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Description  |
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TECHNICAL FIELD
The present invention relates to novel halogenated hydrocarbon solvents and
use thereof.
BACKGROUND ART
1,1,2-Trichloro-1,2,2-trifluoroethane (hereinafter referred to simply as
R113) is non flammable, non-explosive and stable with low toxicity and as
such, is widely used as a cleaning agent for a flux employed in the
assembling process of electronic parts or precision machine parts or for
cutting oils, or as a cleaning agent for clothings such as fur coats or
suits. Further, R113 is widely used for removing deposited water after the
washing treatment with water of liquid crystal display device parts,
electronic parts or precision machine parts. On the other hand, a rinsing
agent such as trichloroethylene 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 buffing agent deposited on precision metal parts or decorative
parts after the buffing treatment thereof. Further, 1,1,1-trichloroethane
is used for developing a resist in the preparation of a printed circuit
board or a semiconductor circuit, and methylene chloride or
perchloroethylene is used for removing the resist after etching treatment.
In spite of its various merits, R113 has been found to destroy ozone in the
stratosphere, which in turn brings about a skin cancer. On the other hand,
methylene chloride, trichloroethylene, perchloroethylene and
1,1,1-trichloroethane are likely to bring about a pollution of underground
water, and it is required to minimize the amount of their use.
Under these circumstances, it is an object of the present invention to
solve such problems and to provide a novel halogenated hydrocarbon solvent
as a substitute for the conventional solvents
DISCLOSURE OF THE INVENTION
The present invention provides a halogenated hydrocarbon solvent consisting
essentially of a hydrogencontaining chlorofluoropropane having a
difluoromethylene group represented by the formula:
CH.sub.a Cl.sub.b F.sub.c CF.sub.2 CH.sub.x Cl.sub.y F.sub.z(I)
wherein a+b+c=3, x+y+z=3, a+x.gtoreq.1, b+y.gtoreq.1, and 0.ltoreq.a, b, c,
x, y, z.ltoreq.3.
Now, the present invention will be described in detail with reference to
the preferred embodiments.
Specific examples of the compound of the formula I are as follows:
______________________________________
CClF.sub.2 CF.sub.2 CHCl.sub.2 (R224ca)
CCl.sub.2 FCF.sub.2 CHClF (R224cb)
CF.sub.3 CF.sub.2 CHCl.sub.2 (R225ca)
CClF.sub.2 CF.sub.2 CHClF (R225cb)
CClF.sub.2 CF.sub.2 CH.sub.2 Cl (R234cc)
CHF.sub.2 CF.sub.2 CHClF (R235ca)
CH.sub.3 CF.sub.2 CCl.sub.2 F (R243cc)
CHF.sub.2 CF.sub.2 CH.sub.2 Cl (R244ca)
CH.sub.2 ClCF.sub.2 CH.sub.2 Cl (R252ca)
CHCl.sub.2 CF.sub.2 CH.sub.3 (R252cb)
CH.sub.3 CF.sub.2 CH.sub.2 Cl (R262ca)
CHF.sub.2 CF.sub.2 CCl.sub.2 F (R225cc)
CHClFCF.sub.2 CHClF (R234ca)
CHF.sub.2 CF.sub.2 CHCl.sub.2 (R234cb)
CH.sub.2 FCF.sub.2 CCl.sub.2 F (R234cd)
CF.sub.3 CF.sub.2 CH.sub.2 Cl (R235cb)
CClF.sub.2 CF.sub.2 CH.sub.2 F (R235cc)
CH.sub.2 ClCF.sub.2 CHClF (R243ca)
CH.sub.2 FCF.sub.2 CHCl.sub.2 (R243cb)
CH.sub.2 FCF.sub.2 CHClF (R244cb)
CClF.sub.2 CF.sub.2 CH.sub.3 (R244cc)
CH.sub.2 FCF.sub.2 CH.sub.2 Cl (R253ca)
CH.sub.3 CF.sub.2 CHClF (R253cb)
CF.sub.3 CF.sub.2 CHClF (R226ca)
CClF.sub.2 CF.sub.2 CHF.sub.2 (R226cb)
CCl.sub.3 CF.sub.2 CHCl.sub.2 (R222c)
CCl.sub.2 FCF.sub.2 CHCl.sub.2 (R223ca)
CCl.sub.3 CF.sub.2 CHClF (R223cb)
CCl.sub.3 CF.sub.2 CHF.sub.2 (R224cc)
CHCl.sub.2 CF.sub.2 CHCl.sub.2 (R232ca)
CCl.sub.3 CF.sub.2 CH.sub.2 Cl (R232cb)
CCl.sub.2 FCF.sub.2 CH.sub.2 Cl (R233cb)
CHCl.sub.2 CF.sub.2 CHClF (R233ca)
CCl.sub.3 CF.sub.2 CH.sub.2 F (R233cc)
CCl.sub.3 CF.sub.2 CH.sub.3 (R242cb)
CHCl.sub.2 CF.sub.2 CH.sub.2 Cl (R242ca)
______________________________________
The compounds of the present invention represented by the formula I may be
used alone or in combination as a mixture of two or more. They are useful
as various cleaning agents including a cleaning agent for dry cleaning, a
degreasing agent, a cleaning agent for removing a buffing agent, a flux
cleaning agent and a rinsing agent, or as a resist developing agent or a
resist removing agent, or as a solvent for removing deposited water. They
are useful also for the following various purposes:
As a solvent for extracting nicotine contained in tobacco leaves or for
extracting pharmeceutical substances from animal or plants, as a diluent
for various chemical agents including a coating material, a releasing
agent, a water and oil repellant, a moisture-proof coating, a
water-proofing agent, a lustering agent and an antistatic agent, to
disperse or dissolve them to facilitate their application to the
respective objects, as an aerosol solvent for dissolving a chemical agent
or an active agent contained in an aerosol of e.g. a coating material, an
insecticide, a pharmaceutical, a sweat-preventing agent, a deodorant, a
hair conditioner or a cosmetic, and as an insulating medium for insulating
and cooling e.g. an oil-filled transformer or a gas-insulated transformer.
When the compounds of the present invention are employed for the
above-mentioned various purposes, it is preferred to incorporate various
other compounds depending upon the particular purposes.
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 in the use
as a cleaning solvent or to improve the effects in other uses. Such an
organic solvent may be incorporated usually in an amount of from 0 to 80%
by weight, preferably from 0 to 50% by weight, more preferably from 10 to
40% by weight, in the composition. The surfactant may be used usually in
an amount of from 0 to 10% by weight, preferably from 0.1 to 5% by weight,
more preferably from 0.2 to 1% by weight.
The hydrocarbon is preferably a linear or cyclic saturated or unsaturated
hydrocarbon having from 1 to 15 carbon atoms and is usually selected from
the group constiting 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-methylheptane, 4-methylheptane, 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. More preferred are
n-pentane, n-hexane, cyclohexane and n heptane.
The alcohol is preferably an aliphatic or cyclic saturated or unsaturated
alcohol having from 1 to 17 carbon atoms and is usually selected from the
group consisting of methanol, ethanol, n-propyl alcohol, isopropyl
alcohol, n-butyl alcohol, sec butyl aclohol, isobutyl alcohol, tert-butyl
aclohol, pentyl alcohol, sec-amyl alcohol, 1-ethyl-1-propanol,
2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol,
3-methyl-2butanol, neopentyl alcohol, 1-hexanol. 2-methyl-1pentanol,
4-methyl-2-pentanol, 2-ethyl-1-butanol, 1heptanol, 2-heptanol, 3-heptanol,
1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1 nonanol,
3,5,5-trimethyl-1-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, trimethyl nonylalcohol, tetradecyl alcohol and
heptadecyl alcohol. More preferred are methanol, ethanol and isopropyl
alcohol.
The ketone is preferably represented by one of the formulas
##STR1##
wherein each of R, R' and R" is a saturated or unsaturated hydrocarbon
group having from 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,
mesityl oxide, phorone, methyl-n-amyl ketone, ethyl butyl ketone, methyl
hexyl ketone, cyclohexanone, methylcyclohexanone, isophorone,
2,4-pentanedione, diacetone alcohol, acetophenone and fenchone. More
preferred are acetone and methyl ethyl ketone.
The chlorinated hydrocarbon is preferably a satuarted or unsaturated
chlorinated hydrocarbon having 1 or 2 carbon atoms and is usually 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, 1,1,2,2-tetrachloroethane,
pentachloroethane, 1,1-dichloroethylene, 1,2-dichloroethylene,
trichloroethylene and tetrachloroethylene. More preferred are methylene
chloride, 1,1,1-trichloroethane, trichloroethylene and
tetrachloroethylene.
The surfactant for a solvent for removing deposited water 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
alkyl phenol, a polyoxyethylene polypropylene alkyl phenol, a
polyoxyethylene sorbitan ester, a polyoxyethylene polyoxypropylene
sorbitan ester, caprylic acid caprylamine and a polyoxyethylene
alkylamide. More preferred are caprylic acid caprylamine and a
polyoxyethylene alkylamide. As the surfactant for a cleaning agent for dry
cleaning, various surfactants including non-ionic, cationic, anionic and
amphoteric surfactants may be employed. It is preferably 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
alkylphenyl ether phosphate, an .alpha.-olefin sulfonate, an
alkylsulfosuccinate, a polyoxyethylene alkyl ether, a polyoxyethylene
alkyl ester, 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
hydroxysulfobetaine, a polyoxyethylenelauryl ether, a
polyoxyethylenelauryl ether sodium sulfate, sodium dodecylbenzene
sulfonate and a higher alcohol sodium sulfate. More preferred are a
polyoxyethylenelauryl ether, a polyoxyethylenelauryl ether sodium sulfate,
sodium dodecylbenzene sulfonate and a higher alcohol sodium sulfate.
The aromatic compound is preferably a benzene derivative or a naphthalene
derivative and is usually selected from the group consisting of benzene,
toluene, xylene, ethylbenzene, isopropylbenzene, diethylbenzene,
sec-butylbenzene, triethylbenzene, diisopropylbenzene, styrene, an
alkylbenzene sulfonic acid, phenol, mesitylene, naphthalene, tetralin,
butylbenzene, p-cymene, cyclohexylbenzene, pentylbenzene, dipentylbenzene,
dodecylbenzene, biphenyl, o-cresol, m-cresol and xylenol. More preferred
are an alkylbenzene sulfonic acid and phenol.
The ester is preferably represented by one of the following formulas:
##STR2##
wherein each of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 is
H, OH or a saturated or unsaturated hydrocarbon group having from 1 to 19
carbon atoms. Specifically, it is selected from the group consisting of
methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl
formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate,
isopropyl acetate, butyl acetate, isobutyl acetate, secbutyl 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-methylpropionate, butyl stearate, methyl benzoate, ethyl
benzoate, propyl benzoate, butyl benzoate, isopentyl benzoate, benzyl
benzoate, ethyl abietate, benzyl abietate, bis-2ethylhexyl adipate,
.upsilon.-butyrolactone, diethyl oxalate, dibutyl oxalate, dipentyl
oxalate, diethyl malonate, dimethyl maleate, diethyl maleate, dibutyl
maleate, dibutyl tertarate, tributyl citrate, dibutyl sebacate, bis-2
ethylhexyl cebacate, dimethyl phthalate, diethyl phthalate, dibutyl
phthalate, bis-2-ethylhexyl phthalate and dioctyl phthalate. More
preferred are methyl acetate and ethyl acetate.
A chlorofluorinated hydrocarbon other than the compound of the formula I
may be incorporated to the compound of the present invention. When
azeotropy or pseudoazeotropy exists with a composition obtained by the
combination of the compound of the present invention with other compound,
it is preferred to use them under an azeotropic or pseudoazeotropic
condition so that there will be no variation in the composition when used
by recycling, or no substantial change from the conventional technique
will be required.
The cleaning agent for dry cleaning of the present invention may contain
various additives such as an antistatic agent, a softening agent, a stain
removing agent, a flame retardant, a water and oil repellant or a
stabilizer. As the stabilizer, various types which are commonly used for
the cleaning agent for dry cleaning, may be employed, including
nitroalkanes, epoxides, amines or phenols.
Various cleaning additives or stabilizers may be incorporated also to the
degreasing agent, the cleaning agent for the removal of a buffing agent,
or a flux cleaning agent. In the case of the cleaning agent for removing a
buffing agent, water may further be incorporated. As the cleaning method,
wiping by manual operation, dipping, spraying, shaking, supersonic
cleaning, steam cleaning or any other conventional method may be employed.
When it is necessary to stabilize the rinsing agent, it is preferred to
employ a nitroalkane, such as nitromethane, nitroethane or nitropropane,
or a cyclic ether such as propylene oxide, 1,2-butylene oxide,
2,3-butylene oxide, epichlorohydrin, styrene oxide, butyl glycidyl ether,
phenyl glycidyl ether, glycidol, 1,4-dioxane, 1,3,5-trioxane,
1,3-dioxolan, dimethoxymethane or 1,2-dimethoxyethane, in an amount of
from 0.001 to 5.0% by weight, in combination.
There is no particular restriction as to the resist to be developed or to
be removed by the present invention. The resist may be a positive or
negative resist for exposure, a resist for exposure with far ultraviolet
rays or a resist for exposure with X-rays or with electron beams. The
resist for exposure with light includes a quinone diazide type having
phenol and cresol novolak resin as the base materials, a cyclic rubber
type having cis-1,4-polyisoprene as the essential component and a
polycinnamate type. Likewise, the resist for exposure with far ultraviolet
rays includes polymethyl methacrylate and polymethylisopropenyl ketone.
The resist for exposure with electron beam or with X-rays includes
poly(methyl methacrylate), a glycidyl methacrylate-ethyl acrylate
copolymer, and a methyl methacrylate-methacrylic acid copolymer.
For the removal of deposited water by means of the solvent for removing
deposited water according to the present invention, it is possible to
employ a spraying or showering method or a dipping method in a cool bath,
a warm bath, a steam bath or a supersonic bath, or a dipping method with a
combination of these baths.
The insulating medium of the present invention may be used in combination
with a mineral oil type insulating medium, a completely halogenated
hydrocarbon type insulating medium or a silicone oil insulating medium,
which is commonly employed in this field. Further, for the purpose of
stabilization, a stabilizing agent such as a phosphite compound, a
phosphine sulfide compound or a glycidyl ether compound may be
incorporated, or a phenol or amine antioxidant may be used in combination.
Now, the present invention will be described in further detail with
reference to Examples. However, it should be understood that the present
invention is by no means restricted to such specific Examples.
EXAMPLES 1--1 to 1-16
Cleaning tests for cleaning power were conducted by using the dry cleaning
agents as identified in Table 1. A soiled cloth (5.times.5 cm) of wool
having carbon soil fixed by a Yukagaku Kyokai method was put into a
Scrub-O-meter cleaning machine and washed at 25.degree. C. for 25 minutes,
whereupon the cleaning effects were measured by an ELREPHO photoelectric
reflection meter. The results are shown in Table 1.
TABLE 1
______________________________________
Example No.
Dry cleaning agents
Cleaning effects
______________________________________
Example 1-1
R225ca (100) .circleincircle.
Example 1-2
R225cb (100) .circleincircle.
Example 1-3
R224ca (100) .circleincircle.
Example 1-4
R224cb (100) .circleincircle.
Example 1-5
R235ca (100) .circleincircle.
Example 1-6
R234cc (100) .circleincircle.
Example 1-7
R244ca (100) .circleincircle.
Example 1-8
R243cc (100) .circleincircle.
Example 1-9
R252ca (100) .circleincircle.
Example 1-10
R252cb (100) .circleincircle.
Example 1-11
R262ca (100) .circleincircle.
Example 1-12
R225ca (75)/n-heptane (25)
.circleincircle.
Example 1-13
R225ca (75)/ethanol (25)
.circleincircle.
Example 1-14
R225ca (75)/perchloro-
.circleincircle.
ethylene (25)
Example 1-15
R225ca (75)/acetone (25)
.circleincircle.
Example 1-16
R225ca (75)/sodium dodecyl-
.circleincircle.
benzene sulfonate (25)
______________________________________
The value in the bracket () represents a proportion (% by weight).
Evaluation Standards:
.circleincircle. Stain satisfactorily removed.
.largecircle. Stain substantially satisfactorily removed.
.DELTA. Stain slightly remained.
X Stain substantially remained.
EXAMPLES 2-1 to 2-16
Cleaning tests of cutting oil were conducted by using the degreasing agents
as identified in Table 2.
A test piece (25 mm .times. 30 mm .times. 2 mm) of SUS-304 was dipped in
spindle oil, and then dipped in the degreasing agent for 5 minutes. Then,
the test piece was taken out, and the state of the spindle oil remaining
on the surface of the test piece was visually evaluated. The results are
shown in Table 2.
TABLE 2
______________________________________
Example No.
Degreasing agent Degreasing effects
______________________________________
Example 2-1
R225ca (100) .circleincircle.
Example 2-2
R225cb (100) .circleincircle.
Example 2-3
R224ca (100) .circleincircle.
Example 2-4
R224cb (100) .circleincircle.
Example 2-5
R235ca (100) .circleincircle.
Example 2-6
R234cc (100) .circleincircle.
Example 2-7
R244ca (100) .circleincircle.
Example 2-8
R243cc (100) .circleincircle.
Example 2-9
R252ca (100) .circleincircle.
Example 2-10
R252cb (100) .circleincircle.
Example 2-11
R262ca (100) .circleincircle.
Example 2-12
R225ca (75)/n-heptane (25)
.circleincircle.
Example 2-13
R225ca (75)/ethanol (25)
.circleincircle.
Example 2-14
R225ca (75)/acetone (25)
.circleincircle.
Example 2-15
R225ca (75)/trichloro-
.circleincircle.
ethylene (25)
Example 2-16
R225ca (75)/ethyl acetate (25)
.circleincircle.
______________________________________
The value in the bracket () represents a proportion (% by weight).
Evaluation Standards:
.circleincircle. Satisfactorily degreased.
.largecircle. Substantially satisfactorily degreased.
.DELTA. Oil slightly remained.
X Oil substantially remained.
EXAMPLES 3-1 to 3-16
Tests for removing a buffing agent were conducted by using the cleaning
agents for removing a buffing agent as identified in FIG. 3.
A wrist watch frame was polished with a buffing agent (GS-1, manufactured
by Soken Kogyo K. K.) and then immersed in the cleaning agent for removing
a buffing agent, and a supersonic wave was applied thereto for 3 minutes.
Then, it was taken out and inspected for the removal of the buffing agent.
The results are shown in Table 3.
TABLE 3
______________________________________
Cleaning agent for
Example No. removing a buffing agent
Results
______________________________________
Example 3-1 R225ca (100) .circleincircle.
Example 3-2 R225cb (100) .circleincircle.
Example 3-3 R224ca (100) .circleincircle.
Example 3-4 R224cb (100) .circleincircle.
Example 3-5 R235ca (100) .circleincircle.
Example 3-6 R234cc (100) .circleincircle.
Example 3-7 R244ca (100) .circleincircle.
Example 3-8 R243cc (100) .circleincircle.
Example 3-9 R252ca (100) .circleincircle.
Example 3-10
R252cb (100) .circleincircle.
Example 3-11
R262ca (100) .circleincircle.
Example 3-12
R225ca (75)/n-hexane (25)
.circleincircle.
Example 3-13
R225ca (75)/ethanol (25)
.circleincircle.
Example 3-14
R225ca (75)/ethanol (25)
.circleincircle.
Example 3-15
R225ca (75)/1,1,1-trichloro-
.circleincircle.
ethane (25)
Example 3-16
R225ca (75)/ethyl acetate (25)
.circleincircle.
Comparative 1,1,1-trichloroethane (100)
.largecircle.
Example 3-1
______________________________________
The value in the bracket () represents a proportion (% by weight).
Evaluation Standards:
.circleincircle. Buffing agent satisfactorily removed.
.largecircle. Buffing agent substantially satisfactorily removed.
.DELTA. Buffing agent slightly remained.
X Buffing agent substantially remained.
EXAMPLES 4-1 to 4-15
Flux cleaning tests were conducted by using the flux cleaning agents as
identified in Table 4.
A flux (Tamura F-Al-4, manufactured by Kabushiki Kaisha Tamura Seisakusho)
was coated on the entire surface of a printed circuit board (a copper-clad
laminate) and baked in an electric furnace at 200.degree. C. for 2
minutes. Then, the board was immersed in the flux cleaning agent for one
minute. The degree of the removal of the flux is shown in Table 4.
TABLE 4
______________________________________
Example No.
Flux cleaning agents
Cleaning effects
______________________________________
Example 4-1
R225ca (100) .circleincircle.
Example 4-2
R225cb (100) .circleincircle.
Example 4-3
R224ca (100) .circleincircle.
Example 4-4
R224cb (100) .circleincircle.
Example 4-5
R235ca (100) .circleincircle.
Example 4-6
R234cc (100) .circleincircle.
Example 4-7
R244ca (100) .circleincircle.
Example 4-8
R243cc (100) .circleincircle.
Example 4-9
R252ca (100) .circleincircle.
Example 4-10
R252cb (100) .circleincircle.
Example 4-11
R262ca (100) .circleincircle.
Example 4-12
R225ca (75)/n-heptane (25)
.circleincircle.
Example 4-13
R225ca (75)/methanol (25)
.circleincircle.
Example 4-14
R225ca (75)/acetone (25)
.circleincircle.
Example 4-15
R225ca (75)/trichloro-
.circleincircle.
ethylene (25)
______________________________________
The value in the bracket () represents a proportion (% by weight).
Evaluation Standards:
.circleincircle. Flux satisfactorily removed.
.largecircle. Flux substantially satisfactorily removed.
.DELTA. Flux slightly remained.
.DELTA. Flux substantially remained.
EXAMPLES 5-1 to 5-7
A positive resist (OFPR-800, manufactured by Tokyo Okasha) or a negative
resist (OMR-83, manufactured by Tokyo Okasha) was coated on a silicon
wafer, followed by etching treatment, then the silicon wafer was immersed
in an o-dichlorobenzene type resist removing solution (resist removing
solution-502, manufactured by Tokyo Okasha) at 120.degree. C. for 10
minutes and then immersed in the rinsing agent as identified in Table 5 at
25.degree. C. for 3 minutes. Further, it was immersed and cleaned in an
IPA/MEK mixed solution and then in superpure water and then dried,
whereupon the surface condition was inspected by a microscope.
TABLE 5
______________________________________
Rinsing Proportions
Example No.
agents (wt %) Results
______________________________________
Example 5-1
R225ca 100 No fine particles
detected on the surface
Example 5-2
R225cb 100 No fine particles
detected on the surface
Example 5-3
R243cc 100 No fine particles
detected on the surface
Example 5-4
R244ca 100 No fine particles
detected on the surface
Example 5-5
R262ca 100 No fine particles
detected on the surface
Example 5-6
R225 ca 90 No fine particles
Heptane 10 detected on the surface
Example 5-7
R244ca 90 No fine particles
Heptane 10 detected on the surface
______________________________________
EXAMPLES 6-1 to 6-16
Resist developing tests were conducted by using the resist developing
agents as identified in Table 6.
A printed circuit board (a copper-clad laminate) having a photoresist film
(Laminer, manufactured by Dynachem Co.) laminated thereon, was exposed to
have a predetermined circuit pattern and then developed with th resist
developing agent, whereupon the surface was inspected by a microscope to
see if the circuit pattern was properly formed. The results are shown in
Table 6.
TABLE 6
______________________________________
Results of
Example No.
Resist developing agent
inspection
______________________________________
Example 6-1
R225ca (100) .circleincircle.
Example 6-2
R225cb (100) .circleincircle.
Example 6-3
R224ca (100) .circleincircle.
Example 6-4
R224cb (100) .circleincircle.
Example 6-5
R235ca (100) .circleincircle.
Example 6-6
R234cc (100) .circleincircle.
Example 6-7
R244ca (100) .circleincircle.
Example 6-8
R243cc (100) .circleincircle.
Example 6-9
R252ca (100) .circleincircle.
Example 6-10
R252cb (100) .circleincircle.
Example 6-11
R252ca (100) .circleincircle.
Example 6-12
R225ca (75)/n-pentane (25)
.circleincircle.
Example 6-13
R225ca (75)/ethanol (25)
.circleincircle.
Example 6-14
R225ca (75)/acetone (25)
.circleincircle.
Example 6-15
R225ca (75)/1,1,1- .circleincircle.
trichloroethane (25)
Example 6-16
R225ca (75)/methyl acetate (25)
.circleincircle.
Comparative
1,1,1-trichloroethane (100)
.largecircle.
Example 6-1
______________________________________
The value in the bracket () represents a proportion (% by weight).
Evaluation Standards:
.circleincircle. Satisfactorily developed.
.largecircle. Substantially satisfactorily developed.
.DELTA. Slightly inferior
X Inferior
EXAMPLES 7-1 to 7-17
Resist removing tests were conducted by using the resist removing agents as
identified in Table 7.
A printed circuit board (a copper-clad laminate) having a photoresist film
(Laminer, manufactured by Dynachem Co.) laminated thereon, was subjected
to exposure, development and etching treatments to form a printed circuit
and then immersed in the resist removing agent at room temperature for 15
minutes. The board was taken out and inspected by a microscope to see the
state of removal of the cured film. The results are shown in Table 7.
TABLE 7
______________________________________
Example No.
Resist removing agent
Results
______________________________________
Example 7-1
R225ca (100) .circleincircle.
Example 7-2
R225cb (100) .circleincircle.
Example 7-3
R224ca (100) .circleincircle.
Example 7-4
R224cb (100) .circleincircle.
Example 7-5
R235ca (100) .circleincircle.
Example 7-6
R234cc (100) .circleincircle.
Example 7-7
R244ca (100) .circleincircle.
Example 7-8
R243cc (100) .circleincircle.
Example 7-9
R252ca (100) .circleincircle.
Example 7-10
R252cb (100) .circleincircle.
Example 7-11
R262cb (100) .circleincircle.
Example 7-12
R225ca (75)/n-pentane (15)
.circleincircle.
alkylbenzene sulfonic
acid (10)
Example 7-13
R225ca (75)/ethanol (15)
.circleincircle.
alkylbenzene sulfonic
acid (10)
Example 7-14
R225ca (75)/acetone (15)
.circleincircle.
phenol (10)
Example 7-15
R225ca (75)/methylene
.circleincircle.
chloride (15) phenol (25)
Example 7-16
R225ca (75)/phenol (25)
.circleincircle.
Example 7-17
R225ca (75)/methyl acetate (25)
.circleincircle.
Comparative
Tetrachloroethylene (100)
.largecircle.
Example 7-1
Comparative
o-Dichlorobenzene (100)
.largecircle.
Example 7-2
______________________________________
The value in the bracket () represents a proportion (% by weight).
Evaluation Standards:
.circleincircle. Resist satisfactorily removed.
.largecircle. Resist substantially satisfactorily removed.
.DELTA. Resist slightly remained.
X Resist substantially remained.
EXAMPLES 8-1 to 8-16
Tests for removing deposited water were conducted by using the solvents for
removing deposited water as identified in Table 8.
A glass sheet of 30 mm .times. 18 mm .times. 5 mm was immersed in pure
water and then immersed i | | |
