CN107400250A - A kind of black polyamide thin film and preparation method thereof - Google Patents

A kind of black polyamide thin film and preparation method thereof Download PDF

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CN107400250A
CN107400250A CN201710653733.9A CN201710653733A CN107400250A CN 107400250 A CN107400250 A CN 107400250A CN 201710653733 A CN201710653733 A CN 201710653733A CN 107400250 A CN107400250 A CN 107400250A
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titanium dioxide
black
preparation
calcium carbonate
pigment
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任小龙
姬亚宁
朱恒斌
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Guilin Electrical Equipment Scientific Research Institute Co Ltd
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Guilin Electrical Equipment Scientific Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2203/16—Applications used for films

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Abstract

The invention discloses a kind of black polyamide thin film and preparation method thereof.Described preparation method includes：Polyamic acid solution, dispersible pigment dispersion are prepared, is then well mixed them, then film forming is prepared by existing common process；Wherein, when preparing dispersible pigment dispersion, pigment used includes black pigment and Chinese white, and Chinese white is titanium dioxide and/or calcium carbonate, and they meet following condition：5~60nm of average grain diameter, whiteness >=95, oil absorption≤22g/100g, 50~400m of specific surface area2/ g, density≤0.8g/cm2；The dosage of the Chinese white is 2wt%~12wt% of polyimides weight, and the weight proportion of itself and black pigment is 10~1.2：1；The average grain diameter of the black pigment is identical with the average grain diameter of Chinese white.Film made from the method for the invention has more excellent optical property, hot property and insulating properties.

Description

A kind of black polyamide thin film and preparation method thereof
Technical field
The present invention relates to Kapton, and in particular to a kind of black polyamide thin film and preparation method thereof.
Background technology
Black polyamide thin film is a kind of high insulation, the insulation film of high intensity, compared to common (yellow) polyamides Asia Amine film, black polyamide film is opaque, light transmission, has good light-proofness, thermal conductivity etc., is widely used in moving dress Put, the cover layer of computer, automobile and Military Electronic Equipment etc..
The production technology of Kapton is using the polyamic acid resin solution by polycondensation reaction synthesis as original at present Material, salivated on slobbering machine and obtain the polyamic acid thick film with self-supporting, then it is fixed by heating stretching, imidization, cooling Type handles to obtain Kapton.Obtain having low light transmission and the Kapton of insulating properties concurrently, it is thin in polyimides Must be added during film preparation in colour additive (such as：Colorant, dyestuff etc.).In general technique be used colour additive with Reduce the light transmittance of Kapton.Such as the Japanese invention patent JP 201180002A " Jue Vela Port リ イ ミ of application in 2011 De Off ィ Le system, カ バ ー レ イ Off ィ Le system and び Off レ キ シ Block Le プ リ Application ト match somebody with somebody Line Ban に Seki The Ru " disclose by adding Add black pigment (carbon black, primary particle size 20nm -500nm, 1.0wt%-15.0wt%), filler (titanium dioxide/mica/nitridation Boron/aluminum oxide etc., 1.0wt%-15.0wt%, 0.01-40 μm of average grain diameter) be made 12.5 μm of thickness total light transmittance exist ＜ 5%, specific insulation ＞ 2 × 1016Ω cm black matt polyimide film.Equally, South Korea's hair of application in 2011 Bright patent KR101045823B1 " black polyamide thin film " disclose by add carbon black (20nm -1 μm of volume average particle size, 5.0wt%-10.0wt%), 12.5 μm of thickness is made in silica (0.3-10 μm of 3.0wt%-10.0wt%, average grain diameter) Total light transmittance is in ＜ 0.1%, specific insulation ＞ 1015Ω cm and dielectric strength ＞ 40kV/mm black matt polyamides Imines film.The Chinese invention patent CN 104169330B " black polyamide film " of application in 2012 are disclosed by carbon black face Expect (3.0wt%-7.5wt%, 70nm -150nm primary particle sizes), titanium dioxide screener (put down by 0.5wt%-1.5wt%, volume Equal 0.2 μm -0.6 μm of diameter), the black polyamide thin film of light transmission≤1.0% for preparing of polyimide resin etc..
Above-mentioned prior art is that black polyamide is made by introducing pigment and filler in polyimide resin matrix Film, but be to choose for the purpose of black pigment-carbon black reduces film light transmittance, manufactured film exist blackness not enough, hide Cover the problems such as effect is limited and Color uniformity is poor.A large amount of black are must be introduced into if it need to increase blackness, improve screening effect Pigment, but so operation can substantially reduce the insulating properties of Kapton.
It is exactly one layer of polyimide film containing black pigment of coating on the single or double of polyimide base film to have again, To form so-called double-deck or multilayer black polyamide thin film.Although such a method can preferably make Kapton that institute be presented Desired black effect and the certain mechanical performance of polyimide film can be ensured, but the black resin being additionally coated with is usual Manufacturing process and cost can be increased, and Kapton property is adversely affected；In addition, can also be because of resin coated layer Heat resistance is poor to cause polyimide film that performance degradation easily occurs when being exposed to hot adverse circumstance.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of black polyamide thin film and preparation method thereof.Using this hair Black polyamide thin film made from bright methods described effectively lifts its optics on the premise of the original mechanical performance of film is kept Performance, thermal property and insulating properties.
The preparation method of black polyamide thin film of the present invention, comprises the following steps：
1) polyamic acid solution is prepared；
2) take pigment to be scattered in polar non-solute and obtain dispersible pigment dispersion, described pigment include black pigment and Chinese white, wherein Chinese white are titanium dioxide and/or calcium carbonate, and described titanium dioxide and/or calcium carbonate meet following Condition：
5~60nm of average grain diameter, whiteness (CIE L*) >=95, oil absorption≤22g/100g, 50~400m of specific surface area2/g (test of BET methods), density≤0.8g/cm2；
The dosage of the Chinese white is 2wt%~12wt% of polyimides weight, and the weight of itself and black pigment is matched somebody with somebody Than for 10~1.2：1；
The average grain diameter of the black pigment is identical with the average grain diameter of Chinese white；
3) dispersible pigment dispersion and polyamic acid solution are well mixed, prepare film forming by existing common process afterwards.
Applicant has found in testing, researching and analysing, using Chinese white as main colorant, by being selected with black pigment Property allotment can effectively improve the characteristics such as the optics, calorifics and insulation of black polyamide thin film, by the usage amount of Chinese white The 2.0wt% to 12.0wt% of polyimides weight is defined to, blackness when its dosage is less than 2.0wt% is allowed for and it is to be difficult to It is satisfied；And its dosage is when being more than 12.0wt%, then the mechanical performance of gained film, insulating properties etc. can deteriorate, and in polyamide Scattered uneven (sedimentation and reunion) easily occurs in acid resin, film performance uniformity is poor, can also increase the production cost of film. On the other hand, the selection of Chinese white (titanium dioxide and calcium carbonate) can not only influence itself, black pigment and delustering agent exist Dispersing uniformity in system, optical characteristics, thermal property and the insulating properties of gained Kapton can be also influenceed, white Color pigment and black pigment can effectively improve dispersiveness of the various solid packings in resin in the case of having same particle diameter, So that gained Kapton can effectively lift its optical property, calorifics while keeping mechanical performance not decline Energy and insulating properties.
Further, when white filler is titanium dioxide and calcium carbonate in combination, and the weight of titanium dioxide and calcium carbonate is matched somebody with somebody Than for 1：When 1~0.2, it can not only make gained Kapton that there are excellent thermal property and insulating properties, moreover it is possible in nothing I.e. achievable Chinese white, black pigment and delustering agent uniformly divide in system under conditions of dispersant or coupling agent need to be added Dissipate.
In the step 1) of above-mentioned preparation method, polyamic acid solution is prepared using existing conventional method, can be specifically to adopt Obtained with aromatic diamine and dianhydride monomer in polar non-solute by polycondensation reaction.Wherein：Described aromatic series two Amine can be specifically p-phenylenediamine, 4,4 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether and 4,4 '-diaminourea hexichol Any one in methylmethane etc. or two or more combinations；When the selection of aromatic diamine is combination more than above two When, the proportioning between them can be any proportioning.Described dianhydride monomer can be specifically pyromellitic acid anhydride, 3,3 ', 4,4 '-diphenyl ether tetraformic dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) and six Any one in the PMDA of fluorine isopropylidene two or two or more combinations；When the selection of dianhydride monomer is above two During the combination of the above, the proportioning between them can be any proportioning.Described polar non-solute can be specifically N, N- In dimethyl acetamide (DMAC), N,N-dimethylformamide (DMF), METHYLPYRROLIDONE (NMP) any one or Two or more combinations；The dosage of described polar non-solute can be specifically to work as aromatic diamine, dianhydride monomer and pole Property aprotic solvent when forming polyamic acid solution, solid content control in the polyamic acid solution in 10wt%~50wt%, Preferably 15wt%~35wt%.When aromatic diamine and dianhydride monomer carry out polycondensation reaction, the aromatic diamine and two The temperature of mole when polycondensation reaction of anhydride monomer is same as the prior art, specifically, aromatic diamine and the dianhydride list The mol ratio of body can be 0.9~1.1：1, preferably 0.95~1.05：1；The temperature of the polycondensation reaction can be 0~50 DEG C, the time of reaction is usually 3~12h.
In the step 2) of above-mentioned preparation method, more preferably titanium dioxide and/or calcium carbonate meet following condition：Average grain diameter 10~50nm (further preferred 20~40nm), whiteness >=96 (further preferably >=98), oil absorption≤18g/100g is (further It is preferred that≤15g/100g), 150~360m of specific surface area2/ g (further preferred 200~300m2/ g), density≤0.4g/cm2(enter One step preferably≤0.3g/cm2)。
In the step 2) of above-mentioned preparation method, the titanium dioxide as one of Chinese white selection is more preferably hydrophilic Property anatase titanium dioxide, still more preferably oxidized silicon (SiO2) and/or aluminum oxide (AL2O3) surface treatment hydrophily Anatase titanium dioxide；Calcium carbonate as another selection of Chinese white is more preferably then hydrophily calcium carbonate, then enter One step preferred hydrophilic spherical calcium carbonate.It so can further improve Chinese white and black pigment in polyimide resin body Dispersiveness in system, make gained Kapton that there is more excellent thermal property and insulating properties.
In the step 2) of above-mentioned preparation method, the selection of the black pigment is same as the prior art, specific selection Can be the combination more than one or both of insulating properties carbon black, cupric and chromic oxide and iron oxide, preferably insulating properties Carbon black (can be the insulating properties carbon black with O.001 μm~2 μm of average grain diameters, preferably have O.01 μm~1 μm of average grain diameter Insulating properties carbon black, more preferably the insulating properties carbon black with 0.08 μm~0.8 μm average grain diameter).
As hereinbefore, its dosage is distinguished for the selection for the polar non-solute being related in the step 2) of above-mentioned preparation method With can dispersed black pigment be advisable.
In above-mentioned preparation method, involved being separated into is dispersed, can use existing conventional method such as ultrasound point Dissipate, shear the realization of the technological means such as scattered, homogeneous.
Present invention additionally comprises the black matt polyimide film being prepared by the above method.
Compared with prior art, the present invention passes through the Chinese white from specific dosage and particular characteristic parameter and black face Material is matched, and gained film is also further carried while with conventional black matt polyimide film mechanical performance High optical property (blackness, light transmittance etc.), thermal property (shrinkage factor, thermal coefficient of expansion etc.) and the insulating properties of gained film (electrical strength, dielectric constant etc.), can more meet the needs of market, expand product applications.
Embodiment
With reference to specific embodiment, the present invention is described in further detail, to more fully understand present disclosure, but The present invention is not limited to following examples.
The application feature is to be combined use from Chinese white and black pigment, and is particularly limited to Chinese white Various performance parameters (the particularly selection of granularity), because applicant has found in testing, researching and analysing：
When Chinese white particle diameter is less than 5nm, then film is required is presented background color whiteness unobvious；And particle diameter is more than 60nm, then Film color homogeneity is poor, and it is Extinction characteristics unobvious that filler, which disperses inequality,.It is when Chinese white addition is less than 2wt%, then thin Background color whiteness unobvious are presented needed for film, addition is more than 12wt%, then film color homogeneity is poor, filling settlement and disperses not It is that film apparent mass is poor.
For black pigment, its addition is bigger, and film electrical strength is smaller, and electrical property is poorer, and application field is got over It is narrow.The application not only can effectively reduce the addition of black pigment by the introducing of Chinese white, and can be with black face Material forms complementary colours, and film blackness is effectively ensured on the basis of black pigment addition substantially reduces or even improves thin film black Degree, makes black matt polyimide film outward appearance seem more there is aesthetic feeling.On the other hand, nanoscale Chinese white has sky Between steric effect, in polyamic acid resin building-up process, black pigment and delustering agent can be made to suspend, play anti-settling effect. Meanwhile black polyamide thin film can have stronger Extinction Characteristic and homogeneous color and performance.
Embodiment 1
1) using as 400.0kg DMAC N,N' dimethyl acetamides (DMAc) addition of solvent under nitrogen atmosphere protective condition In reactor, amido diphenyl ether (ODA) 47.86kg of polymerized monomer diamines 4,4 '-two is added, is added after stirring and dissolving The polymerized monomer dianhydride pyromellitic acid anhydride (PMDA) of 52.14kg equimolar amounts, stirring condensation polymerization reaction, obtains polyamic acid Solution (solid content 20wt%)；
2) take 50.0kg DMA to be put into 100L containers, it is (flat to add 5.0kg insulating properties carbon black afterwards Equal particle diameter is 5nm), 12.0kg titanium dioxide (average grain diameter 5nm, whiteness (CIE L*) 95, oil absorption 22g/100g, compare table Area 50m2/ g (test of BET methods), density 0.8g/cm2), ultrasonic disperse 60min, then by high pressure homogenizer homogeneous 15min, Obtain dispersible pigment dispersion；
3) by dispersible pigment dispersion and polyamic acid solution mixing, (content of carbon black is in mixed liquor obtained by being controlled during mixing 0.2wt%, content of titanium dioxide 12.0wt%), obtain polyamic acid resin mixed solution after stirring 8h.It will pass through at deaeration The polyamic acid resin solution of reason is passed through by die head 150 μm of thickness of coating on ring steel belt, then at 100~250 DEG C Dry and remove most of solvent, obtain with can self-supporting Polyamic Acid Film.Gained film is removed from ring steel belt And be delivered on high temperature bi-directional stretching-machine, and 550 DEG C are heated to from 180 DEG C, then cool down and obtained thickness is removed from chain pincers 12.5 μm of black polyamide thin film.
Comparative example 1
Embodiment 1 is repeated, unlike：
In step 2), in pigment preparation dispersion liquid, carbon black is only added；
In step 4), when black pigment dispersion liquid and polyamic acid solution are mixed, carbon black in control gained mixed liquor Content be 0.2wt%.
Comparative example 2
Embodiment 1 is repeated, unlike：
In step 2), with the titanium dioxide used in the titanium dioxide alternative embodiment 1 of following parameter：
Average grain diameter is 2nm, whiteness (CIE L*) 68, oil absorption 30g/100g, specific surface area 50m2/ g (survey by BET methods Examination), density 1.2g/cm2。
Comparative example 3
Embodiment 1 is repeated, unlike：
In step 2), with the titanium dioxide used in the titanium dioxide alternative embodiment 1 of following parameter：
Average grain diameter is 90nm, whiteness (CIE L*) 108, oil absorption 20g/100g, specific surface area 120m2/ g (BET methods Test), density 1.2g/cm2。
Comparative example 4
Embodiment 1 is repeated, unlike：
In step 2), the insulating properties carbon black for being 15nm with average grain diameter replaces the insulating properties carbon black in embodiment 1, its dosage It is constant；It is 18nm with average grain diameter, whiteness (CIE L*) 95, oil absorption 22g/100g, specific surface area 50m2/ g (survey by BET methods Examination), density 0.8g/cm2Titanium dioxide replace titanium dioxide in embodiment 1, its dosage is constant.
Comparative example 5
Embodiment 1 is repeated, unlike：
In step 2), the insulating properties carbon black for being 15nm with average grain diameter replaces the insulating properties carbon black in embodiment 1, its dosage It is changed to 12.0kg；It is 15nm with average grain diameter, whiteness (CIE L*) 95, oil absorption 22g/100g, specific surface area 50m2/ g (BET sides Method test), density 0.8g/cm2Titanium dioxide replace titanium dioxide in embodiment 1, its dosage is changed to 6.0kg；
In step 4), when dispersible pigment dispersion and polyamic acid solution are mixed, carbon black contains in control gained mixed liquor Measure as 12wt%, the content of titanium dioxide is 6.0wt%.
Embodiment 2
Embodiment 1 is repeated, unlike：
In step 2), Chinese white is changed to be made up of 6.0kg titanium dioxide and 6.0kg calcium carbonate, wherein titanium dioxide The parameters of titanium are same as Example 1, and calcium carbonate is then to meet following condition：Average grain diameter is 5nm, whiteness (CIE L*) 95, oil absorption 22g/100g, specific surface area 50m2/ g (test of BET methods), density 0.8g/cm2。
Embodiment 3
Embodiment 1 is repeated, unlike：
In step 2), Chinese white is changed to be made up of 10.0kg titanium dioxide and 2.0kg hydrophily spherical calcium carbonates, The parameters of wherein titanium dioxide are same as Example 1, and calcium carbonate is then to meet following condition：Average grain diameter is 5nm, whiteness (CIE L*) 102, oil absorption 18g/100g, specific surface area 320m2/ g (test of BET methods), density 0.5g/cm2。
Embodiment 4
Embodiment 2 is repeated, unlike：
In step 2), after DMA is added, 100g gamma-amino propyl-triethoxysilicane is first added Alkane, insulating properties carbon black is added after stirring 30min；In addition, the weight of titanium dioxide and calcium carbonate ratio is 1 in Chinese white：5, Total dosage of Chinese white is constant.
Embodiment 5
1) using as 720.0kg DMAC N,N' dimethyl acetamides (DMAc) addition of solvent under nitrogen atmosphere protective condition In reactor, amido diphenyl ether (ODA) 38.29kg of polymerized monomer diamines 4,4 '-two is added, is added after stirring and dissolving The polymerized monomer dianhydride pyromellitic acid anhydride (PMDA) of 41.71kg equimolar amounts, stirring condensation polymerization reaction, obtains polyamic acid Solution (solid content 10wt%)；
2) take 80.0kg DMA to be put into 100L containers, it is (flat to add 4.8kg insulating properties carbon black afterwards Equal particle diameter is 50nm), 5.6kg titanium dioxide (average grain diameter 50nm, whiteness (CIE L*) 120, oil absorption 16g/100g, than Surface area 260m2/ g (test of BET methods), density 0.6g/cm2), ultrasonic disperse 60min, then pass through high pressure homogenizer homogeneous 15min, obtain dispersible pigment dispersion；
3) by dispersible pigment dispersion and polyamic acid solution mixing, (content of carbon black is in mixed liquor obtained by being controlled during mixing 6.0wt%, the content of titanium dioxide is 7.0wt%), obtain polyamic acid resin mixed solution after stirring 8h.Deaeration will be passed through The polyamic acid resin solution of processing is passed through by die head 150 μm of thickness of coating on ring steel belt, then at 100~250 DEG C It is lower it is dry remove most of solvent, obtain with can self-supporting Polyamic Acid Film.Gained film is moved up from ring steel belt Remove and be delivered on high temperature bi-directional stretching-machine, and 550 DEG C are heated to from 180 DEG C, then cooling and the obtained thickness of removal from chain pincers The black polyamide thin film of 12.5 μm of degree.
Embodiment 6
1) using as 500.0kg DMAC N,N' dimethyl acetamides (DMAc) addition of solvent under nitrogen atmosphere protective condition In reactor, amido diphenyl ether (ODA) 239.32kg of polymerized monomer diamines 4,4 '-two is added, is added after stirring and dissolving The polymerized monomer dianhydride pyromellitic acid anhydride (PMDA) of 260.68kg equimolar amounts, stirring condensation polymerization reaction, obtains polyamide Acid solution (solid content 50wt%)；
2) take 600.0kg DMA to be put into 100L containers, add 50.0kg insulating properties carbon blacks afterwards (average grain diameter 40nm), 10.0kg titanium dioxide (average grain diameter 40nm, whiteness (CIE L*) 115, oil absorption 15g/ 100g, specific surface area 300m2/ g (test of BET methods), density 0.5g/cm2), ultrasonic disperse 60min, then pass through high pressure homogenizer Homogeneous 15min, obtains dispersible pigment dispersion；
3) by dispersible pigment dispersion and polyamic acid solution mixing, (content of carbon black is in mixed liquor obtained by being controlled during mixing 10.0wt%, the content of titanium dioxide is 2.0wt%), obtain polyamic acid resin mixed solution after stirring 8h.Deaeration will be passed through The polyamic acid resin solution of processing is passed through by die head 150 μm of thickness of coating on ring steel belt, then at 100~250 DEG C It is lower it is dry remove most of solvent, obtain with can self-supporting Polyamic Acid Film.Gained film is moved up from ring steel belt Remove and be delivered on high temperature bi-directional stretching-machine, and 550 DEG C are heated to from 180 DEG C, then cooling and the obtained thickness of removal from chain pincers The black polyamide thin film of 12.5 μm of degree.
Comparative example 6
Embodiment 6 is repeated, unlike：
In step 2), in pigment preparation dispersion liquid, only add carbon black and do not add titanium dioxide；
In step 4), when dispersible pigment dispersion and polyamic acid solution are mixed, carbon black contains in control gained mixed liquor Measure as 10.0wt%.
Embodiment 7
1) using as 720.0kg DMAC N,N' dimethyl acetamides (DMAc) addition of solvent under nitrogen atmosphere protective condition In reactor, amido diphenyl ether (ODA) 48.60kg of polymerized monomer diamines 4,4 '-two is added, is added after stirring and dissolving The polymerized monomer dianhydride 3,3 ' 4 of 71.40kg equimolar amounts, 4 '-BPDA (BPDA), stirring condensation polymerization reaction, obtain Polyamic acid solution (solid content 15wt%)；
2) take 300.0kg DMA to be put into 500L containers, add 0.24kg insulating properties carbon blacks afterwards Oxidized silicon (the SiO of (average grain diameter 20nm), 2.4kg2) surface treatment hydrophilic titanium oxide (average grain diameter 20nm, Whiteness (CIE L*) 115, oil absorption 15g/100g, specific surface area 300m2/ g (test of BET methods), density 0.5g/cm2), ultrasound Scattered 60min, then by high pressure homogenizer homogeneous 15min, obtain dispersible pigment dispersion；
3) by dispersible pigment dispersion and polyamic acid solution mixing, (content of carbon black is in mixed liquor obtained by being controlled during mixing 0.2wt%, the content of titanium dioxide is 2.0wt%), obtain polyamic acid resin mixed solution after stirring 8h.Deaeration will be passed through The polyamic acid resin solution of processing is passed through by die head 150 μm of thickness of coating on ring steel belt, then at 100~250 DEG C It is lower it is dry remove most of solvent, obtain with can self-supporting Polyamic Acid Film.Gained film is moved up from ring steel belt Remove and be delivered on high temperature bi-directional stretching-machine, and 550 DEG C are heated to from 180 DEG C, then cooling and the obtained thickness of removal from chain pincers The black polyamide thin film of 12.5 μm of degree.
Embodiment 8
1) using as 450.0kg DMAC N,N' dimethyl acetamides (DMAc) addition of solvent under nitrogen atmosphere protective condition In reactor, amido diphenyl ether (ODA) 20.25kg of polymerized monomer diamines 4,4 '-two is added, is added after stirring and dissolving The polymerized monomer dianhydride 3,3 ' 4 of 29.75kg equimolar amounts, 4 '-BPDA (BPDA), stirring condensation polymerization reaction, obtain Polyamic acid solution (solid content 10wt%)；
2) take 100.0kg DMA to be put into 150L containers, add 4.0kg insulating properties carbon blacks afterwards Oxidized aluminium (the AL of (average grain diameter 30nm), 6.0kg2O3) (average grain diameter is for the hydrophily anatase titanium dioxide of surface treatment 30nm, whiteness (CIE L*) 185, oil absorption 12g/100g, specific surface area 400m2/ g (test of BET methods), density 0.2g/ cm2), ultrasonic disperse 60min, then by high pressure homogenizer homogeneous 15min, obtain dispersible pigment dispersion；
3) by dispersible pigment dispersion and polyamic acid solution mixing, (content of carbon black is in mixed liquor obtained by being controlled during mixing 8.0wt%, the content of titanium dioxide is 12.0wt%), obtain polyamic acid resin mixed solution after stirring 8h.Deaeration will be passed through The polyamic acid resin solution of processing is passed through by die head 150 μm of thickness of coating on ring steel belt, then at 100~250 DEG C It is lower it is dry remove most of solvent, obtain with can self-supporting Polyamic Acid Film.Gained film is moved up from ring steel belt Remove and be delivered on high temperature bi-directional stretching-machine, and 550 DEG C are heated to from 180 DEG C, then cooling and the obtained thickness of removal from chain pincers The black polyamide thin film of 12.5 μm of degree.
To light transmittance, tensile strength, elongation, the mould of Kapton made from the various embodiments described above and each comparative example The performances such as amount, electrical strength are measured, as a result as described in Table 1.
Table 1
As shown in table 1, the black polyamide thin film prepared by embodiment 1 to 8 has relatively low light transmittance etc. excellent Different optical property and screening performance (blackness parameter value is very low), at the same also show high electric property (electrical strength) with And good thermal property (such as high tensile, high elongation rate).And the Chinese white titanium oxide and carbon used in example 4 Sour calcium weight is not 1:Can also be made during 1~0.2 proportioning number range, during by introducing dispersant with embodiment 1,2,3, 5 to 8 use white pigment titanium dioxide with weight of calcium carbonate 1:The film performance of 1~0.2 proportioning number range；Meanwhile From hydrophily spherical calcium carbonate or oxidized silicon (SiO2) and/or aluminum oxide (AL2O3) surface treatment hydrophily anatase titanium dioxide two The dispersiveness of the embodiment 3,7,8 of titanium oxide is more preferable, and film thermal property, insulating properties (electrical strength) are more preferably.
On the other hand, the black polyamide thin film prepared in the comparative example 1,6 for not using titanium dioxide does not have Desired optical property, thermal property and electric property.And in comparative example 2 to 3, used white pigment property parameter is not In the range of restriction, the black matt polyimide film of preparation has poor optical property, thermal property and insulating properties； Meanwhile in comparative example 4 to 5, used Chinese white and black pigment are matched not in the range of restriction and when particle diameter differs, The black polyamide thin film of preparation equally has poor optical property, thermal property and electric property.
Above-described embodiment, only the purpose of the present invention, technical scheme and beneficial effect are further described specific Individual example, the present invention are not limited to this.All any modifications made within the scope of disclosure of the invention, equivalent substitution, change Enter, be all contained within protection scope of the present invention.

Claims (9)

1. a kind of preparation method of black polyamide thin film, it is characterised in that comprise the following steps：
1) polyamic acid solution is prepared；
2) take pigment to be scattered in polar non-solute and obtain dispersible pigment dispersion, described pigment includes black pigment and white Pigment, wherein Chinese white are titanium dioxide and/or calcium carbonate, and described titanium dioxide and/or calcium carbonate meet following condition：
5~60nm of average grain diameter, whiteness >=95, oil absorption≤22g/100g, 50~400m of specific surface area2/ g, density≤0.8g/ cm2；
The dosage of the Chinese white is 2wt%~12wt% of polyimides weight, and the weight proportion of itself and black pigment is 10~1.2：1；
The average grain diameter of the black pigment is identical with the average grain diameter of Chinese white；
3) dispersible pigment dispersion and polyamic acid solution are well mixed, prepare film forming by existing common process afterwards.
2. preparation method according to claim 1, it is characterised in that：In step 2), the Chinese white is titanium dioxide With the combination of calcium carbonate, the wherein weight proportion of titanium dioxide and calcium carbonate is 1：1~0.2.
3. preparation method according to claim 1 or 2, it is characterised in that：In step 2), described titanium dioxide and/or Calcium carbonate meets following condition：
10~50nm of average grain diameter, whiteness >=96, oil absorption≤18g/100g, 150~360m of specific surface area2/ g, density≤ 0.4g/cm2。
4. preparation method according to claim 1 or 2, it is characterised in that：In step 2), described titanium dioxide is hydrophilic Property anatase titanium dioxide.
5. preparation method according to claim 1 or 2, it is characterised in that：In step 2), described calcium carbonate is hydrophily Calcium carbonate.
6. preparation method according to claim 1 or 2, it is characterised in that：In step 2), described calcium carbonate is hydrophily Spherical calcium carbonate.
7. preparation method according to claim 1 or 2, it is characterised in that：In step 2), described titanium dioxide is through two Silica and/or the hydrophily anatase titanium dioxide of aluminum oxide surface treatment.
8. preparation method according to claim 1 or 2, it is characterised in that：In step 2), the black pigment is selected from exhausted Combination more than one or both of edge carbon black, cupric and chromic oxide and iron oxide.
9. the black polyamide thin film that method any one of claim 1~8 is prepared.
CN201710653733.9A 2017-08-02 2017-08-02 A kind of black polyamide thin film and preparation method thereof Pending CN107400250A (en)

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CN108752931A (en) * 2018-06-27 2018-11-06 桂林电器科学研究院有限公司 Micro-nano inorganic particle hybrid modified black matt polyimide film and preparation method thereof
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