regeneration mechanism 3 for regenerating the waste liquid of the azeotropic cleaning agent 4. Since the reproduction mechanism 3 has the same configuration as that of the first embodiment, the same reference numerals are given and detailed description thereof is omitted.

  The cleaning mechanism 2 performs shower cleaning, and the first liquid tank 21A, the second liquid tank 21B, the third liquid tank 21C, and the liquid tanks 21A, 21B, 21C in which the industrial azeotropic cleaning agent 4 is stored. A shower nozzle 41 for injecting the industrial azeotropic cleaning agent 4, and a transport device 42 for transporting articles provided between the shower nozzle 41 and the liquid tanks 21A, 21B, 21C. Yes. As the shower nozzle 41, a known arbitrary shower nozzle can be used. Further, as the transport device 42, any known transport device such as a roller conveyor or a belt conveyor can be used. As will be described in detail below, the first liquid tank 21A storing the industrial azeotropic cleaning agent 4 that comes into contact with the article with industrial dirt attached first is the industrial azeotrope stored in the first liquid tank 21A. A heat source 23 such as a heater or a heating medium for heating the cleaning agent 4 to a temperature higher than the cloud point is provided. Thereby, the industrial azeotropic cleaning agent 4 heated by the heat source 23 is phase-separated and becomes white turbid, and industrial stains adhering to the article can be effectively removed.

  Also in the cleaning and regenerating apparatus 1 of the second embodiment, similarly to the first embodiment, between the first liquid tank 21A and the second liquid tank 21B and between the second liquid tank 21B and the third liquid tank 21C. Is provided with a flow path 20A, and an outflow path 20D is provided in the first liquid tank 21A. The outflow path 20D is branched into a circulation path 20B that returns to the first liquid tank 21A and a supply path 20C that communicates with the regeneration mechanism 3. Similarly to the first embodiment, the outflow path 20D, the circulation path 20B, and the supply path 20C are provided with a valve V1, a valve V2, and a valve V3, respectively, and a pump P1 is connected to the outflow path 20D. ing.

  Furthermore, in order to inject the industrial azeotropic cleaning agent 4 in each liquid tank 21A, 21B, 21C from the shower nozzle 41, a communication passage 40A that communicates each liquid tank 21A, 21B, 21C and each shower nozzle 41 is provided. Is provided. Each communication passage 40A is connected to a pump P2 that pumps the industrial azeotropic cleaning agent 4 from each liquid tank 21A, 21B, 21C to each shower nozzle 41. On the upstream side and downstream side of the pump P2, a valve V4 for adjusting the outflow amount of the industrial azeotropic cleaning agent 4 and a valve V5 for adjusting the supply amount of the industrial azeotropic cleaning agent 4 to each shower nozzle 41 are provided. And are provided.

  Next, the operation of the cleaning / reproducing apparatus 1 will be described. The industrial azeotropic cleaning agent 4 is stored in each of the liquid tanks 21A, 21B, and 21C. The industrial azeotropic cleaning agent 4 in the first liquid tank 21A is heated by the heat source 23 and is in a suspended state. The industrial azeotropic cleaning agent 4 in each of the liquid tanks 21A, 21B, and 21C is supplied to the shower nozzle 41 through the communication path 40A with the valve V4 and the valve V5 open, and sprayed from the shower nozzle 41. Articles to which industrial dirt adheres are conveyed in the direction of arrow E in FIG. 2 from the first liquid tank 21A side to the third liquid tank 21C side on the conveying device 42 provided below the shower nozzle 41. . In the meantime, by being exposed to the industrial azeotropic cleaning agent 4 sprayed from the shower nozzle 41, the articles to which industrial dirt adheres are shower cleaned. On the other hand, the industrial azeotropic cleaning agent 4 is regenerated as in the first embodiment.

  In the second embodiment, shower cleaning is performed as the cleaning mechanism 2, but spray cleaning can also be performed by changing the shower nozzle 41 that sprays the industrial azeotropic cleaning agent 4 to a spray nozzle.

  In the first and second embodiments, the case where the industrial azeotropic cleaning agent 4 is used as a liquid has been described. However, the industrial azeotropic cleaning agent 4 can also be used as a vapor. For example, the liquid tanks 21A, 21B, and 21C are replaced with washing towers, articles are placed or suspended in the washing tower, and the industrial azeotropic cleaning agent 4 stored at the bottom of the washing tower is vaporized to obtain articles. It is also possible to perform steam cleaning by bringing it into contact. Further, the industrial azeotropic cleaning agent 4 flowing out from the vaporizer 31 as steam can be sprayed onto the article through any known nozzle to perform steam cleaning of the article.

  In the first and second embodiments, three liquid tanks 21A, 21B, and 21C are provided. However, the number of liquid tanks is not limited to three and may be any number.

  The present invention will be specifically described through examples. However, the scope of the present invention is not limited by them.

<Preparation of cleaning agent for confirmation of azeotropic composition>
Preparation Example 1
A 200 ml eggplant-shaped flask was charged with 20 g of diethylene glycol diethyl ether (DEDG) as the component (A) and 80 g of ultrapure water (hereinafter simply referred to as water) as the component (B), and mixed well. 1 was prepared.

  Next, a distillation column, a T-tube, a thermometer, and a Liebig condenser corresponding to the theoretical plate number N = 10 were connected to the eggplant-shaped flask. Subsequently, the eggplant-shaped flask was heated in an oil bath under normal pressure, and the azeotropic mixture was boiled, whereby only a fraction having a boiling point of 100 ° C. or less was collected.

  Subsequently, the composition ratio of the fraction was measured using a digital densitometer PR-201α (manufactured by ATAGO). The results are shown in Table 1.

  On the other hand, for the purpose of changing the ratio of the component (A) to the component (B), 30 g of DEDG and 70 g of water were placed in a 200 ml eggplant-shaped flask and mixed well to prepare the cleaning agent 2. Moreover, the said azeotropic mixture was boiled by the method similar to the above-mentioned method, only the fraction with the boiling point of 100 degrees C or less was extract | collected, and the composition ratio was measured. The results are shown in Table 1.

Preparation Examples 2 to 4 and Comparative Preparation Examples 1 to 7
In Preparation Example 1, the cleaning agent 1 and the component (A) were similarly used except that the components shown in Table 1 were used and the ratio of the components (A) and (B) was changed to the values shown in Table 1. 2 were prepared and subjected to a distillation test in the same manner as described above to determine the composition ratio of a fraction having a boiling point of 100 ° C. or lower. However, although both cleaning agents 1 and 2 of Comparative Preparation Examples 1 and 6 were azeotroped, the distillate separated into two layers. In addition, the name and structure of (A) component described in Table 1 are as showing in Tables 2-4.

Preparation Example 5
By mixing 10 g of DEDG as the component (A), 85 g of ultrapure water as the component (B) and 5 g of 2- (diethylamino) ethanol (DEAE) as the component (C) in a 200 ml eggplant-shaped flask Cleaning agent 1 was prepared.

  In addition, for the purpose of changing the ratio of the component (A), the component (B) and the component (C), 20 g of DEDG, 65 g of water and 15 g of DEAE are placed in a 200 ml eggplant type flask and mixed thoroughly. 2 was prepared.

  Next, each of cleaning agents 1 and 2 was distilled according to the method of Preparation Example 1, and only fractions having a boiling point of 100 ° C. or lower were collected. Subsequently, the contents of the component (A) and the component (C) in the fraction were quantified according to the absolute calibration curve method in a gas chromatography 6850 Network GC System (manufactured by Agilent Technologies) (this quantification means is described below). , Sometimes simply the GC method). The results are shown in Table 5.

Preparation Examples 6-11 and Comparative Preparation Examples 8-13
In Preparation Example 5, the components shown in Table 1 were used as the component (A) and the component (C), and the ratios of the components (A), (B) and (C) were changed to the values shown in Table 5. In the same manner as above, cleaning agents 1 and 2 were prepared and subjected to a distillation test in the same manner as described above to determine the composition ratio of a fraction having a boiling point of 100 ° C. or lower. However, the cleaning agents 1 and 2 of Comparative Preparation Example 8 were azeotroped, but the distillate separated into two layers. In addition, the name and structure of (A) component described in Table 5 are as showing in Tables 2-4, and the name and structure of (C) component are as showing in Tables 6-9.

<Preparation of azeotropic detergent for washing test and waste liquid regeneration>
Example 1
Based on the ratio of the azeotropic fractions of cleaning agents 1 and 2 of Preparation Example 1, 49.0 g (24.5 wt%) of DEDG and 151.0 g (75.5 wt%) of water were placed in a 200 ml beaker, The detergent was prepared by mixing well. The azeotropic point was considered to be the same as the azeotropic point as the result of Preparation Example 1. Moreover, when the flash point of the said cleaning agent was measured based on the Cleveland open method (JIS K2265-4), it was not recognized. In addition, 30 g of the cleaning agent was put in a screw tube, which was gradually heated in a thermostatic bath, and the temperature at which the appearance became cloudy (cloud point) was measured.

Example 2
Based on the ratio of the fractions at the time of azeotroping of cleaning agents 1 and 2 of Preparation Example 2, cleaning agents (200 g) having the compositions shown in Table 10 below were prepared. In addition, the azeotropic point, flash point, and cloud point described in Table 10 were in accordance with the interpretation and measurement method of Example 1 (the same applies hereinafter).

Example 3
Based on the ratio of the fractions at the time of azeotropic distillation of cleaning agents 1 and 2 of Preparation Example 3, cleaning agents (200 g) having the compositions shown in Table 10 below were prepared.

Example 4
Based on the ratio of the fractions at the time of azeotropic distillation of cleaning agents 1 and 2 of Preparation Example 4, cleaning agents (200 g) having the compositions shown in Table 10 below were prepared.

Example 5
Based on the ratio of the fractions at the time of azeotroping of cleaning agents 1 and 2 of Preparation Example 5, cleaning agents (200 g) having the compositions shown in Table 10 below were prepared.

Example 6
Based on the ratio of the fractions at the time of azeotropy of cleaning agents 1 and 2 of Preparation Example 6, cleaning agents (200 g) having the compositions shown in Table 10 below were prepared.

Example 7
Based on the ratio of the fractions at the time of azeotropic distillation of cleaning agents 1 and 2 of Preparation Example 7, cleaning agents (200 g) having the compositions shown in Table 10 below were prepared.

Example 8
Based on the ratio of the fractions at the time of azeotropic distillation of cleaning agents 1 and 2 of Preparation Example 8, cleaning agents (200 g) having the compositions shown in Table 10 below were prepared.

Example 9
Based on the ratio of the fractions at the time of azeotropic distillation of cleaning agents 1 and 2 of Preparation Example 9, cleaning agents (200 g) having the compositions shown in Table 10 below were prepared.

Example 10
Based on the ratio of the fractions at the time of azeotropic distillation of cleaning agents 1 and 2 of Preparation Example 10, cleaning agents (200 g) having the compositions shown in Table 10 below were prepared.

Example 11
Based on the ratio of the fractions at the time of azeotropic distillation of cleaning agents 1 and 2 of Preparation Example 11, cleaning agents (200 g) having the compositions shown in Table 10 below were prepared.

Comparative Example 1
Based on the ratio of the fractions at the time of azeotropy of cleaning agents 1 and 2 of Comparative Preparation Example 2, cleaning agents (200 g) having the compositions shown in Table 10 below were prepared.

Comparative Example 2
Based on the ratio of the fractions at the time of azeotropy of cleaning agents 1 and 2 of Comparative Preparation Example 3, cleaning agents (200 g) having the compositions shown in Table 10 below were prepared.

Comparative Example 3
Based on the ratio of the fractions at the time of azeotropy of cleaning agents 1 and 2 of Comparative Preparation Example 5, cleaning agents (200 g) having the compositions shown in Table 10 below were prepared.

Comparative Example 4
Based on the ratio of the fractions at the time of azeotroping of cleaning agents 1 and 2 of Comparative Preparation Example 9, cleaning agents (200 g) having the compositions shown in Table 10 below were prepared.

<Production of cleaning test article>
Production Example 1
Lead-free solder paste (trade name “Pine Solder TAS LF219-1”, manufactured by Arakawa Chemical Industries, Ltd.) is placed on a copper pattern of a glass epoxy copper clad laminate (30 × 30 × T1.5 mm) through a metal mask. The obtained laminate was reflowed with the following profile to prepare a substrate (hereinafter referred to as test base material A) to which a flux residue was adhered.

(Test substrate reflow profile)
Atmosphere: Air heating rate: 2 ° C / second Preheating: 150 ° C, 60 seconds Peak temperature: 250 ° C, 60 seconds

Production Example 2
It was obtained by printing a lead-free solder paste (Pine Solder TAS LF219-1) on a copper pattern of a copper-clad laminate (30 × 30 × T1.5 mm) coated with a solder resist through a metal mask. By reflowing the laminate with the above profile, a substrate (hereinafter referred to as “test base material B”) having a flux residue adhered thereto was produced.

Production Example 3
Using a soft bristle brush with 50 mg of rosin-based postflux (trade name “Pineflux WHS-002”, manufactured by Arakawa Chemical Industries, Ltd.) on a copper pattern of a JIS2 type comb-shaped substrate (50 × 50 × T1.5 mm) And then uniformly applied, dried in a dryer at 100 ° C. for 5 minutes, and then immersed in a eutectic solder bath (tin-lead alloy) at 235 ± 5 ° C. for 5 seconds. A substrate (hereinafter referred to as test substrate C) was produced.

Production Example 4
By applying 500 mg of lead-free solder paste (Pine Solder TAS LF219-1) on a stainless steel test piece (75 × 25 × T0.5 mm) uniformly using a resin squeegee, A material (hereinafter referred to as test base material D) was produced.

Production Example 5
100 mg of commercially available tap drill oil for ironworks (trade name “No. 167”, manufactured by Sankyo Corporation) is uniformly applied onto the stainless steel test piece (75 × 25 × T0.5 mm), and a cleaning test is performed. A base material (hereinafter referred to as “test substrate E”) was prepared.

<Cleaning test>
In a 200 mL beaker A ′, 200 g of the cleaning agent of Example 1 was placed, heated to 65 ° C., immersed in the test substrate A, and irradiated with 28 kHz ultrasonic waves for 15 minutes. And then dried for 10 minutes in a circulating dryer at 80 ° C.

  200 g of the cleaning agent of Example 1 was put in a 200 mL beaker B ′, heated to 65 ° C., the test substrate B was immersed, and irradiated with 28 kHz ultrasonic waves for 15 minutes. The product was taken out and dried in a circulating dryer at 80 ° C. for 10 minutes.

  200 g of the cleaning agent of Example 1 was put in a 200 mL beaker C ′, heated to 65 ° C., the test substrate C was immersed, irradiated with 28 kHz ultrasonic waves for 5 minutes, and then the substrate C was taken out. And dried in a circulating dryer at 80 ° C. for 10 minutes.

  200 g of the cleaning agent of Example 1 was put in a 200 mL beaker D ′, heated to 65 ° C., the test substrate D was immersed, and irradiated with 28 kHz ultrasonic waves for 1 minute. The product was taken out and dried in a circulating dryer at 80 ° C. for 10 minutes.

  200 g of the cleaning agent of Example 1 was put in a 200 mL beaker E ′, heated to 65 ° C., immersed in the test substrate E, stirred for 1 minute using a stirrer, and then removed. It was dried for 10 minutes in a circulating dryer at 80 ° C.

  The cleaning agents of Examples 2 to 11 and Comparative Examples 1 to 4 were also applied to the substrates A, B, C, D, and E, respectively, and the cleaning test was performed in the same manner as described above.

(Evaluation method and evaluation criteria)
The detergency of the flux and the post-flux was determined by determining the removal rate by visual inspection using an optical microscope. The criteria for determining the cleaning properties of the flux and post flux are as follows.

Removal rate (%) = (1−Flux adhesion area after washing / Flux adhesion area before washing) × 100
◎: Removal rate of 95% or more ○: Removal rate of 80% or more and less than 95% Δ: Removal rate of 60% or more and less than 80% ×: Removal rate of less than 60%

  The detergency of the solder paste and industrial oil was determined by determining the removal rate from the weight difference between the test substrates before and after cleaning. In addition, the judgment criteria of the detergency of solder paste and industrial oil are as follows.

Removal rate (%) = (Test substrate weight before cleaning−Test substrate weight after cleaning) / Coating amount × 100
◎: Removal rate of 95% or more ○: Removal rate of 80% or more and less than 95% Δ: Removal rate of 60% or more and less than 80% ×: Removal rate of less than 60%

<Distillation of washing waste liquid>
1. Distillation test of waste liquid containing flux residue derived from solder paste 10 g of commercially available lead-free solder paste (trade name “Pine Solder TAS LF219-1,” manufactured by Arakawa Chemical Industries, Ltd.) is placed in an ointment can, and this is 250 ° C. The mixture was heated on a hot plate heated for 15 minutes to melt the lead-free solder powder, thereby forming a flux residue.

  Next, 99 g of the cleaning agent of Example 1 and 1 g of the flux residue were placed in a 200 ml eggplant-shaped flask and mixed by stirring to prepare a waste liquid.

  Next, a toroid, a thermometer, and a Liebig condenser were attached to the eggplant-shaped flask, and this was immersed in an oil bath, and the waste liquid was heated to boiling under 1 atm. Then, 20 g of the first fraction and 20 g of the middle fraction were collected three times respectively, and less than about 20 g of the latter fraction was collected.

  Table 12 shows the ratio of component (A) in each distillation section (measured value by digital densitometer PR-201α).

  From the description in Table 12, it was found that the composition ratio of the waste liquid in the distillate was substantially constant in each distillation section, and almost no different from the composition ratio of the detergent before distillation. From this, it was confirmed that the cleaning agent of the present invention was regenerated from the waste liquid.

2. Distillation test of waste liquid containing flux residue derived from post-flux

   10 g of a commercially available post flux (trade name “Pine Flux WHS-002”, manufactured by Arakawa Chemical Industries, Ltd.) is placed in an ointment can and left in a dryer at 100 ° C. for 1 hour to volatilize the solvent component. As a result, a flux residue was formed.

   Next, 99 g of the cleaning agent of Example 1 and 1 g of the flux residue were placed in a 200 ml eggplant-shaped flask and mixed by stirring to prepare a waste liquid. Subsequently, the waste liquid was distilled in the same manner as described above. Table 12 shows the ratio of component (A) in each section of the distillate.

  From the description in Table 12, it was found that the composition ratio of the waste liquid in the distillate was substantially constant in each distillation section, and almost no different from the composition ratio of the detergent before distillation. From this, it was confirmed that the cleaning agent of the present invention was regenerated from the waste liquid.

3. Distillation test of waste liquid containing solder paste In a 200 ml eggplant-shaped flask, 99 g of the cleaning agent of Example 1 and 1 g of pine solder TAS LF219-1 (manufactured by Arakawa Chemical Co., Ltd.) are added, and mixed by stirring. Prepared. Subsequently, the waste liquid was distilled in the same manner as described above. Table 12 shows the ratio of component (A) in each section of the distillate.

  From the description in Table 12, it was found that the composition ratio of the waste liquid in the distillate was substantially constant in each distillation section, and almost no different from the composition ratio of the detergent before distillation. From this, it was confirmed that the cleaning agent of the present invention was regenerated from the waste liquid.

4). Distillation test of waste liquid containing industrial oil In a 200 ml eggplant-shaped flask, 99 g of the cleaning agent of Example 1 and a commercial iron tap drill oil No. 1 g of 167 (manufactured by Sankyo Corporation) was added and stirred and mixed to prepare a waste liquid. Subsequently, the waste liquid was distilled in the same manner as described above. Table 12 shows the ratio of component (A) in each section of the distillate.

  From the description in Table 12, it was found that the composition ratio of the waste liquid in the distillate was substantially constant in each distillation section, and almost no different from the composition ratio of the detergent before distillation. From this, it was confirmed that the cleaning agent of the present invention was regenerated from the waste liquid.

  In addition, the above-described distillation tests of 1, 2, 3, and 4 were performed for the cleaning agents of Examples 2, 3, 6, 7, and 11, respectively. The results are shown in Table 12.

  In Table 12, the numerical values (wt%) of Examples 2 and 3 are measured values obtained using a digital densitometer PR-201α. Each numerical value (wt%) in Examples 6, 7 and 11 is a measured value obtained by using the GC method.

DESCRIPTION OF SYMBOLS 1 Cleaning and regenerating apparatus 2 Cleaning mechanism 3 Regenerating mechanism 4 Industrial azeotropic detergent 20C Supply path 30A Return path 31 Vaporizer

Claims (10)

Formula _{^{(1): R 1 -O -}} [- CH 2 -CH (X) -O] n -R 2 ( formula (1), both ^{R 1} and ^{R 2} is an alkyl group having 1 to 3 carbon atoms N represents 2 or 3, X represents hydrogen or a methyl group), a glycol solvent (A) having a boiling point of 160 to 230 ° C. under normal pressure, water (B), If necessary, an azeotropic mixture containing a tertiary amine (C) having a boiling point of 160 to 230 ° C. under normal pressure,
The ratio of the component (A), the component (B) and the component (C) is 5 to 35 wt%, 65 to 95 wt% and 0 to 30 wt% in order, and the azeotropic point under normal pressure is 90 to 100 ° C A recyclable industrial azeotropic cleaning agent, characterized by comprising: (C) component is
General formula (2): (R ³ ) R ⁴ N—C ₂ H ₄ —OH (in formula (2), R ³ and R ⁴ each represent an alkyl group having 1 to 3 carbon atoms) Monoamine (C1) and / or
General formula (3): (R ⁵ ) R ⁶ N—C ₂ H ₄ —Y—C ₂ H ₄ —NR ⁷ (R ⁸ ) (in formula (3), R ⁵ , R ⁶ , R ⁷ and R ⁸ Each represents an alkyl group having 1 to 3 carbon atoms, and Y represents any one of —CH ₂ —, — (CH ₂ ) ₂ —, —O—, —NH—, and —N (CH ₃ ) —. ) Represented by the formula (C2)
The industrial azeotropic cleaning agent of claim 1. The industrial azeotropic cleaning agent according to claim 1 or 2, which has a cloud point of 30 to 90 ° C. A method for cleaning an article, comprising bringing the industrial azeotropic cleaning agent according to any one of claims 1 to 3 into contact with an article to which industrial dirt has adhered. The cleaning method according to claim 4, wherein the industrial azeotropic cleaning agent is heated above its cloud point. The cleaning method according to claim 4 or 5, wherein the industrial dirt is a kind selected from the group consisting of soldering flux, solder paste, flux residue and industrial oil. Regenerating the azeotropic mixture from which industrial dirt has been removed by distilling the waste liquid of industrial azeotropic detergent containing industrial dirt, which is produced after the cleaning method according to any one of claims 4 to 6 is carried out. A method for regenerating an industrial azeotropic detergent. An industrial azeotropic detergent comprising the azeotropic mixture obtained by the regeneration method of claim 7.   The industrial azeotropic detergent of claim 8, wherein the azeotropic mixture is steam. A cleaning mechanism for cleaning an article to which industrial dirt has adhered using the industrial azeotropic cleaning agent according to claim 1;
A regeneration mechanism for regenerating the waste liquid of the industrial azeotropic detergent used in the cleaning mechanism;
A supply path for supplying the waste liquid of the industrial azeotropic cleaning agent to the regeneration mechanism;
A return flow path for returning the regenerated industrial azeotropic cleaning agent to the cleaning mechanism,
The said regeneration mechanism is a washing | cleaning reproduction | regeneration apparatus containing the vaporizer which obtains the industrial azeotropic cleaning agent from which industrial dirt was removed by vaporizing the waste liquid of industrial azeotropic cleaning agent containing industrial dirt.

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