CN116891571A - Organosilicon modified polyimide resin composition and application thereof - Google Patents

Organosilicon modified polyimide resin composition and application thereof Download PDF

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Publication number
CN116891571A
CN116891571A CN202311021106.5A CN202311021106A CN116891571A CN 116891571 A CN116891571 A CN 116891571A CN 202311021106 A CN202311021106 A CN 202311021106A CN 116891571 A CN116891571 A CN 116891571A
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Prior art keywords
modified polyimide
fluorescent powder
resin composition
organosilicon modified
silicone
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鳗池勇人
斎藤幸广
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Jiaxing Super Lighting Electric Appliance Co Ltd
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Jiaxing Super Lighting Electric Appliance Co Ltd
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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
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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    • 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
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    • 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
    • C08G73/1003—Preparatory processes
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    • 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
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
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    • 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
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    • H01—ELECTRIC ELEMENTS
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    • H01L25/04—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers
    • H01L25/075—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H01L33/00
    • H01L25/0753—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H01L33/00 the devices being arranged next to each other
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
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    • C—CHEMISTRY; METALLURGY
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    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
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Abstract

The invention discloses an organosilicon modified polyimide resin composition, which comprises organosilicon modified polyimide and a thermosetting agent, wherein the organosilicon modified polyimide contains a repeating unit represented by the following general formula (I):ar in the general formula (I) 1 Ar is a 4-valent organic group having a benzene ring or an alicyclic hydrocarbon structure 2 R is independently selected from methyl or phenyl, and the thermosetting agent is epoxy resin, isocyanate or bisoxazoline compound. The organosilicon modified polyimide resin composition has excellent heat resistance, mechanical strength and light transmittance.

Description

Organosilicon modified polyimide resin composition and application thereof
The invention discloses a division application of a silicone modified polyimide resin composition and application thereof, wherein the division application is filed in China patent office, application number 201811097472.8 and the invention name is "an organosilicon modified polyimide resin composition and application thereof" on the 18 th month of 2018.
Technical Field
The invention relates to the field of illumination, in particular to an organosilicon modified polyimide resin composition.
Background
The LED is gradually replacing the place of the conventional lighting lamp due to the advantages of environmental protection, energy saving, high efficiency and long life. However, the light emitted by the conventional LED light source has directivity, unlike the conventional lamp, which can illuminate in a wide-angle range. In recent years, filaments capable of enabling an LED light source to emit light to achieve 360-degree full-angle illumination similar to a traditional tungsten filament lamp are paid attention to in the industry.
Patent publication No. CN103994349a discloses a high light efficiency LED lamp, in which a plurality of LED chips are fixed on a transparent substrate having filament electrodes at both ends, the transparent substrate is made of transparent glass, glass ceramics, transparent ceramics, yttrium aluminum garnet, alumina (sapphire), chlorine oxynitride, yttrium oxide ceramics, calcium oxide ceramics or transparent heat-resistant PC/PS/PMMA, and although the transparent substrate can avoid blue light loss caused by downward blue light emission from the LED chips back through P-N junction, the substrate is a hard substrate, and cannot be bent, so that there is a disadvantage of small light emission angle.
Patent publication number CN204289439U discloses a full-circumference luminous LED filament, which comprises a substrate mixed with fluorescent powder, an electrode arranged on the substrate, at least one LED chip mounted on the substrate, and a packaging adhesive covering the LED chip. The substrate formed by the silicon resin containing the fluorescent powder avoids the cost of glass or sapphire serving as the substrate, and the filament manufactured by using the substrate avoids the influence of the glass or sapphire on the light emitting of the chip, so that 360-degree light emitting is realized, and the light emitting uniformity and the light efficiency are greatly improved. However, the substrate is formed of silicone resin, which has a disadvantage of poor heat resistance.
The present application is further optimized for the above application to further cope with various process requirements.
Disclosure of Invention
The application mainly solves the technical problems of poor heat resistance of the existing base material and unstable performance/light emission of a filament product by providing an organosilicon modified polyimide resin composition and using the composition as a filament base material or a light conversion layer.
The LED bulb lamp comprises a lamp shell and a lamp cap connected with the lamp shell, wherein at least two conductive brackets, a driving circuit, a cantilever, a stem and an LED filament are arranged in the lamp shell, the driving circuit is electrically connected with the conductive brackets and the lamp cap, and the LED filament is connected with the stem through the conductive brackets;
adopting an organosilicon modified polyimide resin composition composite film as an LED filament base material;
the base layer adopts an organosilicon modified polyimide resin composition composite film;
the organic silicon modified polyimide resin composition comprises organic silicon modified polyimide, a thermosetting agent, fluorescent powder and radiating particles;
The heat dissipation particles comprise particles with high transmittance and particles with low transmittance, and the weight ratio of the particles with high transmittance to the particles with low transmittance is 3-5:1;
the organosilicon modified polyimide contains a repeating unit represented by the following general formula (I):
(Ⅰ)；
wherein, in the general formula (I), R is selected from methyl or phenyl, and n is 1-5;
ar1 is a 4-valent organic group with a benzene ring structure or an alicyclic hydrocarbon structure containing an active hydrogen functional group, wherein the active hydrogen functional group is any one of hydroxyl, amino, carboxyl or thiol;
ar2 is a 2-valent organic group containing an active hydrogen functional group, wherein the active hydrogen functional group is any one of hydroxyl, amino, carboxyl or thiol;
the content of siloxane of the organosilicon modified polyimide is 30-70 wt%, the content of siloxane is the weight ratio of siloxane diamine to organosilicon modified polyimide, and the weight of organosilicon modified polyimide is the sum of diamine and dianhydride weight used for synthesizing the organosilicon modified polyimide minus the weight of water generated in the synthesis process.
In one embodiment of the present invention, the thermosetting agent is any one of epoxy resin, isocyanate, bismaleimide and bisoxazoline compound.
In an embodiment of the invention, the fluorescent powder is spherical, plate-shaped or needle-shaped.
In one embodiment of the present invention, the amount of the fluorescent powder is not less than 0.05 times and not more than 8 times the weight of the silicone-modified polyimide.
In one embodiment of the invention, the fluorescent powder comprises red fluorescent powder and green fluorescent powder, and the adding ratio of the red fluorescent powder to the green fluorescent powder is 1:5-8.
In one embodiment of the present invention, the fluorescent powder includes a red fluorescent powder and a yellow fluorescent powder, and an adding ratio of the red fluorescent powder to the yellow fluorescent powder is 1:5-8.
In one embodiment of the invention, an antifoaming agent, a leveling agent or an adhesive is added in the synthetic process of the organosilicon modified polyimide resin composition, and the dosage of the additive is not more than 10% of the weight of the organosilicon modified polyimide.
In one embodiment of the present invention, the amount of the fluorescent powder is greater than or equal to 0.05 times the weight of the silicone-modified polyimide.
In an embodiment of the present invention, the heat dissipation particles are any one or a combination of more than one of silicon dioxide, aluminum oxide, magnesium carbonate, aluminum nitride, boron nitride and diamond.
The organosilicon-modified polyimide in one embodiment of the invention comprises fluorinated aromatic organosilicon-modified polyimide and aliphatic organosilicon-modified polyimide.
Compared with the prior art, the invention comprises any one or any combination of the following effects:
(1) The organic silicon modified polyimide resin composition which is prepared by taking organic silicon modified polyimide as a main body and adding a thermosetting agent, light-transmitting particles and the like has excellent heat resistance, mechanical strength and light transmission;
(2) The organic silicon modified polyimide resin composition is used as a base material of the lamp filament, so that the lamp filament has good flexibility, and various shapes are presented to the lamp filament, and 360-degree full-ambient lighting is realized;
(3) The amidation reaction is carried out by adopting a vacuum defoaming method or under the nitrogen atmosphere, so that the volume content percentage of the foam holes in the organic silicon modified polyimide is 5-20%, and the light emitted by the LED chip is more uniform after the light is refracted by the foam holes.
Drawings
FIG. 1 shows a polyimide before and after the addition of a thermosetting agent T MA analysis chart;
FIG. 2A is an SEM image of an embodiment of a silicone modified polyimide resin composition composite film (substrate);
FIG. 2B is an SEM image of an embodiment of a silicone modified polyimide resin composition composite film (substrate);
FIG. 3 is a schematic cross-sectional view of a silicone modified polyimide resin composition composite film (substrate);
FIG. 4 is a schematic view of a perspective partial cross section of an embodiment of an LED filament of the present invention;
FIG. 5 is a schematic cross-sectional view of an embodiment of a filament laminate structure of the present invention;
fig. 6 is a schematic perspective view of the LED bulb of the present invention.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
The invention provides an organosilicon modified polyimide, which comprises a repeating unit represented by the following general formula (I):
ar in the general formula (I) 1 Is a 4-valent organic group. The organic group has a benzene ring or an alicyclic hydrocarbon structure, and the alicyclic hydrocarbon structure may be an alicyclic hydrocarbon of a single ring systemThe structure may have an alicyclic hydrocarbon structure containing a bridged ring, and the alicyclic hydrocarbon structure containing a bridged ring may be a two-ring alicyclic hydrocarbon structure or a three-ring alicyclic hydrocarbon structure. The organic group may be a benzene ring structure or an alicyclic hydrocarbon structure containing an active hydrogen functional group, and the active hydrogen functional group may be any one or more of a hydroxyl group, an amino group, a carboxyl group and a thiol group. In other embodiments, the active hydrogen functionality may also be an amide group.
Ar 2 The organic group may have, for example, an alicyclic hydrocarbon structure of a monocyclic system, and is preferably a 2-valent organic group containing an active hydrogen functional group, which is any one or more of a hydroxyl group, an amino group, a carboxyl group, and a thiol group. In other embodiments, the active hydrogen functionality may also be an amide group.
R is independently selected from methyl or phenyl.
n is 1 to 5, preferably n is 1 or 2 or 3 or 5.
The number average molecular weight of the general formula (I) is 5000 to 100000, preferably 10000 to 60000, more preferably 20000 to 40000. The number average molecular weight is a polystyrene equivalent based on a calibration curve prepared by a Gel Permeation Chromatography (GPC) apparatus using standard polystyrene.
Ar 1 The acid anhydride may include aromatic acid anhydrides and aliphatic acid anhydrides, and the aromatic acid anhydrides include aromatic acid anhydrides containing only benzene rings, fluorinated aromatic acid anhydrides, aromatic acid anhydrides containing amide groups, aromatic acid anhydrides containing ester groups, aromatic acid anhydrides containing ether groups, aromatic acid anhydrides containing sulfur groups, aromatic acid anhydrides containing sulfone groups, aromatic acid anhydrides containing carbonyl groups, and the like.
Examples of the aromatic acid anhydride having only a benzene ring include pyromellitic anhydride (PMDA), 2, 3',4' -biphenyltetracarboxylic dianhydride (appda), 3',4' -biphenyltetracarboxylic dianhydride (sBPDA), 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic anhydride (TDA), and the like; fluorinated aromatic anhydrides such as 4,4' - (hexafluoroisopropenyl) diphthalic anhydride abbreviated to 6 FDA; the amide group-containing aromatic acid anhydrides include N, N ' - (5, 5' - (perfluoropropyl-2, 2-diyl) bis (2-hydroxy-5, 1-phenylene)) bis (1, 3-dioxo-1, 3-dihydroisobenzofuran) -5-carboxamide) (6 FAP-ATA), N ' - (9H-fluoren-9-ylidenedi-4, 1-phenylene) bis [1, 3-dihydro-1, 3-dioxo-5-isobenzofuran carboxamide ] (FDA-ATA), and the like; the ester group-containing aromatic acid anhydrides include p-phenyl bis (trimellitate) dianhydride (TAHQ) and the like; the ether group-containing aromatic acid anhydrides include 4,4' - (4, 4' -isopropyldiphenoxy) bis (phthalic anhydride) (BPADA), 4' -oxybisphthalic anhydride (sODPA), 2, 3',4' -diphenylether tetracarboxylic dianhydride (aODPA), 4' - (4, 4' -isopropyldiphenoxy) bis (phthalic anhydride) (BPADA), and the like; the aromatic acid anhydride containing sulfur group includes 4,4' -bis (phthalic anhydride) sulfide (TPDA) and the like; the aromatic acid anhydride containing sulfone group includes 3,3',4' -diphenyl sulfone tetracarboxylic dianhydride (DSDA) and the like; the carbonyl group-containing aromatic acid anhydride includes 3,3',4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) and the like.
The alicyclic acid anhydrides include 1,2,4, 5-cyclohexane tetracarboxylic dianhydride abbreviated as HPMDA, 1,2,3, 4-butane tetracarboxylic dianhydride (BDA), tetrahydro-1H-5, 9-methano [3,4-d ] dioxin-1, 3,6,8 (4H) -Tetraone (TCA), hexahydro-4, 8-ethylene-1H, 3H-benzo [1,2-C:4,5-C' ] difuran-1, 3,5, 7-tetraone (BODA), cyclobutane tetracarboxylic dianhydride (CBDA), 1,2,3, 4-cyclopenta tetracarboxylic dianhydride (CpDA), or the like, or alicyclic anhydrides having an olefin structure such as bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride (COeDA). If an anhydride having an acetylene group such as 4,4' - (acetylene-1, 2-diyl) diphthalic anhydride (EBPA) is used, the film strength of the light conversion layer can be further ensured by post-hardening.
From the viewpoint of solubility, 4 '-oxybisphthalic anhydride (sODPA), 3',4 '-Benzophenone Tetracarboxylic Dianhydride (BTDA), cyclobutane tetracarboxylic dianhydride (CBDA), 4' - (hexafluoroisopropenyl) diphthalic anhydride (6 FDA) are preferable. The above-mentioned dianhydrides may be used singly or in combination.
Ar 2 Is a component derived from diamine, and the diamine is classified into aromatic diamine and aliphatic diamine, wherein the aromatic diamine includes aromatic diamine having only benzene ring structure, fluorinated aromatic diamine, aromatic diamine having ester group, aromatic diamine having ether group, aromatic diamine having amide group, aromatic diamine having carbonyl group, aromatic diamine having hydroxyl group, and aromatic diamine having carboxyl group Aromatic diamines having a group, aromatic diamines having a sulfone group, aromatic diamines having a sulfur group, and the like.
Aromatic diamines containing only benzene ring structures include meta-phenylenediamine, para-phenylenediamine, 2, 4-diaminotoluene, 2, 6-diamino-3, 5-diethyltoluene, 4 '-diamino-3, 3' -dimethylbiphenyl, 9-bis (4-aminophenyl) Fluorene (FDA), and 9, 9-bis (4-amino-3-tolyl) fluorene, 2-bis (4-aminophenyl) propane, 2-bis (3-methyl-4-aminophenyl) propane, 4 '-diamino-2, 2' -dimethylbiphenyl (APB); fluorinated aromatic diamines include 2,2' -BIS (trifluoromethyl) diaminobiphenyl (TFMB), 2-BIS (4-aminophenyl) hexafluoropropane (6 FDAM), 2-BIS [4- (4-aminophenoxy) phenyl ] Hexafluoropropane (HFBAPP), 2-BIS (3-amino-4-tolyl) hexafluoropropane, etc. (BIS-AF-AF), etc.; the aromatic diamine containing an ester group includes [4- (4-aminobenzoyl) oxyphenyl ] -4-Aminobenzoate (ABHQ), di-p-aminophenyl terephthalate (BPTP), p-aminophenyl p-aminobenzoate (APAB), and the like; the ether group-containing aromatic diamine includes 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane) (BAPP), 2' -bis [4- (4-aminophenoxyphenyl) ] propane (ET-BDM), 2, 7-bis (4-aminophenoxy) -naphthalene (ET-2, 7-Na), 1, 3-bis (3-aminophenoxy) benzene (TPE-M), 4' - [1, 4-phenylbis (oxy) ] bis [3- (trifluoromethyl) aniline ] (p-6 FAPB), 3,4' -diaminodiphenyl ether, 4' -diaminodiphenyl ether (ODA), 1, 3-bis (4-aminophenoxy) benzene (TPE-R), 1, 4-bis (4-aminophenoxy) benzene (TPE-Q), 4' -bis (4-aminophenoxy) biphenyl (BAPB), and the like; the aromatic diamine containing amide groups includes N, N ' -bis (4-aminophenyl) benzene-1, 4-dicarboxamide (BPTPA), 3,4' -diaminoanilide (m-APABA), 4' -Diaminoanilide (DABA) and the like; the carbonyl-containing aromatic diamines include 4,4 '-diaminobenzophenone (4, 4' -DABP), bis (4-amino-3-carboxyphenyl) methane (or referred to as 6,6 '-diamino-3, 3' -methylenedibenzoic acid), and the like; the hydroxyl group-containing aromatic diamines include 3,3' -dihydroxybenzidine (HAB), 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6 FAP), and the like; the aromatic diamine containing carboxyl group includes 6,6 '-diamino-3, 3' -methylenedibenzoic acid (MBAA), 3, 5-diaminobenzoic acid (DBA) and the like; the aromatic diamine containing sulfone group includes 3,3' -diaminodiphenyl sulfone (DDS), 4' -diaminodiphenyl sulfone, bis [4- (4-aminophenoxy) phenyl ] sulfone (BAPS) (or referred to as 4,4' -bis (4-aminophenoxy) diphenyl sulfone), 3' -diamino-4, 4' -dihydroxydiphenyl sulfone (ABPS); the sulfur-containing aromatic diamine includes 4,4' -diaminodiphenyl sulfide.
The aliphatic diamine is diamine without aromatic structure (such as benzene ring), the alicyclic diamine comprises monocyclic alicyclic diamine and linear aliphatic diamine, the linear aliphatic diamine comprises silicon-oxygen diamine, linear alkyl diamine and linear aliphatic diamine containing ether group, the monocyclic alicyclic diamine comprises 4,4' -diamino dicyclohexylmethane (PACM) and 3, 3-dimethyl-4, 4-diamino dicyclohexylmethane (DMDC); the siloxy diamine (or amino modified silicone) includes alpha, omega- (3-aminopropyl) polysiloxane
(KF 8010), X22-161A, X22-161B, NH D, 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane (PAME), and the like; the linear alkyl diamine has 6 to 12 carbon atoms, and is preferably unsubstituted; the ether group-containing linear aliphatic diamine includes ethylene glycol di (3-aminopropyl) ether and the like.
The diamine can also be selected from diamines containing fluorenyl groups, wherein the fluorenyl groups have huge free volume and rigid condensed ring structures, so that polyimide has good heat resistance, thermal oxidation stability, mechanical properties, optical transparency and good solubility in organic solvents, and the diamines containing fluorenyl groups, such as 9, 9-bis (3, 5-difluoro-4-aminophenyl) fluorene, can be obtained by reacting 9-fluorenone with 2, 6-dichloroaniline. The fluorinated diamine can also be 1, 4-bis (3 '-amino-5' -trifluoromethyl phenoxy) biphenyl, the diamine is meta-substituted fluorine-containing diamine with a rigid biphenyl structure, the meta-substituted structure can block charge flow along the molecular chain direction, and the intermolecular conjugation effect is reduced, so that the absorption of visible light is reduced, and the transparency of the composite film can be improved to a certain extent by selecting diamine or anhydride with an asymmetric structure. The above diamines may be used singly or in combination of two or more.
Examples of diamines having active hydrogen include hydroxyl group-containing diamines such as 3,3 '-diamino-4, 4' -dihydroxybiphenyl, 4 '-diamino-3, 3' -dihydroxy-1, 1 '-biphenyl (or referred to as 3,3' -dihydroxybenzidine) (HAB), 2-bis (3-amino-4-hydroxyphenyl) propane
(BAP), 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6 FAP), 1, 3-bis (3-hydroxy-4-aminophenoxy) benzene, 1, 4-bis (3-hydroxy-4-aminophenyl) benzene, 3 '-diamino-4, 4' -dihydroxydiphenyl sulfone (ABPS) may be mentioned, and as a diamine having a carboxyl group, for example, 3, 5-diaminobenzoic acid, bis (4-amino-3-carboxyphenyl) methane (or referred to as 6,6 '-diamino-3, 3' -methylenedibenzoic acid), 3, 5-bis (4-aminophenoxy) benzoic acid, 1, 3-bis (4-amino-2-carboxyphenoxy) benzene may be mentioned. Diamines having an amino group such as 4,4' -Diaminoanilide (DABA), 2- (4-aminophenyl) -5-aminobenzimidazole, diethylenetriamine, 3' -diaminodipropylamine, triethylenetetramine, N ' -bis (3-aminopropyl) ethylenediamine (or referred to as N, N-bis (3-aminopropyl) ethylamine) and the like. Diamines containing thiol groups, such as 3, 4-diaminobenzenethiol. The above diamines may be used singly or in combination of two or more.
The silicone-modified polyimide can be synthesized by a known synthesis method. The dianhydride and diamine can be prepared by imidizing them by dissolving them in an organic solvent in the presence of a catalyst, examples of which include acetic anhydride/triethylamine type, valerolactone/pyridine type, etc., and preferably, water produced during the azeotropic course of imidization is used to facilitate removal of water using a dehydrating agent such as toluene.
Or the acid anhydride and diamine are subjected to equilibrium reaction to obtain amic acid, and then the amic acid is heated and dehydrated to obtain polyimide. In addition, the method of directly heating and dehydrating alicyclic anhydride and diamine can be utilized to obtain the solubilized polyimide, and the solubilized polyimide is used as a glue material, so that the light transmittance is better, and the solubilized polyimide is liquid, so that other solid substances (such as inorganic heat dissipation particles and fluorescent powder) can be more uniformly dispersed in the glue material.
In one embodiment, the silicone modified polyimide can be prepared by dissolving a polyimide obtained by heating and dehydrating a diamine and an acid anhydride and a silicon-oxygen diamine in a solvent. In another embodiment, the reaction is carried out with a siloxy diamine in the amic acid (acid-amic) state prior to the polyimide being obtained.
In addition, acid anhydrides and diamines may also be used which are dehydrated to form ring-closed and polycondensed imide compounds, for example acid anhydrides and diamines in a molecular weight ratio of 1:1. 200 millimoles (mmol) of 4,4'- (hexafluoroisopropenyl) diphthalic anhydride (6 FDA), 20 millimoles (mmol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6 FAP), 50 millimoles (mmol) of 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFMB), 130 millimoles (mmol) of aminopropyl-terminated poly (dimethylsiloxane) were used in one example to give a PI synthesis solution.
The above method can give a polyimide compound having an amino group as a terminal, but a polyimide compound having a carboxyl group as a terminal can be produced in other manners. In addition, when the main chain of the anhydride contains a carbon-carbon triple bond in the reaction of the anhydride and the diamine, the bonding force of the carbon-carbon triple bond can strengthen the molecular structure of the anhydride; or a diamine containing a vinyl siloxane structure is used.
The molar ratio of dianhydride to diamine was 1:1. Wherein the diamine containing active hydrogen functional groups accounts for 5-25% of the mole fraction of the whole diamine. The reaction temperature for synthesizing polyimide is preferably 80 to 250 ℃, more preferably 100 to 200 ℃, and the reaction time can be adjusted according to the size of the batch, for example, the reaction time for obtaining 10 to 30g of polyimide is 6 to 10 hours.
The organosilicon-modified polyimide includes fluorinated aromatic organosilicon-modified polyimide and aliphatic organosilicon-modified polyimide. Fluorinated aromatic silicone-modified polyimide is synthesized from a siloxane diamine, an aromatic diamine containing a fluorine (F) group (or referred to as an F-converted aromatic diamine), and an aromatic dianhydride containing a fluorine (F) group (or referred to as an F-converted aromatic anhydride); the aliphatic silicone-modified polyimide is synthesized from dianhydride, a siloxane-type diamine, and at least one diamine (or referred to as an aliphatic diamine) that does not contain an aromatic structure (such as a benzene ring), or diamine (one of which is a siloxane-type diamine) and at least one dianhydride (or referred to as an aliphatic anhydride) that does not contain an aromatic structure (such as a benzene ring). The raw materials required for synthesizing the organosilicon modified polyimide and the silicon content of the organosilicon modified polyimide have certain influence on the transmittance, the color changing performance, the mechanical performance, the warping degree and the refractive index of the base material.
The silicone modified polyimide of the present invention has a silicone content of 20 to 75wt%, preferably 30 to 70wt%, and a glass transition temperature of 150 ℃ or lower. The content of siloxane in the invention is the weight ratio of siloxane diamine (structural formula is shown as formula (A)) to organosilicon modified polyimide, and the weight of the organosilicon modified polyimide is the sum of diamine and dianhydride weight used for synthesizing the organosilicon modified polyimide minus the weight of water generated in the synthesis process.
Wherein R is selected from methyl or phenyl; r is preferably methyl and n is 1 to 5, preferably 1,2,3,5.
The organic solvent required for synthesizing the silicone-modified polyimide is not limited as long as it can dissolve the silicone-modified polyimide and ensure affinity (wettability) with the phosphor or filler to be added, but it is sufficient to avoid a large amount of solvent remaining in the product, and the number of moles of solvent is generally equal to the number of moles of water produced from the diamine and the acid anhydride, for example, 1 mole of water produced from 1 mole of diamine and 1 mole of acid anhydride, and the amount of solvent used is 1 mole. In addition, the organic solvent selected has a boiling point of 80 ℃ or more and less than 300 ℃, more preferably 120 ℃ or more and less than 250 ℃ at normal atmospheric pressure. Because drying and curing at low temperatures are required after coating, if the temperature is below 120 ℃, the drying rate may be too high to be well coated during the coating process. If the boiling point temperature of the organic solvent selected is higher than 250 c, drying at low temperature may be delayed. Specifically, the organic solvent is an ether-type organic solvent, an ester-type organic solvent, a dimethyl ether-type organic solvent, a ketone-type organic solvent, an alcohol-type organic solvent, an aromatic hydrocarbon-type solvent, or others. The ether-type organic solvent includes ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether (or referred to as ethylene glycol dibutyl ether), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether (or referred to as diethylene glycol methyl ethyl ether), dipropylene glycol dimethyl ether or diethylene glycol dibutyl ether (diethylene glycol dibutyl ether), diethylene glycol butyl methyl ether; the ester organic solvent comprises acetate, wherein the acetate comprises ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, propylene glycol diacetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, benzyl acetate or butyl carbitol acetate, and the ester solvent can be methyl lactate, ethyl lactate, butyl ester, methyl benzoate or ethyl benzoate; the dimethyl ether solvent comprises triglyme or tetraglyme; the ketone solvent comprises acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone or 2-heptanone; alcohol solvents include butanol, isobutanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol or diacetone alcohol; the aromatic hydrocarbon solvent includes toluene or xylene; other solvents include gamma-butyrolactone, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide or dimethylsulfoxide.
The invention provides an organosilicon modified polyimide resin composition, which comprises the organosilicon modified polyimide and a thermosetting agent, wherein the thermosetting agent is epoxy resin, isocyanate or bisoxazoline compound. In one embodiment, the thermal curing agent is used in an amount of 5 to 12% by weight of the silicone modified polyimide based on the weight of the silicone modified polyimide.
The addition of a thermosetting agent can increase heat resistance and glass transition temperature. As shown in fig. 1, A1 and A2 represent curves before and after adding the thermosetting agent, and D1 and D2 represent values obtained by differentiating the values of the curves A1 and A2, respectively, and represent the degree of change of the curves A1 and A2, respectively, and as shown in the analysis result of TMA (thermomechanical analysis) in fig. 1, there is a tendency that the curve of thermal deformation is retarded when the thermosetting agent is added. Therefore, it is known that the addition of the thermosetting agent has an effect of improving heat resistance.
When the organosilicon modified polyimide and the thermosetting agent are subjected to crosslinking reaction, the thermosetting agent has an organic group which can react with an active hydrogen functional group in the polyimide, and the amount and the type of the thermosetting agent have a certain influence on the color changing performance, the mechanical performance and the refractive index of the substrate, so that some thermosetting agents with better heat resistance and transmittance can be selected, and examples of the thermosetting agents include epoxy resin, isocyanate, bismaleimide or bisoxazoline compound. The epoxy resin may be bisphenol A type epoxy resin, such as BPA, and may also be silicone type epoxy resin, such as KF105, X22-163A, and may also be alicyclic epoxy resin, such as 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexylformate (2021P), EHPE3150, and EHPE3150CE. Through the bridging reaction of the epoxy resin, a three-dimensional bridging structure is formed between the organosilicon modified polyimide and the epoxy resin, and the structural strength of the adhesive material is improved. In one embodiment, the amount of the thermosetting agent may also be determined based on the molar amount of the thermosetting agent that reacts with the active hydrogen functional groups in the silicone-modified polyimide, and in one embodiment, the molar amount of the active hydrogen functional groups that react with the thermosetting agent is equal to the molar amount of the thermosetting agent, for example, 1mol of the active hydrogen functional groups that react with the thermosetting agent, and then 1mol of the thermosetting agent.
The specific information for BPA is shown in table 1:
TABLE 1
The specific information of 2021P is shown in table 2:
specific information of EHPE3150 and EHPE3150CE is shown in table 3:
TABLE 3 Table 3
Specific information for PAME, KF8010, X22-161A, X22-161B, NH15D, X22-163A, KF-105 is shown in Table 4, and the refractive index in Table 4 may also be referred to as refractive index.
TABLE 4 Table 4
The silicone-modified polyimide resin composition may further contain a phosphor for obtaining desired light-emitting characteristics, the phosphor being capable of converting the wavelength of light emitted from the light-emitting semiconductor, for example, a yellow phosphor capable of converting blue light into yellow light, and a red phosphor capable of converting blue light into red light. Yellow phosphors, e.g. (Ba, sr, ca) 2 SiO 4 :Eu、(Sr,Ba) 2 SiO 4 Eu (barium orthosilicate (BOS)) and other transparent fluorescent powder, Y 3 Al 5 O 12 Ce (YAG (yttrium aluminum garnet): ce), tb 3 Al 3 O 12 Silicate fluorescent powder with silicate structure such as Ce (YAG (terbium aluminum garnet): ce) and nitrogen oxide fluorescent powder such as Ca-alpha-SiAlON. The red phosphor comprises a nitride phosphor, such as CaAlSiN 3 :Eu、CaSiN 2 Eu. Green phosphors, such as rare earth-halate phosphors, silicate phosphors, and the like. The content ratio of the phosphor in the silicone-modified polyimide resin composition can be arbitrarily set according to the desired light emission characteristics, and when the silicone-modified polyimide resin composition is used as a filament base material, the content, shape, and particle diameter of the phosphor in the silicone-modified polyimide resin composition have a certain influence on the mechanical properties (e.g., elastic modulus, elongation, tensile strength), warpage degree, and thermal conductivity of the base material. In order to provide the substrate with excellent mechanical properties, thermal conductivity and a small degree of warpage, the phosphor contained in the silicone-modified polyimide resin composition is in the form of particles, the shape of the phosphor may be spherical, plate-like or needle-like, preferably the shape of the phosphor is spherical; the maximum average length (average particle diameter in the case of spherical shape) of the phosphor is 0.1 μm or more, preferably 1 μm or more, and more preferably 1 to 100. Mu.m More preferably 1 to 50. Mu.m; the amount of the fluorescent powder is not less than 0.05 times, preferably not less than 0.1 times, and not more than 8 times, preferably not more than 7 times, the weight of the silicone-modified polyimide, for example, 100 parts by weight, and the content of the fluorescent powder is not less than 5 parts by weight, preferably not less than 10 parts by weight, and not more than 800 parts by weight, preferably not more than 700 parts by weight. In one embodiment, two kinds of fluorescent powder are added simultaneously, for example, when red fluorescent powder and green fluorescent powder are added simultaneously, the addition ratio of the red fluorescent powder to the green fluorescent powder is 1:5-8, and preferably the addition ratio of the red fluorescent powder to the green fluorescent powder is 1:6-7. In another embodiment, when two kinds of phosphors are added simultaneously, for example, red phosphor and yellow phosphor are added simultaneously, the addition ratio of red phosphor to yellow phosphor is 1:5-8, preferably the addition ratio of red phosphor to yellow phosphor is 1:6-7.
The silicone modified polyimide resin composition may further include heat dissipating particles. The heat dissipation particles in the organosilicon modified polyimide resin composition of the invention are preferably transparent powder, or particles with high light transmittance or particles with high light reflectivity, and because the LED soft filament is mainly used for emitting light, the filament substrate needs to have good light transmittance. In addition, in the case of mixing two or more types of heat dissipation particles, particles having high transmittance and particles having low transmittance may be used in combination, and the proportion of the particles having high transmittance is made larger than the particles having low transmittance. For example, in one embodiment, the weight ratio of high transmittance particles to low transmittance particles is 3-5:1. In order to give the base material superior in tensile strength, elastic modulus, elongation and thermal conductivity, regarding the particle diameter of the heat dissipation particles, the particle size distribution and the mixing ratio may be appropriately selected so that the average particle diameter is in the range of 0.1 μm to 100 μm, preferably in the range of 1 μm to 50 μm. Examples of the heat dissipation particles include silica, alumina, magnesia, magnesium carbonate, aluminum nitride, boron nitride, diamond, or the like, and silica, alumina, or a combination of both are preferable from the viewpoint of dispersibility. The particle shape of the heat dissipating particles may be spherical, block, or the like, and the spherical shape includes a shape similar to a sphere, and in one embodiment, spherical and non-spherical heat dissipating particles may be used to ensure dispersibility of the heat dissipating particles and thermal conductivity of the substrate, and the content ratio of the spherical and non-spherical heat dissipating particles is 1:0.15 to 0.35. The particle diameter of the heat dissipation particles is, for example, 0.1 to 100. Mu.m, alumina having an average particle diameter of 12 μm or alumina having a particle diameter of 0.1 to 20. Mu.m, and an average particle diameter of 4.1. Mu.m, and the particle diameter is in the range of the particle diameter of alumina, and in one embodiment, 1/5 to 2/5, preferably 1/5 to 1/3 of the thickness of the substrate can be selected from the viewpoint of smoothness of the substrate. The amount of the heat dissipating particles is 1 to 12 times the weight (amount) of the silicone modified polyimide, for example, 100 parts by weight of the silicone modified polyimide, the content of the heat dissipating particles is 100 to 1200 parts by weight, preferably 400 to 900 parts by weight, and two kinds of heat dissipating particles are added simultaneously, for example, silica and alumina are added simultaneously, and the weight ratio of alumina to silica is 0.4 to 25:1, preferably 1 to 10:1.
In the synthesis of the organosilicon modified polyimide resin composition, a coupling agent (such as a silane coupling agent) can be added to improve the adhesiveness between solid substances (such as fluorescent powder and radiating particles) and a glue material (such as organosilicon modified polyimide) and improve the dispersion uniformity of the whole solid substances, so that the heat dissipation performance and the film strength of a light conversion layer are improved, and the coupling agent can also adopt a titanate coupling agent, preferably an epoxy titanate coupling agent. The amount of the coupling agent is related to the addition amount of the heat dissipation particles and the specific surface area thereof, the amount of the coupling agent= (the amount of the heat dissipation particles is the specific surface area of the heat dissipation particles)/the minimum coating area of the coupling agent, for example, an epoxy titanate coupling agent is adopted, and the amount of the coupling agent= (the amount of the heat dissipation particles is the specific surface area of the heat dissipation particles)/331.5.
In other embodiments of the present invention, in order to further improve the properties of the silicone-modified polyimide resin composition in the synthesis process, additives such as an antifoaming agent, a leveling agent, or an adhesive may be optionally added during the synthesis process of the silicone-modified polyimide resin composition, as long as they do not affect the light resistance, mechanical strength, heat resistance, and discoloration of the product. The defoaming agent is used for eliminating bubbles generated at the time of printing, coating and curing, and for example, an acrylic or silicone-based surfactant is used as the defoaming agent. Leveling agents are used to eliminate irregularities on the surface of a coating film generated during printing and coating. Specifically, the surfactant component is preferably contained in an amount of 0.01 to 2wt%, and bubbles can be suppressed, and the coating film can be smoothed by using a leveling agent such as an acrylic or silicone, preferably a nonionic surfactant containing no ionic impurities. Examples of the binder include imidazole compounds, thiazole compounds, triazole compounds, organoaluminum compounds, organotitanium compounds, and silane coupling agents. Preferably, these additives are used in an amount of not more than 10% by weight of the silicone-modified polyimide. When the mixing amount of the additive exceeds 10wt%, the physical properties of the resulting coating film tend to be lowered, and also a problem of deterioration in light resistance due to volatile components may occur.
The silicone-modified polyimide resin composition of the present invention can be used as a substrate in the form of a film or attached to a carrier. The film forming process includes three steps, (a) a coating step: spreading and coating the organosilicon modified polyimide resin composition on a stripper to form a film; (b) a drying and heating step: heating and drying the film together with the stripping body to remove the solvent in the film; (c) stripping: after the completion of the drying, the film was peeled from the peeled body to obtain a film-form silicone-modified polyimide resin composition. The separator may be a centrifugal film or other material which does not react with the silicone-modified polyimide resin composition, and for example, a PET centrifugal film may be used.
The organic silicon modified polyimide resin composition is attached to a carrier to obtain a composition film, the composition film can be used as a base material, and the formation process of the composition film comprises two procedures: (a) a coating process: spreading and coating the organosilicon modified polyimide resin composition on a carrier to form a film; (b) a drying and heating step: the constituent films are heat dried to remove the solvent from the films.
As the coating method in the coating step, a roll-to-roll type coating apparatus such as a roll coater, a die coater, a doctor blade coater, or a simple coating method such as a printing method, an ink jet method, a dispensing method, or a spraying method can be used.
The drying method corresponding to the above-mentioned heat drying step may be a vacuum drying method, a heat drying method, or the like. The heating method may adopt a heat source such as an electric heater or a heating medium to generate heat energy and generate indirect convection, or a heat radiation method using infrared rays emitted from the heat source to heat.
The above silicone-modified polyimide resin composition can be dried and cured after coating to obtain a high thermal conductive film to obtain a property having any one or a combination of the following: excellent in light transmittance, chemical resistance, heat resistance, thermal conductivity, film mechanical properties and light resistance. The temperature and time used in the drying and curing process may be appropriately selected depending on the solvent and the film thickness of the coating in the silicone-modified polyimide resin composition, and whether the drying and curing are complete may be determined depending on the weight change before and after the drying and curing of the silicone-modified polyimide resin composition and the peak change of the thermosetting agent functional group on the infrared spectrum, for example, when an epoxy resin is used as the thermosetting agent, the weight difference before and after the drying and curing of the silicone-modified polyimide resin composition is equal to the weight of the added solvent and the peak value of the epoxy group before and after the drying and curing becomes larger or smaller, and whether the drying and curing are complete may be determined.
In one embodiment, the amidation reaction is performed under nitrogen atmosphere or vacuum defoaming method or both methods are adopted in synthesizing the organosilicon modified polyimide resin composition, so that the volume percentage of the cells in the film of the organosilicon modified polyimide resin composition or the composite film of the organosilicon modified polyimide resin composition is 5-20%, preferably 5-10%. Adopting an organosilicon modified polyimide resin composition composite film as a base material of an LED soft filament, wherein the base material 420B is provided with an upper surface 420B1 and an opposite lower surface 420B2, and as shown in figures 2A-2B, SEM images of different base material surfaces are shown, wherein cells 4d exist in the base material, the cells 4d account for 5-20% of the volume content of the base material 420B, preferably 5-10%, the cross section of the cells 4d is in an irregular shape, as shown in figure 3, the cross section schematic diagram of the base material 420B is shown, the dotted line in figure 3 is a datum line, the upper surface 420B1 of the base material comprises a first area 4a and a second area 4B, the second area 4B comprises cells 4d, the surface roughness of the first area 4a is smaller than that of the second area 4B, and light emitted by an LED chip is scattered through the cells of the second area, so that the light is more uniform; the lower surface 420b2 of the substrate includes a third area 4c, the surface roughness of the third area 4c is greater than the surface roughness of the first area 4a, when the LED chip is placed in the first area 4a, the first area 4a is flat, so that the subsequent fixing and wire bonding are facilitated, and when the LED chip is placed in the second area 4b and the third area 4c, the contact area between the die bond adhesive and the substrate is large during die bonding, and the bonding strength between the die bond adhesive and the substrate can be increased, so that the LED chip is placed on the upper surface 420b1, and the bonding strength between the die bond adhesive and the substrate can be ensured. When the organic silicon modified polyimide resin composition film or the organic silicon modified polyimide resin composition composite film is used as the LED soft filament base material, light emitted by the LED chip is scattered by bubbles in the base material, the light is more uniform, and meanwhile, the glare phenomenon can be further improved.
When the silicone modified polyimide resin composition is prepared by a vacuum defoaming method, the vacuum degree in vacuum defoaming is-0.5 to-0.09 MPa, preferably-0.2 to-0.09 MPa. When the sum of the weights of the raw materials used for preparing the organosilicon modified polyimide resin composition is less than or equal to 250g, the revolution speed is 1200-2000 rpm, the rotation speed is 1200-2000 rpm, and the vacuum defoaming time is 3-8 min. Not only can a certain air bubble be kept in the film to increase the uniformity of light emission, but also can maintain better mechanical properties. The total weight of the raw materials required for preparing the silicone-modified polyimide resin composition may be appropriately adjusted, and generally the higher the total weight is, the lower the vacuum degree may be, and the stirring time and stirring speed may be appropriately increased.
According to the present invention, a resin excellent in light transmittance, chemical resistance, thermochromatic resistance, thermal conductivity, film mechanical properties and light resistance, which is required as a base material for an LED soft filament, can be obtained. In addition, the high thermal conductive resin film may be formed by a simple coating method such as a printing method coating method, an inkjet method, or a dispensing method.
The aliphatic organosilicon modified polyimide resin composition comprises aliphatic organosilicon modified polyimide and a thermosetting agent, and the F-modified aromatic organosilicon modified polyimide resin composition comprises F-modified aromatic organosilicon modified polyimide and a thermosetting agent. Since the aliphatic silicone-modified polyimide has an alicyclic structure, the film of the aliphatic silicone-modified polyimide resin composition has high light transmittance. When the composite film of the silicone-modified polyimide resin composition is used as a filament substrate, the elongation at break of the composite film should be more than 0.5%, preferably 1 to 5%, and most preferably 1.5 to 5% in order to give the substrate good bending property. When the filament is manufactured, the LED chip and the electrode are generally fixed on the base layer through the die bond adhesive, then the adjacent LED chip, the LED chip and the electrode are electrically connected through the lead, and in order to ensure the die bond wire bonding quality and improve the product quality, the elastic modulus of the composite film is more than 2.0Gpa, preferably 2-6 Gpa, and most preferably 4-6 Gpa. In addition, when light emitted from the LED chip passes through the interface between the two substances, the refractive index of the two substances is closer, the light extraction efficiency is higher, and the refractive index of the substance (for example, die bond glue) in contact with the substrate (or base layer) is close, so that the refractive index of the organosilicon modified polyimide composite film is 1.4-1.7, preferably 1.4-1.55. When the organosilicon modified polyimide resin composition is used for a filament substrate, the organosilicon modified polyimide resin composition is required to have good light transmittance at the peak wavelength of InGaN of a blue excited white LED. In order to obtain a good transmittance, the raw materials, the thermosetting agent and the heat dissipating particles for synthesizing the silicone-modified polyimide can be changed, and since the fluorescent powder in the silicone-modified polyimide resin composition has a certain influence on the transmittance test, the silicone-modified polyimide resin composition used for the transmittance test does not contain the fluorescent powder, and the transmittance of the silicone-modified polyimide resin composition is 86 to 93%, preferably 88 to 91%, or preferably 89 to 92%, or preferably 90 to 93%.
When the organic silicon modified polyimide resin composition composite film is used as a filament base material (or a base layer), the LED chip is a hexahedral illuminant, at least two sides of the LED chip are wrapped by a top layer when the LED filament is manufactured, the phenomenon that the color temperature of the top layer and the color temperature of the base layer are uneven or the base layer can feel granular when the existing LED filament is lightened, and therefore the composite film used as the filament base material needs to have excellent transparency. In other embodiments, means such as sulfone groups, non-coplanar structures, meta-substituted diamines, etc., may be introduced into the backbone of the silicone-modified polyimide to enhance the transparency of the silicone-modified polyimide resin composition. In addition, in order to realize the full-cycle light luminous effect of the bulb lamp adopting the filament, the composite film serving as a base material needs to have certain flexibility, so that flexible structures such as ether groups (such as 4,4' -4-amino-2-trifluoromethyl phenoxy) diphenyl ether, carbonyl groups, methylene and the like can be introduced into the main chain of the organosilicon modified polyimide. In other embodiments, diamines or dianhydrides containing pyridine rings may be used, and the rigid structure of the pyridine rings may enhance the mechanical properties of the composite film, while the use of the same with strongly polar groups (e.g., -F) may provide the composite film with excellent light transmission properties, with anhydrides having pyridine structures such as 2, 6-bis (3 ',4' -dicarboxyphenyl) -4- (3 ', 5' -bistrifluoromethylphenyl) pyridine dianhydride.
As shown in fig. 4, the LED filament 100 includes a plurality of LED chips 102, 104, at least two electrodes 110, 112, and a light conversion layer 120, wherein the light conversion layer 120 includes a glue 122 and wavelength conversion particles 124, the glue 122 may be replaced by Polyimide (Polyimide) or the aforementioned silicone modified Polyimide (Polyimide) to have better toughness and reduce cracking or embrittlement probability, and the light conversion particles (which may be any light conversion material such as fluorescent powder, dye, etc., and will be exemplified by fluorescent powder 124) in the light conversion layer 120 can absorb some radiation (such as light) and emit light. The light conversion layer 120 may further have inorganic heat dissipation particles to increase heat dissipation capability.
As shown in fig. 5, the LED filament 400a has: a light conversion layer 420; LED chips 402,404; electrodes 410,412; and gold wires 440 for electrically connecting the LED chip and the LED chip (or electrode). The light conversion layer 420 is coated on at least two sides of the LED chip/electrode. The light conversion layer 420 exposes a portion of the electrodes 410, 412. The light conversion layer 420 may have at least a top layer 420a and a bottom layer 420b, which are respectively used as an upper layer and a lower layer of the filament, and in this embodiment, the top layer 420a and the bottom layer 420b are respectively located at two sides of the LED chip/electrode.
The top layer 420a is a layered structure of at least one layer. The layered structure may be selected from: a fluorescent powder adhesive with high shapeability, a fluorescent powder film with low shapeability, a transparent layer or any layered combination of the three. The phosphor glue/phosphor film comprises the following components: glue 422, phosphor 424, inorganic oxide nanoparticles 426. The glue 422 may be, but is not limited to, a silicone gel. In one embodiment, polyimide (PI) may be included in the paste 422 in an amount of 10% wt or less to increase the overall hardness, insulation, thermal stability and mechanical strength of the filament, the PI solid content may be 5-40% wt, and the rotational viscosity may be 5-20pa.s. Inorganic oxide nanoparticles 426 may be, but are not limited to, aluminum oxide, aluminum nitride particles, which may have a particle size of 100-600 nanometers or 0.1 to 100 microns, which function to promote heat dissipation from the filament, and the incorporated inorganic heat dissipation particles may have a variety of particle sizes. The glue, such as the phosphor film and the phosphor glue, can be adjusted to be greater than 20%, 50%, or 70% as desired. The Shore hardness of the fluorescent powder glue can be D40-70; the thickness of the fluorescent powder adhesive can be 0.2-1.5 mm; and the Shore hardness of the fluorescent powder film can be D20-70. The thickness of the fluorescent powder film can be 0.1-0.5 mm; a refractive index of 1.4 or higher; the light transmittance is 40% -95%. The transparent layer (glue layer, insulating layer) may be composed of a high light-transmitting resin such as silica gel, PI or a combination thereof. In one embodiment, the transparent layer may be used as an index matching layer, which has the function of adjusting the light-emitting efficiency of the filament.
The base layer 420b is a layered structure of at least one layer, which may be selected from: high-shapeability fluorescent powder glue, low-shapeability fluorescent powder film, transparent layer or any layered combination of the three; the phosphor glue/phosphor film comprises the following components: silicone modified polyimide 422', phosphor 424', inorganic oxide nanoparticles 426'. In one embodiment, the silicone-modified polyimide can be replaced with the silicone-modified polyimide resin composition described above. The inorganic oxide nanoparticles 426 may be, but are not limited to, aluminum oxide, aluminum nitride particles, which may have a particle size of 100-600 nm or 0.1 to 100 μm, which serve to promote the overall heat dissipation of the filament, and the incorporated inorganic heat dissipation particles may have various sizes. The transparent layer (glue layer, insulating layer) may be composed of a high light-transmitting resin such as silica gel, silicone polyimide, or a combination thereof. In one embodiment, the transparent layer may be used as an index matching layer, which has the function of adjusting the light-emitting efficiency of the filament. In one embodiment, the base layer may be PI or a composite film of the above-described silicone-modified polyimide resin composition.
As shown in fig. 6, the LED bulb 10c includes a lamp housing 12, a lamp cap 16 connected to the lamp housing 12, at least two conductive brackets 14a, 14b disposed in the lamp housing 12, a driving circuit 18, a cantilever 15, a stem 19, and a single LED filament 100. The conductive brackets 14a, 14b are used for electrically connecting the two electrodes 110, 112 of the LED filament 100, and can also be used for supporting the weight of the LED filament 100; the LED filament 100 is connected to the stem 19 via the conductive brackets 14a, 14b, and the stem 19 can be used to replace the gas in the LED bulb 10b and provide a heat conducting function; the stem 19 further has a vertical rod 19a extending vertically to the center of the lamp housing 12, a first end of each cantilever 15 is connected to the vertical rod 19a, and a second end of each cantilever 15 is connected to the LED filament; the driving circuit 18 is electrically connected to the conductive brackets 14a, 14b and the lamp cap 16, and when the lamp cap 16 is connected to a lamp base of a conventional bulb lamp, the lamp base provides power to the lamp cap 16, and the driving circuit 18 obtains power from the lamp cap 16 and drives the LED filaments 100 to emit light. Since the LED filament 100 emits light on the entire surface, the entire LED bulb can generate light on the entire surface. The LED filament 100 may be any one of the LED filaments described in fig. 5 to 6.
The definition of full ambient light described herein will also vary over time depending on the specifications of the particular light bulb in each country, and thus the examples of full ambient light described herein are not intended to limit the scope of the invention. The definition of the total ambient Light, for example, the us energy star program (US Energy Star Program Requirements for Lamps (Light bulb)) defines the Light shape of a bulb lamp (total bulb), when the bulb lamp is arranged with the base up and the bulb down, 180 degrees above vertical and 0 degrees below vertical, requires that the brightness (luminous intensity (cd)) at each angular position between 0 and 135 degrees should not differ from the average brightness by more than 25%, and the total luminous flux (total flux (lm)) between 135 and 180 degrees should be at least 5% of the total lamp. For another example, JEL 801 specifications in japan require that the LED lamp has a luminous flux in the range of 120 degrees, which is less than 70% of the total luminous flux.
The following examples are presented to further illustrate the invention in detail, but are not intended to limit the scope of the invention.
EXAMPLE 1 preparation of organosilicon modified polyimide A-1 (siloxane content: 41%)
In a reaction vessel equipped with a stirrer and a Deans Stark trap, 62.04g (200 mmol) of 4,4' -oxydiphthalic anhydride (sODPA), 32.84g (80 mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), 67.2g (80 mmol) of α, ω - (3-aminopropyl) polysiloxane (KF 8010), 8.64g (40 mmol) of 3,3' -diamino-4, 4' -dihydroxybiphenyl, 0.5g of pyridine, 300g of γ -butyrolactone (GBL) and 30g of toluene were charged into the reaction vessel. After stirring at 20rpm for 30min under nitrogen atmosphere, the temperature was raised to 180℃and stirring was carried out at 180rpm for 4h. During the reaction, the azeotropic portion of toluene-water was removed. By removing the reflux, a silicone-modified polyimide having a solid content of 35% was obtained.
EXAMPLE 2 preparation of organosilicon modified polyimide A-2 (siloxane content: 64%)
Using the same reaction vessel as in example 1, 62.04g (200 mmol) of sODPA, 8.21g (20 mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), 126g (150 mmol) of α, ω - (3-aminopropyl) polysiloxane (KF 8010), 6.48g (30 mmol) of 3,3 '-diamino-4, 4' -dihydroxybiphenyl, 0.5g of pyridine, 350g of γ -butyrolactone (GBL) and 30g of toluene were charged into the reaction vessel. After stirring at 20rpm for 30min under nitrogen atmosphere, the temperature was raised to 180℃and stirred at 180rpm for 4h. During the reaction, the azeotropic portion of toluene-water was removed. By removing the reflux, a silicone-modified polyimide having a solid content of 37% was obtained.
EXAMPLE 3 preparation of organosilicon modified polyimide A-3 (siloxane content: 73%)
Using the same reaction vessel as in example 1, 62.04g (200 mmol) of sODPA, 2.05g (5 mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), 171.6g (165 mmol) of NH15D (amino-modified silicone), 6.48g (30 mmol) of 3,3 '-diamino-4, 4' -dihydroxybiphenyl, 0.5g of pyridine, 350g of gamma-butyrolactone (GBL) and 30g of toluene were charged into the reaction vessel. After stirring at 20rpm for 30min under nitrogen atmosphere, the temperature was raised to 180℃and stirred at 180rpm for 4h. During the reaction, the azeotropic portion of toluene-water was removed. By removing the reflux, a silicone-modified polyimide having a solid content of 40% was obtained.
EXAMPLE 4 preparation of organosilicon modified polyimide A-4 (siloxane content: 37%)
Using the same reaction vessel as in example 1, 62.04g (200 mmol) of sODPA, 36.84g (90 mmol) of PACM, 58.8g (70 mmol) of KF8010 (amino-modified silicone), 9.08g (40 mmol) of 4,4' -Diaminobenzidine (DABA), 0.5g of pyridine, 300g of gamma-butyrolactone (GBL) and 30g of toluene were reacted. After stirring at 20rpm for 30min under nitrogen atmosphere, the temperature was raised to 180℃and stirred at 180rpm for 4h. During the reaction, the azeotropic portion of toluene-water was removed. By removing the reflux, a silicone-modified polyimide having a solid content of 44% was obtained.
EXAMPLE 5 preparation of organosilicon modified polyimide A-5 (siloxane content: 45%)
Using the same reaction vessel as in example 1, 39.26g (200 mmol) of cyclobutane tetracarboxylic dianhydride (CBDA), 34.26g (80 mmol) of 4,4' - [1, 4-phenylbis (oxy) ] bis [3- (trifluoromethyl) aniline ] (6 FAPB), 67.2g (80 mmol) of KF8010, 14.66g (40 mmol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6 FAP), 0.5g of pyridine, 300g of gamma-butyrolactone (GBL) and 30g of toluene were charged into the reaction vessel. After stirring at 20rpm for 30min under nitrogen atmosphere, the temperature was raised to 180℃and stirred at 180rpm for 4h. During the reaction, the azeotropic portion of toluene-water was removed. By removing the reflux, a silicone-modified polyimide having a solid content of 45% was obtained.
EXAMPLE 6 preparation of organosilicon modified polyimide A-6 (siloxane content 44%)
Using the same reaction vessel as in example 1, 62.04g (200 mmol) of sODPA, 16.82g (80 mmol) of 4,4' -diaminodicyclohexylmethane (PACM), 67.2g (80 mmol) of KF8010, 14.66g (40 mmol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6 FAP), 0.5g of pyridine, 300g of gamma-butyrolactone (GBL) and 30g of toluene were charged into the reaction vessel. After stirring at 20rpm for 30min under nitrogen atmosphere, the temperature was raised to 180℃and stirred at 180rpm for 4h. During the reaction, the azeotropic portion of toluene-water was removed. By removing the reflux, a silicone-modified polyimide having a solid content of 35% was obtained.
EXAMPLE 7 preparation of organosilicon modified polyimide A-7 (siloxane content 47%)
Using the same reaction vessel as in example 1, 19.62g (100 mmol) of cyclobutane tetracarboxylic dianhydride (CBDA), 31.0g (100 mmol) of sODPA, 16.82g (80 mmol) of PACM, 67.2g (80 mmol) of KF8010, 14.66g (40 mmol) of 4,4' -Diaminobenzanilide (DABA), 0.5g of pyridine, 300g of gamma-butyrolactone (GBL) and 30g of toluene were charged into the reaction vessel. After stirring at 20rpm for 30min under nitrogen atmosphere, the temperature was raised to 180℃and stirred at 180rpm for 4h. During the reaction, the azeotropic portion of toluene-water was removed. By removing the reflux, a silicone-modified polyimide having a solid content of 33% was obtained.
EXAMPLE 8 preparation of organosilicon modified polyimide A-8 (siloxane content 44%)
Using the same reaction vessel as in example 1, 88.86g (200 mmol) of 4,4'- (hexafluoroisopropenyl) isophthalic acid (6 FDA), 21.42g (50 mmol) of 4,4' - [1, 4-phenylbis (oxy) ] bis [3- (trifluoromethyl) aniline ] (6 FAPB), 92.4g (110 mmol) of KF8010, 14.66g (40 mmol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6 FAP), 0.5g of pyridine, 300g of gamma-butyrolactone (GBL) and 30g of toluene were charged into the reaction vessel. After stirring at 20rpm for 30min under nitrogen atmosphere, the temperature was raised to 180℃and stirred at 180rpm for 4h. During the reaction, the azeotropic portion of toluene-water was removed. By removing the reflux, a silicone-modified polyimide having a solid content of 34% was obtained.
EXAMPLE 9 preparation of organosilicon modified polyimide A-9 (siloxane content 76%)
Using the same reaction vessel as in example 1, 62.04g (200 mmol) of sODPA, 0.82g (2 mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), 185.12g (178 mmol) of NH15D (amino-modified silicone), 4.32g (20 mmol) of 3,3 '-diamino-4, 4' -dihydroxybiphenyl, 0.5g of pyridine, 350g of gamma-butyrolactone (GBL) and 30g of toluene were charged into the reaction vessel. After stirring at 20rpm for 30mmin under nitrogen atmosphere, the temperature was raised to 180℃and stirred at 180rpm for 4 hours. During the reaction, the azeotropic portion of toluene-water was removed. By removing the reflux, a silicone-modified polyimide having a solid content of 41% was obtained.
EXAMPLE 10 preparation of organosilicon modified polyimide A-10 (siloxane content 29%)
The same reaction vessel as in example 1 was used. A reaction vessel was charged with 62.04g (200 mmol) of sODPA, 39.38g (110 mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), 42.0g (50 mmol) of KF8010, 8.64g (40 mmol) of 3,3 '-diamino-4, 4' -dihydroxybiphenyl, 0.5g of pyridine, 300g of gamma-butyrolactone (GBL) and 30g of toluene. After stirring at 20rpm for 30min under nitrogen atmosphere, the temperature was raised to 180℃and stirred at 180rpm for 4h. During the reaction, the azeotropic portion of toluene-water was removed. By removing the reflux, a silicone-modified polyimide having a solid content of 33% was obtained.
Comparative example 1 preparation of film of organosilicon modified polyimide resin composition
The silicone-modified polyimide obtained in example 1 was spread on a separator using a doctor blade having a gap of 300 μm, coated to form a film, and then the film was dried at 100℃for 30 minutes to remove the residual solvent, and then the temperature was adjusted to 160℃and drying was continued for 90 minutes to cause a curing reaction. After the completion of the drying, the film was peeled off from the peeled body to obtain a film of the silicone-modified imine resin composition.
EXAMPLE 11 preparation of film of organosilicon-modified polyimide resin composition
The silicone-modified polyimide obtained in examples 1 to 10 was mixed with an epoxy resin, and then subjected to vacuum defoaming to obtain a silicone-modified polyimide resin composition, and the parameters of the defoaming method were as follows: vacuum degree is-0.095 MPa, revolution speed is 1500rpm, rotation speed is 1500rpm; the vacuum defoaming time is 3min. The silicone-modified polyimide resin composition was spread on the separator using a doctor blade having a gap of 300 μm, coated to form a film, and then the film was dried at 100 ℃ for 30 minutes to remove the residual solvent, and then the temperature was adjusted to 160 ℃ and drying was continued for 90 minutes to cause a curing reaction. After the completion of the drying, the film was peeled off from the peeled body to obtain a film of the silicone-modified imine resin composition.
EXAMPLE 12 preparation of Silicone-modified polyimide resin composition composite film
The silicone-modified polyimide obtained in examples 1 to 10 was mixed with an epoxy resin, a phosphor, and alumina having a particle size distribution of 0.2 to 30. Mu.m, and an average particle size of 9.6. Mu.m, respectively. The content ratio of the fluorescent powder is 240 percent (namely, 2.4 times of the weight of the organic silicon modified polyimide) based on the organic silicon modified polyimide, wherein the adding ratio of (Ba, sr, ca) 2SiO4:Eu to CaAlSiN3:Eu is 7:1. Based on the weight of the silicone modified polyimide, the content ratio of alumina was 560% (560 PHR) (i.e., 5.6 times the weight of the silicone modified polyimide), and then a composite film was prepared by the method described in example 11.
EXAMPLE 13 preparation of organosilicon modified polyimide A-11 (siloxane content 44%)
Using the same reaction vessel as in example 1, 100 mmole of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (HPMDA), 40 mmole of 4,4' - [1, 4-phenylbis (oxy) ] bis [3- (trifluoromethyl) aniline ] (6 FAPB), 40 mmole of KF8010, 20 mmole of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6 FAP), 0.25g of pyridine, 100g of gamma-butyrolactone (GBL) and 45g of methyl benzoate were charged into the reaction vessel. After stirring at 20rpm for 30mmin under nitrogen atmosphere, the temperature was raised to 185℃and stirred at 170rpm for 4 hours. During the reaction, the methyl benzoate-water azeotropic fraction is removed. By removing the reflux, a silicone-modified polyimide having a solid content of 35% was obtained.
EXAMPLE 14 preparation of organosilicon modified polyimide A-12 (siloxane content 42%)
Using the same reactor as in example 1, 100mmol HPMDA, 40mmol HFBAPP, 40mmol KF8010, 20mmol 6FAP, 0.25g pyridine, 350g gamma-butyrolactone (GBL) and 45g methyl benzoate were charged into the reactor. After stirring at 20rpm for 30mmin under nitrogen atmosphere, the temperature was raised to 170℃and stirred at 185rpm for 4 hours. During the reaction, the methyl benzoate-water azeotropic fraction is removed. By removing the reflux, a silicone-modified polyimide having a solid content of 36% was obtained.
EXAMPLE 15 preparation of organosilicon modified polyimide A-13 (siloxane content: 50%)
Using the same reactor as in example 1, 100mmol HPMDA, 40mmol PACM, 40mmol KF8010, 20mmol 6FAP, 0.25g pyridine, 350g gamma-butyrolactone (GBL) and 45g methyl benzoate were charged into the reactor. After stirring at 20rpm for 30mmin under nitrogen atmosphere, the temperature was raised to 170℃and stirred at 185rpm for 4 hours. During the reaction, the methyl benzoate-water azeotropic fraction is removed. By removing the reflux, a silicone-modified polyimide having a solid content of 32% was obtained.
EXAMPLE 16 preparation of organosilicon-modified polyimide A-14 (siloxane content: 51%)
Using the same reactor as in example 1, 100mmol HPMDA, 40mmol PACM, 40mmol KF8010, 20mmol ABPS, 0.25g pyridine, 350g gamma-butyrolactone (GBL) and 45g methyl benzoate were charged into the reactor. After stirring at 20rpm for 30mmin under nitrogen atmosphere, the temperature was raised to 170℃and stirred at 185rpm for 3.5 hours. During the reaction, the methyl benzoate-water azeotropic fraction is removed. By removing the reflux, a silicone-modified polyimide having a solid content of 32% was obtained.
EXAMPLE 17 preparation of organosilicon modified polyimide A-15 (siloxane content: 51%)
Using the same reactor as in example 1, 100mmol HPMDA, 40mmol PACM, 40mmol KF8010, 20mmol DABA, 0.25g pyridine, 350g gamma-butyrolactone (GBL) and 45g methyl benzoate were charged into the reactor. After stirring at 20rpm for 30mmin under nitrogen atmosphere, the temperature was raised to 170℃and stirred at 185rpm for 4 hours. During the reaction, the methyl benzoate-water azeotropic fraction is removed. By removing the reflux, a silicone-modified polyimide having a solid content of 31% was obtained.
EXAMPLE 18 preparation of organosilicon-modified polyimide A-16 (siloxane content 40%)
Using the same reactor as in example 1, 50mmol HPMDA, 50mmol 6FDA, 40mmol PACM, 40mmol KF8010, 20mmol 6FAP, 0.25g pyridine, 350g gamma-butyrolactone (GBL) and 45g methyl benzoate were charged into the reactor. After stirring at 20rpm for 30mmin under nitrogen atmosphere, the temperature was raised to 170℃and stirred at 185rpm for 4 hours. During the reaction, the methyl benzoate-water azeotropic fraction is removed. By removing the reflux, a silicone-modified polyimide having a solid content of 35% was obtained.
EXAMPLE 19 preparation of organosilicon modified polyimide A-17 (siloxane content 44%)
Using the same reaction vessel as in example 1, 200mmol 6FDA, 50mmol 6FABP, 110mmol KF8010, 40mmol 6FAP, 0.5g pyridine, 40g gamma-butyrolactone (GBL) and 30g toluene were charged into the reaction vessel. After stirring at 20rpm for 30mmin under nitrogen atmosphere, the temperature was raised to 180℃and stirred at 180rpm for 4 hours. During the reaction, the azeotropic portion of toluene-water was removed. By removing the reflux, a silicone-modified polyimide having a solid content of 34% was obtained.
EXAMPLE 20 preparation of organosilicon-modified polyimide A-18 (siloxane content 44%)
Using the same reaction vessel as in example 1, 200mmol 6FDA, 50mmol 6FABP, 110mmol KF8010, 40mmol 6FAP, 0.5g pyridine, 40g gamma-butyrolactone (GBL) and 30g toluene were charged into the reaction vessel. After stirring at 20rpm for 30mmin under nitrogen atmosphere, the temperature was raised to 180℃and stirred at 180rpm for 4 hours. During the reaction, the azeotropic portion of toluene-water was removed. By removing the reflux, a silicone-modified polyimide having a solid content of 34% was obtained.
EXAMPLE 21 preparation of organosilicon-modified polyimide A-19 (siloxane content 70%)
Using the same reaction vessel as in example 1, 50mmol of 6FDA, 50mmol of sBPDA, 5mmol of TFMB, 85mmol of NH15D, 10mmol of 6FAP, 0.5g of pyridine, 50g of methyl benzoate and 150g of gamma-butyrolactone (GBL) were charged into the reaction vessel. After stirring at 20rpm for 30mmin under nitrogen atmosphere, the temperature was raised to 180℃and stirred at 180rpm for 4 hours. During the reaction, the azeotropic portion of toluene-water was removed. By removing the reflux, a silicone-modified polyimide having a solid content of 39% was obtained.
EXAMPLE 22 preparation of organosilicon modified polyimide A-20 (siloxane content 48%)
Using the same reaction vessel as in example 1, 100mmol of DSDA, 25mmol of p-6FAPB, 55mmol of NH15D, 20mmol of 6FAP, 0.5g of pyridine, 43.5g of diethylene glycol butyl methyl ether and 101.5g of gamma-butyrolactone (GBL) were charged into the reaction vessel. After stirring at 20rpm for 30mmin under nitrogen atmosphere, the temperature was raised to 180℃and stirred at 180rpm for 4 hours. During the reaction, the azeotropic portion of toluene-water was removed. By removing the reflux, a silicone-modified polyimide having a solid content of 40% was obtained.
EXAMPLE 23 preparation of organosilicon modified polyimide A-21 (siloxane content: 69%)
Using the same reaction vessel as in example 1, 100mmol of CBDA, 5mmol of PACM, 60mmol of NH15D, 35mmol of 6FAP, 0.5g of pyridine, 101g of gamma-butyrolactone (GBL) and 43g of diethylene glycol butyl methyl ether were charged into the reaction vessel. After stirring at 20rpm for 30mmin under nitrogen atmosphere, the temperature was raised to 180℃and stirred at 180rpm for 4 hours. During the reaction, the azeotropic portion of toluene-water was removed. By removing the reflux, a silicone-modified polyimide having a solid content of 40% was obtained.
EXAMPLE 24 preparation of film of organosilicon-modified polyimide resin composition
The silicone-modified polyimide obtained in examples 13 to 20 was mixed with an epoxy resin, and then subjected to vacuum defoaming to obtain a silicone-modified polyimide resin composition, and the parameters of the defoaming method were as follows: vacuum degree is-0.095 MPa, revolution speed is 1500rpm, rotation speed is 1500rpm; the vacuum defoaming time is 3min. The silicone-modified polyimide resin composition was spread on the separator using a doctor blade having a gap of 300 μm, coated to form a film, and then the film was dried at 100 ℃ for 30 minutes to remove the residual solvent, and then the temperature was adjusted to 160 ℃ and drying was continued for 90 minutes to cause a curing reaction. After the completion of the drying, the film was peeled off from the peeled body to obtain a film of the silicone-modified imine resin composition.
EXAMPLE 25 preparation of Silicone-modified polyimide resin composition composite film
The silicone-modified polyimides obtained in examples 1 to 18 and 21 to 22 were mixed with an epoxy resin, a phosphor, and alumina having a particle size distribution of 0.2 to 30. Mu.m, and an average particle size of 9.6. Mu.m, respectively. The content ratio of the fluorescent powder is 240 percent (namely, 2.4 times of the weight of the organic silicon modified polyimide) based on the organic silicon modified polyimide, wherein the adding ratio of (Ba, sr, ca) 2SiO4:Eu to CaAlSiN3:Eu is 7:1. Based on the weight of the silicone modified polyimide, the content ratio of alumina was 560% (560 PHR) (i.e., 5.6 times the weight of the silicone modified polyimide), and then a composite film was prepared by the method described in example 24.
EXAMPLE 26 preparation of Silicone-modified Polyimido resin composition composite Membrane
The silicone-modified polyimide obtained in example 19 was mixed with an epoxy resin, alumina having a particle size distribution of 0.2 to 30. Mu.m, and a phosphor having an average particle size of 9.6. Mu.m. The content ratio of the fluorescent powder is 240 percent (namely, 2.4 times of the weight of the organic silicon modified polyimide) based on the organic silicon modified polyimide, wherein the adding ratio of (Ba, sr, ca) 2SiO4:Eu to CaAlSiN3:Eu is 7:1. The content ratio of alumina is 760 percent (760 PHR) based on the weight of the organosilicon modified polyimide
(i.e., 7.6 times the weight of the silicone-modified polyimide) and then a composite film was prepared by the method described in example 24.
EXAMPLE 27 preparation of Silicone-modified Polyimido resin composition composite Membrane
The silicone-modified polyimide obtained in example 20 was mixed with an epoxy resin, alumina having a particle size distribution of 0.2 to 30. Mu.m, and a phosphor having an average particle size of 9.6. Mu.m, respectively. The content ratio of the fluorescent powder is 240 percent (namely, 2.4 times of the weight of the organic silicon modified polyimide) based on the organic silicon modified polyimide, wherein the adding ratio of (Ba, sr, ca) 2SiO4:Eu to CaAlSiN3:Eu is 7:1. Based on the weight of the organosilicon modified polyimide, the content ratio of alumina is 960 percent (960 PHR)
(i.e., 9.6 times the weight of the silicone-modified polyimide) and then a composite film was prepared by the method described in example 24.
EXAMPLE 28 preparation of Silicone-modified Polyimido resin composition composite Membrane
Mixing the organosilicon modified polyimide obtained in the example 23 with epoxy resin, heat dissipation particles and fluorescent powder respectively, wherein the heat dissipation particles comprise alumina and silicon dioxide, the particle size distribution of the alumina is 0.2-30 mu m, and the average particle size is 9.6 mu m; the average particle size of the silica was 2. Mu.m. The content ratio of the fluorescent powder is 600 percent (namely 6.0 times of the weight of the organic silicon modified polyimide) based on the organic silicon modified polyimide, wherein the adding ratio of (Ba, sr, ca) 2SiO4:Eu to CaAlSiN3:Eu is 6:1. Based on the weight of the organosilicon modified polyimide, the content ratio of the heat dissipation particles is 400% (400 PHR) (namely, 4.0 times of the weight of the organosilicon modified polyimide), wherein the addition ratio of the alumina to the silica is 1:1, and then the composite film is prepared by adopting the method described in the embodiment 24.
Performance test of film (film thickness: 50 μm) of organosilicon-modified polyimide resin composition
1. Heat resistance: the glass transition temperature (Tg) was measured using TMA-60 manufactured by Shimadzu corporation. Test conditions: load: 5 g; heating rate: 10 ℃/min; the method comprises the steps of carrying out a first treatment on the surface of the Measuring atmosphere: a nitrogen atmosphere; nitrogen flow rate: 20 ml/min; measuring temperature range: -40 to 300 ℃.
2. Chemical resistance: cotton impregnated with various chemicals was left to stand on the coating film for 30 minutes at room temperature (25 ℃). The chemicals evaluated were ethanol, acetone, dimethylformamide (DMF). The evaluation result is in the form of: o: no abnormality;
delta: expansion and slight deformation; x: surface anomalies or dissolution.
3. Light transmission (transmittance): the light transmittance of Shimadzu was measured by using an ultraviolet-visible spectrophotometer UV-1800. It is based on the luminescence of a white LED, with a transmittance at a wavelength of 460nm, 460nm being the peak wavelength of InGaN used to excite the white LED in blue.
4. Resistance to thermal discoloration: the film used for the test was the same as that used for the light transmittance test, and the film was left to stand at 200℃under an air atmosphere for 24 hours, and the transmittance of the film after the standing at a wavelength of 460nm was measured.
5. Mechanical properties: the film width was 10mm and the tensile properties of the film were tested using the ISO527-3:1995 standard at a tensile speed of 10mm/min.
Performance test of organosilicon modified imine resin composition composite film
1. Thermal conductivity: the resulting film was cut into a circle having a film thickness of 300um and a diameter of 30mm as a test piece, and the thermal conductivity was measured by a thermal conductivity measuring device DRL-III manufactured by Hunan, test conditions: hot electrode temperature: 90 ℃; cold electrode temperature: 20 ℃; load: 350N.
2. Warp phenomenon: the film with the thickness of 100um and the length and width of 100mm is placed in a 160 ℃ incubator for 5 minutes, taken out of the incubator, the edge of the film can generate warping phenomenon at room temperature, the warping height is less than 1mm and is qualified, 1 mm-5 mm is undetermined delta, and more than 5mm is unqualified.
3. Scanning Electron Microscope (SEM) analysis: the surface of the composite film was sprayed with gold, and the surface morphology of the composite film was observed under a vega3 electron microscope from Tescan company.
4. Mechanical properties: the film had a film thickness of 50 μm and a film width of 10mm, and the tensile properties of the film were measured by the ISO527-3:1995 standard, and the tensile speed was 10mm/min.
The test results of the obtained films of the silicone-modified polyimide resin composition are shown in tables 5 and 7, and the test results of the properties of the composite films of the silicone-modified polyimide resin composition are shown in tables 6 and 8
TABLE 5
TABLE 6
TABLE 7
TABLE 8
While the invention has been disclosed in terms of preferred embodiments, it will be understood by those skilled in the art that the examples are illustrative of only some of the embodiments of the invention and are not to be construed as limiting. It should be noted that reasonable combinations of equivalent variations and permutations or embodiments to the embodiments are intended to be included within the scope of the present invention supported by the description. The scope of the invention is therefore intended to be defined only by the appended claims.

Claims (10)

1. The utility model provides a LED ball bubble lamp, includes the lamp body, connects the lamp holder of lamp body, is equipped with two at least conductive support, drive circuit, cantilever, stem and LED filament in the lamp body, drive circuit electric connection conductive support and lamp holder, the LED filament passes through conductive support connection the stem, its characterized in that: the LED lamp filament comprises a plurality of LED chips and light conversion layers coated on at least two sides of the LED chips, and the light conversion layers comprise a top layer and a base layer;
adopting an organosilicon modified polyimide resin composition composite film as an LED filament base material;
the base layer adopts an organosilicon modified polyimide resin composition composite film;
the organic silicon modified polyimide resin composition comprises organic silicon modified polyimide, a thermosetting agent, fluorescent powder and radiating particles;
the heat dissipation particles comprise particles with high transmittance and particles with low transmittance, and the weight ratio of the particles with high transmittance to the particles with low transmittance is 3-5:1;
the organosilicon modified polyimide contains a repeating unit represented by the following general formula (I):
wherein, in the general formula (I), R is selected from methyl or phenyl, and n is 1-5;
Ar 1 is a 4-valent organic group having a benzene ring structure or an alicyclic hydrocarbon structure containing an active hydrogen functional group, wherein the active hydrogen functional group is any one of a hydroxyl group, an amino group, a carboxyl group, and a thiol group;
Ar 2 Is a 2-valent organic group containing active hydrogen functional groups, wherein the active hydrogen functional groups are any one of hydroxyl, amino, carboxyl or thiol groups;
the content of siloxane of the organosilicon modified polyimide is 30-70 wt%, the content of siloxane is the weight ratio of siloxane diamine to organosilicon modified polyimide, and the weight of organosilicon modified polyimide is the sum of diamine and dianhydride weight used for synthesizing the organosilicon modified polyimide minus the weight of water generated in the synthesis process.
2. The LED bulb lamp of claim 1, wherein: the thermosetting agent is any one of epoxy resin, isocyanate, bismaleimide and bisoxazoline compound.
3. The LED bulb lamp of claim 1, wherein: the fluorescent powder is spherical, plate-shaped or needle-shaped.
4. The LED bulb lamp of claim 1, wherein: the amount of the fluorescent powder is not less than 0.05 times and not more than 8 times of the weight of the organosilicon-modified polyimide.
5. The LED bulb lamp of claim 1, wherein: the fluorescent powder comprises red fluorescent powder and green fluorescent powder, and the adding ratio of the red fluorescent powder to the green fluorescent powder is 1:5-8.
6. The LED bulb lamp of claim 1, wherein: the fluorescent powder comprises red fluorescent powder and yellow fluorescent powder, and the adding ratio of the red fluorescent powder to the yellow fluorescent powder is 1:5-8.
7. The LED bulb lamp of claim 1, wherein: and adding an antifoaming agent, a leveling agent or an adhesive in the synthetic process of the organosilicon modified polyimide resin composition, wherein the dosage of the additive is not more than 10% of the weight of the organosilicon modified polyimide.
8. The LED bulb lamp of claim 1, wherein: the amount of the fluorescent powder is more than or equal to 0.05 times of the weight of the organosilicon modified polyimide.
9. The LED bulb lamp of claim 1, wherein: the heat dissipation particles are any one or more than one of silicon dioxide, aluminum oxide, magnesium carbonate, aluminum nitride, boron nitride and diamond.
10. The LED bulb lamp of claim 1, wherein: the organosilicon modified polyimide comprises fluorinated aromatic organosilicon modified polyimide and aliphatic organosilicon modified polyimide.
CN202311021106.5A 2017-09-18 2018-09-18 Organosilicon modified polyimide resin composition and application thereof Pending CN116891571A (en)

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