U.S. patent number 3,617,438 [Application Number 05/011,019] was granted by the patent office on 1971-11-02 for electric insulating paper and its production process.
This patent grant is currently assigned to Tomoegawa Paper Manufacturing Co., Ltd.. Invention is credited to Juichi Hirose, Shinji Matsuda, Toshio Nakamura, Osakazu Nakao, Hidetaro Suzuki, Hiroyuki Yamamoto.
United States Patent |
3,617,438 |
Nakao , et al. |
November 2, 1971 |
ELECTRIC INSULATING PAPER AND ITS PRODUCTION PROCESS
Abstract
A process for the production of an electric insulating paper and
the insulating paper thus produced, having superior characteristics
such as a low dielectric constant, a low dielectric loss tangent,
and a high dielectric strength, is disclosed. The process comprises
the steps of preparing a graft-cellulose solution, or a mixed
solution or suspension consisting of a synthetic polymer mixed into
a cellulose solution or a graft-cellulose solution, solidifying the
solution, mixed solution, or suspension into a regenerating
substance such as air or a precipitant, forming the regenerated
substance thus solidified into a pulplike substance adapted to be
fabricated into a paper, and forming the pulplike substance only or
the pulplike substance mixed with the ordinary beaten pulp into an
insulating paper.
Inventors: |
Nakao; Osakazu (Shizuoka,
JA), Hirose; Juichi (Shizuoka, JA),
Nakamura; Toshio (Shizuoka, JA), Yamamoto;
Hiroyuki (Shizuoka, JA), Matsuda; Shinji
(Shizuoka, JA), Suzuki; Hidetaro (Shizuoka,
JA) |
Assignee: |
Tomoegawa Paper Manufacturing Co.,
Ltd. (Tokyo, JA)
|
Family
ID: |
11744934 |
Appl.
No.: |
05/011,019 |
Filed: |
February 12, 1970 |
Foreign Application Priority Data
|
|
|
|
|
Feb 12, 1969 [JA] |
|
|
10246/1969 |
|
Current U.S.
Class: |
162/138; 264/188;
162/146; 162/158; 162/157.7; 264/187; 264/207 |
Current CPC
Class: |
H01B
3/485 (20130101); D21H 5/143 (20130101); D21H
11/04 (20130101); D21H 11/20 (20130101) |
Current International
Class: |
H01B
3/48 (20060101); H01B 3/18 (20060101); D21h
003/02 (); D21h 005/12 () |
Field of
Search: |
;260/17.4R,17.4CL
;252/63.2 ;106/203 ;162/138,146,157,158,182 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Bashore; S. Leon
Assistant Examiner: Frei; Frederick
Claims
What is claimed is:
1. A method of producing an electrical insulating paper comprising
the steps of (1) preparing a synthetic polymer cellulose liquid
mixture by mixing a synthetic polymer with a member selected from
the group consisting of a cellulose and a grafted cellulose
solution; (2) extruding the thus-prepared liquid mixture into a
medium for regenerating the polymer cellulose as a solid; (3)
forming the regenerated polymer cellulose into a configuration
adapted to be processed into a paper; and (4) processing the thus
formed polymer cellulose into a paper of sheet form; said paper in
a sheet form containing a synthetic polymer in a range of from 20
to 80 weight percent.
2. The process of claim 1 wherein said liquid mixture of step (1)
is a solution.
3. The process of claim 1 wherein said liquid mixture of step (1)
is a dispersion.
4. The process of claim 1 wherein said medium of step (2) is
air.
5. The process of claim 1 wherein said medium of step (2) is a
liquid precipitant.
6. The process of claim 1 wherein said configuration of step (3) is
pulp.
7. The process of claim 1 wherein said polymer cellulose of step
(4) is blended with additional beaten pulp containing no synthetic
polymer.
8. The process of claim 7 wherein said configuration of step (3) is
a granular configuration.
9. The method of claim 1 wherein the synthetic polymer cellulose
liquid mixture is prepared using a solvent system selected from the
group consisting of (a) a system consisting of an organic solvent,
sulfurous acid anhydride, and an amine, selected from the group
consisting of aliphatic primary amines, aliphatic secondary amines,
aliphatic tertiary amines and alicyclic secondary amines, (b) a
system consisting of an organic solvent, and nitrogen dioxide, (c)
a system consisting of an organic solvent and nitrosyl chloride,
(d) a system consisting of an organic solvent, and chloral
anhydride, and (e) a system consisting of liquefied sulfurous acid
and an amine selected from the group consisting of aliphatic
primary amines, aliphatic secondary amines, aliphatic tertiary
amines and alicyclic secondary amines.
10. The method of claim 1 wherein said synthetic polymer is
selected from a group consisting of a polycarbonate, a
polyphenylenoxide, a polysulfone, a polystyrene, a cross-linked
polyethylene, a polytetrafluoroethylene, a
polytrifluorochloroethylene, a polypropylene, a polyacetal, a
poly-4-methyl pentane-1, a polyvinylcarbazole, a polyester, and a
polyfluoroethylenepropylene copolymer.
11. The method of claim 1 wherein said graft cellulose is selected
from the group consisting of a styrene grafted cellulose, a
silicone-grafted cellulose, and a vinyl-grafted cellulose.
12. An electric insulating paper having superior electrical
characteristics, produced by the steps (1) preparing a synthetic
polymer cellulose liquid mixture by mixing a synthetic polymer with
a member selected from the group consisting of a cellulose solution
and a grafted cellulose solution; (2) extruding the thus prepared
liquid mixture into a medium for regenerating the polymer cellulose
as a solid; (3) forming the regenerated polymer cellulose into a
configuration adapted to be processed into a paper; and (4)
processing the thus formed polymer cellulose into a paper of sheet
form; said paper in a sheet form containing a synthetic polymer in
a range of from 20 to 80 weight percent.
13. The electric insulating paper of claim 12 wherein said
synthetic polymer is selected from the group consisting of a
polycarbonate, a polyphenyleneoxide, a polysulfone, a polystyrene,
a cross-linked polyethylene, a polytetrafluoroethylene, a
polytrifluorochloroethylene, a polypropylene, a polyacetal, a
poly-4-methylpentane-1, a polyvinylcarbazole, a polyester, and a
polyfluoroethylenepropylene copolymer.
14. The electric insulating paper of claim 12 wherein said grafted
cellulose is selected from the group consisting of a
styrene-grafted cellulose, silicone-grafted cellulose, and a
vinyl-grafted cellulose.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a process for the production of an
electric insulating paper and also to the insulating paper itself,
which has a far lower dielectric constant and dielectric loss
tangent (tan .delta.), a higher dielectric strength, and superior
oil resistance and heat resistance than conventional electric
insulating papers.
2. Prior Art
Recently, the voltage rating of electric power cables has
increased, for example, extrahigh-voltage electric power cables of
500kv. are now being employed, and furthermore, with the progress
in atomic power generation, a cable of more than 750 kv. is going
to be needed in the near future.
In electric power cables carrying such extrahigh voltages, electric
insulating materials of far lower dielectric constants and
dielectric loss tangents, of higher dielectric strengths, and of
superior oil resistance and heat resistance, and having structures
easily impregnated with insulating oil are required for their
construction. Furthermore, the above-mentioned features of the
insulating materials must be maintained for long periods. For
instance, in an extrahigh voltage cable of 500 kv., it is
considered essential that the dielectric constant be lower than 3.0
and the dielectric loss tangent (tan .delta.) be less than 0.1
percent (under the condition of 80.degree. C., oil filled, and with
the application of 10 kv./mm.).
Heretofore, deionized insulating paper has been employed in a 275
kv. transmission cable. However, in a transmission cable of a
voltage of 500 kv. or more, and when the cable is employed as a
long distance line, even the dielectric constant and the dielectric
loss tangent of the deionized insulating paper are still too large,
resulting in the disadvantage that the transmission capacity of the
cable is considerably decreased by use of such insulating
paper.
Recently, various synthetic polymers having lower dielectric
constants and dielectric loss tangents well adapted to be employed
in the extrahigh-voltage transmission cables have been developed.
For instance, polycarbonates or polyphenylene oxides employed in
the form of film or tape have been suggested for use in the cables.
However, such a material has the drawbacks of an inferior
mechanical strength when it is employed in the form of a thin film
of from 20 to 30 microns, although the impulse breakdown strength
thereof is considerably high, and of abruptly decreasing its
impulsive breakdown strength when it is employed in the form of
thick film of more than 100 microns although the mechanical
strength is improved. In the last case, the impulse breakdown
strength is decreased to about 100 kv./mm. Furthermore, when the
above described synthetic materials are employed in the cable,
there is a great chance of causing crazing and cracking, and the
materials have a tendency to swell under the action of the
insulating oil, so that when used in the cable sufficient passages
for the insulating oil are difficult to be maintained. For these
reasons, the synthetic polymers or plastic films have not yet been
employed practically in extrahigh-voltage transmission cables.
To eliminate the above-described drawbacks of the synthetic polymer
or plastic film, a method of winding the plastic film
interleavingly between sheets of paper on conductor or bonding the
plastic film beforehand with a sheet of paper has also been
proposed. However, with such a method, the above-described
disadvantages of the plastic film, namely, the tendency for
swelling or being dissolved in the insulating oil or of causing
crazing and cracking cannot be fully eliminated. Furthermore, the
dielectric strength of the composite material is comparatively low
and the oil passages are also difficult to be maintained as in the
case of the plastic tape.
Another attempt for eliminating the above-mentioned drawbacks of
the plastic film and for utilizing joiningly the advantageous
features of the synthetic polymers and those of paper, an
insulating paper wherein fine particles, filaments, or fibers of
the polymer are built into the paper together with the pulp has
also been studied. However, difficulties have been experienced in
this process due to the difference of specific gravities between
the synthetic polymer and cellulose pulp and in its lowered
mechanical strength. Since the mixing process of the synthetic
polymer and cellulose is carried out in a macroscopic scale,
various disadvantages found in the plastic film result in this
mixed paper, and the dielectric loss tangent of the mixed paper is
increased abruptly during its long working period, or the density
and air tightness of the mixed paper tend to be low because of the
difference in affinity of the synthetic polymer and the cellulose.
This results in an inferior dielectric strength to the ordinary
insulating paper. For this reason, this method has not yet been
successfully employed in the production of an insulating paper to
be employed in extrahigh-voltage cables.
Investigations into this problem from the point that, for the
purpose of obtaining a superior electric insulating paper by
combining the oil-resistant and stable nature of cellulose, the
facility for oil immersion due to the porous structure of paper,
and the low dielectric constant, the low dielectric loss tangent,
the high dielectric strength, and the high heat resistance of the
synthetic polymer, there is the necessity for coupling the
component elements on a more microscopic molecular level, differing
from the above-described macroscopic coupling, between the
cellulose and the synthetic polymers. As a result, a successful
production of an insulating paper employable in extrahigh-voltage
power cables and having a low dielectric constant, a low dielectric
loss tangent, a high dielectric strength, superior heat-resistance
and oil-resistance nature, and a high mechanical strength has
resulted.
SUMMARY OF THE INVENTION
The insulating paper according to the present invention is
characterized in that the synthetic polymer and the cellulose are
coupled or connected at a molecular level. More specifically, novel
organic solvent capable of dissolving the cellulose is employed and
the thus-obtained solution is added to another solution containing
the synthetic polymer for blending the cellulose together with the
synthetic polymer. By regeneratively solidifying the solution thus
blended in a precipitant, a mixed product of the cellulose and the
synthetic polymer can be obtained. When the product is beaten and
made into a fibrillic substance, a pulplike substance can be
obtained, and when this pulplike substance is added to the required
amount of beaten pulp and made into paper, a product having a
paperlike structure and a porous nature and wherein the synthetic
polymer and the cellulose are mixed in a molecular level can be
obtained.
Comparing the electric insulating paper thus obtained with the
conventional electric insulating paper, the electric insulating
paper of this invention has a far lower dielectric constant, a
lower dielectric loss tangent, a high dielectric strength, and
sufficient oil passages due to its porous nature than the
conventional paper. Furthermore, the mechanical characteristics,
such as tensile strength, elongation, tearing strength, and Young's
coefficient, is equivalent or slightly higher than those of
conventional insulating paper. In the insulating paper according to
the present invention, since the synthetic polymer and the
cellulose are mixed on a microscopic molecular level, the cracking
and crazing caused in the conventional plastic films are not
created therein, and the advantageous features of having a
sufficient oil resistance, facility in making into paper in
comparison with the conventional construction wherein particles or
fibers of the synthetic polymer are mixed together, a high density
and air tightness, and a superior dielectric strength are thereby
achieved. Furthermore, in the novel insulating paper, the heat
resistance of the synthetic polymer is utilized, so that a cable
employing the insulating paper can endure higher temperatures than
conventional insulating papers and can be used for a longer period
than the conventional insulating paper.
Furthermore, also in accordance with the present invention, a
suitable synthetic polymer which is insoluble in organic solvents
but has a superior electric nature, for example, cross-linked
polyethylene, polytetrafluoroethylene, or polypropylene, is added
in the form of fine particles into the cellulose solution so that
the synthetic polymer and the cellulose are blended together. The
mixed solution may be solidified thereafter in a fibrous or
granular configuration. In this way, the fine particles of the
synthetic polymer are incorporated within the cellulose in such a
manner that the synthetic polymer is enveloped by the cellulose,
and the insulating paper, obtained from the fibrous or granular
substance subsequently being made into paper together with the
beaten pulp, has equivalent characteristics to that obtained by the
above-described procedure wherein the synthetic polymer is blended
in its liquid state. That is, the insulating paper thus obtained
has a far superior heat resistance, oil resistance, and a more
stable nature than the conventional insulating paper made of
synthetic fibers or of synthetic polymer fibers.
Various methods other than those described herein for dissolving
cellulose have been known,. However, most of the methods utilize
water as the solvent, hence it is impossible to blend cellulose
with the synthetic polymer. Furthermore, since most of the methods
also use inorganic metallic salts in the procedure, the remaining
metallic ions in the regenerated cellulose deleteriously affect the
dielectric loss tangent even if the cellulose is blended with the
synthetic polymer.
In contrast to the above methods, the method according to the
present invention utilizes an organic solvent for dissolving the
cellulose, so that the blending of cellulose with the synthetic
polymer can be facilitated. The mixture thus blended does not
include any metallic ions which deleteriously affect the dielectric
loss tangent.
DETAILED DESCRIPTION OF THE INVENTION
Prior to describing the invention in more detail, four methods for
dissolving cellulose will be briefly indicated as follows:
1. A method for dissolving cellulose employing an organic solvent,
an amine, and sulfurous anhydride (SO.sub.2) is described in
Japanese Pat. Pub. Nos. 32671/1969, 2113/1970, and Japanese
Application No. 38808/1968.
As the amine employed in this method, an aliphatic primary,
secondary, or tertiary amine, or an alicyclic secondary amine, for
example, isobutylamine, secondary butylamine, tertiary butylamine,
dimethylamine, diethylamine, trimethylamine, triethylamine,
piperidine, or pyrolydone is advantageously employed. As an organic
solvent, following substances can be employed:
Formamide, N-methylformamide, N,N-dimethylformamide, acetamide,
dimethylsulfoxide, diethylsulfoxide, acetonitrile, propionitrile,
n-butyronitrile, benzonitrile, nitrobenzene, methylene chloride,
chloroform, 1,1-dichloroethane, ethylenechloride,
.gamma.-butyrolactone, methylthiocyanate, ethylthiocyanate,
ethylene carbonate, and propylene carbonate.
Cellulose is added to any one of the above-described solvents so
that the cellulose is dispersed in a slurrylike manner in the
solvent, and more than 3 mols of an amine and sulfurous acid
anhydride respectively for each glucose residue are added so that
the cellulose is dissolved.
2. A method for dissolving cellulose employing an organic solvent
and nitrogen dioxide is described in Japanese Pat. Publication No.
2114/1970 and Japanese application No. 38809/1968:
Organic solvents not including an active hydrogen, such as
N,N-dimethylformamide, N,N-diethylformamide, acetonitrile,
propionitrile, diethylsulfoxide, N-methyl-2-pyrrolidone, methyl
formate, ethyl formate, methyl acetate, ethyl acetate, n-butyl
acetate, methyl propionate, cellosolve acetate,
.delta.-butyroloctone, nitromethane, nitroethane, nitrobenzene,
1,4-dioxane, tetrahydrofuran, pyridine, and the like can be
employed, and any one of the above-described organic solvents is
added to the cellulose so that the cellulose is thereby dispersed.
More than 3 mols for each residue of glucose, of nitrogen dioxide
as a liquid or a gas are added to the above-described solution so
that the cellulose is thereby dissolved.
3. A method for dissolving cellulose employing an organic solvent
and nitrosyl chloride (NOC1) is described in Japanese Pat.
Application No. 92225/1968:
Cellulose is dispersed into an organic solvent such as
dimethylsulfoxide, diethylsulfoxide, N,N-dimethylformamide,
N,N-dinethylacetamide, N-methyl-2-pyrrolidone, pyridine and the
like, Nitrosyl chloride, more than 3 mols for each glucose residue,
is added so that the cellulose is dissolved in the solvent.
4. A method for dissolving cellulose employing an organic solvent
and chloral anhydride is described in Japanese Pat. Application NO.
92224/1968:
Cellulose is dispersed into an organic solvent such as
dimethylsulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide,
pyridine, N-methyl-2-pyrrolidone, and the like, and adding chloral
anhydride of more than 5 mols per each glucose residue is added so
that the cellulose is dissolved in the solvent.
All of the above-described methods for dissolving cellulose can be
carried out generally at room temperature and atmospheric pressure,
and the time period required for the dissolution ranges from
several minutes to several hours. Cellulose to be dissolved in the
solvent can be selected from a group consisting of chemical
woodpulp, cotton linter, depolymerized cellulose, and regenerated
cellulose. However, from the point of view of employing in an
electric insulting paper, any kind of cellulose not including any
impurity, for instance, nonbleached kraft-pulp, can be
employed.
Furthermore, still another method for dissolving cellulose
employing substances including no hydrogen is as follows:
5. A method for dissolving cellulose employing liquid sulfurous
acid and an amine:
In this method, no organic solvent is employed, and an amine as
described in method (1) above is added into the liquid sulfurous
acid whereby the cellulose is dissolved at a room temperature and
at atmospheric pressure.
Production processes of electric insulating paper according to the
present invention will not be described in greater detail.
A cellulose solution is produced firstly employing any one of the
five methods described above, and, in this solution, one, two, or
more types of synthetic polymers having low dielectric loss tangent
are added as a liquid or as a fine powder, thus blending the
cellulose with the synthetic polymer or polymers. The blended
solution is thereafter extruded into air or into a precipitant for
the blended solution so that a regenerative solidification thereof
can be obtained. For the purpose of obtaining a pulplike substance
or granules thereof to be made into paper from the mixed
solidification of the cellulose and the synthetic polymer or
polymers, the following methods are suitable.
1. As in the case of spinning viscose or synthetic polymeric
threads, the blended solution of cellulose and the synthetic
polymer or polymers is spun into air or a liquid, employing a dry
or wet method, and, after the spun solution is solidified, the
solid material is then cut into short fibers. When these short
fibers are beaten, if it is required, and then fibrillated, the
pulplike substance to be employed for producing insulating paper
can be obtained.
2. Employing a nozzle diameter larger than in the case of item (1)
but less than 3 mm., the blended solution is spun into air or into
a precipitant from a predetermined height in a manner not exerting
any elongating force, so that the spun substance is solidified into
fibers. The fibers thus obtained are subsequently cut into a
predetermined length and beaten, if it is required, so that the
material is thereby fibrillated, and the pulplike substance to be
used in insulating paper can be obtained.
3. A blended solution of cellulose and a synthetic polymer is
extruded through a nozzle into a precipitant for the blended
solution, and the regenerated substance thus obtained is fibrilized
into a pulplike substance by rotating quickly the precipitant and
employing a shearing force.
4. After the above-described blended solution is solidified
regeneratively into a filmlike configuration, the solidified
substance is split into a split-fiber, which is thereafter made
into pulplike substance through a beating process, if it is
required.
5. After the above-described blended solution is solidified
regeneratively into any desired configuration, the solidified
substance is formed into any granular configuration such as
globular, flat, or any other shape.
6. In any of the above-described five methods from (1) to (5), a
water-soluble polymer, for instance, methyl cellulose, or ethyl
cellulose is further added for the purpose of promoting
fibrillation, and after solidification, the water-soluble polymer
can be removed by dissolving it during the beating process for
fibrillating the solidified substance.
Although the pulplike substance obtained from the blended solution
of cellulose and a polymer in accordance with the above-described
methods is in itself easily made into paper, if it is required, an
ordinary beaten pulp can be further added to the above-described
pulp-like or granular substance which is thereafter made into
paper, so that the content of the synthetic polymer is about 20 to
80 weight percent of the paper, and, in this way, an electric
insulating paper of superior electrical and mechanical
characteristics can be obtained.
As the mixing methods of the cellulose and the synthetic polymer,
not only merely adding the synthetic polymer into the cellulose
solution as described above, but also a method which comprises
dispersing cellulose in slurry state into a synthetic polymer
solution or a suspension thereof can be employed, and the synthetic
polymer can be mixed with the cellulose. As for the synthetic
polymer adapted to produce an insulating paper having a low
dielectric loss tangent, those having a low dielectric loss tangent
and a high heat resistance are desirable. Such polymers can be
selected from a group consisting of polycarbonates,
polyphenyleneoxides, polysulfones, polystyrenes, cross-linked
polyethylenes, polytetrafluorethylenes, polytrifluoroethylene
chlorides, polypropylenes, polyacetals, poly-4-methylpentene-1,
polyvinylcarbazoles, polyesters, and polyfluoroethylene-propylene
copolymers.
Although methods for producing electric insulating papers from a
mixed solution consisting of cellulose and a synthetic polymer have
been described above, the electric insulating paper of an
advantageous quality can also be produced from a solution of graft
cellulose.
More specifically, within the above-described solvent systems
described in (1) through (4) for cellulose, a solvent system
employing an organic solvent soluble for grafted polymers is
selected, which system is utilized with another solvent system (5)
for cellulose for the purpose of dissolving graft-cellulose, and
whereby a graft-cellulose solution can be obtained. According to
this method, styrenegraftcellulose, various kinds of vinyl monomer
graft-celluloses, and silicone graft-cellulose can be dissolved,
and from which solution, a pulplike or granular substance easily
made into paper can be obtained. In this way, an electric
insulating paper can also be produced from graft-cellulose which
has been heretofore difficult to be processed with beating and
which has been difficult to be made into paper. When it is desired,
one or more types of above-described synthetic polymers can be
added to the graft-cellulose solution so that a mixed solution or
suspension thereof is obtained, and from this solution or
suspension the insulating paper can also be produced.
Kinds of monomers to be grafted to cellulose and the kinds of
organic solvents adapted for use and selected from the
above-described systems (1) through (4) are indicated in the table
shown below. ##SPC1##
The present invention will now be described with reference to
specific examples although the invention is not necessarily limited
by these examples. In the examples, an insulating paper of more
than 100-micron thickness is used from the practical point of view.
However, it will be further apparent that insulating papers of a
thickness equal or less than 50 microns exhibits better
characteristics than those for the more than 100-micron thickness.
In the following examples, the measurements of the dielectric
constants and dielectric loss tangents have been carried out under
the conditions of a 10 kv./mm. electric field strength, 60 cps.
frequency, and the insulating paper is immersed with JIS class 1
oil, and impulse breakdown strength is measured at room temperature
impregnated with JIS Class 1 oil (sheet test) also. The measured
densities are the apparent values obtained at 20.degree. C. and 65
percent R.H., and the gas air-tightness was measured by means of
"Oken Type" airtightness measuring instrument. It should be noted
that the conventional electric insulating paper which is made of
pulp mixed with substances of better insulating characteristics has
a structural construction in which the substances of better
insulating characteristics are sandwiched between the pulp fibers,
whereas the insulating paper according to the present invention has
a construction in which the substance or substances of better
insulating characteristics are involved in or enveloped by the
cellulose fiber itself.
EXAMPLE 1
Three parts of nonbleached kraft pulp for producing insulating
paper are added into a mixed solution consisting of 50 parts of
N,N-dimethylformamide and 50 parts of dioxane, and the mixed
solution thus obtained has 6 parts of nitrogen dioxide added to it
and stirred at room temperature under atmospheric pressure. After
about 30 minutes of stirring, a cellulose solution of transparent,
green-blue, and viscous nature is obtained. A solution consisting
of three parts of a polysulfone, P-1700 Union Carbide C., and 15
parts of dioxane is further added to the cellulose solution and
stirred, so that a transparent uniformly blended solution of
cellulose and polysulfone is obtained. The blended solution is
thereafter extruded through nozzles of 0.6 mm. diameter into air
under a pressure of 2 kg./ cm.sup.2 and immediately thereafter the
extruded solution is placed into water to be solidified, so that a
blended substance between the cellulose and polysulfone having a
fibrous shape can be obtained. The fibrous substance is cut into
lengths of 3 mm. or less, washed with hot water for removing any
remaining organic solvent, and subjected to a beating process using
a beating machine, whereby a pulplike substance fibrilized as in
the case of an ordinary pulp and beat-processed to about 50.degree.
SR can be obtained. Eighty parts of the pulplike substance thus
obtained is mixed with 20 parts of a nonbleached kraft pulp of
88.degree. SR beating degree to be produced into an insulating
paper, and the resultant mixture is made into paper using pure
water. The characteristics of the thus produced insulating paper
are indicated in table I together with those for a conventional
insulating paper made of nonbleached kraft pulp for comparison.
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TABLE I
Insulating Conventional Paper of Insulating this Invention Paper
__________________________________________________________________________
Density g./cm..sup.3) 0.56 0.72 Thickness (micron) 130 130 Polymer
Content (weight %) 40 Dielectric Constant at 30.degree. C. 2.70
3.57 at 80.degree. C. 2.73 3.59 at 100.degree. C. 2.75 3.61
Dielectric Loss Tangent (%) at 30.degree. C. 0.075 0.210 at
80.degree. C. 0.079 0.212 at 100.degree. C. 0.099 0.246 Impulse
Breakdown Strength (kv./mm.) 178.2 125.4 Tensile Strength
(kg./mm..sup.2) 6.1 7.3
__________________________________________________________________________
As is apparent from table I, the insulating paper according to the
present invention has a dielectric constant, a dielectric loss
tangent, and an impulse breakdown characteristic which are far
superior to those of the conventional insulating paper made of the
nonbleached kraft pulp only.
EXAMPLE 2
Thirty (30) parts of dimethylsulfoxide and 6 parts of diethylamine
are added to 3 parts of nonbleached kraft pulp employed for
producing insulating paper so that the kraft pulp is well mixed and
swollen by these substances. The mixture is then blended with 5
parts of sulfurous acid anhydride in a liquid state and stirred for
about 30 minutes at a room temperature. A cellulose of viscous,
transparent, and yellowish-brown can be obtained. On the other
hand, 3 parts of polyphenylenoxide, PPO 691-111 made by the General
Electric Co., is dissolved in 70 parts of chloroform, and the thus
obtained solution is further mixed with three parts of diethylamine
and one part of sulfurous acid anhydride. The resultant
polyphenylenoxide solution is thereafter added to the above
prepared cellulose solution little by little and stirred thoroughly
so that a blended solution of cellulose and polyphenylenoxide can
be obtained. The blended solution is extruded through nozzles of
0.6 mm. diameter into air as described in example I and solidified
in a regenerative bath consisting of water and methanol mixed at a
ratio of 3:7 so that a fibrous substance is obtained. The fibrous
substance is then cut into lengths less than 3 mm., washed with
pure water, and beaten to obtain a fibrillated pulplike substance
of 63.degree. SR beating degree. Eighty parts of this pulplike
substance is mixed with 20 parts of nonbleached kraft pulp of
beating degree 88.degree. SR, and then made into paper employing
pure water. The characteristics of the thus obtained insulating
paper are shown in table II. For the purpose of comparison, the
characteristics of a paper made of polyphenylenoxide of granular
form less than 150 mesh and of nonbleached kraft pulp for
insulating paper are also shown in table II.
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TABLE II
Insulating Paper Polyphenylen- According to This oxide Powder
Invention Mixed Paper
__________________________________________________________________________
Density (g./cm..sup.3) 0.58 0.66 Thickness (micron) 120 120 Polymer
Content (%) 40 40 Dielectric Constant at 30.degree. C. 2.64 2.83
Dielectric Loss Tangent (%) at 30 .degree. C. 0.077 0.089 at
80.degree. C. 0.080 0.094 at 100.degree. C. 0.108 0.125 Impulse
Breakdown Strength (kv./mm.) 171.4 93.6 Tensile Strength
(kg./mm..sup.2) 5.8 2.0
__________________________________________________________________________
As is apparent from the table II, the insulating paper according to
this invention has a superior impulse breakdown strength and
tensile strength in comparison with the paper wherein the granular
polyphenylenoxide is simply mixed with the kraft pulp.
EXAMPLE 3
Three parts of nonbleached kraft pulp for producing insulating
paper is dispersed into a mixture consisting of 30 parts of
formamide, 70 parts of chloroform, and 10 parts of diethylamine,
and thereafter bubbling into the solution eight parts of sulfurous
acid anhydride in gas state, a cellulose solution of viscous,
transparent, and yellowish-brown can be obtained. On the other
hand, three parts of polysulfone is dissolved into 15 parts of
chloroform, and the thus-obtained liquid is added to the above
described cellulose solution so that a uniformly blended solution
of cellulose and polysulfone is thereby obtained. The blended
solution is extruded through nozzles of 06. mm. diameter into
methanol rotated at a high speed and cut into short fibers by a
propeller with blades. The short fibers are then beaten to
45.degree.0 SR, so that pulplike substance fibrillated can be
obtained, 60 parts of the pulplike substance is mixed with
nonbleached pulp for producing insulating paper of 75.degree. SR
beating degree, and the mixture is made into paper employing pure
water. The insulating paper thus obtained has the characteristics
shown in table III.
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TABLE III
Insulating Paper of This Invention
__________________________________________________________________________
Density g./cm..sup.3) 0.60 Thickness (micron) 135 Polymer Content
(%) 30 Dielectric Constant at 30.degree. C. 2.80 Dielectric Loss
Tangent (%) at 30.degree. C. 0.098 at 30.degree. C. 0.102 at
100.degree. C. 0.131 Impulse Breakdown Strength (kv./mm.) 165.3
__________________________________________________________________________
EXAMPLE 4
In the example 3, although methanol is employed for solidifying the
mixed solution, the solidifying speed of the mixture consisting of
cellulose and polysulfone is found to be too fast, whereby the
obtained fibers turned out to be too hard and too long of a period
was required for beating. To overcome this difficulty, the blended
solution of cellulose and polysulfone obtained as in example 3 is
extruded through nozzles of 0.6 mm. diameter into water in a
stationary state for solidification. Thus solidified substance is
thereafter placed into methanol for removing the remaining
chloroform completely so that a fibrous substance is regenerated.
The regenerated substance is then beaten. Since the substance now
obtained can be more easily beaten, the beating degree can be
raised to 70.degree. SR. When the pulplike substance thus obtained
is made into paper employing the same preparation ratio as in
example 3, an insulating paper of higher airtightness and impulse
breakdown strength can be obtained. The test results are indicated
in the following table IV.
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TABLE IV
Example 3 Example 4
__________________________________________________________________________
Airtightness (sec./100 cc.) 3,000 26,000 Impulse Breakdown Strength
(kv./mm.) 165.3 185.0
__________________________________________________________________________
EXAMPLE 5 A blended solution of cellulose and polysulfone prepared
according to example 1 was extruded through a spinning nozzle
having 30 holes of 70-micron diameter into water, and after the
solution was solidified, the solidified fibers were elongated by
about 250 percent and blended fibers of cellulose and polysufone
were obtained. These fibers were cut to lengths less than 3 mm.,
beaten to about 70.degree. SR of pulplike substance, and made into
paper employing pure water. The insulating paper thus produced
exhibited the characteristics shown in table 5.
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TABLE V
Insulating Paper of This Invention
__________________________________________________________________________
Density (g./cm..sup.3) 0.60 Thickness (.mu.) 130 Polymer Content
(%) 50 Dielectric Constant at 30.degree. C. 2.82 Dielectric Loss
Tangent (%) at 30.degree. C. 0.061 at 80.degree. C. 0.064 at
100.degree. C. 0.093 Impulse Breakdown Strength (kv./mm.) 174.5
__________________________________________________________________________
EXAMPLE 6
Twelve parts of polyphenylene oxide, 20 parts of dimethylsulfoxide,
80 parts of methylene chloride, and eight parts of diethylamine
were added to three parts of unbleached kraft pulp to be produced
into an insulating paper, the mixture was further added to five
parts of sulfurous acid anhydride and cooled for about 3 hours at
0.degree. C. In this way, the cellulose was dissolved and a
solution of viscous and yellow, with a mixing ratio of cellulose
and polymer being about 1:4, could be obtained. This solution was
extruded through nozzles of 0.6 mm. diameter into air maintained at
40.degree. C. so that most of the methylene chloride was
evaporated. The remaining substance was dropped into methanol for
completely removing the remaining dimethylsulfoxide, diethylamine,
and methylene chloride, a fibrous substance could be obtained. The
fibrous substance was then cut and beaten to 55.degree. SR, and the
resultant pulplike substance, 50 parts, was mixed with 50 parts of
unbleached kraft pulp for insulating paper and of 88.degree. SR
beating degree and made into paper employing pure water. The
thus-obtained insulating paper exhibited the characteristics shown
in table 6.
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TABLE VI
Insulating Paper of This Invention
__________________________________________________________________________
Density (g./cm..sup.3) 0.55 Thickness (micron) 110 Polymer Content
(%) 40 Dielectric Constant 2.64 Dielectric Loss Tangent (%) at
30.degree. C. 0.080 at 80.degree. C. 0.084 at 100.degree. C. 0.100
Impulse Breakdown Strength kv./mm.) 170.6
__________________________________________________________________________
EXAMPLE 7
Three parts of cotton linter was dispersed into 100 parts of
dimethylsulfoxide, 12 parts of chloral anhydride was added thereto
so that the cellulose was dissolved at room temperature into a
cellulose solution colorless and transparent. This solution was
further mixed with 12 parts of a denatured polyphenyloxide ground
to less than 200 mesh, Noryl 731-802, made by the General Electric
Co., so that a suspension of a cellulose solution was obtained. The
suspension was therefore extruded through nozzles of 1.3 mm.
diameter into water in a manner as described in example 1 for
solidifying the cellulose. The solidified substance was then beaten
by means of a Lumpen Mill so that a granular substance of from 50
to 200 mesh was obtained. Forty parts of this granular
cellulose-polymer blended substance was then mixed with 60 parts of
unbleached kraft pulp of insulating paper use and beaten to
75.degree. SR, and made into paper employing pure water. The
characteristics of the insulating paper thus obtained were as
indicated in table 7.
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TABLE VII
Insulating Paper of This invention
__________________________________________________________________________
Density (g./cm..sup.3) 0.40 Thickness (micron) 120 Polymer Content
(%) 32 Dielectric Constant at 30.degree. C. 2.58 Dielectric Loss
Tangent (%) at 30.degree. C. 0.078 at 80.degree. C. 0.080 at
100.degree. C. 0.110 Impulse Breakdown Strength (kv./mm.) 136.4
__________________________________________________________________________
EXAMPLE 8
Six parts of polycarbonate was dissolved into a mixed solution
consisting of 60 parts of dioxane and 40 parts of
N,N-dimethylformamide, and the mixture was further added to four
parts of insulating paper use unbleached kraft pulp and six parts
of nitrogen dioxide so that the cellulose was thereby dissolved.
The mixed solution of the green-blue color of cellulose and
polycarbonate thus obtained was then filtered and solidified by
extruding through nozzles having 30 holes of 70-micron diameter
into water, and further elongated by 250 percent so that blended
fibers of cellulose and polycarbonate were obtained. The fibers
were then cut into lengths less than 3 mm. and further beaten for
fibrillation to obtain a pulplike substance of about 50.degree. SR.
The pulplike substance was then made into paper employing pure
water, pressed, and dried, and thereafter dipped into methylene
chloride solution for about 10 seconds for dissolving one part of
the polycarbonate and for strengthening the bonding force between
fibers and also for raising air resistance thereof. The
characteristics of the insulating paper thus obtained are indicated
in table 8.
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TABLE VIII
Insulating Paper of This invention
__________________________________________________________________________
Density (g./cm..sup.3) 0.50 Thickness (micron) 120 Polymer Content
(%) 60 Dielectric Constant at 30.degree. C. 2.68 Dielectric Loss
Tangent (%) at 30.degree. C. 0.080 at 80.degree. C. 0.082 at
100.degree. C. 0.108 Impulse Breakdown Strength (kv./mm.) 158.1
__________________________________________________________________________
EXAMPLE 9
One hundred parts of formamide and 6 parts of diethylamine were
added to three parts of insulating paper use unbleached kraft pulp
so that the pulp was thereby wetted and swollen. The thus-swollen
pulp was further mixed with five parts of sulfurous acid anhydride
in a liquid state so that the cellulose was dissolved. Three parts
of electron beam irradiated cross-linked polyethylene was then
added to this solution and stirred well to obtain a suspension
liquid thereof. The suspension thus obtained was then extruded
through nozzles of 2.0 mm. diameter into water for solidifying the
cellulose. The cellulose thus solidified was then cut into lengths
less than 3 mm., ground by a Lumpen Mill into a granular substance
of from 50 to 200 mesh. Forty parts of the granular mixture of
cellulose and cross-linked polyethylene was then mixed with 60
parts of insulating paper use unbleached kraft pulp beaten to
88.degree. SR and made into paper having characteristics shown in
table 9. From this result, it was made apparent that any polymer
lighter than water could be easily mixed with pulp and made into
paper employing the method described above.
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TABLE IX
Insulating Paper of This Invention
__________________________________________________________________________
Density (g./cm..sup.3) 0.40 Thickness (micron) 150 Polymer Content
(%) 20 Dielectric Constant at 30.degree. C. 2.71 Dielectric Loss
Tangent (%) at 30.degree. C. 0.067 at 80.degree. C. 0.071 at
100.degree. C. 0.095 Impulse Breakdown Strength (kv./mm.) 130.4
__________________________________________________________________________
EXAMPLE 10
Six parts of polystyrene was dissolved into 100 parts of
N,N-dimethylformamide, and the thus-obtained solution was further
added with three parts of bleached kraft pulp and five parts of
nitrosyl chloride so that the cellulose was thereby dissolved for
rendering a blended solution of cellulose and polystyrene. The
blended solution was then extruded through nozzles of 0.6 mm.
diameter into water wherein a propeller having blades was rotated
at a high speed so that the blended solution was solidified into
short fibers.
The short fibers were thereafter beaten to about 50.degree. SR of a
pulplike substance. Sixty parts of the pulplike substance was mixed
with 40 parts of insulating paper use unbleached kraft pulp of
75.degree. SR beating degree and was made into paper employing pure
water. The insulating paper thus obtained exhibited characteristics
as indicated in table 10.
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TABLE X
Insulating Paper of This Invention
__________________________________________________________________________
Density (g./cm..sup.3) 0.60 Thickness (micron) 100 Polymer content
(%) 40 Dielectric Constant at 30.degree. C. 2.75 Dielectric loss
Tangent (%) at 30.degree. C. 0.84 at 80.degree. C. 0.090 at
100.degree. C. 0.115 Impulse Breakdown Strength (kv./mm.) 154.2
__________________________________________________________________________
EXAMPLE 11
Twenty parts of cotton linter, 40 parts of styrene monomer, and
1000 parts of water containing ceric ammonium nitrate at a
concentration of 2.7 x 10 .sup.-3 mol//liter were mixed, and the
styrene was grafted by heating the mixture at 70.degree. C. under a
nitrogen gas flow. The reaction was continued for about 5 hours so
that styrene graft-cellulose of 104 percent degree of grafting was
obtained. Five parts of this graft-cellulose was dispersed into 100
parts of ethylacetate, 10 parts of nitrogen dioxide was further
added thereto for dissolving the graft-cellulose, and the mixture
was extruded through a nozzle having 30 holes of 70-micron diameter
into methanol so that the mixture was solidified. The solidified
substance was thereafter elongated to 200 percent length for
obtaining fibers of styrene graft-cellulose, and the fibers were
then cut, beaten to about 45.degree. SR, and the thus-obtained
pulplike substance, 80 parts, was mixed with 20 parts of insulating
paper use unbleached kraft pulp of 75.degree. SR beating degree to
be made into paper employing pure water. The insulating paper,
having the characteristics as shown in table 11, was obtained.
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TABLE XI
Insulating Paper of This Invention
__________________________________________________________________________
Density (g./cm..sup.3) 0.53 Thickness (micron) 130 Polymer Content
(%) 40 Dielectric Constant at 30.degree. C. 2.67 Dielectric Loss
Tangent at 30.degree. C. 0.081 at 80.degree. C. 0.087 at
100.degree. C. 0.105 Impulse Breakdown Strength (kv./mm.) 144.3
__________________________________________________________________________
EXAMPLE 12
In a manner similar to example 11, styrene was grafted to cotton
linter so that styrene grafted cellulose of a graft ratio of 40
percent was thereby obtained. Five parts of this grafted cellulose
and three parts of polysulfone were added to 100 parts of dioxane
and dispersed well. The mixture thus obtained was further mixed
with nitrogen dioxide so that the grafted cellulose was thereby
dissolved and a blended solution of a styrene-grafted cellulose and
polysulfone was simultaneously obtained. This blended solution was
extruded through a nozzle having holes of 0.6 mm. diameter into
water for solidification, and the solidified substance was then
cut, beaten to about 65.degree. SR, so that the thus-obtained
pulplike substance was thereafter made into paper employing pure
water. The insulating paper thus obtained has the characteristics
shown in table 12.
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TABLE XII
Insulating Paper of This invention
__________________________________________________________________________
Density (g./cm..sup.3) 0.60 Thickness (micron) 120 Polymer Content
(%) 44 Dielectric Constant at 30.degree. C. 2.84 Dielectric Loss
Tangent at 30.degree. C. 0.071 at 80.degree. C. 0.080 at
100.degree. C. 0.102 Impulse Breakdown Strength (kv./mm.) 168.5
__________________________________________________________________________
EXAMPLE 13
Sulfurous acid anhydride as a gas was cooled at -30.degree. C. so
that sulfurous acid in a liquid state could be collected in a
pressure proof container, and three parts of polysulfone was added
to 100 parts of thus-obtained liquefied sulfurous acid so that the
polysulfone was thereby dissolved. Three parts of cotton linter and
six parts of diethylamine were then added to the above-described
liquefied solution, and by raising the temperature to a room
temperature, the cellulose was dissolved. The thus-obtained mixed
solution of cellulose and polysulfone was extruded through nozzles
of 0.6 mm. diameter into methanol so that the mixture was
solidified. After washing the solidified substance was beaten to
about 45.degree. SR, and 40 parts of the pulplike substance thus
obtained was mixed with 60 parts of insulating paper use unbleached
draft pulp of beating degree 88.degree. and made into paper
employing pure water. The characteristics of the insulating paper
thus obtained are shown in table 13.
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TABLE XIII
Insulating Paper of This Invention
__________________________________________________________________________
Density (g./cm..sup.3) 0.50 Thickness (micron) 105 Polymer Content
(%) 20 Dielectric Constant at 30.degree. C. 2.85 Dielectric Loss
Tangent at 30.degree. C. 0.102 at 80.degree. C. 0.106 at
100.degree. C. 0.134 Impulse Breakdown Strength (kv./mm.) 164.4
__________________________________________________________________________
* * * * *