Photosensitive composition and thin film formed therefrom

Abstract

Disclosed are a photosensitive composition and a thin film formed therefrom. The photosensitive composition includes 100 parts by weight of a polyimide; 0.25-50 parts by weight of an initiator; and 0.25-100 parts by weight of a crosslinking agent. The polyimide is a reaction product of a reactant (a) and a reactant (b). The reactant (a) consists of a first dianhydride and a second dianhydride, wherein the molar ratio of the first dianhydride to the second dianhydride is 3:7 to 8:2. The reactant (b) includes a first diamine. The first dianhydride, the second dianhydride, and the first diamine are as described in detail in the specification.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a photosensitive composition, and a thin film formed using the photosensitive composition. BACKGROUND

[0002] Due to the excellent thermal stability and insulating properties of polyimide, in addition to being used as an insulating material and special industrial plastic, the most widely used application is currently flexible printed circuit board (FPC). In recent years, with the development of information and communication mobility and personalization becoming more and more vigorous, the market and demand for flexible printed circuit boards (soft boards-FPC) with light and thin have increased dramatically. With the overall demand for the integration of terminal application products (IOT and wearable devices) becoming stronger, the resolution requirement becoming higher, the reaction speed becoming faster, and the storage capacity becoming larger, the soft board technology must also be matched. Therefore, the trend of high-frequency and high-speed, functionalization of soft boards is becoming more and more obvious, and high-frequency soft boards have become one of the trends of soft board technology, mainly to meet the strengthening and integration of mobile communication electronic products. Low-dielectric and low-transmission-loss substrate materials will be the main requirement of future high-frequency.

[0003] Traditional photosensitive polyimide materials generally use polyimide acid polymers in combination with photosensitizers and initiators. After the traditional photosensitive polyimide material is coated on the substrate and exposed to light and developed, high-temperature treatment (process temperature of about 250°C to 350°C) is still required to close the ring of the polyimide acid to become a polyimide. However, such a high process temperature can easily cause stress between the polyimide and the substrate due to the large difference in thermal expansion coefficient, causing the substrate to bend, deform, or crack, and even delamination, which damages the components.

[0004] Therefore, the industry needs a polyimide composition with high-frequency dielectric properties, photosensitivity, and low film-forming temperature to solve the above problems. SUMMARY

[0005] The present disclosure provides a photosensitive composition, which comprises 100 parts by weight of a polyimide, 0.25-50 parts by weight of an initiator, and 0.25-100 parts by weight of a crosslinking agent. According to an embodiment of the present disclosure, the polyimide of the present disclosure is the reaction product of a reactant (a) and a reactant (b), wherein the reactant (a) is composed of a first dianhydride and a second dianhydride, wherein the molar ratio of the first dianhydride and the second dianhydride is 3:7 to 8:2, wherein the first dianhydride has a structure represented by Formula (I), and the second dianhydride has a structure represented by Formula (II):

[0006]

[0007] wherein R 1and R 2 each independently is hydrogen, fluorine, methyl, ethyl, propyl, fluoromethyl, fluoroethyl, or fluoropropyl, and Ar 1 is and the reactant (b) comprises a first diamine, wherein the first diamine is wherein R 3 , R 4 , R 5 , and R 6 each independently is hydrogen, fluorine, methyl, ethyl, propyl, fluoromethyl, fluoroethyl, or fluoropropyl.

[0008] According to embodiments of the present disclosure, the photosensitive composition can further comprise a solvent, and the photosensitive composition can have a solid content of 20 wt% to 40 wt%.

[0009] According to embodiments of the present disclosure, the present disclosure also provides a thin film. The thin film can comprise a cured product of the photosensitive composition described above. DETAILED DESCRIPTION

[0010] The following detailed description is provided to provide a number of different embodiments or examples of the present disclosure. However, this is not intended to limit the scope of the present disclosure. In the present disclosure, the word "about" can mean that the relevant numerical value includes a tolerance of ±10%, ±5%, ±3%, or ±1% around the numerical value.

[0011] Further, the use of ordinal terms such as "first", "second", "third", etc., in the description and claims to modify a member of a group of components is used for purposes of distinction only and does not necessarily imply a sequence or order to the members of the group, or a sequence or order of manufacturing processes. The use of ordinal terms in the description and claims is used to distinguish one component with the same name from another component with the same name.

[0012] The present disclosure provides a photosensitive composition and a thin film formed using the photosensitive composition. According to embodiments of the present disclosure, a photosensitive composition with a patternable and high resolution is obtained by using a polyimide with a specific structure, further in combination with a specific ratio of a photoinitiator and a crosslinking agent. In the present disclosure, the polyimide with the specific structure is obtained by reacting two specific dianhydrides (e.g., aryl-moiety-containing dianhydrides) with a specific molar ratio and a specific diamine (e.g., aryl-moiety-containing diamine). In this way, by the specific ingredients (components) and the specific composition ratio, the photosensitive composition of the present disclosure can be directly coated on a copper foil, and can be cured by a photo-reaction at a lower temperature (i.e., has a lower film-forming temperature), greatly improving the processability of the photosensitive composition. In addition, the cured product of the photosensitive composition of the present disclosure also has a low dielectric constant (Dk) and a low dielectric loss (Df) at high frequencies (a frequency band of 10 GHz or more), and can be widely used in electronic components or semiconductor devices as a passivation film, a buffer coating film, an interlayer insulation film, or an α-ray shielding film.

[0013] According to embodiments of the present disclosure, the photosensitive composition of the present disclosure can include a polyimide, an initiator (e.g., a photoinitiator), and a crosslinking agent. In the photosensitive composition, the polyimide can be used in an amount of 100 parts by weight. In addition, the initiator can be used in an amount of 0.25 parts by weight to 50 parts by weight (e.g., 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, or 45 parts by weight), and the crosslinking agent can be used in an amount of 0.25 parts by weight to 100 parts by weight (e.g., 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, or 95 parts by weight).

[0014] According to embodiments of the present disclosure, the polyimide described herein can be a product of reactant (a) and reactant (b) via a reaction (e.g., a polymerization reaction). The reactant (a) can be at least one dianhydride (e.g., an aryl-moiety-containing dianhydride). According to embodiments of the present disclosure, the reactant (a) can consist of a first dianhydride and a second dianhydride. According to embodiments of the present disclosure, the first dianhydride can have a structure represented by Formula (I), and the second dianhydride can have a structure represented by Formula (II):

[0015]

[0016] wherein R 1 and R 2 each independently is hydrogen, fluorine, methyl, ethyl, propyl, fluoromethyl, fluoroethyl, or fluoropropyl; and Ar 1 is

[0017] According to embodiments of the present disclosure, the fluoromethyl group described herein can be a monofluoromethyl group, a difluoromethyl group, or a perfluoromethyl group; the fluoroethyl group can be a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, or a perfluoroethyl group; and the fluoropropyl group can be a monofluoropropyl group, a difluoropropyl group, a trifluoropropyl group, a tetrafluoropropyl group, a pentafluoropropyl group, a hexafluoropropyl group, or a perfluoropropyl group. According to embodiments of the present disclosure, the propyl group described herein can be a n-propyl group, or an i-propyl group, and the fluoropropyl group can be a n-fluoropropyl group, or an i-fluoropropyl group.

[0018] According to embodiments of the present disclosure, the first dianhydride can be

[0019] According to embodiments of the present disclosure, the first dianhydride can be 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propanedianhydride (BPADA).

[0020] According to embodiments of the present disclosure, the second dianhydride can be

[0021] According to embodiments of the present disclosure, the second dianhydride can be p-phenylenebis(trimellitate anhydride) (TAHQ), or 2,6-dihydroxynaphthalenebis(trimellitate anhydride) (2,6-TANA).

[0022] According to embodiments of the present disclosure, the molar ratio of the first dianhydride to the second dianhydride can be 3:7 to 8:2, such as about 4:6, 5:5, 6:4, 7:3, or 7.5:2.5. When the molar ratio of the first dianhydride to the second dianhydride is too high or too low, the film prepared from the film composition comprising the polyimide is prone to directional cracking, or the prepared film (cured product) has poor dielectric loss properties (>0.005 (measured at 10 GHz)) and high moisture absorption (>1.0%).

[0023] According to embodiments of the present disclosure, the reactant (b) can be at least one diamine (e.g., an aryl-moiety-containing diamine). According to embodiments of the present disclosure, the reactant (b) comprises a first diamine. According to embodiments of the present disclosure, the first diamine can be wherein R 3 , R 4 , R 5 , and R 6 are each independently hydrogen, fluorine, methyl, ethyl, propyl, fluoromethyl, fluoroethyl, or fluoropropyl.

[0024] According to embodiments of the present disclosure, the reactant (b) is the first diamine. According to embodiments of the present disclosure, the first diamine can be

[0025] According to embodiments of the present disclosure, the first diamine can be 4,4'-oxybis[3-(trifluoromethyl)aniline] (TMDA), 4,4'-oxydianiline (ODA), or 1,3-bis(3-aminophenoxy)benzene (APB-N).

[0026] According to embodiments of the present disclosure, the molar ratio of the reactant (a) and the reactant (b) participating in the reaction (e.g., a polymerization reaction) to form the polyimide can be substantially in the range of about 0.95: 1.05 to 1.05: 0.95, for example, close to about 1 : 1.

[0027] According to embodiments of the present disclosure, in addition to the first diamine, the reactant (b) can further comprise a second diamine, wherein the second diamine is wherein R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 each independently is hydrogen, fluorine, methyl, ethyl, propyl, fluoromethyl, fluoroethyl, or fluoropropyl. In addition, the first diamine and the second diamine are not the same.

[0028] According to embodiments of the present disclosure, the second diamine can be According to embodiments of the present disclosure, the second diamine can be 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 4,4'-oxydianiline (ODA), or 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP). According to embodiments of the present disclosure, when the first diamine is 4,4'-oxydianiline (ODA), the second diamine is 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), or 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP).

[0029] According to embodiments of the present disclosure, the reactant (b) can consist of the first diamine and the second diamine. According to embodiments of the present disclosure, the molar ratio of the first diamine and the second diamine can be 1 : 9 to 9: 1, for example, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, or 8:2.

[0030] According to embodiments of the present disclosure, the reactant (b) can further comprise a third diamine, wherein the third diamine can be According to embodiments of the present disclosure, the third diamine can be bis(4-aminophenyl) terephthalate (BPTP).

[0031] According to embodiments of the present disclosure, the reactant (b) can consist of the first diamine, the second diamine, and the third diamine. According to embodiments of the present disclosure, the molar ratio of the first diamine and the second diamine can be 1:9 to 9:1 (e.g., 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, or 8:2), and the ratio of the molar amount of the third diamine to the sum of the molar amounts of the first diamine and the second diamine is about 1:99 to 1:9 (e.g., about 2:98, 3:97, 4:96, 5:95, 6:94, 7:93, 8:92, or 9:91).

[0032] According to embodiments of the present disclosure, the polyimide described herein can have a weight average molecular weight (Mw) of about 5,000 g / mol to 3,000,000 g / mol, e.g., about 8,000 g / mol to 2,500,000 g / mol, 10,000 g / mol to 2,300,000 g / mol, 15,000 g / mol to 2,000,000 g / mol, 10,000 g / mol to 1,000,000 g / mol, 10,000 g / mol to 500,000 g / mol, or 10,000 g / mol to 300,000 g / mol. The weight average molecular weight (Mw) of the polyimide described herein can be measured by gel permeation chromatography (GPC) with polystyrene as the standard.

[0033] According to embodiments of this disclosure, the initiator described herein may be a photoinitiator. According to embodiments of this disclosure, the initiator may be a benzoin-based compound, an acetophenone-based compound, a thioxanthone-based compound, a ketal compound, a benzophenone-based compound, an α-aminoacetophenone compound, an acylphosphine oxide compound, a biimidazole-based compound, a triazine-based compound, or a combination thereof. The initiator may be a benzoin-based compound, such as benzoin, benzoin methyl ether, or benzoin dimethyl ether. dimethylketal); acetophenone compounds, such as p-dimethylamino-acetophenone, α,α'-dimethoxyazoxy-acetophenone, 2,2'-dimethyl-2-phenyl-acetophenone, p-methoxy-acetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl -2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone; benzophenone compounds, such as benzophenone, 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, 2,4,6-trimethylaminobenzophenone, methyl o-benzoyl benzoate, 3,3-dimethyl-4-methoxybenzophenone.3-dimethyl-4-methoxybenzophenone), and 3,3,4,4-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone compounds, such as thioxanthone, 2,4-diethyl-thioxanthanone, and thioxanthone-4-sulfone; biimidazole compounds, such as 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole [2] 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole, 2,2'-bis(o-fluorophenyl)-4,4',5,5'-tetraphenyl-biimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyl-biimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyl-biimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyl-biimidazole 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyl-biimidazole, 2,2'-bis(o-ethylphenyl)-4,4',5,5'-tetraphenyl-biimidazole, 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyl-biimidazole [phenyl-biimidazole], 2,2'-bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole5'-Tetraphenylbiimidazole [2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole]; acylphosphine oxides, such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; triazine compounds, such as 3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionic acid. 1,1,1,3,3,3-hexafluoroisopropyl-3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionate, 2-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}ethyl acetate 2-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate, methyl 2-epoxyethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate methyl cyclohexyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate, methyl benzyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate), 3-{chloro-4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionic acid, 3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionamide, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl)-1,3,-butadienyl-s-triazine, or 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine.

[0034] According to an embodiment of the present disclosure, the acetophenone-based compound can be a photoinitiator manufactured by Ciba Geigy and having a trade name of Irgacure 2959, Irgacure 184, Irgacure 500, Irgacure 651, Irgacure 369, Irgacure 379, Irgacure 907, or Darocur 1173.

[0035] According to an embodiment of the present disclosure, the acylphosphine oxide-based compound can be a photoinitiator manufactured by Ciba Geigy and having a trade name of Irgacure 819, or Irgacure 1800, and a photoinitiator manufactured by BASF and having a trade name of Lucirin TPO or Lucirin TPO-L.

[0036] According to embodiments of the present disclosure, the initiator described in the present disclosure can also be a photoinitiator manufactured by LAMBSON Company and having a product number of Esacure 1001M, Esacure KIP150, Speedcure BEM, Speedcure EHA, Speedcure BMS, Speedcure MBP, Speedcure PBZ, Speedcure ITX, Speedcure DETX, Speedcure EBD, Speedcure MBB, Speedcure BP, or a photoinitiator manufactured by Ciba Geigy and having a product number of Irgacure 2100, Irgacure 250, or Irgacure 784.

[0037] According to embodiments of the present disclosure, the initiator can be an azo compound, a cyanovaleric-acid-based compound, a peroxide, or a combination thereof. The azo compound can be 2,2'-azobis(2,4-dimethyl valeronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2-azobisisobutyronitrile (hereinafter referred to as AIBN), 2,2-azobis(2-methylisobutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 1-[(cyano-1-methylethyl)azo]formamide, 2,2'-azobis(N-butyl-2-methylpropionamide), or 2,2'-azobis(N-cyclohexyl-2-methylpropionamide).and the peroxide can be benzoyl peroxide, 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylcyclohexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-cyclohexyne, bis(1-(tert-butylperoxy)-1-methylethyl)benzene, tert-butyl hydroperoxide, tert-butyl peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, or lauroyl peroxide.

[0038] According to embodiments of the present disclosure, the photo-initiator described herein can have a main absorption wavelength in the range of about 300 nm to 410 nm. According to embodiments of the present disclosure, the photo-initiator described herein can also be used in combination with a photo-initiator having a main absorption wavelength less than about 300 nm to meet the current commercial I-line and H-line UV exposure requirements.

[0039] According to embodiments of the present disclosure, the cross-linking agent described herein can be a compound having two or more cross-linkable functional groups (e.g., a compound having two cross-linkable functional groups, a compound having three cross-linkable functional groups, a compound having four cross-linkable functional groups, or a compound having five cross-linkable functional groups), wherein the cross-linkable functional group can be C 2-5an alkenyl group (e.g., a vinyl group, an allyl group, a butenyl group, a 1,3-butanedienyl group, a 1-methyl vinyl group, a 1-methyl allyl group, a 1,1-dimethyl allyl group, a 2-methyl allyl group, or a 1,2-dimethyl allyl group), a methacrylate group, an acrylate group, an acryloyl group, an epoxy group, a carboxyl group, or a combination thereof.

[0040] According to embodiments of the present disclosure, the crosslinking agent can have a number average molecular weight (Mn) of less than or equal to 10,000 g / mol, such as from about 50 to 8,000 g / mol, from about 60 to 8,000 g / mol, from about 70 to 6,000 g / mol, from about 80 to 5,000 g / mol, or from about 90 to 3,000 g / mol.

[0041] According to embodiments of the present disclosure, the crosslinking agent can include a methacrylate-type agent, for example, triethylene glycol dimethacrylate (TiEGDMA), ethylene glycol dimethacrylate (EGDMA), tetraethylene glycol dimethacrylate (TTEGDMA), polyethylene glycol (200) dimethacrylate (PEG200DMA), 1,4-butanediol dimethacrylate (BDDMA), diethylene glycol dimethacrylate (DEGDMA), 1,6-hexanediol dimethacrylate (HDDMA), polyethylene glycol (600) dimethacrylate (PEG600DMA), 1,12-dodecanediol dimethacrylate (DDDDMA), 1,3-butanediol dimethacrylate (1,3-BDDMA), 1,4-butanediol dimethacrylate (1,4-BDDMA), 1,5-pentanediol dimethacrylate (1,5-PDDMA), 1,6-hexanediol dimethacrylate (1,6-HDDMA), 1,8-octanediol dimethacrylate (1,8-ODDMA), 1,10-decanediol dimethacrylate (1,10-DDDMA), 1,12-dodecanediol dimethacrylate (1,12-DDDMA), 1,4-cyclohexanediol dimethacrylate (1,4-CHDDMA), 1,2-ethanediol dimethacrylate (1,2-EDDMA), 1,3-propanediol dimethacrylate (1,3-PDDMA), 1,4-butanediol dimethacrylate (1,4-BDDMA), 1,5-pentanediol dimethacrylate (1,5-PDDMA), 1,6-hexanediol dimethacrylate (1,6-HDDMA), 1,8-octanediol dimethacrylate (1,8-ODDMA), 1,10-decanediol dimethacrylate (1,10-DDDMA), 1,12-dodecanediol dimethacrylate (1,12-DDDMA), 1,4-cyclohexanediol dimethacrylate (1,4-CHDDMA), 1,2-ethanediol dimethacrylate (1,2-EDDMA), 1,3-propanediol dimethacrylate (1,3-PDDMA), 1,4-butanediol dimethacrylate (1,4-BDDMA), 1,5-pentanediol dimethacrylate (1,5-PDDMA), 1,6-hexanediol dimethacrylate (1,6-HDDMA), 1,8-octanediol dimethacrylate (1,8-ODDMA), 1,10-decanediol dimethacrylate (1,10-DDDMA), 1,12-dodecanediol dimethacrylate (1,12-DDDMA), 1,4-cyclohex3-butyleneglycol dimethacrylate, BGDMA), ethoxylated (3) bisphenol A dimethacrylate, BPA3EODMA), ethoxylated (2) bisphenol A dimethacrylate, BPA2EODMA), trimethylolpropane trimethacrylate, TMPTMA), ethoxylated (10) bisphenol A dimethacrylate, BPA10EODMA), ethoxylated (4) bisphenol A dimethacrylate, BPA4EODMA), alkoxylated pentaerythritol tetramethacrylate, PETTMA), polypropylene glycol monomethacrylate, PPGMA), or tricyclodecanedimethanol dimethacrylate, TCDDMDMA).

[0042] According to embodiments of the present disclosure, the crosslinking agent can include an acrylate-type agent, for example, dipentaerythritol hexaacrylate (DPHA), 1,6-hexanediol diacrylate (HDDA), polyethylene glycol (200) diacrylate (PEG200DA), tetraethylene glycol diacrylate (TTEGDA), triethylene glycol diacrylate (TIEGDA), pentaerythritol tetraacrylate (PETTA), tripropylene glycol diacrylate (TPGDA), polybutadiene diacrylate (PBDDA), 3-methyl 1,5-pentanediol diacrylate (3-MPD), 1,3-butanediol diacrylate (BDDA), 1,4-butanediol diacrylate (BDDA), 1,6-hexanediol diacrylate (HDDA), 1,4-cyclohexanediol diacrylate (CHDDA), 1,2-ethylene glycol diacrylate (EGDA), 1,3-propanediol diacrylate (PDDA), 1,4-benzenediol diacrylate (BDDA), 1,2-phenylenediol diacrylate (PDDA), 1,3-phenylenediol diacrylate (PDDA), 1,4-phenylenediol diacrylate (PDDA), 1,2-phenylenediol diacrylate (PDDA), 1,3-phenylenediol diacrylate (PDDA), 1,4-phenylenediol diacrylate (PDDA), 1,2-phenylenediol diacrylate (PDDA), 1,3-phenylenediol diacrylate (PDDA), 1,4-phenylenediol diacrylate (PDDA), 1,2-phenylenediol diacrylate (PDDA), 1,3-phenylenediol diacrylate (PDDA), 1,4-phenylenediol diacrylate (PDDA), 1,2-phenylenediol diacrylate (PDDA), 1,3-phenylenediol diacrylate (PDDA), 1,4-phenylenediol diacrylate (PDDA), 1,2-phenylenediol diacrylate (PDDA), 1,5-pentanedioldiacrylate, MPDA), polyethylene glycol (400) diacrylate (PEG400DA), ethoxylated (3) bisphenol A diacrylate (BPA3EODA), trimethylolpropane triacrylate (TMPTA), di-trimethylolpropane tetraacrylate (Di-TMPTTA), tris(2-hydroxyethyl)isocyanurate triacrylate (THEICTA), dipentaerythritol pentaacrylate (DPPA), ethoxylated (20) trimethylolpropane triacrylate (TMP20EOTA), pentaerythritol triacrylate (PETIA), ethoxylated (3) trimethylolpropane triacrylate (TMP3EOTA), propoxylated (3) trimethylolpropane triacrylate (TMP3POTA), ethoxylated (4) pentaerythritol tetraacrylate, ethoxylated (6) trimethylolpropane triacrylate (TMP6EOTA), ethoxylated (9) trimethylolpropane triacrylate (TMP9EOTA), dipropylene glycol diacrylate (DPGDA), 1,10-decanediol diacrylate (1,10-decanedioldiacrylate, DDDA), ethoxylated (4) bisphenol A diacrylate, BPA4EODA), ethoxylated (10) bisphenol A diacrylate, BPA10EODA), ester diol diacrylate, EDDA), polyethylene glycol (600) diacrylate, PEG600DA), alkoxylated diacrylate, tricyclodecanedimethanoldiacrylate, TCDDMDA), propoxylated (2) neopentylglycol diacrylate, PONPGDA), propoxylated (3) glyceryl triacrylate, GPTA), ethoxylated (15) trimethylolpropane triacrylate, TMP15EOTA), or ethoxylated (12) glyceryl triacrylate, G12EOTA).

[0043] According to embodiments of the present disclosure, the crosslinking agent can include an allylic type reagent, such as triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), triallyl phosphate (TAP), triallyl borate (TAB), trimethallyl isocyanurate (TMAIC), diallyl terephthalate (DATP), diallyl carbonate, diallyl maleate, diallyl fumarate, diallyl phosphite, trimethylolpropane diallyl ether, or 1,1,2,2-tetraallyloxyethane.

[0044] According to embodiments of the present disclosure, the crosslinking agent can include a vinylic type reagent, such as bis(vinylphenyl)ethane (BVPE), bis(4-vinylphenyl)methane, 1,4-butadiene, divinylacetylene, divinylbenzene (DVB), divinyl ether, divinyl sulfide, divinyl sulfone, divinyl sulfoxide, 1,3-divinylcyclohexane, 1,3-divinylcyclopentane, 1,5-hexadiene, isoprene, or 1,2,4-trivinyl cyclohexane (TVCH).

[0045] According to embodiments of the present disclosure, the crosslinking agent described in the present disclosure can be a commercially available product, such as a crosslinking agent of the Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), a crosslinking agent of product number Photomer 6173 (manufactured by Diamond Shamrock Co., Ltd.), a crosslinking agent of product number Viscoat R-264 (manufactured by Osaka Organic Chemical Industry Ltd.), a crosslinking agent of product number KS Resist 106 (manufactured by Osaka Organic Chemical Industry Ltd.), a crosslinking agent of the CYCLOMER P series (manufactured by Daicel Corporation), a crosslinking agent of the PLACCEL CF200 series (manufactured by Daicel Corporation), a crosslinking agent of the Ebecryl series (manufactured by Daicel UCB Co., Ltd.), a crosslinking agent of product number Acrycure RD-F8 (manufactured by Nippon Shokubai Co., Ltd.), a crosslinking agent of the VISIOMER series (manufactured by Evonik Performance Materials GmbH), a crosslinking agent of the BECKOPOX series (manufactured by Cytec Industries), a crosslinking agent of the CRYLCOAT series (manufactured by Cytec Industries Inc), a crosslinking agent of the SETAL series (manufactured by Nuplex resins), a crosslinking agent of the ANCAMIDE series (manufactured by Air Products, Inc.), or a combination thereof.

[0046] According to embodiments of the present disclosure, the photosensitive composition can further include a solvent such that all components of the photosensitive composition are uniformly dispersed in the solvent. According to embodiments of the present disclosure, the solvent can be benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, cyclohexane, cyclohexene, decahydronaphthalene, dipentene, pentane, hexane, heptane, octane, nonane, decane, ethyl cyclohexane, methylcyclohexane, p-menthane, dipropyl ether, dibutyl ether, anisole, butyl acetate, pentyl acetate, methyl isobutyl ketone, cyclohexylbenzene, cyclohexanone, cyclopentanone (CPN), triglyme, 1,3-dimethyl-2-imidazolidinone (DMI), N-methyl-2-pyrrolidone (NMP), methyl ethyl ketone (MEK), N,N-dimethylacetamide (DMAc), γ-butyrolactone (GBL), N,N-dimethylformamide (DMF), propylene glycol methyl ether acetate (PGMEA), dimethyl sulfoxide (DMSO), or a combination thereof.According to embodiments of the present disclosure, the photosensitive composition can have a solid content of 20 to 40 wt% (e.g., about 21 wt%, 22 wt%, 25 wt%, 27 wt%, 29 wt%, 30 wt%, 32 wt%, 34 wt%, 35 wt%, or 38 wt%). Here, the solid content refers to the weight percentage of all ingredients except the solvent, based on the total weight of the photosensitive composition. According to embodiments of the present disclosure, the thickness of a film prepared from the photosensitive composition is directly proportional to the solid content of the photosensitive composition. In other words, the thickness of a film prepared from the photosensitive composition can be adjusted by the solid content of the photosensitive composition.

[0047] According to embodiments of the present disclosure, the photosensitive composition of the present disclosure consists essentially of the polyimide, the initiator, the crosslinking agent, and the solvent. In other words, the polyimide, the initiator, the crosslinking agent, and the solvent are the main components of the photosensitive composition. The photosensitive composition can further include other components. According to embodiments of the present disclosure, the other components can be a catalyst used to prepare the polyimide, reactants (a) and / or (b) used to prepare the polyimide but not completely reacted, an additive, or a combination thereof. If the photosensitive composition includes other components, the content of the other components can be 0.01 to 20 parts by weight. According to embodiments of the present disclosure, the additive can be an additive known in the art, such as a filler, a flame retardant, a viscosity modifier, a thixotropic agent, a defoamer, a colorant, a leveling agent, a surface treatment agent, a stabilizer, an antioxidant, or a combination thereof. According to other embodiments of the present disclosure, the photosensitive composition of the present disclosure can consist of the above-mentioned main components and other components. According to another embodiment of the present disclosure, the photosensitive composition of the present disclosure can include other polyimides in addition to the polyimide obtained by the reaction of reactant (a) and reactant (b), and the amount of the other polyimides can be less than or equal to 80 parts by weight, based on 100 parts by weight of the polyimide obtained by the reaction of reactant (a) and reactant (b). According to one embodiment of the present disclosure, the photosensitive composition of the present disclosure does not include other polyimides in addition to the polyimide obtained by the reaction of reactant (a) and reactant (b), so that the photosensitive composition maintains a low film formation temperature and the cured product of the photosensitive composition has a low dielectric constant (Dk) and a low dielectric loss (Df) at high frequencies (a frequency band of 10 GHz or more).

[0048] According to embodiments of the present disclosure, the present disclosure also provides a thin film, which is a cured product of the photosensitive composition of the present disclosure after a photolithography process and a baking process.

[0049] According to embodiments of the present disclosure, the thin film of the present disclosure can be prepared by the following steps. First, the photosensitive composition of the present disclosure is formed into a coating layer on a substrate by a coating process. According to embodiments of the present disclosure, the coating process can be screen printing (e.g., silk screen printing), spin coating, bar coating, blade coating, roller coating, dip coating, spray coating, or brush coating. According to embodiments of the present disclosure, the substrate can be a metal sheet (e.g., a copper foil), a silicon substrate, or a glass, and any desired film layer can have been formed on the substrate. Next, the coating layer is subjected to a pre-bake process (the process temperature can be about 60°C to 120°C, and the baking time can be adjusted as appropriate, e.g., can be several seconds to several minutes). Next, the coated substrate is exposed to actinic rays, such as X-ray, electron beam, ultraviolet light, visible light, or other light sources that can be used as actinic rays, under a photomask. After exposure, the coated substrate is then developed by a developer to remove the exposed portions of the thin film to obtain a patterned film layer. Finally, the patterned film layer is subjected to a baking process (the process temperature can be about 120°C to 200°C. The baking time can be adjusted as appropriate, e.g., can be several seconds to several hours). The development can be done by immersion, spraying, or coating with a liquid, or using other known development methods. The developed photoresist pattern is then washed with deionized water. According to embodiments of the present disclosure, the developer can be an aqueous alkaline developer, such as an aqueous solution of an inorganic base (e.g., potassium hydroxide, sodium hydroxide, sodium bicarbonate, or sodium carbonate), a primary amine (e.g., ethylamine), a secondary amine (e.g., diethylamine), a tertiary amine (e.g., triethylamine), or a quaternary ammonium salt (e.g., tetramethylammonium hydroxide).

[0050] Due to the photosensitive composition of the present disclosure having the specific polyimide of the present disclosure, the photosensitive composition can be baked at a lower temperature (i.e., the photosensitive composition has a lower film formation temperature (in the range of about 160°C to 200°C)) to obtain the thin film. In addition, the thin film (i.e., the cured product of the photosensitive composition) obtained after the photolithography process has not only good resolution, electrical properties, chemical resistance, and heat resistance, but also has a low dielectric constant (Dk) (e.g., less than or equal to 2.81) and a low dielectric loss (Df) (e.g., less than or equal to 0.0097) at high frequencies (frequency bands above 10 GHz), meeting the needs of future 5G high-frequency patterning insulation materials.

[0051] In order to make the above and other objects, features, and advantages of the present disclosure more apparent, several embodiments are described in detail below, as follows:

[0052] Table 1 lists the reagents involved in the examples and comparative examples of the present disclosure:

[0053] Table 1

[0054]

[0055]

[0056]

[0057] Preparation of polyimide

[0058] Preparation Example 1

[0059] BPADA (75 mole parts), TAHQ (25 mole parts), TMDA (32 mole parts), BAPP (40 mole parts), and BPTP (8 mole parts) were added to a reaction flask and dissolved in GBL to obtain a solution (solid content: about 35 wt%). Next, isoquinoline (as a catalyst, used in an amount of about 0.3 parts by weight, based on 100 parts by weight of the total weight of BPADA, TAHQ, TMDA, BAPP, and BPTP) was added to the reaction flask. After the resultant was allowed to react at 180°C for 6 hours, TMDA (8 mole parts), BAPP (10 mole parts), and BPTP (2 mole parts) were added. After the resultant was allowed to react at 90°C for 3 hours, xylene was added to obtain a solution (1) of polyimide (solid content: about 30 wt%).

[0060] Preparation Example 2

[0061] Preparation Example 2 was performed in the same manner as described in Preparation Example 1, except that 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) was increased from 75 to 80 mole parts, and p-phenylenebis(trimellitate anhydride) (TAHQ) was decreased from 25 to 20 mole parts, to obtain a solution (2) having a polyimide.

[0062] Preparation Example 3

[0063] Preparation Example 3 was performed in the same manner as described in Preparation Example 1, except that 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) was decreased from 75 to 70 mole parts, and p-phenylenebis(trimellitate anhydride) (TAHQ) was increased from 25 to 30 mole parts, to obtain a solution (3) having a polyimide.

[0064] Comparative Preparation Example 1

[0065] Comparative Preparation Example 1 was performed in the same manner as described in Preparation Example 1, except that 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) was increased from 75 to 90 mole parts, and p-phenylenebis(trimellitate anhydride) (TAHQ) was decreased from 25 to 10 mole parts, to obtain a solution (4) having a polyimide.

[0066] Comparative Preparation Example 2

[0067] Into a reaction flask, 3,3,4,4-biphenyl tetracarboylic dianhydride (BPDA) (100 parts by mole), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) (48 parts by mole), and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF) (32 parts by mole) were charged and dissolved in gamma-butyrolactone (GBL) to obtain a solution (solid content: about 35 wt%). Then, isoquinoline (as a catalyst, used in an amount of about 0.3 wt% based on the total weight of BPDA, BAPP, and BAHF) was added to the reaction flask. After the resultant was reacted at 180°C for 6 hours, 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) (12 parts by mole) and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF) (8 parts by mole) were added. After the resultant was reacted at 90°C for 3 hours, xylene was added to obtain a solution (5) of polyimide (solid content: about 30 wt%).

[0068] The dianhydrides and diamines used in Preparation Examples 1 to 3 and Comparative Preparation Examples 1 to 2 and their amounts are shown in Table 2.

[0069] Table 2

[0070]

[0071] Preparation of photosensitive composition

[0072] Example 1

[0073] Into the solution (1) of polyimide obtained in Preparation Example 1 (100 parts by weight of solid content), 19.6 parts by weight of a photoinitiator (trade name: Irgacure 907, manufactured by Ciba Geigy), 17.65 parts by weight of a photoinitiator (trade name: Irgacure 184, manufactured by Ciba Geigy), and 58.8 parts by weight of a crosslinking agent (dipentaerythritol hexaacrylate, DPHA) were dissolved to obtain a photosensitive composition (1).

[0074] Example 2

[0075] Example 2 was carried out in the same manner as in Example 1, except that the polyimide-containing solution (1) obtained in Preparation Example 1 was replaced with the polyimide-containing solution (2) obtained in Preparation Example 2, to obtain a photosensitive composition (2).

[0076] Example 3

[0077] Example 3 was carried out in the same manner as in Example 1, except that the polyimide-containing solution (1) obtained in Preparation Example 1 was replaced with the polyimide-containing solution (3) obtained in Preparation Example 3, to obtain a photosensitive composition (3).

[0078] Comparative Example 1

[0079] Comparative Example 1 was carried out in the same manner as in Example 1, except that the polyimide-containing solution (1) obtained in Preparation Example 1 was replaced with the polyimide-containing solution (4) obtained in Comparative Preparation Example 1, to obtain a photosensitive composition (4).

[0080] Example 4

[0081] Example 4 was carried out in the same manner as in Example 1, except that the polyimide-containing solution (1) obtained in Preparation Example 1 was replaced with the polyimide-containing solution (2) obtained in Preparation Example 2, to obtain a photosensitive composition (5).

[0082] Example 5

[0083] Example 5 was carried out in the same manner as in Example 1, except that the polyimide-containing solution (1) obtained in Preparation Example 1 was replaced with the polyimide-containing solution (2) obtained in Preparation Example 2, to obtain a photosensitive composition (6).

[0084] Comparative Example 2

[0085] Comparative Example 2 was carried out in the same manner as in Example 4, except that the polyimide-containing solution (2) obtained in Preparation Example 2 was replaced with the polyimide-containing solution (5) obtained in Comparative Preparation Example 2, to obtain a photosensitive composition (7).

[0086] Comparative Example 3

[0087] Comparative Example 3 was performed in the same manner as described in Example 5, except that the solution (2) having polyimide obtained in Preparation Example 2 was replaced with the solution (5) having polyimide obtained in Comparative Preparation Example 2, to obtain a photosensitive composition (8).

[0088] Example 6

[0089] A photosensitive composition (9) was obtained by dissolving 0.37 parts by weight of a photoinitiator (trade name: Irgacure 907, manufactured by Ciba Geigy), 0.74 parts by weight of a photoinitiator (trade name: Irgacure 184, manufactured by Ciba Geigy), and 21.9 parts by weight of a crosslinking agent (dipentaerythritol hexaacrylate, DPHA) in the solution (2) having polyimide obtained in Preparation Example 2 (100 parts by weight of solid content).

[0090] Example 7

[0091] A photosensitive composition (10) was obtained by dissolving 0.89 parts by weight of a photoinitiator (trade name: Irgacure 907, manufactured by Ciba Geigy), 0.38 parts by weight of a photoinitiator (trade name: Irgacure 184, manufactured by Ciba Geigy), and 25.6 parts by weight of a crosslinking agent (dipentaerythritol hexaacrylate, DPHA) in the solution (2) having polyimide obtained in Preparation Example 2 (100 parts by weight of solid content).

[0092] Photosensitive composition property test

[0093] The photosensitive compositions (1) to (4) obtained were subjected to a photolithography process. The photolithography process included the following steps: the photosensitive compositions (1) to (4) were respectively coated on a substrate, and a soft-baking process was performed at 110°C for 2 minutes to obtain a thin film. Subsequently, a digital lithography technology (DLT) (wavelength: 405 nm, exposure amount: 800 mj / cm2) was used to perform exposure on the thin film, and a developing process was performed using an aqueous solution of 2.38% by weight of ammonium 2) The film was irradiated. Next, development was performed using a Microposit MF-319 developer system (manufactured by Rohm and Hass Electronic Materials LLC) for 60 seconds, and wet cleaning was performed using propylene glycol methyl ether acetate (PGMEA) for 30 seconds, and whether the photoetched cured layer was developable or not was observed, and if it was developable, O was recorded, and if it was not developable, X was recorded. Next, baking was performed at 160°C to obtain a cured product. Next, the dielectric coefficient (Dk) and the dielectric loss factor (Df) of the cured product of the photosensitive composition (1)-(4) obtained were measured, the thickness, the light transmittance, and the b* value, and the results are shown in Table 3. The dielectric coefficient (Dk) and the dielectric loss factor (Df) were measured using a microwave dielectrometer (purchased from AET Corporation) at a frequency of 10 GHz. The thickness was measured using optical microscopy (OM). The light transmittance was measured using visible light at a wavelength of 550 nm. The b* value was measured using the method specified in JIS-Z8722 0-45° method, double-beam cross-illumination method.

[0094] Table 3

[0095]

[0096] As shown in Table 3, since the photosensitive composition (4) of Comparative Example 1 could not be prepared into a film due to the molar ratio of BPADA (first dianhydride) and TAHQ (second dianhydride) of the polyimide used in Comparative Example 1 being 1:9. In addition, the photosensitive compositions (1)-(3) of Examples 1-3 could be baked at a lower temperature (about 160°C), which indicates that the photosensitive compositions of the present disclosure indeed have a lower film forming temperature. In addition, the films obtained after the photoetching process of the photosensitive compositions (1)-(3) of Examples 1-3 have a low dielectric constant (Dk) (less than 2.65) and a low dielectric loss (Df) (less than or equal to 0.0092) at high frequencies (10 GHz).

[0097] Next, the obtained photosensitive compositions (5)-(8) were subjected to a photolithography process, and the film formation temperature evaluation and resolution test were performed. The photolithography process included the following steps: the above photosensitive compositions (5)-(8) were coated on a substrate, respectively, and a soft-baking process was performed at 110°C for 2 minutes to obtain a thin film. Next, the thin film was irradiated with a broadband UV light source (wavelength: 250-405 nm, exposure amount: 500 mj / cm 2 ) using a broadband UV light source (wavelength: 250-405 nm, exposure amount: 500 mj / cm2). Next, the thin film was developed with a tetramethylammonium hydroxide (TMAH) aqueous solution (concentration: 2.38 wt%) developer for 60 seconds, and wet cleaned with propylene glycol methyl ether acetate (PGMEA) for 30 seconds. Next, baking was performed (the temperature range was adjusted to 160-250°C as required), and the lowest film formation temperature was recorded to obtain a cured product. The resolution test was represented by the minimum line width at which the dry film pattern after development of the photoresist could be clearly resolved, and the results are shown in Table 4. Next, the dielectric coefficient (Dk) and dielectric loss factor (Df) of the cured product of the obtained photosensitive compositions (5)-(8) were measured, and the results are shown in Table 4.

[0098] Table 4

[0099]

[0100] As shown in Table 4, since the dianhydride and diamine used to prepare the polyimides of Comparative Examples 2 and 3 were not the specific dianhydride and diamine described in the present disclosure, the obtained photosensitive compositions (7) and (8) had a higher film formation temperature (greater than 200°C), and the thin film obtained after the photolithography process of the photosensitive compositions (7) and (8) had a high dielectric loss (Df) (greater than 0.015) at high frequency (10 GHz). In addition, the photosensitive compositions (5) and (6) of Examples 4-5 could be baked at a lower temperature (about 160°C), which indicated that the photosensitive compositions described in the present disclosure indeed had a lower film formation temperature. Furthermore, the thin film obtained after the photolithography process of the photosensitive compositions (5) and (6) described in Examples 4-5 had a low dielectric constant (Dk) (less than 2.55) and a low dielectric loss (Df) (less than or equal to 0.0093) at high frequency (10 GHz).

[0101] Next, the obtained photosensitive compositions (9) and (10) were subjected to photolithography, and the film deposition temperature and resolution were evaluated. The photolithography process included the following steps: the above photosensitive compositions (9) and (10) were respectively coated on a substrate, and a pre-bake process was performed at 110°C for 2 minutes to obtain a thin film. Then, a digital lithography technology (DLT) was used (wavelength of 405nm, exposure amount of 800mJ / cm). 2 The film was then irradiated. Next, it was developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, and then wetted and cleaned with propylene glycol monomethyl ether acetate (PGMEA) for 30 seconds. Finally, it was baked at 160°C to obtain a cured product. Resolution was measured as the minimum linewidth at which the dry film pattern could be clearly resolved after photoresist development, and the results are shown in Table 5. Next, the dielectric constant (Dk) and dielectric loss factor (Df) of the cured photosensitive compositions (9) and (10) were measured, and the results are shown in Table 5.

[0102] Table 5

[0103]

[0104] As shown in Table 5, the photosensitive compositions (9) and (10) of Examples 6 and 7 can be baked at a lower temperature (about 160°C), indicating that the photosensitive compositions described in this disclosure do indeed have a lower film-forming temperature. Furthermore, the films obtained by photolithography of the photosensitive compositions (9) and (10) of Examples 6 and 7 have a low dielectric constant (Dk) (less than or equal to 2.81) and a low dielectric loss (Df) (less than or equal to 0.0097) at high frequencies (10 GHz).

[0105] Although this disclosure has been described above with several embodiments, it is not intended to limit the content of this disclosure. Those skilled in the art can make any modifications and refinements without departing from the spirit and scope of this disclosure. Therefore, the scope of protection of this disclosure shall be determined by the appended claims.

Claims

1. A photosensitive composition comprising: 100 parts by weight of polyimide; 0.25-50 parts by weight of initiator; and 0.25-100 parts by weight of crosslinking agent, The polyimide is the reaction product of reactant (a) and reactant (b). The reactant (a) is composed of a primary dianhydride and a secondary dianhydride, wherein the molar ratio of the primary dianhydride to the secondary dianhydride is 6:4 to 8:2, wherein the primary dianhydride has the structure shown in formula (I), and the secondary dianhydride has the structure shown in formula (II). Where R 1 and R 2 Each is independently hydrogen, fluorine, methyl, ethyl, propyl, fluoromethyl, fluoroethyl, or fluoropropyl; and Ar 1 for as well as Reactant (b) contains a primary diamine, a secondary diamine, and a tertiary diamine. Wherein the first diamine is Where R 3 R 4 R 5 and R 6 Each can be independently hydrogen, fluorine, methyl, ethyl, propyl, fluoromethyl, fluoroethyl, or fluoropropyl. The second diamine is Where R 11 and R 12 Each can be independently hydrogen, fluorine, methyl, ethyl, propyl, fluoromethyl, fluoroethyl, or fluoropropyl, and The third diamine is 2. The photosensitive composition of claim 1, wherein the molar ratio of the first dianhydride to the second dianhydride is 7:3 to 8:

2.

3. The photosensitive composition of claim 1, wherein the molar ratio of the first diamine to the second diamine is 1:9 to 9:

1.

4. The photosensitive composition of claim 1, wherein the molar ratio of the first diamine to the second diamine is 4:6 to 5:

5.

5. The photosensitive composition of claim 1, wherein the molar ratio of the third diamine to the sum of the molar ratios of the first diamine and the second diamine is 1:99 to 1:

9.

6. The photosensitive composition of claim 1, wherein the molar ratio of the third diamine to the sum of the molar ratios of the first diamine and the second diamine is 5:95 to 9:

91.

7. The photosensitive composition of claim 1, wherein the polyimide has a weight-average molecular weight of 5,000 to 3,000,000 g / mol.

8. The photosensitive composition of claim 1, wherein the initiator is a benzoin-based compound, an acetophenone-based compound, a thioxanthone-based compound, a ketal compound, an benzophenone-based compound, an α-aminoalkyl phenyl ketone compound, an acylphosphine oxide compound, a bimidazole-based compound, a triazine-based compound, an azo compound, a cyanopentanoic acid-based compound, a peroxide, or a combination thereof.

9. The photosensitive composition of claim 1, wherein the crosslinking agent is a compound having two or more crosslinkable functional groups, wherein the crosslinkable functional group is C 2-5 Alkenyl, methacrylate, acrylate, acryloyl, epoxy, or carboxyl.

10. The photosensitive composition of claim 1, further comprising a solvent, wherein the solid content of the photosensitive composition is 20 wt% to 40 wt%.

11. The photosensitive composition of claim 10, wherein the solvent is benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, cyclohexane, cyclohexene, decahydronaphthalene, dipentene, pentane, hexane, heptane, octane, nonane, decane, ethylcyclohexane, methylcyclohexane, p-menthane, dipropyl ether, dibutyl ether, anisole, butyl acetate, amyl acetate, methyl isobutyl ketone, cyclohexylbenzene, cyclohexanone, cyclopentanone, triethylene glycol dimethyl ether, 1,3-dimethyl-2-imidazolinone, N-methyl-2-pyrrolidone, butanone, N,N-dimethylacetamide, γ-butyrolactone, N,N-dimethylformamide, propylene glycol methyl ether acetate, dimethyl sulfoxide, or a combination thereof.

12. A film, wherein the film is a cured product of the photosensitive composition as described in any one of claims 1-11.

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