TWI850579B - Photosensitive resin composition and use thereof, display device, semiconductor device - Google Patents

Abstract

A photosensitive resin composition comprises an alkali-soluble resin, a polymerizable monomer different from the alkali-soluble resin, and a photoinitiator including 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 generally used to prepare photosensitive resin compositions, and can make the photosensitive resin composition have good film-forming properties, developing properties and photosensitivity. The photosensitive resin composition is suitable for use in preparing photocurable materials such as semiconductor photoresists, colored photoresists, and photospacers.

Description

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

The present invention relates to a photosensitive resin composition, in particular to a photosensitive resin composition containing oxime ester compounds and its application.

Oxime ester compounds are widely used as photoinitiators due to their excellent photosensitivity and are applied in the preparation of photocurable materials for optoelectronic components such as RGB color photoresists, black matrix photoresists, photospacers, and semiconductor photoresists.

The Republic of China patent publication TW 201140240A discloses a photopolymerization initiator represented by the following general formula:

wherein ^R1 to ^R11 each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring atoms, a substituted or unsubstituted cycloalkenyl group having 4 to 20 carbon atoms, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyloxy group having 2 to 20 carbon atoms, a substituted or unsubstituted wherein the present invention is an alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms forming a ring, or a substituted or unsubstituted heterocyclic group having 3 to 14 ring atoms; Ar represents a substituted or unsubstituted aryl group having 6 to 14 carbon atoms forming a ring, or a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms forming a ring; 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' is connected to R ³ to form a ring together with the nitrogen atom).

As the requirements for the properties of various optoelectronic components increase, the solubility and thermal stability of oxime ester compounds as photoinitiators, as well as the film-forming properties, developing properties, and sensitivity of photosensitive resin compositions containing oxime ester compounds, are also required to be improved. Therefore, oxime ester compounds still need to be further improved to meet the subsequent application requirements of various optoelectronic components.

Therefore, the first purpose of the present invention is to provide a photosensitive resin composition.

Therefore, the photosensitive resin composition of the present invention 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:

In the formula I, ^R1 to ^R4 each independently represents a _C1 to _C20 straight chain alkyl group, a _C3 to _C20 branched chain alkyl group, a _C2 to _C20 straight chain alkenyl group, a _C4 to _C20 branched chain alkenyl group, a cycloalkyl group or an aromatic group, wherein the cycloalkyl group and the aromatic group are unsubstituted or any hydrogen atom contained therein is substituted by the aforementioned alkyl group or alkenyl group, ^R5 represents hydrogen, a halogen, a nitro group, a cyano group, a _C1 to _C20 straight chain alkyl group, a _C3 to _C20 branched chain alkyl group, a cycloalkyl group or an aromatic group, wherein the cycloalkyl group and the aromatic group are unsubstituted or any hydrogen atom contained therein is substituted by the aforementioned alkyl group, R6 represents hydrogen, a _C1 to _C20 straight chain alkyl group, a C3 to _C20 branched chain alkyl group, a _C2 to C20 straight chain alkyl group, a C4 to C20 branched chain alkyl group, a cycloalkyl group or an aromatic group, wherein the cycloalkyl group and the aromatic ^group _are unsubstituted or any hydrogen atom contained therein is substituted by the aforementioned alkyl group, _R1 to R6 _are 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} may not be substituted by the above substituents at the same time; and ^R7 is a bridged cyclic group or a derivative having a bridged cyclic ^group .

Therefore, the second purpose of the present invention is to provide an oxime ester compound.

Therefore, the oxime ester compound of the present invention is represented by Formula I:

In the formula I, ^R1 to ^R4 each independently represents a _C1 to _C20 straight chain alkyl group, a _C3 to _C20 branched chain alkyl group, a _C2 to _C20 straight chain alkenyl group, a _C4 to _C20 branched chain alkenyl group, a cycloalkyl group or an aromatic group, wherein the cycloalkyl group and the aromatic group are unsubstituted or any hydrogen atom contained therein is substituted by the aforementioned alkyl group or alkenyl group; ^R5 represents hydrogen, a halogen, a nitro group, a cyano group, a _C1 to _C20 straight chain alkyl group, a _C3 to _C20 branched chain alkyl group, a cycloalkyl group or an aromatic group, wherein the cycloalkyl group and the aromatic group are unsubstituted or any hydrogen atom contained therein is substituted by the aforementioned alkyl group; R6 represents hydrogen, a _C1 to C20 straight chain alkyl group, a C3 to C20 branched chain alkyl group, a C2 to _C20 straight chain alkyl group, a C2 to C20 branched chain alkyl group, a _C4 to _C20 branched chain alkyl group, a ^cycloalkyl group or an aromatic group, wherein the _cycloalkyl group and the aromatic group are unsubstituted or any hydrogen atom contained therein is substituted by the aforementioned alkyl group; _R1 to R6 represent a straight-chain alkenyl group, a _C4 to _C20 branched alkenyl group, a cycloalkyl group or an aromatic group, wherein the cycloalkyl group and the aromatic group are unsubstituted or any hydrogen atom contained therein is substituted by the aforementioned alkyl group or alkenyl group; any _-CH2- contained in the groups represented by the aforementioned ^R1 to ^R6 is unsubstituted or substituted by a substituent 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 may not be substituted by the aforementioned substituents at the same time; and ^R7 represents a bridged cyclic group or a derivative having a bridged cyclic group.

Therefore, the third purpose of the present invention is to provide a use of the photosensitive resin composition as described above.

Therefore, the uses of the photosensitive resin composition described above in the present invention include application in the preparation of photospacers, colored photoresists or semiconductor photoresists.

Therefore, the fourth purpose of the present invention is to provide a display device.

Therefore, the display device of the present invention includes a colored photoresist formed by the photosensitive resin composition as described above.

Therefore, the fifth purpose of the present invention is to provide a semiconductor device.

Therefore, the semiconductor device of the present invention includes a semiconductor photoresist formed by the photosensitive resin composition as described above.

The efficacy of the present invention is that the molecular structure of the oxime ester compound of the present invention includes a carbazole group as the main skeleton, two substituents including an oxime ester group, and a bridged ring group or a derivative having a bridged ring group, so that the oxime ester compound has high thermal stability and good solubility in solvents generally used to prepare photosensitive resin compositions, and is therefore particularly suitable as a photoinitiator for photosensitive resin compositions.

Another effect of the present invention is that the photosensitive resin composition containing the above-mentioned oxime ester compound has high photosensitivity and is suitable for use in preparing photocurable materials such as semiconductor photoresists, colored photoresists, and photospacers, and is particularly suitable for use in preparing black matrix photoresists. The photosensitive resin composition has good film-forming and developing properties, thereby preventing the display device from having mura defects. In addition, since the oxime ester compound has high thermal stability, the photosensitive resin composition also has good thermal stability.

The term "(meth)acrylate" in this article refers to methacrylate and/or acrylate.

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

The type of the alkali-soluble resin is not particularly limited, and can be any alkali-soluble resin known in the field of photocurable material technology, and can be flexibly selected by those familiar with the art of photocurable material technology according to the subsequent practical application of the photosensitive resin composition. In some embodiments of the present invention, the alkali-soluble resin is selected from one or more of (meth)acrylate resins, novolac resins, epoxy resins, polyvinylphenol resins, and carboxyl-containing urethane resins. Among them, the (meth)acrylate resins are, for example, but not limited to, one or more of carboxyl-containing (meth)acrylate resins, hydroxyl-containing (meth)acrylate resins, and epoxy-containing (meth)acrylate resins. The novolac resin is, for example, but not limited to, a novolac resin containing a carboxyl group. The epoxy resin is, for example, but not limited to, a carboxyl epoxy resin. Preferably, 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, so that the photosensitive resin composition has better developing properties; more preferably, the content of the alkali-soluble resin ranges from 10% by weight to 50% by weight; most preferably, the content of the alkali-soluble resin ranges from 12% by weight to 30% by weight.

The polymerizable monomer is different from the alkali-soluble resin. The type of the polymerizable monomer is not particularly limited and can be any polymerizable monomer known in the field of photocurable material technology. It can be flexibly selected by a person familiar with the technical field of photocurable material technology according to the subsequent practical application of the photosensitive resin composition. In some embodiments of the present invention, the polymerizable monomer is selected from one or more of a polymerizable monomer containing an epoxy group, a polymerizable monomer containing at least one ethylenic unsaturated bond, and a polymerizable monomer containing an epoxy group and an ethylenic unsaturated bond. Among them, the polymerizable monomer containing an epoxy group is, for example, but not limited to, epoxybisphenol fluorene, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, etc. The polymerizable monomer containing epoxy group and ethylenic unsaturated bond includes, but is not limited to, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ether di(meth)acrylate, glycerol polyglycidyl ether poly(meth)acrylate, 1,2-epoxy-4-vinylcyclohexane, etc. The polymerizable monomer containing at least one ethylenic unsaturated bond is one or more selected from compounds containing one vinyl group and compounds containing two or more vinyl groups. The compound containing one vinyl group includes, but is not limited to, (meth)acrylate compounds, (meth)acrylamide compounds, or hydroxy (meth)acrylate compounds. 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). Preferably, the solid content of the photosensitive resin composition is 100% by weight, and the content of the polymerizable monomer ranges from 5% to 60% by weight, so that the photosensitive resin composition has better curability; more preferably, the content of the polymerizable monomer ranges from 10% to 50% by weight; most preferably, the content of the polymerizable monomer ranges from 12% to 30% by weight.

The photoinitiator comprises at least one oxime ester compound represented by formula I:

In the formula I, ^R1 to ^R4 each independently represents a _C1 to _C20 straight chain alkyl group, a _C3 to _C20 branched chain alkyl group, a _C2 to _C20 straight chain alkenyl group, a _C4 to _C20 branched chain alkenyl group, a cycloalkyl group or an aromatic group, wherein the cycloalkyl group and the aromatic group are unsubstituted or any hydrogen atom contained therein is substituted by the aforementioned straight chain alkyl group, branched chain alkyl group, straight chain alkenyl group or branched chain alkenyl group. Preferably, ^R1 to ^R4 each independently represents a _C1 to _C8 straight chain alkyl group, a _C3 to _C10 branched chain alkyl group or a _C3 to _C6 cycloalkyl group. More preferably, ^R1 and ^R2 each independently represent a _C1 to _C2 straight chain alkyl group, and ^R3 and ^R4 each independently represent a _C1 to _C5 straight chain alkyl group or a _C3 to _C10 branched chain alkyl group.

R ⁵ represents hydrogen, halogen, nitro, cyano, C ₁ to C ₂₀ straight chain alkyl, C ₃ to C ₂₀ branched chain alkyl, cycloalkyl or aromatic group, wherein the cycloalkyl and aromatic group are unsubstituted or any hydrogen atom contained therein is substituted by the aforementioned straight chain alkyl or branched chain alkyl. Preferably, R ⁵ represents hydrogen, cyano, C ₁ to C ₈ straight chain alkyl or C ₃ to C ₇ cycloalkyl. More preferably, R ⁵ represents hydrogen, cyano, C ₁ to C ₃ straight chain alkyl or C ₇ cycloalkyl.

R ⁶ represents hydrogen, C ₁ to C ₂₀ straight chain alkyl, C ₃ to C ₂₀ branched chain alkyl, C ₂ to C ₂₀ straight chain alkenyl, C ₄ to C ₂₀ branched chain alkenyl, cycloalkyl or aromatic group, wherein the cycloalkyl and aromatic group are unsubstituted or any hydrogen atom contained therein is substituted by the aforementioned straight chain alkyl, branched chain alkyl, straight chain alkenyl or branched chain alkenyl. Preferably, R ⁶ represents hydrogen, C ₁ to C ₈ straight chain alkyl or phenyl. More preferably, R ⁶ represents hydrogen, CH ₃ or phenyl.

Any -CH ₂ - contained in the groups represented by R ¹ to R ⁶ is unsubstituted or substituted with a substituent 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 -CH ₂ - groups may not be substituted with the above substituents at the same time. Preferably, any -CH ₂ - contained in the groups represented by R ¹ to R ⁶ is unsubstituted or substituted with a substituent selected from the group consisting of -C=O-, -O(C=O)- and -(C=O)O-, and adjacent -CH ₂ - groups may not be substituted with the above substituents at the same time.

In the above ^R1 to ^R6 , the carbon number of the cycloalkyl group when it is unsubstituted is, for example, but not limited to, 3 to 10. The specific embodiment of the cycloalkyl group when it is unsubstituted is, for example, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. The carbon number of the aryl group when it is unsubstituted is, for example, but not limited to, 5 to 10. The specific embodiment of the aryl group when it is unsubstituted is, for example, but not limited to, phenyl, naphthyl, etc. It should be noted that when the cycloalkyl group and the aryl group are substituted, in addition to any hydrogen atom contained therein being substituted by the aforementioned straight-chain alkyl group, branched-chain alkyl group, straight-chain alkenyl group or branched-chain alkenyl group, they may also be substituted by halogen, alkynyl, aryl, cycloalkyl or heterocyclic group.

、

、

、

、

或

。更佳地，該L¹表示單鍵、C₁至C₃直鏈伸烷基或C₃至C₅支鏈伸烷基，該R^7’表示

、

、

、

、

或

R ⁷ represents a bridged cyclic group or a derivative having a bridged cyclic group. Preferably, R ⁷ represents -L ¹ -R ^7' , wherein L ¹ represents a single bond, a C ₁ to C ₂₀ straight chain alkyl group, a C ₃ to C ₂₀ branched chain alkyl group or a C ₄ to C ₂₀ (cycloalkylalkyl) group, and R ^7' represents

,

,

,

,

or

More preferably, the L ¹ represents a single bond, a C ₁ to C ₃ straight chain alkyl group or a C ₃ to C ₅ branched chain alkyl group, and the R ^7' represents

,

,

,

,

or

Preferably, the oxime ester compound represented by formula I is one or more selected from the oxime ester compounds represented by formula I-1 to formula I-15.

The common preparation method of the oxime ester compound represented by Formula I is as follows, and the specific synthesis conditions can be flexibly selected and adjusted according to conventional organic synthesis methods:

Preferably, the solid content of the photosensitive resin composition is 100 weight percent, and the content of the oxime ester compound represented by formula I ranges from 1 weight percent to 30 weight percent, so that the photosensitive resin composition has better film-forming and curing properties; more preferably, the content of the oxime ester compound represented by formula I ranges from 2 weight percent to 20 weight percent; most preferably, the content of the oxime ester compound represented by formula I ranges from 5 weight percent to 15 weight percent.

The photosensitive resin composition of the present invention may optionally contain other reagents, such as but not limited to dispersants, pigments, solvents, coupling agents, surfactants, coating enhancers, developer modifiers, ultraviolet absorbers, antioxidants, etc.

The photosensitive resin composition of the present invention can be used in the preparation of photoresists, colored photoresists, photospacers and other photocurable materials for semiconductors.

The display device of the present invention includes a colored photoresist formed by the photosensitive resin composition. The colored photoresist is, for example, a black matrix photoresist or an RGB color photoresist.

The semiconductor device of the present invention includes a semiconductor photoresist formed by the photosensitive resin composition.

The present invention will be further described with reference to the following embodiments, but it should be understood that the embodiments are only for illustrative purposes and should not be interpreted as limitations on the implementation of the present invention.

[Example 1] Oxime ester compound represented by formula I-1

The oxime ester compound represented by formula I-1 is synthesized according to the following reaction route:

(1) In an ice bath, 16.7 g of carbazole and 200 ml of dichloromethane were poured into a three-necked flask, 33.33 g of aluminum chloride was added to the three-necked flask and stirred for 30 minutes, 24.5 g of butyryl chloride was slowly dripped into the three-necked flask and reacted at room temperature for 2 hours, and then ice water was poured into the three-necked flask to terminate the reaction to obtain a reaction product. The reaction product was extracted with dichloromethane and the organic layer was collected. Then, the organic layer was first neutralized with a 5 wt% sodium bicarbonate aqueous solution, then washed with water and saturated brine, then dehydrated with anhydrous magnesium sulfate, and finally concentrated to obtain a crude product. The crude product was purified by column chromatography [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%).

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

The molecular structure of compound 1a was analyzed by nuclear magnetic resonance spectrometer (Bruker Avance III HD 400 MHz): ¹ H-NMR (CDCl ₃ , 400 MHz), δ (ppm): 8.772 (2H, d, J=1.2 Hz), 8.633 (1H, s), 8.141-8.117 (2H, m), 7.478 (2H, d, J=8.4 Hz), 3.084 (4H, t, J=7.2 Hz), 1.871-1.797 (4H, m), 1.054 (6H, t, J=7.6 Hz).

(2) 30.7 g of the 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 bottle at room temperature, and the mixture in the reaction bottle was reacted at 50°C for 6 hours to obtain a reaction product. The reaction product was poured into water, then extracted with ethyl acetate and the organic layer was collected. The organic layer was then washed with water and saturated brine, then dehydrated with anhydrous magnesium sulfate, and finally concentrated to obtain a 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%).

The molecular weight of compound 1b was analyzed by mass spectrometry (Thermo Scientific TSQ Altis), and the result was MS (m/z): 528.4 (M+H) ⁺ .

The molecular structure of compound 1b was analyzed by nuclear magnetic resonance spectrometer: ¹ H-NMR (CDCl ₃ , 400 MHz), δ (ppm): 8.772 (2H, d, J=1.2 Hz), 8.171-8.145 (2H, m), 7.480 (2H, d, J=8.8 Hz), 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=7.2 Hz).

(3) Add 52.8 g of the compound 1b, 200 ml of tetrahydrofuran and 20.3 g of concentrated hydrochloric acid to a reaction bottle in an ice bath environment, then slowly drip 29.3 g of isoamyl nitrite into the reaction bottle and react in an ice bath environment to obtain a reaction product. The reaction product is first neutralized to neutrality 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 is collected. The organic layer is washed with water and saturated saline water, then dehydrated with anhydrous magnesium sulfate, and finally concentrated to obtain a 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 = 1:3] to obtain 23.4 g of compound 1c (yield 40%).

The molecular weight of compound 1c was analyzed by mass spectrometry (Thermo Scientific TSQ Altis), and the result was MS (m/z): 586.4 (M+H) ⁺ .

The molecular structure of compound 1c was analyzed by nuclear magnetic resonance spectrometer: ¹ H-NMR (CDCl ₃ , 400 MHz), δ (ppm): 8.954 (2H, s), 8.563 (2H, s), 8.030-8.004 (2H, m), 7.236 (2H, d, J=8.8 Hz), 4.526- 4.472 (1H, m), 4.200-4.141 (1H, m), 2.990-2.900 (1H, m), 2.767 (4H, q, J=7.6 Hz), 2.115 (3H, s), 1.968 (6H, s), 1.610 (6H, s), 1.148 (6H, t, J=7.6 Hz), 1.063 (3H, d, J=6.8 Hz).

(4). Add 23.4 g of the compound 1c, 80 ml of ethyl acetate and 12.3 g of acetic anhydride to a reaction bottle in an ice bath and react to obtain a reaction product. The reaction product was first neutralized with a saturated potassium carbonate aqueous solution to neutrality, then extracted with ethyl acetate and the organic layer was collected. The organic layer was washed with water and saturated salt water, then dehydrated with anhydrous magnesium sulfate, and finally concentrated to obtain a 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 = 1:3] to obtain 18.7 g of compound 1d, which is the oxime ester compound shown in formula I-1 (yield 70%).

The molecular weight of compound 1d was analyzed by mass spectrometry (Thermo Scientific TSQ Altis), and the result was MS (m/z): 692.3 (M+Na) ⁺ .

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

[Comparative Example 1] Oxime ester compounds

(購自於常州強力公司，品名TR-PBG-345)。 The structure of the oxime ester compound of Comparative Example 1 is as follows:

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

[Comparative Example 2] Oxime ester compounds

The structure of the oxime ester compound of Comparative Example 2 is as follows:

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

[Comparative Example 3] Oxime ester compounds

(為專利公開號WO 2008078678A1公開的化合物No.10)。 The structure of the oxime ester compound of Comparative Example 3 is as follows:

(Compound No. 10 disclosed in Patent Publication No. WO 2008078678A1).

[Evaluation of properties of oxime ester compounds]

Solubility:

The oxime ester compounds of Example 1 and Comparative Examples 1 to 3 were subjected to the following solubility tests: In an environment of 25°C, the oxime ester compounds were continuously added to 10.0 grams of propylene glycol methyl ether acetate (PGMEA) while stirring until the oxime ester compounds could not be dissolved in PGMEA. The amount of oxime ester compounds at this time was recorded as the upper limit of solubility and was substituted into the following formula to calculate the solubility: Solubility (wt%) = upper limit of solubility of oxime ester compounds ÷ (upper limit of solubility of oxime ester compounds + amount of PGMEA) × 100%.

Thermal stability:

The oxime ester compounds of Example 1 and Comparative Examples 1 to 3 were subjected to the following thermal stability tests: Using a thermogravimetric analyzer (TGA, manufacturer TA instruments, model Q500), the oxime ester compounds were heated from room temperature (25°C) to 110°C in a nitrogen environment, maintained at 110°C for 30 minutes, and then heated from 110°C to 400°C at a heating rate of 10°C/min, and the temperature at which the oxime ester compounds lost 5% of their weight was recorded. The evaluation criteria for the thermal stability of oxime ester compounds are: when the temperature at which 5% weight loss occurs is greater than 230°C, the evaluation is "◎"; when the temperature at which 5% weight loss occurs is between 200°C and 230°C, the evaluation is "○"; when the temperature at which 5% weight loss occurs is less than 200°C, the evaluation is "●". The results are recorded in Table 1.

Referring to the solubility results in Table 1, compared with the oxime ester compounds in Comparative Examples 1 to 3, the oxime ester compound of Formula I-1 in Example 1 has a higher solubility in PGMEA, proving that the oxime ester compound of the present invention has better solubility in solvents.

Referring to the thermal stability results in Table 1, compared with the temperature at which the oxime ester compounds of Comparative Examples 1 to 3 lose 5% of their weight, the temperature at which the oxime ester compound of Formula I-1 in Example 1 loses 5% of its weight is higher, proving that the oxime ester compound of the present invention has better thermal stability. It is worth mentioning that people familiar with the technical field of photocurable materials generally recognize that the thermal stability of photosensitive resin compositions is mainly determined by the thermal stability of photoinitiators. Therefore, since the oxime ester compounds of the present invention have better thermal stability, it can be seen that the photosensitive resin composition of the present invention should also have better thermal stability.

[Application 1] Photosensitive resin composition

The photosensitive resin composition of Application Example 1 uses the oxime ester compound of Formula I-1 of Example 1 as a photoinitiator. The preparation method of the photosensitive resin composition of Application Example 1 includes the following steps:

(1). 40 mol of methacrylic acid, 40 mol of benzyl methacrylate, 10 mol of hydroxyethyl methacrylate and 10 mol of 2-[4-(1-methyl-1-phenylethyl)phenoxy]ethyl acrylate were copolymerized at 80°C for 5 hours to obtain an alkali-soluble resin A (weight average molecular weight of 10,000, acid value of 90 mg KOH/g).

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

(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.

[Reference Examples 1 to 2] Photosensitive resin composition

The difference between the photosensitive resin compositions of Reference Examples 1 and 2 and Example 1 is that Reference Examples 1 and 2 respectively use the following oxime ester compounds as photoinitiators:

[Evaluation of properties of photosensitive resin compositions]

Mura defect detection:

The photosensitive resin compositions of Application Example 1 and Reference Examples 1 to 2 were subjected to the following mura defect detection: the photosensitive resin composition was coated on the substrate and dried at 100°C for 1 minute to form a coating with a thickness of 1.5μm. After the coating was cooled to room temperature, the coating was exposed by I-line, and then the exposed coating was developed at 24°C for 40 seconds using a 1wt% KOH aqueous solution to form a patterned coating. The patterned coating was then high-pressure cleaned for 30 seconds using a high-pressure spray cleaning machine, and then hard-baked at 230°C for 20 minutes to form a black photoresist. The mura defects of the black photoresist were visually inspected under yellow light.

Referring to Table 2, compared with the mura defects in the black photoresist formed by the photosensitive resin compositions of Reference Examples 1 and 2, the mura defects in the black photoresist formed by the photosensitive resin composition of Application Example 1 are almost invisible, proving that the photosensitive resin composition of the present invention has better film-forming properties, developing properties and photosensitivity.

However, the above is only an example of the implementation of the present invention, and it cannot be used to limit the scope of the implementation of the present invention. All simple equivalent changes and modifications made according to the scope of the patent application of the present invention and the content of the patent specification are still within the scope of the patent of the present invention.

without.

Claims (14)

A 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:

In the formula I, ^R1 to ^R4 each independently represents a _C1 to _C20 straight chain alkyl group, a _C3 to _C20 branched chain alkyl group, a _C2 to _C20 straight chain alkenyl group, a _C4 to _C20 branched chain alkenyl group, a cycloalkyl group or an aromatic group, wherein the cycloalkyl group and the aromatic group are unsubstituted or any hydrogen atom contained therein is substituted by the aforementioned alkyl group or alkenyl group, ^R5 represents hydrogen, a halogen, a nitro group, a cyano group, a _C1 to _C20 straight chain alkyl group, a _C3 to _C20 branched chain alkyl group, a cycloalkyl group or an aromatic group, wherein the cycloalkyl group and the aromatic group are unsubstituted or any hydrogen atom contained therein is substituted by the aforementioned alkyl group, R6 represents hydrogen, a _C1 to _C20 straight chain alkyl group, a C3 to _C20 branched chain alkyl group, a _C2 to C20 straight chain alkyl group, a C4 to C20 branched chain alkyl group, a cycloalkyl group or an aromatic group, wherein the cycloalkyl group and the aromatic ^group _are unsubstituted or any hydrogen atom contained therein is substituted by the aforementioned alkyl group, wherein the _cycloalkyl group and the aromatic group are unsubstituted or any hydrogen atom contained therein is substituted by the aforementioned alkyl group or ^alkenyl group; any _-CH2- contained in the groups represented by the ^{aforementioned} _R1 to _R6 is unsubstituted or substituted by a substituent 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- may not be substituted by the aforementioned substituents at the same time; and R ⁷ represents a bridged ring or a derivative having a bridged ring; wherein, taking the solid content of the photosensitive resin composition as 100 weight %, the content of the oxime ester compound ranges from 1 weight % to 30 weight %, and the content of the alkali-soluble resin ranges from 5 weight % to 60 weight %. The photosensitive resin composition of claim 1, wherein in the formula I, the R ⁷ represents -L ¹ -R ^7' , wherein the L ¹ represents a single bond, a C ₁ to C ₂₀ straight chain alkyl group, a C ₃ to C ₂₀ branched chain alkyl group or a C ₄ to C ₂₀ (cycloalkylalkyl) group, and the R ^7' represents

,

,

,

,

,

The photosensitive resin composition as claimed in claim 2, wherein in the formula I, the L ¹ represents a single bond, a C ₁ to C ₃ straight chain alkyl group or a C ₃ to C ₅ branched chain alkyl group, and the R ^7' represents

,

,

,

,

or

. The photosensitive resin composition as described in claim 1, wherein in the formula I, ^R1 to ^R4 each independently represents a _C1 to _C8 straight chain alkyl group, a _C3 to _C10 branched chain alkyl group or a _C3 to _C6 cycloalkyl group, ^R5 represents hydrogen, cyano, a _C1 to _C8 straight chain alkyl group or a _C3 to _C7 cycloalkyl group, and ^R6 represents hydrogen, a _C1 to _C8 straight chain alkyl group or a phenyl group, any _-CH2- contained in the groups represented by the above ^R1 to ^R6 is unsubstituted or substituted by a substituent selected from the group consisting of: -C=O-, -O(C=O)- and -(C=O)O-, and adjacent _-CH2- groups cannot be substituted by the above substituents at the same time. A photosensitive resin composition as described in claim 4, wherein in formula I, ^R1 and ^R2 each independently represent a _C1 to _C2 straight-chain alkyl group, ^R3 and ^R4 each independently represent a _C1 to _C5 straight-chain alkyl group or a _C3 to _C10 branched alkyl group, ^R5 represents hydrogen, cyano, _C1 to _C3 straight-chain alkyl group or _C7 cycloalkyl group, and ^R6 represents hydrogen, _CH3 or phenyl. The photosensitive resin composition as described in claim 1, wherein the solid content of the photosensitive resin composition is 100 weight %, and the content of the polymerizable monomer ranges from 5 weight % to 60 weight %. An oxime ester compound is represented by formula I:

In the formula I, ^R1 to ^R4 each independently represents a _C1 to _C20 straight chain alkyl group, a _C3 to _C20 branched chain alkyl group, a _C4 to C20 cycloalkylalkyl group, a _C2 to _C20 straight chain alkenyl group, a _C4 to _{C20 branched} chain alkenyl group, a cycloalkyl group or an aromatic group, wherein the cycloalkyl group and the aromatic group are unsubstituted or any hydrogen atom contained therein is substituted by the aforementioned alkyl group or alkenyl group; ^R5 represents hydrogen, a halogen, a nitro group, a cyano group, a _C1 to _C20 straight chain alkyl group, a _C3 to _C20 branched chain alkyl group, a cycloalkyl group or an aromatic group, wherein the cycloalkyl group and the aromatic group are unsubstituted or any hydrogen atom contained therein is substituted by the aforementioned alkyl group; ^R6 represents hydrogen, a _C1 to _C20 straight chain alkyl group, a _C3 to C20 branched chain alkyl group, a cycloalkyl group or an aromatic group, wherein the cycloalkyl group and the aromatic group are unsubstituted or any hydrogen atom contained therein is substituted by the aforementioned alkyl group; The invention further comprises a _C2 to C20 branched alkyl group, a _C2 to _C20 straight-chain alkenyl group, a _C4 to _C20 branched alkenyl group, a cycloalkyl group or an aromatic group, wherein the cycloalkyl group and the aromatic group are unsubstituted or any hydrogen atom contained therein is substituted by the aforementioned alkyl group or alkenyl group; any _-CH2- contained in the groups represented by the aforementioned ^R1 to ^R6 is unsubstituted or substituted by a substituent 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 may not be substituted by the aforementioned substituents at the same time; and ^R7 represents a bridged cyclic group or a derivative having a bridged cyclic group. The oxime ester compound as claimed in claim 7, wherein in the formula I, the R ⁷ represents -L ¹ -R ^7' , wherein the L ¹ represents a single bond, a C ₁ to C ₂₀ straight chain alkyl group, a C ₃ to C ₂₀ branched chain alkyl group or a C ₄ to C ₂₀ (cycloalkylalkyl) group, and the R ^7' represents

The oxime ester compound as claimed in claim 8, wherein in the formula I, the L ¹ represents a single bond, a C ₁ to C ₃ straight chain alkyl group or a C ₃ to C ₅ branched chain alkyl group, and the R ^7' represents

,

,

,

,

or

The oxime ester compound as described in claim 7, wherein in the formula I, ^R1 to ^R4 each independently represents a _C1 to _C8 straight-chain alkyl group, a _C3 to _C10 branched-chain alkyl group or a _C3 to _C6 cycloalkyl group, ^R5 represents hydrogen, cyano, a _C1 to _C8 straight-chain alkyl group or a _C3 to _C7 cycloalkyl group, and ^R6 represents hydrogen, a _C1 to _C8 straight-chain alkyl group or a phenyl group, any _-CH2- contained in the groups represented by the above ^R1 to ^R6 is unsubstituted or substituted by a substituent selected from the group consisting of: -C=O-, -O(C=O)- and -(C=O)O-, and adjacent _-CH2- groups cannot be substituted by the above substituents at the same time. The oxime ester compound as described in claim 10, wherein, in formula I, ^R1 and ^R2 each independently represent a _C1 to _C2 straight-chain alkyl group, ^R3 and ^R4 each independently represent a _C1 to _C5 straight-chain alkyl group or a _C3 to _C10 branched alkyl group, ^R5 represents hydrogen, cyano, _C1 to _C3 straight-chain alkyl group or _C7 cycloalkyl group, and ^R6 represents hydrogen, _CH3 or phenyl. A use of a photosensitive resin composition as described in any one of claims 1 to 6, including application in the preparation of photospacers, colored photoresists or semiconductor photoresists. A display device comprising a colored photoresist formed by a photosensitive resin composition as described in any one of claims 1 to 6. A semiconductor device comprising a semiconductor photoresist formed from a photosensitive resin composition as described in any one of claims 1 to 6.