DD289556A5 - SOLVENT - Google Patents

Abstract

The invention relates to a solvent substantially consisting of a compound of the following formula * abc3, xyz3, ax1, by1 and 0a, b, c, x, y, z3. The inventive solvent consists essentially of 10 to 100% of the compound of the formula * of 0 to 80 * of an organic solvent selected from the group consisting of a hydrocarbon, an alcohol, a ketone, a chlorinated hydrocarbon, an ester, an aromatic compound , and from 0 to 10 * of a surfactant. {solvents; Cleaning preparations for clothing; Flux; cutting oils; Water; Polishes; resist}

Description

CH ₈ Cl _b F _c CF ₂ CH _x Cl _y F _{2 (} '(I)

where a + b + c = 2, χ + y + ζ = 3, a + χ S 1, b + y> 1, and 0 <a, b, c, x, y, zS3, characterized in that they are as a solvent or cleaning solvent or> r used in a cleaning solvent or for the preparation of a cleaning solvent.

5. Use according to claim 4, characterized in that the cleaning solvent is a cleaning solvent for dry cleaning purposes, a degreasing agent, a cleaning agent for removing a cleaning or polishing agent, a flux removing agent or a rinsing agent.

Use according to claim 4, characterized in that the solvent is a resist developing agent or a resist removing agent.

7. Use according to claim 4, characterized in that the solvent is a solvent for removing separated water, a solvent for extraction purposes, a diluent, a solvent for an aerosol or an insulating medium.

8. Use according to claim 4, characterized in that the compound of formula (I) CF ₃ CF ₂ CHCl ₂ , CCIf ₂ CF ₂ CHCIF or CHF ₂ CF ₂ CH ₂ CI.

Field of application of the invention

The invention relates to novel halogenated hydrocarbon solvents and their use.

Characteristic of the known state of the art

1,1,2-Trichloro-1,2,2-trifluoroethane (hereinafter referred to simply as R113) is not flammable, non-explosive, and stable at low toxicity, and is therefore widely used as a cleaning agent, for example, a flux used in the assembly of electronic components or precision machinery parts, or for cutting oils or as a cleaning agent for clothing such as fur coats or suits.

Further, R113 is widely used to remove the separated water in the liquid crystal display device parts, electronic parts or precision machine parts after the water washing treatment. On the other hand, a rinsing agent such as trichlorethylene is used to remove a resist-removing agent deposited on a wafer. 1,1,1-Trichloroethane is used as a cleaning agent to remove a deposited polishing agent on precision metal parts or decorative parts after surface treatment. Further, 1,1,1-trichloroethane is used to develop a resist in the manufacture of printed circuit boards or semiconductor circuits. Methylene chloride or perchlorethylene are used to remove the resist after the etching treatment. Despite its various advantageous properties, R113 has the disadvantage of destroying the ozone in the stratosphere, which in turn increases the risk of skin cancer. On the other hand, methylene chloride, trichlorethylene, perchlorethylene and 1,1,1-trichloroethane lead to contamination of the groundwater. It is therefore necessary to keep the quantities of these substances used as low as possible.

Object of the invention

Starting from this state of the art as the go! of the present invention to avoid the above-mentioned problems.

Explanation of the essence of the invention

It is an object of the present invention to provide a novel halogenated hydrocarbon solvent which can serve as a substitute for the conventional solvents.

According to the present invention, there is provided a halogenated hydrocarbon solvent consisting essentially of a hydrogen-containing chlorofluoropropane having a difluoromethylene group represented by the formula:

CH ₁ Cl ₁₁ FcCFjCH _x CIyF ₁ (I)

where a + b + c = 3, x + y + z = 3, a + xa1, b + y> 1, and 0 ^ a, b, c, x, y, zs3. In the following the invention will be explained with reference to preferred embodiments. Specific examples of the compounds according to formula (I) are as follows:

CCIFjCF ₂ CHCl ₂ (R224ca) CCI ₂ FCF ₂ CHCIF (R 224 cb) CF ₃ CF ₂ CHCl ₂ (R225ca) CCIF ₂ CFjCHCIF (R 225 cb) CCIF ₂ CF ₂ CH ₂ Cl (R 234 cc) CHF ₂ CF ₂ CHCIF (R 235 ca) CH ₃ CF ₂ CCI ₂ F (R 243 cc) CHF ₂ CF ₂ CH ₂ Cl (R 244ca) CH ₂ CICF ₂ ^ H ₂ CI (R 252 ca) CHCI ₂ CF ₂ CH ₃ (R 252 cb) CH ₃ CF ₂ CH ₂ Cl (R 262 ca) CHF ₂ CF ₂ CCI ₂ F (R 225 cc) CHCIFCF ₂ CHClF (R 234 ca) CHF ₂ CF ₂ CHCl ₂ (R 234 cb) CH ₂ FCF ₂ CCI ₂ F (R 234 cd) CF ₃ CF ₂ CH ₂ Cl (R 235 cb) CCIF ₂ CF ₂ CH ₂ F (R 235 cc) Ch ₂ CICF ₂ CHCIF (R 243 ca) CH ₂ FCF ₂ CHCl ₂ (R 243 cb) CH ₂ FCF ₂ CHClF (R244 cb) CCIF ₂ CF ₂ CH ₃ (R 244 cc) CH ₂ FCF ₂ CH ₂ Cl (253 ca) CH ₃ CF ₂ CHClF (R 253 cb) CF ₃ CF ₂ CHClF (R 226 ca) CCIF ₂ CF ₂ CHF ₂ (R 226 cb) CCI ₃ CFjCHCl ₂ (R 222 c) CCIjFCF ₂ CHCl ₂ (R 223 ca) CCI ₃ CFjCHCIF (R 223 cb) CCI ₃ CFjCHFj (R 224 cc) CHCl ₂ CF ₂ CHC :. : .T232ca) CCI ₃ CF ₂ CH ₂ Cl (R 232 cb) CCI ₂ FCF ₂ CHjCl (R 233 cb) CHClIjCFjCHCIF (R233ca) CCI ₃ CF ₂ CH ₂ F (R 233 cc) CCICF ₂ CH ₃ (R 242 cb ) CHCl ₂ CF ₂ CH ₂ Cl (R 242 ca)

The compounds of the present invention according to the formula (I) may be used either alone or in combination as a mixture of two or more. They are useful as detergents for a variety of purposes, including as cleaning agents for dry cleaning, as degreasing agents, as cleaning agents for removing a polishing agent as a flux cleaner and as a rinsing agent or as a resist developing agent or as a resist removing agent or as a solvent for removing separated water. Furthermore, they are also suitable for the following different uses:

As a solvent for the extraction of nicotine contained in tobacco leaves, or for the extraction of pharmaceutical substances from animals or plants; as a diluent to disperse or dissolve various chemical agents including a coating material, a molding material, a water and oil repellent, a moisture repellent coating, a water repellent coating, a brightener or an antistatic agent to facilitate their application to the respective objects ; as an aerosol solvent, to provide a chemical agent or agent which is dispersed in an aerosol of e.g. A coating material, an insecticide, a pharmaceutical, an antiperspirant, a deodorant, a hair conditioner or a cosmetic, to dissolve; and as insulation medium for insulating and cooling z. As an oil-filled transformer or a gas-insulated transformer

When employing the compounds of the present invention for the various uses mentioned above, various other compounds are preferably incorporated, depending on the particular purpose intended.

For example, an organic solvent such as a hydrocarbon, an alcohol, a ketone, a chlorinated hydrocarbon, an ester or an aromatic compound or a surfactant may be incorporated to improve the cleaning effects when used as a cleaning agent or to improve the effects in other uses. Such an organic solvent may generally be incorporated in an amount of 0 to 80% by weight, preferably 0 to 50% by weight, more preferably 10 to 40% by weight of the composition. The surfactant may usually be present in an amount of from 0 to 10% by weight, preferably from 0.1 to 5% by weight, most preferably from 0.2 to

1% by weight.

The hydrocarbon is preferably a linear or cyclic, saturated or unsaturated hydrocarbon having 1 to 15 carbon atoms and is generally selected from the group consisting of n-pentane, isopentane, n-hexane, isohexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, n-heptane, isoheptane, 3-methylhexane, 2,4-dimethylpentane, n-octane, 2-methylheptane, 3-ethylheptane, 2,2-dimethylhexane, 2,5-dimethylhexane, 3,3 Dimethylhexane, 2-methyl-3-ethylpentane, 3-methyl-3-ethylpentane, 2,3,3-trimethylpentane, 2,3,4-trimethylpentane, 2,2,3-trimethylpentane, isooctane, nonane, 2,2, 5-trimethylhexane, decane, dodecane, 1-pentene, 2-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, bicyclohexane, cyclohexene, alpha-pinene, Dipentene, decalin, tetralin, amylene and amylnaphthalene. Particularly preferred are n-pentane, η-hexane, cyclohexane and n-heptane.

The alcohol is preferably an aliphatic or cyclic, saturated or unsaturated alcohol having 1 to 17 carbon atoms and is usually selected from the group consisting of methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, pentyl alcohol, sec- Amyl alcohol, 1-ethyl-m-propanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol _t 3-methyl-2-butanol, neo-pentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2 pentanol, 2-ethyl-1-butanoi, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethylm-hexanol, 1-nonanol, 3,5,5-trimethyl-i hexanol, 1-decanol, 1-undecanol, 1-dodecanol, allyl alcohol, propargyl alcohol, benzyl alcohol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, alpha-terpineol, abietinol, 2.6 Dimethyl 4-heptanol, trimethylnonyl alcohol, tetradecyl alcohol and heptadecyl alcohol. Particularly preferred are methanol, ethanol and isopropyl alcohol.

The ketone is preferably represented by one of the following formulas:

η t- 'r^CHn

R-CO-R ', R-CO, R-CO-R'-CO-R ", R-CO-R ¹ and R-CO-R ¹ , wherein R, R ¹

and R "are each a saturated or unsaturated hydrocarbon group having 1 to 9 carbon atoms, and is usually selected from the group consisting of acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl n-butyl ketone, methyl butyl ketone, 2- Heptanone, 4-heptanone, diisobutyl ketone, acetonitrile, acetone, Mesltyloxid, Phoron, methyl-n-nyl ketone, Ethylbul / Iketon, methyl hexyl ketone, cyclohexanone, methylcyclohexanone, isophorone, 2,4-pentanediol; i, diacetone alcohol, acetophenone and fenchone methyl ethyl ketone.

Further, as the organic solvent, a conventional nitrile solvent such as, for. For example acetonitrile.

The chlorinated hydrocarbon is preferably a saturated or unsaturated chlorinated hydrocarbon with 1 or

2 carbon atoms and is generally selected from the group consisting of methylene chloride, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,1, 2, -tetrachloroethane, iji ^ -Tetrrachlorethan.Pentachlorethan.i, 1-dichloroethylene, 1,2-dichloroethylene, trichlorethylene and tetrachlorethylene. Particularly preferred are methylene chloride, 1,1,1-trichloroethane, trichlorethylene and tetrachlorethylene.

The surfactant surfactant solvent is preferably selected from the group consisting of a polyoxyethylene alkyl ether, a polyoxyethylene polyoxypropylene alkyl ether, a polyoxyethylene alkyl ester, a polyoxyethylene polyoxypropylene alkyl ester, a polyoxyethylene alkylphenol, a polyoxyethylene polyoxypropylene alkylphenol, a polyoxyethylene sorbitan ester, a polyoxyethylene polyoxypropylene sorbitan ester, caprylic caprylamine and a polyoxyethylene alkylamide. Particularly preferred are caprylic caprylamine and a polyoxyethylene alkylamide.

As the surfactant for a dry cleaning detergent, various surfactants including nonionic, cationic, anionic and amphoteric surfactants can be used. Preferably, the surfactant is selected from the group consisting of a linear alkyl benzene sulfonate, a long chain alcohol sulfate, a polyoxyethylene ether sulfate, a polyoxyethylene alkyl ether phosphate, a polyoxyethylene alkyl ether sulfate, a polyoxyethylene alkyl phenyl ether phosphate, an alpha olefin sulfonate, an alkyl sulfosuccinate, a polyoxyethylene alkyl ether, a Polyoxyethylene alkyl esters, a polyoxyethylene alkylallyl ether, a fatty acid diethanolamide, a polyoxyethylene alkylamide, a sorbitan fatty acid ester, a polyoxyethylene fatty acid ester, a quaternary ammonium salt, a hydroxy sulfobetaine, a polyoxyethylene lauryl ether, a polyoxyethylene lauryl ether sodium sulfate, sodium dodecyl benzene sulfonate and a higher alcohol sodium sulfate. Particularly preferred are a polyoxyethylene lauryl ether, a polyoxyethylene lauryl ether sodium sulfate, sodium dodecylbenzenesulfonate and a higher alcohol sodium sulfate.

The aromatic compound is preferably a benzene derivative or a naphthalene derivative and is generally selected from the group consisting of benzene, toluene, xylene, ethylbenzene, isopropylbenzene, diethylbenzene, sec-butylbenzene, triethylbenzene, diisopropylbenzene, styrene, an alkylbenzenesulfonic acid, phenol, mesitylol, naphthalene , Tetralin, butylbenzene, p-cymene, cyclohexylbenzene, pentylbenzene, dipentylbenzene, dodecylbenzene, biphenyl, o-cresol, m-cresol and xylene. Particularly preferred are an alkylbenzenesulfonic acid and phenol.

The ester is preferably one of the following formulas:

R ₂

Ri-COO-R ₂ . R ₁ -CR ₃ -COO-R ,,

OR ₅

R ₁ -C -COOR ₂ .Ri-COO-R ₂ -COO-R ₃ .R ₁ -CO, (COOR ₁ ) 2 IR ₃

COO-R ₁ R ₁ -COO-H ₂

R ₅ -CR ₂ R ₆ -COO-R ₃

II ^and

R ₆ -CR ₃ R ₄ -COOR ₆

COOR,. '

wherein the radicals R ₁ , R ₂ , R ₃ , R ₄ , R ₆ and R _{6 are} each H, OH or a saturated or unsaturated hydrocarbon group having 1 to 19 carbon atoms.

Specifically, the ester is selected from the group consisting of methyl, ethyl, propyl, butyl, isobutyl, phenyl, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, see butyl acetate, pentyl acetate, isopentyl acetate, 3-methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, isopentyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isopentyl butyrate, isobutyl isobutyrate, ethyl 2-hydroxy-2-methyl-propionate, butyl stearate, methyl benzoate, ethyl benzoate,

Propyl benzoate, bytylbenzoate, isopentyl benzoate, benzyl benzoate, ethylabietate, benzylabietate, bis-2-ethylhexyl adipate, gamma-butyrolactone, diethyl oxalate, dibutyl oxalate, diphenyl oxalate, diethyl malonate, dimethyl maleate, ethyl maleate, dibutyl maleate, dibutyltertarate, tributyl citrate, dibutyl sebacate, bis-2-ethylhexylcebacate, dimethyl phthalate, Diethyl phthalate, dibutyl phthalate, bis-2-ethylhexyl phthalate and dioctyl phthalate. Particularly preferred are methyl acetate and ethyl acetate.

A chlorofluorohydrocarbon which does not fall under the formula (I) may be in agreement with the compound of the invention. In a composition consisting of an azeotrope or a pseudo-azeotrope by the combination of the compounds of the present invention with another compound, it is preferred to use the compound in an azeotropic or pseudo-azeotropic state so that there is no change in the composition when recovering or so that no substantial change in the conventional technique is required.

The dry cleaning detergent according to the present invention may contain various additives such as an antistatic agent, a plasticizer, a soil removing agent, a flame retardant, a water and oil repellent or a stabilizer. As the stabilizer, there may be used various types conventionally used for the cleaning agent for dry cleaning purposes, including nitroalkanes, epoxies, amines or phenols.

Various cleaning additives or stabilizers may also be included in the degreasing agent, the cleaning agent for removing a polishing or abrasive agent, or a flux cleaning agent. Further, in the case of the cleaning agent for removing a polishing or abrasive, water may be incorporated. As the cleaning method, one can use a manual wiping method, dipping, spraying, shaking, ultrasonic cleaning, steam cleaning, or any conventional method.

If stabilization of the rinsing agent is required, it is preferable to use a nitroalkane such as nitromethane, nitroethane or nitropropane or a cyclic ether such as propylene oxide, 1,2-butylene oxide, epichlorohydrin, styrene oxide, butylglycidyl ether, phenylglycidyl ether, glycidol, 1,4-dioxane, 1 , 3,4-trioxane, 1,3-dioxolane, dimethoxymethane or 1,2-dimethoxyethane, in an amount of 0.001 to 5.0% by weight, in combination.

There are no particular restrictions on the resist to be developed or removed using the solvent of the present invention. The resist may be a positive or negative resist for irradiation with light, a resist for irradiation with far ultraviolet rays, or a resist for irradiation with X-rays or electron beams. The light-irradiating resist comprises a quinone diazide type having phenol and cresol novolak resin as the base materials, a cyclic rubber type having cis-1,4-polyisoprene as an essential component, and a polycinnamate type. The ultraviolet ray irradiation resist includes polymethylene methacrylate and polymethyl isopropenyl ketone. The electron beam or X-ray irradiation resist comprises poly (methyl methacrylate), a glycidyl methacrylate-ethyl acrylate copolymer and a methyl methacrylate-methacrylic acid copolymer.

In order to achieve removal of separated water by means of the separated water removal solvent of the present invention, one can use a spray or shower method or a dip in a cold bath, a warm bath, a steam bath or an ultrasonic bath or a dip method using a combination these baths works, apply.

The isolation mode according to the present invention may be used in combination with a mineral oil type isolation medium, a fully halogenated hydrocarbon type isolation medium, or a silicone oil isolation medium conventionally used in this field. Further, for the purpose of stabilization, a stabilizer such as a phosphite compound, a phosphine sulfide compound or a glycidyl ether compound may be incorporated, or a phenol or amino antioxidant which may be used in combination.

embodiment

In the following the invention will be explained in more detail by means of examples. It should be understood, however, that the present invention is not limited by these specific examples.

Examples 1-1 to 1-16

Cleansing power cleaning tests are performed using the dry cleaning agents shown in Table 1. A soiled cloth (5 cm 5cm χ) of wool having carbon soil fixed by a Yukagaku Kyokai method, is placed into a Scrub-O-meter cleaning machine and washed at 25 ⁰ C 25 minutes. Thereafter, the cleaning effect is measured by means of an ELREPHO photoelectric reflection meter. The results are shown in Table 1.

Table 1

Example no. Dry cleaners cleaning effect 1-1 R225ca (100) O 1-2 R225cb (100) O 1-3 R224ca (100) O 1-4 R224cb (100) O 1-5 R235ca (100) O 1-6 R234CC (100) O 1-7 R244ca (100) O 1-8 R243CC (100) O 1-9 R252ca (100) O 1-10 R252cb (100) O 1-11 R262ca (100) O 1-12 R225ca (75) / n-heptane (25) O 1-13 R225ca (75) / ethanol (25) O 1-14 R225ca (75) / perchlorethylene (25) O 1-15 R225ca (75) / acetone (25) O 1-16 R225ca (75) / sodium dodecyl benzenesulfonate (25) O

The value in parentheses () means a proportion (wt%). Evaluation standards: O Dirt-satisfactorily removed O dirt substantially satisfactorily removed

Δ minor dirt residues

X significant dirt residues

Examples 2-1 to 2-16

Cleaning tests on cutting oil are carried out using the degreasing agents given in Table 2. A test piece (25 mm χ 30 mm χ 2 mm) made of SUS-304 stainless steel is immersed in spindle oil and then immersed in the degreaser for 5 minutes. Subsequently, the test piece is taken out and the state of the spindle oil remaining on the surface of the test piece is visually evaluated. The results are shown in Table 2.

Table 2

Example No. degreaser degreasing effect

2Λ R225ca (100) Ö

2-2 R225cb (100) O

2-3 R224ca (100) O

2-4 R224cb (100) O

2-5 R235ca (100) O

2-6 R234cc (100) O

2-7 R244ca (100) O

2-8 R243CC (100) O

The value in parentheses () means a proportion (% by weight)

Example no. degreasing Entfettungseffekt 2-9 R252ca (100) O 2-10 R252cb (100) O 2-11 R262ca (100) O 2-12 R225ca (75) / n-heptane (25) O 2-13 R225ca (75) / ethanol (25) O 2-14 R » ⁿ 25ca (75) / acetone (25) O 2-15 R225ca (75) / trichlorethylene (25) O 2-16 R225ca (75) / ethyl acetate (25) O

The value in parentheses {) means a fraction (% by weight) of evaluation jwitandardi:

O satisfactorily degreased O essentially satisfactorily degreased Δ minor residual oil X essential oil residues

Examples 3-1 to 3-16

Tests are performed to remove a polishing agent using the cleaning agents shown in Table 3 to remove a polishing agent.

A wristwatch frame is polished with a polishing agent and then dipped in the cleaning agent to remove a polishing agent and subjected to ultrasonic waves for 3 minutes. Then the frame is removed and examined for the removal of the Pol'srmittels. The results are summarized in Table 3.

Table 3

Example No. Detergent for removal results

a polish

3-13-23-33-43-53-63-73-83-9 3-10 3-11 3-12 3-13 3-143-15 3-16

Comparative Ex. 3-1 1,1,1-Trichloroethane (100)

The value in parentheses () means a proportion (% by weight)

Evaluation standards:

θ polishing agent satisfactorily removed O polish substantially satisfactorily removed Δ minor polish residue X significant polish residue

Examples 4-1 to 4-15 Flux purification tests are conducted using the flux cleaners shown in Table 4.

A flux is applied to ce entire surface of a gtdruckten circuit board (a copper-clad laminate) and baked in an electric oven at 200 ⁰ C for 2 minutes. Then the panel is immersed in the flux cleaner for one minute. The degree of removal of the flux is shown in Table 4.

R225ca (100) O R225cb (100) O R 224 ca (100) O R224cb (100) O R 235 ca (100) O R234cc (100) O R 244 ca (1C0) O R 243 cc (100) O R 252 ca (100) O R 252 cb (100) O R 262 ca (100) O R225ca (75) / ivHexan (25) O R225ca (75) / ethanol (25) O R225ca (75) / acetone (25) O R225ca (75) / 1,1,1-rrichlorethan (25) O R 225 ca (75) / ethyl acetate (25) O

Example no. Fluxreinigungsmittel cleaning effect 4-1 R225ca (100) O 4-2 R225cb (100) O 4-3 R 224 ca (100) O 4-4 R 224 cb (100) O 4-5 R 235 ca (100) O 4-6 R 234 cc (1P0) O • 4-7 R244ca (100) O 4-8 R 243 cc (100) O 4-9 R 252 ca (100) O 4-10 R 252 cb (100) O 4-11 R 262 ca (100) O 4-12 R225ca (75) / n-heptane (25) O 4-13 R225ca (75) / methanol (25) O 4-14 R225ca (75) / acetone (25) O 4-15 R 225 ca (75) / trichlorethylene (25) O

The value in parentheses () means a proportion (% by weight) Bewertungsltandardi: O Flux satisfactorily removed O flux substantially satisfactory removed

Δ minor flux residues

X essential flux residues Examples 5-1 to 5-7

A positive resist or a negative resist is applied to a silicon plate (wafer), followed by an etching treatment.

Subsequently, the silicon plate is immersed in an o-dichlorobenzene type resist removal solution at a temperature of 120 ° C for 10 minutes. Then the plate is immersed in the detergent indicated in Table 5, at 25 ⁰ C for three minutes. Further, the plate is dipped in an IPA / MEK mixed solution and cleaned, followed by drying in super-pure water and then drying. Subsequently, the surface condition is examined by means of a microscope.

The results are shown in Table 5.

Table 5

Example no. dish soap Proportions (% by weight) Results 5-1 R 225 approx 100 no fine particles discovered on the surface 5-2 R225cb 100 no fine particles discovered on the surface 5-3 R243 cc 100 no fine particles discovered on the surface 5-4 R244 approx 100 no fine particles discovered on the surface 5-5 R 262 approx 100 no fine particles discovered on the surface C-6 R 225 approx 90 no fine particles on the heptane 10 Surface discovered 5-7 R 244 approx 90 no fine particles on the heptane 10 Surface discovered

Examples 6-1 to 6-16 Resist development tests are conducted using the resist developers shown in Table 6.

A printed circuit board (a Cu-clad laminate) having a photoresist film laminated thereon is exposed so that a predetermined circuit pattern is formed. Subsequently, development is carried out with the resist developing agent, whereupon the surface is examined by means of a microscope to determine whether the circuit pattern is properly formed.

The results are shown in Table 6.

Example No. Resist Developer Results

6-1 6-26-36-46-K6-66-76-86-96-106-11 6-12 6-13 6-146-156-16

Comparative Ex. No. 1,1,1-Trichloroethane (100)

6-1

The value in brackets () means a proportion (% by weight) Bewertungiitindard ": O satisfactorily developed O developed substantially satisfactorily

Δ slightly badX bad

Examples 7-1 to 7-17 Resist removal tests are performed using the resist removal agents shown in Table 7. A printed circuit board (a Cu-clad laminate) having a photoresist film laminated thereon is exposed,

developed and etched to form a printed circuit. Subsequently, the panel is immersed in the resist removing agent at room temperature for 15 minutes. The board is taken out and inspected by a microscope to the

State of removal of the cured film. The results are shown in Table 7. Table 7

R 225 ca (100) O R225cb (100) O R 224 ca (100) O R224cb (100) O R 235 ca (100) O R 234 cc (100) O R 244 ca (100) O R 243 cc (100) O R 252 ca (100) O R 252 cb (100) O R 262 ca (100) O R225ca (75) / n-Hentan (25) O R225ca (75) / ethanol (25) O R225ca (75) / acetone (25) O R 225 ca (75) / 1,1,1-trichloroethane (25) O R 225 ca (75) / M ethyl acetate (25) O

Example no. Resist remover Results 7-1 R 225 ca (100) O 7-2 R225cb (100) O 7-3 R 224 ca (100) O 7-4 R224cb (100) O 7-5 R 235 ca (100) O 7-6 R 234 cc (100) O 7-7 R244ca (100) O 7-8 R 243 cc (100) O 7-9 R 252 ca (100) O 7-10 R252cb (100) O 7-11 R 262 ca (100) O 7-12 R225ca (75Vn-pentane (15) O Alkylbenzenesulfonic acid (10) 7-13 R225ca (75) / ethanol (15) O Alkylbenzenesulfonic acid (10) 7-14 R 225 ca (75) / acetone (15) phenol (10) O 7-15 R 225 ca (75) / methylene chloride (15) phenol (25) O 7-16 R225ca (75) / phenol (25) O 7-17 R 225 ca (75 / methyl acetate (25) O Comparative Ex. Tetrachlorethylene (100) O 7-1 Comparative Ex. o-DichlorbenzoldOO) O 7-2

The value in parentheses () means a proportion (% by weight) Evaluation standards: O Resist satisfactorily removed O Re.'is essentially satisfactorily removed

Δ Minor strikes

X Essential Resistreste Examples 8-1 to 8-16

Remote water removal tests are performed using the solvents listed in Table 8 to remove separated water.

A glass plate of 30mm χ 18mm χ 5mm is immersed in pure water and then immersed for 20s in the solvent to remove any separated water. Thereafter, the glass plate is taken out and immersed in dry methanol, whereupon the state of removal of separated water is determined by the increase of the water content.

The results are shown in Table 8.

Table 8

Example No. Solvent for removal results

of separated water

8-1 8-2 8-3 8-4 8-5 8-6 8-7 8-8 8-9 8-10 8-11 8-12 8-13

8-14 8-15 8-16

The value in parentheses () means a proportion (% by weight) Review "ft" ndard $: O deposited water satisfactorily removed O deposited water substantially satisfyingly.

Δ small residues of separated water

X essential residues of separated water

Examples 9-1 to 9-11 Tests are carried out to extract the nicotine contained in tobacco leaves using the extraction solvent compositions of the present invention shown in the table.

A predetermined amount of a tobacco sample (hut, commercial product) is poured into a Soxhlet extractor. Using the extraction solvent composition of the present invention, it is refluxed with heating for 8 hours. After refluxing, the solvent is evaporated to dryness and the amount of extract is determined. The results are shown in Table 9. Using methanol as reference solvent, a similar test is performed. The amount of extract in this case is rated as 100. The results of the other tests are given as relative values relative to this value.

As further comparative examples, similar tests are carried out with acetone and hexane.

The evaporation residues of the respective tests are analyzed by gas chromatography. It is found that nicotine is contained in each of the residues.

Table 9

R225ca (100) O R225cb (100) O R 224 ca (100) O R 224 cb (100) O R 235 ca (100) O R 234 cc (100) O R 244 ca (100) O R 243 cc (100) O R 252 ca (100) O R252cb (100) O R 262 ca (100) O R 225 ca (75) / methanol (25) O R225ca (75) / acetone (5) / O Isopropyl alcohol (20) R 225 ca (75) / trichlorethylene (5) / ethanol (20) O R 225 ca (75) / n-haptan (15) / methanol (20) O R 225 ca (99.5) / caprylamine caprylic acid (0.5) O

Example no. Extraction solvent composition extraction rates 9-1 R224 approx 150 9-2 R 224 cb 150 9-3 R225 approx 140 9-4 R225cb 140 9-5 R 234 cc 140 9-6 R235 approx 150 9-7 R243 cc 150 9-8 R 244 approx 160 9-9 R252 approx 160

Table 9 (continued) Extraction solvent composition extraction rates Example no. R262cb 150 9-10 R262 approx 160 9-11 methanol 100 Comparative Ex. 9-1 acetone 90   Comparative Ex. 9-2 hexane 90 Comparative Ex. 9-3

Examples 10-1 to 10-51

Using the diluents shown in Tables 10-1 to 10-3, a moisture-repellent coating agent composed of a polyfluoroalkyl group-containing polymer is diluted. The thus-obtained diluted composition is applied to the surface of a printed circuit board and air-dried to form a moisture-repellent coating film on the surface of the printed circuit board. The drying state of this moisture-repellent coating film is visually examined. The results are given in Tables 10-1 to 10-3.

Table 10-1

Example no. thinner Film formation properties 10-1 R 224 ca (100) O 10-2 R 224 cb (100) O 10-3 R 225 ca (100) ö 10-4 R225cb (100) O 10-5 R234cc (100) O 10-6 R 235 ca (100) O 10-7 R 243 cc (100) O 10-8 R 244 ca (100) O 10-9 R 252 ca (100) O 10-10 R 252 cb (100) O 10-11 R262ca (100) O 10-12 R225ca (75) / n-heptane (25) O 10-13 R225ca (75) / ethanol (25) O 10-14 225ca (75) / acetone (25) O 10-15 225 ca (75) / trichlorethylene (25) O 10-15 225ca (75) / ethyl acetate (25) O

The value in parentheses () means a proportion (% by weight) Evaluation standards: O Excellent

Δ Slight non-uniformity is observed

X It is observed a substantial non-uniformity Table 10-2

Example no. thinner Film formation properties 10-17 R 225 cc (100) O 10-18 R 234 ca (100) O 10-19 R 234 cb {100) O Ί0-20 R 234 cd (100) O 10-21 R 235 cb (100) O 10-22 R 235 cc (100) O 10-23 R 243 ca (100) O 10-24 R 243 cb (100) O 10-25 R 244 cb (100) O 10-26 R 244 cc (100) O 10-27 R 253 ca (100) O 10-28 R 253 cb (100) O 10-29 R244cb (75) / n-heptane (25 O 10-30 R244cb (75) / ethanol (25) O 10-31 244cb (75) / acetone (25) O 10-32 244 cb (75) / trichlorethylene (25) O 10-33 244 cb (75) / ethyl acetate (25) O

The value in parentheses () means a proportion (% by weight) Evaluation standards: O Excellent

Δ Slight non-uniformity is observed

X Significant non-uniformity is observed Table 10-3

Example no. thinner Film formation properties 10-34 R226ca (100) O 10-35 R 226 cb (100) O 10-36 R 222c (100) O 10-37 R223ca (100) O 10-38 R 223 cb (100) O 10-39 R 224 cc (100) O 10-40 R 232 ca (100) O 10-41 R 232 cb (100) O 10-42 R233cb (100) O 10-43 R 233 ca (100) O 10-44 R 233 cc (100) O 10-45 R 242 cb (100) O 10-46 R 242 ca (100) O 10-47 R 226ca (75) / n-heptane (25) O 10-48 R226ca (75) / ethanol (25) O 10-49 226ca (75) / acetone (25) O 10-50 226 ca (75) / trichlorethylene (25) O 10-51 226ca (75) / ethyl acetate (25) O

The value in parentheses () means a proportion (% by weight) Evaluation standards: O Excellent

Δ Slight non-uniformity is observed

X Significant non-uniformity is observed Examples 11-1 to 11-51

A composition is prepared by mixing three parts by weight of the solvent composition given in Tables 11-1 to 11-3, 9.4 parts by weight of pure water, 0.4 parts by weight of a surfactant, 1.6 parts by weight of isopropyl myristate, 0.4 parts by weight of talc powder, 0.2 parts by weight of perfume and 85 parts by weight of a propellant (1,1-dichloro-2,2,2-trifluoroethane). The whole is poured into an aerosol container and shaken a few times. The dispersibility of the aerosol composition is then visually examined. The results are summarized in Tables 11-1 to 11-3.

Table 11-1

Example no. Solvent composition dispersing effects 11-1 R 224 ca (100) O 11-2 R 224 cb (100) O 11-3 R225ca (100) O 11-4 R? 25cb (100) O 11-5 R 234 cc (100) O 11-6 R 235 ca (100) O 11-7 R243cc (10C " O 11-8 R 244 ca (100) O 11-9 R 252 ca (100) O 11-10 R 252 cb (100) O 11-11 R 262 ca (100) O 11-12 R225ca (75) / n-heptane (25) O 11-13 R225ca (75) / ethanol (25) O 11-14 225ca {75) / acetone (25) O 11-15 225 ca (75) / trichlorethylene (25) O 11-15 225ca (75) / ethyl acetate (25) O

The value in parentheses () indicates a proportion (% by weight) of evaluation standards:

O uniformly dispersed O substantially uniformly dispersed Δ minor N'id uniformity X significant nonuniformity

Table 11-2

Example no. Lösurjsmittelzusammensetzung Dispiergiereffekte 11-17 R 225 cc (100) O 11-18 R 234 ca (100) O 11-19 R 234 cb (100) O 11-20 R 234 cd (100) θ 11-21 R 235 cb (100) O 11-22 R 235 cc (100) O 11-23 R243ca (100) O 11-24 R 243 cb (100) O 11-25 R244cb (100) O 11-26 R244cc (100) O

-13- 289 Table 11-2 (Cont

Example no. Solvent composition dispersing effects 11-27 R253ca (100) O 11-28 R 253 cb (100) O 11-29 R244cb (75) / n-heptane (25) O 11-30 R244cb (75) / ethanol (25) O .11-31 244cb (75) / Acoton (25) O 11-32 244 cb (75) / trichlorethylene (25) O 11-33 244cb (75) / Ethyfacetat (25) O

The value in parentheses () means a proportion (% by weight) of evaluation standards:

O uniformly dispersed O substantially uniformly dispersed Δ slight nonuniformity X substantial nonuniformity

Table 11-3

Example no. Solvent composition dispersing effects 11-34 R226ca (100) O 11-35 R226cb (100) O 11-36 R 222c (100) O 11-37 R 223 ca (100) O 11-38 R 223 cb (100) O 11-39 R 224 cc (100) O 11-40 R 232 ca (100) O 11-41 R 232 cb (100) O 11-42 R233cb (100) O 11-43 R 233 ca (100) O 11-44 R233cc (100) O 11-45 R 242 cb (100) O 11-46 R 242 ca (100) O 11-47 R226ca (75) / n-heptane (25) O 11-48 R226ca (75) / ethanol (25) O 11-49 226ca (75VAceton (25) O 11-50 226ca (75) / trichlorethylene (25) O 11-51 226ca (75) / ethyl acetate (25) O

The value in brackets () means a percentage (6w%) of evaluation standards:

O uniformly dispersed O substantially uniformly dispersed Δ slight nonuniformity X substantial non-uniformity

Examples 12-1 to 12-11 The most important insulating property among insulating medium properties is volume resistivity.

Generally, a medium is considered to be a useful insulating medium if it has a volume resistivity of at least 10 ¹³ ncm.

The volume resistivity values of the insulating medium compositions of the present invention are shown in Table 12, in each case satisfying the above volume resistivity standard.

Example no. insulating volume resistivity 12-1 R 224 approx O 12-2 R224cb O 12-3 R225 approx O 12-4 R225cb O .12-5 R 234 cc O 12-6 R 235 approx O 12-7 R 243 cc O 12-8 R 244 approx O 12-9 R 252 approx O 12-10 R252cb O 12-11 R262 approx O

O: Volume resistance of at least 1 χ 10 ' ³ flcm.

The novel halogenated hydrocarbon solvents of the present invention are characterized by having extremely low ozone destruction power as compared with Π113, which has conventionally been used as a solvent, and lower in toxicity than conventional chlorinated hydrocarbon solvents such as trichlorethylene or perchlorethylene , They therefore do not pose any significant problem with regard to groundwater contamination.

When used for the various purposes, the solvents of the present invention are capable of providing substantially equivalent or even higher performance than the conventional R113 or chlorinated hydrocarbon type solvents.

Claims (4)

1. solvent mixture, characterized in that it consists essentially of at least 10 wt .-% of a compound of formula CH _a Cl _b F _c CF ₂ CH _x Cl _y F, _f (I) where a + b + c = 3, x + y + z = 3, a + xa1, b + y> 1, and 0: £ a, b, c, x, y, ζ ^ 3, and additionally off-to 80% by weight of an organic solvent selected from the group consisting of hydrocarbons, alcohols, ketones, chlorinated hydrocarbons, esters, aromatic compounds and / or up to 10% by weight of a surfactant. 2. A solvent mixture according to claim 1, characterized in that the compound of formula (I) CF ₃ CF ₂ CHCl ₂ is. 3. A solvent mixture according to claim 1, characterized in that the compound of formula (I) is CCIF ₂ CF ₂ CH ₂ CI. 4. Use of a compound of the formula