CN106832280A - A kind of thermoplasticity conducting liquid crystal Kapton and preparation method thereof - Google Patents
A kind of thermoplasticity conducting liquid crystal Kapton and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of thermoplasticity conducting liquid crystal Kapton and preparation method thereof, preparation method is as follows：First with alicyclic diamine and alicyclic dianhydride as raw material, needle inorganic nano heat filling is added simultaneously, polyamic acid solution has been synthesized in aprotic polar solvent by situ aggregation method at low temperature, then to addition dehydrating agent and catalyst in polyamic acid solution, and thermoplasticity conducting liquid crystal Kapton is prepared by curtain coating and biaxial stretch-formed orientation technology.The Kapton has good heat conductivility, flexility, thermoplastic property, adhesive property, heat resistance, dimensional stability and chemical-resistant stability, as little as 12~50 μm of the thickness of film, with versatile, the thermal conductivity aluminum matrix copper-clad plate obtained based on the film preparation has peel strength higher, dimensional stability, heat resistance, and excellent dielectric properties, it is particularly useful for making 3D thermal conductivity aluminum matrix copper-clad plates.
Description
Technical field
The invention belongs to technical field of polymer materials, it is related to a kind of thermoplasticity conducting liquid crystal Kapton and its system
Preparation Method.
Background technology
Aluminum-based copper-clad plate is the main flow substrate used on current LED lamp circuit board.Compared to FR-4 copper-clad plates, it has
The performance such as thermal conductivity higher and high temperature resistant, but due to its hardness and fragility higher, it is difficult to bent, had for preparing
Particular configuration requires relatively difficult during the printed circuit board as having various 3-D solid structure moulding.It is thus new to adapt to this
The bent 3D aluminum-based copper-clad plates of emerging market demands engender.The heat conduction printed circuit board of this nonplanar structure is manufactured,
The heat-conducting substrate material of flexible shaping need to be used.It is punched out by bent 3D aluminum-based copper-clad plates, is stamped and formed out making
The different 3D heat conduction printed circuit boards of type, then directly weld LED chip, you can obtain various on 3D heat conduction printed circuit boards
The unique 3D LED lamps of moulding.
3D LED lamps are handsome in appearance, and designability is strong, while manufacture craft is also fairly simple, are not required to introducing price high
Equipment and technology, thus have stronger market development prospect.Preparing the critical material 3D aluminum-based copper-clad plates of 3D LED lamps is
Aluminium sheet and Copper Foil are superimposed upon what hot pressing behind the two sides of conductive adhesive film was prepared from, wherein conductive adhesive film plays heat conduction.Mesh
Preceding most conductive adhesive film is that certain inorganic heat filling is added in composition epoxy resin, such as CN103275629A reports
A kind of epoxy conductive adhesive film in road, its main component is that halogen-free epoxy resin, curing agent, toughener, class Graphene boron nitride are received
Rice piece.The epoxy conductive adhesive film have heat conductivility higher (>6.0W/mk), proof voltage (>5kV), peel strength (>
2.0N/mm), heat resistance (300 DEG C of ＞), but its glued membrane it is thicker (>100 μm), poor in flexibility can not bend, nothing after solidification
Method is used to prepare 3D thermal conductivity aluminum matrix copper-clad plates.
In order to solve the above problems, the present invention provides a kind of thermoplasticity conducting liquid crystal Kapton, with liquid crystal polyamides
Imines is matrix resin, adds a certain amount of needle inorganic nano heat filling and is obtained, with good pliability, insulating properties and
Thermal conductivity, the thickness of film can be controlled at 12~50 μm, can be used for the excellent 3D thermal conductivity aluminum matrix copper-clad plates of processability.
The content of the invention
The technical problems to be solved by the invention are directed to above shortcomings in the prior art, there is provided a kind of thermoplasticity
Conducting liquid crystal Kapton and preparation method thereof, the thermoplasticity conducting liquid crystal Kapton is applied to copper-clad plate class
There is high-fire resistance, high-termal conductivity, low-dielectric energy and high-dimensional stability in laminate product, and with good flexure
Property, it is particularly suited for 3D thermal conductivity aluminum matrix copper-clad plates.
In order to solve the above technical problems, the technical scheme that the present invention is provided is：
A kind of thermoplasticity conducting liquid crystal Kapton is provided, preparation method is as follows：First with alicyclic diamine and fat
Ring race dianhydride is raw material, while needle inorganic nano heat filling is added, at low temperature by situ aggregation method in non-proton pole
Property solvent in synthesized polyamic acid solution, then in polyamic acid solution add dehydrating agent and catalyst, and by curtain coating
Thermoplasticity conducting liquid crystal Kapton is prepared with biaxial stretch-formed orientation technology.The thermoplasticity conducting liquid crystal polyimides is thin
Shown in film reaction formula such as formula (3)：
By such scheme, the raw material for preparing the thermoplasticity conducting liquid crystal Kapton include having with following formula (1)
The alicyclic diamine of structural formula：
H2N-R1-NH2(1),
With the alicyclic dianhydride monomer with formula (2) structural formula：
And needle inorganic nano heat filling；
The R1Structure is the one kind in following structural formula：
R1Optional position with the link position of amino, including the ring, preferably aligns, R1Alicyclic ring on substitution base be
C1~C6Low alkyl group or lower alkoxy or without substitution base；X is O, S, SO in structure above2、CO、CH2、CF2、
C(CH3)2、C(CF3)2Or do not exist；
The R2Structure is the one kind in following structural formula：
R2Alicyclic ring on substitution base be C1~C6Low alkyl group or lower alkoxy or without substitution base, it is above-mentioned
Y is O, S, SO in structural formula2、CO、CH2、CF2、C(CH3)2、C(CF3)2Or do not exist.
By such scheme, the alicyclic diamine is 1,3- diaminos cyclopentane (DACP), Isosorbide-5-Nitrae-DACH
(DACH), one or more the mixture in 4,4 '-diamino-dicyclohexyl methane (DCHM).
By such scheme, the alicyclic dianhydride monomer be 1,2,3,4- cyclobutane tetracarboxylic dianhydrides (CBDA), 1,2,3,
One or more mixed in 4- pentamethylene tetracarboxylic dianhydride (CPDA), 1,2,4,5- cyclopentanetetracarboxylics dianhydride (CHDA)
Compound.
By such scheme, the needle inorganic nano heat filling is aluminum oxide, magnesia, the oxidation of acicular nanometer size
One or more mixing in silicon, zinc oxide, nickel oxide, aluminium nitride, boron nitride, silicon nitride, carborundum, diamond
Thing.
Preferably, the needle inorganic nano heat filling is aluminum oxide, magnesia, the nitridation of acicular nanometer size
One or more mixture in boron, aluminium nitride.
Preferably, quality of the needle inorganic nano heat filling in thermoplasticity conducting liquid crystal Kapton
Fraction is 5~30%.
The present invention also provides the preparation method of above-mentioned thermoplasticity conducting liquid crystal Kapton, and it is comprised the following steps：
1) polyamic acid solution is prepared：By alicyclic diamine, needle inorganic nano heat filling and aprotic polar solvent
Add in reactor, reactor temperature is 10~30 DEG C, is stirred in a nitrogen atmosphere, then by temperature in reactor
Degree is down to 0~5 DEG C, and alicyclic dianhydride monomer is divided into 2~10 equal parts, in adding reactor in batches in 0.5~5h, adds
After continue to react 5~48h at 0~5 DEG C and obtain high-viscosity polyamic acid solution, be placed in storing up in -10~-30 DEG C of freezer
Deposit；
2) thermoplasticity conducting liquid crystal Kapton is prepared：By step 1) gained polyamic acid solution be warming up to 0~10
DEG C, dehydrating agent and catalyst are added, it is cast on steel band after being uniformly mixed, obtained by after low temperature drying tunnel and fiberglass band
The polyamide sorrel of part imidization, polyamide sorrel continues through high temperature drying tunnel, drying residual solvent and imidization completely, together
When the stretched biaxial stretch-formed orientation than for 1.1~1.2 after, cutting edge winding obtain the thermoplasticity heat conduction that thickness is 12~50 μm
Liquid crystal polyimide film.
By such scheme, step 1) the ratio between the amount of material of the alicyclic diamine and alicyclic dianhydride for 0.90~
1.10；The needle inorganic nano heat filling；The aprotic polar solvent is 1-METHYLPYRROLIDONE (NMP), N, N- bis-
In NMF (DMF), DMAC N,N' dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO), dimethyl suflfate, sulfolane, fourth
One or more mixing in fat, cresols, cyclobutanone, tetrahydrofuran, diethylene glycol dimethyl ether, TRIGLYME
Thing；The polyamic acid solution solid content is 5~30%.
Preferably, the ratio between amount of material of the alicyclic diamine and alicyclic dianhydride is 0.95~1.05.
Preferably, the aprotic polar solvent is the mixed of one or more in NMP, DMF, DMAc, DMSO
Compound.
Preferably, the polyamic acid solution solid content is 8~20%.
By such scheme, step 2) dehydrating agent be acetic anhydride, propionic andydride, butyric anhydride, TFAA, chloroacetic chloride,
One or more mixture in benzoyl oxide, Dicyclohexylcarbodiimide (DCC), TFAA, thionyl chloride,
Dehydrating agent addition is the 0.1~0.5% of polyamic acid solution quality；The catalyst is triethylamine, triethanolamine, N, N- bis-
Methylethanolamine, N, accelerine, N, in N- diethylanilines, pyridine, picoline, lutidines, quinoline, imidazoles
One or more mixture, catalyst charge for polyamic acid solution quality 0.1~0.5%.
Preferably, the dehydrating agent is one or more the mixing in acetic anhydride, propionic andydride, benzoyl oxide
Thing.
Preferably, the catalyst is one or more the mixture in triethylamine, triethanolamine, pyridine.
By such scheme, step 2) each section of temperature of the low temperature drying tunnel be respectively 50~70 DEG C, 100~120 DEG C, 150~
170℃；Each section of temperature of the high temperature drying tunnel is respectively 160~180 DEG C, 200~220 DEG C, 240~260 DEG C.
It is described present invention additionally comprises the layered product prepared according to above-mentioned thermoplasticity conducting liquid crystal Kapton
Layered product is laminated with least one of which thermoplasticity conducting liquid crystal Kapton on metal foil.
By such scheme, the layered product is 3D thermal conductivity aluminum matrix copper-clad plates, the preparation side of the 3D thermal conductivity aluminum matrixes copper-clad plate
Method includes：The thermoplasticity conducting liquid crystal Kapton that thickness is 12~50 μm is placed in the Copper Foil that thickness is 12~35 μm thick
Between the mat surface of matte and 0.5~2mm aluminium sheets, be superimposed 5~20 layers, be positioned in vacuum press, vacuumize, pressure 5~
20MPa, 1~3h is pressed under the conditions of 280 DEG C~300 DEG C, cutting edge is taken out after cooling and obtains 3D thermal conductivity aluminum matrix copper-clad plates.
The beneficial effects of the present invention are：The present invention passes through situ aggregation method synthesis of polyimides, and in the liquid of synthesis
A certain amount of needle inorganic nano heat filling is added during brilliant polyimides matrix resin, to be cast and biaxial stretch-formed work
Skill obtains thermoplasticity conducting liquid crystal Kapton, and it has good heat conductivility, flexility, thermoplastic property, bonding
Performance, heat resistance, dimensional stability and chemical-resistant stability, as little as 12~50 μm of the thickness of the film, with versatile,
Peel strength higher, chi are had based on the thermal conductivity aluminum matrix copper-clad plate that the thermoplasticity conducting liquid crystal Kapton is prepared
Very little stability, heat resistance, and excellent dielectric properties, are particularly useful for making 3D thermal conductivity aluminum matrix copper-clad plates.
Specific embodiment
To make those skilled in the art more fully understand technical scheme, the present invention is made with reference to embodiment
Describe in further detail.
Embodiment 1
Polyamic acid solution is prepared, method is as follows：In 50L reactors, 15000g is first added under room temperature (15~30 DEG C)
Aprotic polar solvent NMP, then the needle inorganic nano heat filling for adding the alicyclic diamine DCHM and 250g of 806.5g
Boron nitride, nitrogen charging gas shielded stirs 2.0h at 10 DEG C, fully dissolving alicyclic diamine and by needle inorganic nano heat filling
Be uniformly dispersed, 860.2g alicyclic dianhydrides CHDA be divided into 2 equal parts, point 2 addition reactors in 0.5h, and at 0 DEG C after
Continuous stirring reaction 48h, obtains high-viscosity polyamic acid solution, in putting it into holding vessel, and in -10~-30 DEG C of freezer
Middle storage.
Thermoplasticity conducting liquid crystal Kapton is prepared, method is as follows：Polyamic acid solution is taken out from freezer, is solved
Jelly is warming up to 0 DEG C, adds the dehydrating agent acetic anhydride of 40g and the catalyst of triethylamine of 40g, after being uniformly mixed, is cast to steel
Take, by 50 DEG C, 120 DEG C, 170 DEG C of temperature drying tunnel, dry out solvent and chemical imidization, then passing through must after fiberglass band
To the polyamide sorrel of part imidization, polyamide sorrel continues through 160 DEG C, 220 DEG C, 260 DEG C of temperature drying tunnel, continues to dry
Remaining solvent and imidization completely are done, while after the stretched biaxial stretch-formed orientation than for 1.1, cutting edge winding obtains thickness
It is 12 μm of thermoplasticity conducting liquid crystal Kapton.
3D thermal conductivity aluminum matrix copper-clad plates are prepared, method is as follows：By the thermoplasticity heat conduction that thickness manufactured in the present embodiment is 12 μm
Liquid crystal polyimide film is placed between the Copper Foil mat surface that thickness is 12 μm and the mat surface of 0.5mm aluminium sheets, is superimposed 20 layers, is put
It is placed in vacuum press, vacuumizes, 1h is pressed under the conditions of pressure 20MPa, 300 DEG C of temperature, cutting edge is taken out after cooling and obtains 3D
Thermal conductivity aluminum matrix copper-clad plate.
Embodiment 2~8
Use method similar to Example 1 prepare polyamic acid solution, thermoplasticity conducting liquid crystal Kapton with
And 3D thermal conductivity aluminum matrix copper-clad plates, difference is each raw material type, consumption and preparation technology parameter difference, embodiment 1~8
Raw material is as shown in table 1.
Table 1
The technological parameter of embodiment 1~8 is as shown in table 2.
Table 2
Embodiment 9
The thermoplasticity conducting liquid crystal Kapton and its copper-clad plate of 3D thermal conductivity aluminum matrixes prepared to embodiment 1~8 are carried out
Detailed performance test, as a result as shown in Table 3 and Table 4.
Table 3
Table 4
From table 3 and table 4, thermoplasticity conducting liquid crystal Kapton prepared by the present invention has good thermal conductivity
Energy, flexility, thermoplastic property, adhesive property, heat resistance, dimensional stability and chemical-resistant stability, combination property are good,
Especially 3D bendings property is substantially better than epoxy conductive adhesive film, is prepared based on the thermoplasticity conducting liquid crystal Kapton
The copper-clad plate of 3D thermal conductivity aluminum matrixes has peel strength higher, dimensional stability, heat resistance, and excellent dielectric properties, performance
Market application demand is met, with good economic worth.
Claims (10)
1. a kind of thermoplasticity conducting liquid crystal Kapton, it is characterised in that preparation method is as follows：First with alicyclic diamine
It is raw material with alicyclic dianhydride, while needle inorganic nano heat filling is added, at low temperature by situ aggregation method in non-matter
Polyamic acid solution is synthesized in sub- polar solvent, then to addition dehydrating agent and catalyst in polyamic acid solution, and has passed through
Curtain coating and biaxial stretch-formed orientation technology prepare thermoplasticity conducting liquid crystal Kapton.
2. thermoplasticity conducting liquid crystal Kapton according to claim 1, it is characterised in that prepare the thermoplasticity and lead
The raw material of hot liquid crystal polyimide film include having with the alicyclic diamine of following formula (1) structural formula：
H2N-R1-NH2(1),
With the alicyclic dianhydride monomer with formula (2) structural formula：
And needle inorganic nano heat filling；
The R1Structure is the one kind in following structural formula：
R1With the optional position on the link position of amino, including the ring, R1Alicyclic ring on substitution base be C1~C6Lower alkyl
Base or lower alkoxy or no substitution base；X is O, S, SO in structure above2、CO、CH2、CF2、C(CH3)2、C
(CF3)2Or do not exist；
The R2Structure is the one kind in following structural formula：
R2Alicyclic ring on substitution base be C1~C6Low alkyl group or lower alkoxy or without substitution base, said structure
Y is O, S, SO in formula2、CO、CH2、CF2、C(CH3)2、C(CF3)2Or do not exist.
3. thermoplasticity conducting liquid crystal Kapton according to claim 1, it is characterised in that the alicyclic diamine
For one or more in 1,3- diaminos cyclopentane, 1,4- DACHs, 4,4 '-diamino-dicyclohexyl methane
Mixture.
4. thermoplasticity conducting liquid crystal Kapton according to claim 1, it is characterised in that the alicyclic dianhydride
Monomer is 1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,2,3,4- pentamethylene tetracarboxylic dianhydride, 1,2,4,5- cyclopentanetetracarboxylics
One or more mixture in dianhydride.
5. thermoplasticity conducting liquid crystal Kapton according to claim 1, it is characterised in that the needle inorganic is received
Rice heat filling is aluminum oxide, magnesia, silica, zinc oxide, nickel oxide, aluminium nitride, boron nitride, the nitrogen of acicular nanometer size
One or more mixture in SiClx, carborundum, diamond；The needle inorganic nano heat filling is in thermoplasticity
Mass fraction in conducting liquid crystal Kapton is 5~30%.
6. a kind of preparation method of any described thermoplasticity conducting liquid crystal Kaptons of claim 1-5, its feature exists
In comprising the following steps：
1) polyamic acid solution is prepared：Alicyclic diamine, needle inorganic nano heat filling and aprotic polar solvent are added
In reactor, reactor temperature is 10~30 DEG C, is stirred in a nitrogen atmosphere, then drops reactor temperature
To 0~5 DEG C, alicyclic dianhydride monomer is divided into 2~10 equal parts, in adding reactor in batches in 0.5~5h, added follow-up
Continue 5~48h of reaction at 0~5 DEG C and obtain high-viscosity polyamic acid solution, be placed in being stored in -10~-30 DEG C of freezer；
2) thermoplasticity conducting liquid crystal Kapton is prepared：By step 1) gained polyamic acid solution be warming up to 0~10 DEG C, add
Plus dehydrating agent and catalyst, it is cast on steel band after being uniformly mixed, by obtaining part after low temperature drying tunnel and fiberglass band
The polyamide sorrel of imidization, polyamide sorrel continues through high temperature drying tunnel, drying residual solvent and imidization completely, while through
After overstretching is than the biaxial stretch-formed orientation for 1.1~1.2, cutting edge winding obtains the thermoplasticity conducting liquid crystal that thickness is 12~50 μm
Kapton.
7. preparation method according to claim 6, it is characterised in that step 1) alicyclic diamine and alicyclic dianhydride
The ratio between the amount of material be 0.90~1.10；The aprotic polar solvent is 1-METHYLPYRROLIDONE, N, N- dimethyl formyls
Amine, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, dimethyl suflfate, sulfolane, fourth lactones, cresols, cyclobutanone, tetrahydrofuran, two
One or more mixture in EGME, TRIGLYME；The polyamic acid solution solid content is 5
~30%.
8. preparation method according to claim 6, it is characterised in that step 2) dehydrating agent be acetic anhydride, propionic andydride,
In butyric anhydride, TFAA, chloroacetic chloride, benzoyl oxide, Dicyclohexylcarbodiimide, TFAA, thionyl chloride one
Plant or two or more mixtures, dehydrating agent addition is the 0.1~0.5% of polyamic acid solution quality；The catalyst is
Triethylamine, triethanolamine, N, N- dimethylethanolamines, N, accelerine, N, N- diethylanilines, pyridine, picoline,
One or more mixture in lutidines, quinoline, imidazoles, catalyst charge is polyamic acid solution quality
0.1~0.5%.
9. preparation method according to claim 6, it is characterised in that step 2) each section of temperature of the low temperature drying tunnel be respectively
50~70 DEG C, 100~120 DEG C, 150~170 DEG C；Each section of temperature of the high temperature drying tunnel be respectively 160~180 DEG C, 200~220
DEG C, 240~260 DEG C.
10. a kind of stacking prepared according to any described thermoplasticity conducting liquid crystal Kaptons of claim 1-5
Body, the layered product is laminated with least one of which thermoplasticity conducting liquid crystal Kapton on metal foil.
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Application publication date: 20170613 |