CN205086428U - Double -deck polyimide film of low glossiness - Google Patents
Double -deck polyimide film of low glossiness Download PDFInfo
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- CN205086428U CN205086428U CN201520227691.9U CN201520227691U CN205086428U CN 205086428 U CN205086428 U CN 205086428U CN 201520227691 U CN201520227691 U CN 201520227691U CN 205086428 U CN205086428 U CN 205086428U
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- polyimide film
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Abstract
The utility model provides a double -deck polyimide film of low glossiness, including a polyimide film of lower floor, and an upper polyimide film, its compound composition is the same with the polyimide film of this lower floor, lie in the polyimide film of this lower floor one on the surface, it is thoughtlessly mixed has black pigment to reach the thickness orientation at the membrane has be formed with the hole in court's membrane in a plurality of concave parts of formation and the mould, the degree of depth of this concave part of is 0 -5 mu m, and this concave part and hole volume account for this mould bulk volume 30 -70%. Consequently, can be had concurrently the height and hide optical activity, low glossiness and the double -deck polyimide film of warping not, and its manufacturing cost is cheap relatively.
Description
Technical field
The utility model relates to a kind of double-deck polyimide film of low-luster, refers to that a kind of height that has concurrently hides optical activity and the double-deck polyimide film of non-warpage especially.
Background technology
Pliability copper foil laminates (Flexiblecoppercladlaminate, FCCL) be widely used in electronic industry as circuit substrate (PCB), FCCL is except having light, thin and flexible advantage, also have outside electrical property and the excellent feature of hot property with polyimide film, its lower dielectric constant (Dk) property, the signal of telecommunication is transmitted fast, good hot property, assembly can be made to be easy to cooling, higher vitrification point (Tg), can make assembly well run at a higher temperature.
But polyimide film has high surface flatness usually, most incident ray is made to be produced high gloss by reflecting.Again, the face of high gloss may cause during visually uncomfortable or long-time viewing and easily make eye fatigue.Especially, the coloured high gloss polyimide film of tool, such as: the Kaptons such as black, white, blueness, redness, irradiates a large amount of reverberation produced in its surface visually more remarkable.In addition, low light transmission and low-luster PI film are usually used in the base material and cover layer (coverlay) etc. of flexible circuit board (flexibleprintedcircuitboards), low light transmission system is in order to hide the circuit design on circuit board, prevent the circuit on circuit board from being plagiarized, these flexible circuit boards are widely used in 3C Product, optical lens module, LCD module etc.Low-luster can make assembly outward appearance have more texture and attractive in appearance.
There is research to point out, can principle of optical interference be utilized, by adding delustering agent to improve the roughness of film surface in Kapton, reducing its glossiness with scatter incident light line.
But the delustering agent that tradition uses utilizes the surface roughness manufacturing projection to reduce glossiness, the organic fillers such as inorganic particulate and polyimides such as delustering agent is silica as used, aluminium oxide, calcium carbonate, barium sulfate and titanium dioxide.But, because inorganic particulate has higher dielectric constant, thus may improve the dielectric constant of Kapton, and reduce the electrical insulating property of Kapton.In addition, add polyimides organic filler as delustering agent, have increase material cost problem outside, add a large amount of delustering agent and can cause again the easy embrittlement of polyimide film material nature, in order to reduce cost, increase the mechanical strength of polyimide film material itself and reduce its glossiness, top layer can be used to be the double-deck polyimide film adding a large amount of polyimide particle, but to find that this kind of double-deck polyimide film has the problem of the tension force inequality of warpage.The doubt of this tension force inequality uses for flexible circuit board industry and brings puzzlement.
In view of this, industry needs a kind of delustring mode using low cost badly, high hides optical activity, low-luster and the double-deck Kapton of non-warpage to prepare to have concurrently.
Utility model content
The purpose of this utility model is to provide a kind of double-deck polyimide film of low-luster.
For achieving the above object, the double-deck polyimide film of the low-luster that the utility model provides, it includes layer polyimide film; And a upper strata polyimide film, itself and this lower floor's polyimide film is made by " black dicarboxylic anhydride diamines polyimides ", be positioned at one of this lower floor's polyimide film on the surface, it has to be formed in a plurality of recess and mould in film at the thickness direction of film and is formed with hole, the degree of depth of this recess is 0-5 μm, and this recess and pore volume account for this mould cumulative volume 30-70%.
Therefore, can obtain having concurrently and highly hide optical activity, low-luster and the double-deck Kapton of non-warpage, and its manufacturing cost relative moderate.
Accompanying drawing explanation
Fig. 1 is the double-deck polyimide film schematic diagram of the utility model low-luster.
Fig. 2 is the double-deck polyimide film cost schematic diagram of the utility model low-luster.
Fig. 3 is the utility model first manufacture method flow chart.
Fig. 4 is that polyimides top layer, upper strata forms the electronic pictures (multiplying power x800) with a plurality of shrinkage pool.
Symbol description in accompanying drawing:
Lower floor's polyimide film 10, upper strata polyimide film 12, organic material 14, shrinkage pool 16.
Detailed description of the invention
Refer to shown in Fig. 1, for the double-deck polyimide film of the utility model low-luster, it includes layer polyimide film 10 and a upper strata polyimide film 12 identical with the chemical composition of this lower floor's polyimide film 10, this polyimides high molecular polymer of upper and lower two layers can be formed through condensation reaction by diamine compound (diamine) and anhydride compounds (dianhydride), at this referred to as " dicarboxylic anhydride diamines polyimides ".In embodiment or comparative example, this diamines is selected from:
4, 4 '-diaminodiphenyl ether (4, 4 '-oxydianiline (4, 4 '-ODA)), p-phenylenediamine (PPD) (phenylenediamine (p-PDA), 1, two (the 4 '-amido phenoxy group) (1 of 3-, 3-bis (4-aminophenoxy) benzene (TPER)), 1, two (the 4-amido phenoxy group) benzene (1 of 4-, 4-bis (4-aminophenoxy) benzene (TPEQ)), 4, 4 '-two amido-2, 2 '-dimethyl-1, 1 '-Lian (2, 2 '-dimethyl [1, 1 '-biphenyl]-4, 4 '-diamine (m-TB-HG)), 1, two (the 3-amido phenoxy group) benzene (1 of 3-, 3 '-Bis (3-aminophenoxy) benzene (APBN)), 3, 5-bis-amido benzotrifluoride (3, 5-DiamiNobenzotrifluoride (DABTF)), 2, 2 '-bis-(trifluoromethyl) benzidine (2, 2 '-Bis (trifluoromethyl) benzidine (TFMB)), 2, 2 '-bis-[4-(4-amido Phenoxyphenyl)] propane (2, 2 '-bis [4-(4-aminophenoxy) phenyl] propane (BAPP)), 6-amido-2-(4-aminocarbonyl phenyl)-benzoxazoles (6-amino-2-(4-aminophenyl) benzoxazole (6PBOA)), 5-amido-2-(4-aminocarbonyl phenyl)-benzoxazoles (5-amino-2-(4-aminopenyl) benzoxazole (5PBOA)) etc., can be used alone or in combination.
In the polyimide layer of this bilayer, in embodiment or comparative example, this dicarboxylic anhydride is selected from Pyromellitic Acid dicarboxylic anhydride (pyromelliticdianhydride (PMDA)), 3, 3 ', 4, 4 '-biphenyltetracarboxyacid acid dicarboxylic anhydride (3, 3 ', 4, 4 '-biphenyltetracarboxylicdianhydride (BPDA)), 2, two [the 4-(3 of 2-, 4-di carboxyl phenyloxy) phenyl] propane dianhydride (2, 2-bis [4-(3, 4dicarboxyphenoxy) phenyl] propanedianhydride (BPADA)), 4, 4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids (2, 2 '-Bis-(3, 4-Dicarboxyphenyl) hexafluoropropanedianhydride (6FDA)), diphenyl ether tetraformic dicarboxylic anhydride (4, 4-Oxydiphthalicanhydride (ODPA)), Benzophenone carboxylic diacid acid anhydride (Benzophenonetetracarboxylicdianhydride (BTDA)), 3, 3 ', 4, 4 '-dicyclohexyl tetracarboxylic acid dianhydride (3, 3 ', 4, 4 '-dicyclohexyltetracarboxylicaciddianhydride (HBPDA) etc., can be used alone or in combination.
Stick up for making the polyimide film outward appearance of this bilayer not roll up, this diamines selected by upper and lower polyimide layer 10,12 and anhydride compounds need consistent, such as, the high molecular polymer of the first polyimide layer is formed through condensation reaction by diamine compound (4,4 '-ODA) and anhydride compounds (PMDA); The high molecular polymer of the second polyimide layer also must be selected and be formed through condensation reaction by diamine compound (4,4 '-ODA) and anhydride compounds (PMDA).
In upper strata polyimide film 12, blending has containing heat decomposable organic material 14, heat decomposable organic material 14 is crosslinked methyl methacrylate particle (cross-linking type PMMA) and polystyrene particle etc. in the present embodiment, can be used alone or combinationally use, wherein the density of polyimide film 12 is 1.49g/cm
3, the density of crosslinked methyl methacrylate particle (cross-linking type PMMA) is 1.18g/cm
3, the density g/cm of polystyrene particle
3.
As used the average grain diameter of this heat decomposable organic material particle 14 for about 1 to 2 μm, this heat decomposable organic material particle 14 can account for upper strata polyimide layer 12 about 40 to 60wt%; And the average grain diameter maximum of upper strata polyimides layer thickness≤heat decomposable organic material particle, such as, heat decomposable organic material particle addition is the value between 40wt%, 45wt%, 50wt%, 55wt%, 60wt% or aforementioned wantonly 2; And thickness is the value between 1 μm, 1.5 μm, 2 μm or aforementioned wantonly 2.As used the average grain diameter of this heat decomposable organic material particle for about 4 to 5 μm, this heat decomposable organic material particle can account for this upper strata polyimide layer about 35 to 65wt%; And the average grain diameter maximum of upper strata polyimides layer thickness≤heat decomposable organic material particle, such as, the value between 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt% or aforementioned wantonly 2; And thickness is the value between 1 μm, 1.5 μm, 2 μm, 3 μm, 4 μm, 4.5 μm, 5 μm or aforementioned wantonly 2.
Equal blending black pigment in double-deck polyimide film 10,12, at this referred to as " black dicarboxylic anhydride diamines polyimides " film; There is no particular restriction for black pigment kind, can be carbon particulate, chromium or titanium system black pigment.Specifically, black pigment can be that carbon black, titanium are black, bone black (boneblack), cyanine black (cyanineblack), acetylene black, dim, graphite, iron oxide black, nigrosine or flower cyanines black etc., but not as limit.With regard to the consideration of shading rate, can use carbon black or titanium black.In addition, also can above-mentioned black pigment used in combination; And the black pigment as institute's blending accounts for this layer when being 4.5wt%, need lower floor's polyimide film 10 thickness >=8 μm, such as, thickness is the value between 8 μm, 9 μm, 10 μm, 20 μm, 40 μm, 80 μm, 100 μm or aforementioned wantonly 2.
Refer to Fig. 3, for the flow chart of an embodiment of the present utility model, layer polyimide film 10 (step S1) is once provided, there is provided one with the upper strata polyimide precursor solution (step S2) of the same compound of lower floor's polyimide film 10 surface in lower floor's polyimide film 10, carry out thermal decomposition organic material material 14 (step S3), carry out upper strata polyimide precursor solution sclerosis operation (step S4), lower floor's polyimide film 10 surface is made to form a upper strata polyimide film 12 (S5), as shown in Figure 2, because the organic filler 14 on upper strata polyimide film 12 surface is thermal decomposited, therefore, upper strata polyimides 12 top layer can be formed has a plurality of shrinkage pool 16 (as shown in Figure 4).The thickness of this upper strata polyimide film is 1-2 μm, and this recess and pore volume account for this cumulative volume 40-60%.
By manufacture method as above, when upper strata polyimide film 12 top layer forms a plurality of shrinkage pool 16, can obtain using the delustring mode of low cost, highly hide optical activity, low-luster and the double-deck Kapton of non-warpage to prepare to have concurrently.60 degree of angle glossiness (gloss) on its upper strata polyimide film 12 top layer lower than about 20, such as 19.7,18.2,15.4,10.3,1.2 etc., or the value between aforementioned wantonly 2.Its light transmittance (TT) lower than about 0.2, such as 0.17,0.14,0.09,0.02,0.01 etc., or the value between aforementioned wantonly 2.
60 degree of angle glossiness measure (gloss)
60 degree of angle glossiness measurements record with hand-held Grossmeters (model: MicroTriGloss-BYKGardner).
Light transmittance measures (TT)
The penetration of Kapton is recorded (%) by NipponDenshokuNDH2000HazeMeter.
Embodiment
The preparation of carbon black slurry
By the DMAc mix and blend 15 minute of 500 grams of carbon blacks (Regal-R400, purchased from CABOT company) with 4000 grams, then via after grinder grinding.
The preparation of polyamic acid solution
The DMAc of 52.63 grams 4,4 '-ODA and 440 grams is inserted in three-neck flask.The PMDA (4,4 '-ODA with PMDA total monomer weight percentage be 20wt%) adding 56.51 grams after dissolving completely is again stirred at 30 DEG C.Then, continuous holding is stirred and in 25 DEG C of sustained responses 20 hours, can obtain polyamic acid solution, its in the rotation viscosity of 25 DEG C be 140,000cps.
The preparation of black polyamic acid solution
By the polyamic acid solution of the carbon black slurry of 42.39 grams and 500 grams, (20wt%, by 4,4 '-ODA, p-phenylenediamine (para-phenylenediamine; P-PDA) and PMDA combined polymerization obtain, its viscosity about 140,000cps) mix with 129 grams of DMAc stirring solvent, obtain 15wt% and the black polyamic acid solution (it is 4.5wt% that carbon black powders accounts for total monomer weight) of weight about 671.39 grams.
Embodiment 1
Get in gained black polyamic acid solution 50 grams, the catalyst (its adding proportion is polyamic acid solution: acetic anhydride: the mol ratio of picoline is about 1: 2: 1) of proper amount of acetic acid acid anhydride and picoline is added again after stirring, the complete selection coating clearance of deaeration is that the scraper for coating of 600 μm is on glass plate, and the baking oven putting into 80 DEG C heats about 30 minutes, to remove most solvent.Then, the above-mentioned glass plate being coated with black polyamic acid solution is put into the baking oven of 170 DEG C ~ 350 DEG C, heat about 4 hours, dry film forming to make polyamic acid solution.Gained lower floor polyimides film thickness is 25 μm.Next, with the mode of operation obtaining lower floor's polyimide film, but (cross-linking type PMMA powder average particle size is 1 ~ 2 μm to add the cross-linking type PMMA powder of 5 grams in the black polyamic acid solution of 50 grams, and to account for total monomer weight be 40wt%), selection coating clearance is the scraper of 30 μm, black polyamic acid solution gained being contained cross-linking type PMMA powder is coated on lower floor's polyimide film of gained, and obtaining upper strata polyimides film thickness is 1 μm.
Embodiment 2
With embodiment 1, but the cross-linking type PMMA powder addition in the polyimide film of upper strata is changed into 7.5 grams (it is 50wt% that cross-linking type PMMA powder accounts for total monomer weight).
Embodiment 3
With embodiment 1, but the cross-linking type PMMA powder addition in the polyimide film of upper strata is changed into 11.25 grams (it is 60wt% that cross-linking type PMMA powder accounts for total monomer weight).
Embodiment 4
With embodiment 1, but change the average grain diameter of the cross-linking type PMMA powder in the polyimide film of upper strata into 4 ~ 5 μm, and addition changes 4 grams (it is 60wt% that cross-linking type PMMA powder accounts for total monomer weight) into.
Embodiment 5
With embodiment 1, but change the average grain diameter of the cross-linking type PMMA powder in the polyimide film of upper strata into 4 ~ 5 μm, and addition changes 7.5 grams (it is 50wt% that cross-linking type PMMA powder accounts for total monomer weight) into.
Embodiment 6
With embodiment 1, but change the average grain diameter of the cross-linking type PMMA powder in the polyimide film of upper strata into 4 ~ 5 μm, and addition changes 13.93 grams (it is 65wt% that cross-linking type PMMA powder accounts for total monomer weight) into.
Embodiment 7
With embodiment 2, but the gap of the coating blade of obtained upper strata polyimide film is changed into the scraper of 40 μm.
Embodiment 8
With embodiment 5, but the gap of the coating blade of obtained upper strata polyimide film is changed into the scraper of 80 μm.
Embodiment 9
With embodiment 2, but the gap of the coating blade of obtained lower floor polyimide film is changed into the scraper of 120 μm.
Embodiment 10
With embodiment 2, but the gap of the coating blade of obtained lower floor polyimide film is changed into the scraper of 1500 μm.
Embodiment 11
With embodiment 5, but the gap of the coating blade of obtained first polyimide film is changed into the scraper of 120 μm.
Embodiment 12
With embodiment 5, but the gap of the coating blade of obtained first polyimide film is changed into the scraper of 1500 μm.
Comparative example
the preparation of polyimides powder
By 14.35 grams 4,4 '-diaminodiphenyl ether (4,4 '-oxydianiline, 4,4 '-ODA), the pyromellitic acid anhydride (pyromelliticdianhydride of 15.65 grams; PMDA) with the dimethylacetylamide (dimethylacetamide of 570 grams, DMAc) three-neck flask interior (4 is inserted, 4 '-ODA and PMDA total monomer weight percentage are 5wt%), add the 3-picoline of 3.35 grams after being stirred to dissolving completely again.Then, continuous holding is stirred and adds thermal response 18 hours in 165 DEG C, can obtain polyimides precipitate.Subsequently, with water and ethanol purge polyimides precipitate, again via collecting this precipitate after vacuum filtration.Finally, polyimides precipitate to be positioned in 160 DEG C of baking ovens heat drying 1 hour, average grain diameter 1 ~ 2 μm can be obtained, the polyimides powder (PIpowder) of 26.7 grams.Repeat aforesaid way, if change above-mentioned solvent DMAc into 470 grams, namely 4,4 '-ODA is 6wt% with PMDA total monomer weight percentage, can obtain average grain diameter 4 ~ 5 μm, the PIpowder of 32.3 grams.
Comparative example 1
With embodiment 1, but the cross-linking type PMMA powder addition in the polyimide film of upper strata is changed into 4 grams (it is 35wt% that cross-linking type PMMA powder accounts for total monomer weight).
Comparative example 2
With embodiment 1, but the cross-linking type PMMA powder addition in the polyimide film of upper strata is changed into 13.93 grams (it is 65wt% that cross-linking type PMMA powder accounts for total monomer weight).
Comparative example 3
With embodiment 4, but the cross-linking type PMMA powder addition in the polyimide film of upper strata is changed into 3.21 grams (it is 30wt% that cross-linking type PMMA powder accounts for total monomer weight).
Comparative example 4
With embodiment 4, but the cross-linking type PMMA powder addition in the polyimide film of upper strata is changed into 17.5 grams (it is 70wt% that cross-linking type PMMA powder accounts for total monomer weight).
Comparative example 5
With embodiment 2, but the gap of the coating blade of obtained upper strata polyimide film is changed into the scraper of 45 μm.
Comparative example 6
With embodiment 5, but the gap of the coating blade of obtained upper strata polyimide film is changed into the scraper of 90 μm.
Comparative example 7
With embodiment 2, but the gap of the coating blade of obtained lower floor polyimide film is changed into the scraper of 95 μm.
Comparative example 8
With embodiment 5, but the gap of the coating blade of obtained lower floor polyimide film is changed into the scraper of 95 μm.
Comparative example 9
With embodiment 2, but change the cross-linking type PMMA powder of obtained upper strata polyimide film into PIpowder that average grain diameter is 1 ~ 2 μm.
Comparative example 10
With embodiment 5, but change the cross-linking type PMMA powder of obtained upper strata polyimide film into PIpowder that average grain diameter is 4 ~ 5 μm.
Test result is as shown in table 1.
Table 1
Claims (3)
1. a double-deck polyimide film for low-luster, is characterized in that, include:
Layer polyimide film once; And
One upper strata polyimide film, itself and this lower floor's polyimide film is made by " black dicarboxylic anhydride diamines polyimides ", be positioned at one of this lower floor's polyimide film on the surface, it has to be formed in a plurality of recess and mould in film at the thickness direction of film and is formed with hole, the degree of depth of this recess is 0-5 μm, and this recess and pore volume account for this mould cumulative volume 30-70%.
2. the double-deck polyimide film of low-luster according to claim 1, is characterized in that, thickness >=8 μm of this upper strata polyimide film.
3. the double-deck polyimide film of low-luster according to claim 1, is characterized in that, the thickness of this upper strata polyimide film is 1-2 μm, and this recess and pore volume account for this mould cumulative volume 40-60%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201520227691.9U CN205086428U (en) | 2015-04-16 | 2015-04-16 | Double -deck polyimide film of low glossiness |
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| CN201520227691.9U CN205086428U (en) | 2015-04-16 | 2015-04-16 | Double -deck polyimide film of low glossiness |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104742461A (en) * | 2015-04-16 | 2015-07-01 | 达迈科技股份有限公司 | Low-glossiness dual-layer polyimide film and manufacturing method thereof |
| CN106957445A (en) * | 2016-10-19 | 2017-07-18 | 达迈科技股份有限公司 | Low-gloss polyimide film and method for producing same |
-
2015
- 2015-04-16 CN CN201520227691.9U patent/CN205086428U/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104742461A (en) * | 2015-04-16 | 2015-07-01 | 达迈科技股份有限公司 | Low-glossiness dual-layer polyimide film and manufacturing method thereof |
| CN106957445A (en) * | 2016-10-19 | 2017-07-18 | 达迈科技股份有限公司 | Low-gloss polyimide film and method for producing same |
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Granted publication date: 20160316 Termination date: 20180416 |