JP2016209789A - Method and apparatus for cleaning and rinsing article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a system and an apparatus where an article attached with various industrial stains such as flux for soldering and the like is cleaned by a predetermined detergent and rinsed by a glycol-based rinsing liquid capable of being regenerated by distillation and the rinsing liquid is regenerated.SOLUTION: A method for cleaning and rinsing an article includes: [1] a step cleaning the article attached with industrial stains by a nonazeotropic detergent (A1) containing a glycol-based solvent (a1) having general formula (1): R1-O-[CH2-CH(X)-O]n-R2 and a boiling point at normal pressure of 160-230°C, water (a2) and an amine-based compound (a3) being nonazeotropic with a (a1) component and a (a2) component at normal pressure; [2] a step rinsing the article cleaned in the step [1] by an azeotropic rinsing liquid (A2) containing the (a1) component and the (a2) component, not substantially containing the (a3) component and having an azeotropic point at normal pressure of 90-100°C; and [3] a step regenerating the azeotropic rinsing liquid (A2) by distilling a waste liquid produced in the step [2].SELECTED DRAWING: Figure 1

Description

  The present invention is a glycol-based rinsing liquid that can wash an article to which various industrial stains such as soldering flux, solder paste, flux residue, and industrial oil adhere, with a predetermined cleaning agent, and can recycle the article after washing. And a method enabling distillation regeneration of the rinsing waste liquid, and an apparatus capable of carrying out the method.

  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 the industrial cleaning agents, for example, the flux residue cleaning agent is used to remove flux residues that inevitably occur after joining electronic components to the electrodes of the printed wiring board using solder paste, yarn solder, or the like. used.

  Among the industrial cleaners, for example, metal degreasing cleaners are industrial products such as lubricants, rust preventive oils, mineral oils, cutting oils and processing oils attached to metal parts and products having the parts. Used to remove oil.

  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, in recent years, non-halogen type hydrocarbon-based cleaning agents, glycol-based cleaning agents, and the like have become mainstream.

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

  By the way, after washing an article with a glycol-based cleaning agent, in order to increase the cleanliness of the article, it is generally rinsed with a rinsing liquid such as water, volatile alcohols, and volatile hydrocarbons. However, since industrial waste remains in the waste liquid generated after rinsing, when the waste liquid is repeatedly used as a rinse liquid, the concentration of the soil in the waste liquid gradually increases and must be discarded. However, appropriate equipment and costs are required for disposal.

  In this regard, there is a system that makes it possible to distill and regenerate the waste liquid of the hydrocarbon-based rinse liquid by defining the composition at the time of azeotropy within a predetermined range. For example, Patent Document 3 describes a hydrocarbon-based cleaning agent having sufficient detergency for various processing oils and fluxes, which is composed of a saturated aliphatic hydrocarbon having a predetermined boiling range and a predetermined alcohol. However, since it is an azeotropic mixture, it can be used as a rinsing liquid and is considered to be recyclable. Patent Documents 4 and 5 also describe a rinsing system using a cleaning agent using an azeotropic rinsing liquid made of a predetermined hydrocarbon compound.

  However, since the hydrocarbon-based rinsing liquid is a flammable hazardous material, it requires appropriate facilities and costs such as the need for safety measures such as an explosion-proof device, and there is also a problem in terms of odor. Therefore, it is conceivable to construct a system using a glycol-based rinsing solution that can be distilled and regenerated, but as far as the present applicant knows, there is no such example.

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 present invention is a glycol-based rinsing liquid that can wash an article to which various industrial stains such as soldering flux, solder paste, flux residue, and industrial oil adhere, with a predetermined cleaning agent, and can recycle the article after washing. It is a main object to provide a system that can be rinsed with water and that enables distillation and regeneration of the rinsing waste liquid and an apparatus that can implement the system.

  As a result of studies, the present inventors can configure the system and apparatus according to the above problem by adopting a predetermined non-azeotropic cleaning agent and an azeotropic rinsing liquid having the same main component as the cleaning agent. It was. That is, the present invention relates to the following method and apparatus.

1. [1]: An article to which industrial dirt is adhered 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 Each represents an alkyl group having 1 to 3 carbon atoms which may be the same or different, X represents a hydrogen or methyl group, n represents 2 or 3, and the boiling point under atmospheric pressure is 160 to 230 ° C. Wash with glycol solvent (a1), water (a2), and non-azeotropic detergent (A1) containing amine compound (a3) that does not azeotrope with components (a1) and (a2) under normal pressure And [2]: the azeotropic point of the article washed in the step [1] containing the component (a1) and the component (a2) and substantially free of the component (a3) under normal pressure. A step of rinsing with an azeotropic rinsing liquid (A2) at 90 to 100 ° C., and [3]: distilling the waste liquid generated in the step [2]. To regenerate the azeotropic rinsing liquid (A2), thereby washing and rinsing the article

2. Item 2. The method according to Item 1, wherein the component (a3) is N-alkylalkanolamines and / or N-alkyldialkanolamines.

3. Item 1 or 2 above, wherein the ratio of the component (a1), the component (a2) and the component (a3) in the component (A1) is 10 to 90% by weight, 5 to 80% by weight and 0.1 to 5% by weight in order. Method 2.

4). Item 4. The method according to any one of Items 1 to 3, wherein the ratio of the component (a1) and the component (a2) in the component (A2) is 5 to 35% by weight and 65 to 95% by weight, respectively.

5. The cleaning method according to any one of Items 1 to 4, wherein the industrial dirt is at least one selected from the group consisting of soldering flux, solder paste, flux residue, and industrial oil.

6). An article to which industrial dirt is adhered 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 all the same. Or a C1-C3 alkyl group which may be different, X is hydrogen or a methyl group, n is 2 or 3, and a glycol solvent having a boiling point of 160 to 230 ° C. under normal pressure ( a washing mechanism for washing with a1), water (a2), and a non-azeotropic detergent (A1) containing an amine compound (a3) that does not azeotrope with the components (a1) and (a2) under normal pressure; The article cleaned by the cleaning mechanism is azeotropically rinsed at 90 to 100 ° C. under an atmospheric pressure containing the component (a1) and the component (a2) and substantially not including the component (a3). A mechanism for rinsing with the liquid (A2) and a component (A2) by distilling the waste liquid generated by the rinsing mechanism A regeneration mechanism, a supply path for supplying waste liquid generated by the rinsing mechanism to the regeneration mechanism, and a return path for returning the component (A2) regenerated by the regeneration mechanism to the rinsing mechanism. An apparatus for washing and rinsing an article, comprising a vaporizer that obtains (A2) component from which industrial waste and (a3) component have been substantially removed by vaporizing the waste liquid generated by the rinsing mechanism.

  In the method and apparatus of the present invention, industrial dirt adhering to various articles can be suitably removed with a predetermined cleaning agent, and the article is further rinsed with a rinsing liquid having the same main component as the cleaning agent. The surfaces of these articles can be cleaned. In addition, the rinsing liquid is an azeotropic composition, and the waste liquid can be reused by repeated distillation, so that the amount of the waste liquid generated after rinsing can be greatly reduced.

1 is a schematic diagram showing a first embodiment of an apparatus according to the present invention.

<About the method of the present invention>
The steps [1], [2] and [3] according to the method of the present invention will be described below in order.

  In the step [1], an article with industrial dirt attached is treated with a predetermined glycol solvent (a1) (hereinafter also referred to as “(a1) component”), water (a2) (hereinafter referred to as “(a2) component”). And a non-azeotropic detergent containing the component (a1) and the amine compound (a3) (hereinafter also referred to as “component (a3)”) that does not azeotrope with the component (a2) under normal pressure ( A1) (hereinafter also referred to as “component (A1)”).

  Although the said industrial stain | pollution | contamination is not specifically limited, As a typical thing, a flux for soldering, a solder paste, a flux residue, industrial oil, and a cutting powder etc. are mentioned, for example. 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. Agents and organic solvents, and optionally thixotropic agents, antioxidants and other additives. The soldering flux is classified according to its composition into, for example, solder paste flux, non-solder paste flux such as thread 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. Examples of the non-rosin base resin include epoxy resin, acrylic resin, polyimide resin, nylon resin, polyacrylonitrile resin, vinyl chloride resin, vinyl acetate resin, polyolefin resin, fluorine resin, ABS resin, isoprene rubber, styrene. Examples thereof include butadiene rubber (SBR), butadiene rubber (BR), chloroprene rubber, nylon rubber, nylon elastomer and polyester elastomer.

  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 , Diethylamine bromate, diethylamine hydrochloride and methylamine bromate.

  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, Examples include dodecane and tetradecene.

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

  Examples of the antioxidant 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-t-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 trithiophosphate and tris (tridecyl) ) Phosphite and the like.

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

  The 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, or Sn-Zn-based lead-free solder powder, and lead-containing solder powder containing lead as a constituent component. These solder metals are doped with at least one element selected from the group consisting of Ag, Al, Au, Bi, Co, Cu, Fe, Ga, Ge, IN, Ni, P, Pt, Sb and Zn. It's okay. 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 the 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. For the corresponding products, electronic components such as ICs, capacitors, resistors, diodes, transistors, coils, and CSPs are soldered, BGA, PGA, LGA, etc. are formed, before soldering leveling, etc. Processing 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 grease, and grease. In fields such as machining and metalworking, they reduce friction between materials and tools to prevent seizure, reduce the force required for processing to make them easier to form, and prevent rust and corrosion of products. Used to In addition, if industrial oil remains in a part that is scheduled to be plated, defective plating may occur. Therefore, the cleaning agent according to the present invention is particularly suitable for cleaning such parts.

  The articles to which the 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 components such as lead frames.

  Examples of the cutting powder include cutting powder generated when a printed circuit board, a ceramic wiring board, a semiconductor element mounting board, a cover glass, a wafer, and the like are diced.

Next, the component (A1) will be described. The component (a1) which is the main component of the component (A1) 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 is a glycol solvent represented by: an alkyl group having 1 to 3 carbon atoms, X represents hydrogen or a methyl group, and n represents 2 or 3. Specific examples of the component (a1) 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, and 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 Recall 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. The component (A1) is selected from the group consisting of diethylene glycol ethyl methyl ether (MEDG), diethylene glycol diethyl ether (DEDG), diethylene glycol isopropyl methyl ether (IPDM), and tripropylene glycol dimethyl ether (MTPOM) in terms of detergency. At least one selected from the above is preferred.

  The component (a1) has a boiling point under atmospheric pressure of about 160 to 230 ° C, preferably about 170 to 220 ° C, more preferably about 175 to 190 ° C. “Normal pressure” means standard atmospheric pressure (the same applies hereinafter).

  Examples of the component (a2) include ultrapure water, pure water, purified water, distilled water, ion exchange water, and tap water.

  As the component (a3), various known compounds can be used without particular limitation as long as they are amine compounds that do not azeotrope with the components (a1) and (a2) under normal pressure. The boiling point under normal pressure is not particularly limited, but is usually about 160 to 290 ° C, preferably about 165 to 280 ° C. Specific examples thereof include alkanolamines having no alkyl group in the molecule (monoethanolamine, diethanolamine, triethanolamine, etc.), N-alkylalkanolamines (N-ethylethanolamine, N-propylethanol). Amine, N-butylethanolamine, etc.), N-alkyl dialkanolamines (N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, etc.), and two or more of them can be used in combination. Among these, the N-alkylalkanolamines and / or N-alkyldialkanolamines are preferable from the viewpoint of detergency.

  In the component (A), additives such as various known surfactants and chelating agents, the antioxidant, the rust preventive, the sealing agent, the pH adjuster, and the antifoaming agent (hereinafter referred to as “the component (A)”) , Also referred to as “(a4)” component).

  As the surfactant, various known ones can be used without particular limitation. Specific examples include polyoxyalkylene phosphate ester surfactants and / or nonionic surfactants.

  Examples of the polyoxyalkylene phosphate-based surfactant include a compound represented by the following general formula (2) and / or a salt thereof. By using this, the detergency is improved.

(In Formula (2), R ² represents a phenyl group substituted with a linear or branched alkyl group having 5 to 20 carbon atoms, a phenyl group, or a linear or branched alkyl group having 7 to 12 carbon atoms. , M is an integer of 2 to 20, Y is a hydroxyl group or general formula (3): R ³ —O (CH ₂ CH ₂ —O) _q — (in formula (3), R ³ has 5 to 20 carbon atoms. A linear or branched alkyl group, a phenyl group, or a phenyl group substituted with a C7-12 linear or branched alkyl group, q represents an integer of 0 to 20).

Examples of the nonionic surfactant include general formula (4): R ⁴ O— (CH ₂ CH ₂ O) _r — (CH ₂ C (R ⁵ ) HO) _s —H (wherein R ⁴ represents A linear or branched alkyl group having 6 to 20 carbon atoms, a phenyl group, or a phenyl group substituted with a linear or branched alkyl group having 7 to 12 carbon atoms, r is an integer of 0 to 20; ⁵ represents a hydrogen or methyl group, s represents an integer of 0 to 20, and r + s is an integer of 2 to 20.).

  Examples of the chelating agent include citric acid, isocitric acid, malic acid, tartaric acid, orthophosphoric acid, pyrophosphoric acid and triphosphoric acid, and salts thereof (sodium salt, potassium salt, ammonium salt, alkanolamine salt, and the like). It is done.

  The component (A1) can be prepared by mixing the components by various known means. Moreover, content of each component is not specifically limited, What is necessary is just to set suitably according to the kind of industrial stain | pollution | contamination. Specifically, the ratio of the component (a1), the component (a2), and the component (a3) may be about 10 to 90% by weight, about 5 to 80% by weight, and about 0.1 to 5% by weight. That's fine. Moreover, when using the said (a4) component, the ratio of (a1) component, (a2) component, (a3) component, and (a4) component is about 10 to 90 weight% in order, and about 5 to 80 weight% The range may be about 0.1 to 5% by weight and about 0.01 to 5% by weight.

  The means for cleaning the article with the component (A1) is not limited. For example, immersion cleaning, shower cleaning, spray cleaning, steam cleaning, ultrasonic cleaning, submerged jet cleaning, and 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.

  In the step [2], the article washed in the step [1] contains the component (a1) and the component (a2) and does not substantially contain the component (a3). This is a step of rinsing with an azeotropic rinsing liquid (A2) (hereinafter also referred to as component (A2)) having a boiling point of 90 to 100 ° C. The azeotropic point is preferably about 95 to 100 ° C, more preferably 97 to 99 ° C.

  The contents of the component (a1) and the component (a2) in the component (A2) are not particularly limited, but for the purpose of increasing the rinsing efficiency and enabling distillation regeneration of the rinsing waste liquid in the step [3] described later. Usually, the order is about 5 to 35% by weight and about 65 to 95% by weight, preferably about 15 to 35% by weight and about 65 to 85% by weight.

  In addition, since the component (A2) is a rinsing liquid unlike the component (A1), the component (a3), which is a cleaning auxiliary component, is substantially not included. In the case where the component (a3) is included, the composition of the component (A1) is usually such that the content of the component (a1) and the component (a2) is about 5 to 35% by weight (preferably about 15 to 35% by weight) and It is about 65 to 94% by weight (preferably about 65 to 84.9% by weight), and the content of the component (a3) is less than about 1% by weight (preferably less than about 0.1% by weight). At this time, the waste liquid generated after rinsing the article after washing with the component (A1) can be efficiently distilled and regenerated.

  For the same reason, the component (A2) does not substantially contain the component (a4) which is a cleaning auxiliary component. In the case where the component (a4) is included, the composition of the component (A1) is usually such that the content of the component (a1) and the component (a2) is about 5 to 35% by weight (preferably about 15 to 35% by weight) and About 65 to 94% by weight (preferably about 65 to 84.9% by weight), and the content of the component (a4) is less than about 1% by weight (preferably less than about 0.1% by weight). At this time, the waste liquid generated after rinsing the article after washing with the component (A1) can be efficiently distilled and regenerated.

  The method of rinsing the article with the component (A2) is not limited. For example, immersion rinsing, shower rinsing, spray rinsing, steam rinsing, ultrasonic rinsing, submerged jet rinsing, direct washing (direct path (registered trademark)) )) And the like. Further, when heating the component (A2), it is desirable to use various mixing means such as a mechanical stirrer, a magnetic stirrer, and an ultrasonic wave in combination.

  Moreover, this process [2] may be repeated twice or more, and the cleanliness of the article can be increased each time. In addition to the step [2], a step of rinsing the article with a rinsing liquid other than the component (A2) may be provided. Examples of the rinsing liquid include water such as pure water and ion exchange water; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol.

  The step [3] is a step in which the waste liquid generated in the step [2] is distilled to obtain again the component (A2) from which the soil component has been removed as a fraction.

  The means for distilling the rinsing waste liquid is not particularly limited, and various methods can be employed. Specific examples include 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. The azeotropic rinsing liquid (component (A2)) as the liquid can be regenerated. Further, in the still, the dirt component brought from step [1] to step [2], the component (a3) derived from the component (A1) and the component (a4) used as necessary Concentrate to a residue that is discarded.

  In order to bring the composition of the distillate closer to the azeotropic composition, the distillation apparatus is provided with a packing accelerator such as Raschig ring or Dixon packing, a separation accelerator such as a bubble cap tray or a demister, if necessary. Also good. The number of theoretical plates is arbitrary and can be increased or decreased as necessary.

  The regenerated azeotropic rinsing liquid (component (A2)) can be used again as the rinsing liquid in step [2]. The ratio of the component (a1) and the component (a2) in the regenerated rinsing liquid is usually about 5 to 35% by weight and 65 to 95% by weight in order, preferably 15 to 35% by weight and It is about 65 to 85% by weight.

<About the apparatus of the present invention>
The apparatus of the present invention includes a predetermined cleaning mechanism, a rinsing mechanism and a regeneration mechanism, a predetermined supply path and a return path, and a predetermined vaporizer.

  The cleaning mechanism is a mechanism for cleaning an article to which industrial dirt has adhered with the component (A1). The industrial stains and articles are the same as described above. Further, the composition, composition ratio and physical properties of the component (A1) are the same as described above. Also, the cleaning means for carrying out the cleaning mechanism and the use mode of the component (A1) are the same as described above.

  The rinsing mechanism is a mechanism for rinsing the article cleaned by the cleaning mechanism with the component (A2). The composition, composition ratio and physical properties of the component (A2) are the same as described above. Further, the means for carrying out the rinsing mechanism and the mode of use of the component (A2) are the same as described above. In the apparatus of the present invention, two or more rinsing mechanisms may be provided.

  The regeneration mechanism is a mechanism for regenerating the component (A2) by distilling the waste liquid generated in the rinsing mechanism. Examples of the regeneration means include the distillation means. The mechanism is also concentrated with the dirt component brought into the rinsing mechanism from the cleaning, the component (a3) derived from the component (A1), the component (a4) used as necessary, and the like. You may provide the flow path for discarding the residue which becomes.

  The supply path is a line for supplying industrial regeneration and waste liquid containing the component (a3) and the component (a4) used as necessary to the regeneration mechanism.

  The return flow path is a line for returning the component (A2) regenerated by the regeneration mechanism to the rinsing mechanism.

  Further, the machine regeneration mechanism vaporizes the waste liquid generated in the rinsing mechanism, so that the industrial dirt and the component (a3) and the component (a4) used as necessary are substantially removed (A2). Equipped with a vaporizer to obtain Details of the vaporizer will be described later.

  Hereinafter, the apparatus of the present invention will be described in detail through one specific embodiment (FIG. 1). However, it goes without saying that the invention is not limited by the embodiment.

  FIG. 1 shows an apparatus 1 according to the first embodiment. The apparatus 1 includes a cleaning mechanism 2 for cleaning an article to which industrial dirt has adhered using a cleaning agent 4 corresponding to the component (A1), and a rinsing liquid 5 corresponding to the component (A2) after the cleaning. And a mechanism 3 for regenerating the waste liquid generated (hereinafter also referred to as a rinsing / regeneration mechanism 3).

  The rinsing / regeneration mechanism 3 includes a first rinsing liquid tank 21B and a second rinsing liquid tank 21C in which the rinsing liquid 5 is stored, and an ultrasonic transducer 22 is installed at the bottom thereof. Between the liquid tank 21B and the liquid tank 21C, a flow path 20A for flowing the rinsing liquid 5 in the direction of arrow D is provided. The liquid tank 21B is provided with an outflow path 20D through which the rinsing liquid 5 flows out. The outflow path 20D is branched into a circulation path 20B for returning the rinsing liquid 5 to the liquid tank 21B and a supply path 20C for supplying the rinsing liquid 5 to the regeneration mechanism 3. The outflow passage 20D and the circulation passage 20B are provided with valves V1 and V2 for adjusting the flow rate of the rinsing liquid 5, respectively. Further, a valve V3 is also provided in the supply path 20C, and the inflow of the rinsing liquid 5 to 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.

  Further, the rinsing / regeneration mechanism 3 includes a vaporizer 31 for vaporizing a waste liquid of the rinsing liquid 5 containing dirt components and the like generated after rinsing articles in the first liquid tank 21B and the second liquid tank 21C. And a condenser 32 for condensing the rinsing liquid 5 which has been vaporized into vapor. The vaporizer 31 and the condenser 32 constitute a distiller for distilling the rinsing liquid 5.

  The vaporizer 31 has a liquid reservoir portion for storing the rinsing liquid 5 at the bottom, and a heat source 33 such as a heater and a heating medium for heating and vaporizing the rinsing liquid 5 is provided in the liquid reservoir portion. . Further, in the vaporizer 31, in order to make the composition of the distillate (rinsing solution 5) after distillation closer to the azeotropic composition, the above-described packing 34 such as Raschig ring and Dixon packing, bubble cap tray, demister, etc. A separation accelerator 35 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. Although not shown in FIG. 1, a discharge path for discharging the bottom fraction out of the system may be installed at the bottom of the vaporizer 31. The bottom fraction contains industrial dirt brought into the rinsing / regeneration mechanism 3 from the liquid tank 21A, an amine component derived from the cleaning agent A, a surfactant, and the like.

  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 flow path 30A for returning the condensed liquefied rinsing liquid 5 to the cleaning mechanism 2, specifically, the second liquid tank 21C.

  On the other hand, the rinsing / regeneration mechanism 3 is provided with a cleaning mechanism 2. The cleaning mechanism 2 includes a liquid tank 21A in which an article to which the cleaning agent 4 is stored and industrial dirt adheres is placed, and an ultrasonic vibrator 22 provided at the bottom of the liquid tank 21A. As the ultrasonic transducer 22, any known transducer such as a piezo element or an electromagnetic transducer can be used. Further, a heater for heating the cleaning agent 4 and a heat source 23 such as a heat medium are provided at the bottom of the liquid tank 21A. In the cleaning mechanism 2, physical convection means such as a mechanical stirrer or a magnetic stirrer may be used without using the ultrasonic vibrator 22. Further, in-liquid jet cleaning can be performed by providing a jet spray nozzle in each liquid tank 21 </ b> A instead of the ultrasonic transducer 22. Further, direct cleaning can be performed by replacing the liquid tank 21A with a cleaning tower disclosed in Japanese Patent Laid-Open No. 7-328565. Further, the cleaning mechanism 2 can be replaced with a shower cleaning mechanism or a steam cleaning mechanism. The cleaning agent 4 heated by the heat source 23 is phase-separated and becomes cloudy, and effectively removes industrial dirt adhering to the article. The cleaned article is transferred in the direction of arrow E and is put into the first rinsing liquid tank 21B. At this time, the cleaning liquid 4 and the industrial dirt residue adhering to the cleaned article are brought into the rinsing liquid tank 21B.

  Next, the operation of the apparatus 1 will be described. A rinsing liquid 5 is stored in each of the first rinsing liquid tank 21B and the second rinsing liquid tank 21C. The cleaned article transferred from the cleaning liquid tank 21A is loaded into the rinsing liquid tank 21B, and the ultrasonic vibrator 22 is operated to rinse the article. The article rinsed in the first rinsing liquid tank 21B is transferred in the direction of arrow E to the second rinsing liquid tank 21C in which a cleaner rinsing liquid 5 is stored, and finish rinsing is performed. This finishing rinsing is also performed in a state where the ultrasonic vibrator 22 is operated.

  The rinsing liquid 5 is constantly circulated 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 industrial dirt and components derived from the cleaning agent 4 in the rinsing liquid in the liquid tank 21B increase, the valve V3 is opened, and the rinsing liquid 5 is supplied to the vaporizer 31 of the regeneration mechanism 3 through the supply path 20C. In the vaporizer 31, the rinsing liquid 5 is vaporized, and at that time, industrial dirt contained in the rinsing liquid 5 is removed. The removed industrial dirt accumulates in the vaporizer 31 and is discarded. The vaporized rinsing liquid 5 flows to the condenser 32 and is condensed in the condenser 32. Then, the rinse solution 5 regenerated after removing industrial dirt is returned to the liquid tank 21C through the return flow path 30A.

  When the rinsing liquid 5 flows out from the first rinsing liquid tank 21B to the regeneration mechanism 3, the rinsing liquid 5 stored in the first rinsing liquid tank 21B decreases. The reduced rinsing liquid 5 is supplemented from the liquid tank 21C through the flow path 20A. The rinsing liquid 5 decreased in the second rinsing liquid tank 21C is supplemented by returning the rinsing liquid 5 regenerated by the regenerating mechanism 3 through the return flow path 30A. In this way, the rinsing liquid 5 is circulated and regenerated in the apparatus 1.

  In this embodiment, the two liquid tanks 21A and 21C are provided as the liquid tank for cleaning and the liquid tanks 21B and 21C as the liquid tank for rinsing. Any number can be used.

  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>
Preparation Example 1
(A1) 28 g of diethylene glycol ethyl methyl ether (MEDG) as component (a2) 70 g of distilled water as component (a2) and 2 g of N, N-butyldiethanolamine (MBD) as component (a3) were mixed well in a beaker. A cleaning agent (A1) was prepared. In addition, 27.7 g of MEDG and 72.3 g of water were mixed well in a beaker to prepare a rinsing liquid (A2) according to the embodiment.

<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 printed board was reflowed with the following profile to prepare a substrate (hereinafter referred to as “base material A”) to which a flux residue was adhered.

(Test substrate reflow profile)
Atmosphere: Air temperature rising rate: 2 ° C / second Preheating: 150 ° C, 60 seconds Peak temperature: 250 ° C, 30 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 following profile, a substrate (hereinafter referred to as a base material B) to which a flux residue was adhered was produced.

(Test substrate reflow profile)
Atmosphere: Air temperature rising rate: 2 ° C / second Preheating: 150 ° C, 60 seconds Peak temperature: 300 ° C, 60 seconds

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 base material (hereinafter referred to as base material C) was produced.

<Washing and rinsing tests>
Example 1
200 g of the cleaning agent of Preparation Example 1 was placed in a 200 mL beaker A, and heated to 65 ° C. with stirring using a stirrer. On the other hand, 200 g of the rinsing liquid of Example 1 was put into 200 mL beaker B and beaker C, respectively, and heated to 25 ° C. while stirring using a stirrer. Next, the base material A was immersed for 10 minutes in the order of beaker A, beaker B and beaker C, respectively, and the base material A was taken out and dried in an air circulation dryer at 80 ° C. for 10 minutes. Further, according to the same procedure, the base material B and the base material C were also washed, rinsed and dried.

(Evaluation methods and evaluation criteria for base materials A, B and C)
The detergency of the flux and 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. The results are shown in Table 1.

Removal rate (%) = (1−Flux adhesion area after washing / Flux adhesion area before washing) × 100
◎: Removal rate of 95% or more ○: Removal rate of 85% or more and less than 95% Δ: Removal rate of 75% or more and less than 85% ×: Removal rate of less than 75%

<Distillation of rinsing waste liquid>
In Example 1, the remaining waste liquid obtained by removing the substrate A from the beaker C was placed in a 200 ml eggplant-shaped flask. Next, a toroid, a thermometer, and a Liebig condenser were attached to the eggplant-shaped flask, which were 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. And as a result of measuring the ratio of the (a1) component and (a2) component in each distillation division with digital densitometer PR-201α (product made from Atago Co., Ltd.), the composition ratio in each division is substantially constant (error 0. 1 to 0.8%), and it was found that the ratio of the component (a1) and the component (a2) in the rinsing liquid (stock solution) is not substantially different (within an error of 0.1 to 0.8%). In any fraction, the components (a3) and (a4) were not measured. From the above, it was considered that the rinsing liquid according to Example 1 is suitable for the distillation regeneration of the waste liquid after rinsing.

Preparation Examples 2 to 52
In the same manner as in Preparation Example 1 except that the components (a1), (a2), (a3) and (a4) shown in Tables 1 to 4 were used, the cleaning agents and rinsing liquids of the example embodiments were used. Prepared. Next, the cleaning test and the rinsing test were performed using each cleaning agent. Next, a distillation test was performed on the waste liquid of each rinsing liquid in the same manner as described above, and the ratio of the components (a1) and (a2) in each distillation section was measured. As a result, any rinsing liquid was suitable for distillation regeneration. I understood that.

(A1) Component MEDG: Diethylene glycol ethyl methyl ether (C ₂ H ₅ O— (CH ₂ CH ₂ O) ₂ —CH ₃ )

(A3) Component EA: Ethanolamine TEA: Triethanolamine MEM: N-ethylethanolamine (C ₂ H ₅ —NH—CH ₂ CH ₂ —OH)
MBM: N, N-butyl ethanolamine _{(C 4 H 9 -NH-CH} 2 CH 2 -OH)
MED: N-ethyl-diethanolamine _{(C 4 H 9 -N (CH} 2 CH 2 OH) 2)
MBD: N, N-butyldiethanolamine (CH ₃ ) ₃ CN (CH ₂ CH ₂ OH) ₂

(A4) Component A212C: Polyoxyethylene tridecyl ether phosphate ester (trade name “Pricesurf A212C”, Daiichi Kogyo Seiyaku Co., Ltd., acid value: 100 to 120 mgKOH / g)
A215C: Polyoxyethylene tridecyl ether phosphate ester (trade name “Plisurf A215C”, Daiichi Kogyo Seiyaku Co., Ltd., acid value 80 to 95 mgKOH / g)
ET-115; polyoxyethylene alkyl ether (trade name “Neugen ET-115”, Daiichi Kogyo Seiyaku Co., Ltd.)
ET-135; polyoxyethylene alkyl ether (trade name “Neugen ET-135”, Daiichi Kogyo Seiyaku Co., Ltd.)

(A1) Component DEDG: Diethylene glycol diethyl ether (C ₂ H ₅ O— (CH ₂ CH ₂ O) ₂ —C ₂ H ₅ )

(A1) Component IPDM: Diethylene glycol isopropyl methyl ether (isoC ₃ H ₇ O— (CH ₂ CH ₂ O) ₂ —CH ₃ )

(A1) Component MTPOM: Tripropylene glycol dimethyl ether (CH ₃ O— (CH ₂ CH (CH ₃ ) O) ₃ —CH ₃ )

Preparation Examples 52-57
In the same manner as in Preparation Example 1 except that the solvent shown in Table 5 was used as the solvent (component (a1 ′)), component (a2) and component (a3) other than component (a1), A rinse solution was prepared. Next, as a result of performing the cleaning test and the rinsing test using each cleaning agent, as shown in Table 5, it was defective. Next, a distillation test was carried out in the same manner as described above for the waste liquid of each rinsing liquid, and the ratio of the (a1 ′) component and the (a2) component in each distillation section was measured. It was constant within 0.8%, and the components (a3) and (a4) were not measured in any fraction.

Preparation Examples 58-60
In the same manner as in Preparation Example 1 except that the solvent shown in Table 5 was used as the solvent (component (a1 ′)), component (a2) and component (a3) other than component (a1), A rinse solution was prepared. Next, the cleaning test and the rinsing test were performed using the cleaning test using each cleaning agent. Although the cleaning and rinsing tests were good, the distilled and regenerated rinsing liquid separated into water and benzyl alcohol.

(A1 ′) Component MFDG: Methyl propylene diglycol (CH ₃ O— (CH ₂ CH (CH ₃ ) O) ₂ —H)
MMB: 3-methyl 3-methoxybutanol (CH ₃ OC (CH ₃ ) ₂ C ₂ H ₄ OH)
BzA: benzyl alcohol

DESCRIPTION OF SYMBOLS 1 Rinse / regeneration apparatus 2 Cleaning mechanism 3 Rinse / regeneration mechanism 4 Cleaning agent 5 Rinsing liquid 20A Flow path 20B Circulation path 20C Supply path 21A Cleaning liquid tank 21B 1st rinse liquid tank 21C 2nd rinse liquid tank 22 Ultrasonic vibrator 30A Return Flow path 31 Vaporizer 32 Condenser 33 Heat source 34 Filling material 35 Separation accelerator V1 Flow rate adjustment valve V2 Flow rate adjustment valve V3 Flow rate adjustment valve P1 Pressure feed pump

Claims (6)

[1]: An article to which industrial dirt is adhered 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 Each represents an alkyl group having 1 to 3 carbon atoms which may be the same or different, X represents a hydrogen or methyl group, n represents 2 or 3, and the boiling point under atmospheric pressure is 160 to 230 ° C. Wash with glycol solvent (a1), water (a2), and non-azeotropic detergent (A1) containing amine compound (a3) that does not azeotrope with components (a1) and (a2) under normal pressure Process,
[2]: The article cleaned in the step [1] has an azeotropic point of 90 to 90 at normal pressure, which contains the component (a1) and the component (a2) and does not substantially contain the component (a3). Rinsing with an azeotropic rinsing liquid (A2) at 100 ° C .;
[3]: Regenerating the azeotropic rinsing liquid (A2) by distilling the waste liquid generated in the step [2];
A method for cleaning and rinsing articles, comprising: The method of Claim 1 that the said (a3) component is N-alkyl alkanolamines and / or N-alkyl dialkanolamines. The ratio of the component (a1), the component (a2), and the component (a3) in the component (A1) is 10 to 90% by weight, 5 to 80% by weight, and 0.1 to 5% by weight, respectively. Method 2. The method in any one of Claims 1-3 whose ratios of the (a1) component and the (a2) component in the said (A2) component are 5-35 weight% and 65-95 weight% in order. The method according to claim 1, wherein the industrial dirt is at least one selected from the group consisting of soldering flux, solder paste, flux residue, and industrial oil. An article to which industrial dirt is adhered 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 all the same. Or a C1-C3 alkyl group which may be different, X is hydrogen or a methyl group, n is 2 or 3, and a glycol solvent having a boiling point of 160 to 230 ° C. under normal pressure ( a washing mechanism for washing with a1), water (a2), and a non-azeotropic detergent (A1) containing an amine compound (a3) that does not azeotrope with the components (a1) and (a2) under normal pressure;
The article cleaned by the cleaning mechanism is azeotropically rinsed at 90 to 100 ° C. under an atmospheric pressure containing the component (a1) and the component (a2) and substantially not including the component (a3). A mechanism for rinsing with the liquid (A2);
A mechanism for regenerating component (A2) by distilling the waste liquid generated by the rinsing mechanism;
A supply path for supplying waste liquid generated by the rinsing mechanism to the regeneration mechanism;
A return flow path for returning the component (A2) regenerated by the regeneration mechanism to the rinsing mechanism;
With
The regeneration mechanism includes a vaporizer that obtains the component (A2) from which industrial waste and the component (a3) are substantially removed by vaporizing the waste liquid generated by the rinsing mechanism.
Article washing and rinsing equipment.

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