Photosensitive resin composition, use thereof, display device, and semiconductor device

Abstract

Disclosed are a photosensitive resin composition, use thereof, a display device, and a semiconductor device. The photosensitive resin composition comprises: an alkali-soluble resin, a polymerizable monomer different from the alkali-soluble resin, and a photoinitiator comprising at least one oxime ester compound represented by Formula I. The oxime ester compound represented by Formula I has high thermal stability, good solubility in solvents commonly used for preparing photosensitive resin compositions, and can impart good film-forming properties, developability, and photosensitivity to the photosensitive resin composition. The photosensitive resin composition is suitable for use in preparing photo-cured materials such as a photoresist for semiconductors, a colored photoresist, a photo-spacer, etc. The definitions of the substituents in Formula I are as described in the specification and claims.[Formula I]

Description

Technical Field

[0001] This invention relates to a photosensitive resin composition, and more particularly to a photosensitive resin composition comprising an oxime ester compound and its application. Background Technology

[0002] Oxime esters are widely used as photoinitiators due to their excellent photosensitivity and are applied to the preparation of photocurable materials for optoelectronic components such as RGB (red, green, blue) color photoresists, black matrix photoresists, optical spacers, and semiconductor photoresists.

[0003] Taiwan Patent Publication No. TW 201140240A discloses a photopolymerization initiator represented by the following general formula:

[0004]

[0005] Among them, R 1 To R 11 Each of the following independently represents a hydrogen atom, a halogen atom, an alkyl group (substituted or unsubstituted) having 1 to 20 carbon atoms, an alkenyl group (substituted or unsubstituted) having 2 to 20 carbon atoms, a cycloalkyl group (substituted or unsubstituted) having 3 to 10 ring-forming atoms, a cycloalkenyl group (substituted or unsubstituted) having 4 to 20 carbon atoms, a hydroxyl group, an alkoxy group (substituted or unsubstituted) having 1 to 20 carbon atoms, an alkenoxy group (substituted or unsubstituted) having 2 to 20 carbon atoms, or a carbon atom (substituted or unsubstituted). The following groups are represented: alkanoyl group (1 to 20), enoyl group (2 to 20 carbon atoms, substituted or unsubstituted), aryl group (6 to 14 carbon atoms forming the ring, substituted or unsubstituted), or heterocyclic group (3 to 14 carbon atoms forming the ring, substituted or unsubstituted); Ar represents aryl group (6 to 14 carbon atoms forming the ring, substituted or unsubstituted), or heteroaryl group (5 to 14 carbon atoms forming the ring, substituted or unsubstituted); W represents a single bond or an oxygen atom; Z represents a single bond, an oxygen atom, or >NR. 3’ (R 3’ Represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or R 3’ With R 3 (It connects and forms a ring with nitrogen atoms).

[0006] As the performance requirements for various optoelectronic components increase, the requirements for the solubility and thermal stability of oxime ester compounds as photoinitiators, as well as the film-forming properties, developability, and photosensitivity of photosensitive resin compositions containing oxime ester compounds, are also being raised. Therefore, oxime ester compounds still need to be further improved to meet the application requirements of various optoelectronic components. Summary of the Invention

[0007] Therefore, the first object of the present invention is to provide a photosensitive resin composition.

[0008] Therefore, the photosensitive resin composition of the present invention comprises:

[0009] Alkali-soluble resins;

[0010] Polymerizable monomers, unlike the alkali-soluble resin; and

[0011] Photoinitiators include at least one oxime ester compound represented by Formula I:

[0012] [Formula I]

[0013]

[0014] In equation I, R 1 To R 4 Each of the C1 to C1 represents an independent value. 20 Straight-chain alkyl, C3 to C 20 Branched alkyl groups, C2 to C 20 Straight-chain alkenyl, C4 to C 20 Branched alkenyl, cycloalkyl, or aromatic groups, wherein the cycloalkyl or aromatic group is unsubstituted or any one of the hydrogen atoms contained therein is replaced by the aforementioned alkyl or alkenyl group.

[0015] R 5 Indicates hydrogen, halogen, nitro, cyano, C1 to C 20 Straight-chain alkyl, C3 to C 20 Branched alkyl, cycloalkyl, or aromatic groups, wherein the cycloalkyl and aromatic groups are unsubstituted or any one of the hydrogen atoms contained therein is replaced by the aforementioned alkyl group.

[0016] R 6 Indicates hydrogen, C1 to C 20 Straight-chain alkyl, C3 to C 20 Branched alkyl groups, C2 to C 20 Straight-chain alkenyl, C4 to C 20 Branched alkenyl, cycloalkyl, or aromatic groups, wherein the cycloalkyl or aromatic group is unsubstituted or any one of the hydrogen atoms contained therein is replaced by the aforementioned alkyl or alkenyl group.

[0017] The above R 1 To R 6 The -CH2- group represented hereindicates that any one of the -CH2- groups is either unsubstituted or substituted by a group selected from the group consisting of: -O-, -S-, -NH-, -C=O-, -O(C=O)-, -(C=O)O-, -NH(C=O)-, and -(C=O)NH-, and adjacent -CH2- groups cannot be simultaneously substituted by the above groups.

[0018] R 7 This indicates a bridged ring group or a group having a bridged ring group.

[0019] Therefore, a second objective of the present invention is to provide an oxime ester compound.

[0020] Therefore, the oxime ester compounds of the present invention are represented by Formula I:

[0021] [Formula I]

[0022]

[0023] In equation I, R 1 To R 4 Each of the C1 to C1 represents an independent value. 20 Straight-chain alkyl, C3 to C 20 Branched alkyl groups, C2 to C 20 Straight-chain alkenyl, C4 to C 20 Branched alkenyl, cycloalkyl, or aromatic groups, wherein the cycloalkyl and aromatic groups are unsubstituted or any one of the hydrogen atoms contained therein is replaced by the aforementioned alkyl or alkenyl groups;

[0024] R 5 Indicates hydrogen, halogen, nitro, cyano, C1 to C 20 Straight-chain alkyl, C3 to C 20 Branched alkyl, cycloalkyl, or aromatic group, wherein the cycloalkyl and aromatic group are unsubstituted or any one of the hydrogen atoms contained therein is replaced by the aforementioned alkyl group;

[0025] R 6 Indicates hydrogen, C1 to C 20 Straight-chain alkyl, C3 to C 20 Branched alkyl groups, C2 to C 20 Straight-chain alkenyl, C4 to C 20 Branched alkenyl, cycloalkyl, or aromatic groups, wherein the cycloalkyl and aromatic groups are unsubstituted or any one of the hydrogen atoms contained therein is replaced by the aforementioned alkyl or alkenyl groups;

[0026] The above R 1 To R 6 The -CH2- group represented is either unsubstituted or substituted by a group selected from the group consisting of: -O-, -S-, -NH-, -C=O-, -O(C=O)-, -(C=O)O-, -NH(C=O)-, and -(C=O)NH-, and adjacent -CH2- groups cannot be substituted by the above groups simultaneously; and

[0027] R 7 This indicates a bridged ring group or a group having a bridged ring group.

[0028] Therefore, a third object of the present invention is to provide a use of the photosensitive resin composition as described above.

[0029] Therefore, the use of the photosensitive resin composition of the present invention as described above includes its application in the preparation of photoresists, colored photoresists, or photoresists for semiconductors.

[0030] Therefore, the fourth objective of this invention is to provide a display device.

[0031] Therefore, the display device of the present invention includes a colored photoresist formed from the photosensitive resin composition described above.

[0032] Therefore, the fifth objective of this invention is to provide a semiconductor device.

[0033] Therefore, the semiconductor device of the present invention includes a semiconductor photoresist formed from the photosensitive resin composition described above.

[0034] One advantage of this invention is that the molecular structure of the oxime ester compounds of this invention includes a carbazole group as the main skeleton, two substituents including the oxime ester group, and a bridged ring group or a group having a bridged ring group, which makes the oxime ester compounds have high thermal stability and good solubility in solvents commonly used to prepare photosensitive resin compositions, and thus are particularly suitable as photoinitiators for use in photosensitive resin compositions.

[0035] Another advantage of the present invention is that the photosensitive resin composition containing the above-mentioned oxime ester compounds has high photosensitivity, and is therefore suitable for use in the preparation of photocurable materials such as semiconductor photoresists, colored photoresists, and photospacers, especially suitable for the preparation of black matrix photoresists. Furthermore, the photosensitive resin composition has good film-forming and developing properties, thereby avoiding mura defects in the display device. In addition, because the oxime ester compounds have high thermal stability, the photosensitive resin composition also has good thermal stability. Detailed Implementation

[0036] The term "(meth)acrylate" in this article refers to methacrylates and / or acrylates in general.

[0037] The photosensitive resin composition of the present invention comprises an alkali-soluble resin, a polymerizable monomer, and a photoinitiator.

[0038] The type of alkali-soluble resin is not particularly limited and can be any alkali-soluble resin known in the field of photocurable materials technology, allowing for flexible selection by those skilled in the art based on the subsequent practical application of the photosensitive resin composition. In some embodiments of the invention, the alkali-soluble resin is selected from one or more of (meth)acrylate resins, phenolic varnish resins, epoxy resins, polyvinylphenol resins, and carboxyl-containing urethane resins. The (meth)acrylate resins include, but are not limited to, one or more of carboxyl-containing (meth)acrylate resins, hydroxyl-containing (meth)acrylate resins, and epoxy-containing (meth)acrylate resins. The phenolic varnish resins include, but are not limited to, carboxyl-containing phenolic varnish resins. The epoxy resins include, but are not limited to, carboxyl-containing epoxy resins. Preferably, with the solid content of the photosensitive resin composition being 100% by weight and the content of the alkali-soluble resin ranging from 5% by weight to 60% by weight, the photosensitive resin composition can have better developability; more preferably, the content of the alkali-soluble resin ranging from 10% by weight to 50% by weight; most preferably, the content of the alkali-soluble resin ranging from 12% by weight to 30% by weight.

[0039] The polymerizable monomer differs from the alkali-soluble resin. There are no particular limitations on the type of polymerizable monomer; it can be any polymerizable monomer known in the field of photocurable materials technology, and can be flexibly selected by those skilled in the art based on the subsequent practical application of the photosensitive resin composition. In some embodiments of the invention, the polymerizable monomer is selected from one or more of epoxy-containing polymerizable monomers, polymerizable monomers containing at least one ethylene (olefinic) unsaturated bond, and polymerizable monomers containing both epoxy and ethylene unsaturated bonds. Among these, the epoxy-containing polymerizable monomer is, for example, but not limited to, bisphenol A epoxyfluorene, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, etc. The polymerizable monomer containing epoxy groups and vinyl unsaturated bonds is, but not limited to, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl ether di(meth)acrylate of phthalic acid, glycerol polyglycidyl ether poly(meth)acrylate, 1,2-epoxy-4-vinylcyclohexane, etc. The polymerizable monomer containing at least one vinyl unsaturated bond is selected from one or more compounds containing one vinyl group and compounds containing two or more vinyl groups. The compound containing one vinyl group is, but not limited to, (meth)acrylate compounds, (meth)acrylamide compounds, or hydroxy(meth)acrylate compounds, etc. The compound containing two or more vinyl groups is, for example, but not limited to, tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), or dipentaerythritol hexaacrylate (DPHA). More preferably, with a solid content of 100% by weight and a polymerizable monomer content ranging from 5% to 60% by weight, the photosensitive resin composition exhibits better curability; more preferably, the polymerizable monomer content ranges from 10% to 50% by weight; most preferably, the polymerizable monomer content ranges from 12% to 30% by weight.

[0040] The photoinitiator includes at least one oxime ester compound represented by Formula I:

[0041] [Formula I]

[0042]

[0043] In equation I, R 1 To R 4Each of the C1 to C1 represents an independent value. 20 Straight-chain alkyl, C3 to C 20 Branched alkyl groups, C2 to C 20 Straight-chain alkenyl, C4 to C 20 Branched alkenyl, cycloalkyl, or aromatic groups, wherein the cycloalkyl and aromatic groups are unsubstituted or any one of the hydrogen atoms contained therein is replaced by the aforementioned straight-chain alkyl, branched alkyl, straight-chain alkenyl, or branched alkenyl groups. More preferably, the R... 1 To R 4 Each independently represents a C1 to C8 straight-chain alkyl group, or a C3 to C8 straight-chain alkyl group. 10 Branched alkyl or C3 to C6 cycloalkyl. More preferably, R 1 and R 2 Each independently represents a C1 to C2 straight-chain alkyl group, and R 3 and R 4 Each independently represents a C1 to C5 straight-chain alkyl group or a C3 to C5 straight-chain alkyl group. 10 Branched alkyl groups.

[0044] R 5 Indicates hydrogen, halogen, nitro, cyano, C1 to C 20 Straight-chain alkyl, C3 to C 20 Branched alkyl, cycloalkyl, or aromatic groups, wherein the cycloalkyl and aromatic groups are unsubstituted or any one of the hydrogen atoms contained therein is replaced by the aforementioned straight-chain alkyl or branched alkyl groups. More preferably, the R... 5 This indicates hydrogen, cyano, C1 to C8 straight-chain alkyl, or C3 to C7 cycloalkyl. More preferably, the R... 5 It can represent hydrogen, cyano, C1 to C3 straight-chain alkyl or C7 cycloalkyl.

[0045] R 6 Indicates hydrogen, C1 to C 20 Straight-chain alkyl, C3 to C 20 Branched alkyl groups, C2 to C 20 Straight-chain alkenyl, C4 to C 20 Branched alkenyl, cycloalkyl, or aromatic groups, wherein the cycloalkyl and aromatic groups are unsubstituted or any one of the hydrogen atoms contained therein is replaced by the aforementioned straight-chain alkyl, branched alkyl, straight-chain alkenyl, or branched alkenyl groups. More preferably, the R... 6 It represents hydrogen, a C1 to C8 straight-chain alkyl group, or a phenyl group. More preferably, the R... 6 It represents hydrogen, CH3, or phenyl.

[0046] The above R 1 To R 6The -CH2- group represented hereindicates that any one of the -CH2- groups is either unsubstituted or replaced by a group selected from the group consisting of: -O-, -S-, -NH-, -C=O-, -O(C=O)-, -(C=O)O-, -NH(C=O)-, and -(C=O)NH-, and adjacent -CH2- groups cannot be simultaneously replaced by the above groups. More preferably, the above R... 1 To R 6 The -CH2- group represented is replaced by an unsubstituted group or a group selected from the group consisting of -C=O-, -O(C=O)- and -(C=O)O-, and adjacent -CH2- groups cannot be replaced by the above groups at the same time.

[0047] The above R 1 To R 6 In this context, when the cycloalkyl group is unsubstituted, the carbon number range is, for example, but not limited to, 3 to 10. Specific examples of unsubstituted cycloalkyl groups include, for example, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. When the aromatic group is unsubstituted, the carbon number range is, for example, but not limited to, 5 to 10. Specific examples of unsubstituted aromatic groups include, for example, but not limited to, phenyl or naphthyl. It should also be noted that when the cycloalkyl group and the aromatic group are substituted, any hydrogen atom may be replaced by a halogen, alkynyl, aryl, cycloalkyl, or heterocyclic group, in addition to being replaced by the aforementioned straight-chain alkyl, branched-chain alkyl, straight-chain alkenyl, or branched-chain alkenyl groups.

[0048] R 7 The term "bridged ring group" or a group having a bridged ring group (or a derivative having a bridged ring group) is used herein. As used herein, "a group having a bridged ring group" does not encompass bridged ring groups; in other words, a group having a bridged ring group is different from a bridged ring group. Preferably, the R... 7 Indicates -L 1 -R 7’ , among which, the L 1 Indicates single bond, C1 to C 20 Straight-chain alkylene, C3 to C 20 Branched alkylene or C4 to C5 20 (cycloalkylalkyl) and the R 7’ express More preferably, the L 1 It represents a single bond, a C1 to C3 straight-chain alkylene group, or a C3 to C5 branched alkylene group, and the R 7’ express

[0049] More preferably, the oxime ester compound represented by Formula I is selected from one or more of the oxime ester compounds represented by Formulas I-1 to I-15.

[0050]

[0051]

[0052]

[0053]

[0054]

[0055] The common preparation method for the oxime esters represented by Formula I is shown below, and the specific synthesis conditions can be flexibly selected and adjusted according to conventional organic synthesis methods:

[0056]

[0057] More preferably, with the solid content of the photosensitive resin composition being 100% by weight, the content of the oxime ester compound represented by Formula I ranging from 1% by weight to 30% by weight, the photosensitive resin composition can have better film-forming and curing properties; more preferably, the content of the oxime ester compound represented by Formula I ranging from 2% by weight to 20% by weight; most preferably, the content of the oxime ester compound represented by Formula I ranging from 5% by weight to 15% by weight.

[0058] The photosensitive resin composition of the present invention may selectively contain other reagents, such as, but not limited to, dispersants, pigments, solvents, coupling agents, surfactants, coatability improvers, development modifiers, ultraviolet absorbers, antioxidants, etc.

[0059] The photosensitive resin composition of the present invention can be used to prepare photocurable materials such as semiconductor photoresists, colored photoresists, and photospacers. Therefore, the present invention also relates to the use of the photosensitive resin composition in preparing photocurable materials such as semiconductor photoresists, colored photoresists, and photospacers.

[0060] The display device of the present invention includes a colored photoresist formed from the photosensitive resin composition. The colored photoresist includes, for example, a black matrix photoresist and an RGB color photoresist.

[0061] The semiconductor device of the present invention includes a semiconductor photoresist formed from the photosensitive resin composition.

[0062] The present invention will be further described with reference to the following embodiments, but it should be understood that the embodiments are for illustrative purposes only and should not be construed as limiting the scope of the present invention.

[0063] [Example 1] Oxime ester compounds represented by Formula I-1

[0064] The oxime esters shown in Formula I-1 are synthesized via the following reaction pathway:

[0065]

[0066]

[0067] (1) 16.7 g of carbazole and 200 mL of dichloromethane were poured into a three-necked flask in an ice bath environment. 33.33 g of aluminum trichloride was then added to the flask and stirred for 30 minutes. 24.5 g of butyryl chloride was then slowly added dropwise to the flask and the reaction was carried out at room temperature for 2 hours. Ice water was then poured into the flask to terminate the reaction, yielding the reaction product. The reaction product was extracted with dichloromethane and the organic layer was collected. The organic layer was then neutralized with a 5 wt% sodium bicarbonate aqueous solution, washed with water and saturated brine, and dehydrated with anhydrous magnesium sulfate. Finally, the crude product was concentrated to obtain the crude product. The crude product was purified by column chromatography [stationary phase: Merck silica gel 60 (70-230 mesh ASTM), mobile phase: ethyl acetate: n-heptane = 1:4 to 1:2 gradient elution] to obtain 18.4 g of compound 1a (yield 60%).

[0068] The molecular weight of compound 1a was analyzed using a mass spectrometer (Perkin Elmer GC Clarus 600), and the result was MS (m / z): 307.2 (M+H). + .

[0069] The molecular structure of compound 1a was analyzed using nuclear magnetic resonance spectroscopy (Bruker Avance III HD 400MHz): 1 H-NMR (CDCl3, 400MHz), δ (ppm): 8.772 (2H, d, J = 1.2Hz), 8.633 (1H, s), 8.141-8.117 (2H, m), 7.478(2H,d,J=8.4Hz), 3.084(4H,t,J=7.2Hz), 1.871-1.797(4H,m), 1.054(6H,t,J=7.6Hz).

[0070] (2) 30.7 g of compound 1a, 100 mL of dimethyl sulfoxide, 22.0 g of 1-adamantyl methacrylate, and 27.64 g of potassium carbonate were added to a reaction flask at room temperature. The mixture was reacted at 50 °C for 6 hours to obtain the reaction product. The reaction product was poured into water, and then extracted with ethyl acetate. The organic layer was collected, washed with water and saturated brine, and then dehydrated with anhydrous magnesium sulfate. Finally, the crude product was concentrated to obtain the crude product. The crude product was purified by column chromatography [stationary phase: Merck silica gel 60 (70-230 mesh ASTM), mobile phase: ethyl acetate: n-heptane = 1:4] to obtain 26.4 g of compound 1b (yield 50%).

[0071] The molecular weight of compound 1b was analyzed using a Thermo Scientific TSQ Altis mass spectrometer, and the result was MS (m / z): 528.4 (M+H). + .

[0072] The molecular structure of compound 1b was analyzed using nuclear magnetic resonance spectroscopy: 1 H-NMR (CDCl3, 400MHz), δ (ppm): 8.772 (2H, d, J = 1.2Hz), 8.171-8.145 (2H, m), 7.480 (2H, d, J = 8.8Hz), 4.678-4.622 (1H, m), 4.307- 4.251(1H,m),3.098-3.010(5H,m),2.059(3H,s),1.866-1.811(9H,m),1.563(5H,s),1.233-1.166(4H,m),1.051(6H,t,J=7.2Hz).

[0073] (3) 52.8 g of compound 1b, 200 mL of tetrahydrofuran, and 20.3 g of concentrated hydrochloric acid were added to a reaction flask in an ice bath environment. Then, 29.3 g of isoamyl nitrite was slowly added dropwise to the reaction flask, and the reaction was carried out in an ice bath environment to obtain the reaction product. The reaction product was first neutralized to neutral with a saturated potassium carbonate aqueous solution, then concentrated to remove tetrahydrofuran, and then extracted with 200 mL of ethyl acetate and the organic layer was collected. The organic layer was washed with water and saturated brine, then dehydrated with anhydrous magnesium sulfate, and finally concentrated to obtain the crude product. The crude product was purified by column chromatography [stationary phase: Mercksilica gel 60 (70-230 mesh ASTM), mobile phase: ethyl acetate: n-heptane = 1:3] to obtain 23.4 g of compound 1c (yield 40%).

[0074] The molecular weight of compound 1c was analyzed using a Thermo Scientific TSQ Altis mass spectrometer, and the result was MS (m / z): 586.4 (M+H). + .

[0075] The molecular structure of compound 1c was analyzed using nuclear magnetic resonance spectroscopy: 1 H-NMR (CDCl3, 400MHz), δ (ppm): 8.954 (2H, s), 8.563 (2H, s), 8.030-8.004 (2H, m), 7.236 (2H, d, J = 8.8Hz), 4.526-4.472 (1H, m), 4.200-4.141 ( 1H,m),2.990-2.900(1H,m),2.767(4H,q,J=7.6Hz),2.115(3H,s),1.96 8(6H,s),1.610(6H,s),1.148(6H,t,J=7.6Hz),1.063(3H,d,J=6.8Hz).

[0076] (4) 23.4 g of compound 1c, 80 mL of ethyl acetate, and 12.3 g of acetic anhydride were added to a reaction flask in an ice bath environment and reacted to obtain the reaction product. The reaction product was first neutralized to neutral with a saturated potassium carbonate aqueous solution, then extracted with ethyl acetate and the organic layer was collected. The organic layer was washed with water and saturated brine, then dehydrated with anhydrous magnesium sulfate, and finally concentrated to obtain the crude product. The crude product was purified by column chromatography [stationary phase: Mercksilica gel 60 (70-230 mesh ASTM), mobile phase: ethyl acetate: n-heptane = 1:3] to obtain 18.7 g of compound 1d, which is the oxime ester compound represented by formula I-1 (yield 70%).

[0077] The molecular weight of this compound at 1 day was analyzed using a Thermo Scientific TSQ Altis mass spectrometer, and the result was MS (m / z): 692.3 (M+Na). + .

[0078] The molecular structure of this compound at 1d was analyzed using nuclear magnetic resonance spectroscopy: 1H-NMR (CDCl3, 400MHz), δ (ppm): 8.915 (2H, d, J = 1.2Hz), 8.287-8.261 (2H, m), 7.510 (2H, d, J = 8.8Hz), 4.688-4.632 (1H, m), 4.303-4.247 ( 1H,m),3.081-2.991(1H,m),2.852(4H,q,J=7.6Hz),2.285(6H,s),2.073(3H,s),1.935-1.868(6H,m),1.574(6H,s),1.250-1.112(9H,m).

[0079] [Comparative Example 1] Oxime esters

[0080] The structures of the oxime ester compounds in Comparative Example 1 are as follows:

[0081] (Purchased from Changzhou Qiangli Company, product name TR-PBG-345).

[0082] [Comparative Example 2] Oxime esters

[0083] The structures of the oxime ester compounds in Comparative Example 2 are as follows:

[0084]

[0085] The preparation method of the oxime ester compound in Comparative Example 2 is similar to that of the oxime ester compound of Formula I-1, except that in Comparative Example 2, 1-adamantyl methacrylate in step (2) is replaced with cyclohexyl acrylate.

[0086] [Comparative Example 3] Oxime esters

[0087] The structures of the oxime ester compounds in Comparative Example 3 are as follows:

[0088] (Compound No. 10 disclosed in patent publication number WO 2008078678A1).

[0089] [Property Evaluation of Oxime Esters]

[0090] Solubility:

[0091] The following solubility tests were performed on the oxime ester compounds of Example 1 and Comparative Examples 1 to 3: In an environment of 25°C, the oxime ester compounds were continuously added to 10.0 g of propylene glycol methyl ether acetate (PGMEA) while stirring until the oxime ester compounds could no longer dissolve in PGMEA. The amount of oxime ester compounds used at this point was recorded as the upper limit of solubility (by weight), and the solubility was calculated by substituting it into the following formula: Solubility (wt%) = Upper limit of solubility of oxime ester compound ÷ (Upper limit of solubility of oxime ester compound + Amount of PGMEA) × 100%.

[0092] Thermal stability:

[0093] The oxime esters of Examples 1 and Comparative Examples 1 to 3 were subjected to the following thermal stability tests: Using a thermogravimetric analyzer (TGA, TA Instruments, model Q500), the oxime esters were heated from room temperature (25°C) to 110°C in a nitrogen atmosphere, held at 110°C for 30 minutes, and then heated from 110°C to 400°C at a rate of 10°C / min. The temperature at which the oxime esters experienced a 5% weight loss was recorded. The evaluation criteria for the thermal stability of the oxime esters were as follows: a temperature greater than 230°C at which a 5% weight loss occurred was rated "◎"; a temperature between 200°C and 230°C at which a 5% weight loss occurred was rated "○"; and a temperature less than 200°C at which a 5% weight loss occurred was rated "●". The results are recorded in Table 1.

[0094] Table 1

[0095]

[0096]

[0097] Referring to the solubility results in Table 1, the oxime ester compound of Formula I-1 in Example 1 has higher solubility in PGMEA compared to the oxime ester compounds of Comparative Examples 1 to 3, demonstrating that the oxime ester compounds of the present invention have better solubility in solvents.

[0098] Referring to the thermal stability results in Table 1, the temperature at which the oxime ester compounds of Formula I-1 in Example 1 exhibited a 5% weight loss was higher than that of the oxime ester compounds of Comparative Examples 1 to 3, demonstrating that the oxime ester compounds of the present invention possess superior thermal stability. It is worth noting that those skilled in the art of photocurable materials generally recognize that the thermal stability of photosensitive resin compositions primarily depends on the thermal stability of the photoinitiator. Therefore, given the superior thermal stability of the oxime ester compounds of the present invention, it is reasonable to assume that the photosensitive resin compositions of the present invention should also possess superior thermal stability.

[0099] [Application Example 1] Photosensitive Resin Composition

[0100] The photosensitive resin composition of Application Example 1 was prepared using an oxime ester compound of Formula I-1 from Example 1 as a photoinitiator. The preparation method of the photosensitive resin composition of Application Example 1 includes the following steps:

[0101] (1). 40 moles of methacrylic acid, 40 moles of benzyl methacrylate, 10 moles of hydroxyethyl methacrylate and 10 moles of 2-[4-(1-methyl-1-phenylethyl)phenoxy]ethyl acrylate were copolymerized at 80 °C for 5 hours to obtain alkali-soluble resin A (weight average molecular weight of 10000 g / mol and acid value of 90 mg KOH / g).

[0102] (2) 60 g of epoxy compound (manufacturer: DIC, model: N740, epoxy equivalent: 181 g / equivalent), 15 g of acrylic acid, 200 g of PGMEA, 2.5 g of 1-methylimidazole, and 0.15 g of p-methoxyphenol were reacted at 100 °C for 10 hours to obtain an epoxy acrylate solution (acid value below 5 mg KOH / g). Then, 25 parts by weight of this epoxy acrylate solution and 2.5 parts by weight of tetrahydrophthalic anhydride (THPA) were reacted at 80 °C for 4 hours to obtain alkali-soluble resin B (weight-average molecular weight 8000 g / mol, acid value 100 mg KOH / g).

[0103] (3) 25 parts by weight of the alkali-soluble resin B, 6 parts by weight of the alkali-soluble resin A, 30 parts by weight of dipentaerythritol hexaacrylate, 6 parts by weight of the oxime ester compound of formula I-1 of Example 1, 260 parts by weight of black pigment and 500 parts by weight of solvent (composed of 100 parts by weight of ethyl 3-ethoxypropionate and 400 parts by weight of PGMEA) were uniformly mixed to prepare the photosensitive resin composition of Application Example 1.

[0104] [Refer to Examples 1 and 2] Photosensitive resin composition

[0105] The photosensitive resin compositions of Reference Examples 1 and 2 differ from the photosensitive resin composition of Application Example 1 only in that Reference Examples 1 and 2 use the following oxime ester compounds as photoinitiators:

[0106]

[0107] [Property Evaluation of Photosensitive Resin Compositions]

[0108] Cloud-like defect detection:

[0109] Corresponding to Example 1 and Reference Examples 1 to 2, the photosensitive resin compositions were subjected to the following moiré defect detection: The photosensitive resin composition was coated onto a substrate and dried at 100°C for 1 minute to form a 1.5 μm thick coating. After the coating cooled to room temperature, it was exposed with an I-line. Then, the exposed coating was developed at 24°C for 40 seconds using a 1 wt% KOH aqueous solution to form a patterned coating. The patterned coating was then subjected to high-pressure cleaning for 30 seconds using a high-pressure jet cleaner, followed by hard baking at 230°C for 20 minutes to form a black photoresist. The moiré defects of the black photoresist were visually inspected under yellow light.

[0110] Table 2

[0111]

[0112] Referring to Table 2, the black photoresist formed from the photosensitive resin compositions of Reference Examples 1 and 2 has moiré defects, while the black photoresist formed from the photosensitive resin composition of Application Example 1 has almost no visible moiré defects, proving that the photosensitive resin composition of the present invention has better film-forming properties, developability and photosensitivity.

[0113] The above description is merely an embodiment of the present invention and should not be construed as limiting the scope of the invention. Any simple equivalent changes and modifications made based on the claims and description of the present invention shall still fall within the scope of this application.

Claims

1. A photosensitive resin composition comprising: Alkali-soluble resins; Polymerizable monomers, unlike the alkali-soluble resin; and Photoinitiators include at least one oxime ester compound represented by Formula I: [Formula I] In equation I, R 1 To R 4 Each of the C1 to C1 represents an independent value. 20 Straight-chain alkyl, C3 to C 20 Branched alkyl groups, C2 to C 20 Straight-chain alkenyl, C4 to C 20 Branched alkenyl, cycloalkyl, or aromatic groups, wherein, The cycloalkyl group and the aromatic group are either unsubstituted or any hydrogen atom contained therein is replaced by the aforementioned alkyl or alkenyl group. R 5 Indicates hydrogen, halogen, nitro, cyano, C1 to C 20 Straight-chain alkyl, C3 to C 20 Branched alkyl, cycloalkyl, or aromatic groups, wherein the cycloalkyl and aromatic groups are unsubstituted or any one of the hydrogen atoms contained therein is replaced by the aforementioned alkyl group. R 6 Indicates hydrogen, C1 to C 20 Straight-chain alkyl, C3 to C 20 Branched alkyl groups, C2 to C 20 Straight-chain alkenyl, C4 to C 20 Branched alkenyl, cycloalkyl, or aromatic groups, wherein the cycloalkyl or aromatic group is unsubstituted or any one of the hydrogen atoms contained therein is replaced by the aforementioned alkyl or alkenyl group. The above R 1 To R 6 The indicated group contains any −CH2− that is either unsubstituted or replaced by a group selected from the group consisting of: −O−, −S−, −NH−, −C=O−, −O(C=O)−, −(C=O)O−, −NH(C=O)−, and −(C=O)NH−, and adjacent −CH2− cannot be replaced by the above groups simultaneously. R 7 This indicates a bridged ring group or a group having a bridged ring group, where "a group having a bridged ring group" does not include "bridged ring group".

2. The photosensitive resin composition of claim 1, wherein, In formula I, R 7 Represents −L 1 -R 7’ , among which, the L 1 Indicates single bond, C1 to C 20 Straight-chain alkylene, C3 to C 20 Branched alkylene or C4 to C5 20 (cycloalkylalkyl) and the R 7’ express , , , , , , , , , , , , , or .

3. The photosensitive resin composition according to claim 2, wherein, The L 1 It represents a single bond, a C1 to C3 straight-chain alkylene group, or a C3 to C5 branched alkylene group, and the R 7’ express , , , , or .

4. The photosensitive resin composition of claim 1, wherein, In formula I, R 1 To R 4 Each independently represents a C1 to C8 straight-chain alkyl group, or a C3 to C8 straight-chain alkyl group. 10 Branched alkyl or C3 to C6 cycloalkyl, R 5 It represents hydrogen, cyano, C1 to C8 straight-chain alkyl or C3 to C7 cycloalkyl, and R 6 Represents hydrogen, C1 to C8 straight-chain alkyl or phenyl, and the above R 1 To R 6 The represented group contains any −CH2− that is either unsubstituted or replaced by a group selected from the group consisting of −C=O−, −O(C=O)− and −(C=O)O−, and adjacent −CH2− cannot be replaced by the above groups simultaneously.

5. The photosensitive resin composition of claim 4, wherein, In equation I, R 1 and R 2 Each independently represents a C1 to C2 straight-chain alkyl group, R 3 and R 4 Each independently represents a C1 to C5 straight-chain alkyl group or a C3 to C5 straight-chain alkyl group. 10 Branched alkyl groups, R 5 It represents hydrogen, cyano, C1 to C3 straight-chain alkyl or C7 cycloalkyl, and R 6 It represents hydrogen, CH3, or phenyl.

6. The photosensitive resin composition of claim 1, wherein, The solid content of the photosensitive resin composition is 100% by weight, and the content of the oxime ester compound ranges from 1% by weight to 30% by weight.

7. The photosensitive resin composition of claim 1, wherein, The solid content of the photosensitive resin composition is 100% by weight, and the content of the alkali-soluble resin ranges from 5% by weight to 60% by weight.

8. The photosensitive resin composition of claim 1, wherein, The solid content of the photosensitive resin composition is 100% by weight, and the content of the polymerizable monomer ranges from 5% by weight to 60% by weight.

9. An oxime ester compound, as shown in Formula I: [Formula I] In equation I, R 1 To R 4 Each of the C1 to C1 represents an independent value. 20 Straight-chain alkyl, C3 to C 20 Branched alkyl, C4 to C 20 cycloalkylalkyl, C2 to C 20 Straight-chain alkenyl, C4 to C 20 Branched alkenyl, cycloalkyl, or aromatic groups, wherein, The cycloalkyl group and the aromatic group are either unsubstituted or any hydrogen atom contained therein is replaced by the aforementioned alkyl or alkenyl group; R 5 Indicates hydrogen, halogen, nitro, cyano, C1 to C 20 Straight-chain alkyl, C3 to C 20 Branched alkyl, cycloalkyl, or aromatic group, wherein the cycloalkyl and aromatic group are unsubstituted or any one of the hydrogen atoms contained therein is replaced by the aforementioned alkyl group; R 6 Indicates hydrogen, C1 to C 20 Straight-chain alkyl, C3 to C 20 Branched alkyl groups, C2 to C 20 Straight-chain alkenyl, C4 to C 20 Branched alkenyl, cycloalkyl, or aromatic groups, wherein the cycloalkyl and aromatic groups are unsubstituted or any one of the hydrogen atoms contained therein is replaced by the aforementioned alkyl or alkenyl groups; The above R 1 To R 6 The indicated group contains any −CH2− that is either unsubstituted or replaced by a group selected from the group consisting of: −O−, −S−, −NH−, −C=O−, −O(C=O)−, −(C=O)O−, −NH(C=O)−, and −(C=O)NH−, and adjacent −CH2− cannot be replaced by the above groups simultaneously; and R 7 This indicates a bridged ring group or a group having a bridged ring group, where "a group having a bridged ring group" does not include "bridged ring group".

10. The oxime ester compound of claim 9, wherein, In formula I, R 7 Represents −L 1 -R 7’ , among which, the L 1 Indicates single bond, C1 to C 20 Straight-chain alkylene, C3 to C 20 Branched alkylene or C4 to C5 20 (cycloalkylalkyl) and the R 7’ express , , , , , , , , , , , , , or .

11. The oxime ester compound of claim 10, wherein, The L 1 It represents a single bond, a C1 to C3 straight-chain alkylene group, or a C3 to C5 branched alkylene group, and the R 7’ express , , , , or .

12. The oxime ester compound of claim 9, wherein, In formula I, R 1 To R 4 Each independently represents a C1 to C8 straight-chain alkyl group, or a C3 to C8 straight-chain alkyl group. 10 Branched alkyl or C3 to C6 cycloalkyl, R 5 It represents hydrogen, cyano, C1 to C8 straight-chain alkyl or C3 to C7 cycloalkyl, and R 6 Represents hydrogen, C1 to C8 straight-chain alkyl or phenyl, and the above R 1 To R 6 The represented group contains any −CH2− that is either unsubstituted or replaced by a group selected from the group consisting of −C=O−, −O(C=O)− and −(C=O)O−, and adjacent −CH2− cannot be replaced by the above groups simultaneously.

13. The oxime ester compound of claim 12, wherein, In equation I, R 1 and R 2 Each independently represents a C1 to C2 straight-chain alkyl group, R 3 and R 4 Each independently represents a C1 to C5 straight-chain alkyl group or a C3 to C5 straight-chain alkyl group. 10 Branched alkyl groups, R 5 It represents hydrogen, cyano, C1 to C3 straight-chain alkyl or C7 cycloalkyl, and R 6 It represents hydrogen, CH3, or phenyl.

14. Use of the photosensitive resin composition according to any one of claims 1 to 8, including its application in the preparation of photoresists, colored photoresists, or photoresists for semiconductors.

15. A display device comprising a colored photoresist formed from the photosensitive resin composition as described in any one of claims 1 to 8.

16. A semiconductor device comprising a semiconductor photoresist formed from a photosensitive resin composition as described in any one of claims 1 to 8.

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