JP2023026377A - Photosensitive resin composition and apparatus using the same - Google Patents

Abstract

To provide a more excellent photosensitive resin composition.SOLUTION: A photosensitive resin composition includes an alkali-soluble resin, a polymerizable monomer different from the alkali-soluble resin, and a photoinitiator including at least one kind of oxime ester compounds represented by formula I.

Description

TECHNICAL FIELD The present invention relates to a photosensitive resin composition, and more particularly to a photosensitive resin composition containing an oxime ester compound and its application.

Oxime ester compounds are widely used as photoinitiators due to their excellent photosensitivity, and are also used in applications such as RGB color resists, black matrix resists, photospacers, and semiconductors. It has been applied in the production of photocurable materials for optoelectronic device applications, such as photoresists for photovoltaics.

Patent Document 1 discloses a photopolymerization initiator represented by the following chemical formula.

In the formula,
Each of R ¹ -R ¹¹ is independently hydrogen, halogen, substituted or unsubstituted C ₁ -C ₂₀ alkyl group, substituted or unsubstituted C ₂ -C ₂₀ alkenyl group, substituted substituted or unsubstituted C ₃ -C ₁₀ cycloalkyl groups, substituted or unsubstituted C ₄ -C ₂₀ cycloalkenyl groups, hydroxy groups, substituted or unsubstituted C ₁ -C ₂₀ alkoxy groups , substituted or unsubstituted C ₂ -C ₂₀ alkenyloxy groups, substituted or unsubstituted C ₁ -C ₂₀ alkanoyl groups, substituted or unsubstituted C ₂ -C ₂₀ alkenoyl groups, represents a substituted or unsubstituted aryl group having 6 to 14 ring-constituting carbon atoms or a substituted or unsubstituted heterocyclic group having 3 to 14 ring-constituting atoms;
Ar is a substituted or unsubstituted aryl group having 6 to 14 ring-constituting carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 14 ring-constituting atoms represents
W represents a single bond or an oxygen atom,
Z is a single bond, an oxygen atom or >NR ^3′ (R ^3′ represents a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, or is connected to R ³ to form a ring together with a nitrogen atom to do).

With the increasing demand for the properties of various photoelectric devices, the solubility and thermal stability of oxime ester compounds used as photoinitiators, and the film forming properties of photosensitive resin compositions containing oxime ester compounds, Demands on properties such as developability and photosensitivity are also increasing. Therefore, in order to meet the needs of various photoelectric devices in the future, it is necessary to develop better oxime ester compounds.

WO2011/105518

An object of the present invention is to provide an oxime ester compound, a photosensitive resin composition containing the oxime ester compound, and an apparatus using the same.

In order to achieve the above objects, the present invention provides an alkali-soluble resin,
a polymerizable monomer different from the monomer constituting the alkali-soluble resin;
a photoinitiator comprising at least one oxime ester compound of Formula I;

In Formula I above,
Each of R ¹ -R ⁴ is independently a C ₁ -C ₂₀ straight chain alkyl group, a C ₃ -C ₂₀ branched alkyl group, a C ₂ -C ₂₀ straight chain alkenyl group, a C ₃ -C ₂₀ branched alkenyl group group, cycloalkyl group or aryl group, and said cycloalkyl group and said aryl group are unsubstituted or any hydrogen atom is a C ₁ -C ₂₀ linear alkyl group, C ₃ -C ₂₀ branched substituted with an alkyl group, a C ₂ -C ₂₀ straight chain alkenyl group or a C ₃ -C ₂₀ branched alkenyl group,
R ⁵ represents hydrogen, halogen, nitro group, cyan group, C ₁ -C ₂₀ linear alkyl group, C ₃ -C ₂₀ branched alkyl group, cycloalkyl group or aryl group, and the cycloalkyl group and the aryl group is unsubstituted or any hydrogen atom is substituted with a C ₁ -C ₂₀ straight chain alkyl group or a C ₃ -C ₂₀ branched alkyl group;
R ⁶ is hydrogen, C ₁ -C ₂₀ straight chain alkyl group, C ₃ -C ₂₀ branched alkyl group, C ₂ -C ₂₀ straight chain alkenyl group, C ₃ -C ₂₀ branched alkenyl group, cycloalkyl group or represents an aryl group, and the cycloalkyl group and the aryl group are unsubstituted or any hydrogen atom is a C ₁ -C ₂₀ straight chain alkyl group, a C ₃ -C ₂₀ branched alkyl group, a C ₂ - substituted with a _C20 straight chain alkenyl group or a C3 _{- C20} branched alkenyl group;
In the groups represented by R ¹ to R ⁶ , any —CH ₂ — in the structure is not substituted or —O—, —S—, —NH—, —C═O—, —O( C=O)-, -(C=O)O-, -NH(C=O)- and -(C=O)NH-, and , two adjacent —CH ₂ — are not substituted with the substituents at the same time,
Provided is a photosensitive resin composition characterized in that R ⁷ represents a bridging ring group or a derivative having a bridging ring group.

The present invention is also represented by Formula I,

In Formula I above,
Each of R ¹ -R ⁴ is independently a C ₁ -C ₂₀ straight chain alkyl group, a C ₃ -C ₂₀ branched alkyl group, a C ₂ -C ₂₀ straight chain alkenyl group, a C ₃ -C ₂₀ branched alkenyl group group, cycloalkyl group or aryl group, and said cycloalkyl group and said aryl group are unsubstituted or any hydrogen atom is a C ₁ -C ₂₀ linear alkyl group, C ₃ -C ₂₀ branched substituted with an alkyl group, a C ₂ -C ₂₀ straight chain alkenyl group or a C ₃ -C ₂₀ branched alkenyl group,
R ⁵ represents hydrogen, halogen, nitro group, cyan group, C ₁ -C ₂₀ linear alkyl group, C ₃ -C ₂₀ branched alkyl group, cycloalkyl group or aryl group, and the cycloalkyl group and the aryl group is unsubstituted or any hydrogen atom is substituted with a C ₁ -C ₂₀ straight chain alkyl group or a C ₃ -C ₂₀ branched alkyl group;
R ⁶ is hydrogen, C ₁ -C ₂₀ straight chain alkyl group, C ₃ -C ₂₀ branched alkyl group, C ₂ -C ₂₀ straight chain alkenyl group, C ₃ -C ₂₀ branched alkenyl group, cycloalkyl group or represents an aryl group, and the cycloalkyl group and the aryl group are unsubstituted or any hydrogen atom is a C ₁ -C ₂₀ straight chain alkyl group, a C ₃ -C ₂₀ branched alkyl group, a C ₂ - substituted with a _C20 straight chain alkenyl group or a C3 _{- C20} branched alkenyl group;
In the groups represented by R ¹ to R ⁶ , any —CH ₂ — in the structure is not substituted or —O—, —S—, —NH—, —C═O—, —O( C=O)-, -(C=O)O-, -NH(C=O)- and -(C=O)NH-, and , two adjacent —CH ₂ — are not substituted with the substituents at the same time,
Provided is an oxime ester compound characterized in that R ⁷ represents a bridging ring group or a derivative having a bridging ring group.

The present invention also provides a display device comprising a colored resist formed from the above photosensitive resin composition.

The present invention also provides a semiconductor device comprising a semiconductor photoresist formed from the above photosensitive resin composition.

The molecular structure of the oxime ester compound of the present invention includes a carbazole group as a main skeleton, two substituents containing an oxime ester group, and a bridged ring group or a derivative having a bridged ring group. Oxime ester compounds are particularly suitable as photoinitiators for photosensitive resin compositions because they have high thermal stability and good solubility in solvents generally used in the production of photosensitive resin compositions. .

In addition, since the photosensitive resin composition of the present invention containing the oxime ester compound has high photosensitivity, it is suitable for application to the production of photocurable materials such as photoresists for semiconductors, colored resists, and photospacers. and is particularly suitable for application to the production of black matrix resists. Moreover, since the photosensitive resin composition of the present invention has good film formability and developability, it is possible to avoid the occurrence of uneven defects in the display device of the present invention to which it is applied.

Moreover, since the oxime ester compound of the present invention has high thermal stability, the photosensitive resin composition of the present invention also has good thermal stability.

As used herein, the term "(meth)acrylate" refers to acrylates and methacrylates.

As used herein, the term "alkenyl group" refers to a hydrocarbon group having at least one carbon-carbon double bond, i.e., a hydrocarbon group having two carbon-carbon double bonds and a hydrocarbon group having three carbon-carbon double bonds. including hydrocarbon groups with one carbon-carbon double bond.

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

The type of the alkali-soluble resin is not particularly limited, and an alkali-soluble resin known in the technical field of photocurable materials can be used, and a person having ordinary knowledge in the technical field of photocurable materials can make a photosensitive resin composition. It can be selected according to the actual application of the object.

In some embodiments, the alkali-soluble resin is one selected from the group consisting of (meth)acrylate-based resins, novolak-based resins, epoxy resins, polyvinylphenol-based resins, and carboxyl group-containing urethane-based resins. Or a variety is selected.

As the (meth)acrylate resin, for example, one or more of carboxyl group-containing (meth)acrylate resins, hydroxyl group-containing (meth)acrylate resins, and epoxy group-containing (meth)acrylate resins are selected. However, it is not limited to that.

As the novolac resin, for example, a carboxyl group-containing novolac resin is selected, but the resin is not limited thereto.

As the epoxy resin, for example, a carboxyl group-containing epoxy resin is selected, but the epoxy resin is not limited thereto.

In order for the photosensitive resin composition of the present invention to have better development properties, the solid content of the photosensitive resin composition is 100 wt%, and the content of the alkali-soluble resin is 5 wt% to 60 wt%. is preferably in the range of 10 wt % to 50 wt %, more preferably in the range of 12 wt % to 30 wt %.

The polymerizable monomer is different from the monomer constituting the alkali-soluble resin, and the type of the polymerizable monomer is not particularly limited, and is known in the technical field of photocurable materials. Polymerizable monomers can be used and can be selected according to the practical application of the photosensitive resin composition by those having ordinary knowledge in the technical field of photocurable materials.

In some embodiments, the polymerizable monomer comprises an epoxy group-containing polymerizable monomer, a polymerizable monomer containing at least one ethylenically unsaturated bond and an epoxy group and an ethylenically unsaturated bond. One or more kinds are selected from the group consisting of polymerizable monomers containing

Examples of epoxy group-containing polymerizable monomers include bisphenol fluorene epoxy, 3,4-epoxy-1-cyclohexanecarboxylic acid 3,4-epoxycyclohexan-1-ylmethyl (3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, CAS registration number: 2386-87-0), etc., but not limited thereto.

Polymerizable monomers containing an epoxy group and an ethylenically unsaturated bond include, for example, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate. ) acrylate (diethylene glycol diglycidyl ether di(meth)acrylate), phthalic acid diglycidyl ether di(meth)acrylate, glycerol polyglycidyl ether poly(meth)acrylate (meth)acrylate), 4-vinyl-1,2-epoxycyclohexane (1,2-epoxy-4-vinylcyclohexane, CAS number: 106-86-5), etc., but not limited thereto.

Examples of the polymerizable monomer containing at least one ethylenically unsaturated bond include a polymerizable monomer containing one vinyl group and a polymerizable monomer containing two or more vinyl groups. Or a variety is selected, but not limited to that.

Examples of the polymerizable monomer containing one vinyl group include, but are not limited to, (meth)acrylate compounds, (meth)acrylamide compounds, hydroxy group (meth)acrylate compounds, and the like.

Polymerizable monomers containing two or more vinyl groups include, for example, tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate. triacrylate, PETA) or di-pentaerythritol hexaacrylate (DPHA), etc., but not limited thereto.

In order for the photosensitive resin composition of the present invention to have better curability, the solid component of the photosensitive resin composition is 100 wt%, and the content of the polymerizable monomer is 5 wt% to It is preferably in the range of 60 wt%, more preferably in the range of 10 wt% to 50 wt%, even more preferably in the range of 12 wt% to 30 wt%.

The photoinitiator comprises at least one oxime ester compound represented by Formula I.

In Formula I above, each of R ¹ to R ⁴ is independently a C ₁ to C ₂₀ straight chain alkyl group, a C ₃ to C ₂₀ branched alkyl group, a C ₂ to C ₂₀ straight chain alkenyl group, a C ₃ to represents a _C20 branched alkenyl group, a cycloalkyl group or an aryl group, and the cycloalkyl group and the aryl group are unsubstituted or any hydrogen atom is a _C1 - _C20 linear alkyl group, a _C3 ~ _C20 branched alkyl group, _C2 - _C20 straight chain alkenyl group or _C3 - _C20 branched alkenyl group.

In some embodiments, each of said R ¹ through said R ⁴ independently represents a C ₁ -C ₈ straight chain alkyl group, a C ₃ -C ₁₀ branched alkyl group, or a C ₃ -C ₆ cycloalkyl group. show. In some embodiments, each of said R ¹ - said R ² independently represents a C ₁ -C ₂ straight chain alkyl group, and each of said R ³ - said R ⁴ independently represents a C ₁ - It represents a C ₅ straight chain alkyl group or a C ₃ -C ₁₀ branched alkyl group.

In formula I, R ⁵ represents hydrogen, halogen, nitro group, cyan group, C ₁ -C ₂₀ linear alkyl group, C ₃ -C ₂₀ branched alkyl group, cycloalkyl group or aryl group, and The cycloalkyl groups and the aryl groups are unsubstituted or any hydrogen atom is substituted with a C ₁ -C ₂₀ straight chain alkyl group or a C ₃ -C ₂₀ branched alkyl group.

In some embodiments, said R ⁵ represents hydrogen, a cyan group, a C ₁ -C ₈ straight chain alkyl group or a C ₃ -C ₇ cycloalkyl group. In some embodiments, said R ⁵ represents hydrogen, a cyan group, a C ₁ -C ₃ straight chain alkyl group or a C ₇ cycloalkyl group.

In formula I, R ⁶ is hydrogen, C ₁ -C ₂₀ straight chain alkyl group, C ₃ -C ₂₀ branched alkyl group, C ₂ -C ₂₀ straight chain alkenyl group, C ₃ -C ₂₀ branched alkenyl group , represents a cycloalkyl group or an aryl group, and the cycloalkyl group and the aryl group are unsubstituted or any hydrogen atom is a C ₁ to C ₂₀ straight chain alkyl group, a C ₃ to C ₂₀ branched alkyl group. a C ₂ -C ₂₀ straight chain alkenyl group or a C ₃ -C ₂₀ branched alkenyl group;
In some embodiments, said R ⁶ represents hydrogen, a C ₁ -C ₈ straight chain alkyl group or a phenyl group. In some embodiments, said ^R6 represents hydrogen, _CH3 or a phenyl group.

In the groups represented by R ¹ to R ⁶ , any —CH ₂ — in the structure is not substituted or —O—, —S—, —NH—, —C═O—, —O( C=O)-, -(C=O)O-, -NH(C=O)- and -(C=O)NH-, and , two adjacent —CH ₂ — cannot be substituted with said substituents at the same time, so they are not substituted with said substituents at the same time.

In some embodiments, the groups represented by R ¹ through R ⁶ are not substituted at any —CH ₂ — in the structure or —C═O—, —O(C═O)—, and — is substituted with one substituent selected from the group consisting of (C═O)O—, and two adjacent —CH ₂ — are not substituted with the substituent at the same time.

In R ¹ to R ⁶ , the cycloalkyl group, when unsubstituted, has a carbon number within the range of, for example, 3 to 10. Specific embodiments of the unsubstituted cycloalkyl group include, for example, cyclo Examples include, but are not limited to, propyl, cyclobutyl, cyclopentyl, cyclohexyl groups. The aryl group, when unsubstituted, has a carbon number in the range of, for example, 5 to 10. Examples of the unsubstituted aryl group include, but are not limited to, phenyl group, naphthyl group, and the like. do not have.

Said cycloalkyl group and said aryl group, when in a substituted embodiment, any hydrogen atom may _be a C ₁ -C ₂₀ straight chain alkyl group, a C ₃ -C ₂₀ branched alkyl group, _a Any hydrogen atom except substituted by a chain alkenyl group or a C ₃ -C ₂₀ branched alkenyl group (for R ⁵ , a C ₁ -C ₂₀ straight chain alkyl group or a C ₃ -C ₂₀ branched alkyl group) can be substituted by halogen, alkynyl group, aryl group, cycloalkyl group or heterocyclic ring.

^R7 represents a bridging ring group or a derivative having a bridging ring group.

As used herein, the term "bridged ring group" refers to a ring group having a structure in which two or more rings share two atoms that are not directly connected.

In some embodiments, R ⁷ represents -L ¹ -R ^7′ , wherein L ¹ is a single bond, a C ₁ -C ₂₀ straight chain alkylene group, a C ₃ -C ₂₀ branched alkylene group or a C ₄ -C ₂₀ represents a divalent cycloalkylalkyl group, and R ^7′ is

represents

In some embodiments, said L ¹ represents a single bond, a C ₁ -C ₃ straight chain alkylene group or a C ₃ -C ₅ branched alkylene group, and R ^7′ is

represents

In some embodiments, the oxime ester compounds of Formula I are selected from one or more of the oxime ester compounds of Formulas I-1 through I-15 below.

A common method for preparing the oxime ester compound represented by Formula I is shown in the following chemical reaction formula I, and specific synthesis conditions are selected or adjusted as necessary based on general organic synthesis methods. be able to.

In order to make the photosensitive resin composition of the present invention have better film-forming properties and curability, the solid component of the photosensitive resin composition is 100 wt %, and the oxime ester compound represented by the formula I is The content of is preferably in the range of 1 wt% to 30 wt%, more preferably in the range of 2 wt% to 20 wt%, and even more preferably in the range of 5 wt% to 15 wt%.

The photosensitive resin composition of the present invention can optionally further contain other agents, such as dispersants, pigments, solvents, coupling agents, surfactants, coating properties improving They include, but are not limited to, coating improving agents, development modifying agents, UV absorbers, antioxidants, and the like.

The photosensitive resin composition of the present invention can be applied to the field of production of photocurable materials such as photospacers, colored resists, and photoresists for semiconductors.

A display device of the present invention includes a colored resist formed from the photosensitive resin composition of the present invention. Examples of the colored resist include RGB color resists and black matrix resists.

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

Examples of the present invention will be described below. It should be understood that these examples are exemplary and explanatory and should not be construed as limiting the invention.

[Example 1] The oxime ester compound represented by formula I-1 was prepared by the reaction route shown below together with chemical reaction formulas I-1 to I-4. Synthesized.

(1) Charge 16.7 g of carbazole and 200 mL of dichloromethane into a three-necked flask in an ice bath environment, and add 33.33 g of aluminum trichloride into the three-necked flask and stir for 30 minutes. After that, 24.5 g of butanoyl chloride was slowly added dropwise and reacted at room temperature for 2 hours, and ice water was added into the three-necked flask to stop the reaction to obtain the reaction product.

After extracting the reaction product with dichloromethane and collecting the organic layer, the organic layer was neutralized with 5 wt% aqueous sodium bicarbonate solution, washed with water and saturated brine, and dried over anhydrous magnesium sulfate. and finally concentrated to give an intermediate product.

The intermediate product was purified by column chromatography [stationary phase is Merck silica gel 60 (70-230 mesh ASTM), mobile phase is ethyl acetate: n-heptane = 1:4 to 1:2 gradient elution]. was performed to give 18.4 g of compound 1a (60% yield).

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

The molecular structure of the compound 1a was analyzed with a nuclear magnetic resonance apparatus (Bruker Avance III HD 400 MHz), the result was 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 = 8.4Hz), 3.084 (4H , t, J=7.2 Hz), 1.871-1.797 (4H, m), 1.054 (6H, t, J=7.6 Hz).
(2) In a room temperature environment, 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 are put into a flask. After that, the mixture in the flask was reacted at 50° C. for 6 hours to obtain a reaction product.

The reaction product is put into water and extracted with ethyl acetate, and the organic layer is collected, then the organic layer is washed with water and saturated brine, dried over anhydrous magnesium sulfate, and finally concentrated to intermediate. got the product.

The intermediate product was purified by column chromatography [Stationary phase is Merck silica gel 60 (70-230 mesh ASTM), mobile phase is ethyl acetate:n-heptane=1:4] to obtain 26.4 g of compound 1b. obtained (50% yield).

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

The molecular structure of the compound 1b was analyzed with a nuclear magnetic resonance apparatus, and the results were 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=8.8Hz), 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).
(3) Charge 52.8 g of compound 1b, 200 mL of tetrahydrofuran and 20.3 g of concentrated hydrochloric acid into a flask in an ice bath environment, and add 29.3 g of isoamyl nitrite into the three-necked flask. and reacted in an ice bath environment to obtain the reaction product.

After the reaction product was neutralized with saturated aqueous potassium carbonate until neutral, it was concentrated to remove tetrahydrofuran and extracted with 200 mL of ethyl acetate while collecting the organic layer. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and finally concentrated to obtain an intermediate product.

The intermediate 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. obtained (40% yield).

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

The molecular structure of the compound 1c was analyzed with a nuclear magnetic resonance apparatus, and the results were 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=8.8Hz), 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), 1.968 (6H,s ), 1.610 (6H,s), 1.148 (6H,t,J=7.6Hz), 1.063 (3H,d,J=6.8Hz).
(4) In an ice bath environment, 23.4 g of the compound 1c, 80 mL of ethyl acetate, and 12.3 g of acetic anhydride were put into a flask and reacted to obtain a reaction product.

The reaction product was neutralized with a saturated aqueous potassium carbonate solution until neutral, extracted with ethyl acetate, and the organic layer was collected. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and finally concentrated to obtain an intermediate product.

The intermediate product was purified by column chromatography [Stationary phase is Merck silica gel 60 (70-230 mesh ASTM), mobile phase is ethyl acetate: n-heptane = 1:3] to obtain the formula I-1. 18.7 g of compound 1d, which is an oxime ester compound, was obtained (70% yield).

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

The molecular structure of the compound 1d was analyzed with a nuclear magnetic resonance apparatus, and the results were 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=8.8Hz), 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).

[Comparative Example 1] Oxime Ester Compound The oxime ester compound of Comparative Example 1 is represented by the following formula.

[Comparative Example 2] Oxime ester compound The oxime ester compound of Comparative Example 2 is represented by the following formula.

The method for producing an oxime ester compound of Comparative Example 2 is substantially the same as the method for producing an oxime ester compound represented by formula I-1, except that 1-adamantyl methacrylate in step (2) is replaced with cyclohexyl acrylate. The point is that it was changed to lacto (cyclohexyl acrylate).
[Comparative Example 3] Oxime Ester Compound The oxime ester compound of Comparative Example 3 is represented by the following formula.

[Evaluation items for oxime ester compounds]
<Solubility>
The solubility of the oxime ester compounds of Example 1 and Comparative Examples 1 to 3 was measured by the following method.

In an environment of 25 ° C., while stirring, the oxime ester compound was continuously added to 10.0 g of PGMEA until the oxime ester compound could not be dissolved in propylene glycol methyl ether acetate (abbreviated as PGMEA). The amount of the ester compound used was recorded as the upper limit of solubility, and the solubility was calculated by the following formula.
Solubility (wt%) = upper limit of solubility of oxime ester compound / (upper limit of solubility of oxime ester compound + amount of PGMEA used) x 100%
<Thermal stability>
The thermal stability of the oxime ester compounds of Example 1 and Comparative Examples 1 to 3 was measured by the following method.

With a thermogravimetric analyzer (abbreviation TGA, TA instruments, model number: Q500), the oxime ester compound was heated from room temperature (25 ° C.) to 110 ° C. in a nitrogen atmosphere, then maintained at 110 ° C. for 30 minutes, and then heated to 10 ° C. /min, and the temperature at which the weight of the oxime ester compound decreased by 5% was recorded.

The evaluation of the thermal stability of the oxime ester-based compound is "◎" when the temperature exceeds 230 ° C. when the weight decreases by 5%, and when the temperature when the weight decreases by 5% is 200 ° C. to 230 ° C. The results are recorded in Table 1.

The solubility results in Table 1 show that the oxime ester compound represented by formula I-1 of Example 1 has a higher solubility in PGMEA than the oxime ester compounds of Comparative Examples 1 to 3. It was proved that the oxime ester compounds of the invention have better solubility in solvents.

From the results of thermal stability in Table 1, the temperature at which the weight of the oxime ester compound shown in Comparative Examples 1 to 3 decreased by 5% was higher than that of Formula I-1 of Example 1. It was proved that the oxime ester compound of the present invention has better thermal stability because the temperature at which the weight loss of 5% of the oxime ester compound occurs is high.

Also, those of ordinary skill in the art of photocurable materials generally recognize that the thermal stability of a photosensitive resin composition is primarily determined by the thermal stability of the photoinitiator. Therefore, it can be seen that the photosensitive resin composition of the present invention also has excellent thermal stability due to the excellent thermal stability of the oxime ester compound of the present invention.
[Application Example 1] Photosensitive Resin Composition A photosensitive resin composition of Application Example 1 was produced by the following production method using an oxime ester compound represented by Formula I-1 as a photoinitiator.
(1) 40 moles of methyl acrylic acid, 40 moles of benzyl methacrylate, 10 moles of 2-hydroxyethyl methacrylate, and 10 moles of 2-[4-(1 -methyl-1-phenylethyl)phenoxy]ethyl acrylate (2-[4-(1-methyl-1-phenylethyl)phenyl]ethyl acrylate) was subjected to a copolymerization reaction at 80° C. for 5 hours to obtain an alkali-soluble resin A ( A weight average molecular weight of 10000 and an acid value of 90 mgKOH/g) were obtained.

(2) 60 g of an epoxy compound (DIC, model number: N740, epoxy equivalent: 181 g/equivalent), 15 g of acrylic acid, 200 g of PGMEA, 2.5 g of 1-methylimidazole (1-methylimidazole), 0.15 g of 4-methoxyphenol was reacted at 100° C. for 10 hours to obtain an epoxy acrylate solution (acid value of 5 mg KOH/g or less). Then, 25 parts by weight of the epoxy acrylate solution and 2.5 parts by weight of 1,2,3,6-tetrahydrophthalic anhydride (CAS number: 85-43-8 (THPA).
(3) 25 parts by weight of alkali-soluble resin B, 6 parts by weight of alkali-soluble resin A, 30 parts by weight of dipentaerythritol hexaacrylate (DPHA, CAS number: 29570-58-9), 6 parts by weight of an oxime ester compound represented by formula I-1, 260 parts by weight of a black pigment, 500 parts by weight of a solvent (100 parts by weight of ethyl 3-ethoxypropionic acid ethyl) and 400 parts by weight of (constituted by parts by weight of PGMEA) were uniformly mixed to obtain a photosensitive resin composition of Application Example 1.
[Reference Example 1 and Reference Example 2] Photosensitive Resin Composition The method for producing the photosensitive resin composition of Reference Example 1 and Reference Example 2 is substantially the same as the method for producing the photosensitive resin composition of Application Example 1. The difference is that Reference Examples 1 and 2 each used the oxime ester compound shown in Table 2 as a photoinitiator.

[Evaluation items of photosensitive resin composition]
Mura defect inspection:
The photosensitive resin compositions of Application Example 1, Reference Example 1, and Reference Example 2 were inspected for uneven defects by the following method.

After applying the photosensitive resin composition to the substrate, it is dried at 100 ° C. for 1 minute to form a coating film with a thickness of 1.5 μm, and after cooling the coating film to room temperature, it is irradiated with I rays (mercury with a wavelength of 365 nm). The coating film was exposed to a spectral line), and the exposed coating film was developed with an aqueous solution of KOH having a concentration of 1 wt% at 24°C for 40 seconds to form a patterned coating film. The patterned coating film was subjected to high-pressure cleaning for 30 seconds using a jet cleaning machine, and then post-baked at 230° C. for 20 minutes to form a black resist. The black resist was visually inspected for uneven defects under yellow light. The results are shown in Table 3.

As shown in Table 3, the black resists formed from the photosensitive resin compositions of Reference Examples 1 and 2 have significant unevenness defects, whereas the photosensitive properties of Application Example 1 The black resist formed from the resin composition showed almost no uneven defects, proving that the photosensitive resin composition of the present invention has superior film formability, developability and photosensitivity.

Although the embodiments of the present invention have been described above, the present invention is not limited to these, and includes all modifications and equivalent configurations as various configurations included within the spirit and scope of the broadest interpretation. shall be

The photosensitive resin composition of the present invention is suitable for producing photocurable materials such as photospacers, colored resists, and photoresists for semiconductors.

Claims (16)

an alkali-soluble resin;
a polymerizable monomer different from the monomer constituting the alkali-soluble resin;
a photoinitiator comprising at least one oxime ester compound of Formula I;

In Formula I above,
Each of R ¹ -R ⁴ is independently a C ₁ -C ₂₀ straight chain alkyl group, a C ₃ -C ₂₀ branched alkyl group, a C ₂ -C ₂₀ straight chain alkenyl group, a C ₃ -C ₂₀ branched alkenyl group group, cycloalkyl group or aryl group, and said cycloalkyl group and said aryl group are unsubstituted or any hydrogen atom is a C ₁ -C ₂₀ linear alkyl group, C ₃ -C ₂₀ branched substituted with an alkyl group, a C ₂ -C ₂₀ straight chain alkenyl group or a C ₃ -C ₂₀ branched alkenyl group,
R ⁵ represents hydrogen, halogen, nitro group, cyan group, C ₁ -C ₂₀ linear alkyl group, C ₃ -C ₂₀ branched alkyl group, cycloalkyl group or aryl group, and the cycloalkyl group and the aryl group is unsubstituted or any hydrogen atom is substituted with a C ₁ -C ₂₀ straight chain alkyl group or a C ₃ -C ₂₀ branched alkyl group;
R ⁶ is hydrogen, C ₁ -C ₂₀ straight chain alkyl group, C ₃ -C ₂₀ branched alkyl group, C ₂ -C ₂₀ straight chain alkenyl group, C ₃ -C ₂₀ branched alkenyl group, cycloalkyl group or represents an aryl group, and the cycloalkyl group and the aryl group are unsubstituted or any hydrogen atom is a C ₁ -C ₂₀ straight chain alkyl group, a C ₃ -C ₂₀ branched alkyl group, a C ₂ - substituted with a _C20 straight chain alkenyl group or a C3 _{- C20} branched alkenyl group;
In the groups represented by R ¹ to R ⁶ , any —CH ₂ — in the structure is not substituted or —O—, —S—, —NH—, —C═O—, —O( C=O)-, -(C=O)O-, -NH(C=O)- and -(C=O)NH-, and , two adjacent —CH ₂ — are not substituted with the substituents at the same time,
A photosensitive resin composition, wherein ^R7 represents a crosslinked ring group or a derivative having a crosslinked ring group. In Formula I above,
The R ⁷ represents -L ¹ -R ^7' ,
said L ¹ represents a single bond, a C ₁ to C ₂₀ linear alkylene group, a C ₃ to C ₂₀ branched alkylene group or a C ₄ to C ₂₀ divalent cycloalkylalkyl group;
R7 ^' is

The photosensitive resin composition according to claim 1, characterized by representing: In Formula I above,
L ¹ represents a single bond, a C ₁ -C ₃ linear alkylene group or a C ₃ -C ₅ branched alkylene group,
R7 ^' is

3. The photosensitive resin composition according to claim 2, wherein: In Formula I above,
each of said R ¹ to said R ⁴ independently represents a C ₁ to C ₈ straight chain alkyl group, a C ₃ to C ₁₀ branched alkyl group or a C ₃ to C ₆ cycloalkyl group;
R ⁵ represents hydrogen, a cyan group, a C ₁ -C ₈ linear alkyl group or a C ₃ -C ₇ cycloalkyl group,
R ⁶ represents hydrogen, a C ₁ to C ₈ linear alkyl group or a phenyl group,
In the groups represented by R ¹ to R ⁶ , any —CH ₂ — in the structure is not substituted or —C═O—, —O(C═O)— and —(C═O) 2. The substituent according to claim 1, which is substituted with one substituent selected from the group consisting of O—, and two adjacent —CH ₂ — are not substituted with the substituent at the same time. The photosensitive resin composition of. In Formula I above,
each of R ¹ to R ² independently represents a C ₁ to C ₂ linear alkyl group;
each of said R ³ to said R ⁴ independently represents a C ₁ to C ₅ linear alkyl group or a C ₃ to C ₁₀ branched alkyl group;
R ⁵ represents hydrogen, a cyan group, a C ₁ to C ₃ linear alkyl group or a C ₇ cycloalkyl group,
5. The photosensitive resin composition of claim 4, wherein ^R6 represents hydrogen, _CH3 or a phenyl group. 2. The photosensitive resin composition according to claim 1, wherein the content of the oxime ester compound is in the range of 1 wt % to 30 wt %, with the solid component being 100 wt %. 2. The photosensitive resin composition according to claim 1, wherein the content of the alkali-soluble resin is in the range of 5 wt % to 60 wt %, with the solid component being 100 wt %. 2. The photosensitive resin composition according to claim 1, wherein the content of the polymerizable monomer is in the range of 5 wt % to 60 wt %, with the solid component being 100 wt %. shown in formula I,

In Formula I above,
Each of R ¹ -R ⁴ is independently a C ₁ -C ₂₀ straight chain alkyl group, a C ₃ -C ₂₀ branched alkyl group, a C ₂ -C ₂₀ straight chain alkenyl group, a C ₃ -C ₂₀ branched alkenyl group group, cycloalkyl group or aryl group, and said cycloalkyl group and said aryl group are unsubstituted or any hydrogen atom is a C ₁ -C ₂₀ linear alkyl group, C ₃ -C ₂₀ branched substituted with an alkyl group, a C ₂ -C ₂₀ straight chain alkenyl group or a C ₃ -C ₂₀ branched alkenyl group,
R ⁵ represents hydrogen, halogen, nitro group, cyan group, C ₁ -C ₂₀ linear alkyl group, C ₃ -C ₂₀ branched alkyl group, cycloalkyl group or aryl group, and the cycloalkyl group and the aryl group is unsubstituted or any hydrogen atom is substituted with a C ₁ -C ₂₀ straight chain alkyl group or a C ₃ -C ₂₀ branched alkyl group;
R ⁶ is hydrogen, C ₁ -C ₂₀ straight chain alkyl group, C ₃ -C ₂₀ branched alkyl group, C ₂ -C ₂₀ straight chain alkenyl group, C ₃ -C ₂₀ branched alkenyl group, cycloalkyl group or represents an aryl group, and the cycloalkyl group and the aryl group are unsubstituted or any hydrogen atom is a C ₁ -C ₂₀ straight chain alkyl group, a C ₃ -C ₂₀ branched alkyl group, a C ₂ - substituted with a _C20 straight chain alkenyl group or a C3 _{- C20} branched alkenyl group;
In the groups represented by R ¹ to R ⁶ , any —CH ₂ — in the structure is not substituted or —O—, —S—, —NH—, —C═O—, —O( C=O)-, -(C=O)O-, -NH(C=O)- and -(C=O)NH-, and , two adjacent —CH ₂ — are not substituted with the substituents at the same time,
An oxime ester compound, wherein ^R7 represents a crosslinked ring group or a derivative having a crosslinked ring group. In Formula I above,
R ⁷ represents -L ¹ -R ^7' ,
said L ¹ represents a single bond, a C ₁ to C ₂₀ linear alkylene group, a C ₃ to C ₂₀ branched alkylene group or a C ₄ to C ₂₀ divalent cycloalkylalkyl group;
R7 ^' is

The oxime ester compound according to claim 9, characterized by representing: In Formula I above,
said L ¹ represents a single bond, a C ₁ -C ₃ linear alkylene group or a C ₃ -C ₅ branched alkylene group;
R7 ^' is

The oxime ester compound according to claim 10, characterized by representing: In Formula I above,
each of said R ¹ to said R ⁴ independently represents a C ₁ to C ₈ straight chain alkyl group, a C ₃ to C ₁₀ branched alkyl group or a C ₃ to C ₆ cycloalkyl group;
R ⁵ represents hydrogen, a cyan group, a C ₁ -C ₈ linear alkyl group or a C ₃ -C ₇ cycloalkyl group,
R ⁶ represents hydrogen, a C ₁ to C ₈ linear alkyl group or a phenyl group,
In the groups represented by R ¹ to R ⁶ , any —CH ₂ — in the structure is not substituted or —C═O—, —O(C═O)— and —(C═O) 10. The substituent according to claim 9, which is substituted with one substituent selected from the group consisting of O—, and two adjacent —CH ₂ — are not substituted with the substituent at the same time. oxime ester compounds. In Formula I above,
each of R ¹ to R ² independently represents a C ₁ to C ₂ linear alkyl group;
each of said R ³ to said R ⁴ independently represents a C ₁ to C ₅ linear alkyl group or a C ₃ to C ₁₀ branched alkyl group;
R ⁵ represents hydrogen, a cyan group, a C ₁ to C ₃ linear alkyl group or a C ₇ cycloalkyl group,
13. The oxime ester compound according to claim 12, wherein ^R6 represents hydrogen, _CH3 or a phenyl group. 9. The photosensitive resin composition according to any one of claims 1 to 8, characterized by being applied to the production of photospacers, colored resists, and photoresists for semiconductors. A display device comprising a colored resist formed from the photosensitive resin composition according to any one of claims 1 to 8. A semiconductor device comprising a semiconductor photoresist formed from the photosensitive resin composition according to any one of claims 1 to 8.