CN107312191A - A kind of multilayer black matt polyimide film and preparation method thereof - Google Patents

A kind of multilayer black matt polyimide film and preparation method thereof Download PDF

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Publication number
CN107312191A
CN107312191A CN201710653731.XA CN201710653731A CN107312191A CN 107312191 A CN107312191 A CN 107312191A CN 201710653731 A CN201710653731 A CN 201710653731A CN 107312191 A CN107312191 A CN 107312191A
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black
matt
film
polyamide acid
acid film
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任小龙
韩艳霞
周福龙
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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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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • C08J2479/00—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 C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08K3/22—Oxides; Hydroxides of metals
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Abstract

The invention discloses a kind of multilayer black matt polyimide film and preparation method thereof, the multilayer black matt polyimide film includes the matt polyimide layer formed by matt polyamide acid film of one layer of black polyimide layer and surface disposed thereon formed by black polyamide acid film and/or lower surface；In the preparation, including prepare black polyamide acid film method and prepare matt polyamide acid film method, the former is to form black pigment dispersion liquid with being produced in conventional fashion after being mixed by polyamic acid solution；The latter is to be well mixed dispersible pigment dispersion, delustring agent dispersing liquid with polyamic acid solution, and gained mixed material is in the upper surface of black polyamide acid film and/or lower surface formation matt polyamide acid film.The film as made from the method for the invention has more excellent optical property, hot property and insulating properties.

Description

A kind of multilayer black matt polyimide film and preparation method thereof
Technical field
The present invention relates to Kapton, and in particular to a kind of multilayer black matt polyimide film and its preparation side Method.
Background technology
Black matt polyimide film is a kind of high insulation, the insulation film of high intensity, is gathered compared to common (yellow) Acid imide film, black polyamide film is opaque, light transmission and reflectance factor are low, with good light-proofness, thermal conductivity etc., It is widely used in cover layer of mobile device, computer, automobile and Military Electronic Equipment etc..
The production technology of current Kapton is using the polyamic acid resin solution synthesized by polycondensation reaction as original Material, salivation obtains the polyamic acid thick film with self-supporting on slobbering machine, then fixed by heating stretching, imidization, cooling Type processing obtains Kapton.Obtain having concurrently the Kapton of low-luster, low light transmission and insulating properties, poly- It must be added in imide membrane preparation process in colour additive (for example：Colorant, dyestuff etc.) and delustering agent.General technique is Colour additive is used to reduce the light transmittance of Kapton, or addition delustering agent causes Kapton surface shape Into concave-convex micro-structure to reduce the glossiness of Kapton.Such as South Korea's patent of invention of application in 2011 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 in ＜ 0.1%, glossiness ＜ 40.0%, specific insulation ＞ 1015Ω cm and dielectric strength ＞ 40kV/ Mm black matt polyimide film.The Chinese invention patent CN 104169330B " black polyamides of application in 2012 Film " is disclosed by charcoal blacks (3.0wt%-7.5wt%, 70nm -150nm primary particle sizes), titanium dioxide screener Light transmission≤1.0% of (0.2 μm -0.6 μm of 0.5wt%-1.5wt%, volume mean diameter), polyimide resin preparation, Black polyamide thin film of glossiness≤60% etc..But it is to reduce film to choose black pigment-carbon black in the prior art Light transmittance, choose inorganic filler-delustering agent reduction film glossiness for the purpose of, manufactured film exist blackness not enough, masking effect Really limited and Color uniformity is poor etc. not enough.Because inorganic particulate has higher dielectric constant, this will improve gained polyamides The dielectric constant of imines film, reduces its electrical insulating property.
And existing double-deck or multilayer black matt polyimide film then it is mostly be by the one side in polyimide base film or One layer of polyimide film containing black pigment and photoextinction of two-sided upper coating is prepared from.Although such a method can be preferably Make the desired black of Kapton presentation and matt effect and the certain mechanical performance of polyimide film can be ensured, But the black matt resin being additionally coated with would generally increase manufacturing process and cost, and Kapton property is caused not The influence of profit；In addition, can also cause polyimide film to be exposed to easy generation property during hot adverse circumstance because resin coated layer heat resistance is poor Can deterioration.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of multilayer black matt polyimide film and preparation method thereof. The premise of the original mechanical performance of film is being kept using multilayer black matt polyimide film made from the method for the invention Its optical property, thermal property and insulating properties are effectively lifted down.
The preparation method of multilayer black matt polyimide film of the present invention, the multilayer black matt polyimide Film includes one layer of black polyimide layer and surface disposed thereon for being formed by black polyamide acid film and/or lower surface The matt polyimide layer formed by matt polyamide acid film；In the preparation, including prepare the method for black polyamide acid film with And the method for preparing matt polyamide acid film, wherein：
Preparing the method for black polyamide acid film includes：Take black pigment to be scattered in polar non-solute and obtain black Dispersible pigment dispersion, by gained black pigment dispersion liquid and the polycondensation reaction in polar non-solute by aromatic diamine and dianhydride Obtained polyamic acid solution is well mixed, and is prepared into black polyamide acid film by existing common process afterwards；
The method for preparing matt polyamide acid film 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 >=95, oil absorption≤22g/100g, 50~400m of specific surface area2/ g, density≤ 0.8g/cm2；
The consumption of the Chinese white is 2wt%~12wt% of strata acid imide weight where it, itself and black pigment Weight proportion be 10~1.2：1；
The average grain diameter of the black pigment is identical with the average grain diameter of Chinese white；
3) cancellation photo etching, which is scattered in polar non-solute, obtains delustring agent dispersing liquid；
4) dispersible pigment dispersion, delustring agent dispersing liquid are well mixed with polyamic acid solution, gained mixed material is in black The upper surface of polyamide acid film and/or lower surface are by existing common process formation matt polyamide acid film.
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 matt polyimide film, by making for Chinese white The 2.0wt% of strata acid imide weight where consumption is defined to it allows for its consumption less than layer where it to 12.0wt% Blackness is unsatisfactory during the 2.0wt% of polyimides weight；And its consumption is more than its place strata acid imide weight During 12.0wt%, then mechanical performance, insulating properties of gained film etc. can be deteriorated, and easily generation is scattered in polyamic acid resin Uneven (sedimentation and reunion), film performance uniformity is poor, can also increase the production cost of film.On the other hand, Chinese white The selection of (titanium dioxide and calcium carbonate) can not only influence itself, black pigment and delustering agent being uniformly dispersed in system Property, optical characteristics, thermal property and the insulating properties of gained Kapton can be also influenceed, in Chinese white and black pigment Dispersiveness of the various solid packings in resin can be effectively improved in the case of with same particle diameter.
Further, when white filler is titanium dioxide and calcium carbonate in combination, and the weight of titanium dioxide and calcium carbonate matches 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 technical scheme of the present invention, in the method for preparing black polyamide acid film, involved black pigment Selection and consumption are same as the prior art, and specific selection can be selected from insulating properties carbon black, cupric and chromic oxide and iron oxide One or both of more than combination, preferably insulating properties carbon black (can be with the exhausted of O.001 μm~2 μm of average grain diameters Edge carbon black, preferably the insulating properties carbon black with O.01 μm~1 μm of average grain diameter, it is more preferably average with 0.08 μm~0.8 μm The insulating properties carbon black of particle diameter)；Its consumption can be the 5wt~25wt%, preferably 8wt% of polyimides weight in layer where it ~16wt%.
In technical scheme of the present invention, in the method for preparing matt polyamide acid film, involved black pigment Selection is same as the prior art, and specific selection can be one kind in insulating properties carbon black, cupric and chromic oxide and iron oxide Or two or more combinations, preferably insulating properties carbon black (can be the insulating properties carbon black with O.001 μm~2 μm of average grain diameters, It is preferred that the insulating properties carbon black with O.01 μm~1 μm of average grain diameter, the more preferably insulation with 0.08 μm~0.8 μm average grain diameter Property carbon black).
In technical scheme of the present invention, the selection of involved aromatic diamine, dianhydride and polar non-solute And consumption is same as the prior art, specifically：Aromatic diamine can be p-phenylenediamine, 4,4 '-diamino-diphenyl ether, 3, Any one in 4 '-diamino-diphenyl ether and 4,4 '-diaminodiphenyl-methane etc. or two or more combinations；Work as fragrance When the selection of race's diamines is combination more than above two, the proportioning between them can be any proportioning.Described dianhydride tool Body can be pyromellitic acid anhydride, 3,3 ', 4,4 '-diphenyl ether tetraformic dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 3, Any one in 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) and the PMDA of hexafluoroisopropyli,ene two or two or more groups Close；When the selection of dianhydride monomer is the combination of more than above two, the proportioning between them can be any proportioning.Described Polar non-solute can be DMAC N,N' dimethyl acetamide (DMAC), N,N-dimethylformamide (DMF), N- methyl -2- pyrroles Any one in pyrrolidone (NMP) or two or more combinations；The consumption of described polar non-solute can be specifically When aromatic diamine, dianhydride monomer and polar non-solute formation polyamic acid solution, consolidating in the polyamic acid solution Content is controlled in 10wt%~50wt%, preferably 15wt%~35wt%.Polycondensation is carried out in aromatic diamine and dianhydride monomer During reaction, the temperature of mole when polycondensation reaction of the aromatic diamine and dianhydride monomer is same as the prior art, specifically Ground, the mol ratio of the aromatic diamine and dianhydride monomer can be 0.9~1.1：1, preferably 0.95~1.05：1；The contracting The temperature of poly- reaction can be 0~50 DEG C, and the time of reaction is usually 3~12h.
In above-mentioned technical proposal, the step 1 of matt polyamic acid film method is being prepared) in, using existing conventional method system Standby polyamic acid solution, can be specifically to be obtained using aromatic diamine and dianhydride in polar non-solute by polycondensation reaction Arrive.The selection of the aromatic diamine, dianhydride and the polar non-solute that refer here to and consumption are as hereinbefore.
In above-mentioned technical proposal, prepare matt polyamic acid film method step 2) in, more preferably titanium dioxide and/or Calcium carbonate meets following condition：10~50nm of average grain diameter (further preferred 20~40nm), whiteness >=96 (further preferably >= 98), oil absorption≤18g/100g (further preferably≤15g/100g), 150~360m of specific surface area2/ g (further preferred 200 ~300m2/ g), density≤0.4g/cm2(further preferably≤0.3g/cm2)。
In above-mentioned technical proposal, the step 2 of matt polyamic acid film method is being prepared) in, select it as Chinese white One titanium dioxide is more preferably hydrophily 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 then enters One step is preferably hydrophily calcium carbonate, still further preferably hydrophily spherical calcium carbonate.It so can further improve white face Material, the dispersiveness of black pigment and delustering agent in polyimide resin system, have gained Kapton more excellent Thermal property and insulating properties.
In above-mentioned technical proposal, prepare matt polyamic acid film method step 3) in, the selection of the delustering agent and Consumption is same as the prior art, and specific selection can be that (their average grain diameter can be with for silica and/or titanium dioxide Be O.8 μm~15 μm, preferably 1 μm~10 μm, more preferably 3 μm~6 μm)；Its consumption can be polyimides weight 4wt%~15wt%, preferably 6wt%~12wt%.
In above-mentioned preparation method, involved being separated into is dispersed, can be using existing conventional method such as ultrasound point Dissipate, shear the realization of the technological means such as scattered, homogeneous.
Present invention additionally comprises the multilayer black matt polyimide film prepared by the above method.
Compared with prior art, the method have the characteristics that：
1st, by selecting specific consumption and the Chinese white and black face of particular characteristic parameter in matt polyimide layer Material is matched, and makes gained matt polyimide layer while with conventional black matt polyimide film mechanical performance, It further improves optical property (blackness, light transmittance, glossiness etc.), thermal property (shrinkage factor, the thermal expansion of gained film Coefficient etc.) and insulating properties (electrical strength, dielectric constant etc.), the demand in market can be more met, expands product applications；
When the 2nd, making multilayer black polyamide thin film product, nanoscale Chinese white has space steric effect, poly- In amic acid resin synthesis process, black pigment and delustering agent can be made to suspend, play anti-settling effect, filler is uniformly dispersed surely It is fixed, and the time of storage-stable is longer；
3rd, the method for the invention is easy to operate, it is easy to accomplish industrialized production.
Brief description of the drawings
Fig. 1 is a kind of embodiment of multilayer black matt polyimide film (two layers of knot made from the method for the invention Structure, wherein lower floor are black polyimide layer, and upper strata is matt polyimide layer)；
Fig. 2 is (three layers of multilayer black matt polyimide film another embodiment made from the method for the invention Structure, wherein intermediate layer are black polyimide layer, and upper and lower two layers is matt polyimide layer).
In figure marked as：
1st, matt polyimide layer, 2, black polyimide layer, 3, black pigment, 4, Chinese white.
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 from Chinese white 4 and black pigment 3 in matt polyimide layer 1 and made With, and the various performance parameters (the particularly selection of granularity) of Chinese white 4 are particularly limited to, because applicant is in experiment, research Found in analysis：
When the particle diameter of Chinese white 4 is less than 5nm, then background color whiteness is presented needed for film unobvious；And particle diameter is more than 60nm, then Film color homogeneity is poor, and it is that Extinction characteristics are not obvious that filler, which disperses inequality,.Strata where the addition of Chinese white 4 is less than it The 2wt% of acid imide weight, then presentation background color whiteness is not obvious needed for film, and addition is more than strata acid imide weight where its 12wt%, then film color homogeneity is poor, filling settlement and scattered inequality is that film apparent mass is poor.
For black pigment 3, 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 introduces Chinese white 4 in matt polyimide layer 1, not only can effectively reduce the addition of black pigment 3, and And film blackness can be effectively ensured on the basis of the addition of black pigment 3 is substantially reduced with the formation complementary colours of black pigment 3 Film blackness is even improved, black matt polyimide film outward appearance is seemed that more there is aesthetic feeling.On the other hand, nanoscale Chinese white 4 has space steric effect, in polyamic acid resin building-up process, and black pigment 3 and delustering agent can be made to suspend, Play anti-settling effect.Meanwhile, gained black matt polyimide film can have stronger Extinction Characteristic and homogeneous color And performance.
Embodiment 1
1) preparation of black polyamide acid film：
1.1) DMA for weighing 50.0kg is put into 100L containers, and 5.0kg insulating properties charcoals are added afterwards Black (average grain diameter is 0.9um), ultrasonic disperse 60min, then by high pressure homogenizer homogeneous 15min, obtain black pigment and disperse Liquid；
1.2) it will add under nitrogen atmosphere protective condition as the 400.0kg DMAC N,N' dimethyl acetamides (DMAc) of solvent Enter in reactor, added after adding amido diphenyl ether (ODA) 47.86kg of polymerized monomer diamines 4,4 '-two, 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 is 20wt%)；
1.3) black pigment dispersion liquid mixes to (carbon black contains in control gained mixed liquor during mixing with polyamic acid solution Measure as 5.0wt%), stir and black polyamic acid resin mixed solution is obtained after 8h.The black polyamide that will be handled by deaeration Acid resin solution passes through the thickness for coating 75 μm by die head on ring steel belt, and the big portion of removing is then dried at 100~250 DEG C Divide solvent, obtain the black polyamide acid film with self-supporting；
2) preparation of matt polyamide acid film：
2.1) it will add under nitrogen atmosphere protective condition as the 400.0kg DMAC N,N' dimethyl acetamides (DMAc) of solvent Enter in reactor, added after adding amido diphenyl ether (ODA) 47.86kg of polymerized monomer diamines 4,4 '-two, 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 is 20wt%)；
2.2) take 50.0kg DMA to be put into 100L containers, 5.0kg insulating properties carbon blacks are added afterwards (average grain diameter is 5nm, whiteness (CIE L for (average grain diameter is 5nm), 12.0kg titanium dioxide*) 95, oil absorption 22g/100g, than Surface area 50m2/ g (test of BET methods), density 0.8g/cm2), ultrasonic disperse 60min, then pass through high pressure homogenizer homogeneous 15min, obtains dispersible pigment dispersion；
2.3) 10.0kg delustering agents silica (average grain diameter is 8um) is taken to be placed in 50.0kg DMAC N,N' dimethyl acetamides In, after the scattered 1h of shearing, ultrasonic disperse 2h obtains delustring agent dispersing liquid；
2.4) dispersible pigment dispersion, delustring agent dispersing liquid are mixed with polyamic acid solution and (gained mixed liquor is controlled during mixing The content of middle carbon black is 0.2wt%, and content of titanium dioxide is 12.0wt%, and the content of silica is 10.0wt%), stir 8h Polyamic acid resin mixed solution is obtained afterwards.The polyamic acid resin solution handled by deaeration is passed through and coats 75 μm by die head Thickness in step 1) above shaped black polyamide acid film, then dried at 100~250 DEG C remove it is most of molten Agent film forming, it is that black polyamide acid film, upper strata are matt polyamide acid film and with self-supporting two membranes to obtain lower floor.
3) by step 2) obtained by two membranes be delivered on high temperature bi-directional stretching-machine, and be heated to 550 DEG C from 180 DEG C, so Cool down and removed from chain pincers afterwards and lower floor is made for black polyimide layer 2, upper strata is matt polyimide layer 1 and thickness 12.5 μm two layers of black matt polyimide film, its structure is as shown in Figure 1.
Comparative example 1：The preparation of two layers of black matt polyimide film
Embodiment 1 is repeated, unlike：
Step 2.2) in, in pigment preparation dispersion liquid, only add carbon black；
Step 2.4) in, when dispersible pigment dispersion, delustring agent dispersing liquid are mixed with polyamic acid solution, control gained is mixed The content for closing carbon black in liquid is 0.2wt%, and the content of silica is 10.0wt%.
Comparative example 2：The preparation of two layers of black matt polyimide film
Embodiment 1 is repeated, unlike：
Step 2.2) in, 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：The preparation of two layers of black matt polyimide film
Embodiment 1 is repeated, unlike：
Step 2.2) in, 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：The preparation of two layers of black matt polyimide film
Embodiment 1 is repeated, unlike：
Step 2.2) in, the insulating properties carbon black for being 15nm with average grain diameter replaces the insulating properties carbon black in embodiment 1), its Consumption is constant；It is 18nm, whiteness (CIE L with average grain diameter*) 95, oil absorption 22g/100g, specific surface area 50m2/ g (BET methods Test), density 0.8g/cm2Titanium dioxide replace titanium dioxide in embodiment 1, its consumption is constant.
Comparative example 5：The preparation of two layers of black matt polyimide film
Embodiment 1 is repeated, unlike：
Step 2.2) in, the insulating properties carbon black for being 15nm with average grain diameter replaces the insulating properties carbon black in embodiment 1), its Consumption is changed to 12.0kg；It is 15nm, whiteness (CIE L with average grain diameter*) 95, oil absorption 22g/100g, specific surface area 50m2/g (test of BET methods), density 0.8g/cm2Titanium dioxide replace titanium dioxide in embodiment 1, its consumption is changed to 6.0kg；
Step 2.4) in, when dispersible pigment dispersion, delustring agent dispersing liquid are mixed with polyamic acid solution, control gained is mixed The content for closing carbon black in liquid is 12wt%, and the content of titanium dioxide is 6.0wt%, and the content of silica is 10.0wt%.
Embodiment 2：The preparation of two layers of black matt polyimide film
Embodiment 1 is repeated, unlike：
Step 2.2) in, Chinese white 4 is changed to be made up of 6.0kg titanium dioxide and 6.0kg calcium carbonate, wherein dioxy The parameters for changing 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：The preparation of two layers of black matt polyimide film
Embodiment 1 is repeated, unlike：
Step 2.2) in, Chinese white 4 is changed to by 10.0kg titanium dioxide and 2.0kg hydrophily spherical calcium carbonate groups Into 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：The preparation of two layers of black matt polyimide film
Embodiment 2 is repeated, unlike：
Step 2.2) in, after DMA is added, first add 100g gamma-amino propyl-triethoxysilicane Insulating properties carbon black is added after alkane, stirring 30min；In addition, the weight ratio of titanium dioxide and calcium carbonate is 1 in Chinese white 4：5, Total consumption of Chinese white 4 is constant.
Embodiment 5：The preparation of three layers of black matt polyimide film
1) preparation of black polyamide acid film：
1.1) DMA for weighing 50.0kg is put into 100L containers, and 5.0kg insulating properties charcoals are added afterwards Black (average grain diameter is 0.9um), ultrasonic disperse 60min, then by high pressure homogenizer homogeneous 15min, obtain black pigment and disperse Liquid；
1.2) it will add under nitrogen atmosphere protective condition as the 400.0kg DMAC N,N' dimethyl acetamides (DMAc) of solvent Enter in reactor, added after adding amido diphenyl ether (ODA) 47.86kg of polymerized monomer diamines 4,4 '-two, 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 is 20wt%)；
1.3) black pigment dispersion liquid mixes to (carbon black contains in control gained mixed liquor during mixing with polyamic acid solution Measure as 5.0wt%), stir and black polyamic acid resin mixed solution is obtained after 8h.The black polyamide that will be handled by deaeration Acid resin solution passes through the thickness for coating 75 μm by die head on ring steel belt, and the big portion of removing is then dried at 100~250 DEG C Divide solvent, obtain the black polyamide acid film with self-supporting；
2) preparation of matt polyamide acid film：
2.1) it will add under nitrogen atmosphere protective condition as the 720.0kg DMAC N,N' dimethyl acetamides (DMAc) of solvent Enter in reactor, added after adding amido diphenyl ether (ODA) 38.29kg of polymerized monomer diamines 4,4 '-two, 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 is 10wt%)；
2.2) take 80.0kg DMA to be put into 100L containers, 4.8kg insulating properties carbon blacks are added afterwards (average grain diameter is 50nm, whiteness (CIE L for (average grain diameter is 50nm), 5.6kg titanium dioxide*) 120, oil absorption 16g/100g, Specific surface area 260m2/ g (test of BET methods), density 0.6g/cm2), ultrasonic disperse 60min, then pass through high pressure homogenizer homogeneous 15min, obtains dispersible pigment dispersion；
2.3) 3.2kg delustering agents silica (average grain diameter is 0.08um) is taken to be placed in 80.0kg N, N- dimethylacetamides In amine, after the scattered 1h of shearing, ultrasonic disperse 2h obtains delustring agent dispersing liquid；
2.4) dispersible pigment dispersion, delustring agent dispersing liquid are mixed with polyamic acid solution and (gained mixed liquor is controlled during mixing The content of middle carbon black is 6.0wt%, and the content of titanium dioxide is 7.0wt%, and the content of silica is 4.0wt%), stir 8h Polyamic acid resin mixed solution is obtained afterwards.The polyamic acid resin solution handled by deaeration is passed through and coats 75 μm by die head Thickness in step 1) form one layer of matt polyamide acid film above shaped black polyamide acid film, afterwards again Black polyamide acid film one layer of matt polyamide acid film formed below of shaping, then dries at 100~250 DEG C and removes big portion Divide solvent film forming, it is black polyamide acid film to obtain middle, is the trilamellar membrane of matt polyamide acid film above and below it.
3) by step 2) obtained by trilamellar membrane be delivered on high temperature bi-directional stretching-machine, and be heated to 550 DEG C from 180 DEG C, so Afterwards cooling and from chain pincers remove be made intermediate layer be black polyimide layer 2, upper and lower two layers be matt polyimide layer 1 and Three layers of black matt polyimide film of 12.5 μm of thickness, its structure is as shown in Figure 2.
Embodiment 6：The preparation of three layers of black matt polyimide film
1) preparation of black polyamide acid film：
Be the same as Example 5；
2) preparation of matt polyamide acid film：
2.1) it will add under nitrogen atmosphere protective condition as the 500.0kg DMAC N,N' dimethyl acetamides (DMAc) of solvent Enter in reactor, added after adding amido diphenyl ether (ODA) 239.32kg of polymerized monomer diamines 4,4 '-two, 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 is 50wt%)；
2.2) take 600.0kg DMA to be put into 100L containers, 50.0kg insulating properties charcoals are added afterwards (average grain diameter is 40nm, whiteness (CIE L for black (average grain diameter is 40nm), 10.0kg titanium dioxide*) 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；
2.3) 75.0kg TITANIUM DIOXIDE DELUSTRANTs (average grain diameter is 15.0um) are taken to be placed in 500.0kg N, N- dimethyl second In acid amides, after the scattered 1h of shearing, ultrasonic disperse 2h obtains delustring agent dispersing liquid；
2.4) dispersible pigment dispersion, delustring agent dispersing liquid are mixed with polyamic acid solution and (gained mixed liquor is controlled during mixing The content of middle carbon black is 10.0wt%, and the content of titanium dioxide is 2.0wt%, and the content of silica is 15.0wt%), stirring Polyamic acid resin mixed solution is obtained after 8h.The polyamic acid resin solution handled by deaeration is passed through and coats 75 by die head μm thickness in step 1) form one layer of matt polyamide acid film above shaped black polyamide acid film, afterwards again Shaped black polyamide acid film one layer of matt polyamide acid film formed below, then dries at 100~250 DEG C and removes greatly Partial solvent film forming, it is black polyamide acid film to obtain middle, and its upper and lower is the trilamellar membrane of matt polyamide acid film.
3) by step 2) obtained by trilamellar membrane be delivered on high temperature bi-directional stretching-machine, and be heated to 550 DEG C from 180 DEG C, so Afterwards cooling and from chain pincers remove be made intermediate layer be black polyimide layer 2, upper and lower two layers be matt polyimide layer 1 and Three layers of black matt polyimide film of 12.5 μm of thickness.
Comparative example 6：The preparation of three layers of black matt polyimide film
Embodiment 6 is repeated, unlike：
Step 2) in, in pigment preparation dispersion liquid, carbon black is only added without titanium dioxide；
Step 4) in, when dispersible pigment dispersion, delustring agent dispersing liquid are mixed with polyamic acid solution, control gained is mixed The content of carbon black is 10.0wt% in liquid, and the content of silica is 15.0wt%.
Embodiment 7：The preparation of two layers of black matt polyimide film
Embodiment 1 is repeated, unlike：Step 2) carried out by following programs：
2.1) it will add under nitrogen atmosphere protective condition as the 720.0kg DMAC N,N' dimethyl acetamides (DMAc) of solvent Enter in reactor, added after adding amido diphenyl ether (ODA) 48.60kg of polymerized monomer diamines 4,4 '-two, stirring and dissolving The polymerized monomer dianhydride 3,3 ' 4 of 71.40kg equimolar amounts, 4 '-BPDA (BPDA), stirring condensation polymerization reaction is obtained Polyamic acid solution (solid content is 15wt%)；
2.2) take 300.0kg DMA to be put into 500L containers, 0.24kg insulating properties charcoals are added afterwards Black (average grain diameter is 20nm), the oxidized silicon (SiO of 2.4kg2) (average grain diameter is for the hydrophilic titanium oxide of surface treatment 20nm, 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 by high pressure homogenizer homogeneous 15min, obtain dispersible pigment dispersion；
2.3) 12.0kg delustering agents silica (average grain diameter is 15.0um) is taken to be placed in 100.0kg N, N- dimethyl second In acid amides, after the scattered 1h of shearing, ultrasonic disperse 2h obtains delustring agent dispersing liquid；
2.4) dispersible pigment dispersion, delustring agent dispersing liquid are mixed with polyamic acid solution and (gained mixed liquor is controlled during mixing The content of middle carbon black is 0.2wt%, and the content of titanium dioxide is 2.0wt%, and the content of silica is 10.0wt%), stirring Polyamic acid resin mixed solution is obtained after 8h.The polyamic acid resin solution handled by deaeration is passed through and coats 75 by die head μm thickness in step 1) above shaped black polyamide acid film, then dried at 100~250 DEG C remove it is most of Solvent film forming, it is that black polyamide acid film, upper strata are matt polyamide acid film and with self-supporting two membranes to obtain lower floor.
Embodiment 8：The preparation of two layers of black matt polyimide film
Embodiment 1 is repeated, unlike：Step 2) carried out by following programs：
2.1) it will add under nitrogen atmosphere protective condition as the 450.0kg DMAC N,N' dimethyl acetamides (DMAc) of solvent Enter in reactor, added after adding amido diphenyl ether (ODA) 20.25kg of polymerized monomer diamines 4,4 '-two, stirring and dissolving The polymerized monomer dianhydride 3,3 ' 4 of 29.75kg equimolar amounts, 4 '-BPDA (BPDA), stirring condensation polymerization reaction is obtained Polyamic acid solution (solid content is 10wt%)；
2.2) take 100.0kg DMA to be put into 150L containers, 4.0kg insulating properties carbon blacks are added afterwards (average grain diameter is 30nm), the oxidized aluminium (AL of 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；
2.3) 3.5kg delustering agents silica (average grain diameter is 3.5um) is taken to be placed in 100.0kg N, N- dimethylacetamides In amine, after the scattered 1h of shearing, ultrasonic disperse 2h obtains delustring agent dispersing liquid；
2.4) dispersible pigment dispersion, delustring agent dispersing liquid are mixed with polyamic acid solution and (gained mixed liquor is controlled during mixing The content of middle carbon black is 8.0wt%, and the content of titanium dioxide is 12.0wt%, and the content of silica is 7.0wt%), stirring Polyamic acid resin mixed solution is obtained after 8h.The polyamic acid resin solution handled by deaeration is passed through and coats 75 by die head μm thickness in step 1) above shaped black polyamide acid film, then dried at 100~250 DEG C remove it is most of Solvent film forming, it is that black polyamide acid film, upper strata are matt polyamide acid film and with self-supporting two membranes to obtain lower floor.
To the light transmittance of Kapton made from the various embodiments described above and each comparative example, glossiness, tensile strength, stretch The performances such as long rate, modulus, electrical strength are measured.As a result as described in Table 1.
Table 1：
As shown in table 1, by embodiment 1 to 8 prepare black matt polyimide film have relatively low glossiness, The excellent optical property such as light transmittance and screening performance (blackness parameter value is very low), while also showing high electric property (electrical strength) and good thermal property (such as high tensile, high elongation rate).And the white face used in example 4 Expect 4 titanium oxide with weight of calcium carbonate not 1:During 1~0.2 proportioning number range, it can also be made during dispersant by introducing With embodiment 1,2,3,5 to 8 using the titanium dioxide of Chinese white 4 and weight of calcium carbonate 1:1~0.2 proportioning number range Film performance；Meanwhile, from hydrophily spherical calcium carbonate or oxidized silicon (SiO2) and/or aluminum oxide (AL2O3) surface treatment The dispersiveness of the embodiment 3,7,8 of hydrophily anatase titanium dioxide is more preferable, film thermal property, insulating properties (electrical strength) More preferably.
On the other hand, the black matt polyimide film prepared in the comparative example 1,6 for not using titanium dioxide is not With desired optical property, thermal property and electric property.And in comparative example 2 to 3, the used performance of Chinese white 4 Parameter is not in the range of restriction, and the black matt polyimide film of preparation has poor optical property, thermal property and absolutely Edge performance；Meanwhile, in comparative example 4 to 5, used Chinese white 4 and black pigment 3 are matched not in the range of restriction and particle diameter When differing, the black matt polyimide film of preparation equally has poor optical property, thermal property and electric property.
Above-described embodiment, is only to the specific of the purpose of the present invention, technical scheme and beneficial effect further description Individual example, the present invention is 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 (10)

1. a kind of preparation method of multilayer black matt polyimide film, it is characterised in that：The multilayer black matt polyamides is sub- Amine film include one layer of black polyimide layer (2) and surface disposed thereon for being formed by black polyamide acid film and/or under The matt polyimide layer (1) formed by matt polyamide acid film on surface；In the preparation, including black polyamide acid film is prepared Method and prepare matt polyamide acid film method, wherein：
Preparing the method for black polyamide acid film includes：Take black pigment (3) to be scattered in polar non-solute and obtain black Dispersible pigment dispersion, by gained black pigment dispersion liquid and the polycondensation reaction in polar non-solute by aromatic diamine and dianhydride Obtained polyamic acid solution is well mixed, and is prepared into black polyamide acid film by existing common process afterwards；
The method for preparing matt polyamide acid film 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 (3) and Chinese white (4), wherein Chinese white (4) are titanium dioxide and/or calcium carbonate, and described titanium dioxide and/or calcium carbonate are full It is enough lower 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 consumption of the Chinese white (4) is 2wt%~12wt% of strata acid imide weight where it, itself and black pigment (3) weight proportion is 10~1.2：1；
The average grain diameter of the black pigment (3) is identical with the average grain diameter of Chinese white (4)；
3) cancellation photo etching, which is scattered in polar non-solute, obtains delustring agent dispersing liquid；
4) dispersible pigment dispersion, delustring agent dispersing liquid are well mixed with polyamic acid solution, gained mixed material is in black polyamides The upper surface of amino acid film and/or lower surface are by existing common process formation matt polyamide acid film.
2. preparation method according to claim 1, it is characterised in that：In the method for preparing matt polyamide acid film, institute Combination of the Chinese white (4) for titanium dioxide and calcium carbonate is stated, 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 the method for preparing matt polyamide acid film, 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 the method for preparing matt polyamide acid film, Described titanium dioxide is hydrophily anatase titanium dioxide.
5. preparation method according to claim 1 or 2, it is characterised in that：In the method for preparing matt polyamide acid film, Described calcium carbonate is hydrophily calcium carbonate.
6. preparation method according to claim 1 or 2, it is characterised in that：In the method for preparing matt polyamide acid film, Described calcium carbonate is hydrophily spherical calcium carbonate.
7. preparation method according to claim 1 or 2, it is characterised in that：In the method for preparing matt polyamide acid film, Described titanium dioxide is the hydrophily anatase titanium dioxide being surface-treated through silica and/or aluminum oxide.
8. preparation method according to claim 1 or 2, it is characterised in that：In the method for preparing matt polyamide acid film, The delustering agent is silica and/or titanium dioxide.
9. preparation method according to claim 1 or 2, it is characterised in that：The black pigment (3) is selected from insulating properties carbon Combination more than one or both of black, cupric and chromic oxide and iron oxide.
10. the multilayer black matt polyimide film that method any one of claim 1~9 is prepared.
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CN110476123B (en) * 2019-01-23 2022-02-08 律胜科技股份有限公司 Photosensitive polyimide resin composition and polyimide film thereof
CN110818928A (en) * 2019-10-31 2020-02-21 安徽国风塑业股份有限公司 Matte polyimide black film with low thermal shrinkage and preparation method thereof
CN110818928B (en) * 2019-10-31 2022-05-31 安徽国风新材料股份有限公司 Matte polyimide black film with low thermal shrinkage and preparation method thereof
CN112920600A (en) * 2019-12-06 2021-06-08 无锡顺铉新材料有限公司 Black polyimide composite film with two different gloss degrees and preparation method thereof
CN115521706A (en) * 2022-09-29 2022-12-27 广东粤港澳大湾区黄埔材料研究院 Polyimide glue solution, preparation method thereof, black film and flexible printed circuit board
CN115521706B (en) * 2022-09-29 2024-04-30 广东粤港澳大湾区黄埔材料研究院 Polyimide glue solution, preparation method thereof, black film and flexible printed circuit board

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Application publication date: 20171103