WO2002002728A1

WO2002002728A1 - Detergent and method of cleansing

Info

Publication number: WO2002002728A1
Application number: PCT/JP2001/003624
Authority: WO
Inventors: Takanobu Mase; Kiyoshi Watanabe
Original assignee: Zeon Corporation
Priority date: 2000-06-30
Filing date: 2001-04-26
Publication date: 2002-01-10
Also published as: JP2004123762A

Abstract

A detergent comprising tetrahydrodicyclopentadiene in which the endo/exo isomer ratio by weight is from 70/30 to 0/100. The detergent preferably has a kauri-butanol value of 60 ml or higher. It has the excellent ability to remove fouling substances adherent to products in various industrial fields. The detergent poses no hygienic problems unlike aromatic hydrocarbon type detergents.

Description

Cleaning agents and cleaning methods

The present invention relates to a cleaning agent comprising tetrahydrodicyclopentene, and a method for cleaning and removing contaminants adhering to the surface of an article using the cleaning agent. Background art

Conventionally, in the fields of the precision machinery industry, the electronics and electronics industry, the optical machinery industry, and the automobile industry, to clean dirt-based products mainly containing organic substances such as oils, fats, oils, greases, fluxes, and scales. Various cleaning agents have been widely used. Examples of such cleaning agents include (1) chlorinated hydrocarbon solvents such as trichloroethane, trichloroethylene, tetrachloroethane, and tetrachloroethylene; (2) chlorofluorocarbon solvents such as trichlorotrifluoroethylene; and (3) sodium orthosilicate. Water-based detergents containing surfactants and builders mixed with sodium hydroxide and caustic soda; (4) Terpenes such as limonene, pinene and dipentene; and (5) Hydrocarbon solvents such as kerosene, benzene and xylene. It has been known.

In particular, parts used in the fields of electronics and electronics, machinery, etc., require high cleaning performance, flame resistance, and chemical stability. Therefore, the chlorinated hydrocarbon solvents and ( 2) CFC-based solvents have been used for many years. However, these chlorine-containing general-purpose cleaners were suspected of being a cause of airborne destruction of the stratospheric ozone layer, and their production and use have recently been banned worldwide.

On the other hand, the water-based detergent of the above (3) has less adverse effects on the environment and is less toxic than the organic solvent-based detergent, but is inferior in detergency by several steps. In addition, the terpenes (4) above are compounds that can achieve both safety and detergency, but they are prone to deterioration at the time of use and have problems with durability, and are supplied at a high price because they are derived from natural products The amount is limited, making it impractical as an industrial cleaner.

By the way, the hydrocarbon solvents of the above (5), especially aromatics such as benzene and xylene Aromatic hydrocarbons are highly irritating and toxic to mucous membranes and skin, and the cleaning work involving them is subject to various regulations under the Industrial Safety and Health Act. For this reason, hydrocarbon solvents are required to reduce the content of aromatic components as much as possible while maintaining the cleaning performance shown by aromatic hydrocarbons. In addition, since articles are generally heated and cleaned in the presence of air, the emergence of a detergent that is stable under heating conditions is desired.

Several detergents containing aliphatic hydrocarbons as the main component have been marketed as detergents with reduced aromatic component content, and are reported in the literature. For example, Nappar 11 from Exxon Chemical Co., Ltd. and Naphthesol from Nippon Petrochemical Co., Ltd. are detergents mainly composed of petroleum fractions called naphthenic fractions. It contains only small amounts of aromatic compounds such as alkylbenzene. UK Patent No. 2,175,004 discloses that 85-97 parts by weight of non-aromatic hydrocarbons containing aliphatic and / or alicyclic compounds, and that the number of carbon atoms is 8-18. A cleaning composition for removing fats and oils from a metal or plastic surface, comprising 3 to 15 parts by weight of an aromatic compound containing at least one alkyl group is described.

Further, JP-A-3-62896 describes a detergent composition containing 70% by weight or more of a cyclic saturated hydrocarbon having 9 to 18 carbon atoms. The publication also proposes a detergent composition containing 0.1 to 30% by weight of an aliphatic alcohol having 8 to 18 carbon atoms and Z or a surfactant in addition to the hydrocarbon.

Further, Japanese Patent Application Laid-Open No. 11-503,783 discloses cleaning of a cycloalkane mixture having a flash point of 55 ° C or more and a distillation temperature of 175 to 235 ° C. Use as a degreasing agent has been proposed. The publication discloses, as specific examples of such cycloalkane mixtures, tetrahydrodicyclopentadiene, methyltetrahydrodicyclopene, dimethyltetrahydrodicyclopene, ethylpropylcyclohexane, hexane, and alkyldeca. A mixture of two or more selected from hydronaphthalenes is mentioned.

Further, the publication states that it is preferable to use a mixture containing at least 40% by weight of endo-tetrahydrodicyclopentadiene as the cycloalkane mixture. However, the exotetrahide in a stereoisomeric relationship > Nothing is described for the mixture. Disclosure of the invention

In view of the above-mentioned problems and the actual situation of the prior art, an object of the present invention is to provide an excellent cleaning performance for contaminants adhering to the surface of an article used in various industrial fields, and to provide the article with excellent cleaning performance. An object of the present invention is to provide a novel aliphatic hydrocarbon-based cleaning agent and a cleaning method which do not swell or erode the surface and are stable under heating conditions in the presence of air. In order to achieve the above object, the present inventors focused on tetrahydrodicyclopentene, a kind of cycloaliphatic hydrocarbon, and examined the weight ratio of the endo- and exo-forms and the cleaning performance. After careful investigations into the relationship between the end product and the exo-form mixture, which have a specific weight ratio, a good cleaning and removal performance against contaminants adhering to the product surface The present invention was also found to be excellent in handleability as a detergent, and the present invention was completed.

Thus, according to the first aspect of the present invention, there is provided a detergent comprising tetrahydrodicyclopentene, wherein the weight ratio of the tetra- and di-exo-forms of tetrahydrodicyclopentene is in the range of 70Z30 to 0Z100. A cleaning agent characterized by the following is provided. A Kauributanol (KB) value indicating the cleaning performance of this cleaning agent is preferably 6 Oml or more.

Further, according to the second aspect of the present invention, there is provided an article characterized by using a detergent comprising tetrahydrodicyclopentadiene, wherein the weight ratio of the endo-form and the exo-form is in the range of 70/30 to 0/100. Is provided. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the cleaning agent and the cleaning method of the present invention will be described in detail.

Cleaning agent consisting of tetrahydrodicyclopentene

The cleaning agent comprising tetrahydrodicyclopentadiene (hereinafter, referred to as THDC) of the present invention has a weight ratio of an endo-THDC represented by the following formula 1 to an exo-THDC represented by the following formula 2 of 70 /. The range is from 30 to 0/100. 徵. The weight ratio of the endo-form and the exo-form is preferably in the range of 40/60 to 0Z100, more preferably 20/80 to 100, more preferably ΟΖΙ00, and most preferably 5 to 95 to 100. is there.

(Formula 1: End-form) (Formula 2: Exo-form) The cleaning agent of the present invention is one of the indicators of the dissolving power for removing dirt and the like, and a standard kauri resin butanol solution at 25 ° C. It is preferable that the Kauburinoru value (KB value), which indicates the volume (ml) of the solvent required to precipitate the Kauri resin from 20 g, is 60 ml or more. It is more preferably at least 63 ml, still more preferably at least 70 ml. In general, the higher the KB value, the higher the dissolving power.

End-THDC, which constitutes the cleaning agent of the present invention, is a known substance having a boiling point of 193 ° C (under normal pressure) and a melting point of 77 ° C, which is a colorless and slightly odorous substance. Exo-THDC has a boiling point of 187 ° C

It is a known substance with a colorless faint odor (under normal pressure) with a melting point of 79 ° C. Although both compounds have a stereoisomeric relationship, their production methods are not particularly limited, and those obtained by known production methods may be used.

End-to-end THDC can be obtained, for example, by fully hydrogenating end-to-end mouth penges obtained from naphtha fractions of crude oil. In addition, exo-THDC can be obtained by isomerizing endo-THDC in the presence of a catalyst according to a known method (for example, see Japanese Patent Application Laid-Open No. 55-72.122).

The cleaning agent of the present invention mixes endo-THDC and exo-THDC produced as described above so that the weight ratio is in the range of 70/30 to 0/100 for the endo- / exo-form. It can be obtained by: In addition, an isomerization reaction is performed using endo-THDC as a raw material in the presence of an acid catalyst, and the weight ratio between the endo-form (raw material) and the exo-form (product) is in the range of 70 to 30 to 0Z100. It can also be produced by stopping the reaction at the point. The method of mixing the endo-form and the exo-form is not particularly limited, and a mixing and stirring device generally used in industry may be used. The mixing ratio (weight ratio) of the endo form and the exo form is

It is essential to set it in the range of 70/30 to 100/100. If the content is out of this range, that is, if the content of the end body is excessively large, the solution viscosity at around room temperature increases, and the handleability as a cleaning agent is significantly deteriorated. Further, when the content of the end body is 100%, it is practically impossible to use it as a detergent at a temperature lower than the melting point (77 ° C).

The detergent of the present invention may be used alone or as a mixture of THDC with other detergents. Such other cleaning agents are not particularly limited, but include, for example, hydrocarbons, alcohols, esters, chlorinated hydrocarbons, fluorinated hydrocarbons, ethers, ketones, and volatile organic silicons. At least one organic solvent selected from the group consisting of: The mixing ratio of the THDC detergent of the present invention to other detergents is usually at least 5 wt%, preferably at least 30 wt%, more preferably at least 50 wt%.

The hydrocarbons are not particularly limited, but include, for example, n-pentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, n-decane, isodecane Linear or branched aliphatic hydrocarbons such as n-ndecane, n-dodecane, n-tridecane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, p-menthane, decalin, diisoprovir Alicyclic hydrocarbons such as cyclohexane; terpenes such as limonene, pinene and dipentene;

Examples of the alcohol include, but are not particularly limited to, for example, methanol, ethanol, isopropanol, n-propanol, n-butanol, s-butanol, t-butanol, n-pentanol, and isopentanol. And aliphatic monohydric alcohols such as n-hexanol, isohexanol, 2-ethylhexanol, and n-butanol.

Examples of the above-mentioned esters are not particularly limited. For example, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isoptyl acetate, pentyl acetate, methyl propionate, ethyl propionate, propyl propionate, Alkyl esters of aliphatic sulfonic acids such as isopropyl lopionate, methyl butyrate, ethyl butyrate, isopropyl butyrate, methyl valerate, and ethyl valerate.

The chlorinated hydrocarbons are not particularly limited, but include, for example, saturated and unsaturated chlorinated aliphatic hydrocarbons such as methylene chloride, dichloroethane, dichloroethylene, trichloroethylene, and perchlorethylene.

Examples of the fluorinated hydrocarbons include, but are not particularly limited to, compounds mainly composed of carbon, hydrogen and fluorine, which may contain an oxygen atom or an unsaturated bond. Above all, those having a boiling point of 25 ° C. or higher are preferable. Examples of such fluorinated hydrocarbons include pentafluoro-n-propane, hexafluoro-n-butane, decafluoro-η-pentane, and hexafluoro. Cyclopentane, octafluorocyclopentane, perfluoropropyl methyl ether, perfluorobutyl methyl ether, perfluorobutyl ethyl ether, hexafluorosiloxane and the like. Among them, hexafluorocyclopentane, heptanefluorocyclopentane and the like are more preferable.

Examples of the above ketones include, but are not limited to, acetone, 2-butane nonone, 2-pentene nonone, 3-pentene nonone, 2-hexanone, 3-methyl-2-butane nonone, and cyclopentane. Non-, cyclohexanone, 2-methylcyclopentanone, 2-methylcyclohexanone and the like can be mentioned.

The volatile organic silicon is not particularly limited, but includes, for example, hexamethyihexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane.

Further, the cleaning agent of the present invention is used for the purpose of maintaining the liquid stability of the cleaning agent, improving the stability to the object to be cleaned, or improving the workability, as needed, as long as the effect is not impaired. In addition, various additives conventionally known can be contained.

Such additives include, for example, stabilizers, surfactants, chelating agents, Preservatives, antioxidants, abrasives, lubricants, defoamers and the like. Examples of such additives include alcohols, ethers, glycoethers, acetals, ketones, fatty acids, nitroalkanes, amines, amides, aminoethanols, benzotriazols, and the like. A variety of compounds are known. The content of additives is usually from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, based on the total amount of the detergent.

Examples of the stabilizer include aliphatic nitro compounds such as nitromethane and nitroethane; acetylene alcohols such as 3-methyl-1-butyn-1-ol and 3-methyl_1-pentin-1-ol; glycidol, methyl Epoxides such as daricidyl ether and acrylidaricydyl ether; ethers such as dimethoxyethane and 1,4-dioxane; unsaturated hydrocarbons such as hexene, heptene, cyclopentene and cyclohexene; Unsaturated alcohols such as alcohol and 1-buten-3-ol; and acrylates such as methyl acrylate and ethyl acrylate.

As the above-mentioned surfactant, known anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants can be used. Examples of anionic surfactants include carboxylate, sulfonate, sulfate, phosphate and the like. Examples of the cationic surfactant include salts of amine with various acids, and quaternary ammonium salts. Examples of nonionic surfactants include polyether ethers, polyoxyethylene-polyoxypropylene alcohol, polyoxyethylene-polyoxypropylene alkyl ethers, and fatty acid partial esters of polyalcohols. Is mentioned. Examples of amphoteric surfactants include veins, amino organic acids, and amine salts of fatty acids.

Items to be cleaned

In the context of the present description, "cleaning" refers to a contaminant that has adhered to, adhered to, or adhered to the surface of the article to be cleaned, or, in the case of an article to be cleaned consisting of a porous member, a contaminant that has penetrated into the article. ^ Substantially removing various substances from articles that have an undesirable effect on the quality, function, or action of the articles to be cleaned. The contaminants are artificially attached, fixed, adhered, or penetrated. Substances are also included. Further, “cleaning” includes all operations related to the removal of contaminants, such as degreasing, peeling, polishing, rinsing, draining and drying.

In the present invention, the articles to be washed are not particularly limited, and include, for example, a precision machine industry, an automobile industry, an aircraft industry, a heavy machinery industry, a metal processing industry, a metal assembly industry, a steel industry, a non-ferrous industry, a steel pipe industry, a heat treatment industry, Metal, ceramic, glass, etc. in the fields of Metsuki, metallurgy, optical machinery, office equipment, electronics, electrical, plastics, glass, ceramics, printing, textile, cleaning, etc. All items made of plastic, elastomers, textiles, etc. are subject to cleaning.

More specifically, automotive parts such as bumpers, gears, transmission parts, and Rage and One-day parts; used in computers and their peripherals, home appliances, communications equipment, OA equipment, and other electronic equipment Hoop materials used for contact materials such as printed wiring boards, IC parts, lead frames, resistors, relays, relays, motor parts, capacitors, liquid crystal displays, magnetic recording parts, and semiconductor materials such as silicon wafers and ceramic wafers Electronic and electrical parts such as electrostriction parts such as crystal oscillators, photoelectric conversion parts, ticketing parts such as brushes, rotors, and vending machines, and currency inspection parts such as vending machines and cash dispensers; Precision machine parts such as bearings, gears, engineer gears, clock parts, camera parts, optical lenses; printing machines Machinery, printing machine blades, printing rolls, rolling machines, construction machinery, large machinery parts such as heavy machinery parts; precision resin products such as cameras and automobiles; tableware, metal fittings, tools, eyeglass frames, watch belts, etc. Life products; textile products (stain removal, degreasing of raw cotton, removal and cleaning of attached oil stains and proteins, etc.) Examples of various types of contaminants include, but are not limited to, cutting oils. , Water-soluble cutting oil, quenching oil, heat treatment oil, rolling oil, stretching oil, lubricating oil, oil for protection, forging oil, machine oil, machine oil, machining oil, press working oil, punching oil, die cutting oil, drawing oil Oils, assembly oils, wire drawing oils, oils with extreme pressure additives, synthetic oils (silicone, glycol, ester), etc., greases, waxes, paints, a Yellow, rubber, varnishes, co one coating material, abrasives, adhesives, adhesive solvents, surface release material, fats and oils, mold release agents in molding, asphalt pitch, dirt from hands, fingerprints, proteins, after soldering flat Powder, resist, anti-reflective coating of resist, protective film of optical lens, OPC drum photosensitizer, masking agent, compound, surfactant, solder paste, cutting chips, chips, lens pitch (lens abrasive), metal powder , Metal abrasives, lubricants, various resins

(Melamine, urethane, polyester, epoxy, rosin), processing waste, burrs, 榭 fat powder, inorganic powder, paper powder, puff powder, particles, ionic dirt, dust (dust), moisture, etc. Can be

Cleaning method

The cleaning method of the present invention is characterized in that an article is cleaned using the above-mentioned cleaning agent of the present invention. As a cleaning method, a cleaning agent may be brought into contact with the article to be cleaned, and a normal cleaning method can be employed. For example, it can be used in various cleaning methods such as an immersion method, an ultrasonic cleaning method, an oscillating method, a spray method, a sealing method, a steam cleaning method, a hand wiping method, and a favorable result can be obtained. In these washing treatments, physical means such as stirring, vibration, and brushing may be used in combination as necessary.

When the dirt-adhered articles are cleaned by using the cleaning agent of the present invention by an immersion method, for example, (1) a cleaning tank containing the cleaning agent of the present invention alone or mixed with another cleaning agent is used. (2) After washing the articles in the above-mentioned washing tank, the washing agent of the present invention or another washing agent alone or the washing method of the present invention is used. A method of rinsing the articles in a rinsing tank containing a mixture of the cleaning agent and another cleaning agent, and then removing the rinsed articles and drying the articles is adopted.

In the above-mentioned washing tank and rinsing tank, not only immersion washing, but also a combination of rocking, vibration, ultrasonic waves, submerged jet, spray, shower, etc. is effective for improving the washing performance etc. . Each of the washing tank and the rinsing tank may be a single tank or may be composed of two or more tanks. Furthermore, a system combining these with a steam cleaning tank can be adopted.

The method for drying the cleaning agent is not particularly limited, and examples thereof include a method of drying in a reduced-pressure dryer, and a method of blowing hot air such as nitrogen or air. In addition, when such washing of articles is repeated, the detergent is gradually contaminated with various contaminants.If necessary, the detergent can be removed by performing a distillation operation commonly used in industry. Can be collected and reused. The mixture of Endo THDC and Exo-THDC constituting the cleaning agent of the present invention is used in many fields in addition to the cleaning agent. Examples of applications include jet propellant fuels, various fuels, fuel additives, reaction solvents, extraction solvents, adhesive solvents, azole solvents, paint solvents, lacquer thinners, varnish solvents, diluents, Surfactant diluent, wax, polish diluent, plastic surface treatment and protective polish, release agent, pesticide solvent, pressure sensitive paper auxiliary solvent, aluminum rolling oil, ink solvent, resin dispersant, Examples include lubricating oils, lubricant additives, punching oils, cutting oils, organic synthetic intermediates, and fragrance carriers.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Parts and percentages in the examples and comparative examples are based on weight unless otherwise specified.

Production example 1 End-one THDC production

An autoclave equipped with a stirrer was charged with 157 parts of 99% -purity endodicyclopentene and 1.5 parts of 5% palladium carbon, and the inside of the autoclave was replaced several times with nitrogen gas. Next, after the inside of the autoclave was replaced with hydrogen gas several times, a hydrogen gas of 0.6 MPa (gauge pressure) was pressurized. The contents were subjected to a hydrogenation reaction at 100 ° C. for 2 hours while stirring. After the reaction was completed, hydrogen gas in the system was released, and the contents were filtered while hot (about 80 ° C) to remove the catalyst. The obtained filtrate (150 parts) was immediately cooled and solidified in a filtration receiver. A small amount of this solid was collected, dissolved in toluene, and subjected to gas chromatography analysis. As a result, no peak of endocyclopentagen as a raw material was observed. The retention time of the main component by gas chromatography was completely consistent with that of the end-THDC preparation, and its purity was 99%.

Production example 2 Production of exo-THD C

In a glass reaction vessel equipped with a stirrer, reflux condenser, and thermometer, 35 parts of the end-THDC obtained in Production Example 1, 135 parts of normal hexane (reaction solvent), and 90 parts of powdered trichloride Aluminum (isomerization catalyst) 4.6 parts were charged. The contents were heated to 80 ° C and the isomerization reaction was carried out for 7 hours with good stirring. After completion of the reaction, the reaction solution was allowed to cool, and insolubles in the reaction system were separated by filtration. The obtained crude product was rectified under reduced pressure in a distillation column with 5 theoretical plates to obtain about 120 parts of a fraction having a boiling point of 100 ° C (45 mmHg). Was. This product did not solidify at room temperature, and as a result of gas chromatography analysis, the peak completely coincided with that of the exo-THDC sample. The purity of exo THDC obtained by this isomerization reaction was 99.5%.

Examples 1 to 7, Comparative Example 1 Preparation of detergent and measurement of physical properties

(Preparation of detergent)

Using the endo-THDC and exo-THD C obtained according to the above Production Examples 1-2, detergent samples in which the weight ratio of the end-form / exo-form was changed as shown in Table 1 (Example 1) To 7 and Comparative Example 1) were prepared.

(Kauributanol value [KB value] measurement)

12.5 parts of Kauri resin (natural product) was added to 87.5 parts of n-butanol. The Kauri resin was sufficiently dissolved while stirring at 50 ° C, and then allowed to stand for 48 hours. This solution was filtered to obtain a kauributanol (KB) solution. In a constant temperature room at 25 ° C, 20 g of the KB solution was placed in a 200 ml measuring cylinder. While stirring the KB solution in the measuring cylinder with a stirrer, a measurement sample was dropped from the puret at a speed of about 5 m1Z seconds, and the end point was determined when the KB solution became completely turbid (kauri resin precipitated). The amount (KB value, unit: ml) was measured. Table 1 shows the results of performing this measurement operation on seven types of samples. In addition, since the sample of Comparative Example 1 was a solid at 25 ° C., it was impossible to measure the KB value.

(Kinematic viscosity measurement)

Using a B-type viscometer (Tokyo Keiki DVM-B), the solution viscosities of the seven samples were measured at a constant temperature of 25 ° C. The measurement was repeated three times for the same sample, and the average value was taken as the viscosity of each sample. Since the sample of Comparative Example 3 was a solid at 25 ° C, viscosity measurement was not possible. The density of each sample was measured using a Gelsack-type pycnometer. Table 1 shows the kinematic viscosities calculated by dividing the viscosity thus measured by the density. Example End body Z exo body KB value Kinematic viscosity

Comparative example (weight ratio) (ml) (c St)

1 0/1 00 86 5. 1 9

Real-2 5/95 7 1 5.28

1 0/90 63 5.42

20/80 6 1 6.35

40/60 60 6.72

50/50 59 6.8 1

70/30 58 1 0.96

Ratio 1 1 00/0 Measurement impossible Measurement not possible

From Table 1, it can be seen that the larger the content of the exo-form, the higher the KB value, which is one of the indicators of the soil dissolving power of the detergent. Also, the conventional hydrocarbon-based cleaning agent is generally said to have a KB value of 25 to 40 m1, but the cleaning agent of the present invention (Examples 1 to 7) has a higher KB value. Value.

Example 8 Cleaning test of cutting oil adhering to articles

A 200-mesh wire mesh (4 cm x 6 cm square) was immersed in cutting oil (Duff 21 Marda Plus LA15, manufactured by Idemitsu Co., Ltd.) for 1 day at room temperature. What was left to stand for a day was used as a test object to be cleaned. The object to be washed was immersed in a container containing 20 ml of exo-THDC prepared according to Production Example 2, and ultrasonically washed at room temperature for 1 minute. Thereafter, the object to be cleaned was pulled up and dried. Gas chromatography-analysis confirmed that no exo-THDC remained on the surface of the material to be washed after drying. The residual oil content on the surface of the object to be cleaned was measured with an oil content measuring device (OCMA-350 manufactured by Horiba). As a result, the remaining oil content was less than 0.1 mg, and the cutting oil was sufficiently washed and removed.

Example 9 Cleaning test of machine oil adhering to articles A cleaning test was performed by the same test method as in Example 8, except that a machine oil (G-6040 manufactured by Japan Machine Oil Co., Ltd.) was used as a soil component. After cleaning and drying, there was no residual exo-THDC on the surface of the object to be cleaned, the residual oil content was 0.1 mg or less, and the machine oil was sufficiently cleaned and removed.

Example 10 Cleaning Test of Silicon Oil Adhered to Article

A cleaning test was performed by the same test method as in Example 8 except that a silicone oil (KF-96-100 CS manufactured by Shin-Etsu Silicone Co., Ltd.) was used as a dirt component. After cleaning and drying, there was no residual exo-THDC on the surface of the object to be cleaned, the residual oil content was 0.1 mg or less, and the silicon oil was sufficiently washed and removed.

Example 1 1 Cleaning test of printed circuit board with flux attached

Cream soldering Z 63—221 CM 5—4 2-10 (manufactured by Senju Metal Co., Ltd.) on a printed circuit board (40 mmX 6 OmmX 0.8 mm) of a copper-clad laminate of BT resin glass cloth (Mitsubishi Gas Chemical) ) Was applied in a size of 12 mm x 5 Omm, and left in an electric furnace at 250 ° C for 5 minutes to perform a heat treatment to prepare an object to be cleaned. After the heat treatment, the solder was sufficiently melted and solidified on the surface of the object to be cleaned, and the entire surface of the solder was coated with the residual flux.

The object to be washed was immersed in a container containing 200 ml of exo-THDC obtained according to Production Example 2, and subjected to ultrasonic treatment at room temperature for 1 minute. Then, it was pulled up and dried. The solder surface of the object to be cleaned after drying was in an extremely good condition without turbidity, and there was no change in the substrate itself. In addition, it was confirmed by gas chromatography analysis that no exo-THD C remained on the substrate surface. Further, the object to be cleaned was subjected to ultrasonic treatment with 15% aqueous solution of isopropyl alcohol (75%), and then the electric conductivity of the treated liquid was measured by an electric conductivity meter. The conductivity was 0.3 s / cm or less, indicating that the ionic components remaining on the substrate were sufficiently cleaned and removed.

Example 12 Cleaning Test of Printed Circuit Board with Flux Adhered

The exo-THD C used in Example 11 was obtained by converting the weight ratio of the endo- and exo-forms to 5/95 (Example 12), 10/90 (Example 13), and 20/80 (Example 14). ) And 40Z60 (Example 15) As a result of performing a cleaning test in the same manner as in 11, the surface of the substrate after drying was in an extremely favorable state without turbidity, and no change was observed in the substrate itself in all cases using any of the cleaning agents. In addition, it was confirmed by gas chromatography analysis that no THDC remained. Further, as in Example 11, the ionic component remaining on the substrate was analyzed, and as a result, the conductivity was 0.3 ^ sZcm or less, indicating that the substrate was sufficiently cleaned and removed.

Example 16 Cleaning test of printed circuit board with flux

Example 11 A glass epoxy (F R4) printed circuit board was used in place of the printed circuit board of the BT resin glass cloth in Example 1, and a THDC cleaning agent with an end / exo weight ratio of 3/97 instead of exo-THDC was used. The substrate was washed and dried in the same manner as in Example 11 except that the substrate was used. The solder surface of the dried substrate was in a very good condition without turbidity, and there was no change in the substrate itself. In addition, gas chromatography analysis confirmed that no THDC remained on the substrate. Furthermore, the result of measuring the electric conductivity according to Example 11 was 0.3 sZcm or less, and the ion component remaining on the substrate was sufficiently cleaned and removed.

Comparative Examples 2 and 3 Cleaning test of printed circuit board with flux

A washing test was performed in the same manner as in Example 11 except that the exo-THDC used in Example 11 was replaced with P-menthane (Comparative Example 2) and diisopropylcyclohexane (Comparative Example 3). As a result, in each of the comparative examples, the solder surface of the dried substrate was turbid, and it was visually confirmed that the flux was not completely removed.

Example 17 Dry cleaning test of fiber with oil stain

Thick cotton cloth (70 cm x 70 cm square) with acryl resin button is impregnated with 5 g of edible oil as a dirt component, and 2 g of artificial human fat component is applied to the surface and left for 3 days did. The cotton fabric was immersed in a container containing 5 l of exo-THDC prepared according to Production Example 2, and washed by stirring at room temperature for 10 minutes. After the fabric taken out of the container was dried with warm air, the appearance of the button and the presence or absence of dirt on the fabric surface were visually observed.

As a result, no swelling and deformation of the acrylic resin button was observed. Also, the two types of dirt components were completely removed from the fabric surface.

Comparative Examples 4 to 8 Dry cleaning test

The exo-THD C used in Example 17 was converted into Tricrene (Comparative Example 4), AK-225 (manufactured by Asahi Glass Co., Ltd., Comparative Example 5), naphthesol (manufactured by Nippon Petrochemical Co., Ltd., Comparative Example 6), A dry cleaning test was performed in the same manner as in Example 17 except that p-menthane (Comparative Example 7) and n-decane (Comparative Example 8) were used instead.

As a result, in the test using Tricrene and AK-225, the acrylic resin button was deformed. In all the comparative examples, stains due to edible oil were removed. However, in the tests using naphthezol, p-menthane, and n-decane, soil from human fat components remained on the fabric surface.

Example 18 Test for confirming effects on various materials

Test specimens of various polymer materials (17 types) shown in Table 2 were prepared and weighed. Exor T HDC prepared according to Production Example 2 was placed in a glass container equipped with a reflux condenser and a thermometer, and each test piece was immersed at 50 ° C for 4 hours. After completion of the heat immersion, the test piece was taken out and dried under reduced pressure. The weight of each test piece was measured, the rate of weight change (% by weight) before and after immersion was determined, and the appearance was visually observed. The results of the visual observation were shown in accordance with the following three grade evaluation criteria.

Grade 1: No change in appearance

Grade 2: slight swelling, but little change in appearance Grade 3: swelling, but no noticeable change in appearance

Table 2 shows the weight change rate (% by weight) before and after immersion and the results of appearance observation. Many polymer materials (plastic, rubber) showed little change in weight when immersed in exo-THC. No change in appearance was observed. Table 2

Example 19 Heat stability test.

A 100 ml eggplant flask was charged with 30 g of exo-THDC prepared according to Production Example 2, and equipped with a reflux condenser. This was heated to 60 ° C for 8 hours a day for 8 hours a day in an air atmosphere. Every day, a small amount of a sample was collected from the container and analyzed by gas chromatography to measure the change over time of exo-THDC. As a result of comparing the gas chromatography charts before heating and after heating for 1 to 5 days, no degraded products were generated. Also, no change in the color tone of the solution was observed. Industrial applicability

The cleaning agent of the present invention is superior in cleaning performance to contaminants adhering to an article and does not corrode the material (plastic, rubber, etc.) of the article as compared with a conventional aliphatic hydrocarbon-based cleaning agent. In addition, since this detergent does not contain chlorine atoms, there are few environmental problems such as depletion of the ozone layer, and since it does not contain aromatic hydrocarbons, it may be subject to regulations under the Industrial Safety and Health Law applicable to similar compounds. Absent.

Accordingly, the cleaning agent of the present invention may be an article to be cleaned as specifically enumerated above, for example, a precision machine industry, an automobile industry, an aircraft industry, a heavy machinery industry, a metal processing industry, a metal assembly industry, a steel industry, a non-ferrous industry. Industries, steel pipe industry, heat treatment industry, metalwork industry, metallurgy industry, optical machine industry, office equipment industry, electronics industry, electric industry, plastic industry, glass industry, ceramics industry, printing industry, textile industry, cleaning industry, etc. It can be used for cleaning a wide range of items such as metals, ceramics, glass, plastics, elastomers, and textiles.

Claims

The scope of the claims

1. Tetrahydrology

0 ~ 0Ζ1

A cleaning agent having a range of 00.

2. The cleaning agent according to claim 1, wherein the weight ratio of the end body and the exo body is in the range of 40/600/100.

3. The cleaning agent according to claim 1, which has a Kauriburi nol value of 6 Oml or more.

4. The cleaning agent according to claim 1, further comprising at least one organic solvent selected from hydrocarbons, alcohols, esters, chlorinated hydrocarbons, fluorinated hydrocarbons, ethers, ketones, and volatile organic silicon.

5. A method for cleaning an article, comprising using the cleaning agent according to any one of claims 1 to 4.

6. The cleaning method according to claim 5, wherein the article is an electronic / electric part.

7. The cleaning method according to claim 5, wherein the article to which the flux is adhered as the substance to be cleaned is cleaned.