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

Abstract

The present application provides a photosensitive resin composition with excellent sensitivity and capable of forming a gap body with excellent step difference, a gap body, a protective film, and a liquid crystal display element. The photosensitive resin composition includes an alkali-soluble resin A, a compound containing an ethylenically unsaturated group B, a photoinitiator C, and a solvent D. The alkali-soluble resin A includes an alkali-soluble resin A-1, which is obtained by copolymerization of a mixture including an ethylenically unsaturated monomer a-1-1 containing a carboxylic acid group or a carboxylic anhydride group and an ethylenically unsaturated monomer a-1-2 containing an oxyalkylene group represented by formula (I). The photoinitiator C includes a photoinitiator C-1, which is a compound represented by formula (II).

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a spacer, a protective film and a liquid crystal display element, and in particular to a photosensitive resin composition suitable for the spacer and the protective film and a liquid crystal display element using the spacer and the protective film. Background Art

[0002] Generally speaking, the color-printed pixels and the black matrix on the surface of the color filter layer are uneven. Therefore, a protective film is usually formed on the surface of the color filter layer to hide the unevenness and achieve the flatness requirement.

[0003] However, in the manufacture of optical elements such as liquid crystal display elements or solid-state imaging devices, it is often necessary to process them under harsh conditions. For example, when the substrate surface is immersed in an acidic solvent or alkaline solution or a wiring electrode layer is formed by sputtering, local corrosion or high temperature will be generated. Therefore, a protective film needs to be laid on the surface of these elements to prevent the elements from being damaged during manufacturing. In order for the protective film to have the characteristics of withstanding the above-mentioned treatments, the protective film needs to have excellent adhesion to the substrate, and also needs to have high transparency, high surface hardness and a smooth surface. In addition, the protective film also needs to have a protective film with high heat resistance and light resistance to avoid discoloration, yellowing or whitening and other deterioration during long-term use. In addition, the protective film also needs to have good water resistance, chemical resistance, solvent resistance, acid resistance and alkali resistance.

[0004] On the other hand, in the prior art, in a color liquid crystal display element, in order to maintain a fixed interlayer spacing between two substrates, beads such as polystyrene beads or silicon beads are randomly sprayed on the entire substrate, wherein the diameter of the beads is the spacing between the two substrates. However, this existing method is not uniform due to the uneven distribution of the position and density of the beads, causing the light of the backlight source to be affected by the beads and scattered, further reducing the contrast of the display element. Therefore, the photosensitive composition for the gap body developed by the light micro-photography process (photolithography) has become the mainstream of the industry. The formation method of the gap body is to first apply the photosensitive composition for the gap body to the substrate, and then place a specified shape mask between the substrate and the exposure source, and then develop the gap body after the exposure step. According to this method, a gap body can be formed at a specified position outside the pixels of red, green, blue, etc. to solve the problems of the prior art; the interlayer spacing can also be controlled by the thickness of the coating formed by the photosensitive component, so that the distance of the interlayer spacing becomes easy to control, with the advantage of high precision.

[0005] Because protective films or spacers are formed on color filters or substrates, they have extremely high transparency requirements. If the protective films or spacers have poor transparency, when used in liquid crystal displays (LCDs), they will result in insufficient brightness and affect the display quality of the LCD.

[0006] To improve the transparency of a protective film or spacer, Japanese Patent Application Laid-Open No. 2010-054561 discloses a photosensitive composition for a protective film. The composition comprises (A) an alkali-soluble binder resin, (B) a compound having an ethylenically unsaturated group, (C) a photoinitiator, and (D) a solvent. The equivalent weight of the unsaturated bond in the compound having an ethylenically unsaturated group (B) is between 90 and 450 g / eq. The number of unsaturated double bonds in a single compound of the ethylenically unsaturated group (B) is between 2 and 4. The weight-average molecular weight of the binder resin (A) is between 10,000 and 20,000. Meanwhile, Japanese Patent Application Laid-Open No. 2004-240241 discloses a photosensitive composition comprising (A) a copolymer formed from an ethylenically unsaturated carboxylic acid (anhydride), a compound having an ethylenically unsaturated group containing an epoxy group, and another compound having an ethylenically unsaturated group; (B) a polymerizable compound having an ethylenically unsaturated group; and (C) a photopolymerization initiator such as 2-butanedione-(4-(methylthio)phenyl)-2-(O-oxime acetate), 1,2-butanedione-1-(4-morpholinophenyl)-2-(O-benzoyloxime), or 1,2-octanedione-1-(4-(phenylthio)phenyl)-2-[O-(4-methylbenzoyl)oxime]. However, these photosensitive resin compositions still suffer from poor sensitivity, and the resulting spacers also have poor step height.

[0007] Therefore, how to improve the sensitivity of the photosensitive resin composition and improve the step difference of the spacer is an urgent problem that those skilled in the art want to solve. Summary of the Invention

[0008] In view of this, the present invention provides a photosensitive resin composition having excellent sensitivity and capable of forming a spacer with excellent step difference, which is suitable for use in a spacer and a protective film.

[0009] The present invention provides a photosensitive resin composition comprising an alkali-soluble resin (A), a compound containing an ethylenically unsaturated group (B), a photoinitiator (C), and a solvent (D). Specifically, the alkali-soluble resin (A) comprises an alkali-soluble resin (A-1), wherein the alkali-soluble resin (A-1) is obtained by copolymerizing a mixture. Furthermore, the mixture comprises an ethylenically unsaturated monomer (a-1-1) containing a carboxylic acid group or a carboxylic anhydride group, and an ethylenically unsaturated monomer (a-1-2) containing an oxyalkylene group represented by the following formula (I).

[0010]

[0011] In formula (I),

[0012] R 1 、R 2 and R 3 each independently represents hydrogen or methyl;

[0013] R 4 represents a substituted or unsubstituted C1-C 20 A linear or branched alkyl group, a substituted or unsubstituted C2-C 20 a straight chain or branched alkenyl group, or a substituted or unsubstituted C6-C 20 Aromatic hydrocarbon groups;

[0014] AO stands for C2-C 20 Oxyalkylene;

[0015] x represents an integer from 0 to 2;

[0016] y represents 0 or 1;

[0017] n represents 2 or more.

[0018] In addition, the photoinitiator (C) includes a photoinitiator (C-1), wherein the photoinitiator (C-1) is a compound represented by the following formula (II).

[0019]

[0020] In formula (II),

[0021] A represents hydrogen, halogen, nitro, C1-C 20 Straight or branched alkyl, C3-C 10 Alkylcycloalkyl, C4-C 10 Alkylcycloalkyl, C4-C 10 Cycloalkylalkyl, Among them, C1-C 20 Straight or branched alkyl, C3-C 10 Alkylcycloalkyl, C4-C 10 Alkylcycloalkyl, C4-C 10 Cycloalkylalkyl, Any -CH2- contained in it can be replaced by O, N, S or carbonyl;

[0022] R 5 Represents hydrogen, halogen, C1-C 20 Straight or branched alkyl, C4-C 20 Cycloalkylalkyl or C2-C 20Alkenyl, wherein C1-C 20 Straight or branched alkyl, C4-C 20 Cycloalkylalkyl and C2-C 20 The -CH2- in the alkenyl group can be replaced by O, N, S or carbonyl. 5 A ring structure can be formed between them;

[0023] R 6 Indicates C1-C 20 Straight or branched alkyl, C2-C 20 Alkenyl, C3-C 20 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Alkylcycloalkyl, C6-C 20 Aryl or C6-C 20 wherein one or more hydrogen atoms in these groups may be independently replaced by alkyl, halogen, hydroxyl or nitro groups, and R 6 -CH2- in it can be replaced by O, N, S or carbonyl;

[0024] R 7 Indicates C1-C 20 Straight or branched alkyl, C3-C 20 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Alkylcycloalkyl, C6-C 20 Aryl, C6-C 20 alkylaryl, 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), when R 7 Indicates C1-C 20 Straight or branched alkyl, C3-C 20 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Alkylcycloalkyl, C6-C 20 Aryl or C6-C 20 When the alkylaryl group is an alkyl group, one or more hydrogen atoms in these groups may be independently replaced by an alkyl group, a halogen group, a hydroxyl group or a nitro group, and R 7 -CH2- in it can be replaced by O, N, S or carbonyl;

[0025] R 6 With R 7 A ring structure can be formed between them;

[0026]

[0027] In formula (II-A), m represents an integer of 0 or 1, and R 11 represents hydrogen, a C1-C8 alkyl group, or a phenyl group, R 12 、R 13 and R 14 Each independently represents hydrogen or a C1-C4 alkyl group;

[0028]

[0029] In formula (II-B), p is an integer from 0 to 3;

[0030]

[0031] In formula (II-C), R 15 represents hydrogen, C1-C8 alkyl, or phenyl, Ar is substituted or unsubstituted phenyl, naphthyl, furyl, thienyl or pyridyl;

[0032] R 8 represents N-morpholinyl, N-piperidinyl, N-pyrrolyl or N-dialkyl, wherein one or more hydrogen atoms in these groups may be replaced by halogen or hydroxyl;

[0033] R 9 、R 9 'Each independently represents C1-C 20 Straight or branched alkyl, C4-C 20 Cycloalkyl, C2-C 20 Alkenyl, C6-C 20 Aryl or C6-C 20 wherein one or more hydrogen atoms in these groups may be independently replaced by alkyl, halogen, hydroxyl or nitro, and -CH2- in these groups may be replaced by -O-; or R 9 and R 9 'Can be connected to each other or via -O-, -S- or -NH- to form a five-membered ring or a six-membered ring;

[0034] R 10 Indicates C1-C 20 Straight or branched alkyl, C4-C 20 Cycloalkyl, C4-C 20 Alkylcycloalkyl, C2-C 20 Alkenyl, C6-C 20 Aryl or C6-C 20 Alkylaryl, wherein -CH2- in these groups may be substituted by -O- or -S-, and one or more hydrogens of these groups may be independently selected from alkyl, halogen, nitro, cyano, SR 16 OR 17 replaced by;

[0035] R 16 and R 17 Each independently represents hydrogen, or C1-C 20 A straight-chain or branched-chain alkyl group.

[0036] In one embodiment of the present invention, the mixture further comprises an ethylenically unsaturated monomer (a-1-3) containing a maleimide group or two alkenyl groups.

[0037] In one embodiment of the present invention, the maleimide group- or two alkenyl-containing ethylenically unsaturated monomer (a-1-3) comprises at least one monomer selected from the group consisting of the following formulae (1) to (5).

[0038]

[0039] In formula (4) and formula (5), R 18 、R 19 and R 20 Each independently represents hydrogen, or C1-C 30 A straight-chain or branched-chain alkyl group.

[0040] In one embodiment of the present invention, the alkali-soluble resin (A-1) contains an ethylenically unsaturated group.

[0041] In one embodiment of the present invention, the photoinitiator (C) further comprises a photoinitiator (C-2), wherein the photoinitiator (C-2) is a compound represented by the following formula (III).

[0042]

[0043] In formula (III),

[0044] Ar1 represents an o-arylene group or an o-heteroarylene group, wherein the o-arylene group or the o-heteroarylene group is a ring structure formed by two adjacent atoms with Y1 and a carbonyl group, and the substituents on the remaining atoms are each selected from hydrogen; halogen; C1-C 12 C5-C7 cycloalkyl; C1-C4 alkyl substituted by C5-C7 cycloalkyl; phenyl; C1-C4 alkyl, carboxyl, C1-C 12 Alkyl acyl, C1-C 12 phenyl, halogen or CN substituted phenyl; C1-C4 alkylbenzyloxy; Substituted C1-C4 alkoxy, C1-C3 alkylenedioxy; ;C1-C 12 Alkylthio; C1-C4 alkylphenylthio; Substituted C1-C4 alkylthio; CN; carboxyl; C1-C12 The group consisting of alkoxyformyl; aryl acyl; heteroaryl acyl and JT5; or

[0045] Two adjacent substituents of the above substituents of Ar1 or between the substituent and Ar1 form a ring structure via a single bond, a carbon atom, or a carbonyl group;

[0046] Among them, in JT4 and JT5, J is selected from the group consisting of O, S, and NT6;

[0047] Y1 is selected from the group consisting of O, S, NT7, BT7, CT2T3, SiT2T3, S═O and C═O;

[0048] T1 represents hydrogen, C1-C 18 Alkyl or C1-C 18 an alkoxy group; or

[0049] T1 represents a C2-C4 group substituted with one or more halogens, C1-C4 alkyl, C5-C7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C1-C4 alkanoyloxy or aroyloxy groups and / or inserted with C5-C7 cycloalkylene, phenylene, O, S or NT4. 18 Alkyl; C2-C 18 C2-C4 substituted with one or more halogens, C1-C4 alkyl, C5-C7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C1-C4 alkanoyloxy or aroyloxy and / or inserted with C5-C7 cycloalkylene, phenylene, O, S or NT4 18 , or both of the above situations exist; or

[0050] T1 represents a C5-C7 cycloalkyl group, or a C5-C7 cycloalkyl group substituted with one or more C1-C4 alkyl groups, phenyl groups, halogen groups or CN; or

[0051] T1 represents phenyl, or phenyl substituted by one or more C1-C4 alkyl, C1-C4 alkoxy, phenyl, halogen or CN; or

[0052] T1 represents naphthyl, benzoyl or phenoxycarbonyl, wherein the phenyl group of benzoyl and phenoxycarbonyl is arbitrarily substituted by one or more halogens, T4, C5-C6 cycloalkyl, CN, OH or JT4;

[0053] T2 and T3 each independently represent hydrogen, C1-C 18 C1-C5 alkyl substituted by a carboxyl group, C1-C4 alkyl substituted by an alkoxy acyl group or C1-C5 alkyl substituted by a substituted C1-C4 alkyl; or

[0054] T2 and T3 each independently represent a C2-C4 alkyl group substituted with one or more halogen, C1-C4 alkyl, C5-C7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C1-C4 alkanoyloxy, or aroyloxy group. 18 or a C2-C7 cycloalkylene group, a phenylene group, O, S or NT4 inserted into a C5-C7 cycloalkylene group. 18 or both of the above situations exist; or

[0055] T2 and T3 each independently represent a C5-C7 cycloalkyl group, or a C5-C7 cycloalkyl group substituted with one or more C1-C4 alkyl groups, phenyl groups, halogen groups or CN; or

[0056] T2 and T3 each independently represent a phenyl group, or a phenyl group substituted with one or more C1-C4 alkyl groups, C1-C4 alkoxy groups, carboxyl groups, C1-C 12 C2-C4 alkylacyl, arylacyl, JT4, phenyl, halogen or CN substituted phenyl; or

[0057] T2 and T3, together with the carbon or silicon atom to which they are attached, form a ring structure with 4 to 7 atoms; or

[0058] T2 and T3 each form a cyclic structure together with an adjacent substituent, and the number of atoms forming the ring is 4 to 7;

[0059] T4 represents a C1-C4 alkyl group;

[0060] T5 represents hydrogen, C1-C 18 Alkyl, C1-C5 alkyl substituted by C1-C4 alkoxy acyl or substituted C1-C4 alkyl; or

[0061] T5 represents a C2-C7 substituted with one or more halogen, C1-C4 alkyl, C5-C7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C1-C4 alkanoyloxy or aroyloxy group. 18 or a C2-C7 cycloalkylene group, a phenylene group, O, S or NT4 inserted into a C5-C7 cycloalkylene group. 18 or both of the above situations exist; or

[0062] T5 represents a C5-C7 cycloalkyl group, or a C5-C7 cycloalkyl group substituted with one or more C1-C4 alkyl groups, phenyl groups, halogen groups or CN; or

[0063] T5 represents a phenyl group, or is substituted with one or more C1-C 12Alkyl, carboxyl, C1-C 12 Alkyl acyl, C2-C inserted by phenylene, O, S or NT4 12 alkylacyl, C5-C6 cycloalkylformyl, C5-C6 cycloalkyl-substituted C2-C4 alkylacyl, arylacyl, heteroarylacyl, JT4, phenyl, halogen, CN or NO2 substituted phenyl; or

[0064] T5 represents a C1-C4 alkyl acyl group, a C1-C4 conjugated alkenoyl group, a benzoyl group or a phenoxycarbonyl group, wherein the phenyl group in the benzoyl group and the phenoxycarbonyl group may be arbitrarily substituted with one or more halogens, T4, a cyclopentyl group, a cyclohexyl group, CN, OH or JT4; or

[0065] T5 forms a ring structure with the aromatic ring in Ar1 via a single bond, a carbon atom or a carbonyl group;

[0066] T6 and T7 each independently represent hydrogen, C1-C 18 Alkyl, C1-C5 alkyl substituted by C1-C4 alkoxy acyl or substituted C1-C4 alkyl; or

[0067] T6 and T7 each independently represent a C2-C4 alkyl group substituted with one or more halogens, C1-C4 alkyl groups, C5-C7 cycloalkyl groups, heterocycloalkyl groups, phenyl groups, heteroaryl groups, CN, C1-C4 alkanoyloxy groups or aroyloxy groups. 18 Alkyl, C2-C7 cycloalkylene, phenylene, O, S or NT4 inserted 18 or both of the above situations exist; or

[0068] T6 and T7 each independently represent a C5-C7 cycloalkyl group, or a C5-C7 cycloalkyl group substituted with one or more C1-C4 alkyl groups, phenyl groups, halogen groups or CN; or

[0069] T6 and T7 each independently represent a phenyl group, or substituted with one or more C1-C4 alkyl groups, carboxyl groups, C1-C 12 C2-C4 alkylacyl, arylacyl, JT4, phenyl, halogen or CN substituted phenyl; or

[0070] T6 each forms a ring structure through a single bond, a carbon atom, a carbonyl group and an aromatic ring in Ar1;

[0071] When Ar1 is a substituted carbazole group, Y1 is not C, O, S or NT7.

[0072] In one embodiment of the present invention, based on 100 parts by weight of the alkali-soluble resin (A), the amount of the alkali-soluble resin (A-1) is 50 to 100 parts by weight, the amount of the compound containing an ethylenically unsaturated group (B) is 50 to 600 parts by weight, the amount of the photoinitiator (C) is 10 to 140 parts by weight, the amount of the photoinitiator (C-1) is 10 to 90 parts by weight, and the amount of the solvent (D) is 500 to 5000 parts by weight.

[0073] In one embodiment of the present invention, the amount of the oxyalkylene group-containing ethylenically unsaturated monomer (a-1-2) is 1 to 55 parts by weight based on 100 parts by weight of the total amount of the mixture.

[0074] In one embodiment of the present invention, the amount of the ethylenically unsaturated monomer (a-1-3) containing a maleimide group or two alkenyl groups is 5 to 50 parts by weight based on 100 parts by weight of the total amount of the mixture.

[0075] In one embodiment of the present invention, based on 100 parts by weight of the alkali-soluble resin (A), the amount of the photoinitiator (C-2) used is 5 parts by weight to 50 parts by weight.

[0076] The present invention also provides a spacer formed from the photosensitive resin composition.

[0077] The present invention also provides a protective film formed from the photosensitive resin composition.

[0078] The present invention also provides a liquid crystal display element, which includes the above-mentioned spacer.

[0079] The present invention also provides a liquid crystal display element, which includes the protective film.

[0080] Based on the above, the present invention improves the sensitivity of the photosensitive resin composition by combining a specific alkali-soluble resin (A-1) and a specific photoinitiator (C-1) with the photosensitive resin composition, thereby forming a spacer with excellent step difference. Therefore, the spacer is suitable for use in spacers, protective films, and liquid crystal display devices.

[0081] In order to make the above features and advantages of the present invention more clearly understood, embodiments are given below and described in detail. DETAILED DESCRIPTION

[0082] Hereinafter, (meth)acrylic acid refers to acrylic acid and / or methacrylic acid, and (meth)acrylate refers to acrylate and / or methacrylate. Similarly, (meth)acryloyl refers to acryloyl and / or methacryloyl. (meth)acrylamide refers to acrylamide and / or methacrylamide.

[0083] <Photosensitive resin composition>

[0084] The present invention provides a photosensitive resin composition comprising an alkali-soluble resin (A), a compound containing an ethylenically unsaturated group (B), a photoinitiator (C), and a solvent (D). Furthermore, if desired, the photosensitive resin composition may optionally include an additive (E). The components of the photosensitive resin composition of the present invention are described in detail below:

[0085] Alkali soluble resin (A)

[0086] The alkali-soluble resin (A) of the present invention includes an alkali-soluble resin (A-1) and may further include another alkali-soluble resin (A-2).

[0087] Alkali-soluble resin (A-1)

[0088] The alkali-soluble resin (A-1) is obtained by copolymerization of a mixture, wherein the mixture (also referred to as "monomer mixture" in the synthesis example of the alkali-soluble resin (A-1) described below) includes an ethylenically unsaturated monomer (a-1-1) containing a carboxylic acid group or a carboxylic anhydride group and an ethylenically unsaturated monomer (a-1-2) containing an oxyalkylene group.

[0089] In addition, the mixture may further include an ethylenically unsaturated monomer (a-1-3) containing a maleimide group or two alkenyl groups, and may optionally further include other ethylenically unsaturated monomers (a-1-4).

[0090] 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 condensing the polymer obtained from the above mixture with an ethylenically unsaturated monomer (a-1-5).

[0091] The various monomers forming the alkali-soluble resin (A-1) are described in detail below:

[0092] Ethylenically unsaturated monomer containing a carboxylic acid group or a carboxylic anhydride group (a-1-1)

[0093] The ethylenically unsaturated monomer (a-1-1) containing a carboxylic acid group or a carboxylic anhydride group has a carboxylic acid group or a carboxylic anhydride group (hereinafter referred to as "acid group"), so that the synthesized polymer has an acid group on the side chain, which makes it alkali-soluble. Specific examples of the ethylenically unsaturated monomer (a-1-1) containing a carboxylic acid group or a carboxylic anhydride group include ethylenically unsaturated monomers containing carboxylic acid groups such as acrylic acid, methacrylic acid, 2-acryloylethoxysuccinate, 2-methacryloylethoxysuccinate (HOMS), itaconic acid, ω-carboxy-polycaprolactone monoacrylate (ω-carboxy-polycaprolactone monoacrylate); ethylenically unsaturated monomers containing carboxylic acid anhydride groups 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 a carboxylic anhydride group preferably include acrylic acid, methacrylic acid, 2-methacryloylethoxysuccinate, or combinations thereof.

[0094] Based on 100 parts by weight of the total usage of the mixture, the usage of the ethylenically unsaturated monomer containing a carboxylic acid group or a carboxylic anhydride group (a-1-1) can be 10 to 90 parts by weight, preferably 15 to 85 parts by weight, and more preferably 20 to 80 parts by weight.

[0095] Oxyalkylene-containing ethylenically unsaturated monomer (a-1-2)

[0096] The oxyalkylene group-containing ethylenically unsaturated monomer (a-1-2) is a monomer having two or more oxyalkylene groups. Specifically, the oxyalkylene group-containing ethylenically unsaturated monomer (a-1-2) has a structure represented by formula (I).

[0097]

[0098] In formula (I),

[0099] R 1 、R 2 and R 3 Each independently represents hydrogen or methyl, preferably each independently represents hydrogen;

[0100] R 4 represents a substituted or unsubstituted C1-C 20 A linear or branched alkyl group, a substituted or unsubstituted C2-C 20 a straight chain or branched alkenyl group, or a substituted or unsubstituted C6-C 20 An aromatic hydrocarbon group, preferably C1-C 20 Straight-chain alkyl, unsubstituted C6-C 20 Aromatic hydrocarbon groups, C6-C 20Aromatic hydrocarbon group, or C1-C 10 Alkyl substituted C6-C 20 The aromatic hydrocarbon group is more preferably a methyl group, a phenyl group, a 4-nonylphenyl group or a biphenyl group.

[0101] AO stands for C2-C 20 Oxyalkylene, preferably C2-C 10 The oxyalkylene group is preferably C2-C5 oxyalkylene, and more preferably oxyethylene;

[0102] x represents an integer from 0 to 2;

[0103] y represents 0 or 1;

[0104] n represents 2 or more, preferably 2 to 200, more preferably 2 to 50, and even more preferably 2 to 15.

[0105] It should be noted that the oxyalkylene group-containing ethylenically unsaturated monomer (a-1-2) may contain one or more oxyalkylene groups.

[0106] Specific examples of the ethylenically unsaturated monomer (a-1-2) containing an oxyalkylene group include a mixture of o-phenylphenoxyethylene glycol acrylate (EO1 mol) / o-phenylphenoxydiethylene glycol acrylate (EO2 mol) (the molar ratio between o-phenylphenoxyethylene glycol acrylate and o-phenylphenoxydiethylene glycol acrylate is 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 1 3 moles), methoxytriethylene glycol (meth)acrylate (EO3 moles), ethoxydiethylene glycol (meth)acrylate (EO2 moles), butoxydiethylene glycol (meth)acrylate (EO2 moles), 2-ethylhexyloxydiethylene glycol (meth)acrylate (EO2 moles), methoxydipropylene glycol (meth)acrylate (PO2 moles), methoxypolypropylene glycol (meth)acrylate (PO4 moles), nonylphenoxypolyethylene glycol (meth)acrylate (EO4 to 17 moles), nonylphenoxypolypropylene glycol (meth)acrylate (PO5 moles), ethylene oxide (EO) modified cresol (meth)acrylate (EO2 moles), or a combination of the foregoing monomers.

[0107] Specific examples of the ethylenically unsaturated monomer (a-1-2) containing an oxyalkylene group preferably include o-phenylphenoxyethylene glycol acrylate / o-phenylphenoxydiethylene glycol acrylate (a molar ratio of phenylphenoxyethylene glycol acrylate to phenylphenoxydiethylene glycol acrylate being 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 (EO5 mol), or a combination of the above monomers.

[0108] In the foregoing, "EO" and "PO" represent oxyethylene and oxypropylene, respectively. The moles following "EO" and "PO" represent the average number of moles of oxyethylene or oxypropylene groups per mole of the compound. For example, "methoxypolyethylene glycol acrylate (EO9 mole)" indicates an average of 9 moles of oxyethylene groups per mole of the compound.

[0109] If the oxyalkylene group-containing ethylenically unsaturated monomer (a-1-2) is not used, the sensitivity of the photosensitive resin composition will be poor.

[0110] Based on 100 parts by weight of the total amount of the mixture, the amount of the oxyalkylene-containing ethylenically unsaturated monomer (a-1-2) can be 1 part by weight to 55 parts by weight, preferably 1 part by weight to 50 parts by weight, and more preferably 1 part by weight to 45 parts by weight.

[0111] Ethylenically unsaturated monomer containing a maleimide group or two alkenyl groups (a-1-3)

[0112] The ethylenically unsaturated monomer (a-1-3) containing a maleimide group or two alkenyl groups includes an ethylenically unsaturated monomer containing a maleimide group (also referred to as a "monomer having a cyclic structure"), an ethylenically unsaturated monomer containing two alkenyl groups (also referred to as a monomer that can form a cyclic structure after polymerization), or a combination thereof. It is noteworthy that these monomers, when polymerized, can form structural units having a cyclic structure.

[0113] 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, N-m-chlorophenylmaleimide, N-p-chlorophenylmaleimide, N-o-methylphenylmaleimide, N- Aromatically substituted maleimides such as m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, and N-p-methoxyphenylmaleimide; alkyl-substituted maleimides such as cyclohexylmaleimide, methylmaleimide, ethylmaleimide, propylmaleimide, and isopropylmaleimide, or combinations thereof.

[0114] In one embodiment, the maleimide-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.

[0115]

[0116] The ethylenically unsaturated monomer containing two alkenyl groups may be, for example, a 1,6-diene, including a 1,6-diene represented by formula (4), a 1,6-diene represented by formula (5), or a combination thereof.

[0117]

[0118] In formula (4) and formula (5), R 18 、R 19 and R 20 Each independently represents hydrogen, or C1-C 30 A straight or branched alkyl group, preferably hydrogen or C1-C 10 It is preferably a straight or branched chain alkyl group of C1-C5, more preferably hydrogen or a straight or branched chain alkyl group of C1-C5, and even more preferably a methyl group.

[0119] Specific examples of 1,6-dienes include dimethyl-2,2′-[oxybis(methylene)]bis-2-acrylate, methyl α-(allyloxymethyl)acrylate, or a combination thereof.

[0120] Specific examples of the ethylenically unsaturated monomer (a-1-3) containing a maleimide group or two alkenyl groups preferably include benzylmaleimide, phenylmaleimide, cyclohexylmaleimide, dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, methyl α-(allyloxymethyl)acrylate, or a combination thereof.

[0121] When an ethylenically unsaturated monomer (a-1-3) containing a maleimide group or two alkenyl groups is used, a spacer having a further excellent step difference can be formed.

[0122] Based on 100 parts by weight of the total usage of the mixture, the usage of the ethylenically unsaturated monomer containing a maleimide group or two alkenyl groups (a-1-3) can be 5 to 50 parts by weight, preferably 8 to 45 parts by weight, and more preferably 10 to 40 parts by weight.

[0123] Other ethylenically unsaturated monomers (a-1-4)

[0124] The mixture constituting the alkali-soluble resin (A-1) may further include other ethylenically unsaturated monomers (a-1-4). Other ethylenically unsaturated monomers (a-1-4) include ethylenically unsaturated monomers other than the carboxylic acid group- or carboxylic anhydride group-containing ethylenically unsaturated monomers (a-1-1), the oxyalkylene group-containing ethylenically unsaturated monomers (a-1-2), the maleimide group- or two alkenyl group-containing ethylenically unsaturated monomers (a-1-3), and the ethylenically unsaturated monomers (a-1-5) described below.

[0125] Specific examples of other ethylenically unsaturated monomers (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, stearic (meth)acrylate, phenyl (meth)acrylate, biphenyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethylene glycol (meth)acrylate, acrylate, 2-ethylhexyl glycol di(meth)acrylate, methoxypropylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, biphenoxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tricyclodecyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tricyclodecyloxyethyl (meth)acrylate, (Meth)acrylates such as (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (morpholinyl (meth)acrylate), (meth)acrylamide, N-methyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-butyl (meth)acrylamide, N-isobutyl (meth)acrylamide, N-tert-butyl (meth)acrylamide, N-tert-octyl (meth)acrylamide, diacetone (meth)acrylamide (diacetone (meth)acrylate), (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (Meth)acrylic acid amides such as N-hydroxymethyl (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. These monomers can be used alone or in combination.

[0126] Specific examples of other ethylenically unsaturated monomers (a-1-4) preferably include 2-hydroxyethyl methacrylate, methyl methacrylate, dicyclopentanyl methacrylate, benzyl methacrylate, styrene, or a combination thereof.

[0127] Based on 100 parts by weight of the total amount of the mixture, the amount of other ethylenically unsaturated monomers (a-1-4) can be 0 to 55 parts by weight, preferably 5 to 50 parts by weight, and more preferably 10 to 45 parts by weight.

[0128] Ethylenically unsaturated monomer (a-1-5)

[0129] The alkali-soluble resin (A-1) may further contain an ethylenically unsaturated group. Such an alkali-soluble resin (A-1) is 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 ethylenically unsaturated monomer (a-1-2) containing an oxyalkylene group, an ethylenically unsaturated monomer (a-1-3) containing a maleimide group or two alkenyl groups, and other ethylenically unsaturated monomers (a-1-4), which is further condensed with an ethylenically unsaturated monomer (a-1-5).

[0130] 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, or a combination thereof.

[0131] When the ethylenically unsaturated monomer (a-1-1) containing a carboxylic acid group or a carboxylic anhydride group 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 ethylenically unsaturated monomer containing an epoxy group include glycidyl (meth)acrylate (glycidyl methacrylate), 3,4-epoxycyclohexylmethyl (meth)acrylate, o-vinylbenzyl glycidyl 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 containing an isocyanate group (-N=C=O) include 2-isocyanatoethyl (meth)acrylate.

[0132] When the ethylenically unsaturated monomer (a-1-1) containing a carboxylic acid group or a carboxylic anhydride group is a ethylenically unsaturated monomer containing a carboxylic anhydride group, 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.

[0133] Specific examples of the ethylenically unsaturated monomer (a-1-5) preferably include glycidyl methacrylate (glycidyl methacrylate), 3,4-epoxycyclohexylmethyl methacrylate, o-vinylbenzyl glycidyl ether (o-vinylbenzyl glycidyl ether), or a combination thereof.

[0134] When the alkali-soluble resin (A-1) contains an ethylenically unsaturated group, the photosensitive resin composition has relatively excellent sensitivity.

[0135] Based on 100 parts by weight of the total amount of the mixture, the amount of the ethylenically unsaturated monomer (a-1-5) can be 10 to 180 parts by weight, preferably 15 to 160 parts by weight, and more preferably 20 to 140 parts by weight.

[0136] The preparation method of the alkali-soluble resin (A-1) is described in detail below:

[0137] The alkali-soluble resin (A-1) can be prepared by polymerization of the aforementioned ethylenically unsaturated monomers (a-1-1) containing a carboxylic acid group or a carboxylic anhydride group, the ethylenically unsaturated monomers (a-1-2) containing an oxyalkylene group, the ethylenically unsaturated monomers (a-1-3) containing a maleimide group or two alkenyl groups, and other ethylenically unsaturated monomers (a-1-4). The polymerization method is not particularly limited and can be selected appropriately according to needs. For example, solution polymerization is employed.

[0138] The mixture constituting the alkali-soluble resin (A-1) may include a solvent. The type of solvent is not particularly limited. In detail, 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 3-methoxybutyl acetate; alcohols such as methanol and ethanol; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform; dimethyl sulfoxide, etc. The above-mentioned solvents can be used alone or in combination. The solvent is preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, or a combination thereof.

[0139] The polymerization concentration of the mixture during polymerization is 5 wt % to 90 wt %, preferably 5 wt % to 50 wt %, and more preferably 10 wt % to 50 wt %.

[0140] The mixture constituting the alkali-soluble resin (A-1) may include a polymerization initiator. The type of the polymerization initiator is not particularly limited. Specifically, specific examples of the polymerization initiator include cumene hydroperoxide (CHP), diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-butylperoxyisopropyl carbonate. Organic peroxides such as t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, and azo compounds such as 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and dimethyl 2,2'-azobis(2-methylpropionate) are preferred polymerization initiators. t-butylperoxy-2-ethylhexanoate is preferred. The amount of the polymerization initiator used may be 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of all monomers in the mixture.

[0141] The polymerization temperature of the alkali-soluble resin (A-1) during solution polymerization may be 40°C to 150°C, preferably 60°C to 130°C.

[0142] The polymer formed from the above mixture may be further subjected to an addition reaction with an ethylenically unsaturated monomer (a-1-5) to obtain a polymer containing ethylenically unsaturated groups (carbon double bonds). The method for reacting the polymer with the ethylenically unsaturated monomer (a-1-5) is not particularly limited. For example, in the presence of a polymerization inhibitor and a catalyst, as described below, the ethylenically unsaturated monomer (a-1-5) may be subjected to an addition reaction with some or all of the acid groups (preferably some of the acid groups) of the polymer formed from the above mixture.

[0143] 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 that can function as a chain transfer agent in a free radical polymerization reaction. Chain transfer agents are, for example, alkyl mercaptans such as n-dodecyl mercaptan (1-dodecanethiol, nDM). The amount of the chain transfer agent used can be 0.1 to 15 parts by weight, preferably 1.2 to 5.0 parts by weight, relative to 100 parts by weight of all monomers in the mixture.

[0144] Finally, solution polymerization methods may utilize polymerization inhibitors to terminate free radical polymerization reactions. The type of polymerization inhibitor is not particularly limited; examples include alkylphenol compounds such as 6-tert-butyl-2,4-dimethylphenol. Furthermore, solution polymerization methods may utilize catalysts. The type of catalyst is not particularly limited; examples include tertiary amines such as dimethylbenzylamine and triethylamine.

[0145] The alkali-soluble resin (A-1) may be a random copolymer or a block copolymer.

[0146] The weight average molecular weight of the alkali-soluble resin (A-1) can be measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. The weight average molecular weight of the alkali-soluble resin (A-1) can be 3,000 to 200,000, preferably 4,000 to 100,000, and more preferably 5,000 to 50,000.

[0147] The acid value of the alkali-soluble resin (A-1) may be 20 mg KOH / g to 300 mg KOH / g, preferably 25 mg KOH / g to 200 mg KOH / g, and more preferably 30 mg KOH / g to 150 mg KOH / g.

[0148] When the alkali-soluble resin (A-1) is used, the photosensitive resin composition has excellent sensitivity. Conversely, if the alkali-soluble resin (A-1) is not used, the sensitivity of the photosensitive resin composition is poor.

[0149] Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the alkali-soluble resin (A-1) may be 50 to 100 parts by weight, preferably 60 to 100 parts by weight, and more preferably 70 to 100 parts by weight.

[0150] Other alkali-soluble resins (A-2)

[0151] The alkali-soluble resin (A) may include another alkali-soluble resin (A-2) other than the alkali-soluble resin (A-1).

[0152] There are no particular limitations on the other alkali-soluble resin (A-2), as long as the other alkali-soluble resin (A-2) is different from the alkali-soluble resin (A-1). Furthermore, there are no particular limitations on the method for producing the other alkali-soluble resin (A-2), and for example, the method can be similar to that for the alkali-soluble resin (A-1), so further description is omitted.

[0153] Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the other alkali-soluble resin (A-2) can be 0 to 50 parts by weight, preferably 0 to 40 parts by weight, and more preferably 0 to 30 parts by weight.

[0154] Compound containing an ethylenically unsaturated group (B)

[0155] The ethylenically unsaturated group-containing compound (B) includes a compound having one ethylenically unsaturated group, a compound having two or more (including two) ethylenically unsaturated groups, or a combination thereof.

[0156] Specific examples of the compound having one ethylenically unsaturated group 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, tert-octyl (meth)acrylamide, diacetone (meth)acrylamide, dimethylaminoethyl (meth)acrylate, dodecyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, N,N-dimethyl (meth)acrylamide, Compounds such as amide, 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 mono(meth)acrylate, polypropylene mono(meth)acrylate, or bornyl (meth)acrylate may be used. These compounds having one ethylenically unsaturated group may be used alone or in combination.

[0157] Specific examples of compounds having two or more (including 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)isocyanate di(meth)acrylate, tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, caprolactone-modified tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane tri(meth)acrylate modified with ethylene oxide (abbreviated as "EO"), trimethylolpropane tri(meth)acrylate modified with propylene oxide (abbreviated as "PO"), 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 hexamethacrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate modified with caprolactone, dipentaerythritol penta(meth)acrylate modified with caprolactone, ditrimethylolpropane tetra(meth)acrylate, Compounds such as bisphenol A di(meth)acrylate modified with ethylene oxide, bisphenol A di(meth)acrylate modified with propylene oxide, hydrogenated bisphenol A di(meth)acrylate modified with ethylene oxide, hydrogenated bisphenol A di(meth)acrylate modified with propylene oxide, bisphenol F di(meth)acrylate modified with ethylene oxide, pentaerythritol triacrylate, glycerol triacrylate modified with propylene oxide, or novolac polyglycidyl ether (meth)acrylate can be used. Compounds having two or more (including two) ethylenically unsaturated groups can be used alone or in combination.

[0158] Specific examples of the compound (B) containing an ethylenically unsaturated group preferably include, but are not limited to, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane triacrylate modified with ethylene oxide, trimethylolpropane triacrylate modified with propylene oxide, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate modified with caprolactone, ditrimethylolpropane tetraacrylate, glycerol triacrylate modified with propylene oxide, or a combination of the foregoing.

[0159] The ethylenically unsaturated group-containing compound (B) is more preferably ethylene glycol dimethacrylate, trimethylolpropyl triacrylate, dipentaerythritol hexaacrylate, or a combination thereof.

[0160] Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the compound (B) containing an ethylenically unsaturated group can be 50 parts by weight to 600 parts by weight, preferably 70 parts by weight to 580 parts by weight, and more preferably 90 parts by weight to 550 parts by weight.

[0161] Photoinitiator (C)

[0162] 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 another photoinitiator (C-3).

[0163] Photoinitiator (C-1)

[0164] The photoinitiator (C-1) is a compound represented by the following formula (II).

[0165]

[0166] In formula (II),

[0167] A represents hydrogen, halogen, nitro, C1-C 20 Straight or branched alkyl, C3-C 10 Alkylcycloalkyl, C4-C 10 Alkylcycloalkyl, C4-C 10 Cycloalkylalkyl, Among them, C1-C 20 Straight or branched alkyl, C3-C 10 Alkylcycloalkyl, C4-C 10 Alkylcycloalkyl, C4-C 10 Cycloalkylalkyl, Any -CH2- contained in it can be replaced by O, N, S or carbonyl;

[0168] R 5 Represents hydrogen, halogen, C1-C 20 Straight or branched alkyl, C4-C 20 Cycloalkylalkyl or C2-C 20 Alkenyl, wherein C1-C 20 Straight or branched alkyl, C4-C 20 Cycloalkylalkyl and C2-C 20 The -CH2- in the alkenyl group can be replaced by O, N, S or carbonyl. 5 A ring structure can be formed between them;

[0169] R 6 Indicates C1-C 20 Straight or branched alkyl, C2-C 20 Alkenyl, C3-C20 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Alkylcycloalkyl, C6-C 20 Aryl or C6-C 20 wherein one or more hydrogen atoms in these groups may be independently replaced by alkyl, halogen, hydroxyl or nitro groups, and R 6 -CH2- in it can be replaced by O, N, S or carbonyl;

[0170] R 7 Indicates C1-C 20 Straight or branched alkyl, C3-C 20 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Alkylcycloalkyl, C6-C 20 Aryl, C6-C 20 alkylaryl, 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), when R 7 Indicates C1-C 20 Straight or branched alkyl, C3-C 20 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Alkylcycloalkyl, C6-C 20 Aryl or C6-C 20 When the alkylaryl group is an alkyl group, one or more hydrogen atoms in these groups may be independently replaced by an alkyl group, a halogen group, a hydroxyl group or a nitro group, and R 7 -CH2- in it can be replaced by O, N, S or carbonyl;

[0171] R 6 With R 7 A ring structure can be formed between them;

[0172]

[0173] In formula (II-A), m represents an integer of 0 or 1, and R 11 represents hydrogen, a C1-C8 alkyl group, or a phenyl group, R 12 、R 13 and R 14 Each independently represents hydrogen or a C1-C4 alkyl group;

[0174]

[0175] In formula (II-B), p is an integer from 0 to 3;

[0176]

[0177] In formula (II-C), R 15 represents hydrogen, C1-C8 alkyl, or phenyl, Ar is substituted or unsubstituted phenyl, naphthyl, furyl, thienyl or pyridyl;

[0178] R 8 Represents N-morpholinyl N-piperidinyl N-pyrrolyl or N-dialkyl (N(R 21 )2, where R 21 represents an alkyl group), wherein one or more hydrogens in these groups may be replaced by halogen or hydroxy;

[0179] R 9 、R 9 'Each independently represents C1-C 20 Straight or branched alkyl, C4-C 20 Cycloalkyl, C2-C 20 Alkenyl, C6-C 20 Aryl or C6-C 20 wherein one or more hydrogen atoms in these groups may be independently replaced by alkyl, halogen, hydroxyl or nitro, and -CH2- in these groups may be replaced by -O-; or R 9 and R 9 'Can be connected to each other or via -O-, -S- or -NH- to form a five-membered ring or a six-membered ring;

[0180] R 10 Indicates C1-C 20 Straight or branched alkyl, C4-C 20 Cycloalkyl, C4-C 20 Alkylcycloalkyl, C2-C 20 Alkenyl, C6-C 20 Aryl or C6-C 20 Alkylaryl, wherein -CH2- in these groups may be substituted by -O- or -S-, and one or more hydrogens of these groups may be independently selected from alkyl, halogen, nitro, cyano, SR 16 OR 17 replaced by;

[0181] R 16 and R 17 Each independently represents hydrogen, or C1-C 20 A straight-chain or branched-chain alkyl group.

[0182] In formula (II), A preferably represents hydrogen, methyl, methoxy, chlorine, nitro, or N-morpholinyl, where R 10 Preferably, it represents phenyl, phenyl substituted by one or more methyl groups, phenyl substituted by nitro groups, More preferably, it represents hydrogen, methyl, nitro, phenyl substituted by one or more methyl groups, or N-morpholinyl, wherein * indicates the bonding position.

[0183] In formula (II), R 5 Preferably, it represents hydrogen, methyl, propyl, butyl or allyl (-CH2CH=CH2), more preferably, it represents hydrogen, methyl, butyl or allyl.

[0184] In formula (II), R 6 Preferably it represents a methyl group or an ethyl group.

[0185] In formula (II), R 7 Preferably, it represents a methyl group, an ethyl group or a benzyl group, more preferably, it represents a methyl group or a benzyl group.

[0186] In formula (II), R 8 Preferably, it represents N-morpholinyl, N-piperidinyl, -N(CH3)2, -N(CH2CH2CH3)2 or N-pyrrolyl, more preferably it represents N-morpholinyl, -N(CH3)2, N-pyrrolyl or N-piperidinyl, wherein * represents the bonding position.

[0187] Specific examples of the photoinitiator (C-1) include compounds represented by the following formulas (II-1) to (II-35), or combinations of these compounds.

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196] Specific examples of the photoinitiator (C-1) preferably include a compound represented by formula (II-1), a compound represented by formula (II-5), a compound represented by formula (II-11), a compound represented by formula (II-14), a compound represented by formula (II-17), a compound represented by formula (II-19), a compound represented by formula (II-28), a compound represented by formula (II-35), or a combination of these compounds.

[0197] By using the photoinitiator (C-1), a spacer with excellent step difference can be formed. On the contrary, if the photoinitiator (C-1) is not used, the spacer formed has poor step difference.

[0198] Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the photoinitiator (C-1) may be 10 to 90 parts by weight, preferably 12 to 85 parts by weight, and more preferably 15 to 80 parts by weight.

[0199] Photoinitiator (C-2)

[0200] The photoinitiator (C-2) is a compound represented by the following formula (III).

[0201]

[0202] In formula (III),

[0203] Ar1 represents an o-arylene group or an o-heteroarylene group, wherein the o-arylene group or the o-heteroarylene group is a ring structure formed by two adjacent atoms with Y1 and a carbonyl group, and the substituents on the remaining atoms are each selected from hydrogen; halogen; C1-C 12 C5-C7 cycloalkyl; C1-C4 alkyl substituted by C5-C7 cycloalkyl; phenyl; C1-C4 alkyl, carboxyl, C1-C 12 Alkyl acyl, C1-C 12 phenyl, halogen or CN substituted phenyl; C1-C4 alkylbenzyloxy; Substituted C1-C4 alkoxy, C1-C3 alkylenedioxy; C1-C 12 Alkylthio; C1-C4 alkylphenylthio; Substituted C1-C4 alkylthio; CN; carboxyl; C1-C 12 The group consisting of alkoxyformyl; aryl acyl; heteroaryl acyl and JT5; or

[0204] Two adjacent substituents of the above substituents of Ar1 or between the substituent and Ar1 form a ring structure via a single bond, a carbon atom, or a carbonyl group;

[0205] Among them, in JT4 and JT5, J is selected from the group consisting of O, S, and NT6;

[0206] Y1 is selected from the group consisting of O, S, NT7, BT7, CT2T3, SiT2T3, S═O and C═O;

[0207] T1 represents hydrogen, C1-C 18 Alkyl or C1-C 18 an alkoxy group; or

[0208] T1 represents a C2-C4 group substituted with one or more halogens, C1-C4 alkyl, C5-C7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C1-C4 alkanoyloxy or aroyloxy groups and / or inserted with C5-C7 cycloalkylene, phenylene, O, S or NT4. 18 Alkyl; C2-C 18 C2-C4 substituted with one or more halogens, C1-C4 alkyl, C5-C7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C1-C4 alkanoyloxy or aroyloxy and / or inserted with C5-C7 cycloalkylene, phenylene, O, S or NT4 18 , or both of the above situations exist; or

[0209] T1 represents a C5-C7 cycloalkyl group, or a C5-C7 cycloalkyl group substituted with one or more C1-C4 alkyl groups, phenyl groups, halogen groups or CN; or

[0210] T1 represents phenyl, or phenyl substituted by one or more C1-C4 alkyl, C1-C4 alkoxy, phenyl, halogen or CN; or

[0211] T1 represents naphthyl, benzoyl or phenoxycarbonyl, wherein the phenyl group of benzoyl and phenoxycarbonyl is arbitrarily substituted by one or more halogens, T4, C5-C6 cycloalkyl, CN, OH or JT4;

[0212] T2 and T3 each independently represent hydrogen, C1-C 18 C1-C5 alkyl substituted by a carboxyl group, C1-C4 alkyl substituted by an alkoxy acyl group or C1-C5 alkyl substituted by a substituted C1-C4 alkyl; or

[0213] T2 and T3 each independently represent a C2-C4 alkyl group substituted with one or more halogen, C1-C4 alkyl, C5-C7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C1-C4 alkanoyloxy, or aroyloxy group. 18or a C2-C7 cycloalkylene group, a phenylene group, O, S or NT4 inserted into a C5-C7 cycloalkylene group. 18 or both of the above situations exist; or

[0214] T2 and T3 each independently represent a C5-C7 cycloalkyl group, or a C5-C7 cycloalkyl group substituted with one or more C1-C4 alkyl groups, phenyl groups, halogen groups or CN; or

[0215] T2 and T3 each independently represent a phenyl group, or a phenyl group substituted with one or more C1-C4 alkyl groups, C1-C4 alkoxy groups, carboxyl groups, C1-C 12 C2-C4 alkylacyl, arylacyl, JT4, phenyl, halogen or CN substituted phenyl; or

[0216] T2 and T3, together with the carbon or silicon atom to which they are attached, form a ring structure with 4 to 7 atoms; or

[0217] T2 and T3 each form a cyclic structure together with an adjacent substituent, and the number of atoms forming the ring is 4 to 7;

[0218] T4 represents a C1-C4 alkyl group;

[0219] T5 represents hydrogen, C1-C 18 Alkyl, C1-C5 alkyl substituted by C1-C4 alkoxy acyl or substituted C1-C4 alkyl; or

[0220] T5 represents a C2-C7 substituted with one or more halogen, C1-C4 alkyl, C5-C7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C1-C4 alkanoyloxy or aroyloxy group. 18 or a C2-C7 cycloalkylene group, a phenylene group, O, S or NT4 inserted into a C5-C7 cycloalkylene group. 18 or both of the above situations exist; or

[0221] T5 represents a C5-C7 cycloalkyl group, or a C5-C7 cycloalkyl group substituted with one or more C1-C4 alkyl groups, phenyl groups, halogen groups or CN; or

[0222] T5 represents a phenyl group, or is substituted with one or more C1-C 12 Alkyl, carboxyl, C1-C 12 Alkyl acyl, C2-C inserted by phenylene, O, S or NT4 12or phenyl substituted with the above substituents such as C5-C6 alkyl acyl, C5-C6 cycloalkyl formyl, C2-C4 alkyl acyl, aryl acyl, heteroaryl acyl, phenyl, halogen, CN or NO2, wherein the aryl acyl is benzoyl, or benzoyl substituted with one or more halogen, C1-C4 alkyl or C1-C4 alkoxy; or

[0223] T5 represents a C1-C4 alkyl acyl group, a C1-C4 conjugated alkenoyl group, a benzoyl group or a phenoxycarbonyl group, wherein the phenyl group in the benzoyl group and the phenoxycarbonyl group may be arbitrarily substituted with one or more halogens, T4, a cyclopentyl group, a cyclohexyl group, CN, OH or JT4; or

[0224] T5 forms a ring structure with the aromatic ring in Ar1 via a single bond, a carbon atom or a carbonyl group;

[0225] T6 and T7 each independently represent hydrogen, C1-C 18 Alkyl, C1-C5 alkyl substituted by C1-C4 alkoxy acyl or substituted C1-C4 alkyl; or

[0226] T6 and T7 each independently represent a C2-C4 alkyl group substituted with one or more halogens, C1-C4 alkyl groups, C5-C7 cycloalkyl groups, heterocycloalkyl groups, phenyl groups, heteroaryl groups, CN, C1-C4 alkanoyloxy groups or aroyloxy groups. 18 Alkyl, C2-C7 cycloalkylene, phenylene, O, S or NT4 inserted 18 or both of the above situations exist; or

[0227] T6 and T7 each independently represent a C5-C7 cycloalkyl group, or a C5-C7 cycloalkyl group substituted with one or more C1-C4 alkyl groups, phenyl groups, halogen groups or CN; or

[0228] T6 and T7 each independently represent a phenyl group, or substituted with one or more C1-C4 alkyl groups, carboxyl groups, C1-C 12 C2-C4 alkylacyl, arylacyl, JT4, phenyl, halogen or CN substituted phenyl; or

[0229] T6 each forms a ring structure through a single bond, a carbon atom, a carbonyl group and an aromatic ring in Ar1;

[0230] When Ar1 is a substituted carbazole group, Y1 is not C, O, S or NT7.

[0231] In formula (III), Ar1 preferably represents a group represented by the following formula (III-A).

[0232]

[0233] T8, T9, T 10 and T 11 each independently represents hydrogen; or

[0234] T8, T9, T 10 and T 11 Each independently represents one or more C1-C 12 Alkoxy, C1-C4 alkylbenzyloxy substituted C1-C4 alkoxy, Substituted C1-C4 alkoxy; or

[0235] T8, T9, T 10 and T 11 Each independently represents a phenoxy group substituted with one or more C1-C4 alkyl groups; a phenoxy group substituted with one C1-C8 alkyl acyl group, C5-C6 cycloalkyl acyl group, aryl acyl group, or heteroaryl acyl group; a C1-C4 alkyl acylphenoxy group substituted with a C5-C6 cycloalkyl group; a C1-C3 alkylenedioxy group; C1-C 12 Alkylthio; Substituted C1-C4 alkylthio; C1-C4 alkylphenylthio; Substituted C1-C4 alkylphenylthio; or

[0236] T8, T9, T 10 and T 11 Each independently represents a phenylthio group substituted by a C1-C8 alkylacyl group, a C5-C6 cycloalkylacyl group, an arylacyl group, or a heteroarylacyl group, or a C1-C4 alkylacylphenylthio group substituted by a C5-C6 cycloalkyl group;

[0237] Y1 preferably represents CH2, CHCH3 or C(CH3)2;

[0238] T1 preferably represents methyl, ethyl, phenyl, 2-methylphenyl, 3-methylphenyl, 2,4,6-trimethylphenyl or 2,6-dimethoxyphenyl;

[0239] *Indicates the bond position.

[0240] It is noteworthy that among the substituents of Ar1, it is preferred that at least one substituent is located in the para position relative to the carbonyl group connected to Ar1.

[0241] Specific examples of the photoinitiator (C-1) include compounds represented by the following formulas (III-1) to (III-28), or combinations of these compounds.

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248] Specific examples of the photoinitiator (C-2) preferably include a compound represented by formula (III-2), a compound represented by formula (III-6), a compound represented by formula (III-11), a compound represented by formula (III-17), a compound represented by formula (III-24), a compound represented by formula (III-28), or a combination of these compounds.

[0249] The photosensitive resin composition contains the photoinitiator (C-2), and the photosensitive resin composition has relatively excellent sensitivity.

[0250] Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the photoinitiator (C-2) may be 5 to 50 parts by weight, preferably 6 to 45 parts by weight, and more preferably 7 to 40 parts by weight.

[0251] Other photoinitiators (C-3)

[0252] The present invention may optionally add other photoinitiators (C-3). Specific examples of other photoinitiators (C-3) include, but are not limited to, O-acyl oxime compounds, triazide compounds, phenyl acetophenone compounds, diimidazole compounds, benzophenone compounds, α-diketone compounds, ketoalcohol compounds, ketoalcohol ether compounds, acylphosphine oxide compounds, quinone compounds, halogen-containing compounds, peroxides, or combinations thereof.

[0253] Specific examples of the above-mentioned O-acyl oxime compounds include 1-[4-(phenylthio)phenyl]-propane-3-cyclopentane-1,2-dione 2-(O-benzoyl oxime), 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-benzoyl oxime), 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyl oxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9-hydrogen-carbazole-3-substituent]-, 1-(oxy-acetyl oxime), 1,2-butanedione-1-[4-(methylthio)phenyl] 2-(O-acetyl oxime), or a combination thereof.

[0254] Specific examples of O-acyl oxime compounds preferably include 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 combinations thereof. These O-acyl oxime compounds can be used alone or in combination, depending on actual needs.

[0255] Specific examples of triazine compounds may include, but are not limited to, vinyl-halomethyl-s-triazine compounds, 2-(naphtho-1-substituted)-4,6-bis-halomethyl-s-triazine compounds, 4-(p-aminophenyl)-2,6-bis-halomethyl-s-triazine compounds, or combinations thereof.

[0256] Specific examples of the vinyl-halogenated methyl-s-triazine compound include 2,4-bis(trichloromethyl)-6-p-methoxyphenyl-s-triazine, 2,4-bis(trichloromethyl)-3-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazine, 2-trichloromethyl-3-amino-6-p-methoxyphenyl-s-triazine, or a combination thereof.

[0257] Specific examples of the above-mentioned 2-(naphtho-1-substituted)-4,6-bis-halogenomethyl-s-triazine compounds include 2-(naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazine, 2-(4-methoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazine, 2-(4-ethoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazine, 2-(4-Butoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazine, 2-[4-(2-methoxyethyl)-naphtho-1-substituted]-4,6-bis-trichloromethyl-s-triazine, 2-[4-(2-ethoxyethyl)-naphtho-1-substituted]-4,6-bis-trichloromethyl-s-triazine, 2-[4-(2-butoxyethyl)-naphtho-1-substituted] -4,6-bis-trichloromethyl-s-triazine, 2-(2-methoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazine, 2-(6-methoxy-5-methyl-naphtho-2-substituted)-4,6-bis-trichloromethyl-s-triazine, 2-(6-methoxy-naphtho-2-substituted)-4,6-bis-trichloromethyl-s-triazine, 2-(5-methoxy-naphtho- 1-substituted)-4,6-bis-trichloromethyl-s-triazine, 2-(4,7-dimethoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazine, 2-(6-ethoxy-naphtho-2-substituted)-4,6-bis-trichloromethyl-s-triazine, 2-(4,5-dimethoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazine, or a combination thereof.

[0258] Specific examples of the aforementioned 4-(p-aminophenyl)-2,6-di-halogenomethyl-s-triazine compounds include 4-[p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[o-methyl-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[o-methyl-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-(p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, -triazine, 4-(p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-[p-N,N-di(phenyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-(p-N-chloroethylcarbonylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-[p-N-(p-methoxyphenyl)carbonylaminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[m-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[m-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine )-s-triazine, 4-[m-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[m-fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[o-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[o-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[o-fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine , 4-[o-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[o-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[o-fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[m-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[m-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-[m-fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 4-(m-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-(m-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-(m-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine Azine, 4-(o-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-(o-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-(o-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-(m-bromo-p- N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-(m-chloro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-(m-fluoro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-(o-bromo-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine triazine, 4-(o-chloro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 4-(o-fluoro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-[3-bromo-4-[N,N-bis(ethoxycarbonylmethyl)amino]phenyl]-1,3,5-triazine, or a combination thereof.

[0259] Specific examples of the aforementioned triazine compounds preferably include 4-[m-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-p-methoxyphenyl-s-triazine, or combinations thereof. The aforementioned triazine compounds can be used alone or in combination.

[0260] Specific examples of the above-mentioned acetophenone compounds include p-dimethylaminoacetophenone, α,α'-dimethoxyazoacetophenone, 2,2'-dimethyl-2-phenylacetophenone, p-methoxyacetophenone, 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 acetophenone compounds 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 acetophenone compounds can be used alone or in combination.

[0261] Specific examples of the above-mentioned diimidazole compounds include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-fluorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-ethylphenyl)- -4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole. The aforementioned diimidazole compound is preferably 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, or a combination thereof. The aforementioned diimidazole compounds can be used alone or in combination, depending on actual needs.

[0262] Specific examples of the aforementioned benzophenone compounds include thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfone, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, or combinations thereof. The aforementioned benzophenone compound is preferably 4,4'-bis(diethylamino)benzophenone. The aforementioned benzophenone compounds can be used alone or in combination, depending on actual needs.

[0263] Specific examples of the aforementioned α-diketone compounds include benzyl, acetyl, or a combination thereof.

[0264] Specific examples of the ketone alcohol compounds include benzoyl ketone. Specific examples of the ketone alcohol ether compounds include benzoyl ketone methyl ether, benzoyl ketone ethyl ether, benzoyl ketone isopropyl ether, or a combination thereof.

[0265] Specific examples of the acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylphenylphosphine oxide, or a combination thereof.

[0266] Specific examples of the quinone compounds include anthraquinone, 1,4-naphthoquinone, or a combination thereof.

[0267] Specific examples of the aforementioned halogen-containing compounds include phenacyl chloride, tribromomethylphenylsulfone, tris(trichloromethyl)-s-triazine, or combinations thereof.

[0268] Specific examples of the peroxide include di-t-butyl peroxide, or a combination thereof.

[0269] The aforementioned α-diketone compounds, ketoalcohol compounds, ketoalcohol ether compounds, acylphosphine oxide compounds, quinone compounds, halogen-containing compounds, peroxides, etc. can be used alone or in combination, depending on actual needs.

[0270] Specific examples of other photoinitiators (C-3) preferably include 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-phenylacyl oxime) (e.g., trade name OXE-01, manufactured by Ciba Specialty Chemicals, Inc., with 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 a combination thereof.

[0271]

[0272] Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the photoinitiator (C) used is 10 to 140 parts by weight, preferably 15 to 130 parts by weight, and more preferably 20 to 120 parts by weight.

[0273] Solvent (D)

[0274] The solvent (D) is a solvent that 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 can have appropriate volatility.

[0275] 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, lactic acid alkyl ester compounds, other ester compounds, aromatic hydrocarbon compounds, carboxylic acid amine compounds, or combinations thereof.

[0276] Specific examples of alkyl glycol monoalkyl ether compounds include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene 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 combinations thereof.

[0277] 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 a combination thereof.

[0278] Specific examples of diethylene glycol alkyl ethers include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, or the like, or combinations thereof.

[0279] Specific examples of other ether compounds include tetrahydrofuran or the like.

[0280] Specific examples of ketone compounds include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol or the like, or combinations thereof.

[0281] Specific examples of alkyl lactate compounds include methyl lactate, ethyl lactate or analogs thereof, or combinations thereof.

[0282] Specific examples of other ester compounds include methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 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, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxybutyrate or the like, or combinations thereof.

[0283] Specific examples of aromatic hydrocarbon compounds include toluene, xylene or the like, or combinations thereof.

[0284] Carboxylic acid amine compounds such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or the like, or combinations thereof. The above solvents (D) may be used alone or in combination of two or more.

[0285] Specific examples of the solvent (D) preferably include propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, ethyl 3-ethoxypropionate, or a combination thereof.

[0286] Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the solvent (D) used may be 500 parts by weight to 5,000 parts by weight, preferably 600 parts by weight to 4,500 parts by weight, and more preferably 700 parts by weight to 4,000 parts by weight.

[0287] Additives (E)

[0288] 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, a UV absorber, a surfactant, an anti-agglomeration agent, or a combination thereof.

[0289] Specific examples of fillers include, but are not limited to, glass and aluminum.

[0290] Specific examples of the polymer may include, but are not limited to, polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, or any combination thereof.

[0291] Specific examples of adhesion promoters may include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(2-methoxyethoxy)silane, nitrogen-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, nitrogen-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidolpropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-thiolpropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, or any combination of the foregoing compounds.

[0292] Specific examples of antioxidants may include, but are not limited to, 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, or any combination thereof.

[0293] Specific examples of the UV absorber may include, but are not limited to, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide, alkoxyphenone, or any combination thereof.

[0294] Specific examples of commercially available products of the surfactant include KP (manufactured by Shin-Etsu Chemical), SF-8427 (manufactured by Dow Corning Toray Silicone Co., Ltd.), Polyflow (manufactured by Kyoeisha Oleochemical Industry), F-Top (manufactured by Tochem Products Co., Ltd.), Megafac (manufactured by Dainippon Ink & Chemicals (DIC)), Fluorade (manufactured by Sumitomo 3M Ltd.), Asahi Guard or Surflon (manufactured by Asahi Glass), SINOPOLE 8008 (manufactured by Chu-Nippon Gosei Chemical), F-475 (manufactured by Dainippon Ink & Chemicals), or a combination thereof.

[0295] Specific examples of the anti-aggregating agent include, but are not limited to, sodium polyacrylate.

[0296] Specific examples of the additive (E) preferably include SF-8427 (manufactured by Dow Corning Toray Co., Ltd., a surfactant), 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical), or a combination thereof.

[0297] Based on 100 parts by weight of the alkali-soluble resin (A), the additive (E) may be used in an amount of 0 to 10 parts by weight, preferably 1 to 9 parts by weight, and more preferably 3 to 8 parts by weight.

[0298] Preparation method of photosensitive resin composition

[0299] A method for preparing a photosensitive resin composition, for example, involves placing an alkali-soluble resin (A), an ethylenically unsaturated compound (B), a photoinitiator (C), and a solvent (D) in a stirrer and stirring them until they are uniformly mixed into a solution. Furthermore, an additive (E) may be added if necessary, and after uniform mixing, a solution-like photosensitive resin composition is obtained.

[0300] The method for preparing the photosensitive resin composition is not particularly limited. For example, the photosensitive resin composition may be prepared by first dispersing a portion of the alkali-soluble resin (A) and the ethylenically unsaturated group-containing compound (B) in a portion of the solvent (D) to form a dispersed solution; and then mixing the remaining alkali-soluble resin (A), the ethylenically unsaturated group-containing compound (B), the photoinitiator (C), and the solvent (D). Furthermore, an additive (E) may be added as needed.

[0301] <Protective Film and Spacer>

[0302] The present invention provides a protective film and a spacer, which are formed from the above-mentioned photosensitive resin composition. The preparation methods of the protective film and the spacer are described in detail below.

[0303] In one embodiment, the steps of forming the protective film include: first forming a pixel layer composed of red, green and blue color layers on a transparent substrate, then coating a photosensitive resin composition on the pixel layer, and then performing pre-baking, exposure, development and post-baking steps on the photosensitive resin composition.

[0304] In one embodiment, the step of forming the spacer includes forming a transparent conductive film on a transparent substrate having a protective film and a pixel layer formed thereon, coating a photosensitive resin composition on the transparent conductive film, and then performing pre-baking, exposure, development, and post-baking steps.

[0305] In other words, if a protective film is to be formed, the photosensitive resin composition is coated on the pixel layer on the substrate; and if a spacer is to be formed, the photosensitive resin composition is coated on the transparent conductive film on the substrate.

[0306] Of course, the protective film and spacer of the present invention are not limited to being formed on the pixel layer or transparent conductive film, but can be formed on the substrate or various components on the substrate. Hereinafter, the component coated with the photosensitive resin composition is also referred to as the "coated object".

[0307] Specifically, the method for forming the spacer or protective film includes the following steps in sequence: (a) a film forming step; (b) an exposure step; (c) a development step; and (d) a post-baking step to form the protective film or spacer.

[0308] a. Film forming steps:

[0309] 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 a coating method to form a film.

[0310] The substrate can be a transparent substrate or a transparent conductive substrate. The substrate material is not particularly limited, and examples include glass substrates such as soda-lime glass and alkali-free glass; or resin substrates such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, or polyimide. Glass substrates are preferred.

[0311] The transparent conductive substrate may be a NESA film (a registered trademark of PPG Corporation, USA) formed of tin oxide (SnO2) or an indium tin oxide (ITO) film formed of indium oxide-tin oxide (In2O3-SnO2) on the entire surface of the transparent substrate.

[0312] The method of forming a film by coating is to apply a solution of a photosensitive resin composition to a coated object. The solid content concentration of the photosensitive resin composition solution applied to the coating method is 5% to 50% by weight, preferably 10% to 40% by weight, and more preferably 15% to 35% by weight. The coating method includes but is not limited to spray coating, roller coating, spin coating (spin coating method), slot die coating method, rod coating method or inkjet coating method. In addition, before the coating method, the coating surface of the substrate is preferably first subjected to a heating step.

[0313] The film is preferably pre-baked. Pre-baking conditions vary depending on the ingredients and mixing ratio, but heating at 70°C to 90°C for 1 to 15 minutes is preferred. After pre-baking, the film has a thickness of 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 above thicknesses are after solvent removal.

[0314] b. Exposure steps:

[0315] The film is exposed using a mask with a specific pattern. The light used in the exposure step can be, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray, preferably ultraviolet light with a wavelength of 190 nm to 450 nm. The exposure dose in the exposure step is 100 J / m 2 Up to 20,000 J / m 2 Suitable, preferably 150J / m 2 Up to 10,000 J / m 2 .

[0316] c. Development step:

[0317] After the exposure step, a development process is performed to remove unnecessary portions using alkali development and form a specific pattern.

[0318] Specific examples of the developer include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, or ammonia; primary aliphatic amines such as ethylamine or n-propylamine; secondary aliphatic amines such as diethylamine or n-propylamine; tertiary aliphatic amines such as trimethylamine, diethylaminomethyl, dimethylethylamine, or triethylamine; tertiary aliphatic cyclic acids 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, or quinoline; quaternary ammonium salt alkaline compounds such as aqueous solutions of tetramethylammonium hydroxide or tetraethylammonium hydroxide; or combinations thereof. A water-soluble organic solvent or surfactant, such as methanol or ethanol, may also be added to the developer as needed.

[0319] The developing method is, for example, a dipping method, an impregnation method, or a shower method. The developing is preferably performed at room temperature to 180° C. for about 10 seconds.

[0320] The substrate on which a predetermined pattern is formed is steam cleaned for 30 to 90 seconds after development and then air-dried with compressed air or nitrogen.

[0321] d. Post-baking steps:

[0322] The substrate, after being patterned, is post-baked using a heating device such as a hot plate or oven to form a spacer or protective film. The heating temperature is set between 150°C and 250°C, with a heating time of 5 to 30 minutes using a hot plate and 30 to 90 minutes using an oven.

[0323] After the above processing steps, the protection film and the spacer are formed.

[0324] The protective film and the spacer of the present invention are not limited to being formed on the pixel layer or the transparent conductive film, but can be formed on the substrate or on various elements on the substrate.

[0325] <Method for Manufacturing Color Filter Substrate>

[0326] A method for manufacturing a color filter substrate, for example, involves sputtering an indium tin oxide (ITO) protective film on the surface of a protective film formed on a transparent substrate having red, green, and blue pixel coloring layers and a protective film formed thereon under a vacuum environment at a temperature between 220°C and 250°C. Furthermore, if necessary, the ITO protective film can be etched and patterned, and then a liquid crystal alignment film can be applied to the surface of the ITO protective film. In this manner, a color filter comprising a cured product formed by curing the photosensitive resin composition of the present invention can be manufactured.

[0327] <Liquid crystal display element and manufacturing method thereof>

[0328] The present invention further provides a liquid crystal display element, which includes at least one of a spacer and a protective film formed from the photosensitive resin composition of the present invention. Specifically, the liquid crystal display element of the present invention includes a color filter substrate, an active element substrate, and a liquid crystal layer located between the color filter substrate and the active element substrate. The active element substrate is a substrate provided with a thin film transistor. At least one of the color filter substrate and the active element substrate may include a protective film formed from the photosensitive resin composition of the present invention. In addition, the spacer can be dispersed in the liquid crystal layer in a manner 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.

[0329] The method for manufacturing the liquid crystal display device of the present invention is not particularly limited, and for example, it can be manufactured by the following method.

[0330] First, the color filter substrate and the active device substrate are placed facing each other with a spacer interposed between them. Next, a sealant is used to bond the periphery of the color filter substrate and the active device substrate, leaving an injection hole. Liquid crystal is then injected through the injection hole into the space between the color filter substrate and the active device substrate, as well as into the space defined by the sealant. Finally, the injection hole is sealed to form a liquid crystal layer between the color filter substrate and the active device substrate. The liquid crystal compound or liquid crystal composition contained in the liquid crystal layer is not particularly limited and depends on actual needs.

[0331] In addition, the liquid crystal compound and liquid crystal composition can be aligned through a liquid crystal alignment film under the application of voltage and light. The type of liquid crystal alignment film is not particularly limited and depends on actual needs.

[0332] The present invention will be further described with reference to the following examples. However, it should be understood that these examples are for illustration only and should not be construed as limiting the implementation of the present invention.

[0333] Synthesis Example of Alkali-Soluble Resin (A-1)

[0334] The amounts of the various reaction reagents used in the synthesis examples A-1-1 to A-1-11 and A-2-1 to A-2-2 of the alkali-soluble resin (A-1) of the present invention are listed in Table 1 below, and the names of the various reaction reagents are listed in Table 2 below.

[0335] Synthesis Example A-1-1

[0336] First, two instillators are prepared, one of which is a monomer instillator and the other is a chain transfer agent instillator.

[0337] To a monomer dropper, 45 g of acrylic acid (as a monomer, hereinafter referred to as AA), 40 g of a mixture of phenylphenoxyethylene glycol acrylate and phenylphenoxydiethylene glycol acrylate (molar ratio 1:1, this mixture as a monomer, hereinafter referred to as PGAPDGA), 15 g of benzylmaleimide (as a monomer, hereinafter referred to as BzMI), 2 g of t-butyl peroxy-2-ethylhexanoate (as a polymerization initiator, trade name PERBUTYL O, manufactured by NOF Corporation, hereinafter referred to as PBO), 42 g of propylene glycol monomethyl ether acetate (as a solvent, hereinafter referred to as PGMEA), and 18 g of propylene glycol monomethyl ether (as a solvent, hereinafter referred to as PGME) were added and stirred to prepare a monomer mixture. Next, 2 g of n-dodecyl mercaptan (nDM), 18 g of PGMEA, and 8 g of PGME were added to a chain transfer agent dropper and stirred to mix.

[0338] Prepare a split flask equipped with a condenser as a reaction tank. Add 98g of PGMEA and 42g of PGME to the reaction tank. Then, under a nitrogen atmosphere, heat the reaction tank in an oil bath while stirring until the temperature of the reaction tank is raised to 90°C. When the temperature of the reaction tank stabilizes at 90°C, add the monomer mixture and chain transfer agent to the reaction tank using a monomer dripper and a chain transfer agent dripper respectively. Maintain the monomer dripper and chain transfer agent dripper at 90°C and drip the monomer mixture and chain transfer agent over a period of 180 minutes. After the addition is completed, wait for 30 minutes before adding 0.5g of PBO. Then, after another 30 minutes of reaction, heat the reaction tank to 115°C. After the temperature of the reaction tank stabilizes at 115°C for 1.5 hours, replace the gas in the split flask with a mixed gas of oxygen / nitrogen = 5 / 95 (v / v). Next, 70 g of glycidyl methacrylate (GMA as a monomer), 0.3 g of 6-tert-butyl-2,4-dimethylphenol (Topanol as a polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd.), 0.5 g of dimethylbenzylamine (DMBA as a catalyst), 16 g of PGMEA, and 6 g of PGME were added to the reaction tank. The mixture was then reacted at 110°C for 1 hour, followed by 8 hours at 115°C. The reaction solution was then cooled to room temperature to obtain alkali-soluble resin A-1-1. The weight average molecular weight (Mw) of alkali-soluble resin A-1-1 was 17,200.

[0339] Synthesis Examples A-1-2 to A-1-9 and Synthesis Examples A-2-1 to A-2-2

[0340] 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 using the same steps as Synthesis Example A-1-1, except that the monomers and their amounts used in synthesizing the alkali-soluble resin (A-1) and the amount of the chain transfer agent used were changed (as shown in Table 1).

[0341]

[0342] Table 2

[0343]

[0344]

[0345]

[0346] Examples 1 to 11 and Comparative Examples 1 to 4

[0347] The following describes Examples 1 to 11 and Comparative Examples 1 to 4 of the photosensitive resin composition:

[0348] Example 1

[0349] 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) were added to 500 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as D-1). The mixture was stirred uniformly with a shaking stirrer to produce the photosensitive resin composition of Example 1. The resulting photosensitive resin composition was evaluated using the evaluation method described below. The results are shown in Table 3.

[0350] Examples 2 to 11, Comparative Examples 1 to 4

[0351] The photosensitive resin compositions of Examples 2 to 11 and Comparative Examples 1 to 4 were prepared using the same procedures as Example 1, except that the types and amounts of the components in the photosensitive resin compositions were changed (as shown in Table 3). The components corresponding to the numbers in Table 3 are shown in Table 4. The resulting photosensitive resin compositions were evaluated using the evaluation method described below, with the results shown in Table 3.

[0352]

[0353]

[0354] Table 4

[0355]

[0356] <Evaluation method>

[0357] Sensitivity

[0358] The photosensitive resin compositions prepared in the above examples and comparative examples were respectively coated on plain glass substrates of 100 mm×100 mm×0.7 mm by spin coating and pre-baked at 90° C. for 150 seconds to obtain pre-baked coating films with a thickness of about 4 μm.

[0359] Next, the pre-baked coating film undergoes an exposure step. Specifically, a photomask with a specific pattern is placed between the pre-baked coating film and an exposure machine (Model AG500-4N; manufactured by M&R Nano Technology), and the pre-baked coating film is irradiated with ultraviolet light at varying exposure doses. The film thickness (δ) is then measured at a random point on the coating film. The film is then immersed in a 0.0438 wt% aqueous potassium hydroxide (KOH) solution for 70 seconds, and the film thickness (δd) is measured at the same point. Finally, the residual film rate is calculated using the following formula (V).

[0360] Residual film rate (%) = [(δd) / (δ)] × 100 (V)

[0361] The exposure when the residual film rate reaches 90% or more is called sensitivity, and is evaluated according to the following criteria:

[0362] ◎: Exposure ≤ 70mJ / cm 2 ;

[0363] ○: 70mJ / cm 2 <Exposure ≤ 90mJ / cm 2 ;

[0364] △: 90mJ / cm 2 <Exposure ≤ 110mJ / cm 2 ;

[0365] ╳: Exposure > 110mJ / cm 2 .

[0366] step difference

[0367] The photosensitive resin compositions prepared in the above examples and comparative examples were respectively coated on plain glass substrates of 100 mm×100 mm×0.7 mm by spin coating and pre-baked at 90° C. for 150 seconds to obtain pre-baked coating films of about 4 μm.

[0368] Then, the pre-baked coating was placed under the specified mask pattern (partial halftone, transmittance 30%) and the energy was 60mJ / cm 2 The exposure step is performed by irradiating with ultraviolet light (the exposure machine model is AG500-4N, and it is manufactured by M&RNano Technology Co., Ltd.).

[0369] The exposed coating film was then immersed in a 0.0438 wt% potassium hydroxide (KOH) aqueous solution for 70 seconds to remove the unexposed portion, then rinsed with pure water and post-baked at 235° C. for 30 minutes to obtain a spacer.

[0370] The height of the main gap is Hm, the height of the sub-gap (halftone portion) is Hs, and Hm-Hs is the step difference.

[0371] ◎: 0.1μm≦ step difference≦0.3μm;

[0372] ○: 0.3μm<step difference≦0.4μm;

[0373] △: 0.4μm<step difference≦0.5μm;

[0374] ╳: Step difference > 0.5μm or step difference < 0.1μm.

[0375] <Evaluation Results>

[0376] As shown in Table 3, the photosensitive resin compositions containing both the alkali-soluble resin (A-1) and the photoinitiator (C-1) (Examples 1 to 11) exhibit superior sensitivity and can form spacers with excellent step differences, compared to the photosensitive resin compositions not containing the alkali-soluble resin (A-1) (Comparative Examples 1 and 2), the photosensitive resin composition not containing the photoinitiator (C-1) (Comparative Example 3), and the photosensitive resin composition not containing both the alkali-soluble resin (A-1) and the photoinitiator (C-1) (Comparative Example 4). Furthermore, the photosensitive resin compositions that did not contain the alkali-soluble resin (A-1) (Comparative Examples 1 and 2) exhibited poor sensitivity. The photosensitive resin composition that did not contain the photoinitiator (C-1) (Comparative Example 3) produced a poor step difference in the spacer. Furthermore, the photosensitive resin composition that did not contain both the alkali-soluble resin (A-1) and the photoinitiator (C-1) (Comparative Example 4) exhibited poor sensitivity and also produced a poor step difference in the spacer.

[0377] When the monomer mixture for synthesizing the alkali-soluble resin (A-1) contains an ethylenically unsaturated monomer (a-1-3) containing a maleimide group or two alkenyl groups (Examples 1 to 7, 11), the photosensitive resin composition can form a spacer with excellent step difference.

[0378] When the synthesized 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.

[0379] When the photosensitive resin composition contains the photoinitiator (C-2) (Examples 2 to 6, 10), the photosensitive resin composition has excellent sensitivity.

[0380] In summary, the photosensitive resin composition of the present invention, comprising an alkali-soluble resin (A-1) having a specific structure and a photoinitiator (C-1) having a specific structure, can effectively improve the problems of poor sensitivity and poor spacer step difference. Thus, the present invention provides a photosensitive resin composition with excellent sensitivity and the ability to form a spacer with excellent step difference, suitable for use in spacers and protective films.

[0381] Although the present invention has been disclosed above by way of embodiments, they are not intended to limit the present invention. Any person skilled in the art may make slight changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the claims.

Claims

1. A photosensitive resin composition comprising: Alkali soluble resin A; Compound B containing an ethylenically unsaturated group; Photoinitiator C; as well as Solvent D; The alkali-soluble resin A comprises an alkali-soluble resin A-1, which is obtained by copolymerizing a mixture comprising an ethylenically unsaturated monomer a-1-1 containing a carboxylic acid group or a carboxylic anhydride group and an ethylenically unsaturated monomer a-1-2 containing an oxyalkylene group represented by the following formula (I). In formula (I), R 1 、R 2 and R 3 each independently represents hydrogen or methyl; R 4 represents a substituted or unsubstituted C1-C 20 A linear or branched alkyl group, a substituted or unsubstituted C2-C 20 a straight chain or branched alkenyl group, or a substituted or unsubstituted C6-C 20 Aromatic hydrocarbon groups; AO stands for C2-C 20 Oxyalkylene; x represents an integer from 0 to 2; y represents 0 or 1; n means 2 or more; The photoinitiator C includes a photoinitiator C-1, and the photoinitiator C-1 is a compound represented by the following formula (II): In formula (II), A represents hydrogen, halogen, nitro, C1-C 20 Straight or branched alkyl, C3-C 10 Alkylcycloalkyl, C4-C 10 Alkylcycloalkyl, C4-C 10 Cycloalkylalkyl, Among them, C1-C 20 Straight or branched alkyl, C3-C 10 Alkylcycloalkyl, C4-C 10 Alkylcycloalkyl, C4-C 10 Cycloalkylalkyl, Any -CH2- contained in it can be replaced by O, N, S or carbonyl; R 5 Represents hydrogen, halogen, C1-C 20 Straight or branched alkyl, C4-C 20 Cycloalkylalkyl or C2-C 20 Alkenyl, wherein C1-C 20 Straight or branched alkyl, C4-C 20 Cycloalkylalkyl and C2-C 20 The -CH2- in the alkenyl group can be replaced by O, N, S or carbonyl. 5 A ring structure can be formed between them; R 6 Indicates C1-C 20 Straight or branched alkyl, C2-C 20 Alkenyl, C3-C 20 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Alkylcycloalkyl, C6-C 20 Aryl or C6-C 20 wherein one or more hydrogen atoms in these groups may be independently replaced by alkyl, halogen, hydroxyl or nitro groups, and R 6 -CH2- in it can be replaced by O, N, S or carbonyl; R 7 Indicates C1-C 20 Straight or branched alkyl, C3-C 20 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Alkylcycloalkyl, C6-C 20 Aryl, C6-C 20 alkylaryl, 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), when R 7 Indicates C1-C 20 Straight or branched alkyl, C3-C 20 Cycloalkyl, C4-C 20 Cycloalkylalkyl, C4-C 20 Alkylcycloalkyl, C6-C 20 Aryl or C6-C 20 When the alkylaryl group is an alkyl group, one or more hydrogen atoms in these groups may be independently replaced by an alkyl group, a halogen group, a hydroxyl group or a nitro group, and R 7 -CH2- in it can be replaced by O, N, S or carbonyl; R 6 With R 7 A ring structure can be formed between them; In formula (II-A), m represents an integer of 0 or 1, and R 11 represents hydrogen, a C1-C8 alkyl group, or a phenyl group, R 12 、R 13 and R 14 Each independently represents hydrogen or a C1-C4 alkyl group; In formula (II-B), p is an integer from 0 to 3; In formula (II-C), R 15 represents hydrogen, C1-C8 alkyl, or phenyl, Ar is substituted or unsubstituted phenyl, naphthyl, furyl, thienyl or pyridyl; R 8 represents N-morpholinyl, N-piperidinyl, N-pyrrolyl or N-dialkyl, wherein one or more hydrogen atoms in these groups may be replaced by halogen or hydroxyl; R 9 、R 9 'Each independently represents C1-C 20 Straight or branched alkyl, C4-C 20 Cycloalkyl, C2-C 20 Alkenyl, C6-C 20 Aryl or C6-C 20 wherein one or more hydrogen atoms in these groups may be independently replaced by alkyl, halogen, hydroxyl or nitro, and -CH2- in these groups may be replaced by -O-; or R 9 and R 9 'Can be connected to each other or via -O-, -S- or -NH- to form a five-membered ring or a six-membered ring; R 10 Indicates C1-C 20 Straight or branched alkyl, C4-C 20 Cycloalkyl, C4-C 20 Alkylcycloalkyl, C2-C 20 Alkenyl, C6-C 20 Aryl or C6-C 20 Alkylaryl, wherein -CH2- in these groups may be substituted by -O- or -S-, and one or more hydrogens of these groups may be independently selected from alkyl, halogen, nitro, cyano, SR 16 OR 17 replaced by; R 16 and R 17 Each independently represents hydrogen, or C1-C 20 A straight-chain or branched-chain alkyl group. 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 ethylenically unsaturated monomer a-1-3 containing a maleimide group or two alkenyl groups comprises at least one monomer selected from the group consisting of the monomers represented by the following formulas (1) to (5): In formula (4) and formula (5), R 18 、R 19 and R 20 Each independently represents hydrogen, or C1-C 30 A straight-chain or branched-chain alkyl group. 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, and the photoinitiator C-2 is a compound represented by the following formula (III): In formula (III), Ar1 represents an o-arylene group or an o-heteroarylene group, wherein the o-arylene group or the o-heteroarylene group is a ring structure formed by two adjacent atoms with Y1 and a carbonyl group, and the substituents on the remaining atoms are each selected from hydrogen; halogen; C1-C 12 C5-C7 cycloalkyl; C1-C4 alkyl substituted by C5-C7 cycloalkyl; phenyl; C1-C4 alkyl, carboxyl, C1-C 12 Alkyl acyl, C1-C 12 phenyl, halogen or CN substituted phenyl; C1-C4 alkylbenzyloxy; Substituted C1-C4 alkoxy, C1-C3 alkylenedioxy; C1-C 12 Alkylthio; C1-C4 alkylphenylthio; Substituted C1-C4 alkylthio; CN; carboxyl; C1-C 12 The group consisting of alkoxyformyl; aryl acyl; heteroaryl acyl and JT5; or Two adjacent substituents of Ar1 or a substituent and Ar1 form a ring structure via a single bond, a carbon atom, or a carbonyl group; in, In JT4 and JT5, J is selected from the group consisting of O, S, and NT6; Y1 is selected from the group consisting of O, S, NT7, BT7, CT2T3, SiT2T3, S═O and C═O; T1 represents hydrogen, C1-C 18 Alkyl or C1-C 18 an alkoxy group; or T1 represents a C2-C4 alkyl group substituted with one or more halogens, C1-C4 alkyl groups, C5-C7 cycloalkyl groups, heterocycloalkyl groups, phenyl groups, heteroaryl groups, CN, C1-C4 alkanoyl groups or aroyl groups. 18 C2-C7 cycloalkylene, phenylene, O, S or NT4 inserted 18 C2-C4 alkyl group; C2-C7 alkyl group; C5-C7 cyclo ... 18 Alkyl; C2-C 18 C2-C4 substituted with one or more halogen, C1-C4 alkyl, C5-C7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C1-C4 alkanoyloxy or aroyloxy 18 C2-C7 cycloalkylene, phenylene, O, S or NT4 inserted 18 C2-C4 substituted with one or more halogen, C1-C4 alkyl, C5-C7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C1-C4 alkanoyloxy or aroyloxy and inserted with C5-C7 cycloalkylene, phenylene, O, S or NT4 18 or T1 represents a C5-C7 cycloalkyl group, or a C5-C7 cycloalkyl group substituted with one or more C1-C4 alkyl groups, phenyl groups, halogen groups or CN; or T1 represents phenyl, or phenyl substituted by one or more C1-C4 alkyl, C1-C4 alkoxy, phenyl, halogen or CN; or T1 represents naphthyl, benzoyl or phenoxycarbonyl, wherein the phenyl group of benzoyl and phenoxycarbonyl is arbitrarily substituted by one or more halogens, T4, C5-C6 cycloalkyl, CN, OH or JT4; T2 and T3 each independently represent hydrogen, C1-C 18 C1-C5 alkyl substituted by a carboxyl group, C1-C4 alkyl substituted by an alkoxy acyl group or C1-C5 alkyl substituted by a substituted C1-C4 alkyl; or T2 and T3 each independently represent a C2-C4 alkyl group substituted with one or more halogen, C1-C4 alkyl, C5-C7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C1-C4 alkanoyloxy, or aroyloxy group. 18 or a C2-C7 cycloalkylene group, a phenylene group, O, S or NT4 inserted into a C5-C7 cycloalkylene group. 18 alkyl, or both of the above situations exist at the same time; or T2 and T3 each independently represent a C5-C7 cycloalkyl group, or a C5-C7 cycloalkyl group substituted with one or more C1-C4 alkyl groups, phenyl groups, halogen groups or CN; or T2 and T3 each independently represent a phenyl group, or a phenyl group substituted with one or more C1-C4 alkyl groups, C1-C4 alkoxy groups, carboxyl groups, C1-C 12 C2-C4 alkylacyl, arylacyl, JT4, phenyl, halogen or CN substituted phenyl; or T2 and T3, together with the carbon or silicon atom to which they are attached, form a ring structure with 4 to 7 atoms; or T2 and T3 each form a cyclic structure together with an adjacent substituent, and the number of atoms forming the ring is 4 to 7; T4 represents a C1-C4 alkyl group; T5 represents hydrogen, C1-C 18 Alkyl, C1-C5 alkyl substituted by C1-C4 alkoxy acyl or substituted C1-C4 alkyl; or T5 represents a C2-C7 substituted with one or more halogen, C1-C4 alkyl, C5-C7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C1-C4 alkanoyloxy or aroyloxy group. 18 or a C2-C7 cycloalkylene group, a phenylene group, O, S or NT4 inserted into a C5-C7 cycloalkylene group. 18 alkyl, or both of the above situations exist at the same time; or T5 represents a C5-C7 cycloalkyl group, or a C5-C7 cycloalkyl group substituted with one or more C1-C4 alkyl groups, phenyl groups, halogen groups or CN; or T5 represents a phenyl group, or is substituted with one or more C1-C 12 Alkyl, carboxyl, C1-C 12 Alkyl acyl, C2-C inserted by phenylene, O, S or NT4 12 Alkyl acyl, C5-C6 cycloalkyl formyl, C5-C6 cycloalkyl substituted C2-C4 alkyl acyl, aryl acyl, heteroaryl acyl, JT4, phenyl, halogen, CN or NO2 substituted phenyl or T5 represents a C1-C4 alkyl acyl group, a C1-C4 conjugated alkenoyl group, a benzoyl group or a phenoxycarbonyl group, wherein the phenyl group in the benzoyl group and the phenoxycarbonyl group may be arbitrarily substituted with one or more halogens, T4, a cyclopentyl group, a cyclohexyl group, CN, OH or JT4; or T5 forms a ring structure with the aromatic ring in Ar1 via a single bond, a carbon atom or a carbonyl group; T6 and T7 each independently represent hydrogen, C1-C 18 Alkyl, C1-C5 alkyl substituted by C1-C4 alkoxy acyl or substituted C1-C4 alkyl; or T6 and T7 each independently represent a C2-C4 alkyl group substituted with one or more halogens, C1-C4 alkyl groups, C5-C7 cycloalkyl groups, heterocycloalkyl groups, phenyl groups, heteroaryl groups, CN, C1-C4 alkanoyloxy groups or aroyloxy groups. 18 Alkyl, C2-C7 cycloalkylene, phenylene, O, S or NT4 inserted 18 alkyl, or both of the above situations exist at the same time; or T6 and T7 each independently represent a C5-C7 cycloalkyl group, or a C5-C7 cycloalkyl group substituted with one or more C1-C4 alkyl groups, phenyl groups, halogen groups or CN; or T6 and T7 each independently represent a phenyl group, or substituted with one or more C1-C4 alkyl groups, carboxyl groups, C1-C 12 C2-C4 alkylacyl, arylacyl, JT4, phenyl, halogen or CN substituted phenyl; or T6 each forms a ring structure through a single bond, a carbon atom, a carbonyl group and an aromatic ring in Ar1; When Ar1 is a substituted carbazole group, Y1 is not C, O, S or NT7. The photosensitive resin composition according to claim 1 , wherein Based on 100 parts by weight of the alkali-soluble resin A, the amount of the alkali-soluble resin A-1 is 50 to 100 parts by weight, the amount of the compound B containing an ethylenically unsaturated group is 50 to 600 parts by weight, the amount of the photoinitiator C is 10 to 140 parts by weight, the amount of the photoinitiator C-1 is 10 to 90 parts by weight, and the amount of the solvent D is 500 to 5000 parts by weight.

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

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

9. The photosensitive resin composition according to claim 5, wherein Based on 100 parts by weight of the alkali-soluble resin A, the amount of the photoinitiator C-2 used is 5 parts by weight to 50 parts by weight. 10 . A spacer formed from the photosensitive resin composition according to claim 1 . 11 . A protective film formed from the photosensitive resin composition according to claim 1 . 12 . A liquid crystal display element comprising the spacer according to claim 10 . 13 . A liquid crystal display element comprising the protective film according to claim 11 .

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