CN107226921A - A kind of multilayer black polyamide thin film and preparation method thereof - Google Patents
A kind of multilayer black polyamide thin film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of multilayer black polyamide thin film and preparation method thereof.The multilayer black polyamide thin film includes the black polyimide layer formed by black polyamide acid film of one layer of polyimide precursor film layer and surface disposed thereon formed by polyamic acid solution and/or lower surface；In the preparation, the former is by the former film of existing common process formation polyamic acid by polyamic acid solution；The latter is to form dispersible pigment dispersion 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 the former film of polyamic acid and/or lower surface formation black polyamide acid film.The film as made from the method for the invention has more excellent optical property, hot property and insulating properties.
Description
Technical field
The present invention relates to Kapton, and in particular to a kind of multilayer 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, with 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 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 low light transmission and the Kapton of insulating properties concurrently, it is thin in polyimides
It must be added during film preparation in colour additive (for example：Colorant, dyestuff etc.).General technique be used colour additive with
Reduce the light transmittance of Kapton.Such as the B of Chinese invention patent CN 104169330 " the black polyamides Asias of application in 2012
Amine film " is disclosed by charcoal blacks (3.0wt%-7.5wt%, 70nm -150nm primary particle sizes), titanium dioxide screener
Light transmission≤1.0% prepared by (0.2 μm -0.6 μm of 0.5wt%-1.5wt%, volume mean diameter), polyimide resin
Black polyamide thin film etc..Black polyamides Asia is made by introducing pigment and filler in polyimide resin matrix in this kind of technology
Amine film, but be for the purpose of choosing black pigment-carbon black reduction film light transmittance, manufactured film exist blackness not enough,
Screening effect is limited and the problems such as poor Color uniformity.It must be introduced into if it need to increase blackness, improve screening effect a large amount of black
Color 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 is 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 easily to occur performance degradation 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 multilayer black polyamide thin film and preparation method thereof.Using
Multilayer black polyamide thin film made from the method for the invention is effectively carried on the premise of the original mechanical performance of film is kept
Rise its optical property, thermal property and insulating properties.
The preparation method of multilayer black polyamide thin film of the present invention, the multilayer black polyamide thin film includes
One layer of polyimide precursor film layer and surface disposed thereon for being formed by polyamic acid solution and/or lower surface by black polyamides
The black polyimide layer of amino acid film formation；In the preparation, including prepare the method for the former film of polyamic acid and prepare black polyamides
The method of amino acid film, wherein：
The method for preparing the former film of polyamic acid is：Polyamic acid solution is former by existing common process formation polyamic acid
Film；
The method for preparing black 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) dispersible pigment dispersion and polyamic acid solution are well mixed, gained mixed material is in polyimide precursor film layer upper table
Face and/or lower surface are by existing common process formation black 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 polyamide thin film, by the usage amount of Chinese white
The 2.0wt% of strata acid imide weight where being defined to it allows for its consumption less than strata acyl where it to 12.0wt%
Blackness is unsatisfactory during the 2.0wt% of imines 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 above-mentioned technical proposal, in the method for preparing the former film of polyamic acid, described polyamic acid solution is using existing
Prepared by common process, can be specifically to use aromatic diamine and dianhydride in polar non-solute by polycondensation reaction
Obtain.Wherein described aromatic diamine aromatic diamine can be p-phenylenediamine, 4,4 '-diamino-diphenyl ether, 3,4 '-two
Any one in aminodiphenyl base ether and 4,4 '-diaminodiphenyl-methane etc. or two or more combinations；When aromatic series two
When the selection of amine is combination more than above two, the proportioning between them can be any proportioning.Described dianhydride specifically may be used
To be pyromellitic acid anhydride, 3,3 ', 4,4 '-diphenyl ether tetraformic dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 3,3 ',
Any one in 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) and the PMDA of hexafluoroisopropyli,ene two or two or more combinations；
When the selection of dianhydride monomer is the combination of more than above two, the proportioning between them can be any proportioning.Described pole
Property aprotic solvent can be DMAC N,N' dimethyl acetamide (DMAC), N,N-dimethylformamide (DMF), N- methyl -2- pyrroles
Any one in alkanone (NMP) or two or more combinations；The consumption of described polar non-solute can be worked as
When aromatic diamine, dianhydride monomer and polar non-solute formation polyamic acid solution, consolidating in the polyamic acid solution contains
Amount control is in 10wt%~50wt%, preferably 15wt%~35wt%.It is anti-that polycondensation is carried out in aromatic diamine and dianhydride monomer
At once, the temperature of mole when polycondensation reaction of the aromatic diamine and dianhydride monomer is same as the prior art, specifically,
The mol ratio of the aromatic diamine and dianhydride monomer can be 0.9~1.1：1, preferably 0.95~1.05：1；The polycondensation
The temperature of reaction can be 0~50 DEG C, and the time of reaction is usually 3~12h.
In above-mentioned technical proposal, in the method for preparing black polyamide acid film, the polyamic acid solution being related to is using existing
There is common process to be prepared, it is specific as foregoing.
In technical scheme of the present invention, the selection of involved black pigment is same as the prior art, specific choosing
It can be selected from combination more than one or both of insulating properties carbon black, cupric and chromic oxide and iron oxide to select, and preferably insulate
Property carbon black (can be the insulating properties carbon black with O.001 μm~2 μm of average grain diameters, preferably with O.01 μm~1 μm of average grain diameter
Insulating properties carbon black, the more preferably insulating properties carbon black with 0.08 μm~0.8 μm average grain diameter).
In above-mentioned technical proposal, the step 2 of black polyamide acid film is being prepared) in, more preferably titanium dioxide and/or carbonic acid
Calcium 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 the step, one of selected as Chinese white
Titanium dioxide is more preferably hydrophily anatase titanium dioxide, still more preferably oxidized silicon (SiO2) and/or oxidation
Aluminium (AL2O3) surface treatment hydrophily anatase titanium dioxide；Calcium carbonate as another selection of Chinese white is then further
Preferably hydrophily calcium carbonate, still further preferably hydrophily spherical calcium carbonate.So can further improve Chinese white and
Dispersiveness of the black pigment in polyimide resin system, make gained Kapton have more excellent thermal property and
Insulating properties.
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 polyamide thin 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 black polyimide layer
Material is matched, and is made gained film while with conventional black Kapton mechanical performance, be further improves
Optical property (blackness, light transmittance etc.), thermal property (shrinkage factor, thermal coefficient of expansion etc.) and the insulating properties (electricity of gained film
Gas intensity, 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 be a kind of embodiment of multilayer black polyamide thin film made from the method for the invention (double-layer structure, its
Middle lower floor is polyimide precursor film layer, upper strata black polyimide layer)；
Fig. 2 be multilayer black polyamide thin film another embodiment made from the method for the invention (three-decker,
Wherein intermediate layer is polyimide precursor film layer, and upper and lower two layers is black polyimide layer).
In figure marked as：
1st, black polyimide layer, 11, black pigment, 12, Chinese white, 2, polyimide precursor film layer.
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 in black polyimide layer 1 to be combined from Chinese white 12 and black pigment 11 and made
With, and the various performance parameters (the particularly selection of granularity) of Chinese white 12 are particularly limited to, because applicant is testing, ground
Study carefully in analysis and find：
When the particle diameter of Chinese white 12 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,.Where the addition of Chinese white 12 is less than it
The 2wt% of strata acid imide weight, then presentation background color whiteness is not obvious needed for film, and addition is more than strata acid imide where its
The 12wt% of weight, then film color homogeneity is poor, filling settlement and scattered inequality is that film apparent mass is poor.
For black pigment 11, its addition is bigger, and film electrical strength is smaller, and electrical property is poorer, application field
It is narrower.The application introduces Chinese white 12 in black polyimide layer 1, not only can effectively reduce the addition of black pigment 11
Amount, and can be effectively ensured with the formation complementary colours of black pigment 11 on the basis of the addition of black pigment 11 is substantially reduced
Film blackness even improves film blackness, black polyamide thin film outward appearance is seemed more there is aesthetic feeling.On the other hand, receive
Meter level Chinese white 12 has space steric effect, in polyamic acid resin building-up process, can make black pigment 11 and delustring
Agent suspends, and plays anti-settling effect.Meanwhile, gained black polyamide film can have stronger Extinction Characteristic and homogeneous face
Color and performance.
Embodiment 1：The preparation of two layers of black polyamide thin film
1) preparation of the former film of polyamic acid：
It will be added under nitrogen atmosphere protective condition as the 400.0kg DMAC N,N' dimethyl acetamides (DMAc) of solvent anti-
Answer in kettle, 52.14kg is 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 equimolar amounts, stirring condensation polymerization reaction, obtain polyamic acid solution (Gu
Content is 20wt%)；Gained polyamic acid solution coats 150 μm of thickness in ring steel belt by die head again after being handled through deaeration
On, then dried at 100~250 DEG C and remove most of solvent, obtain the Polyamic Acid Film with self-supporting；Gained
Film is removed from ring steel belt and is delivered on high temperature bi-directional stretching-machine, and is heated to 550 DEG C from 180 DEG C, then cooling and from
The former film of polyamic acid that 12.5 μm of thickness is made is removed on chain pincers.
2) preparation of black 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) 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 is 12.0wt%), stir and polyamic acid resin mixed solution is obtained after 8h.Will be by deaeration
The polyamic acid resin solution of reason is passed through coats 75 μm of thickness in step 1 by die head) on shaped polyamic acid original film
Side, then dries at 100~250 DEG C and removes most of solvent film forming, and it is that black polyamide acid film, lower floor are poly- to obtain upper strata
Amic acid original film and with self-supporting two membranes.
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
Cooling and remove that upper strata is made is that black polyimide layer 1, lower floor are the former film layer 2 of polyamic acid and thickness 12.5 from chain pincers afterwards
μm two layers of black polyamide thin film, its structure is as shown in Figure 1.
Comparative example 1：The preparation of two layers of black polyamide thin film
Embodiment 1 is repeated, unlike：
Step 2.2) in, in pigment preparation dispersion liquid, only add carbon black；
Step 2.3) in, when dispersible pigment dispersion and polyamic acid solution are mixed, carbon black in control gained mixed liquor
Content is 0.2wt%.
Comparative example 2：The preparation of two layers of black polyamide thin 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 polyamide thin 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 polyamide thin 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 polyamide thin 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 2.3) in, when dispersible pigment dispersion and polyamic acid solution are mixed, carbon black in control gained mixed liquor
Content is 12wt%, and the content of titanium dioxide is 6.0wt%.
Embodiment 2：The preparation of two layers of black polyamide thin film
Embodiment 1 is repeated, unlike：
Step 2.2) in, Chinese white 12 is changed to be made up of 6.0kg titanium dioxide and 6.0kg calcium carbonate, wherein two
The parameters of titanium oxide 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 polyamide thin film
Embodiment 1 is repeated, unlike：
Step 2.2) in, Chinese white 12 is changed to by 10.0kg titanium dioxide and 2.0kg hydrophily spherical calcium carbonates
Composition, 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 polyamide thin 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 12：
5, total consumption of Chinese white 12 is constant.
Embodiment 5：The preparation of two layers of black polyamide thin 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) 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) 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%), stir and polyamic acid resin mixed solution is obtained after 8h.Deaeration will be passed through
The polyamic acid resin solution of processing is passed through coats 75 μm of thickness in step 1 by die head) shaped polyamic acid original film
Top, then dries at 100~250 DEG C and removes most of solvent film forming, and it is that black polyamide acid film, lower floor are to obtain upper strata
Polyamic acid original film and with self-supporting two membranes.
Embodiment 6：The preparation of two layers of black polyamide thin 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 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) 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%), stir and polyamic acid resin mixed solution is obtained after 8h.Deaeration will be passed through
The polyamic acid resin solution of processing is passed through coats 75 μm of thickness in step 1 by die head) shaped polyamic acid original film
Top, then dries at 100~250 DEG C and removes most of solvent film forming, and it is that black polyamide acid film, lower floor are to obtain upper strata
Polyamic acid original film and with self-supporting two membranes.
Comparative example 6：The preparation of two layers of black polyamide thin film
Embodiment 6 is repeated, unlike：
Step 2.2) in, in pigment preparation dispersion liquid, carbon black is only added without titanium dioxide；
Step 2.3) in, when dispersible pigment dispersion and polyamic acid solution are mixed, carbon black in control gained mixed liquor
Content is 10.0wt%.
Embodiment 7：The preparation of three layers of black polyamide thin film
1) preparation of the former film of polyamic acid：
It will be added under nitrogen atmosphere protective condition as the 720.0kg DMAC N,N' dimethyl acetamides (DMAc) of solvent anti-
Answer in kettle, 71.40kg is 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 equimolar amounts, 4 '-BPDA (BPDA), stirring condensation polymerization reaction obtains polyamic acid
Solution (solid content is 15wt%)；The thickness that gained polyamic acid solution coats 150 μm by die head again after being handled through deaeration exists
On ring steel belt, then dried at 100~250 DEG C and remove most of solvent, obtain the polyamic acid with self-supporting
Film；Gained film is removed from ring steel belt and is delivered on high temperature bi-directional stretching-machine, and is heated to 550 DEG C from 180 DEG C, then
Cool down and removed from chain pincers the former film of polyamic acid that 12.5 μm of thickness is made.
2) preparation of black 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) 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) 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%), stir and polyamic acid resin mixed solution is obtained after 8h.Deaeration will be passed through
The polyamic acid resin solution of processing is passed through coats 75 μm of thickness in step 1 by die head) shaped polyamic acid original film
Top forms one layer of black polyamide acid film, afterwards again in the former film of shaped polyamic acid one layer of black polyamides formed below
Amino acid film, then dries at 100~250 DEG C and removes most of solvent film forming, obtains middle for the former film of polyamic acid, its upper strata
It is black polyamide acid film with lower floor and there is self-supporting trilamellar membrane.
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
It is that black polyimide layer 1, intermediate layer are the former film layer 2 of polyamic acid that the upper and lower, which are made, in cooling and being removed from chain pincers afterwards
And three layers of black polyamide thin film of 12.5 μm of thickness, its structure is as shown in Figure 2.
Embodiment 8：The preparation of three layers of black polyamide thin film
Embodiment 7 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) 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%), stir and polyamic acid resin mixed solution is obtained after 8h.Deaeration will be passed through
The polyamic acid resin solution of processing is passed through coats 75 μm of thickness in step 1 by die head) shaped polyamic acid original film
Top, then dries at 100~250 DEG C and removes most of solvent film forming, and it is that black polyamide acid film, lower floor are to obtain upper strata
Polyamic acid original film and with self-supporting two membranes.
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 titanium oxide of Chinese white 12 used in example 4 with
Weight of calcium carbonate is not 1:During 1~0.2 proportioning number range, by introduce can also be made during dispersant with embodiment 1,2,
3rd, 5 to 8 the titanium dioxide of Chinese white 12 and weight of calcium carbonate are used 1:The film performance of 1~0.2 proportioning number range；Together
When, from hydrophily spherical calcium carbonate or oxidized silicon (SiO2) and/or aluminum oxide (AL2O3) surface treatment hydrophily rutile titania
More preferably, film thermal property, insulating properties (electrical strength) are more preferably for the dispersiveness of the embodiment 3,7,8 of type titanium dioxide.
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, the used performance parameter of Chinese white 12
Not in the range of restriction, the black polyamide thin film of preparation has poor optical property, thermal property and insulating properties；Together
When, in comparative example 4 to 5, used Chinese white 12 and black pigment 11 are matched not in the range of restriction and particle diameter is differed
When, the black polyamide thin 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 (9)
1. a kind of preparation method of multilayer black polyamide thin film, it is characterised in that：The multilayer black polyamide thin film bag
Include the one layer of polyimide precursor formed by polyamic acid solution film layer (2) and surface disposed thereon and/or lower surface by black
The black polyimide layer (1) of color polyamide acid film formation；In the preparation, including method and the preparation of the former film of polyamic acid are prepared
The method of black polyamide acid film, wherein：
The method for preparing the former film of polyamic acid is：By polyamic acid solution by the former film of existing common process formation polyamic acid；
The method for preparing black 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 (11) and
Chinese white (12), wherein Chinese white (12) are titanium dioxide and/or calcium carbonate, 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 (12) is 2wt%~12wt% of strata acid imide weight where it, itself and black pigment
(11) weight proportion is 10~1.2：1；
The average grain diameter of the black pigment (11) is identical with the average grain diameter of Chinese white (12)；
3) dispersible pigment dispersion and polyamic acid solution are well mixed, gained mixed material is in polyimide precursor film layer (2) upper table
Face and/or lower surface are by existing common process formation black polyamide acid film.
2. preparation method according to claim 1, it is characterised in that：In the method for preparing black polyamide acid film, institute
Combination of the Chinese white (12) 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 black 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 black 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 black 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 black 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 black 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 black polyamide acid film,
The black pigment (11) is the combination more than one or both of insulating properties carbon black, cupric and chromic oxide and iron oxide.
9. the multilayer black polyamide thin film that method any one of claim 1~8 is prepared.
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| CN115335328A (en) * | 2020-03-31 | 2022-11-11 | 住友化学株式会社 | Particle, powder composition, solid composition, liquid composition, and molded body |
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