Cardo photoresist resin and application thereof

Abstract

The invention belongs to the technical field of photosensitive materials, and particularly relates to Cardo photoresist resin and application thereof. The Cardo photoresist resin is prepared by taking oligomeric resin and a modifier D containing one or more phenolic hydroxyl groups as raw materials, wherein the oligomeric resin is formed by copolymerizing a hydroxyl-containing multifunctional (methyl) acrylate monomer A, a polyanhydride monomer B and an end-capping reagent C. The invention further discloses a preparation method of the Cardo photoresist resin. The Cardo photoresist resin provided by the invention has excellent optical performance, curing rate and film-forming performance, has good adhesion with a substrate in practical application, can be thoroughly cured at a relatively low curing temperature, and has high pattern stability and uniform and complete gluing.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of photosensitive materials, and particularly relates to a Cardo photoresist resin and application thereof. BACKGROUND

[0002] In the field of microelectronic manufacturing, photoresist as a key pattern transfer material, its performance directly affects the resolution, precision of chip and reliability of final device, and photosensitive resin as a core component of photoresist, the balance of its optical and mechanical properties is the long-term goal pursued in the field. With the development of photolithography technology to higher resolution and more complex structure, the refractive index of photosensitive resin composition is put forward higher and higher requirements - higher refractive index helps to optimize the optical path design in the photolithography process, improves the imaging quality, especially in the preparation of advanced process and specific optical devices, high refractive index has become one of the key performance indicators.

[0003] In order to realize the high refractive index of photosensitive resin composition, two strategies are generally used in the prior art: by introducing rigid groups (such as polycyclic aromatic hydrocarbons, heterocyclic structures, etc.) in the molecular structure of the resin, using the high molar refractive index characteristics of rigid conjugated system to improve the overall refractive index of the material; secondly, by adding high refractive index nanoparticles (such as ZrO2, TiO2) in organic materials, the refractive index of the material can be effectively improved to 1.66, even more than 1.70. However, the above two strategies have significant defects: increasing rigid groups will lead to the decrease of flexibility of resin molecular chain, the increase of glass transition temperature, which will increase the brittleness of the film formed by the composition and weaken the impact resistance; and the inorganic nanoparticle filling will also cause the organic film to become brittle, which is not conducive to bending. In practical application, this brittleness problem will cause the photolithography pattern to be easily broken and peeled off in development, etching and subsequent processes, which seriously affects the yield and reliability of the device, and becomes a key bottleneck restricting the application of high refractive index photosensitive resin in precision manufacturing field. Because under the same film refractive index index, the development of high refractive index organic material can reduce the amount of inorganic nanoparticles used. Therefore, it is a technical problem to be solved in the field to develop a photosensitive resin that can improve the refractive index and hardness while considering the flexibility of the film. SUMMARY

[0004] To solve the above technical problems, the present application provides a kind of Cardo photoresist resin and its application.Cardo photoresist resin, by oligomeric resin and with one and more phenolic hydroxyl group modifier D as raw material preparation, the oligomeric resin is formed by the copolymerization of multifunctional (methyl) acrylate monomer A containing hydroxyl group, poly anhydride monomer B, blocking agent C;The monomer A contains aromatic core with carbon number of 12 to 50;The blocking agent C contains one or more reactive groups reacted with the hydroxyl group of monomer A;The modifier D has the substituted or unsubstituted alkyl chain with carbon number of 1 to 30, and the chain end of the substituted or unsubstituted alkyl chain with carbon number of 1 to 30 contains one or more amine groups.

[0005] The monomer A has the structural formula shown in formula one: ; Z1 is aromatic core with carbon number of 12 to 50;X1 is selected from O;R1 is selected from divalent hydrocarbon group with carbon number of 1-20;R2 is selected from alkyl with carbon number of 1-20 with (methyl) acrylate group at the end;m is selected from natural integer of 2-5.

[0006] The aromatic core with carbon number of 12 to 50 has at least one substituted or unsubstituted fluorene ring, and the H at 1-4 arbitrary positions of the substituted or unsubstituted fluorene ring can be substituted by R3, R3 is selected from C 1-10 alkyl, C 3-10 cycloalkyl, C 6-10 aryl, C 12-15 heteroaryl, C 7-10 aralkyl, C 1-10 alkoxy, C 3-10 cycloalkoxy, halogen atom, nitro group, cyano group or two or more combinations.

[0007] Multiple R3 are independently fused with fluorene ring, or any two adjacent R3 are fused into aromatic ring.

[0008] Preferably, the H at 1-2 arbitrary positions of the substituted or unsubstituted fluorene ring can be substituted by R3, R3 is selected from phenyl.

[0009] Some non-limiting examples of Z1 are: , , , , , , , , .

[0010] The H at any position in the above examples can be substituted by C 1-4alkyl, phenyl, halogen, etc. substituted with a hydroxyl-containing (meth)acrylate functional group or X1 symmetrically or asymmetrically bonded to the 9-position H atom of the fluorene ring in Z1, or a substituent of the 9-position H atom of the fluorene.

[0011] The divalent hydrocarbon group having 1 to 20 carbon atoms is selected from an alkylene group, an alkylene ether group, an arylene group, and an alkylene oxide group.

[0012] When the divalent hydrocarbon group is selected from an alkylene group, it can be branched, straight, or cyclic.

[0013] An alkyl group having a (meth)acrylate group at the end refers to an alkyl group or any one of the H atoms on the end carbon atom of the alkyl chain being substituted with a (meth)acrylate group. Alkyl refers to an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl, and propyl; and alkyl chain refers to a branched or straight alkyl chain having more than three carbon atoms, which can include, for example, n-butyl, isobutyl, pentyl, hexyl, and the like.

[0014] Examples of the alkyl group having a (meth)acrylate group at the end include, but are not limited to, a (meth)acrylate group, an ethyl (meth)acrylate group, a propyl (meth)acrylate group, a butyl (meth)acrylate group, and the like.

[0015] As the monomer A, it can also be prepared by reacting a monomer containing an epoxy group with a (meth)acrylic monomer. Ultimately, a structure represented by Formula 1 can satisfy the monomer A of the present application.

[0016] m can be selected from any one of 2, 3, 4, and 5.

[0017] m refers to the number of the same functional groups connected to Z1.

[0018] The "poly" in the polyacid anhydride monomer B refers to the number of acid anhydride functional groups being greater than or equal to 2, and the monomer B can be selected from a diacid anhydride monomer, a triacid anhydride monomer, and the like.

[0019] The polyacid anhydride monomer B can be an aliphatic diacid anhydride monomer or an aromatic diacid anhydride monomer. In the present application, the polyacid anhydride monomer is preferably an aromatic diacid anhydride monomer B for heat resistance.

[0020] The monomer B has a structure represented by Formula 2: ; Z2 is selected from a tetravalent aromatic core having 10 to 50 carbon atoms, and the aromatic core having 10 to 50 carbon atoms contains two or more substituted or unsubstituted phenyl groups, which are connected by a single bond, a heteroatom, a carbonyl group, a C 1-4 one of the alkylene groups represented by -C(R1)2-C(R2)2- or a combination thereof, or a pair of chemical bonds to form a fused ring structure.

[0021] an aromatic core having two or more substituted or unsubstituted phenyl groups, means two or more substituted or unsubstituted phenyl groups, each phenyl group being connected by a single bond, a covalent bond, an oxygen atom, a sulfur atom, a substituted or unsubstituted C1to C5alkylene group, a heteroatom-substituted or unsubstituted C3to C6alkylene group, an ethylene group, an ethynylene group, or a carbonyl group without condensation.

[0022] Preferably, the aromatic core having a carbon number of 10 to 50 contains two, three, or four substituted or unsubstituted phenyl groups, each phenyl group being connected by a single bond, a covalent bond, an oxygen atom, a sulfur atom, a substituted or unsubstituted C1to C5alkylene group, a heteroatom-substituted or unsubstituted C3to C6alkylene group, an ethylene group, an ethynylene group, or a carbonyl group without condensation.

[0023] For example, the aromatic core containing two or more phenyl groups can include a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted trityl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, a substituted or unsubstituted bisphenol F group, a substituted or unsubstituted bisphenol A group, a substituted or unsubstituted biphenyloxy group, a substituted or unsubstituted terphenyloxy group, a substituted or unsubstituted quaterphenyloxy group, a substituted or unsubstituted quinquephenyloxy group, and structural isomers thereof, but is not limited thereto.

[0024] Some non-limiting examples of Z2are: , , , , , , , , , , , , , , , , , , , .

[0025] The symmetry of the anhydride group in Formula II is located at both ends of Z2, which is fused with the phenyl group in Z2.

[0026] The reactive functional group of the end-capping agent C is selected from an anhydride group.

[0027] The end-capping agent C is selected from aromatic mono-anhydride monomers.

[0028] Specifically, the end-capping agent C can be represented by the following formula III: wherein Z3 is selected from aromatic groups.

[0029] Specifically, Z3 is selected from aryl groups having 6 to 30 carbon atoms, which can include, but are not limited to, phenyl, naphthyl, anthryl, biphenyl, terphenyl, and the like.

[0030] Preferably, the end-capping agent C is selected from aromatic mono-anhydride monomers having 6 to 12 carbon atoms.

[0031] The modifier D is a phenyl group having one or more hydroxyl groups and one R4, which is a substituted or unsubstituted alkyl chain having 1 to 30 carbon atoms.

[0032] The end of the substituted or unsubstituted alkyl chain having 1 to 30 carbon atoms contains one or more amine groups, which are reactive functional groups that react with the carboxyl groups generated from the anhydride groups. Here, the anhydride groups can come from the monomer B or the end-capping agent C.

[0033] Further, the modifier D includes at least two or more hydroxyl groups; preferably, two or three hydroxyl groups.

[0034] When the modifier D has two hydroxyl groups, the two hydroxyl groups are arranged adjacently, at intervals, or in a para position.

[0035] The substituent of the alkyl chain having 1 to 30 carbon atoms is selected from a carboxyl group, a hydroxyl group, or a halogen. As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom can be mentioned.

[0036] Unless otherwise indicated, substituted or unsubstituted substituents herein can be optionally substituted groups, and can be substituted with one or more substituents, which can be the same or different. Suitable substituents include alkyl, aryl, nitro, cyano, -N(R’)(R”), halogen, hydroxyl, carboxyl, alkenyl, alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkoxycarbonyl, perfluoroalkyl, perfluoroalkoxy, arylalkyl, silyl, siloxy, siloxane, thioalkoxy, -S(O)2-, -C(=O)-. Each R’ and R” is independently optionally alkyl, cycloalkyl, or aryl. R’ and R”, together with the nitrogen atom to which they are bonded, can form a ring system in certain embodiments.

[0037] The Cardo photoresist resin provided by the present application has a weight ratio of monomer A, monomer B, end-capping agent C, and modifier D of (20-40):(1-10):(1-5):(0.1-0.5).

[0038] The weight average molecular weight of the Cardo photoresist resin is preferably 1000 to 40000, and more preferably 2000 to 10000. By setting the weight average molecular weight to the above range, good developability can be obtained, and sufficient heat resistance and film strength can be obtained.

[0039] The acidity value of the Cardo photoresist resin is preferably in the range of 60 to 140 mgKOH / g. In this case, the developability of the photosensitive resin composition can be particularly improved. It is more preferably in the range of 80 to 130 mgKOH / g, and further more preferably in the range of 90 to 120 mgKOH / g.

[0040] Preferably, the amount of D added is 0.2% to 5% by weight of the oligomer resin component.

[0041] In a second aspect, the present application provides a photocurable composition (photosensitive resin composition) comprising a Cardo photoresist resin and a polymerization initiator, a solvent, a resin monomer, and an additive.

[0042] The amount of the Cardo photoresist resin added is preferably 1% to 50% by weight, more preferably 1% to 30% by weight, and further more preferably 10% to 20% by weight of the photosensitive resin composition.

[0043] The resin monomer is selected from a (meth)acrylate resin, and the (meth)acrylate resin is selected from a monofunctional or polyfunctional (meth)acrylate alkyl ester, and a monofunctional or polyfunctional (meth)acrylate aryl ester.

[0044] The polyfunctional (meth)acrylate resin has 2 to 5 (meth)acrylate functional groups.

[0045] The (meth)acrylate resin is not limited to a polyester acrylate, a polyether acrylate, and an epoxy acrylate.

[0046] As the resin monomer, one or more of, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene glycol diglycidyl ether diacrylate, ethylene glycol diglycidyl ether dimethacrylate, diglycidyl phthalate diacrylate, diglycidyl phthalate dimethacrylate, 3,4-epoxycyclohexylmethyl methacrylate, and glycidyl methacrylate can be mentioned. However, the resin monomer is not limited thereto.

[0047] The content of the resin monomer is preferably in the range of 0.1 to 30% by weight, more preferably in the range of 0.1 to 20% by weight, and even more preferably in the range of 0.1 to 10% by weight, based on the photosensitive resin composition. The resin monomer can be one kind or two or more kinds. When two or more kinds of resin monomers are contained, the total content is preferably in the above range.

[0048] The polymerization initiator is selected from a photopolymerization initiator or / and a thermal curing agent.

[0049] The photopolymerization initiator is not particularly limited in kind, unless otherwise specified.

[0050] The photopolymerization initiator includes, but is not limited to, an α-hydroxy ketone initiator, a benzoin initiator, an acyloxyphosphine initiator, an acetophenone initiator, a morpholinyl ketone initiator, a naphthalimide photoinitiator, an oxime ester photoinitiator, a carbazolyl photoinitiator, and the like, and any of them can be used.

[0051] Examples of the photopolymerization initiator include any one or a combination of two or more of 2-hydroxy-2-methyl-l-phenyl-l-propanone, 2-hydroxy-2-methyl-l-[4-(tert-butyl)phenyl]-l-propanone, 2-hydroxy-2-methyl-l-phenylpropan-l-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-l-(4-hydroxyethoxy)phenyl-l-propanone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2,4,6-trimethylbenzoyl, diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, (2,4,6-trimethylbenzoyl)phenylphosphinic acid ethyl ester, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, OXE-02 (1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime), manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), IRGACURE OXE-04 (manufactured by BASF).

[0052] The content of the photopolymerization initiator is 0.1 to 30% by weight, preferably 1 to 10% by weight, of the photosensitive resin composition. When the content of the photoradical initiator is within the range, excellent reliability can be ensured because of sufficient curing during exposure in the pattern forming process, and the pattern can have excellent resolution and heat resistance, light resistance, and chemical resistance of close contact.

[0053] Similarly, the thermal curing agent can be selected from a thermal curing initiator conventionally used for a thermal curing type resin composition, such as an amine-based curing agent, an acid anhydride-based thermal curing agent, an imidazole-based thermal curing agent, an acid anhydride-based curing agent, an isocyanate-based curing agent, and the like.

[0054] The solvent used in the present application is not particularly limited, and specific examples of the solvent include, but are not limited to, one or a mixture of esters, alcohols, ethers, ketones, benzene.

[0055] The ester solvent is selected from one or more of ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxyamyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, cyclohexanol acetate; the alcohol is selected from one or more of methanol, ethanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol; the ether is selected from one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; the ketone is selected from one or more of acetone, methyl amyl ketone, methyl isopropyl ketone, methyl isopentyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone; the benzene is selected from one or more of toluene, xylene, or a combination of at least two of them.

[0056] The content of the solvent is preferably in an amount of 5 to 80 wt% of the photosensitive resin composition, more preferably 5 to 70 wt%, and even more preferably 5 to 60 wt%. The solvent can be only one, or two or more. When two or more solvents are contained, the total amount is preferably within the range.

[0057] The resin monomer can be exemplified by, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, methoxy methyl (meth)acrylate, n-propoxyethyl (meth)acrylate, isopropoxyethyl (meth)acrylate, n-butoxyethyl (meth)acrylate, isobutoxyethyl (meth)acrylate, t-butoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxy-n-propyl (meth)acrylate, 4-hydroxy-n-butyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate.

[0058] The content of the resin monomer is preferably in an amount of 0.1 to 30 wt%, more preferably 0.1 to 20 wt%, and even more preferably 0.1 to 10 wt% of the photosensitive resin composition. The resin monomer can be only one or two or more. When two or more resin monomers are contained, the total amount is preferably within the range.

[0059] The auxiliary agent includes dispersants, defoamers, surfactants, leveling agents, crosslinking agents, adhesion promoters, thickening agents, solubilizers, silane coupling agents, and the like.

[0060] The surfactant is a silicone-based surfactant or a fluorine-based surfactant. Specifically, as the silicone-based surfactant, BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341v344, BYK-345v346, BYK-348, BYK-354, BYK-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390, and the like, but are not limited thereto, of BYK (BYK-Chemie) can be used.

[0061] The content of the auxiliary agent is preferably in an amount of 0.1 to 20 wt%, more preferably 0.1 to 15 wt%, and even more preferably 0.1 to 10 wt% of the photosensitive resin composition. The auxiliary agent can be only one or two or more. When two or more auxiliary agents are contained, the total amount is preferably within the range.

[0062] Within a range that does not affect the effects of the present application, the photosensitive resin composition of the present application can be added with an auxiliary agent or without an auxiliary agent, depending on the actual application needs.

[0063] The third aspect of the present application is the application of the photocuring composition of the present application. The photocuring composition provided by the present application is applied to the preparation of black photoresist, color photoresist, protective film photoresist, PS spacer column, and the like in display devices. Depending on the actual needs, carbon black, pigments, inorganic nanoparticles, and the like can be added to the photosensitive resin composition provided by the present application.

[0064] As other pigments, various pigments used for coloring the photosensitive resin composition can be used, for example. Blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, and brown pigments can be exemplified. All can be selected according to the routine use of those skilled in the art.

[0065] The resin composition can optionally add surface modified or unmodified inorganic nanoparticles with a refractive index of ≥1.8.

[0066] The surface modified or unmodified inorganic nanoparticles are selected from oxides or sulfides of at least one metal element of zirconium (Zr), titanium (Ti), zinc (Zn), germanium (Ge), niobium (Nb), molybdenum (Mo), indium (In), tin (Sn), antimony (Sb), cerium (Ce), neodymium (Nd), hafnium (Hf), tantalum (Ta), bismuth (Bi). More preferably, oxides or sulfides of 1 to 2 metal elements.

[0067] The inorganic nanoparticles are selected from any one of ZrO2, TiO2, ZnS, ZnO, CeO2, GeO2, Ta2O5, Bi4Ti3O2, Nb2O5, HfO2, SnO2, MoO3, Sb2O3, Sb2O5, Nd2O3, or a combination of at least two thereof. The average particle size of the inorganic nanoparticles is 10-50 nm.

[0068] The surface modification methods can include esterification, coupling agent method, surface grafting, organic adsorption coating, etc. The inorganic nanoparticles can be surface modified by silane coupling agent to improve compatibility and dispersibility with the main resin material. In this embodiment, KH-560 silane coupling agent is used to surface modify the nanoparticles by coupling agent method.

[0069] In the embodiment, the inorganic nanoparticles are added in a form mixed with a commercially available dispersant: the dispersing solvent is commercially available PGMEA (propylene glycol methyl ether acetate), and the inorganic nanoparticle addition amount is 40wt%-60wt%.

[0070] The fourth aspect of the present application is a cured film formed using the photosensitive resin composition of the present application.

[0071] The cured film is prepared by coating, spraying, spin coating, blade coating (wire bar), nanoimprinting, inkjet printing, screen printing or pad printing of the photosensitive resin composition described above. It can also be formed by coating, spraying, spin coating, blade coating (wire bar), nanoimprinting, inkjet printing, screen printing or pad printing, followed by baking to form a film, and then aligning and exposing through a mask, and developing.

[0072] In the preparation of the cured film, the steps can be: coating the photosensitive resin composition on a substrate by spin coating, and then removing the solvent by prebaking to form a prebaked coating film. The prebaking conditions vary depending on the type and ratio of each component, and are generally at a temperature of 80-120°C for 5-15 minutes.

[0073] After the pre-baking, the coating film is exposed to light under a mask. As the chemical rays for exposure, ultraviolet rays, visible rays, electron rays, X-rays, etc. are used. In the present application, i-rays (365 nm), h-rays (405 nm), or g-rays (436 nm) of a mercury lamp are preferably used. The ultraviolet irradiation device can be a (super) high-pressure mercury lamp or a metal halide lamp.

[0074] Then, the developer is immersed at a temperature of 20 to 40°C for 1 to 2 minutes to remove the unnecessary portions and form a specific pattern. Specific examples of the developer include, but are not limited to, for example, methanol, ethanol, propanol, isopropanol, butanol, ethyl acetate, n-butyl acetate, γ-butyrolactone, ε-hexyl lactone, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate, methyl ethyl ketone, cyclohexanone, cyclopentanone, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, N,N-dimethylacetamide, or a combination of two or more of these organic solvents.

[0075] Then, a post-bake treatment is performed using a heating device such as a hot plate or an oven, and the temperature of the post-bake treatment is usually 50 to 250°C. After the above treatment steps, a cured film is formed.

[0076] When forming a pattern, the unexposed portions are removed using a developer after exposure. As the developer, an aqueous solution of a compound that exhibits alkalinity, such as tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, 1,6-hexanediamine, etc., is preferably used. Depending on the situation, one or more polar solvents selected from N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, etc.; alcohols such as methanol, ethanol, isopropanol, etc.; esters such as ethyl lactate, propylene glycol monomethyl ether acetate, etc.; and compounds such as cyclopentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone, etc. can be added to the aqueous alkali solution.

[0077] The development time, the development step, and the temperature of the developer are not limited, and the unexposed portions can be removed.

[0078] The film thickness of the cured film can be arbitrarily set, and is preferably 0.5 μm to 100 μm.

[0079] A fifth aspect of the present application is a display device provided with the cured film of the present application.

[0080] The display device is not limited to OLED, Mini LED, Micro LED, and LCD display.

[0081] The Cardo photoresist resin provided by the application is prepared by using monomer A with a substituted or unsubstituted fluorene ring rigid structure and diacid anhydride monomer B, and has the advantages of high refractive index and high glass transition temperature. On the other hand, by adding modifier D, the phenolic hydroxyl group and the polar group on the modifier D are used to reduce the stress in the resin, so that the resin body solves the pain points of brittleness and weakened impact resistance caused by the increase of the refractive index of the resin, effectively improves the problem of device yield caused by the brittleness of the film layer due to excessive rigidity. At the same time, the Cardo photoresist resin provided by the application overcomes the problem of high temperature curing caused by the resin prepared by using traditional methods and raw materials, so that the curing temperature of the cured resin obtained by the reaction is low, and the curing temperature range is between 50℃ and 100℃. And the Cardo photoresist resin provided by the application has excellent solubility after being improved by the modifier D, which not only provides convenience for the film forming process, but also realizes good flexibility on this basis, and takes into account the functionality and practicability of the material. BRIEF DESCRIPTION OF DRAWINGS

[0082] Figure 1 The figure is a curve graph of the refractive index and wavelength of the Cardo photoresist resin 1 (01), the Cardo photoresist resin 2 (02), the Cardo photoresist resin 8 (08) and the oligomer X1 (00) provided by the application. DETAILED DESCRIPTION

[0083] The principles and characteristics of the application are described below, and the examples are only used to explain the application and not to limit the scope of the application. If the specific conditions are not specified in the examples, the conventional conditions or the conditions recommended by the manufacturer are used. If the reagents or instruments used are not specified by the manufacturer, they are all conventional products that can be purchased on the market.

[0084] Cardo photoresist resin preparation example: S1: In a 250ml round-bottom three-necked flask, weigh 30g of propylene glycol methyl ether acetate, add 25g of monomer A, and stir the mixture with a polytetrafluoro stirrer for 30 minutes. Add 0.75g of catalyst benzyl triethyl ammonium bromide, 5g of monomer B, and then heat the mixture to 130℃, and stir for 4 hours. The complete consumption of the acid anhydride in the reaction liquid is detected by infrared detection, and 3g of end-capping agent C is finally added, and the mixture is stirred at 130℃ for 4 hours to obtain oligomer X1; S2: In a 250ml round-bottom three-necked flask, 30g of propylene glycol methyl ether acetate, 50g of the oligomer X1 obtained in step S1 were stirred with polytetrafluoro for 30 minutes, 0.75g of catalyst tetrabutylammonium bromide, 0.5g of modifier D were added in sequence, and then the mixture was heated to 100°C and stirred for 4 hours to obtain a Cardo photoresist resin.

[0085] Preparation examples of Cardo photoresist resins 1-16: Cardo photoresist resins 1-16 were prepared according to the preparation examples of Cardo photoresist resins, and the structures and weight parts of monomer A, monomer B, end-capping agent C and modifier D used are shown in Table 1 and Table 2 below: Table 1 Table 2 Performance test: The oligomer X1 prepared in step S1 of Example 1 and the Cardo photoresist resins 1-16 prepared in Examples 1-16 were respectively tested for performance: 1) Molecular weight: test equipment, gel permeation chromatograph (GPC), mobile phase, tetrahydrofuran (THF), flow rate, 1 ± 0.001 ml / min, column temperature, 25°C, reference sample, polystyrene; 2) Refractive index: the resin was diluted with solvent PMA to a solid content of 20%, 0.5wt% surfactant (BYK-333) was added, then a silicon wafer was used as a substrate, a resin film sample was obtained by spin coating (1000 rpm, 60 s, 100°C baking for 120 s), and the refractive index value of the film was obtained by optical testing on an ellipsometer; 3) Dispersion coefficient: gel permeation chromatography; 4) The transmittance was tested using a visible spectrophotometer; the test results are shown in Table 3 below: Table 3 Example of photosensitive resin composition 1: The 55 parts by weight of propylene glycol methyl ether acetate, 28 parts by weight of 3-MBA (3-methoxy butyl acetate), 0.8 parts by weight of photoinitiator OXE-02, 12 parts by weight of Cardo photoresist resin 1, 2 parts by weight of DPHA (dipentaerythritol hexaacrylate), 1.8 parts by weight of MF-K60x (Japan Asahi Kasei low-temperature sealing type curing agent), 0.2 parts by weight of surfactant BYK-333, 0.2 parts by weight of silane coupling agent KH-570 (γ-methacryloxypropyltrimethoxysilane) are accurately weighed into a photoresist stirred tank, stirred at room temperature for 8h under yellow light environment, and then filtered with a filter pore size of 5 microns to obtain a photosensitive resin composition.

[0086] Photosensitive resin composition 2-6 example: The preparation method of the photosensitive resin composition example 1 is the same, except that the photosensitive resin 1 is replaced by photosensitive resin 2, photosensitive resin 6, photosensitive resin 7, photosensitive resin 10, photosensitive resin 16, respectively, to prepare photosensitive resin composition 2-6.

[0087] Composition comparative example 1: The preparation method of the photosensitive resin composition example 1 is the same, except that the photosensitive resin 1 is replaced by photosensitive resin 2, photosensitive resin 6, photosensitive resin 7, photosensitive resin 10, photosensitive resin 16, respectively, to prepare photosensitive resin composition 2-6.

[0088] Performance test: The viscosity of the photosensitive resin composition 1- is measured using a viscometer; A thickness of 5um is coated on a glass substrate using inkjet printing technology, the substrate is dried in a vacuum drying oven for 30 minutes, then pre-baked on a vacuum hot plate at 80℃ for 1min, cooled on a cold plate, and then placed in a UV curing machine to cure at an intensity of about 80mJ / cm 2 to form an optical film. The transmittance of the film is measured using a haze meter, the curing hardness is tested using a universal testing machine, and the adhesion of the photoresist film on the glass substrate is tested using the crosshatch method.

[0089] The test results are shown in Table 4 below: Table 4 From the above table and Figure 1It can be seen that the Cardo photoresist resin provided by the application has good refractive index and optical performance, so that when it is applied, the refractive index is greatly improved, and at the same time, it is beneficial to form a thin film with good film uniformity, development rate and pattern precision, and solves the natural conflict between the high performance (high refractive / hardness) and processability (dissolution / film formation) of the rigid skeleton. When it is applied to a photosensitive resin composition, it has rigidity and flexibility, and can be applied to a flexible or foldable device, and has excellent application prospects in terminal applications such as flexible or foldable televisions, mobile phones and wearable devices. The completely cured thin film has high resolution and high ductility at the same time, effectively avoiding the problem that the existing optical adhesive cannot simultaneously satisfy resolution and flexibility.

[0090] The above merely describes the preferred embodiments of the present application and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A Cardo photoresist resin, characterized in that: The product is prepared from an oligomer resin and a modifier D containing one or more phenolic hydroxyl groups as raw materials. The oligomer resin is formed by copolymerization of a polyfunctional (meth)acrylate monomer A containing hydroxyl groups, a polyacid anhydride monomer B, and a capping agent C. The monomer A contains an aromatic core with 12 to 50 carbon atoms. The capping agent C contains one or more reactive groups that react with the hydroxyl groups of monomer A. The modifier D has a substituted or unsubstituted alkyl chain with 1 to 30 carbon atoms, and the substituted or unsubstituted alkyl chain with 1 to 30 carbon atoms contains one or more amine groups at its end.

2. The Cardo photoresist resin according to claim 1, characterized in that, The monomer A has the structural formula shown in Formula 1: Z1 is an aromatic core with 12 to 50 carbon atoms; X1 is selected from O; R1 is selected from a divalent hydrocarbon group with 1 to 20 carbon atoms; R2 is selected from an alkyl group with 1 to 20 carbon atoms at the end having a (meth)acrylate group; m is selected from a natural integer of 2 to 5.

3. The Cardo photoresist resin according to claim 1, characterized in that, The aromatic core having 12 to 50 carbon atoms has at least one substituted or unsubstituted fluorene ring, wherein 1 to 4 H atoms at any position on the substituted or unsubstituted fluorene ring can be substituted by R3, wherein R3 is selected from C. 1-10 alkyl, C 3-10 cycloalkyl, C 6-10 aryl, C 12-15 heteroaryl, C 7-10 Aryl groups, C 1-10 alkoxy, C 3-10 The cycloalkoxy group, halogen atom, nitro group, cyano group, or a combination of two or more.

4. The Cardo photoresist resin according to claim 1, characterized in that, The monomer B has the structural formula shown in Formula 2: The Z2 is selected from tetravalent aromatic cores with 10 to 50 carbon atoms, and the tetravalent aromatic cores with 10 to 50 carbon atoms contain two or more substituted or unsubstituted phenyl groups, which are connected by single bonds, heteroatoms, carbonyl groups, or C2 groups. 1-4 One or a combination of alkylene groups are linked together, or they share a pair of chemical bonds to form a fused ring structure.

5. The Cardo photoresist resin according to claim 1, characterized in that, The weight-average molecular weight of the Cardo photoresist resin is in the range of 1000-40000; The amount of modifier D added is 0.2%-5% of the weight of the oligomer resin component.

6. The Cardo photoresist resin according to claim 1, characterized in that, The reactive functional group of the end-capping agent C is selected from acid anhydride groups.

7. The Cardo photoresist resin according to claim 1, characterized in that, The capping agent C is selected from aromatic monoacid anhydride monomers with 6 to 12 carbon atoms.

8. The Cardo photoresist resin according to claim 1, characterized in that, The modifier D is a phenyl group having one or more hydroxyl groups and one R4-substituted phenyl group, wherein R4 is a substituted or unsubstituted alkyl chain having 1 to 30 carbon atoms.

9. The Cardo photoresist resin according to claim 8, characterized in that, The substituents of the alkyl chain having 1 to 30 carbon atoms are selected from carboxyl, hydroxyl, or halogen groups.

10. An application of a Cardo photoresist resin, characterized in that, A photocurable composition is prepared using the Cardo photoresist resin according to any one of claims 1-9 and applied to a display device.

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