CN111856877A

CN111856877A - Photosensitive resin composition, spacer, protective film and liquid crystal display element

Info

Publication number: CN111856877A
Application number: CN202010250123.6A
Authority: CN
Inventors: 周泓佳; 萧君佑; 赖靖璋; 廖豪伟
Original assignee: Chi Mei Corp
Current assignee: Chi Mei Corp
Priority date: 2019-04-30
Filing date: 2020-04-01
Publication date: 2020-10-30
Also published as: TW202041541A

Abstract

The invention provides a photosensitive resin composition, a spacer, a protective film and a liquid crystal display element, wherein the photosensitive resin composition has excellent sensitivity and can form a spacer with excellent step difference. The alkali-soluble resin A comprisesThe alkali-soluble resin A-1 is obtained by copolymerizing a mixture, wherein the mixture comprises an ethylenically unsaturated monomer a-1-1 containing a carboxylic acid group or a carboxylic anhydride group and an oxyalkylene-containing ethylenically unsaturated monomer a-1-2 represented by the formula (I). The photoinitiator C comprises a photoinitiator C-1, and the photoinitiator C-1 is a compound shown in a formula (II).

Description

Photosensitive resin composition, spacer, protective film and liquid crystal display element

Technical Field

The present invention relates to a photosensitive resin composition, a spacer, a protective film and a liquid crystal display device, and more particularly, to a photosensitive resin composition suitable for a spacer and a protective film and a liquid crystal display device using the spacer and the protective film.

Background

Generally, the color printed pixels and the black matrix on the surface of the color filter layer have irregularities, so a protective film is usually formed on the surface of the color filter layer to hide the irregularities and achieve the planarization requirement.

However, in manufacturing optical elements such as liquid crystal display elements and solid-state imaging devices, it is often necessary to perform a treatment under severe conditions, for example, a treatment of immersing the substrate surface in an acidic solvent or an alkaline solution, or a formation of a wiring electrode layer by Sputtering (Sputtering), which causes local corrosion or high temperature. Therefore, a protective film is required to be formed on the surface of these elements to prevent the elements from being damaged during the manufacturing process. In order for the protective film to have characteristics to withstand the above treatment, the protective film needs to have excellent adhesion to the substrate, and also has high transparency, high surface hardness, and a smooth surface. In addition, the protective film is required to have high heat resistance and light resistance so as to prevent deterioration such as discoloration, yellowing, or whitening in long-term use. In addition, the protective film is required to have good properties such as water resistance, chemical resistance, solvent resistance, acid resistance, and alkali resistance.

On the other hand, in the prior art, in the color liquid crystal display device, in order to maintain a fixed layer gap between two substrates, beads such as polystyrene beads or silica beads are randomly sprayed on the whole substrates, wherein the diameter of the beads is the gap between the two substrates. However, in the conventional method, the position and density distribution of the beads are not uniform, so that the light of the backlight is affected by the beads and is scattered, and the contrast of the display device is further reduced. Therefore, photosensitive compositions for spacers developed by photolithography (photolithography) have become the mainstream in the industry. The spacer is formed by applying the photosensitive composition for spacer to the substrate, placing a mask of a predetermined shape between the substrate and the exposure source, and developing after the exposure step. According to the method, the gap body can be formed at the appointed position outside the red, green, blue and the like pixels, so as to solve the problems in the prior art; the interlayer distance can also be controlled by the thickness of the coating film formed by the photosensitive component, so that the distance between layers can be easily controlled, and the advantage of high precision is provided.

Since the protective film or the spacer is formed on the color filter or the substrate, the requirement for transparency is extremely high. If the transparency of the protective film or the spacer is not good, when the protective film or the spacer is applied to a liquid crystal display device, the brightness of the liquid crystal display device is insufficient, and the display quality of the liquid crystal display device is affected.

In order to improve the transparency of the protective film or the spacer, japanese unexamined patent application publication No. 2010-054561 discloses a photosensitive composition for a protective film, which includes (a) an adhesive resin which is an alkali-soluble resin, (B) a compound having an ethylenically unsaturated group, (C) a photoinitiator, and (D) a solvent, wherein the equivalent of an unsaturated bond in the (B) compound having an ethylenically unsaturated group is between 90 and 450 g/eq. (B) In the ethylenically unsaturated group compound, the number of unsaturated double bonds of a single compound is between 2 and 4. (A) The weight average molecular weight of the adhesive resin is between 10,000 and 20,000. On the other hand, Japanese patent laid-open No. 2004-240241 discloses a photosensitive composition, the photopolymerization initiator comprises (A) a copolymer of an ethylenically unsaturated carboxylic acid (anhydride), an ethylenically unsaturated compound having an epoxy group and other ethylenically unsaturated compounds, (B) a polymerizable compound having an ethylenically unsaturated group, and (C) 2-butanedione- (4- (methylthio) phenyl) -2- (O-oxime acetate), 1, 2-butanedione-1- (4-morpholinophenyl) -2- (O-benzoyl oxime), 1, 2-octanedione-1- (4- (phenylthio) phenyl) -2- [ O- (4-methylbenzoyl) oxime ]. However, these photosensitive resin compositions still have the disadvantage of poor sensitivity, and the spacers formed therefrom also have the disadvantage of poor step difference.

Therefore, how to improve the sensitivity of the photosensitive resin composition and improve the step of the spacer is a problem to be solved by those skilled in the art.

Disclosure of Invention

Accordingly, the present invention provides a photosensitive resin composition having excellent sensitivity and capable of forming a spacer having an excellent step difference, which is suitable for a spacer and a protective film.

The invention provides a photosensitive resin composition, which comprises an alkali-soluble resin (A), a compound (B) containing an ethylene unsaturated group, a photoinitiator (C) and a solvent (D). Specifically, the alkali-soluble resin (A) includes an alkali-soluble resin (A-1), wherein the alkali-soluble resin (A-1) is obtained by copolymerizing a mixture. The mixture contains an ethylenically unsaturated monomer (a-1-1) containing a carboxylic acid group or a carboxylic anhydride group and an oxyalkylene-containing ethylenically unsaturated monomer (a-1-2) represented by the following formula (I).

In the formula (I), the compound is shown in the specification,

R¹、R²and R³Each independently represents hydrogen or methyl;

R⁴represents substituted or unsubstituted C₁-C₂₀Linear or branched alkyl, substituted or unsubstituted C₂-C₂₀Or a substituted or unsubstituted C₆-C₂₀An aromatic hydrocarbon group of (1);

AO represents C₂-C₂₀Oxyalkylene of (a);

x represents an integer of 0 to 2;

y represents 0 or 1;

n represents 2 or more.

The photoinitiator (C) includes a photoinitiator (C-1), wherein the photoinitiator (C-1) is a compound represented by the following formula (II).

In the formula (II), the compound is shown in the specification,

a represents hydrogen, halogen, nitro, C₁-C₂₀Linear or branched alkyl of (2), C₃-C₁₀Alkylcycloalkyl of (A), C₄-C₁₀Alkylcycloalkyl of (A), C₄-C₁₀A cycloalkylalkyl group of,

Wherein C is₁-C₂₀Linear or branched alkyl of (2), C₃-C₁₀Alkylcycloalkyl of (A), C₄-C₁₀Alkylcycloalkyl of (A), C₄-C₁₀A cycloalkylalkyl group of,

Any one of-CH contained in (1)₂-may be substituted by O, N, S or a carbonyl group;

R⁵represents hydrogen, halogen, C₁-C₂₀Linear or branched alkyl of (2), C₄-C₂₀Cycloalkylalkyl or C₂-C₂₀Alkenyl of (2), wherein C₁-C₂₀Linear or branched alkyl of (2), C₄-C₂₀Cycloalkylalkyl and C₂-C₂₀-CH contained in the alkenyl group of (1)₂-may be substituted by O, N, S or a carbonyl group, two R⁵Can form a ring structure between;

R⁶is represented by C₁-C₂₀Linear or branched alkyl of (2), C₂-C₂₀Alkenyl of, C₃-C₂₀Cycloalkyl of, C₄-C₂₀Cycloalkylalkyl of (C)₄-C₂₀Alkylcycloalkyl of (A), C₆-C₂₀Aryl or C of₆-C₂₀Wherein one or more hydrogens in these groups may each be independently substituted by an alkyl, halogen, hydroxy or nitro group, and R⁶In (C-CH)₂-may be substituted by O, N, S or a carbonyl group;

R⁷Is represented by C₁-C₂₀Linear or branched alkyl of (2), C₃-C₂₀Cycloalkyl of, C₄-C₂₀Cycloalkylalkyl of (C)₄-C₂₀Alkylcycloalkyl of (A), C₆-C₂₀Aryl of (C)₆-C₂₀When R is an alkylaryl group, a group represented by the following formula (II-A), a group represented by the following formula (II-B) or a group represented by the following formula (II-C)⁷Is represented by C₁-C₂₀Linear or branched alkyl of (2), C₃-C₂₀Cycloalkyl of, C₄-C₂₀Cycloalkylalkyl of (C)₄-C₂₀Alkylcycloalkyl of (A), C₆-C₂₀Aryl or C of₆-C₂₀In which one or more hydrogens of the groups may each be independently substituted by an alkyl, halogen, hydroxy or nitro group, and R is⁷In (C-CH)₂-may be substituted by O, N, S or a carbonyl group;

R⁶and R⁷Can form a ring structure between;

in the formula (II-A), m represents an integer of 0 or 1, R¹¹Represents hydrogen, C₁-C₈Alkyl or phenyl of R¹²、R¹³And R¹⁴Each independently represents hydrogen or C₁-C₄Alkyl groups of (a);

in the formula (II-B), p is an integer of 0 to 3;

in the formula (II-C), R¹⁵Represents hydrogen, C₁-C₈Ar is substituted or unsubstituted phenyl, naphthyl, furyl, thienyl or pyridyl;

R⁸represents N-morpholinyl, N-piperidinyl, N-pyrrolyl or N-dialkyl, wherein one or more of these groups may be substituted by halogen or hydroxy;

R⁹、R⁹' each independently represents C ₁-C₂₀Linear or branched alkyl of (2), C₄-C₂₀Cycloalkyl of, C₂-C₂₀Alkenyl of, C₆-C₂₀Aryl or C of₆-C₂₀Wherein one or more hydrogens in these groups may each be independently substituted with an alkyl, halogen, hydroxy or nitro group, and-CH in these groups₂-may be substituted by-O-; or R⁹And R⁹' may be linked to each other or form a five-or six-membered ring via-O-, -S-or-NH-;

R¹⁰is represented by C₁-C₂₀Linear or branched alkyl of (2), C₄-C₂₀Cycloalkyl of, C₄-C₂₀Alkylcycloalkyl of (A), C₂-C₂₀Alkenyl of, C₆-C₂₀Aryl or C of₆-C₂₀In which-CH in these groups₂-may be substituted by-O-or-S-, and one or more hydrogens of these groups may be independently selected from alkyl, halogen, nitro, cyano, SR¹⁶OR OR¹⁷Substituted;

R¹⁶and R¹⁷Each independently represents hydrogen, or C₁-C₂₀Linear or branched alkyl groups of (1).

In an embodiment of the present invention, the mixture further includes an ethylenically unsaturated monomer (a-1-3) containing a maleimide group or two alkenyl groups.

In an embodiment of the present invention, the maleimide group-or two-alkenyl group-containing ethylenically unsaturated monomer (a-1-3) includes at least one monomer selected from the group consisting of monomers represented by the following formulae (1) to (5).

In the formulae (4) and (5), R ¹⁸、R¹⁹And R²⁰Each independently represents hydrogen, or C₁-C₃₀Linear or branched alkyl groups of (1).

In one embodiment of the present invention, the alkali-soluble resin (a-1) contains an ethylenically unsaturated group.

In an embodiment of the present invention, the photoinitiator (C) further includes a photoinitiator (C-2), wherein the photoinitiator (C-2) is a compound represented by the following formula (III).

In the formula (III), the compound represented by the formula (III),

Ar₁represents ortho-arylene or ortho-heteroarylene, the ortho-arylene or ortho-heteroarylene being adjacent to Y in two atoms₁And the carbonyl groups form a cyclic structure, and the substituents on the remaining atoms are each selected from hydrogen; halogen; c₁-C₁₂Alkyl groups of (a); c₅-C₇Cycloalkyl groups of (a); warp C₅-C₇Cycloalkyl-substituted C of₁-C₄Alkyl groups of (a); a phenyl group; via one or more C₁-C₄Alkyl, carboxyl, C₁-C₁₂Alkyl acyl of (2), C₁-C₁₂Arylacyl, heteroarylacyl, JT₄Phenyl, halogen or CN substituted phenyl; c₁-C₄An alkyl benzyloxy group of (a); warp beam

Substituted C₁-C₄Alkoxy group of (C)₁-C₃(ii) an alkylenedioxy group;

；C₁-C₁₂alkylthio of (a); c₁-C₄Alkylthiophenyl of (a); warp beam

Substituted C₁-C₄Alkylthio of (a); CN; a carboxyl group; c₁-C₁₂An alkoxyformyl group of (a); an arylacyl group; heteroaryl acyl and JT₅The group consisting of; or

Ar₁Between two adjacent substituents in the above substituents or between a substituent and Ar ₁Form a ring structure through a single bond, a carbon atom and a carbonyl group;

wherein, JT₄And JT₅Wherein J is selected from the group consisting of O, S and NT₆The group consisting of;

Y₁selected from the group consisting of O, S, NT₇、BT₇、CT₂T₃、SiT₂T₃S ═ O, and C ═ O;

T₁represents hydrogen, C₁-C₁₈Alkyl or C₁-C₁₈Alkoxy group of (a); or

T₁Represents a halogen atom or atoms, C₁-C₄Alkyl of (C)₅-C₇Cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C₁-C₄Is substituted with alkanoyloxy or aroyloxy and/or is substituted by C₅-C₇Cycloalkylene, phenylene, O, S or NT of₄Inserted C₂-C₁₈Alkyl groups of (a); c₂-C₁₈Alkenyl of (a); via one or more halogens, C₁-C₄Alkyl of (C)₅-C₇Cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C₁-C₄Is substituted with alkanoyloxy or aroyloxy and/or is substituted by C₅-C₇Cycloalkylene, phenylene, O, S or NT of₄Inserted C₂-C₁₈Or both; or

T₁Is represented by C₅-C₇Or through a cycloalkyl groupOne or more C₁-C₄Alkyl, phenyl, halogen or CN substituted C₅-C₇Cycloalkyl groups of (a); or

T₁Represents phenyl, or via one or more C₁-C₄Alkyl of (C)₁-C₄Alkoxy, phenyl, halogen or CN substituted phenyl; or

T₁Represents naphthyl, benzoyl or phenoxycarbonyl, wherein the phenyl of benzoyl and phenoxycarbonyl is optionally substituted by one or more than two halogen, T ₄、C₅-C₆Cycloalkyl, CN, OH or JT₄Substituted;

T₂and T₃Each independently represents hydrogen or C₁-C₁₈Alkyl, carboxyl substituted C₁-C₅Alkyl radical of (1), via C₁-C₄Alkoxy acyl substituted C₁-C₅Alkyl or through

Substituted C₁-C₄Alkyl groups of (a); or

T₂And T₃Each independently represents a halogen atom or a halogen atom via one or more atoms, C₁-C₄Alkyl of (C)₅-C₇Cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C₁-C₄Alkanoyloxy, aroyloxy substituted C of₂-C₁₈Or is substituted by C₅-C₇Cycloalkylene, phenylene, O, S or NT of₄Inserted C₂-C₁₈Or both are present; or

T₂And T₃Each independently represents C₅-C₇Cycloalkyl through one or more C₁-C₄Alkyl, phenyl, halogen or CN substituted C₅-C₇Cycloalkyl groups of (a); or

T₂And T₃Each independently of the other represents phenyl, or via one or more C₁-C₄Alkyl of (C)₁-C₄Alkoxy, carboxyl, C₁-C₁₂Alkyl acyl of (2), C₅-C₆Of cycloalkylformyl or C₅-C₆Cycloalkyl-substituted C of₂-C₄Alkyl acyl, aryl acyl, JT₄Phenyl, halogen or CN substituted phenyl; or

T₂And T₃Each constituting a cyclic structure together with a carbon atom or a silicon atom to which they are commonly bonded and having a ring-forming number of atoms of 4 to 7; or

T₂And T₃Each of which forms a cyclic structure together with an adjacent substituent and has a ring-forming number of atoms of 4 to 7;

T₄Is represented by C₁-C₄Alkyl groups of (a);

T₅represents hydrogen, C₁-C₁₈Alkyl radical of (1), via C₁-C₄Alkoxy acyl substituted C₁-C₅Alkyl or through

Substituted C₁-C₄Alkyl groups of (a); or

T₅Represents a halogen atom or atoms, C₁-C₄Alkyl of (C)₅-C₇Cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C₁-C₄Alkanoyloxy or aroyloxy substituted C of₂-C₁₈Or is substituted by C₅-C₇Cycloalkylene, phenylene, O, S or NT of₄Inserted C₂-C₁₈Or both are present; or

T₅Is represented by C₅-C₇Cycloalkyl through one or more C₁-C₄Alkyl, phenyl, halogen or CN substituted C₅-C₇Cycloalkyl groups of (a); or

T₅Represents phenyl, or via one or more C₁-C₁₂Alkyl, carboxyl, C₁-C₁₂Alkanoyl, phenylenes, O, S or NT₄Inserted intoC₂-C₁₂Alkyl acyl of (2), C₅-C₆Cycloalkyl formyl group, C₅-C₆Cycloalkyl-substituted C of₂-C₄Alkyl acyl, aryl acyl, heteroaryl acyl, JT₄Phenyl, halogen, CN or NO₂Substituted phenyl; or

T₅Is represented by C₁-C₄Alkyl acyl of (2), C₁-C₄Wherein the phenyl in the benzoyl and phenoxycarbonyl group can be optionally substituted by one or more than two halogen, T₄Cyclopentyl, cyclohexyl, CN, OH or JT ₄Substitution; or

T₅Via a single bond, carbon atom or carbonyl group with Ar₁The aromatic ring in (A) forms a cyclic structure;

T₆and T₇Each independently represents hydrogen or C₁-C₁₈Alkyl radical of (1), via C₁-C₄Alkoxy acyl substituted C₁-C₅Alkyl or through

Substituted C₁-C₄Alkyl groups of (a); or

T₆And T₇Each independently represents a halogen atom or a halogen atom via one or more atoms, C₁-C₄Alkyl of (C)₅-C₇Cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C₁-C₄Alkanoyloxy or aroyloxy substituted C of₂-C₁₈Alkyl of (C)₅-C₇Cycloalkylene, phenylene, O, S or NT of₄Inserted C₂-C₁₈Or both are present; or

T₆And T₇Each independently represents C₅-C₇Cycloalkyl through one or more C₁-C₄Alkyl, phenyl, halogen or CN substituted C₅-C₇Cycloalkyl groups of (a); or

T₆And T₇Each independently of the otherRepresents phenyl, or via one or more C₁-C₄Alkyl, carboxyl, C₁-C₁₂Alkyl acyl of (2), C₅-C₆Of cycloalkylformyl or C₅-C₆Cycloalkyl-substituted C of₂-C₄Alkyl acyl, aryl acyl, JT₄Phenyl, halogen or CN substituted phenyl; or

T₆Each via a single bond, carbon atom, carbonyl group and Ar₁The aromatic ring in (A) forms a cyclic structure;

wherein when Ar is₁In the case of substituted carbazole groups, Y₁Is not C, O, S or NT₇。

In one embodiment of the present invention, the alkali-soluble resin (a-1) is used in an amount of 50 to 100 parts by weight, the ethylenically unsaturated group-containing compound (B) is used in an amount of 50 to 600 parts by weight, the photoinitiator (C) is used in an amount of 10 to 140 parts by weight, the photoinitiator (C-1) is used in an amount of 10 to 90 parts by weight, and the solvent (D) is used in an amount of 500 to 5000 parts by weight, based on 100 parts by weight of the alkali-soluble resin (a).

In one embodiment of the present invention, the oxyalkylene-containing ethylenically unsaturated monomer (a-1-2) is used in an amount of 1 to 55 parts by weight based on 100 parts by weight of the total amount of the mixture used.

In one embodiment of the present invention, the maleimide group-or two-alkenyl group-containing ethylenically unsaturated monomer (a-1-3) is used in an amount of 5 to 50 parts by weight, based on 100 parts by weight of the total amount of the mixture.

In one embodiment of the present invention, the photoinitiator (C-2) is used in an amount of 5 to 50 parts by weight based on 100 parts by weight of the alkali-soluble resin (A).

The invention also provides a spacer formed by the photosensitive resin composition.

The invention also provides a protective film formed by the photosensitive resin composition.

The invention also provides a liquid crystal display element which comprises the gap body.

The invention also provides a liquid crystal display element which comprises the protective film.

In view of the above, the present invention is suitable for use in spacers, protective films and liquid crystal display elements because the sensitivity of the photosensitive resin composition is improved and the spacers having a relatively excellent level difference are formed by combining the photosensitive resin composition with the specific alkali-soluble resin (A-1) and the specific photoinitiator (C-1).

In order to make the aforementioned and other features and advantages of the invention more comprehensible, embodiments accompanied with figures are described in detail below.

Detailed Description

Hereinafter, acrylic acid and/or methacrylic acid is represented by (meth) acrylic acid, and acrylate and/or methacrylate is represented by (meth) acrylate; likewise, (meth) acryloyl represents acryloyl and/or methacryloyl; by (meth) acrylamide is meant acrylamide and/or methacrylamide.

< photosensitive resin composition >

The invention provides a photosensitive resin composition, which comprises an alkali-soluble resin (A), a compound (B) containing an ethylene unsaturated group, a photoinitiator (C) and a solvent (D). Further, if necessary, the photosensitive resin composition may optionally include an additive (E). The respective components of the photosensitive resin composition used in the present invention will be described in detail below:

alkali soluble resin (A)

The alkali-soluble resin (A) of the present invention includes the alkali-soluble resin (A-1), and may further include other alkali-soluble resins (A-2).

Alkali soluble resin (A-1)

The alkali-soluble resin (A-1) is obtained by copolymerizing a mixture (hereinafter, in the synthesis example of the alkali-soluble resin (A-1), also referred to as "monomer mixture") comprising an ethylenically unsaturated monomer (a-1-1) containing a carboxylic acid group or a carboxylic acid anhydride group and an oxyalkylene-containing ethylenically unsaturated monomer (a-1-2).

In addition, the above mixture may further include a maleimide group-containing or two-alkenyl group-containing ethylenically unsaturated monomer (a-1-3), and optionally further include other ethylenically unsaturated monomer (a-1-4).

The alkali-soluble resin (A-1) may further contain an ethylenically unsaturated group. Specifically, the alkali-soluble resin (A-1) containing an ethylenically unsaturated group can be obtained by further subjecting the polymer obtained from the above mixture to a condensation reaction with an ethylenically unsaturated monomer (a-1-5).

The various monomers forming the alkali-soluble resin (A-1) are described in detail below:

ethylenically unsaturated monomer (a-1-1) having carboxylic acid group or carboxylic acid anhydride group

Since the ethylenically unsaturated monomer (a-1-1) containing a carboxylic acid group or a carboxylic acid anhydride group has a carboxylic acid group or a carboxylic acid anhydride group (hereinafter, simply referred to as "acid group"), the polymer to be synthesized can have an acid group in a side chain and can be made alkali-soluble. Specific examples of the carboxylic acid group-or carboxylic anhydride group-containing ethylenically unsaturated monomer (a-1-1) include carboxylic acid group-containing ethylenically unsaturated monomers such as acrylic acid, methacrylic acid, 2-acryloyloxyethoxy succinate, 2-methacryloylethoxy succinate (HOMS), itaconic acid, and ω -carboxy-polycaprolactone monoacrylate; carboxylic anhydride group-containing ethylenically unsaturated monomers such as maleic anhydride and itaconic anhydride, or combinations thereof. Specific examples of the ethylenically unsaturated monomer (a-1-1) containing a carboxylic acid group or carboxylic anhydride group preferably include acrylic acid, methacrylic acid, 2-methacryloyl ethoxysuccinate, or a combination thereof.

The ethylenically unsaturated monomer (a-1-1) containing a carboxylic acid group or carboxylic anhydride group may be used in an amount of 10 to 90 parts by weight, preferably 15 to 85 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the total amount of the mixture.

Oxyalkylene group-containing ethylenically unsaturated monomer (a-1-2)

The oxyalkylene group-containing ethylenically unsaturated monomer (a-1-2) is a monomer having 2 or more oxyalkylene groups. Specifically, the oxyalkylene-containing ethylenically unsaturated monomer (a-1-2) has a structure represented by the formula (I).

In the formula (I), the compound is shown in the specification,

R¹、R²and R³Each independently represents hydrogen or methyl, preferably each independently represents hydrogen;

R⁴represents substituted or unsubstituted C₁-C₂₀Linear or branched alkyl, substituted or unsubstituted C₂-C₂₀Or a substituted or unsubstituted C₆-C₂₀Is preferably C₁-C₂₀Linear alkyl group of (2), unsubstituted C₆-C₂₀Of an aromatic hydrocarbon group, an aromatic hydrocarbon group-substituted C₆-C₂₀Or with an aromatic hydrocarbon radical of₁-C₁₀Alkyl-substituted C of₆-C₂₀The aromatic hydrocarbon group of (2) is more preferably a methyl group, a phenyl group, a 4-Nonylphenyl group or a biphenyl group.

AO represents C₂-C₂₀Oxyalkylene of (2), preferably C ₂-C₁₀Oxyalkylene group of (2), more preferably C₂-C₅Oxyalkylene of (a), still more preferably oxyethylene;

x represents an integer of 0 to 2;

y represents 0 or 1;

n represents 2 or more, preferably 2 to 200, more preferably 2 to 50, still more preferably 2 to 15.

It is to be noted that the oxyalkylene-containing ethylenically unsaturated monomer (a-1-2) may contain 1 or 2 or more oxyalkylene groups.

Specific examples of the oxyalkylene group-containing ethylenically unsaturated monomer (a-1-2) include a mixture of o-phenylphenoxyethylene glycol acrylate (EO1 mol)/o-phenylphenoxydiethylene glycol acrylate (EO2 mol) (molar ratio between o-phenylphenoxyethylene glycol acrylate and o-phenylphenoxydiethylene glycol acrylate 1: 1), o-phenylphenoxydiethylene glycol (meth) acrylate (EO2 mol), phenoxydiethylene glycol (meth) acrylate (EO2 mol), phenoxypolyethylene glycol (meth) acrylate (EO4 mol), methoxypolyethylene glycol (meth) acrylate (EO9 mol), methoxypolyethylene glycol (meth) acrylate (EO12 to 13 mol), methoxytriethylene glycol (meth) acrylate (EO3 mol), Ethoxydiglycol (meth) acrylate (EO2 mol), butoxydiglycol (meth) acrylate (EO2 mol), 2-ethylhexyloxydiethylglycol (meth) acrylate (EO2 mol), methoxypropylene glycol (meth) acrylate (PO2 mol), methoxypropylene glycol (meth) acrylate (PO4 mol), nonylphenoxypolyethylene glycol (meth) acrylate (EO4 to 17 mol), nonylphenoxypropylene glycol (meth) acrylate (PO5 mol), Ethylene Oxide (EO) modified cresol (meth) acrylic acid (EO2 mol), or combinations of the above monomers.

Specific examples of the oxyalkylene group-containing ethylenically unsaturated monomer (a-1-2) preferably include o-phenylphenoxyethylene glycol acrylate/o-phenylphenoxydiethylene glycol acrylate (molar ratio between phenylphenoxyethylene glycol acrylate and phenylphenoxydiethylene glycol acrylate 1: 1), phenoxydiethylene glycol acrylate, methoxypolyethylene glycol acrylate (EO9 mol), methoxypolyethylene glycol acrylate (EO12 to 13 mol), nonylphenoxypolyethylene glycol acrylate (EO4 to 17 mol), nonylphenoxypolypropylene glycol acrylate (PO5 mol), or a combination of the above monomers.

As used herein, the terms "EO" and "PO" denote an oxyethylene group and an oxypropylene group, respectively. The number of moles of "EO" and "PO" is the average number of moles of oxyethylene groups or oxypropylene groups contained per unit mole of the compound. For example, "methoxypolyethylene glycol acrylate (EO9 moles)" means having an average of 9 moles of oxyethylene groups per unit mole of compound.

If the oxyalkylene-containing ethylenically unsaturated monomer (a-1-2) is not used, the sensitivity of the photosensitive resin composition is poor.

The oxyalkylene-containing ethylenically unsaturated monomer (a-1-2) may be used in an amount of 1 to 55 parts by weight, preferably 1 to 50 parts by weight, more preferably 1 to 45 parts by weight, based on 100 parts by weight of the total amount of the mixture.

Ethylenically unsaturated monomer (a-1-3) having maleimido group or two alkenyl groups

The maleimide group-or two-alkenyl group-containing ethylenically unsaturated monomer (a-1-3) includes a maleimide group-containing ethylenically unsaturated monomer (may also be referred to as a "monomer having a cyclic structure"), a two-alkenyl group-containing ethylenically unsaturated monomer (may also be referred to as a monomer which forms a cyclic structure after polymerization), or a combination thereof. It is to be noted that these monomers described above can form a structural unit having a cyclic structure when forming a polymer.

Specific examples of the maleimide group-containing ethylenically unsaturated monomer include maleimide, benzylmaleimide, phenylmaleimide, naphthylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-chlorophenylmaleimide, aromatic-substituted maleimides such as N-m-chlorophenylmaleimide, N-p-chlorophenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide and N-p-methoxyphenylmaleimide; maleimides substituted with an alkyl group such as cyclohexylmaleimide, methylmaleimide, ethylmaleimide, propylmaleimide, isopropylmaleimide, or combinations thereof.

In one embodiment, the maleimide group-containing ethylenically unsaturated monomer includes a compound represented by formula (1), a compound represented by formula (2), a compound represented by formula (3), or a combination thereof.

The ethylenically unsaturated monomer having two alkenyl groups may be, for example, 1, 6-dienes. The 1, 6-diolefin includes a 1, 6-diolefin represented by formula (4), a 1, 6-diolefin represented by formula (5), or a combination thereof.

In the formulae (4) and (5), R¹⁸、R¹⁹And R²⁰Each independently represents hydrogen, or C₁-C₃₀Preferably hydrogen or C₁-C₁₀More preferably hydrogen or C₁-C₅The straight or branched alkyl group of (1) is more preferably a methyl group.

Specific examples of 1, 6-dienes include dimethyl-2, 2' - [ oxybis (methylene) ] bis-2-acrylate, alpha- (allyloxymethyl) acrylate, or combinations thereof.

Specific examples of the maleimide group-or two-alkenyl group-containing ethylenically unsaturated monomer (a-1-3) preferably include benzylmaleimide, phenylmaleimide, cyclohexylmaleimide, dimethyl-2, 2' - [ oxybis (methylene) ] bis-2-acrylate, α - (allyloxymethyl) acrylate, or a combination thereof.

When the maleimide group-or two-alkenyl group-containing ethylenically unsaturated monomer (a-1-3) is used, a gapmer having a superior level difference can be further formed.

The maleimide group-or two-alkenyl group-containing ethylenically unsaturated monomer (a-1-3) may be used in an amount of 5 to 50 parts by weight, preferably 8 to 45 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of the total amount of the mixture.

Other ethylenically unsaturated monomer (a-1-4)

The mixture constituting the alkali-soluble resin (A-1) may further include other ethylenically unsaturated monomer (a-1-4). The other ethylenically unsaturated monomer (a-1-4) is an ethylenically unsaturated monomer (a-1-1) containing a carboxylic acid group or a carboxylic anhydride group, an oxyalkylene-containing ethylenically unsaturated monomer (a-1-2), a maleimide group-or both-alkenyl-containing ethylenically unsaturated monomer (a-1-3), and an ethylenically unsaturated monomer other than the following ethylenically unsaturated monomer (a-1-5).

Specific examples of the other ethylenically unsaturated monomer (a-1-4) include methyl acrylate, methyl methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearate (meth) acrylate, phenyl (meth) acrylate, biphenyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyglycol (meth) acrylate, 2-ethylhexylglycol di (meth) acrylate, methoxypropanediol (meth) acrylate, n-propyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-butyl (meth, (meth) acrylates such as phenoxyethyl (meth) acrylate, diphenoxyethyl (meth) acrylate, dicyclopentyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecyloxyethyl (meth) acrylate, nonylphenoxy glycol (meth) acrylate, nonylphenoxy propylene glycol (meth) acrylate, benzyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate; (meth) acryloylmorpholine (morpholinyl (meth) acrylate), (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, N-t-butyl (meth) acrylamide, N-t-octyl (meth) acrylamide, (meth) acrylic acid amides such as diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, N-triphenylmethyl (meth) acrylamide, and N, N-dimethyl (meth) acrylamide; aromatic vinyl compounds such as styrene, vinyltoluene and α -methylstyrene; butadiene or substituted butadiene compounds such as butadiene and isoprene; ethylene or substituted ethylene compounds such as ethylene, propylene, vinyl chloride and acrylonitrile; and vinyl esters such as vinyl acetate (vinyl acetate). These monomers may be used alone or in combination of two or more.

Specific examples of the other ethylenically unsaturated monomer (a-1-4) preferably include 2-hydroxyethyl methacrylate, methyl methacrylate, dicyclopentyl methacrylate, benzyl methacrylate, styrene, or a combination thereof.

The other ethylenically unsaturated monomer (a-1-4) may be used in an amount of 0 to 55 parts by weight, preferably 5 to 50 parts by weight, more preferably 10 to 45 parts by weight, based on 100 parts by weight of the total amount of the mixture.

Ethylenically unsaturated monomer (a-1-5)

The alkali-soluble resin (A-1) may further contain an ethylenically unsaturated group. Such an alkali-soluble resin (A-1) is obtained by further subjecting a polymer formed from monomers such as an ethylenically unsaturated monomer (a-1-1) containing a carboxylic acid group or a carboxylic anhydride group, an oxyalkylene-containing ethylenically unsaturated monomer (a-1-2), a maleimide group or two alkenyl group-containing ethylenically unsaturated monomer (a-1-3), and another ethylenically unsaturated monomer (a-1-4) to a condensation reaction with the ethylenically unsaturated monomer (a-1-5).

The ethylenically unsaturated monomer (a-1-5) includes an epoxy group-containing ethylenically unsaturated monomer, an isocyanate group-containing ethylenically unsaturated monomer, a hydroxyl group-containing ethylenically unsaturated monomer, a combination thereof, or the like.

When the carboxylic acid group-or carboxylic anhydride group-containing ethylenically unsaturated monomer (a-1-1) is a carboxylic acid group-containing ethylenically unsaturated monomer, an epoxy group-containing ethylenically unsaturated monomer and an isocyanate group-containing ethylenically unsaturated monomer can be used as the ethylenically unsaturated monomer (a-1-5). Specific examples of the epoxy group-containing ethylenically unsaturated monomer include epoxy propyl (meth) acrylate (glycidyl methacrylate), 3, 4-epoxycyclohexylmethyl (meth) acrylate, o-vinylbenzyl epoxy propyl ether (o-vinylbenzyl glycidyl ether), m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether, or a combination thereof. Specific examples of the ethylenically unsaturated monomer having an isocyanate group (isocyanato, -N ═ C ═ O) include 2-isocyanatoethyl (meth) acrylate (2-isocyanato ethyl (meth) acrylate).

When the carboxylic acid group-or carboxylic anhydride group-containing ethylenically unsaturated monomer (a-1-1) is a carboxylic anhydride group-containing ethylenically unsaturated monomer, a hydroxyl group-containing ethylenically unsaturated monomer can be used as the ethylenically unsaturated monomer (a-1-5). Specific examples of the hydroxyl group-containing ethylenically unsaturated monomer include 2-hydroxyethyl (meth) acrylate and the like.

Specific examples of the ethylenically unsaturated monomer (a-1-5) preferably include glycidyl methacrylate (glycidyl methacrylate), 3, 4-epoxycyclohexylmethyl methacrylate, o-vinylbenzylglycidyl ether (o-vinylbenzylglycidyl ether), or a combination thereof.

When the alkali-soluble resin (A-1) contains an ethylenically unsaturated group, the photosensitive resin composition has relatively excellent sensitivity.

The ethylenically unsaturated monomer (a-1-5) may be used in an amount of 10 to 180 parts by weight, preferably 15 to 160 parts by weight, more preferably 20 to 140 parts by weight, based on 100 parts by weight of the total amount of the mixture.

The method for producing the alkali-soluble resin (A-1) is explained in detail below:

the method of polymerizing the alkali-soluble resin (A-1) with the ethylenically unsaturated monomer (a-1-1) containing a carboxylic acid group or carboxylic anhydride group, the ethylenically unsaturated monomer (a-1-2) containing an oxyalkylene group, the ethylenically unsaturated monomer (a-1-3) containing a maleimide group or two alkenyl groups, and the other ethylenically unsaturated monomer (a-1-4) is not particularly limited, and an appropriate method can be selected as required. The polymerization method is, for example, a solution polymerization method.

The mixture constituting the alkali-soluble resin (A-1) may include a solvent. The kind of the solvent is not particularly limited. Specific examples of the solvent include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and propylene glycol monomethyl ether; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate (ethyl acetate), butyl acetate (butyl acetate), propylene glycol monomethyl ether acetate, and butyl 3-methoxyacetate; alcohols such as methanol and ethanol; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform; dimethyl sulfoxide, and the like. These solvents can be used alone or in combination of a plurality of them. The solvent is preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, or a combination thereof.

The polymerization concentration of the above mixture during polymerization is 5 to 90% by weight, preferably 5 to 50% by weight, and more preferably 10 to 50% by weight.

The mixture constituting the alkali-soluble resin (A-1) may include a polymerization initiator. The kind of the polymerization initiator is not particularly limited. Specifically, specific examples of the polymerization initiator include organic peroxides such as Cumene Hydroperoxide (CHP), diisopropylbenzene hydroperoxide (diisopropylbenzene hydroperoxide), dibutylperoxide (di-t-butyl peroxide), lauroyl peroxide (lauroyl peroxide), benzoyl peroxide (benzoyl peroxide), tributyl peroxyisopropylcarbonate (t-butylperoxide), tripentyl 2-ethylhexanoate peroxide (t-amyl-2-ethylhexanoate), and tributyl 2-ethylhexanoate peroxide (t-butyl-2-ethylhexanoate); azo compounds such as 2,2'-azobis (isobutyronitrile) (2,2' -azobis (isobutryronitrile)), 1'-azobis (cyclohexanecarbonitrile) (1,1' -azobis (cyclohexenenitrile)), 2'-azobis (2,4-dimethylvaleronitrile) (2,2' -azobis (2,4-dimethylvaleronitrile)), dimethyl 2,2'-azobis (2-methylpropionate) (2,2' -azobis (2-methyl propionate)), and the like. The polymerization initiator is preferably t-butyl peroxy-2-ethylhexanoate. The polymerization initiator may be used in an amount of 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total monomers in the mixture.

The polymerization temperature of the alkali-soluble resin (A-1) when polymerized by the solution polymerization method may be 40 ℃ to 150 ℃, preferably 60 ℃ to 130 ℃.

The polymer formed from the above mixture may further be subjected to addition reaction with the ethylenically unsaturated monomer (a-1-5), thereby obtaining an ethylenically unsaturated group (carbon double bond). The method for reacting the polymer with the ethylenically unsaturated monomer (a-1-5) is not particularly limited, and for example, the addition reaction (addition reaction) is carried out by reacting the ethylenically unsaturated monomer (a-1-5) with part or all of the acid groups (preferably part of the acid groups) of the polymer formed from the above mixture in the presence of a polymerization inhibitor and a catalyst described later.

In addition, a chain transfer agent may be added during the solution polymerization process to control the molecular weight of the polymer. The chain transfer agent is not particularly limited as long as it is a compound capable of functioning as a chain transfer agent in a radical polymerization reaction. The chain transfer agent is, for example, an alkyl mercaptan such as n-dodecyl mercaptan (1-dodecanethiol, nDM). The chain transfer agent may be used in an amount of 0.1 to 15 parts by weight, preferably 1.2 to 5.0 parts by weight, based on 100 parts by weight of the total monomers in the mixture.

Finally, the solution polymerization process may use a polymerization inhibitor to stop the free radical polymerization reaction. The polymerization inhibitor is not particularly limited in kind, and is, for example, an alkylphenol compound such as 6-tert-butyl-2, 4-dimethylphenol. In addition, a catalyst may be used in the solution polymerization method. The kind of the catalyst is not particularly limited, and is, for example, a tertiary amine such as dimethylbenzylamine (dimethylbenzylamine), triethylamine and the like.

The alkali-soluble resin (A-1) may be a random copolymer or a block copolymer.

The weight average molecular weight of the alkali-soluble resin (A-1) can be a value determined by Gel Permeation Chromatography (GPC) using a Tetrahydrofuran (THF) solvent. The weight average molecular weight of the alkali-soluble resin (A-1) may be 3,000 to 200,000, preferably 4,000 to 100,000, more preferably 5,000 to 50,000.

The acid value of the alkali-soluble resin (A-1) may be from 20mg KOH/g to 300mg KOH/g, preferably from 25mg KOH/g to 200mg KOH/g, more preferably from 30mg KOH/g to 150mg KOH/g.

When the alkali-soluble resin (A-1) is used, the photosensitive resin composition has excellent sensitivity. On the other hand, if the alkali-soluble resin (A-1) is not used, the sensitivity of the photosensitive resin composition is poor.

The alkali-soluble resin (A-1) may be used in an amount of 50 to 100 parts by weight, preferably 60 to 100 parts by weight, more preferably 70 to 100 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A).

Other alkali soluble resins (A-2)

The alkali-soluble resin (A) may include an alkali-soluble resin (A-2) other than the alkali-soluble resin (A-1).

The other alkali-soluble resin (A-2) is not particularly limited as long as the other alkali-soluble resin (A-2) is different from the alkali-soluble resin (A-1). The method for producing the other alkali-soluble resin (A-2) is not particularly limited, and for example, it is similar to the alkali-soluble resin (A-1), and therefore, description thereof will be omitted.

The other alkali-soluble resin (A-2) may be used in an amount of 0 to 50 parts by weight, preferably 0 to 40 parts by weight, more preferably 0 to 30 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A).

Compound (B) containing ethylenically unsaturated group

The ethylenically unsaturated group-containing compound (B) includes a compound having one ethylenically unsaturated group, a compound having two or more (two-containing) ethylenically unsaturated groups, or a combination thereof.

Specific examples of the compound having one ethylenically unsaturated group may include, but are not limited to, (meth) acrylamide, (meth) acryloylmorpholine, 7-amino-3, 7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, trioctyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, dodecyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N-dimethyl (meth) acrylamide, N-dimethylglycidyl (meth) acrylate, N-vinyl acetate, N-acrylate, N-vinyl acetate, tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate, and the like. These compounds having one ethylenically unsaturated group may be used alone or in combination of two or more.

Specific examples of the compound having two or more (containing two) ethylenically unsaturated groups include, but are not limited to, ethylene glycol diacrylate, ethylene glycol dimethacrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tris (2-hydroxyethyl) diisocyanato di (meth) acrylate, tris (2-hydroxyethyl) isocyanatetri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanatetri (meth) acrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene oxide (abbreviated as "EO") modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified (abbreviated as "PO") modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified (meth) acrylate, and the like, Tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexaacrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropyl tetra (meth) acrylate, ethylene oxide-modified bisphenol a di (meth) acrylate, propylene oxide-modified bisphenol a di (meth) acrylate, ethylene oxide-modified hydrogenated bisphenol a di (meth) acrylate, ethylene oxide-modified bisphenol a di (meth) acrylate, propylene oxide-modified bisphenol a di (meth) acrylate, Hydrogenated bisphenol a di (meth) acrylate modified with propylene oxide, bisphenol F di (meth) acrylate pentaerythritol triacrylate modified with ethylene oxide, glycerol triacrylate modified with propylene oxide, or novolak polyglycidyl ether (meth) acrylate. The compound having two or more (containing two) ethylenically unsaturated groups may be used alone or in combination of two or more.

Specific examples of the ethylenically unsaturated group-containing compound (B) may preferably include, but are not limited to, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, ethylene oxide-modified trimethylolpropane triacrylate, propylene oxide-modified trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropyl tetraacrylate, propylene oxide-modified glycerol triacrylate, or a combination thereof.

The ethylenically unsaturated group-containing compound (B) is more preferably ethylene glycol dimethacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, or a combination of the above compounds.

The ethylenically unsaturated group-containing compound (B) may be used in an amount of 50 to 600 parts by weight, preferably 70 to 580 parts by weight, more preferably 90 to 550 parts by weight, based on 100 parts by weight of the alkali-soluble resin (a).

Photoinitiator (C)

The photoinitiator (C) may include a photoinitiator (C-1), and may further include a photoinitiator (C-2). In addition, the photoinitiator (C) may optionally include other photoinitiators (C-3).

Photoinitiator (C-1)

The photoinitiator (C-1) is a compound represented by the following formula (II).

In the formula (II), the compound is shown in the specification,

R⁷is represented by C₁-C₂₀Linear or branched alkyl of (2), C₃-C₂₀Cycloalkyl of, C₄-C₂₀Cycloalkylalkyl of (C) ₄-C₂₀Alkylcycloalkyl of (A), C₆-C₂₀Aryl of (C)₆-C₂₀When R is an alkylaryl group, a group represented by the following formula (II-A), a group represented by the following formula (II-B) or a group represented by the following formula (II-C)⁷Is represented by C₁-C₂₀Linear or branched alkyl of (2), C₃-C₂₀Cycloalkyl of, C₄-C₂₀Cycloalkylalkyl of (C)₄-C₂₀Alkylcycloalkyl of (A), C₆-C₂₀Aryl or C of₆-C₂₀In which one or more hydrogens of the groups may each be independently substituted by an alkyl, halogen, hydroxy or nitro group, and R is⁷In (C-CH)₂-may be substituted by O, N, S or a carbonyl group;

R⁶and R⁷Can form a ring structure between;

in the formula (II-B), p is an integer of 0 to 3;

R⁸represents N-morpholinyl

N-piperidinyl radical

N-pyrrolyl

Or N-dialkyl (N (R)²¹)₂Wherein R is²¹Represents alkyl), wherein one or more of these groups may be substituted by halogen or hydroxy;

R⁹、R⁹' each independently represents C₁-C₂₀Linear or branched alkyl of (2), C₄-C₂₀Cycloalkyl of, C ₂-C₂₀Alkenyl of, C₆-C₂₀Aryl or C of₆-C₂₀Wherein one or more hydrogens in these groups may each be independently substituted with an alkyl, halogen, hydroxy or nitro group, and-CH in these groups₂-may be substituted by-O-; or R⁹And R⁹' may be linked to each other or form a five-or six-membered ring via-O-, -S-or-NH-;

In the formula (II), A preferably represents hydrogen, methyl, methoxy, chlorine, nitro, or the like,

Or N-morpholinyl, wherein R¹⁰Preferably represents phenyl, phenyl substituted by one or more methyl groups, phenyl substituted by nitro,

More preferably represents hydrogen, methyl, nitro, phenyl substituted by one or more methyl groups, or N-morpholinyl, wherein X represents a bonding position.

In the formula (II), R⁵Preferably represents hydrogen, methyl, propyl, butyl or allyl (allyl group, -CH) ₂CH＝CH₂) More preferably, it represents hydrogen, methyl, butyl or allyl.

In the formula (II), R⁶Preferably represents a methyl group or an ethyl group.

In the formula (II), R⁷Preferably represents a methyl group, an ethyl group or a benzyl group, more preferably a methyl group or a benzyl group.

In the formula (II), R⁸Preferably represents N-morpholinyl, N-piperidinyl, -N (CH)₃)₂、-N(CH₂CH₂CH₃)₂Or N-pyrrolyl, more preferably N-morpholinyl, -N (CH)₃)₂N-pyrrolyl or N-piperidinyl, wherein denotes a bonding site.

Specific examples of the photoinitiator (C-1) include compounds represented by the following formulas (II-1) to (II-35), or a combination of these compounds.

Specific examples of the photoinitiator (C-1) preferably include a compound represented by the formula (II-1), a compound represented by the formula (II-5), a compound represented by the formula (II-11), a compound represented by the formula (II-14), a compound represented by the formula (II-17), a compound represented by the formula (II-19), a compound represented by the formula (II-28), a compound represented by the formula (II-35), or a combination of these compounds.

By using the photoinitiator (C-1), a gapmer excellent in level difference can be formed. On the other hand, if the photoinitiator (C-1) is not used, the level difference of the resulting gapmer is not good.

The photoinitiator (C-1) may be used in an amount of 10 to 90 parts by weight, preferably 12 to 85 parts by weight, more preferably 15 to 80 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A).

Photoinitiator (C-2)

The photoinitiator (C-2) is a compound represented by the following formula (III).

In the formula (III), the compound represented by the formula (III),

Ar₁represents ortho-arylene or ortho-heteroarylene, the ortho-arylene or ortho-heteroarylene being adjacent to Y in two atoms₁And carbonyl group forms a cyclic junctionAnd the substituents on the remaining atoms are each selected from hydrogen; halogen; c₁-C₁₂Alkyl groups of (a); c₅-C₇Cycloalkyl groups of (a); warp C₅-C₇Cycloalkyl-substituted C of₁-C₄Alkyl groups of (a); a phenyl group; via one or more C₁-C₄Alkyl, carboxyl, C₁-C₁₂Alkyl acyl of (2), C₁-C₁₂Arylacyl, heteroarylacyl, JT₄Phenyl, halogen or CN substituted phenyl; c₁-C₄An alkyl benzyloxy group of (a); warp beam

Substituted C₁-C₄Alkoxy group of (C)₁-C₃(ii) an alkylenedioxy group;

C₁-C₁₂alkylthio of (a); c₁-C₄Alkylthiophenyl of (a); warp beam

Ar₁Between two adjacent substituents in the above substituents or between a substituent and Ar₁Form a ring structure through a single bond, a carbon atom and a carbonyl group;

T₁represents hydrogen, C ₁-C₁₈Alkyl or C₁-C₁₈Alkoxy group of (a); or

T₁Is indicated by aOne or more halogens, C₁-C₄Alkyl of (C)₅-C₇Cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C₁-C₄Is substituted with alkanoyloxy or aroyloxy and/or is substituted by C₅-C₇Cycloalkylene, phenylene, O, S or NT of₄Inserted C₂-C₁₈Alkyl groups of (a); c₂-C₁₈Alkenyl of (a); via one or more halogens, C₁-C₄Alkyl of (C)₅-C₇Cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C₁-C₄Is substituted with alkanoyloxy or aroyloxy and/or is substituted by C₅-C₇Cycloalkylene, phenylene, O, S or NT of₄Inserted C₂-C₁₈Or both; or

T₁Is represented by C₅-C₇Cycloalkyl through one or more C₁-C₄Alkyl, phenyl, halogen or CN substituted C₅-C₇Cycloalkyl groups of (a); or

T₁Represents naphthyl, benzoyl or phenoxycarbonyl, wherein the phenyl of benzoyl and phenoxycarbonyl is optionally substituted by one or more than two halogen, T₄、C₅-C₆Cycloalkyl, CN, OH or JT₄Substituted;

T₂and T₃Each independently represents hydrogen or C₁-C₁₈Alkyl, carboxyl substituted C₁-C₅Alkyl radical of (1), via C₁-C₄Alkoxy acyl substituted C ₁-C₅Alkyl or through

Substituted C₁-C₄Alkyl groups of (a); or

T₂And T₃Each independently representVia one or more halogens, C₁-C₄Alkyl of (C)₅-C₇Cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C₁-C₄Alkanoyloxy, aroyloxy substituted C of₂-C₁₈Or is substituted by C₅-C₇Cycloalkylene, phenylene, O, S or NT of₄Inserted C₂-C₁₈Or both are present; or

T₄is represented by C₁-C₄Alkyl groups of (a);

Substituted C₁-C₄Alkyl groups of (a); or

T₅By one or more halogensElement, C₁-C₄Alkyl of (C)₅-C₇Cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C₁-C₄Alkanoyloxy or aroyloxy substituted C of₂-C₁₈Or is substituted by C₅-C₇Cycloalkylene, phenylene, O, S or NT of₄Inserted C₂-C₁₈Or both are present; or

T₅Represents phenyl, or via one or more C₁-C₁₂Alkyl, carboxyl, C₁-C₁₂Alkanoyl, phenylenes, O, S or NT₄Inserted C₂-C₁₂Alkyl acyl of (2), C₅-C₆Cycloalkyl formyl group, C₅-C₆Cycloalkyl-substituted C of₂-C₄Alkyl acyl, aryl acyl, heteroaryl acyl, JT₄Phenyl, halogen, CN or NO₂Phenyl substituted by the above substituents, wherein arylacyl is benzoyl, or substituted by one or more halogens, C₁-C₄Alkyl or C₁-C₄Alkoxy-substituted benzoyl of (a); or

T₅Is represented by C₁-C₄Alkyl acyl of (2), C₁-C₄Wherein the phenyl in the benzoyl and phenoxycarbonyl group can be optionally substituted by one or more than two halogen, T ₄Cyclopentyl, cyclohexyl, CN, OH or JT₄Substitution; or

Substituted C₁-C₄Alkyl groups of (a); or

T₆And T₇Each independently of the other represents phenyl, or via one or more C₁-C₄Alkyl, carboxyl, C₁-C₁₂Alkyl acyl of (2), C₅-C₆Of cycloalkylformyl or C₅-C₆Cycloalkyl-substituted C of₂-C₄Alkyl acyl, aryl acyl, JT₄Phenyl, halogen or CN substituted phenyl; or

wherein when Ar is₁In the case of substituted carbazole groups, Y ₁Is not C, O, S or NT₇。

In the formula (III), Ar₁Preferably, the group represented by the following formula (III-A).

T₈、T₉、T₁₀And T₁₁Each independently represents hydrogen; or

T₈、T₉、T₁₀And T₁₁Each independently of the other being represented by one or more C₁-C₁₂Alkoxy group of (C)₁-C₄Alkyl benzyloxy substituted C of₁-C₄Alkoxy radical of (1)

Substituted C₁-C₄Alkoxy group of (a); or

T₈、T₉、T₁₀And T₁₁Each independently of the other being represented by one or more C₁-C₄Alkyl-substituted phenoxy of (a); through a C₁-C₈Alkyl acyl of (2), C₅-C₆Cycloalkyl acyl, aryl acyl, heteroaryl acyl substituted phenoxy of (a); warp C₅-C₆Cycloalkyl-substituted C of₁-C₄An alkylacylphenoxy group of (a); c₁-C₃(ii) an alkylenedioxy group;

C₁-C₁₂alkylthio of (a); warp beam

Substituted C₁-C₄Alkylthio of (a); warp C₁-C₄Alkylthiophenyl of (a); warp beam

Substituted C₁-C₄Alkylthiophenyl of (a); or

T₈、T₉、T₁₀And T₁₁Each independently represents a group via C₁-C₈Alkyl acyl of (2), C₅-C₆Phenylthio substituted by cycloalkylacyl, arylacyl, heteroarylacyl, or via C₅-C₆Cycloalkyl-substituted C of₁-C₄An alkylacylphenylthio group of (a);

Y₁preferably represents CH₂、CHCH₃Or C (CH)₃)₂；

T₁Preferably represents methyl, ethyl, phenyl, 2-methylphenyl, 3-methylphenyl, 2,4, 6-trimethylphenyl or 2, 6-dimethoxyphenyl;

denotes a bonding site.

Of note, Ar ₁Of the substituents of (A), preferably at least one substituent is in contact with Ar₁Para to the attached carbonyl.

Specific examples of the photoinitiator (C-1) include compounds represented by the following formulas (III-1) to (III-28), or a combination of these compounds.

Specific examples of the photoinitiator (C-2) preferably include a compound represented by the formula (III-2), a compound represented by the formula (III-6), a compound represented by the formula (III-11), a compound represented by the formula (III-17), a compound represented by the formula (III-24), a compound represented by the formula (III-28), or a combination of these compounds.

The photosensitive resin composition contains the photoinitiator (C-2), and the photosensitive resin composition has relatively excellent sensitivity.

The photoinitiator (C-2) may be used in an amount of 5 to 50 parts by weight, preferably 6 to 45 parts by weight, more preferably 7 to 40 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A).

Other photoinitiators (C-3)

The present invention optionally adds other photoinitiators (C-3). Specific examples of the other photoinitiator (C-3) include, but are not limited to, O-acyloximes, triazabenzenes, phenylethanones, diimidazoles, benzophenones, alpha-diketones, ketols, ketoethers, acylphosphine oxides, quinones, halogen-containing compounds, peroxides, or combinations thereof.

Specific examples of the above-mentioned O-acyloxime compounds include 1- [4- (phenylthio) phenyl ] -propane-3-cyclopentane-1, 2-dione 2- (O-benzoyloxime), 1- [4- (phenylthio) phenyl ] -heptane-1, 2-dione 2- (O-benzoyloxime), 1- [4- (phenylthio) phenyl ] -octane-1, 2-dione 2- (O-benzoyloxime), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9-hydro-carbazole-3-substituent ] -,1- (oxy-acetyloxime), 1, 2-butanedione-1- [4- (methylthio) phenyl ]2- (O-ethaneoxime Acyl oximes), or combinations thereof.

Specific examples of the O-acyloxime compounds include those preferably including 1- [4- (phenylthio) phenyl ] -heptane-1, 2-dione 2- (O-benzoyl oxime), 1- [4- (phenylthio) phenyl ] -octane-1, 2-dione 2- (O-benzoyl oxime), or a combination thereof. The above-mentioned O-acyloximes can be used singly or in combination of plural kinds, depending on the actual requirements.

Specific examples of the triazabenzene-based compound may include, but are not limited to, a vinyl-halomethyl-s-triazabenzene compound, a 2- (naphtho-1-substituent) -4, 6-bis-halomethyl-s-triazabenzene compound, a 4- (p-aminophenyl) -2, 6-bis-halomethyl-s-triazabenzene compound, or a combination thereof.

Specific examples of the above vinyl-halomethyl-s-triazabenzene compounds include 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazabenzene, 2, 4-bis (trichloromethyl) -3- (1-p-dimethylaminophenyl-1, 3-butenedionyl) -s-triazabenzene, 2-trichloromethyl-3-amino-6-p-methoxystyryl-s-triazabenzene, or combinations thereof.

Specific examples of the above-mentioned 2- (naphtho-1-substituent) -4, 6-bis-halomethyl-s-triazabenzene compound include 2- (naphtho-1-substituent) -4, 6-bis-trichloromethyl-s-triazabenzene, 2- (4-methoxy-naphtho-1-substituent) -4, 6-bis-trichloromethyl-s-triazabenzene, 2- (4-ethoxy-naphtho-1-substituent) -4, 6-bis-trichloromethyl-s-triazabenzene, 2- (4-butoxy-naphtho-1-substituent) -4, 6-bis-trichloromethyl-s-triazabenzene, and the like, 2- [4- (2-methoxyethyl) -naphtho-1-substituent ] -4, 6-bis-trichloromethyl-s-triazabenzene, 2- [4- (2-ethoxyethyl) -naphtho-1-substituent ] -4, 6-bis-trichloromethyl-s-triazabenzene, 2- [4- (2-butoxyethyl) -naphtho-1-substituent ] -4, 6-bis-trichloromethyl-s-triazabenzene, 2- (2-methoxy-naphtho-1-substituent) -4, 6-bis-trichloromethyl-s-triazabenzene, 2- (6-methoxy-5-methyl-naphtho-2-substituent) -4, 6-bis-trichloromethyl-s-triazabenzene, 2- (6-methoxy-naphtho-2-substituent) -4, 6-bis-trichloromethyl-s-triazabenzene, 2- (5-methoxy-naphtho-1-substituent) -4, 6-bis-trichloromethyl-s-triazabenzene, 2- (4, 7-dimethoxy-naphtho-1-substituent) -4, 6-bis-trichloromethyl-s-triazabenzene, 2- (6-ethoxy-naphtho-2-substituent) -4, 6-bis-trichloromethyl-s-triazabenzene, and, 2- (4, 5-dimethoxy-naphtho-1-substituent) -4, 6-bis-trichloromethyl-s-triazabenzene, or a combination thereof.

Specific examples of the aforementioned 4- (p-aminophenyl) -2, 6-bis-halomethyl-s-triazabenzene compounds include 4- [ p-N, N-bis (ethoxycarbonylmethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- [ o-methyl-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- [ p-N, N-bis (chloroethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- [ o-methyl-p-N, N-bis (chloroethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- (p-N-chloroethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- (p-N-ethoxycarbonylmethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ p-N, N-bis (phenyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- (p-N-chloroethylcarbonylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ p-N- (p-methoxyphenyl) carbonylaminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ m-N, N-bis (ethoxycarbonylmethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ m-bromo-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ m-chloro-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ m-fluoro-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 2, 6-bis (ethoxycarbonylmethyl) -s-triazobenzene, 4-bis (ethoxycarbonylmethyl) aminophenyl) -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ m-fluoro-p, 4- [ o-bromo-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- [ o-chloro-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl-2, 6-bis (trichloromethyl) -s-triazabenzene, 4- [ o-fluoro-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- [ o-bromo-p-N, N-bis (chloroethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazabenzene, N-tert-butyl-N, N-di (ethoxycarbonylmethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazabenzene, N-di (chloroethyl) aminophenyl-2, 6-bis (, 4- [ o-chloro-p-N, N-bis (chloroethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ o-fluoro-p-N, N-bis (chloroethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ m-bromo-p-N, N-bis (chloroethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ m-chloro-p-N, N-bis (chloroethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazobenzene, 4- [ m-fluoro-p-N, n-bis (chloroethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (m-bromo-p-N-ethoxycarbonylmethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (m-chloro-p-N-ethoxycarbonylmethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (m-fluoro-p-N-ethoxycarbonylmethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (o-bromo-p-N-ethoxycarbonylmethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (o-chloro-p-N-ethoxycarbonylmethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (o-fluoro-p-N-ethoxycarbonylmethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (m-bromo-p-N-chloroethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (m-chloro-p-N-chloroethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, and mixtures thereof, 4- (m-fluoro-p-N-chloroethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (o-bromo-p-N-chloroethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (o-chloro-p-N-chloroethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 4- (o-fluoro-p-N-chloroethylaminophenyl) -2, 6-bis (trichloromethyl) -s-triazabenzene, 2, 4-bis (trichloromethyl) -6- [ 3-bromo-4- [ N, n-bis (ethoxycarbonylmethyl) amino ] phenyl ] -1,3, 5-triazabenzene, or a combination thereof.

Specific examples of the aforementioned triazine-based compounds preferably include 4- [ m-bromo-p-N, N-bis (ethoxycarbonylmethyl) aminophenyl ] -2, 6-bis (trichloromethyl) -s-triazabenzene, 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazabenzene, or a combination thereof. The triazine compounds may be used alone or in combination of two or more.

Specific examples of the above-mentioned phenylethanone compounds include p-dimethylamine-phenethyl-ketone, α '-dimethoxyazoxyphenethyl-ketone, 2' -dimethyl-2-phenylethan-one, p-methoxy-phenethyl-ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, 2-benzyl-2-N, N-dimethylamine-1- (4-morpholinophenyl) -1-butanone, or a combination thereof. The aforementioned phenylethanones are preferably 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, 2-benzyl-2-N, N-dimethylamine-1- (4-morpholinophenyl) -1-butanone, or a combination thereof. The above-mentioned phenylethanone compounds can be used singly or in combination of plural kinds.

Specific examples of the above diimidazole compounds include 2,2 '-bis (o-chlorophenyl) -4, 4', 5,5 '-tetraphenyldiimidazole, 2' -bis (o-fluorophenyl) -4,4 ', 5, 5' -tetraphenyldiimidazole, 2 '-bis (o-methylphenyl) -4, 4', 5,5 '-tetraphenyldiimidazole, 2' -bis (o-methoxyphenyl) -4,4 ', 5, 5' -tetraphenyldiimidazole, 2 '-bis (o-ethylphenyl) -4, 4', 5,5 '-tetraphenyldiimidazole, 2' -bis (p-methoxyphenyl) -4,4 ', 5, 5' -tetraphenyldiimidazole, 2,2 ' -bis (2,2 ', 4,4 ' -tetramethoxyphenyl) -4,4 ', 5,5 ' -tetraphenyldiimidazole, 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyldiimidazole, 2 ' -bis (2, 4-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenyldiimidazole. The aforementioned bisimidazole compound is preferably 2,2 ' -bis (2, 4-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenyldiimidazole, or a combination thereof. The above bisimidazoles can be used alone or in combination of plural ones, depending on the actual need.

Specific examples of the above benzophenone-based compound include thioxanthone, 2, 4-diethylthioxanthone, thioxanthone-4-sulfone, benzophenone, 4 '-bis (dimethylamine) benzophenone, 4' -bis (diethylamine) benzophenone, or a combination thereof. The benzophenone compound is preferably 4, 4' -bis (diethylamine) benzophenone. The benzophenone compound can be used alone or in combination of a plurality of compounds, depending on the actual needs.

Specific examples of the above-mentioned α -diketones include benzil, acetyl, or a combination thereof.

Specific examples of the above ketols include benzoin. Specific examples of the above ketone alcohol ether compounds include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or combinations thereof.

Specific examples of the above acylphosphine oxide-based compound include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis- (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylphenylphosphine oxide, or a combination thereof.

Specific examples of the aforementioned quinone compounds include anthraquinone, 1, 4-naphthoquinone, or a combination thereof.

Specific examples of the above halogen-containing compounds include phenacyl chloride, tribromomethyl phenylsulfone, tris (trichloromethyl) -s-triazabenzene, or combinations thereof.

Specific examples of the above peroxides include di-tertiary butyl peroxide, or a combination thereof.

The above-mentioned α -diketones, ketols, ketoethers, phosphine oxides, quinones, halogens, peroxides and the like may be used alone or in combination of two or more, depending on the necessity.

Specific examples of the other photoinitiator (C-3) preferably include 1- [4- (phenylthio) phenyl ] -octane-1, 2-dione 2- (O-benzoyl oxime) (e.g., trade name OXE-01, manufactured by Ciba specialty Chemicals, Inc., having a structure represented by formula (IV)), 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone (trade name Irgacure 907, manufactured by Ciba specialty Chemicals, Inc.), or combinations thereof.

The photoinitiator (C) is used in an amount of 10 to 140 parts by weight, preferably 15 to 130 parts by weight, more preferably 20 to 120 parts by weight, based on 100 parts by weight of the alkali-soluble resin (a).

Solvent (D)

The solvent (D) is a solvent which can dissolve the alkali-soluble resin (A), the ethylenically unsaturated group-containing compound (B) and the photoinitiator (C) but does not react with the above components, and may have an appropriate volatility.

Specific examples of the solvent (D) include alkyl glycol monoalkyl ether compounds, alkyl glycol monoalkyl ether acetate compounds, diethylene glycol alkyl ether compounds, other ether compounds, ketone compounds, alkyl lactate compounds, other ester compounds, aromatic hydrocarbon compounds, carboxylic acid amine compounds, or a combination of the above compounds.

Specific examples of the alkyl glycol monoalkyl ether compounds include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, or the like, or a combination thereof.

Specific examples of the alkyl glycol monoalkyl ether acetate compounds include ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, or the like, or combinations thereof.

Specific examples of the diethylene glycol alkyl ether include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether or the like, or a combination of the above compounds.

Specific examples of the other ether-based compounds include tetrahydrofuran or the like.

Specific examples of the ketone compound include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol or the like, or a combination of the above compounds.

Specific examples of the alkyl lactate-based compound include methyl lactate, ethyl lactate, or the like, or a combination of the above-mentioned compounds.

Specific examples of the other ester compounds include methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl butyrate, methyl butyrate, ethyl pyruvate, ethyl propionate, ethyl butyrate, methyl propionate, ethyl butyrate, ethyl, N-propyl pyruvate, methyl acetoacetate, ethyl 2-oxybutyrate, or the like, or combinations thereof.

Specific examples of the aromatic hydrocarbon compound include toluene, xylene or the like, or a combination of the above compounds.

The carboxylic amine compound is N-methylpyrrolidinone, N-dimethylformamide, N-dimethylacetamide or the like, or a combination of the above compounds. The above-mentioned solvent (D) may be used singly or in combination of plural kinds.

Specific examples of the solvent (D) preferably include propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, ethyl 3-ethoxypropionate, or a combination thereof.

The solvent (D) may be used in an amount of 500 to 5000 parts by weight, preferably 600 to 4500 parts by weight, more preferably 700 to 4000 parts by weight, based on 100 parts by weight of the alkali-soluble resin (a).

Additive (E)

The photosensitive resin composition of the present invention may optionally include an additive (E) without affecting the efficacy of the present invention. The additive (E) may include a filler, a polymer other than the aforementioned alkali-soluble resin (a), an adhesion promoter, an antioxidant, an ultraviolet absorber, a surfactant, an anti-aggregation agent, or a combination thereof.

Specific examples of the filler include, but are not limited to, glass, aluminum, and the like.

Specific examples of polymers may include, but are not limited to, polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyalkyl fluoroacrylate, or any combination of the foregoing polymers.

Specific examples of the adhesion promoter may include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, or any combination of the foregoing.

Specific examples of antioxidants can include, but are not limited to, 2-thiobis (4-methyl-6-tert-butylphenol), 2, 6-di-tert-butylphenol, or any combination of the foregoing.

Specific examples of the ultraviolet absorber include, but are not limited to, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorophenylazide, alkoxyphenone (alkoxy phenone), or any combination of the above compounds.

Specific examples of commercially available surfactants include KP (manufactured by shin-Etsu chemical industry), SF-8427 (manufactured by Dow Corning Toray Silicone Co., Ltd.), Polyflow (manufactured by Cogrong oil and fat chemical industry), F-Top (manufactured by Tochem products Co., Ltd.), Megafac (manufactured by great Japan ink chemical industry (DIC)), Fluorade (manufactured by Sumitomo 3M Ltd.), Asahi Guard or Surflon (manufactured by Asahi Niger), SINOPOLE8008 (manufactured by Central Japan synthetic chemistry), F-475 (manufactured by great Japan ink chemical industry), or a combination thereof.

Specific examples of the anti-agglutinating agent may include, but are not limited to, sodium polyacrylate (sodium polyacrylate) and the like.

Specific examples of the additive (E) preferably include SF-8427 (manufactured by Dow Corning Toray Co., Ltd., surfactant), 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by shin-Etsu chemical Co., Ltd.), or a combination thereof.

The additive (E) may be used in an amount of 0 to 10 parts by weight, preferably 1 to 9 parts by weight, more preferably 3 to 8 parts by weight, based on 100 parts by weight of the alkali-soluble resin (a).

Method for preparing photosensitive resin composition

Methods that can be used to prepare the photosensitive resin composition include, for example: the alkali-soluble resin (A), the ethylenically unsaturated group-containing compound (B), the photoinitiator (C) and the solvent (D) are placed in a stirrer and stirred to be uniformly mixed into a solution state. Further, if necessary, an additive (E) may be added and uniformly mixed to obtain a photosensitive resin composition in a solution state.

The method for producing the photosensitive resin composition is not particularly limited. The photosensitive resin composition is produced, for example, by dispersing a part of the alkali-soluble resin (a) and the ethylenically unsaturated group-containing compound (B) in a part of the solvent (D) to form a dispersion solution; and mixing the remaining alkali-soluble resin (A), the ethylenically unsaturated group-containing compound (B), the photoinitiator (C), and the solvent (D). Further, an additive (E) may be added as necessary.

< protective film and spacer >

The invention provides a protective film and a spacer, which are formed by the photosensitive resin composition. The method for preparing the protective film and the spacer will be described in detail below.

In one embodiment, the step of forming the protective film includes: the photosensitive resin composition is applied to the pixel layer, and then, the photosensitive resin composition is subjected to steps such as prebaking, exposure, development, and post-baking.

In one embodiment, the step of forming the gapping body comprises: a transparent conductive film is formed on a transparent substrate on which a protective film and a pixel layer are formed, a photosensitive resin composition is coated on the transparent conductive film, and then prebaking, exposure, development, and post-baking are performed.

In other words, if the protective film is to be formed, the photosensitive resin composition is coated on the pixel layer on the substrate; if the spacer is to be formed, the photosensitive resin composition is coated on the transparent conductive film on the substrate.

Of course, the protective film and the spacer of the present invention are not limited to be formed on the pixel layer or the transparent conductive film, and may be formed on the substrate or various elements on the substrate. Hereinafter, the member coated with the photosensitive resin composition is also referred to as "coated article".

Specifically, the method for forming the spacer or the protective film sequentially comprises the following steps: (a) a film forming step; (b) an exposure step; (c) a developing step; and (d) post-baking step to form a protective film or spacer.

a. A film forming step:

the photosensitive resin composition is applied to a substrate (object to be coated) on which a pixel layer or a transparent conductive film is formed by an application method to form a film.

The substrate may be a transparent substrate or a transparent conductive substrate. The material of the substrate is not particularly limited, and examples thereof include glass substrates such as soda-lime glass and alkali-free glass; or a resin substrate such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, or polyimide. The substrate is preferably made of glass.

The transparent conductive substrate may have tin oxide (SnO) on the entire surface of the transparent substrate₂) Formed Nessel (NESA) film (registered trademark of PPG) or indium-tin oxide (In)₂O₃-SnO₂) An Indium Tin Oxide (ITO) film formed.

The coating method is a method of coating a solution of a photosensitive resin composition on an object to be coated. The solid concentration of the photosensitive resin composition solution applied to the coating method is 5 to 50 wt%, preferably 10 to 40 wt%, and more preferably 15 to 35 wt%. Coating methods include, but are not limited to, spray coating, roll coating, spin coating (spin coating), slot die coating, bar coating, or ink jet coating. In addition, the coated surface of the substrate is preferably subjected to a heating step prior to the coating method.

In addition, it is preferable to further perform a pre-baking treatment on the film. The conditions of the pre-baking treatment may vary depending on the components and the mixing ratio, and it is preferable to heat at 70 ℃ to 90 ℃ for 1 minute to 15 minutes. After the pre-baking treatment, the thickness of the film is 0.15 μm to 8.5 μm, preferably 0.15 μm to 6.5 μm, and more preferably 0.15 μm to 4.5 μm. The thickness is a thickness after the solvent is removed.

b. An exposure step:

the film is exposed to light using a mask having a specific pattern. The light used in the exposure step may be, for example, visible light, ultraviolet light, far ultraviolet light, electron beam (electron beam), or X-ray, and preferably ultraviolet light having a wavelength of 190nm to 450 nm. The exposure amount in the exposure step is 100J/m²To 20,000J/m²Preferably 150J/m²To 10,000J/m²。

c. A developing step:

after the above exposure step, development treatment is performed to remove unnecessary portions and form a specific pattern by alkali development.

Specific examples of the developer include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; primary aliphatic amines such as ethylamine and n-propylamine; secondary aliphatic amines such as diethylamine or n-propylamine; tertiary aliphatic amines such as trimethylamine, diethylaminomethyl, dimethylethylamine, and triethylamine; a tertiary aliphatic cyclic acid such as pyrrole, piperidine, N-methylpiperidine, N-methyl-1, 8-diazabicyclo [5.4.0] -7-undecene or 1, 5-diazabicyclo [4.3.0] -5-nonene; tertiary aromatic amines such as pyridine, methylpyrimidine, lutidine, and quinoline; a quaternary ammonium salt basic compound such as an aqueous solution of tetramethylammonium hydroxide or tetraethylammonium hydroxide; or combinations of the foregoing. Water-soluble organic solvents or surfactants, such as methanol or ethanol, may also be added to the developer as needed.

Examples of the developing method include a dipping method, an impregnation method, and a shower method. The development is preferably carried out at room temperature to 180 ℃ for about 10 seconds.

The substrate on which the predetermined pattern is formed is subjected to steam cleaning for 30 to 90 seconds after development, and air-dried by compressed air or nitrogen gas.

d. Post-baking step:

the substrate on which the predetermined pattern is formed is subjected to post-bake (post-bake) processing with a heating device such as a hot plate or an oven to form a spacer or a protective film. The heating temperature is set between 150 ℃ and 250 ℃, wherein the heating time using the heating plate is 5 minutes to 30 minutes, and the heating time using the oven is 30 minutes to 90 minutes.

After the above-mentioned treatment steps, the protective film and the spacer can be formed.

The protective film and the spacer of the present invention are not limited to those formed on the pixel layer or the transparent conductive film, and may be formed on the substrate or various elements on the substrate.

< method for producing color Filter substrate >

The color filter substrate is manufactured, for example, by: sputtering is carried out on the surface of the protective film in the transparent substrate on which the pixel coloring layers of red, green, blue and the like and the protective film are formed under the vacuum environment with the temperature between 220 ℃ and 250 ℃ to form an Indium Tin Oxide (ITO) protective film. In addition, if necessary, the ITO protective film may be etched and wired, and then a liquid crystal alignment film may be coated on the surface of the ITO protective film. Thus, a color filter including a cured product obtained by curing the photosensitive resin composition of the present invention can be manufactured.

< liquid crystal display element and method for producing the same >

The invention further provides a liquid crystal display element, which comprises at least one of a spacer and a protective film formed by the photosensitive resin composition. Specifically, the liquid crystal display element of the invention comprises a color filter substrate, an active element substrate and a liquid crystal layer positioned between the color filter substrate and the active element substrate. The active device substrate is a substrate provided with a thin film transistor. At least one of the color filter substrate and the active device substrate may include a protective film formed of the photosensitive resin composition of the present invention. In addition, the gap body can be dispersed in the liquid crystal layer in a mode of being clamped between the color filter substrate and the active element substrate, so that a gap exists between the color filter substrate and the active element substrate.

The method for manufacturing the liquid crystal display element of the present invention is not particularly limited, and the liquid crystal display element is manufactured by, for example, the following method.

First, the color filter substrate and the active device substrate are disposed to face each other with a gap interposed therebetween. Next, the peripheries of the color filter substrate and the active element substrate are bonded using a sealant, and the injection hole is left. Then, liquid crystal is injected between the color filter substrate and the active element substrate and into the space divided by the sealant through the injection hole. And finally, after the injection hole is sealed, a liquid crystal layer is formed between the color filter substrate and the active element substrate. The liquid crystal compound or the liquid crystal composition contained in the liquid crystal layer is not particularly limited, depending on the actual need.

In addition, the liquid crystal compound and the liquid crystal composition can be aligned through the liquid crystal alignment film under the condition of applying voltage and irradiation light. The kind of the liquid crystal alignment film is not particularly limited, depending on the actual need.

The invention will be further described in the following examples, which are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.

Synthesis example of alkali-soluble resin (A-1)

The amounts of the respective reaction reagents used for the syntheses of the synthesis examples A-1-1 to A-1-11 and the synthesis examples A-2-1 to A-2-2 of the alkali-soluble resin (A-1) of the present invention are shown in Table 1 below, and the names of the respective reaction reagents are shown in Table 2 below.

Synthesis example A-1

First, two droppers (injectors) were prepared, one of which was a monomer drip and the other was a chain transfer agent drip.

To a monomer dropping vessel, 45g of acrylic acid (as a monomer, hereinafter referred to as AA), 40g of a mixture of phenylphenoxyglycol acrylate and phenylphenoxydiethylene glycol acrylate (molar ratio 1: 1, this mixture as a monomer, hereinafter referred to as PGAPDGA), 15g of benzylmaleimide (as a monomer, hereinafter referred to as BzMI), 2g of tributyl 2-ethylhexanoate peroxide (as a polymerization initiator, (trade name of PERBUTYL) O, manufactured by japan grease company, hereinafter referred to as PBO), 42g of propylene glycol monomethyl ether acetate (as a solvent, hereinafter referred to as PGMEA), and 18g of propylene glycol monomethyl ether (as a solvent, hereinafter referred to as PGME) were added and mixed with stirring to prepare a monomer mixture. Subsequently, 2g of n-dodecylmercaptan (nDM), 18g of PGMEA, and 8g of PGME were added to a chain transfer agent dropping vessel and mixed with stirring.

A separable flask equipped with a condenser tube was prepared as a reaction vessel. In the reaction vessel, 98g of PGMEA and 42g of PGME were charged. Subsequently, the reaction vessel was heated in an oil bath under nitrogen atmosphere with stirring to raise the temperature of the reaction vessel to 90 ℃. After the temperature of the reaction tank is stabilized at 90 ℃, the monomer mixture and the chain transfer agent are respectively dripped into the reaction tank by a monomer dripping device and a chain transfer agent dripping device. The monomer and chain transfer agent droppers were maintained at 90 ℃ and the monomer mixture and chain transfer agent were dripped off over a period of 180 minutes. After the addition, 0.5g of PBO was added after the reaction for 30 minutes. Then, after further reaction for 30 minutes, the reaction vessel was heated to 115 ℃. After the temperature of the reaction tank was stabilized at 115 ℃ for 1.5 hours, the gas in the separable flask was replaced with a mixed gas of oxygen/nitrogen (5/95 (v/v)). Subsequently, 70g of glycidyl methacrylate (as a monomer, GMA), 0.3g of 6-tert-butyl-2, 4-dimethylphenol (trade name "Topanol" manufactured by Tokyo chemical industry Co., Ltd., as a polymerization inhibitor), 0.5g of dimethylbenzylamine (as a catalyst, DMBA), 16g of PGMEA, and 6g of PGME were charged into the reaction vessel. Then, the reaction was carried out at a temperature of 110 ℃ for 1 hour, followed by a reaction at a temperature of 115 ℃ for 8 hours. Subsequently, the reaction solution was cooled to room temperature to obtain an alkali-soluble resin A-1-1. The weight-average molecular weight (Mw) of the alkali-soluble resin A-1-1 was 17200.

Synthesis examples A-1-2 to A-1-9 and Synthesis examples A-2-1 to A-2

The alkali-soluble resins (A-1) of Synthesis examples A-1-2 to A-1-9 and Synthesis examples A-2-1 to A-2-2 were prepared in the same procedure as in Synthesis example A-1-1, except that: the monomers used for synthesizing the alkali-soluble resin (A-1) and the amounts thereof used, and the amount of the chain transfer agent used were changed (as shown in Table 1).

TABLE 2

Examples 1 to 11 and comparative examples 1 to 4

Examples 1 to 11 and comparative examples 1 to 4 of the photosensitive resin composition are described below:

example 1

The photosensitive resin composition of example 1 was prepared by adding 100 parts by weight of the alkali-soluble resin of Synthesis example A-1-1 (hereinafter referred to as A-1-1), 50 parts by weight of ethylene glycol dimethacrylate (hereinafter referred to as B-1) and 10 parts by weight of the compound represented by formula (II-1) (hereinafter referred to as C-1-1) to 500 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as D-1) and stirring the mixture uniformly with a shaking type stirrer. The obtained photosensitive resin compositions were evaluated in the following evaluation methods, and the results are shown in table 3.

Examples 2 to 11, and comparative examples 1 to 4

The photosensitive resin compositions of examples 2 to 11 and comparative examples 1 to 4 were prepared by the same procedure as in example 1 except that: the types of components and the amounts of the components used in the photosensitive resin composition were varied (as shown in Table 3), and the components corresponding to the reference numerals in Table 3 are shown in Table 4. The obtained photosensitive resin compositions were evaluated in the following evaluation methods, and the results are shown in table 3.

TABLE 4

< evaluation mode >

Sensitivity of the device

The photosensitive resin compositions obtained in the above examples and comparative examples were spin-coated on a plain glass substrate of 100mm × 100mm × 0.7mm, and prebaked at 90 ℃ for 150 seconds to obtain a prebaked coating film having a thickness of about 4 μm.

Then, the obtained prebaked coating film is exposed. Specifically, a photomask having a specific pattern was placed between the prebaked coating film and an exposure machine (model AG 500-4N; manufactured by Kogyo science Co., Ltd. (M & R Nano Technology)), and the prebaked coating film was irradiated with ultraviolet rays of different exposure amounts. Then, after the film thickness () was measured at any one measurement point on the coating film, the coating film was immersed in a 0.0438 wt% aqueous solution of potassium hydroxide (KOH) for 70 seconds and developed, and another film thickness (d) was measured at the same measurement point. Finally, the residual film rate can be obtained by the calculation of the following formula (V).

Residual film ratio (%) [ (d)/() ]. times.100 (V)

The exposure amount when the residual film ratio is 90% or more is referred to as sensitivity, and is evaluated according to the following criteria:

very good: the exposure is ≦ 70mJ/cm²；

○：70mJ/cm²<The exposure is less than or equal to 90mJ/cm²；

△：90mJ/cm²<The exposure is ≦ 110mJ/cm²；

Gamma rays: the exposure is more than 110mJ/cm²。

Difference in level

The photosensitive resin compositions obtained in the above examples and comparative examples were spin-coated on a plain glass substrate of 100mm × 100mm × 0.7mm, and prebaked at 90 ℃ for 150 seconds to obtain a prebaked coating film of about 4 μm.

Then, the prebaked coating film was placed under a prescribed mask pattern (partial halftone, transmittance 30%) and applied with energy of 60mJ/cm²Ultraviolet rays (exposure machine model is AG500-4N, and it is Kogyi science and technology (stock) Co., Ltd. (M)&RNano Technology manufacturing)) to perform an exposure step.

Next, the coating film after exposure was immersed in an aqueous solution of potassium hydroxide (KOH) having a concentration of 0.0438 wt% for development for 70 seconds to remove unexposed portions. And cleaning the obtained product with pure water, and baking at 235 deg.C for 30 min to obtain the final product.

Wherein the height of the main gap body is Hm, the height of the secondary gap body (halftone part) is Hs, and Hm-Hs is the step difference.

Very good: 0.1 μm or more and an interval of 0.3 μm or less;

o: 0.3 μm < difference between sections ≦ 0.4 μm;

and (delta): 0.4 μm < difference between sections ≦ 0.5 μm;

gamma rays: the step difference is more than 0.5 μm or less than 0.1 μm.

< evaluation results >

As is apparent from Table 3, the photosensitive resin compositions (examples 1 to 11) containing both the alkali-soluble resin (A-1) and the photoinitiator (C-1) exhibited excellent sensitivity and formed gapmers having excellent step differences, as compared with the photosensitive resin compositions (comparative examples 1 and 2) containing no alkali-soluble resin (A-1), the photosensitive resin composition (comparative example 3) containing no photoinitiator (C-1), and the photosensitive resin composition (comparative example 4) containing neither the alkali-soluble resin (A-1) nor the photoinitiator (C-1). Further, the photosensitive resin compositions (comparative examples 1 and 2) containing no alkali-soluble resin (a-1) had poor sensitivity; the level difference of the spacer formed by the photosensitive resin composition (comparative example 3) not containing the photoinitiator (C-1) was not good; the photosensitive resin composition (comparative example 4) which does not contain the alkali-soluble resin (A-1) and the photoinitiator (C-1) is not good in sensitivity and is not good in level difference of the spacer to be formed.

When the monomer mixture for synthesizing the alkali-soluble resin (A-1) contains the ethylenically unsaturated monomer (a-1-3) having a maleimide group or two alkenyl groups (examples 1 to 7 and 11), the photosensitive resin composition can form a spacer having a relatively excellent step difference.

When the synthetic alkali-soluble resin (A-1) contains an ethylenically unsaturated group (examples 1 to 6, 8, and 11), the photosensitive resin composition has relatively excellent sensitivity.

When the photosensitive resin composition contains the photoinitiator (C-2) (examples 2 to 6, 10), the photosensitive resin composition has relatively excellent sensitivity.

In summary, the photosensitive resin composition of the present invention comprises the alkali-soluble resin (A-1) having a specific structure and the photoinitiator (C-1) having a specific structure, and can effectively improve the problems of poor sensitivity and poor level difference of the spacer. Thus, the present invention provides a photosensitive resin composition which has excellent sensitivity and can form a spacer having an excellent step difference, and which is suitable for use in spacers and protective films.

Although the present invention has been described with reference to the above embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention.

Claims

1. A photosensitive resin composition comprising:

an alkali-soluble resin A;

a compound B containing an ethylenically unsaturated group;

a photoinitiator C; and

a solvent D;

wherein the alkali-soluble resin A comprises an alkali-soluble resin A-1, the alkali-soluble resin A-1 is obtained by copolymerizing a mixture, the mixture comprises an ethylenically unsaturated monomer a-1-1 containing a carboxylic acid group or a carboxylic anhydride group and an oxyalkylene-containing ethylenically unsaturated monomer a-1-2 represented by the following formula (I),

in the formula (I), the compound is shown in the specification,

R¹、R²and R³Each independently represents hydrogen or methyl;

AO represents C₂-C₂₀Oxyalkylene of (a);

x represents an integer of 0 to 2;

y represents 0 or 1;

n represents 2 or more;

the photoinitiator C comprises a photoinitiator C-1, the photoinitiator C-1 is a compound shown in the following formula (II),

in the formula (II), the compound is shown in the specification,

Wherein C is₁-C₂₀Linear or branched alkyl of (2), C ₃-C₁₀Alkylcycloalkyl of (A), C₄-C₁₀Alkylcycloalkyl of (A), C₄-C₁₀A cycloalkylalkyl group of,

R⁶is represented by C₁-C₂₀Linear or branched alkyl of (2), C₂-C₂₀Alkenyl of, C₃-C₂₀Cycloalkyl of, C₄-C₂₀Cycloalkylalkyl of (C)₄-C₂₀Alkylcycloalkyl of (A), C₆-C₂₀Aryl or C of₆-C₂₀Wherein one or more hydrogens in these groups may each independently be replaced by an alkaneIs substituted by radicals, halogen, hydroxy or nitro, and R⁶In (C-CH)₂-may be substituted by O, N, S or a carbonyl group;

R⁷is represented by C₁-C₂₀Linear or branched alkyl of (2), C₃-C₂₀Cycloalkyl of, C₄-C₂₀Cycloalkylalkyl of (C)₄-C₂₀Alkylcycloalkyl of (A), C₆-C₂₀Aryl of (C)₆-C₂₀When R is an alkylaryl group, a group represented by the following formula (II-A), a group represented by the following formula (II-B) or a group represented by the following formula (II-C)⁷Is represented by C₁-C₂₀Linear or branched alkyl of (2), C₃-C₂₀Cycloalkyl of, C₄-C₂₀Cycloalkylalkyl of (C)₄-C₂₀Alkylcycloalkyl of (A), C ₆-C₂₀Aryl or C of₆-C₂₀In which one or more hydrogens of the groups may each be independently substituted by an alkyl, halogen, hydroxy or nitro group, and R is⁷In (C-CH)₂-may be substituted by O, N, S or a carbonyl group;

R⁶and R⁷Can form a ring structure between;

in the formula (II-B), p is an integer of 0 to 3;

in the formula (II-C)，R¹⁵Represents hydrogen, C₁-C₈Ar is substituted or unsubstituted phenyl, naphthyl, furyl, thienyl or pyridyl;

R⁹、R⁹' each independently represents C₁-C₂₀Linear or branched alkyl of (2), C₄-C₂₀Cycloalkyl of, C₂-C₂₀Alkenyl of, C₆-C₂₀Aryl or C of₆-C₂₀Wherein one or more hydrogens in these groups may each be independently substituted with an alkyl, halogen, hydroxy or nitro group, and-CH in these groups₂-may be substituted by-O-; or R⁹And R⁹' may be linked to each other or form a five-or six-membered ring via-O-, -S-or-NH-;

R¹⁰is represented by C ₁-C₂₀Linear or branched alkyl of (2), C₄-C₂₀Cycloalkyl of, C₄-C₂₀Alkylcycloalkyl of (A), C₂-C₂₀Alkenyl of, C₆-C₂₀Aryl or C of₆-C₂₀In which-CH in these groups₂-may be substituted by-O-or-S-, and one or more hydrogens of these groups may be independently selected from alkyl, halogen, nitro, cyano, SR¹⁶OR OR¹⁷Substituted;

2. The photosensitive resin composition according to claim 1, wherein the mixture further comprises an ethylenically unsaturated monomer a-1-3 containing a maleimide group or two alkenyl groups.

3. The photosensitive resin composition according to claim 2, wherein the maleimide group-or two-alkenyl group-containing ethylenically unsaturated monomer a-1-3 comprises at least one monomer selected from the group consisting of monomers represented by the following formulae (1) to (5),

in the formulae (4) and (5), R¹⁸、R¹⁹And R²⁰Each independently represents hydrogen, or C₁-C₃₀Linear or branched alkyl groups of (1).

4. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin a-1 contains an ethylenically unsaturated group.

5. The photosensitive resin composition according to claim 1, wherein the photoinitiator C further comprises a photoinitiator C-2, the photoinitiator C-2 being a compound represented by the following formula (III),

In the formula (III), the compound represented by the formula (III),

Ar₁represents an ortho-arylene or ortho-heteroarylene group, the ortho-arylene or ortho-heteroarylene group being adjacent to Y in two atoms₁And the carbonyl groups form a cyclic structure, and the substituents on the remaining atoms are each selected from hydrogen; halogen; c₁-C₁₂Alkyl groups of (a); c₅-C₇Cycloalkyl groups of (a); warp C₅-C₇Cycloalkyl-substituted C of₁-C₄Alkyl groups of (a); a phenyl group; via one or more C₁-C₄Alkyl, carboxyl, C₁-C₁₂Alkyl acyl of (2), C₁-C₁₂Arylacyl, heteroarylacyl, JT₄Phenyl, halogen or CN substituted phenyl; c₁-C₄An alkyl benzyloxy group of (a); warp beam

Substituted C₁-C₄Alkoxy group of (C)₁-C₃(ii) an alkylenedioxy group;

C₁-C₁₂alkylthio of (a); c₁-C₄Alkylthiophenyl of (a); warp beam

Ar₁Between two adjacent substituents or between a substituent and Ar₁Form a ring structure through a single bond, a carbon atom and a carbonyl group;

T₁Represents a halogen atom or atoms, C ₁-C₄Alkyl of (C)₅-C₇Cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C₁-C₄Is substituted with alkanoyloxy or aroyloxy and/or is substituted by C₅-C₇Cycloalkylene, phenylene, O, S or NT of₄Inserted C₂-C₁₈Alkyl groups of (a); c₂-C₁₈Alkenyl of (a); via one or more halogens, C₁-C₄Alkyl of (C)₅-C₇Cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C₁-C₄Is substituted with alkanoyloxy or aroyloxy and/or is substituted by C₅-C₇Cycloalkylene, phenylene ofBasic group, O, S or NT₄Inserted C₂-C₁₈Or both are present; or

Substituted C₁-C₄Alkyl groups of (a); or

T₂And T₃Each independently represents a halogen atom or a halogen atom via one or more atoms, C ₁-C₄Alkyl of (C)₅-C₇Cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C₁-C₄Alkanoyloxy, aroyloxy substituted C of₂-C₁₈Or is substituted by C₅-C₇Cycloalkylene, phenylene, O, S or NT of₄Inserted C₂-C₁₈Or both are present; or

T₄is represented by C₁-C₄Alkyl groups of (a);

Substituted C₁-C₄Alkyl groups of (a); or

T₅Represents a halogen atom or atoms, C₁-C₄Alkyl of (C)₅-C₇Cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C ₁-C₄Alkanoyloxy or aroyloxy substituted C of₂-C₁₈Or is substituted by C₅-C₇Cycloalkylene, phenylene, O, S or NT of₄Inserted C₂-C₁₈Or both are present; or

T₅Represents phenyl, or via one or more C₁-C₁₂Alkyl, carboxyl, C₁-C₁₂Alkanoyl, phenylenes, O, S or NT₄Inserted C₂-C₁₂Alkyl acyl of (2), C₅-C₆Cycloalkyl formyl group, C₅-C₆Cycloalkyl-substituted C of₂-C₄Alkyl acyl, aryl acyl, heteroaryl acyl, JT₄Phenyl, halogen, CN or NO₂Substituted phenyl or

T₅Is represented by C₁-C₄Alkyl acyl of (2), C₁-C₄Wherein the phenyl in the benzoyl and the phenoxycarbonyl group can be optionally substituted by one or more than two halogen, T₄Cyclopentyl, cyclohexyl, CN, OH or JT₄Substitution; or

Substituted C₁-C₄Alkyl groups of (a); or

T₆And T₇Each independently represents a halogen atom or a halogen atom via one or more atoms, C ₁-C₄Alkyl of (C)₅-C₇Cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C₁-C₄Alkanoyloxy or aroyloxy substituted C of₂-C₁₈Alkyl of (C)₅-C₇Cycloalkylene, phenylene, O, S or NT of₄Inserted C₂-C₁₈Or both are present; or

6. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin a-1 is used in an amount of 50 to 100 parts by weight, the ethylenically unsaturated group-containing compound B is used in an amount of 50 to 600 parts by weight, the photoinitiator C is used in an amount of 10 to 140 parts by weight, the photoinitiator C-1 is used in an amount of 10 to 90 parts by weight, and the solvent D is used in an amount of 500 to 5000 parts by weight, based on 100 parts by weight of the alkali-soluble resin a.

7. The photosensitive resin composition according to claim 1, wherein the oxyalkylene group-containing ethylenically unsaturated monomer a-1-2 is used in an amount of 1 to 55 parts by weight based on 100 parts by weight of the total amount of the mixture used.

8. The photosensitive resin composition according to claim 2, wherein the maleimide group-or two alkenyl group-containing ethylenically unsaturated monomer a-1-3 is used in an amount of 5 to 50 parts by weight based on 100 parts by weight of the total amount of the mixture used.

9. The photosensitive resin composition according to claim 5, wherein the photoinitiator C-2 is used in an amount of 5 to 50 parts by weight based on 100 parts by weight of the alkali-soluble resin A.

10. A spacer formed from the photosensitive resin composition according to any one of claims 1 to 9.

11. A protective film formed from the photosensitive resin composition according to any one of claims 1 to 9.

12. A liquid crystal display element comprising the gap body according to claim 10.

13. A liquid crystal display element comprising the protective film according to claim 11.