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JPH05170946

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DESCRIPTION JPH05170946
[0001]
FIELD OF THE INVENTION This invention relates to thermoplastic polyimide films. More
particularly, the present invention relates to a thermoplastic polyimide film suitable for use as a
paper feed belt and a speaker cone of a thermal transfer printer having a specific total light
transmittance and having excellent heat resistance and mechanical properties.
[0002]
2. Description of the Related Art In recent years, technological development in the field of
electronic industry has been remarkable, and development of electronic devices and their parts
has become lighter, thinner and smaller, development of organic materials having easier heat
processing and easier heat processing. Is strongly desired.
[0003]
For example, in a thermal transfer printer, a biaxially stretched polyester film is used as a belt
material for feeding paper while detecting the position of the paper.
However, the paper feed belt made of biaxially oriented polyester film is insufficient in heat
resistance, and when the printing speed of the printer is increased, the heat, the flatness and the
tensile strength of the belt may be reduced due to heat generation, so that it is accurate. There is
a problem that printing can not be performed.
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[0004]
Moreover, a biaxially stretched polyester film is mainly used as a material of the speaker cone.
Recently, the widespread use of automobiles has increased the demand for speakers mounted on
automobiles. Along with this, the demand for speaker cones for car mounting is also increasing.
However, since the temperature in the vicinity of the dashboard in an automobile such as
summer may rise to nearly 100 ° C., the speaker cone made of the biaxially stretched polyester
film is not necessarily sufficiently heat resistant, and is distorted by heat. As a result, problems
such as shortening the life of the speaker cone and lowering the sound quality have occurred.
[0005]
On the other hand, polyimide resin is mentioned as a material excellent in heat resistance.
However, since a conventional polyimide resin is difficult to be thermoformed, a film is
manufactured by a so-called solution casting method in which a solution of polyamic acid, which
is a precursor of polyimide, is cast to manufacture. In the case of processing the film produced by
the solution casting method into the above-mentioned paper feed belt, speaker cone, etc., an
adhesive must be used, and not only the productivity is low, but also the heat resistance of the
adhesive, flexibility, It has the disadvantage that the tee is inferior.
[0006]
SUMMARY OF THE INVENTION The object of the present invention is to solve the above
problems, and it is a heat sealable thermoplastic polyimide having excellent heat resistance,
mechanical properties and having a specific total light transmittance. It is to provide a film.
[0007]
A resin composition comprising a thermoplastic polyimide resin having a specific structure and a
carbon powder having a specific particle diameter mixed with a specific composition as a result
of intensive studies to solve the above problems. It has been found that a thermoplastic
polyimide film obtained by melt-molding of the present invention has properties capable of
solving the above problems, and the present invention has been achieved.
[0008]
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That is, the present invention is a film obtained by melt molding a resin composition containing
100 parts by weight of a thermoplastic polyimide resin and 0.05 to 10 parts by weight of carbon
powder having an average particle diameter of less than 5 μm, It is a thermoplastic polyimide
film having a thickness of 10 to 500 μm and a total light transmittance of less than 10%.
[0009]
The thermoplastic polyimide film of the present invention is characterized by being colored black
by carbon powder and having a total light transmittance of less than 10%.
Furthermore, since it is mainly composed of a thermoplastic polyimide resin having a specific
structure, it is a thermoplastic polyimide film having excellent heat resistance and good heat
sealability in addition to mechanical characteristics, and a paper feed belt for a thermal transfer
printer, a speaker It is suitably used as a material such as corn.
[0010]
Hereinafter, the present invention will be described in detail.
The thermoplastic polyimide used in the present invention is a compound represented by the
general formula (1) which is already known as a heat resistant polyimide.
[0011]
(Wherein R and R 1 each independently represent an aliphatic group having a carbon number of
2 or more, a cyclic aliphatic group, a monocyclic aromatic group, a fused polycyclic aromatic
group, or an aromatic group either directly or by a crosslinking member) R is a group selected
from the group consisting of linked non-condensed polycyclic aromatic groups, R is a tetravalent
group and R 1 is a divalent group) A polyimide having plasticity is used.
Preferably, general formula (2) [formula 2]
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[0012]
(Wherein R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a
monocyclic aromatic group, a fused polycyclic aromatic group, or an aromatic group mutually
linked by a direct or bridge member) A tetravalent group selected from the group consisting of
non-fused polycyclic aromatic groups is shown, and X is a single bond, a sulfur atom, a sulfone
group, a carbonyl group, an isopropylidene group or a divalent group of
hexafluoroisopropylidene group And a polyimide having a repeating structural unit represented
by the general formula (3):
[0013]
[Wherein, A represents a sulfur atom, an oxygen atom, a sulfone group, a methylene group, an
ethylidene group, an isopropylidene group or a divalent group of hexafluoroisopropylidene
group, and R represents a group represented by the general formula (4)
[0014]
(Wherein, B represents a sulfur atom, a sulfone group, a methylene group, an ethylidene group,
an isopropylidene group or a divalent group of hexafluoroisopropylidene group), which is a
polyimide having a repeating structural unit .
[0015]
The polyimide to be further preferably used is a compound represented by general formula (2)
[formula 2] in which R is a group represented by formula (5) [formula 5] to formula (9) [formula
9]
[0020]
Polyimide which is a tetravalent group selected from the group consisting of
The above-mentioned polyimide can be obtained by the dehydration condensation reaction of
aromatic tetracarboxylic acid dianhydride and aromatic diamine.
[0021] Examples of the aromatic tetracarboxylic acid dianhydride used to obtain this polyimide
include butanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride,
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pyromellitic acid dianhydride, 1, 2, 3, 3, 4-benzenetetracarboxylic acid dianhydride, 2,3,6,7naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid
dianhydride, 1,2,5,6- Naphthalenetetracarboxylic acid dianhydride, 3,4,9,10perylenetetracarboxylic acid dianhydride, 2,3,6,7-anthracenetetracarboxylic acid dianhydride,
1,2,7,8-phenanthrene tetrahydrate Carboxylic acid dianhydride, 3,3 ', 4,4'biphenyltetracarboxylic acid dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid dianhydride, 3,3
', 2,4'-benzophenonetetracarboxylic acid dianhydride, 2,2 ', 3,3'-benzophenonetetracarboxylic
acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2 , 2-bis (2,3dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3dicarboxyphenyl) ether dianhydride, bis ( 3,4-dicarboxyphenyl) sulfone dianhydride, bis (2,3dicarboxyphenyl) sulfone dianhydride, 2,2-bis (3,4-dicarboxyphenyl) 1,1,1,3, 3,3hexafluoropropane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) 1,1,1,3,3,3-hexachloropropane
dianhydride, 1,1-bis (2 , -Dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl)
methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 4,4 '-(p-phenylene dianhydride Oxy) diphthalic dianhydride, 4,4 '-(m-phenylenedioxy) diphthalic dianhydride, 4,4'diphenyl sulfide dioxybis (4-phthalic acid) dianhydride, 4,4' -Diphenylsulfone dioxybis (4-phthalic
acid) dianhydride, methylene bis- (4-phenylene oxy-4-phthalic acid) dianhydride, ethylidene bis(4-phenylene oxy-4-phthalic acid) dianhydride , Isopropylidene bis- (4-phenylene oxy-4-phthalic
acid) dianhydride, hexafluoroisopropylidene bis- (4-phenylene oxy-4-phthalic acid) Diacid
anhydride etc. are mentioned.
[0022] Moreover, as an aromatic diamine used in order to obtain a polyimide, the bis [4- (3amino phenoxy) phenyl] sulfide, bis [4- (3-amino phenoxy) phenyl] sulfone, bis [4- (3) is
mentioned, for example. -Aminophenoxy) phenyl] ketone, 4,4'-bis (3-aminophenoxy) biphenyl,
2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3) -Aminophenoxy) phenyl] 1,1,1,3,3,3-hexafluoropropane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl ether, 4,4'diaminodiphenyl sulfone 4,4'-diaminodiphenylmethane, 1,1-di (p-aminophenyl) ethane, 2,2-di (paminophenyl) ester Bread, 2,2-di (p- aminophenyl) -1,1,1,3,3,3-hexafluoropropane, and the like.
[0023]
These aromatic tetracarboxylic acid dianhydrides or aromatic diamines can be used alone or in
combination of two or more.
The polyimide used in the present invention can be prepared by using conventional methods
known in the art, such as suspending or dissolving these aromatic tetracarboxylic acid
dianhydrides and aromatic diamines in an organic solvent, It can be obtained by a general
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method of heating or chemically dehydrating, separating and purifying the product.
[0024] There is no limitation in particular in the kind of carbon used by this invention, and if
particle diameter is less than 5 micrometers, it can use preferably. When the particle size of
carbon is 5 μm or more, the dispersibility with the thermoplastic polyimide resin is low, the
surface of the obtained film is roughened, and a good film having a surface state can not be
obtained, and for example, a filter is used. In the case of melt extrusion molding, the filterability
of the molten resin is deteriorated, the pressure of the resin in the extruder is increased, and the
extrusion stability is unfavorably lowered. As carbon preferably used, for example, one for
general engineering plastics such as trade name, Laven # 1255 manufactured by Columbia
Carbon Co., Ltd. is exemplified. As long as the particle size is less than 5 μm, two or more types
may be mixed and used.
[0025] The thermoplastic polyimide film of the present invention is a thermoplastic resin having
a thickness of 10 to 500 μm and a total light transmittance of less than 10% obtained by melt
molding a resin composition containing the above polyimide resin and carbon powder as
essential components. It is a polyimide film. The film having a thickness of less than 10 μm is
not preferable because the strength is low and it is not suitable for use as a material for a paper
transfer belt for a thermal transfer printer, a speaker cone, and the like. If the thickness exceeds
500 μm, the flexibility is low and it is not suitable for a belt or the like, and when it is used as a
material of a speaker cone, it is not preferable because a speaker that generates a good sound
quality can not be obtained.
[0026] In addition, a film having a total light transmittance of 10% or more is not preferable
because, for example, when it is used as a material of a sheet feeding belt of a thermal transfer
printer, the position of the sheet can not be accurately detected. The preferred total light
transmittance when used as a paper feed belt for a thermal transfer printer is less than 5%, more
preferably less than 1%. The material of the speaker cone is generally a black film, and a film
having a total light transmittance of 10% or more is not preferable because the commercial value
decreases.
[0027] The thermoplastic polyimide film of the present invention having such characteristics is
obtained by the following production method. A carbon powder having a particle diameter of less
than 5 μm is added to a thermoplastic polyimide resin having a repeating structural unit
represented by the general formula (1) [Chemical formula 1], and a mixing device such as a
Henschel mixer, a universal mixer, or a ribbon blender The mixture is used at room temperature
to a temperature lower than the glass transition temperature of the polyimide resin to form a
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resin composition. The polyimide resin containing a predetermined amount of carbon powder
and a master batch consisting of the carbon powder are prepared beforehand, and the polyimide
resin is mixed with the polyimide resin to obtain a predetermined amount of carbon powder. You
can also get
[0028] Then, the obtained resin composition is melt-formed into a film by T-die type extrusion
molding, inflation molding, calendar molding or the like in the temperature range of melting
point to melting point + about 50 ° C. of the polyimide resin A thermoplastic polyimide film is
obtained by casting using a roll having a surface temperature less than the glass transition
temperature of the polyimide resin. There is no restriction ¦ limiting in particular in the kind of Tdie type extruder to be used, an inflation molding machine, a calendar molding machine, etc., It
may be used for melt molding of a thermoplastic resin normally.
[0029] If the molding temperature is lower than the melting point of the polyimide resin to be
used, the polyimide resin is difficult to melt and a film can not be obtained. Further, if the
temperature exceeds the melting point + about 50 ° C. of the polyimide resin to be used, the
decomposition of the polyimide resin proceeds, and the surface state of the film obtained by
bubbles, die lines, decomposition scum, etc. is unfavorably deteriorated.
[0030] The thermoplastic polyimide film of the present invention comprises carbon powder
having an average particle diameter of less than 5 μm with respect to 100 parts by weight of
the thermoplastic polyimide resin having a repeating structural unit represented by the above
general formula (1) [Chemical Formula 1]. It is obtained by melt-molding a resin composition
obtained by adding 0.05 to 10 parts by weight. The preferred amount of carbon powder is 0.5 to
3 parts by weight. If the amount of carbon powder is less than 0.05 parts by weight, the total
light transmittance of the obtained film is 10% or more, which is not preferable because it is not
suitable for use as a material for paper transfer belts for thermal transfer printers, speaker cones
and the like. In addition, when it exceeds 10 parts by weight, the surface of the film obtained is
roughened, resulting in a film having a poor surface condition. For example, in the case of
extrusion using a filter, the extrusion pressure is stable, for example It is not preferable because
the nature is reduced.
[0031] In addition to carbon having a specific particle diameter, inorganic fillers such as
lubricants, heat-resistant stabilizers, pigments, additives such as UV absorbers, surface modifiers,
etc. are used in the above-described thermoplastic polyimide resin used in the present invention
The thermoplastic polyimide resin to be used may be one which melts at the melting point to the
melting point + 50 ° C. or one having a particle diameter of less than 5 μm, among agents,
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sliding agents such as fluorocarbon resins, and the like.
[0032] When the thermoplastic polyimide film of the present invention is used as a paper feed
belt for a thermal transfer printer, the polyimide film cut into a predetermined size and made into
a belt shape has a predetermined hole diameter so as to have a predetermined hole area ratio.
After drilling the pores, heat seal both ends to make an endless belt. The endless belt is a black
belt having a total light transmittance of less than 10%, and further has a predetermined pore
size, and thus, for example, when used as a paper feed belt for a thermal transfer printer, it is
irradiated by irradiating a light beam. The position of the paper, in particular, the end of the
paper can be easily detected, and the start of feeding of each sheet of paper being conveyed and
the timing of the end of conveyance can be accurately detected.
[0033] Further, when used as a material of a speaker cone, a film having a desired sound quality
or thickness corresponding to the scale is cut or punched to a predetermined size, and is adhered
to the main part of the speaker by heat sealing or the like. Since the polyimide film of the present
invention has thermoplasticity, it can be heat-sealed, and further, has excellent heat resistance
and mechanical strength, so it is suitable as a material used for the above-mentioned
applications.
[0034] The present invention will be described in more detail by way of the following examples.
First, 10 parts by weight of fine carbon powder (trade name: Laven # 1255, manufactured by
Columbia Carbon Co., Ltd.) with respect to 90 parts by weight of powder of polyimide (polyimide
resin manufactured by Mitsui Toatsu Chemicals Co., Ltd., trade name: New-TPI) And uniformly
mixed for 5 minutes at room temperature using a universal mixer to obtain a resin composition.
The resin composition was melt-extruded at 400 ° C. using a twin-screw extruder to obtain 2
mmφ × 3 mmL master batch pellets containing 10% by weight of carbon fine powder.
Subsequently, predetermined amounts of the above-mentioned polyimide powder and master
batch pellets were mixed for 5 minutes at room temperature using a ribbon blender so as to
obtain the carbon content shown in [Table 1], to obtain a resin composition. The resin
composition is melt extruded from a T-die at 420 ° C. using a T-die type single screw extruder,
and cast onto a roll having a surface temperature of 200 ° C. to form a thermoplastic resin
having a thickness of 100 μm. A polyimide film was obtained.
[0035] The glass transition temperature, the total light transmittance, and the surface state of the
obtained thermoplastic polyimide film were evaluated, and the results are shown in [Table 1].
Further, when the polyimide film was heat-sealed using a universal sealer (manufactured by
Kyowa Denki Co., Ltd., type: I-600E), it could be easily bonded. The bonded portion did not peel
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off at a tension of about 2 kg / cm. In addition, the characteristic evaluation of the obtained
thermoplastic polyimide film was performed by the following method.
[0036] Total light transmittance: Measured using a DIRECT READING HAZE METER
manufactured by Toyo Seiki Seisaku-sho, Ltd. Glass transition temperature: It measured using
DCS230 made from Rigaku Corporation.
[0037] Comparative Example 1-2 A thermoplastic polyimide film having a thickness of 100 μm
was prepared in the same manner as in Example 1 except that the addition amount of the
masterbatch pellet was changed so that the addition amount of carbon fine powder became the
amount shown in [Table 1]. Obtained. The characteristics of the obtained thermoplastic
polyimide film were evaluated in the same manner as in Example 1, and the results are shown in
Table 1.
[0039] The thermoplastic polyimide film of the present invention is excellent in heat resistance,
mechanical properties and heat sealability and has a total light transmittance of less than 10%.
Therefore, it is suitably used as a paper feed belt for a high-speed thermal transfer printer, a
material for a speaker cone that requires heat resistance, and the like.
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