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

Abstract

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

Description

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

technical field

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

Background technique

Generally speaking, the color printing pixels and black matrix on the surface of the color filter layer are uneven, so a protective film is usually formed on the surface of the color filter layer to hide the unevenness and achieve flattening requirements.

However, in the manufacture of optical elements such as liquid crystal display elements and solid-state imaging devices, it is often necessary to process under severe conditions, such as immersing the substrate surface in an acidic solvent or an alkaline solution, or forming wiring by sputtering. When the electrode layer is used, it will cause local corrosion or high temperature. Therefore, it is necessary to lay a protective film on the surface of these components to prevent the components from being damaged during manufacture. In order for the protective film to have the characteristics to withstand the above-mentioned treatments, the protective film needs to have excellent adhesion with the substrate, and also needs to have high transparency, high surface hardness, and a smooth surface. In addition, the protective film also needs a protective film with high heat resistance and light resistance to avoid deterioration such as discoloration, yellowing or whitening 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.

On the other hand, in the prior art, in the color liquid crystal display element, in order to maintain a fixed layer distance between two substrates, spray beads such as polystyrene beads or silicon beads are randomly sprayed on the entire substrate. The diameter is the distance between the two substrates. However, due to the uneven position and density distribution of the sprayed beads, the light of the backlight source is scattered due to the influence of the sprayed beads, which further reduces the contrast ratio of the display element. Therefore, photosensitive compositions for spacers developed by photolithography have become the mainstream in the industry. The spacer is formed by first applying the photosensitive composition for the spacer to the substrate, then placing a photomask of a specified shape between the substrate and the exposure source, and then developing the spacer after the exposure step to form the spacer. According to this method, spacers can be formed at designated positions outside the red, green, blue, etc. pixels to solve the problems of the prior art; the interlayer spacing can also be controlled by the thickness of the coating film formed by the photosensitive component, so that the layer The distance of the pitch becomes easy to control, which has the advantage of high precision.

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

In order to improve the transparency of the protective film or the spacer, Japanese Patent Laid-Open No. 2010-054561 discloses a photosensitive composition for the protective film, which comprises (A) an adhesive resin (which is an alkali-soluble resin), (B) an ethylenic resin An unsaturated group compound, (C) a photoinitiator, and (D) a solvent, wherein (B) the ethylenically unsaturated group-containing compound has an equivalent weight of unsaturated bonds between 90 and 450 g/eq. (B) In the compound of ethylenically unsaturated group, the number of unsaturated double bonds in a single compound is between 2 and 4. (A) The weight average molecular weight of the adhesive resin is between 10,000 and 20,000. On the other hand, Japanese Patent Laid-Open No. 2004-240241 discloses a photosensitive composition comprising (A) a compound composed of an ethylenically unsaturated carboxylic acid (anhydride), an ethylenically unsaturated group having an epoxy group, and other vinyl groups Copolymers of compounds with ethylenically unsaturated groups, (B) polymerizable compounds having ethylenically unsaturated groups, and (C) 2-butanedione-(4-(methylthio)phenyl)- 2-(O-oxime acetate), 1,2-butanedione-1-(4-morpholinophenyl)-2-(O-benzoyl oxime), 1,2-octanedione- Photopolymerization initiators such as 1-(4-(phenylthio)phenyl)-2-[O-(4-methylbenzoyl)oxime]. However, the above-mentioned photosensitive resin compositions still have the disadvantage of poor sensitivity, and the spacers formed by them still have the disadvantage of poor level difference.

Therefore, how to improve the sensitivity of the photosensitive resin composition and how to improve the level difference of the spacers is a problem that those skilled in the art are eager to solve at present.

SUMMARY OF THE INVENTION

In view of this, the present invention provides a photosensitive resin composition which has excellent sensitivity and can form a spacer having an excellent level difference, which can be applied to a spacer and a protective film.

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

In formula (I),

R ¹ , R ² and R ³ each independently represent hydrogen or methyl;

R ⁴ represents substituted or unsubstituted C ₁ -C ₂₀ linear or branched alkyl, substituted or unsubstituted C ₂ -C ₂₀ linear or branched alkenyl, or substituted Or unsubstituted C ₆ -C ₂₀ aromatic hydrocarbon groups;

AO represents C ₂ -C ₂₀ oxyalkylene;

x represents an integer from 0 to 2;

y represents 0 or 1;

n represents 2 or more.

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

In formula (II),

其中C₁-C₂₀的直链或支链的烷基、C₃-C₁₀的烷基环烷基、C₄-C₁₀的烷基环烷基、C₄-C₁₀的环烷基烷基、

中所含有的任一个-CH₂-可被O、N、S或羰基所取代；A represents hydrogen, halogen, nitro, C ₁ -C ₂₀ straight or branched chain alkyl, C ₃ -C ₁₀ alkyl cycloalkyl, C ₄ -C ₁₀ alkyl cycloalkyl, C ₄ -C ₁₀ cycloalkylalkyl,

Wherein C ₁ -C ₂₀ linear or branched alkyl, C ₃ -C ₁₀ alkyl cycloalkyl, C ₄ -C ₁₀ alkyl cycloalkyl, C ₄ -C ₁₀ cycloalkyl alkane base,

Any -CH ₂ - contained in can be substituted by O, N, S or carbonyl;

R ⁵ represents hydrogen, halogen, C ₁ -C ₂₀ straight or branched chain alkyl, C ₄ -C ₂₀ cycloalkylalkyl or C ₂ -C ₂₀ alkenyl, wherein C ₁ -C ₂₀ The -CH ₂ - contained in the straight or branched chain alkyl, C ₄ -C ₂₀ cycloalkyl alkyl and C ₂ -C ₂₀ alkenyl may be substituted by O, N, S or carbonyl, two A ring structure can be formed between each R ⁵ ;

R ⁶ represents C ₁ -C ₂₀ straight or branched chain alkyl, C ₂ -C ₂₀ alkenyl, C ₃ -C ₂₀ cycloalkyl, C ₄ -C ₂₀ cycloalkyl alkyl, C ₄ - _C20 alkylcycloalkyl group, _C6 - _C20 aryl group or _C6 - _C20 alkylaryl group, wherein one or more hydrogens in these groups can each independently be replaced by alkyl, halogen , hydroxy or nitro, and -CH ₂ - in R ⁶ can be substituted by O, N, S or carbonyl;

R ⁷ represents a C ₁ -C ₂₀ straight or branched chain alkyl group, a C ₃ -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ cycloalkyl alkyl group, a C ₄ -C ₂₀ alkylcycloalkane group, a C ₆ -C ₂₀ aryl group, a C ₆ -C ₂₀ alkylaryl group, a group represented by the following formula (II-A), a group represented by the following formula (II-B), or In the group represented by the following formula (II-C), when R ⁷ represents a C ₁ -C ₂₀ straight or branched chain alkyl group, a C ₃ -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ cyclic alkyl group In the case of alkylalkyl, _C4 - _C20 alkylcycloalkyl, _C6 - _C20 aryl, or _C6 - _C20 alkylaryl, one or more hydrogens in these groups may each independently substituted by alkyl, halogen, hydroxy or nitro, and -CH ₂ - in R ⁷ may be substituted by O, N, S or carbonyl;

A ring structure can be formed between R ⁶ and R ⁷ ;

In formula (II-A), m represents an integer of 0 or 1, R ¹¹ represents hydrogen, a C ₁ -C ₈ alkyl group, or a phenyl group, and R ¹² , R ¹³ and R ¹⁴ each independently represent hydrogen or C ₁ - C ₄ alkyl;

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

In formula (II-C), R ¹⁵ represents hydrogen, C ₁ -C ₈ alkyl, or phenyl, and Ar is substituted or unsubstituted phenyl, naphthyl, furyl, thienyl or pyridyl;

R ⁸ represents N-morpholinyl, N-pyridyl, N-pyrrolyl or N-dialkyl, wherein one or more hydrogens in these groups may be replaced by halogen or hydroxyl;

R ⁹ and R ⁹ ' each independently represent a C ₁ -C ₂₀ straight or branched chain alkyl group, a C ₄ -C ₂₀ cycloalkyl group, a C ₂ -C ₂₀ alkenyl group, and a C ₆ -C ₂₀ aryl group or C ₆ -C ₂₀ alkylaryl groups, wherein one or more hydrogens in these groups may be independently substituted by alkyl, halogen, hydroxyl or nitro, and -CH ₂ - may be substituted by -O-; or R ⁹ and R ⁹ ' may be connected to each other or via -O-, -S- or -NH- to form a five-membered or six-membered ring;

R ¹⁰ represents C ₁ -C ₂₀ straight or branched chain alkyl, C ₄ -C ₂₀ cycloalkyl, C ₄ -C ₂₀ alkyl cycloalkyl, C ₂ -C ₂₀ alkenyl, C ₆ - _C20 aryl or _C6 - _C20 alkylaryl, wherein _-CH2- in these groups may be substituted by -O- or -S-, and one or more hydrogens of these groups may be independently substituted by alkyl, halogen, nitro, cyano, SR ¹⁶ or OR ¹⁷ ;

R ¹⁶ and R ¹⁷ each independently represent hydrogen, or a C ₁ -C ₂₀ straight-chain or branched-chain alkyl group.

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

In an embodiment of the present invention, the above-mentioned ethylenically unsaturated monomer (a-1-3) containing a maleimide group or two alkenyl groups at least includes one selected from the following formulas (1) to A monomer represented by formula (5).

In formula (4) and formula (5), R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent hydrogen or a C ₁ -C ₃₀ linear or branched alkyl group.

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

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

In formula (III),

取代的C₁-C₄的烷氧基、C₁-C₃的亚烷基二氧基；

；C₁-C₁₂的烷基硫基；C₁-C₄的烷基苯硫基；经

取代的C₁-C₄的烷基硫基；CN；羧基；C₁-C₁₂的烷氧基甲酰基；芳基酰基；杂芳基酰基及JT₅所组成的群组；或者Ar ₁ represents an o-arylene group or an o-hetero-arylene group, and the o-arylene group or the o-hetero arylene group forms a ring structure with Y ₁ and a carbonyl group by two adjacent atoms, and the substituents on the remaining atoms are selected from each other. Free hydrogen; halogen; C ₁ -C ₁₂ alkyl; C ₅ -C ₇ cycloalkyl; C ₁ -C ₄ alkyl substituted with C ₅ -C ₇ cycloalkyl; phenyl; or more C ₁ -C ₄ alkyl, carboxyl, C ₁ -C ₁₂ alkyl acyl, C ₁ -C ₁₂ aryl acyl, heteroaryl acyl, JT ₄ , phenyl, halogen or CN substituted Phenyl; C ₁ -C ₄ alkylbenzyloxy; via

Substituted C ₁ -C ₄ alkoxy, C ₁ -C ₃ alkylenedioxy;

; C ₁ -C ₁₂ alkylthio; C ₁ -C ₄ alkylphenylthio;

Substituted C ₁ -C ₄ alkylthio; CN; carboxyl; C ₁ -C ₁₂ alkoxyformyl; aryl acyl; heteroaryl acyl and the group consisting of JT ₅ ; or

In the above-mentioned substituents of Ar ₁ , a cyclic structure is formed between two adjacent substituents or between the substituents and Ar ₁ via a single bond, a carbon atom, and a carbonyl group;

Among them, in JT ₄ and JT ₅ , J is selected from the group consisting of O, S and NT ₆ ;

Y ₁ is selected from the group consisting of O, S, NT ₇ , BT ₇ , CT ₂ T ₃ , SiT ₂ T ₃ , S=O and C=O;

T ₁ represents hydrogen, C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy; or

T ₁ represents via one or more halogen, C ₁ -C ₄ alkyl, C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C ₁ -C ₄ alkane C ₂ -C ₁₈ alkyl substituted with acyloxy or aroyloxy and/or inserted by C ₅ -C ₇ cycloalkylene, phenylene, O, S or NT ₄ ; C ₂ -C ₁₈ alkenyl; via one or more halogens, C ₁ -C ₄ alkyl, C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C ₁ -C ₄ Alkanoyloxy or aroyloxy substituted and/or _{C2 - C18} alkenyl inserted by _{C5 -} C7 cycloalkylene, phenylene, O, S or NT4, or both conditions exist simultaneously; or

T ₁ represents a C ₅ -C ₇ cycloalkyl, or a C ₅ -C ₇ cycloalkyl substituted with one or more C ₁ -C ₄ alkyl, phenyl, halogen or CN; or

T ₁ represents phenyl, or phenyl substituted with one or more C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, phenyl, halogen or CN; or

T ₁ represents naphthyl, benzoyl or phenoxycarbonyl, wherein the phenyl group of benzoyl and phenoxycarbonyl is optionally replaced by one or more halogens, T ₄ , C ₅ -C ₆ cycloalkyl, CN , OH or JT ₄ ;

取代的C₁-C₄的烷基；或者T ₂ and T ₃ each independently represent hydrogen, C ₁ -C ₁₈ alkyl, C ₁ -C ₅ alkyl substituted with carboxyl, C ₁ -C ₅ substituted with C ₁ -C ₄ alkoxyacyl alkyl or

substituted C ₁ -C ₄ alkyl; or

T ₂ and T ₃ each independently represent via one or more halogen, C ₁ -C ₄ alkyl, C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C ₁ -C ₄ alkanoyloxy, aroyloxy substituted C ₂ -C ₁₈ alkyl, or inserted by C ₅ -C ₇ cycloalkylene, phenylene, O, S or NT ₄ C ₂ -C ₁₈ alkyl, or both; or

T ₂ and T ₃ each independently represent a C ₅ -C ₇ cycloalkyl, or a C ₅ -C ₇ cycloalkyl substituted with one or more C ₁ -C ₄ alkyl, phenyl, halogen or CN ;or

T ₂ and T ₃ each independently represent a phenyl group, or via one or more C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxy groups, carboxyl groups, C ₁ -C ₁₂ alkyl acyl groups, C ₅ -C ₆ cycloalkylformyl or C ₅ -C ₆ cycloalkyl substituted C ₂ -C ₄ alkyl acyl, aryl acyl, JT ₄ , phenyl, halogen or CN substituted phenyl; or

Each of T ₂ and T ₃ together with the carbon atom or silicon atom to which they are commonly attached forms a ring structure and the number of atoms forming the ring is 4 to 7; or

Each of T ₂ and T ₃ together with the adjacent substituents forms a cyclic structure and the number of atoms forming the ring is 4 to 7;

T ₄ represents a C ₁ -C ₄ alkyl group;

取代的C₁-C₄的烷基；或者T ₅ represents hydrogen, C ₁ -C ₁₈ alkyl, C ₁ -C ₅ alkyl substituted with C 1 -C 4 alkoxyacyl, or C ₁ -C ₅ alkyl

substituted C ₁ -C ₄ alkyl; or

T ₅ represents via one or more halogen, C ₁ -C ₄ alkyl, C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C ₁ -C ₄ alkane C ₂ -C ₁₈ alkyl substituted with acyloxy or aroyloxy, or C ₂ -C ₁₈ inserted by C ₅ -C ₇ cycloalkylene, phenylene, O, S or NT ₄ , or both of the above; or

T ₅ represents a C ₅ -C ₇ cycloalkyl, or a C ₅ -C ₇ cycloalkyl substituted with one or more C ₁ -C ₄ alkyl, phenyl, halogen or CN; or

T ₅ represents phenyl, or C 2 -C through one or more C ₁ -C ₁₂ alkyl, carboxyl, C ₁ -C ₁₂ alkylacyl, C ₂ -C inserted by phenylene, O, S or NT _{4 12} alkyl acyl, C ₅ -C ₆ cycloalkyl formyl, C ₅ -C ₆ cycloalkyl substituted C ₂ -C ₄ alkyl acyl, aryl acyl, heteroaryl acyl, JT ₄ , phenyl, halogen, CN or NO substituted phenyl _; or

T ₅ represents a C ₁ -C ₄ alkyl acyl group, a C ₁ -C ₄ conjugated alkenoyl group, a benzoyl group or a phenoxycarbonyl group, wherein the phenyl group in the benzoyl group and the phenoxycarbonyl group can be arbitrarily replaced by one or two or more halogen, T ₄ , cyclopentyl, cyclohexyl, CN, OH or JT ₄ substitutions; or

T ₅ forms a cyclic structure with the aromatic ring in Ar ₁ via a single bond, a carbon atom or a carbonyl group;

取代的C₁-C₄的烷基；或者T ₆ and T ₇ each independently represent hydrogen, a C ₁ -C ₁₈ alkyl group, a C ₁ -C ₅ alkyl group substituted with a C 1 -C 4 alkoxyacyl group, or a C ₁ -C ₅ alkyl group substituted with a C 1 -C 4 alkoxyacyl group.

substituted C ₁ -C ₄ alkyl; or

T ₆ and T ₇ each independently represent through one or more halogen, C ₁ -C ₄ alkyl, C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C ₁ -C ₄ alkanoyloxy or aroyloxy substituted C ₂ -C ₁₈ alkyl, C ₂ inserted by C ₅ -C ₇ cycloalkylene, phenylene, O, S or NT ₄ -C ₁₈ alkyl, or both; or

_T6 and _T7 each independently represent a _{C5 -} C7 cycloalkyl, or a _C5 -C7 cycloalkyl substituted with one or more _{C1 - C4} alkyl, phenyl, halogen or CN ;or

T ₆ and T ₇ each independently represent a phenyl group, or via one or more C ₁ -C ₄ alkyl groups, carboxyl groups, C ₁ -C ₁₂ alkyl acyl groups, C ₅ -C ₆ cycloalkylformyl groups or _C5 - _C6 cycloalkyl substituted C2 _{- C4} alkylacyl, arylacyl, _JT4 , phenyl, halogen or CN substituted phenyl; or

Each of T ₆ forms a cyclic structure via a single bond, a carbon atom, a carbonyl group and an aromatic ring in Ar ₁ ;

Wherein when Ar ₁ is a substituted carbazole group, Y ₁ is not C, O, S or NT ₇ .

In an 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) used is 50 to 100 parts by weight, and the ethylenically unsaturated group-containing compound ( The usage amount of B) is 50 to 600 parts by weight, the usage amount of the photoinitiator (C) is 10 to 140 parts by weight, and the usage amount of the photoinitiator (C-1) is 10 to 100 parts by weight 90 parts by weight, and the solvent (D) is used in an amount of 500 parts by weight to 5000 parts by weight.

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

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

In an 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.

The present invention also provides a spacer formed from the above-mentioned photosensitive resin composition.

The present invention also provides a protective film formed from the above-mentioned photosensitive resin composition.

The present invention also provides a liquid crystal display element comprising the above-mentioned spacer.

The present invention also provides a liquid crystal display element comprising the above protective film.

Based on the above, the present invention improves the sensitivity of the photosensitive resin composition by combining the specific alkali-soluble resin (A-1) and the specific photoinitiator (C-1) with the photosensitive resin composition, and forms an excellent step difference. It is suitable for spacers, protective films and liquid crystal display elements.

In order to make the above-mentioned features and advantages of the present invention more obvious and easy to understand, the following examples are given and described in detail as follows.

Detailed ways

In the following text, acrylic acid and/or methacrylic acid is represented by (meth)acrylic acid, and acrylate and/or methacrylic acid is represented by (meth)acrylate; similarly, propylene is represented by (meth)acryloyl Acyl and/or methacryloyl; by (meth)acrylamide acrylamide and/or methacrylamide.

<Photosensitive resin composition>

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

Alkali Soluble Resin (A)

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

Alkali Soluble Resin (A-1)

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

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

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

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

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

Since the ethylenically unsaturated monomer (a-1-1) containing a carboxylic acid group or a carboxylic acid anhydride group has a carboxylic acid group or a carboxylic acid anhydride group (hereinafter referred to as "acid group"), the synthesized polymer can be It has an acid group on the side chain and has alkali solubility. Specific examples of the carboxylic acid group or carboxylic acid anhydride group-containing ethylenically unsaturated monomer (a-1-1) include acrylic acid, methacrylic acid, 2-acryloylethoxysuccinate, 2-methacryloyl Ethoxylated succinate (HOMS), itaconic acid, ω-carboxy-polycaprolactone monoacrylate (ω-carboxy-polycaprolactone monoacrylate) and other carboxylic acid group-containing ethylenically unsaturated monomers; male A carboxylic acid anhydride group-containing ethylenically unsaturated monomer such as acid anhydride and itaconic acid anhydride, or a combination of the above monomers. Specific examples of the carboxylic acid group- or carboxylic acid anhydride group-containing ethylenically unsaturated monomer (a-1-1) preferably include acrylic acid, methacrylic acid, 2-methacryloylethoxysuccinate, or its combination.

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

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

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).

In formula (I),

R ¹ , R ² and R ³ each independently represent hydrogen or methyl, preferably each independently represents hydrogen;

R ⁴ represents substituted or unsubstituted C ₁ -C ₂₀ linear or branched alkyl, substituted or unsubstituted C ₂ -C ₂₀ linear or branched alkenyl, or substituted Or an unsubstituted C ₆ -C ₂₀ aromatic hydrocarbon group, preferably a C ₁ -C ₂₀ straight-chain alkyl group, an unsubstituted C ₆ -C ₂₀ aromatic hydrocarbon group, substituted with an aromatic hydrocarbon group C ₆ -C ₂₀ aromatic hydrocarbon group, or C ₆ -C ₂₀ aromatic hydrocarbon group substituted by C ₁ -C ₁₀ alkyl group, more preferably methyl, phenyl, 4-nonylphenyl (4-nonylphenyl) -Nonylphenyl) or biphenyl.

AO represents a C ₂ -C ₂₀ oxyalkylene group, preferably a C ₂ -C ₁₀ oxyalkylene group, more preferably a C ₂ -C ₅ oxyalkylene group, still more preferably an oxy group Ethylene;

x represents an integer from 0 to 2;

y represents 0 or 1;

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

Notably, the oxyalkylene group-containing ethylenically unsaturated monomer (a-1-2) may contain one or two or more types of oxyalkylene groups.

Specific examples of the oxyalkylene-containing ethylenically unsaturated monomer (a-1-2) include o-phenylphenoxyethylene glycol acrylate (EO 1 mole)/o-phenylphenoxydiethyl A mixture of glycol acrylates (EO2 moles) (1:1 molar ratio between o-phenylphenoxyethylene glycol acrylate and o-phenylphenoxydiethylene glycol acrylate), o-benzene phenoxydiethylene glycol (meth)acrylate (EO2 mole), phenoxydiethylene glycol (meth)acrylate (EO2 mole), phenoxy polyethylene glycol (meth)acrylate (EO4 moles), methoxypolyethylene glycol (meth)acrylate (EO9 moles), methoxypolyethylene glycol (meth)acrylates (EO12 to 13 moles), methoxytriethylene glycol (Meth)acrylic acid (EO3 moles), ethoxydiethylene glycol (meth)acrylate (EO2 moles), butoxydiethylene glycol (meth)acrylate (EO2 moles), 2-ethyl Hexyloxydiethylene glycol (meth)acrylate (EO2 mole), methoxydipropylene glycol (meth)acrylate (PO2 mole), methoxypolypropylene glycol (meth)acrylate (PO4 mole), Nonylphenoxy polyethylene glycol (meth)acrylate (EO4 to 17 moles), nonylphenoxy polypropylene glycol (meth)acrylate (PO5 moles), modified with ethylene oxide (EO) of cresol (meth)acrylic acid (EO2 moles), or a combination of the above monomers.

Specific examples of the oxyalkylene-containing ethylenically unsaturated monomer (a-1-2) preferably include o-phenylphenoxyethylene glycol acrylate/o-phenylphenoxydiethylene Alcohol acrylate (molar ratio between phenylphenoxyethylene glycol acrylate and phenylphenoxydiethylene glycol acrylate 1:1), phenoxydiethylene glycol acrylate, methoxypolyethylene glycol Ethylene glycol acrylate (EO 9 moles), methoxy polyethylene glycol acrylate (EO12 to 13 moles), nonylphenoxy polyethylene glycol acrylate (EO4 to 17 moles), nonylphenoxy polypropylene glycol acrylate Esters (PO5 moles), or a combination of the above monomers.

In the foregoing, "EO" and "PO" represent oxyethylene and oxypropylene, respectively. The number of moles described after "EO" and "PO" is the average number of moles of an oxyethylene group or an oxypropylene group contained in a unit mole of the compound. For example, "methoxy polyethylene glycol acrylate (EO 9 moles)" means having an average of 9 moles of oxyethylene groups per unit mole of compound.

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

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

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

The ethylenically unsaturated monomers (a-1-3) containing maleimide groups or two alkenyl groups include ethylenically unsaturated monomers containing maleimide groups (also called "cyclic unsaturated monomers" structural monomer"), an ethylenically unsaturated monomer containing two alkenyl groups (also referred to as a monomer that can form a cyclic structure upon polymerization), or a combination thereof. It is worth noting that the above-mentioned monomers can form structural units with a cyclic structure when forming polymers.

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-m-methylphenylmaleimide Laminide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N- -Aromatically substituted maleimides such as p-methoxyphenylmaleimide; cyclohexylmaleimide, methylmaleimide, ethylmaleimide, Maleimides substituted with alkyl groups such as propylmaleimide and isopropylmaleimide, or a combination of the above monomers.

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

The ethylenically unsaturated monomer containing two alkenyl groups can be, for example, 1,6-diolefins. The 1,6-diene includes the 1,6-diene represented by the formula (4), the 1,6-diene represented by the formula (5), or a combination thereof.

In formula (4) and formula (5), R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent hydrogen or a C ₁ -C ₃₀ linear or branched alkyl group, preferably hydrogen or C ₁ -C ₁₀ The straight-chain or branched-chain alkyl group is more preferably hydrogen or a C ₁ -C ₅ straight-chain or branched-chain alkyl group, more preferably methyl group.

Specific examples of 1,6-diolefins include dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, methyl α-(allyloxymeth)acrylate, or a combination thereof.

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 alpha-(allyloxymeth)acrylate, or a combination thereof .

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

Based on the total usage amount of the mixture being 100 parts by weight, the usage amount of the ethylenically unsaturated monomer (a-1-3) containing a maleimide group or two alkenyl groups may be 5 parts by weight to 50 parts by weight, It is preferably 8 to 45 parts by weight, more preferably 10 to 40 parts by weight.

Other ethylenically unsaturated monomers (a-1-4)

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) are ethylenically unsaturated monomers (a-1-1) containing carboxylic acid groups or carboxylic acid anhydride groups, ethylenically unsaturated monounsaturated monomers containing oxyalkylene groups Monomer (a-1-2), ethylenically unsaturated monomer containing maleimide group or two alkenyl groups (a-1-3) and the following ethylenically unsaturated monomer (a-1-5 ) other than ethylenically unsaturated monomers.

Specific examples of other ethylenically unsaturated monomers (a-1-4) include methyl acrylate, methyl methacrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, (meth)acrylic acid Isopropyl, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylic acid Cyclohexyl ester, lauryl (meth)acrylate, stearate (meth)acrylate, phenyl (meth)acrylate, biphenyl (meth)acrylate, (meth)acrylate Methoxyethyl acrylate, ethoxyethyl (meth)acrylate, butoxyethylene glycol (meth)acrylate, 2-ethylhexylethylene glycol di(meth)acrylate, methoxy Propylene glycol (meth)acrylate, (phenoxyethyl(meth)acrylate), (meth)acrylate (biphenoxyethyl(meth)acrylate), (meth)acrylate diphenoxyethyl (meth)acrylate Cyclopentyl, tricyclodecyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tricyclodecyl (meth)acrylate oxyethyl(meth)acrylate), nonylphenoxyethylene glycol (meth)acrylate, nonylphenoxypropylene glycol (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid (Meth)acrylates such as 2-hydroxyethyl ester; (meth)acryloyl morpholine (morpholino (meth)acrylate), (meth)acrylamide, N-methyl (methyl) Acrylamide, N-isopropyl (meth)acrylamide, N-butyl (meth)acrylamide, N-isobutyl (meth)acrylamide, N-tert-butyl (meth)acrylamide , N-third octyl (meth) acrylamide, diacetone (meth) acrylamide (diacetone (meth) acrylamide), N-methylol (meth) acrylamide, N-hydroxyethyl (methyl) ) acrylamide, N-cyclohexyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-benzyl(meth)acrylamide, N-triphenylmethyl(meth)propylene (meth)acrylic acid amides such as amides, N,N-dimethyl(meth)acrylamide, etc.; aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene, etc.; butadiene, isotope Butadiene or substituted butadiene compounds such as pentadiene; ethylene or substituted ethylene compounds such as ethylene, propylene, vinyl chloride, acrylonitrile; and vinyl esters such as vinyl acetate (vinyl acetate) Wait. These monomers mentioned above may be used alone or in combination of two or more.

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

Based on the total usage amount of the mixture being 100 parts by weight, the usage amount of the other ethylenically unsaturated monomers (a-1-4) may be 0 parts by weight to 55 parts by weight, preferably 5 parts by weight to 50 parts by weight, more It is preferably 10 to 45 parts by weight.

Ethylenically unsaturated monomer (a-1-5)

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

The ethylenically unsaturated monomers (a-1-5) include epoxy group-containing ethylenically unsaturated monomers, isocyanate group-containing ethylenically unsaturated monomers, hydroxyl group-containing ethylenically unsaturated monomers, or its combination, etc.

When the carboxylic acid group- or carboxylic acid anhydride group-containing ethylenically unsaturated monomer (a-1-1) is a carboxylic acid group-containing ethylenically unsaturated monomer, an epoxy group-containing ethylenically unsaturated monomer can be used and isocyanate group-containing ethylenically unsaturated monomers as ethylenically unsaturated monomers (a-1-5). Specific examples of the epoxy group-containing ethylenically unsaturated monomer 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 isocyanato group (isocyanato, -N=C=O)-containing ethylenically unsaturated monomer include 2-isocyanatoethyl (meth)acrylate (meth)acrylate.

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

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

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

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

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

The alkali-soluble resin (A-1) can be composed of the above-mentioned carboxylic acid group- or carboxylic acid anhydride group-containing ethylenically unsaturated monomer (a-1-1), oxyalkylene-containing ethylenically unsaturated monomer (a- 1-2), the polymerization method of ethylenically unsaturated monomer (a-1-3) containing maleimide group or two alkenyl groups, other ethylenically unsaturated monomer (a-1-4) No With special restrictions, an appropriate polymerization method can be selected according to the needs. The polymerization method is, for example, a solution polymerization method.

The mixture constituting the alkali-soluble resin (A-1) may include a solvent. The kind of solvent is not particularly limited. Specifically, 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; ethyl acetate Esters of (ethyl acetate), butyl acetate (butyl acetate), propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc.; alcohols such as methanol and ethanol; toluene, xylene, ethylbenzene Aromatic hydrocarbons such as chloroform; dimethyl sulfoxide, etc. These solvents mentioned above may be used alone or in combination of two or more. The solvent is preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, or a combination thereof.

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

The mixture constituting the alkali-soluble resin (A-1) may include a polymerization initiator. The kind of the polymerization initiator is not particularly limited. Specifically, specific examples of the polymerization initiator include cumene hydroperoxide (CHP), diisopropylbenzene hydroperoxide (diisopropylbenzene hydroperoxide), di-t-butyl peroxide (di-t- butyl peroxide), lauroyl peroxide (lauroyl peroxide), benzoyl peroxide (benzoylperoxide), t-butylperoxyisopropyl carbonate (t-butylperoxyisopropyl carbonate), 2-ethylhexanoic acid tripentyl peroxide Organic peroxides such as ester (t-amylperoxy-2-ethylhexanoate), t-butylperoxy-2-ethylhexanoate, etc.; 2,2'-azobis(isobutyl) Nitrile)(2,2'-azobis(isobutyronitrile)), 1,1'-azobis(cyclohexanecarbonitrile)(1,1'-azobis(cyclohexanecarbonitrile)), 2,2'-azobis( 2,4-Dimethylvaleronitrile)(2,2'-azobis(2,4-dimethylvaleronitrile)), dimethyl 2,2'-azobis(2-methylpropionate)(dimethyl 2, 2'-azobis (2-methyl propionate) and other azo compounds, etc. The polymerization initiator is preferably t-butylperoxy-2-ethylhexanoate. The used amount of the polymerization initiator may be 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of all the monomers in the mixture.

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

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

In addition, chain transfer agents can 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 can function as a chain transfer agent in a radical polymerization reaction. The chain transfer agent is, for example, alkylthiols such as n-dodecanethiol (1-dodecanethiol, nDM). The chain transfer agent can be used in an amount of 0.1 to 15 parts by weight, preferably 1.2 to 5.0 parts by weight, relative to 100 parts by weight of all the monomers in the mixture.

Finally, solution polymerization methods can use polymerization inhibitors to stop the free radical polymerization reaction. The kind of the polymerization inhibitor is not particularly limited, and for example, it is an alkylphenol compound such as 6-tert-butyl-2,4-dimethylphenol. In addition, the solution polymerization method can also use a catalyst. The type of the catalyst is not particularly limited, for example, tertiary amines such as dimethylbenzylamine and triethylamine.

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

The weight average molecular weight of the alkali-soluble resin (A-1) can be a value measured by colloidal permeation chromatography (Gel permeation chromatography, GPC) of a tetrahydrofuran (THF) solvent. The weight average molecular weight of the alkali-soluble resin (A-1) may be 3,000 to 200,000, preferably 4,000 to 100,000, more preferably 5,000 to 50,000.

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

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

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

Other alkali-soluble resins (A-2)

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

The other alkali-soluble resin (A-2) is not particularly limited as long as the other alkali-soluble resin (A-2) is different from the alkali-soluble resin (A-1). In addition, the manufacturing method of other alkali-soluble resin (A-2) is not particularly limited, for example, it can be similar to alkali-soluble resin (A-1), so it will not be described in detail.

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

Ethylenically unsaturated group-containing compound (B)

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.

Specific examples of compounds having one ethylenically unsaturated group may include, but are not limited to, (meth)acrylamide, (meth)acryloylmorpholine, (meth)acrylic acid-7-amino-3,7-dimethyl Octyl octyl ester, isobutoxymethyl (meth)acrylamide, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, 2-ethylhexyl (meth)acrylate , ethylene glycol di(meth)acrylate, ethoxydiethylene glycol (meth)acrylate, tertiary octyl(meth)acrylamide, diacetone(meth)acrylamide, (meth) Dimethylaminoethyl acrylate, dodecyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, N,N-dicyclopentenyl Methyl (meth)acrylamide, tetrachlorophenyl (meth)acrylate, 2-tetrachlorophenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (meth)acrylic acid Tetrabromophenyl, (meth)acrylate-2-tetrabromophenoxyethyl, (meth)acrylate-2-trichlorophenoxyethyl, (meth)acrylate, tribromophenyl, (meth)acrylate ) 2-Tribromophenoxyethyl acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, vinylcaprolactam, N-vinylpyrrolidone, (meth)acrylate base) phenoxyethyl acrylate, pentachlorophenyl (meth)acrylate, pentabromophenyl (meth)acrylate, polyethylene mono(meth)acrylate, polytrimethylene mono(meth)acrylate Or compounds such as (meth)bornyl acrylate. The above-mentioned compounds having one ethylenically unsaturated group can be used alone or in combination of two or more.

Specific examples of compounds having two or more (containing two) ethylenically unsaturated groups may include, but are not limited to, ethylene glycol diacrylate, ethylene glycol dimethacrylate, dicyclopentene di(meth)acrylate ester, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tris(2-hydroxyethyl)isocyanate di(meth)acrylate, tris(2-hydroxyl) ethyl) isocyanate tri(meth)acrylate, caprolactone-modified tris(2-hydroxyethyl) isocyanate tri(meth)acrylate, trimethylolpropyl triacrylate, trimethylolpropyl triacrylate Trimethylolpropyl methacrylate, trimethylolpropyl tri(meth)acrylate modified by ethylene oxide (abbreviated as "EO"), modified by propylene oxide (abbreviated as "PO" ) of trimethylolpropyl tri(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylic acid Esters, 1,6-hexanediol di(meth)acrylate, polyester di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethyl Acrylates, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol penta (Meth)acrylate, ditrimethylolpropyl tetra(meth)acrylate, bisphenol A di(meth)acrylate modified with ethylene oxide, bisphenol A modified with propylene oxide Di(meth)acrylate, ethylene oxide modified hydrogenated bisphenol A di(meth)acrylate, propylene oxide modified hydrogenated bisphenol A di(meth)acrylate, epoxy modified Compounds such as ethane-modified bisphenol F di(meth)acrylate pentaerythritol triacrylate, propylene oxide-modified glycerol triacrylate, or novolak polyglycidyl ether (meth)acrylate. The compound having two or more (including two) ethylenically unsaturated groups can be used alone or in combination of two or more.

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

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

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

Photoinitiator (C)

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

Photoinitiator (C-1)

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

In formula (II),

其中C₁-C₂₀的直链或支链的烷基、C₃-C₁₀的烷基环烷基、C₄-C₁₀的烷基环烷基、C₄-C₁₀的环烷基烷基、

中所含有的任一个-CH₂-可被O、N、S或羰基所取代；A represents hydrogen, halogen, nitro, C ₁ -C ₂₀ straight or branched chain alkyl, C ₃ -C ₁₀ alkyl cycloalkyl, C ₄ -C ₁₀ alkyl cycloalkyl, C ₄ -C ₁₀ cycloalkylalkyl,

Wherein C ₁ -C ₂₀ linear or branched alkyl, C ₃ -C ₁₀ alkyl cycloalkyl, C ₄ -C ₁₀ alkyl cycloalkyl, C ₄ -C ₁₀ cycloalkyl alkane base,

Any -CH ₂ - contained in can be substituted by O, N, S or carbonyl;

R ⁵ represents hydrogen, halogen, C ₁ -C ₂₀ straight or branched chain alkyl, C ₄ -C ₂₀ cycloalkylalkyl or C ₂ -C ₂₀ alkenyl, wherein C ₁ -C ₂₀ The -CH ₂ - contained in the straight or branched chain alkyl, C ₄ -C ₂₀ cycloalkyl alkyl and C ₂ -C ₂₀ alkenyl may be substituted by O, N, S or carbonyl, two A ring structure can be formed between each R ⁵ ;

R ⁶ represents C ₁ -C ₂₀ straight or branched chain alkyl, C ₂ -C ₂₀ alkenyl, C ₃ -C ₂₀ cycloalkyl, C ₄ -C ₂₀ cycloalkyl alkyl, C ₄ - _C20 alkylcycloalkyl group, _C6 - _C20 aryl group or _C6 - _C20 alkylaryl group, wherein one or more hydrogens in these groups can each independently be replaced by alkyl, halogen , hydroxy or nitro, and -CH ₂ - in R ⁶ can be substituted by O, N, S or carbonyl;

R ⁷ represents a C ₁ -C ₂₀ straight or branched chain alkyl group, a C ₃ -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ cycloalkyl alkyl group, a C ₄ -C ₂₀ alkylcycloalkane group, a C ₆ -C ₂₀ aryl group, a C ₆ -C ₂₀ alkylaryl group, a group represented by the following formula (II-A), a group represented by the following formula (II-B), or In the group represented by the following formula (II-C), when R ⁷ represents a C ₁ -C ₂₀ straight or branched chain alkyl group, a C ₃ -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ cyclic alkyl group In the case of alkylalkyl, _C4 - _C20 alkylcycloalkyl, _C6 - _C20 aryl, or _C6 - _C20 alkylaryl, one or more hydrogens in these groups may each independently substituted by alkyl, halogen, hydroxy or nitro, and -CH ₂ - in R ⁷ may be substituted by O, N, S or carbonyl;

A ring structure can be formed between R ⁶ and R ⁷ ;

In formula (II-A), m represents an integer of 0 or 1, R ¹¹ represents hydrogen, a C ₁ -C ₈ alkyl group, or a phenyl group, and R ¹² , R ¹³ and R ¹⁴ each independently represent hydrogen or C ₁ - C ₄ alkyl;

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

In formula (II-C), R ¹⁵ represents hydrogen, C ₁ -C ₈ alkyl, or phenyl, and Ar is substituted or unsubstituted phenyl, naphthyl, furyl, thienyl or pyridyl;

N-呱啶基

N-吡咯基

或N-二烷基(N(R²¹)₂，其中R²¹表示烷基)，其中这些基团中的一个或多个氢可被卤素或羟基所取代；R ⁸ represents N-morpholinyl

N-Guidinyl

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 substituted by halogen or hydroxy;

R ⁹ and R ⁹ ' each independently represent a C ₁ -C ₂₀ straight or branched chain alkyl group, a C ₄ -C ₂₀ cycloalkyl group, a C ₂ -C ₂₀ alkenyl group, and a C ₆ -C ₂₀ aryl group or C ₆ -C ₂₀ alkylaryl groups, wherein one or more hydrogens in these groups may be independently substituted by alkyl, halogen, hydroxyl or nitro, and -CH ₂ - may be substituted by -O-; or R ⁹ and R ⁹ ' may be connected to each other or via -O-, -S- or -NH- to form a five-membered or six-membered ring;

R ¹⁰ represents C ₁ -C ₂₀ straight or branched chain alkyl, C ₄ -C ₂₀ cycloalkyl, C ₄ -C ₂₀ alkyl cycloalkyl, C ₂ -C ₂₀ alkenyl, C ₆ - _C20 aryl or _C6 - _C20 alkylaryl, wherein _-CH2- in these groups may be substituted by -O- or -S-, and one or more hydrogens of these groups may be independently substituted by alkyl, halogen, nitro, cyano, SR ¹⁶ or OR ¹⁷ ;

R ¹⁶ and R ¹⁷ each independently represent hydrogen, or a C ₁ -C ₂₀ straight-chain or branched-chain alkyl group.

或N-吗啉基，其中R¹⁰较佳为表示苯基、经一个或多个甲基取代的苯基、经硝基取代的苯基、

更佳为表示氢、甲基、硝基、经一个或多个甲基取代的苯基、或N-吗啉基，其中*表示键结位置。In addition, in formula (II), A preferably represents hydrogen, methyl, methoxy, chlorine, nitro,

or N-morpholinyl, wherein R ¹⁰ preferably represents phenyl, phenyl substituted with one or more methyl groups, phenyl substituted with nitro,

More preferably represents hydrogen, methyl, nitro, phenyl substituted with one or more methyl groups, or N-morpholinyl, wherein * represents the bonding position.

In formula (II), R ⁵ preferably represents hydrogen, methyl, propyl, butyl or allyl group (allyl group, -CH ₂ CH=CH ₂ ), more preferably represents hydrogen, methyl, butyl or allyl.

In formula (II), R ⁶ preferably represents a methyl group or an ethyl group.

In formula (II), R ⁷ preferably represents a methyl group, an ethyl group or a benzyl group, more preferably a methyl group or a benzyl group.

In formula (II), R ⁸ preferably represents N-morpholinyl, N-pyridyl, -N(CH ₃ ) ₂ , -N(CH ₂ CH ₂ CH ₃ ) ₂ or N-pyrrolyl, more Preferably, it represents N-morpholinyl, -N(CH ₃ ) ₂ , N-pyrrolyl or N-pyridyl, wherein * represents a bonding position.

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

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

By using the photoinitiator (C-1), a spacer having an excellent level difference can be formed. On the contrary, if the photoinitiator (C-1) is not used, the level difference of the formed spacer is not good.

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

Photoinitiator (C-2)

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

In formula (III),

取代的C₁-C₄的烷氧基、C₁-C₃的亚烷基二氧基；

C₁-C₁₂的烷基硫基；C₁-C₄的烷基苯硫基；经

取代的C₁-C₄的烷基硫基；CN；羧基；C₁-C₁₂的烷氧基甲酰基；芳基酰基；杂芳基酰基及JT₅所组成的群组；或者Ar ₁ represents an o-arylene group or an o-hetero-arylene group, and the o-arylene group or the o-hetero arylene group forms a ring structure with Y ₁ and a carbonyl group by two adjacent atoms, and the substituents on the remaining atoms are selected from each other. Free hydrogen; halogen; C ₁ -C ₁₂ alkyl; C ₅ -C ₇ cycloalkyl; C ₁ -C ₄ alkyl substituted with C ₅ -C ₇ cycloalkyl; phenyl; or more C ₁ -C ₄ alkyl, carboxyl, C ₁ -C ₁₂ alkyl acyl, C ₁ -C ₁₂ aryl acyl, heteroaryl acyl, JT ₄ , phenyl, halogen or CN substituted Phenyl; C ₁ -C ₄ alkylbenzyloxy; via

Substituted C ₁ -C ₄ alkoxy, C ₁ -C ₃ alkylenedioxy;

C ₁ -C ₁₂ alkylthio group; C ₁ -C ₄ alkylphenylthio group;

Substituted C ₁ -C ₄ alkylthio; CN; carboxyl; C ₁ -C ₁₂ alkoxyformyl; aryl acyl; heteroaryl acyl and the group consisting of JT ₅ ; or

In the above-mentioned substituents of Ar ₁ , a cyclic structure is formed between two adjacent substituents or between the substituents and Ar ₁ via a single bond, a carbon atom, and a carbonyl group;

Among them, in JT ₄ and JT ₅ , J is selected from the group consisting of O, S and NT ₆ ;

Y ₁ is selected from the group consisting of O, S, NT ₇ , BT ₇ , CT ₂ T ₃ , SiT ₂ T ₃ , S=O and C=O;

T ₁ represents hydrogen, C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy; or

T ₁ represents via one or more halogen, C ₁ -C ₄ alkyl, C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C ₁ -C ₄ alkane C ₂ -C ₁₈ alkyl substituted with acyloxy or aroyloxy and/or inserted by C ₅ -C ₇ cycloalkylene, phenylene, O, S or NT ₄ ; C ₂ -C ₁₈ alkenyl; via one or more halogens, C ₁ -C ₄ alkyl, C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C ₁ -C ₄ Alkanoyloxy or aroyloxy substituted and/or _{C2 - C18} alkenyl inserted by _{C5 -} C7 cycloalkylene, phenylene, O, S or NT4, or both conditions exist simultaneously; or

T ₁ represents a C ₅ -C ₇ cycloalkyl, or a C ₅ -C ₇ cycloalkyl substituted with one or more C ₁ -C ₄ alkyl, phenyl, halogen or CN; or

T ₁ represents phenyl, or phenyl substituted with one or more C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, phenyl, halogen or CN; or

T ₁ represents naphthyl, benzoyl or phenoxycarbonyl, wherein the phenyl group of benzoyl and phenoxycarbonyl is optionally replaced by one or more halogens, T ₄ , C ₅ -C ₆ cycloalkyl, CN , OH or JT ₄ ;

取代的C₁-C₄的烷基；或者T ₂ and T ₃ each independently represent hydrogen, C ₁ -C ₁₈ alkyl, C ₁ -C ₅ alkyl substituted with carboxyl, C ₁ -C ₅ substituted with C ₁ -C ₄ alkoxyacyl alkyl or

substituted C ₁ -C ₄ alkyl; or

T ₂ and T ₃ each independently represent via one or more halogen, C ₁ -C ₄ alkyl, C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C ₁ -C ₄ alkanoyloxy, aroyloxy substituted C ₂ -C ₁₈ alkyl, or inserted by C ₅ -C ₇ cycloalkylene, phenylene, O, S or NT ₄ C ₂ -C ₁₈ alkyl, or both; or

T ₂ and T ₃ each independently represent a C ₅ -C ₇ cycloalkyl, or a C ₅ -C ₇ cycloalkyl substituted with one or more C ₁ -C ₄ alkyl, phenyl, halogen or CN ;or

T ₂ and T ₃ each independently represent a phenyl group, or via one or more C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxy groups, carboxyl groups, C ₁ -C ₁₂ alkyl acyl groups, C ₅ -C ₆ cycloalkylformyl or C ₅ -C ₆ cycloalkyl substituted C ₂ -C ₄ alkyl acyl, aryl acyl, JT ₄ , phenyl, halogen or CN substituted phenyl; or

Each of T ₂ and T ₃ together with the carbon atom or silicon atom to which they are commonly attached forms a ring structure and the number of atoms forming the ring is 4 to 7; or

Each of T ₂ and T ₃ together with the adjacent substituents forms a cyclic structure and the number of atoms forming the ring is 4 to 7;

T ₄ represents a C ₁ -C ₄ alkyl group;

取代的C₁-C₄的烷基；或者T ₅ represents hydrogen, C ₁ -C ₁₈ alkyl, C ₁ -C ₅ alkyl substituted with C 1 -C 4 alkoxyacyl, or C ₁ -C ₅ alkyl

substituted C ₁ -C ₄ alkyl; or

T ₅ represents via one or more halogen, C ₁ -C ₄ alkyl, C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C ₁ -C ₄ alkane C ₂ -C ₁₈ alkyl substituted with acyloxy or aroyloxy, or C ₂ -C ₁₈ inserted by C ₅ -C ₇ cycloalkylene, phenylene, O, S or NT ₄ , or both of the above; or

T ₅ represents a C ₅ -C ₇ cycloalkyl, or a C ₅ -C ₇ cycloalkyl substituted with one or more C ₁ -C ₄ alkyl, phenyl, halogen or CN; or

T ₅ represents phenyl, or C 2 -C through one or more C ₁ -C ₁₂ alkyl, carboxyl, C ₁ -C ₁₂ alkylacyl, C ₂ -C inserted by phenylene, O, S or NT _{4 12} alkyl acyl, C ₅ -C ₆ cycloalkyl formyl, C ₅ -C ₆ cycloalkyl substituted C ₂ -C ₄ alkyl acyl, aryl acyl, heteroaryl acyl, JT ₄ , phenyl, halogen, CN or NO ₂ and other above-mentioned substituent substituted phenyl, wherein aryl acyl is benzoyl, or through one or more halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy-substituted benzoyl; or

T ₅ represents a C ₁ -C ₄ alkyl acyl group, a C ₁ -C ₄ conjugated alkenoyl group, a benzoyl group or a phenoxycarbonyl group, wherein the phenyl group in the benzoyl group and the phenoxycarbonyl group can be arbitrarily replaced by one or two or more halogen, T ₄ , cyclopentyl, cyclohexyl, CN, OH or JT ₄ substitutions; or

T ₅ forms a cyclic structure with the aromatic ring in Ar ₁ via a single bond, a carbon atom or a carbonyl group;

取代的C₁-C₄的烷基；或者T ₆ and T ₇ each independently represent hydrogen, a C ₁ -C ₁₈ alkyl group, a C ₁ -C ₅ alkyl group substituted with a C 1 -C 4 alkoxyacyl group, or a C ₁ -C ₅ alkyl group substituted with a C 1 -C 4 alkoxyacyl group.

substituted C ₁ -C ₄ alkyl; or

T ₆ and T ₇ each independently represent through one or more halogen, C ₁ -C ₄ alkyl, C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C ₁ -C ₄ alkanoyloxy or aroyloxy substituted C ₂ -C ₁₈ alkyl, C ₂ inserted by C ₅ -C ₇ cycloalkylene, phenylene, O, S or NT ₄ -C ₁₈ alkyl, or both; or

_T6 and _T7 each independently represent a _{C5 -} C7 cycloalkyl, or a _C5 -C7 cycloalkyl substituted with one or more _{C1 - C4} alkyl, phenyl, halogen or CN ;or

T ₆ and T ₇ each independently represent a phenyl group, or via one or more C ₁ -C ₄ alkyl groups, carboxyl groups, C ₁ -C ₁₂ alkyl acyl groups, C ₅ -C ₆ cycloalkylformyl groups or _C5 - _C6 cycloalkyl substituted C2 _{- C4} alkylacyl, arylacyl, _JT4 , phenyl, halogen or CN substituted phenyl; or

Each of T ₆ forms a cyclic structure via a single bond, a carbon atom, a carbonyl group and an aromatic ring in Ar ₁ ;

Wherein when Ar ₁ is a substituted carbazole group, Y ₁ is not C, O, S or NT ₇ .

In addition, in the formula (III), Ar ₁ preferably represents a group represented by the following formula (III-A).

T ₈ , T ₉ , T ₁₀ and T ₁₁ each independently represent hydrogen; or

取代的C₁-C₄的烷氧基；或者T ₈ , T ₉ , T ₁₀ and T ₁₁ each independently represent a C ₁ -C ₄ alkane substituted with one or more of C ₁ -C ₁₂ alkoxy, C ₁ -C ₄ alkylbenzyloxy Oxygen, via

substituted C ₁ -C ₄ alkoxy; or

C₁-C₁₂的烷基硫基；经

取代的C₁-C₄的烷基硫基；经C₁-C₄的烷基苯硫基；经

取代的C₁-C₄的烷基苯硫基；或者T ₈ , T ₉ , T ₁₀ and T ₁₁ each independently represent a phenoxy group substituted with one or more _{C 1 -C 4 alkyl} groups _; cycloalkyl acyl, aryl acyl, heteroaryl acyl substituted phenoxy; C ₅ -C ₆ cycloalkyl substituted C ₁ -C ₄ alkyl acyl phenoxy; C ₁ -C ₃ The alkylene dioxy group;

C ₁ -C ₁₂ alkylthio; via

Substituted C ₁ -C ₄ alkylthio; through C ₁ -C ₄ alkylphenylthio; through

Substituted C ₁ -C ₄ alkylphenylthio; or

T ₈ , T ₉ , T ₁₀ and T ₁₁ each independently represent a phenylthio group substituted with a C ₁ -C ₈ alkylacyl group, a C ₅ -C ₆ cycloalkyl acyl group, an aryl acyl group, and a heteroaryl acyl group , or a C ₁ -C ₄ alkyl acyl phenylthio group substituted with a C ₅ -C ₆ cycloalkyl group;

Y ₁ preferably represents CH ₂ , CHCH ₃ or C(CH ₃ ) ₂ ;

T ₁ preferably represents methyl, ethyl, phenyl, 2-methylphenyl, 3-methylphenyl, 2,4,6-trimethylphenyl or 2,6-dimethoxybenzene base;

* indicates bond position.

It is worth noting that, among the substituents of Ar ₁ , preferably at least one substituent is in the para position to the carbonyl group connected to Ar ₁ .

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

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

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

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

Other photoinitiators (C-3)

In the present invention, other photoinitiators (C-3) can be optionally added as appropriate. Specific examples of other photoinitiators (C-3) include, but are not limited to, O-acyl oxime compounds, triazine compounds, acetophenone compounds, diimidazole compounds, benzophenone compounds, Alpha-diketones, ketone alcohols, ketol ethers, acylphosphine oxides, quinones, halogen-containing compounds, peroxides, or combinations thereof.

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)-9hydro-carbazole-3 -Substituent]-,1-(Oxy-acetyloxime), 1,2-butanedione-1-[4-(methylthio)phenyl]2-(O-acetyloxime), or a combination thereof.

Specific examples of O-acyl oxime compounds include preferably 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-benzoyl oxime), 1- [4-(Phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyl oxime), or a combination thereof. The above-mentioned O-acyl oxime compounds can be used alone or in combination, depending on actual needs.

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

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

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

Specific examples of the aforementioned 4-(p-aminophenyl)-2,6-di-halomethyl-s-triazabenzene compound include 4-[p-N,N-bis(ethoxycarbonyl) Methyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-bis(ethoxycarbonylmethyl) ) aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[p-N,N-bis(chloroethyl)aminophenyl]-2,6 -Bis(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichlorophenyl) Methyl)-s-triazabenzene, 4-(p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(p-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene -N-Ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[p-N,N-bis(phenyl)amino Phenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(p-N-chloroethylcarbonylaminophenyl)-2,6-bis(trichloromethyl) )-s-triazabenzene, 4-[p-N-(p-methoxyphenyl)carbonylaminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene , 4-[m-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-bromo -p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-chloro-p- N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-fluoro-p-N,N -Bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-bromo-p-N,N-bis( Ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-chloro-p-N,N-bis(ethoxy) Carbonylmethyl)aminophenyl-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-fluoro-p-N,N-bis(ethoxycarbonylmethyl) Aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-bromo-p-N,N-bis(chloroethyl)aminophenyl]- 2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis( Trichloromethyl)-s-triazabenzene, 4-[o-fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)- s-triazabenzene, 4-[m-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene , 4-[m-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m- Fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s -Triazabenzene, 4-(m-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4- (m-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-fluoro-p-N -Ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-bromo-p-N-ethoxycarbonylmethylamine phenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6 -Bis(trichloromethyl)-s-triazabenzene, 4-(o-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl) -s-triazabenzene, 4-(m-bromo-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-( m-Chloro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-fluoro-p-N-chloroethyl Aminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-bromo-p-N-chloroethylaminophenyl)-2,6-di (Trichloromethyl)-s-triazabenzene, 4-(o-chloro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triaza Heterobenzene, 4-(o-fluoro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 2,4-bis(trichlorophenyl) methyl)-6-[3-bromo-4-[N,N-bis(ethoxycarbonylmethyl)amino]phenyl]-1,3,5-triazabenzene, or a combination thereof.

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

Specific examples of the above-mentioned acetophenone compounds include p-dimethylamine acetophenone, α,α'-dimethoxy azo acetophenone, 2,2'-dimethyl-2-benzene Ethyl acetophenone, 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 aforementioned acetophenone compounds are preferably 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-acetone, 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.

Specific examples of the above-mentioned diimidazole compounds include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-fluorophenyl) Phenyl)-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 above-mentioned diimidazole compounds can be used alone or in combination, depending on actual needs.

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

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

Specific examples of the above-mentioned ketone alcohol compound include benzophenone. Specific examples of the above-mentioned ketol ether compounds include benzophenone methyl ether, benzophenone ethyl ether, benzophenone isopropyl ether, or a combination thereof.

Specific examples of the above-mentioned acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4 - Trimethylphenylphosphine oxide, or a combination thereof.

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

Specific examples of the above-mentioned halogen-containing compounds include benzoyl methyl chloride, tribromomethyl phenyl sulfone, tris(trichloromethyl)-s-triazabenzene, or combinations thereof.

Specific examples of the above-mentioned peroxides include di-tert-butyl peroxide, or combinations thereof.

The above-mentioned α-diketone compounds, ketone alcohol compounds, ketone alcohol ether compounds, acylphosphine oxide compounds, quinone compounds, halogen-containing compounds, peroxides, etc. can be used alone or in combination. It depends on the actual needs.

Specific examples of other photoinitiators (C-3) preferably include 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyl oxime) (For example, trade name OXE-01, manufactured by Ciba Refinery Co., Ltd., and the structure is represented by formula (IV)), 2-methyl-1-(4-methylthiophenyl)-2-morpholino- 1-acetone (trade name Irgacure 907, manufactured by Ciba Refinery Co., Ltd.), or a combination thereof.

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

Solvent (D)

The solvent (D) refers to 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-mentioned components, and may have Appropriately volatile.

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 esters, other esters, aromatic hydrocarbons, carboxylic acid amines, or a combination of the foregoing.

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

Specific examples of 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 the above compounds. combination.

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

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

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

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

Specific examples of other ester compounds include methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methoxypropionate ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxy acetate, 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, acetic acid Isobutyl, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, pyruvic acid ethyl ester, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxybutyrate, or the like, or a combination of the foregoing.

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

Carboxylic acid amine compound N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or analogs thereof, or a combination of the above compounds. The above-mentioned solvent (D) may be used alone or in combination of two or more.

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

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

Additive (E)

Under the premise of not affecting the efficacy of the present invention, the photosensitive resin composition of the present invention may optionally include an additive (E). The additive (E) may include a filler, a polymer other than the aforementioned alkali-soluble resin (A), an adhesion promoter, an antioxidant, an ultraviolet absorber, a surfactant, an anti-aggregation agent, or a combination thereof.

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

Specific examples of polymers may include, but are not limited to, polyvinyl alcohol, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, or any combination of the foregoing polymers.

Specific examples of adhesion promoters may include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, nitrogen-(2-aminoethyl) -3-aminopropylmethyldimethoxysilane, nitrogen-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 - Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3- Chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-thiolpropyltrimethoxysilane, 3-methyl Acryloyloxypropyltriethoxysilane, or any combination of the above.

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 of the foregoing compounds .

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

Specific examples of commercially available surfactants include KP (manufactured by Shin-Etsu Chemical Industry), SF-8427 (manufactured by Dow Corning Toray Silicone Co., Ltd.), Polyflow (manufactured by Dow Corning Toray Silicone Co., Ltd.), Manufactured by Kyōeisha Oil & Chemical Industries), F-Top (manufactured by Tochem Products Co., Ltd.), Megafac (manufactured by Dainippon Ink Chemical Industries (DIC)), Fluorade (manufactured by Tochem Products Co., Ltd.) Manufactured by Sumitomo 3M Ltd.), Asahi Guard or Surflon (manufactured by Asahi Glass), SINOPOLE8008 (manufactured by Sino-Nippon Synthetic Chemical), F-475 (manufactured by Dainippon Ink Chemical Industry) or its combination.

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

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

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

Preparation method of photosensitive resin composition

The method that can be used to prepare the photosensitive resin composition is, for example: the alkali-soluble resin (A), the ethylenically unsaturated group-containing compound (B), the photoinitiator (C) and the solvent (D) are placed in a stirrer and stirred , so that it is uniformly mixed into a solution state. Moreover, you may add an additive (E) as needed, and after mixing uniformly, the photosensitive resin composition of a solution state can be obtained.

Moreover, the preparation method of the photosensitive resin composition is not specifically limited. The preparation method of the photosensitive resin composition is, for example, first dispersing a part of the alkali-soluble resin (A) and the ethylenically unsaturated group-containing compound (B) in a part of the solvent (D) to form a dispersion solution; and mixing the rest. Alkali-soluble resin (A), ethylenically unsaturated group-containing compound (B), photoinitiator (C), solvent (D). In addition, if necessary, an additive (E) may be added.

<Protective film and spacer>

The present invention provides a protective film and a spacer formed from the above-mentioned photosensitive resin composition. The manufacturing method of the protective film and the spacer will be described in detail below.

In one embodiment, the step of forming the protective film includes: firstly forming a pixel layer consisting of red, green and blue coloring layers on a transparent substrate, then coating the photosensitive resin composition on the pixel layer, and then , the photosensitive resin composition is subjected to the steps of pre-baking, exposing, developing and post-baking.

In one embodiment, the step of forming the spacer includes: forming a transparent conductive film on the transparent substrate on which the protective film and the pixel layer have been formed, and then coating the photosensitive resin composition on the transparent conductive film, and then performing Pre-bake, exposure, development, and post-bake steps.

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

Of course, the protective film and spacer of the present invention are not limited to being formed on the pixel layer or the transparent conductive film, but may be formed on the substrate or various elements on the substrate. Hereinafter, the element to which the photosensitive resin composition is applied is also referred to as "object to be applied".

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

a. Film forming steps:

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

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

The transparent conductive substrate can be a NESA film (registered trademark of PPG) formed by tin oxide (SnO ₂ ) on the entire surface of the transparent substrate, or an indium oxide-tin oxide (In ₂ ) film. Indium tin oxide (Indium tin oxide, ITO) film formed by O ₃ -SnO ₂ ).

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

In addition, it is preferable to further prebake the film. The conditions of the pre-baking treatment may vary depending on the ingredients and the mixing ratio, but preferably heating at 70° C. to 90° C. for 1 minute to 15 minutes. After the pre-baking process, the thickness of the film is 0.15 μm to 8.5 μm, preferably 0.15 μm to 6.5 μm, more preferably 0.15 μm to 4.5 μm. In addition, the said thickness is the thickness after removing a solvent.

b. Exposure steps:

The above film is exposed with a photomask having a specific pattern. The light used in the exposure step can be, for example, visible light, ultraviolet light, extreme ultraviolet light, electron beam, or X-ray, etc., preferably ultraviolet light with a wavelength of 190 nm to 450 nm. The exposure amount of the exposure step is preferably 100 J/m ² to 20,000 J/m ² , preferably 150 J/m ² to 10,000 J/m ² .

c. Development steps:

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

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

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

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

d. Post-baking steps:

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

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

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

<Manufacturing method of color filter substrate>

The manufacturing method of the color filter substrate is, for example, in a vacuum environment with a temperature between 220° C. and 250° C., a protective film in a transparent substrate on which pixel coloring layers such as red, green, and blue and a protective film are formed. The surface is sputtered to form an indium tin oxide (ITO) protective film. In addition, if necessary, the ITO protective film can be etched and wired, and then a liquid crystal alignment film can be coated on the surface of the ITO protective film. Thus, the color filter containing the hardened|cured material which hardened the photosensitive resin composition of this invention can be manufactured.

<Liquid crystal display element and its manufacturing method>

The present invention further provides a liquid crystal display element including 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 thin film transistors. 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 spacers may be dispersed in the liquid crystal layer in a manner of being sandwiched between the color filter substrate and the active element substrate, so that a gap exists between the color filter substrate and the active element substrate.

The manufacturing method of the liquid crystal display element of this invention is not specifically limited, For example, it manufactures by the following method.

First, the color filter substrate and the active element substrate are arranged to face each other with a spacer therebetween. Next, the peripheries of the color filter substrate and the active element substrate are bonded using a sealant, and injection holes are left. Then, liquid crystal is injected into the space between the color filter substrate and the active element substrate and the space divided by the sealant through the injection hole. Finally, after closing the injection hole, a liquid crystal layer is formed between the color filter substrate and the active element substrate. The liquid crystal compound or liquid crystal composition contained in the liquid crystal layer is not particularly limited and depends on actual needs.

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

The present invention will be further described with respect to the following examples, but it should be understood that these examples are only used for illustration and should not be construed as a limitation of the implementation of the present invention.

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

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

Synthesis Example A-1-1

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

Add 45 g of acrylic acid (as a monomer, hereinafter referred to as AA), a mixture of phenylphenoxyethylene glycol acrylate and phenylphenoxydiethylene glycol acrylate (molar ratio 1: 1. This mixture is used as a monomer, hereinafter referred to as PGAPDGA) 40g, benzylmaleimide (as a monomer, hereinafter referred to as BzMI) 15g, 3-butyl peroxide 2-ethylhexanoate (as a polymer Starter, (trade name PERBUTYL O, manufactured by NOF Corporation, hereinafter referred to as PBO)) 2 g, propylene glycol monomethyl ether acetate (as a solvent, hereinafter referred to as PGMEA) 42 g and propylene glycol monomethyl ether (as a solvent). The solvent, hereinafter referred to as PGME) 18 g, was stirred and mixed 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 the chain transfer agent dripper, followed by stirring and mixing.

A separation flask provided with a condenser was prepared as a reaction tank. In the reaction tank, 98 g of PGMEA and 42 g of PGME were added. Next, the temperature of the reaction tank was raised to 90° C. by heating with an oil bath while stirring in a nitrogen atmosphere. When the temperature of the reaction tank was stabilized at 90° C., the monomer mixture and the chain transfer agent were added dropwise to the reaction tank with a monomer dripper and a chain transfer agent dripper, respectively. The monomer dripper and the chain transfer agent dripper were maintained at 90°C, and the monomer mixture and the chain transfer agent were dropped over a period of 180 minutes. After the dropwise addition, 0.5 g of PBO was added after the reaction for 30 minutes. Next, after further 30 minutes of reaction, the reaction tank was heated to 115 degreeC. When the temperature of the reaction tank was stabilized at 115°C for 1.5 hours, the gas in the separation flask was replaced with a mixed gas of oxygen/nitrogen=5/95 (v/v). Next, in the reaction tank, 70 g of glycidyl methacrylate (as a monomer, GMA), 6-tert-butyl-2,4-dimethylphenol (as a polymerization inhibitor, trade name "Topanol") were added , manufactured by Tokyo Chemical Industry Co., Ltd.) 0.3 g, dimethylbenzylamine (as a catalyst, DMBA) 0.5 g, PGMEA 16 g, and PGME 6 g. Then, the reaction was carried out at a temperature of 110°C for 1 hour, followed by a reaction at a temperature of 115°C for 8 hours. Next, the reaction solution was cooled to room temperature to obtain alkali-soluble resin A-1-1. The weight average molecular weight (Mw) of the alkali-soluble resin A-1-1 was 17,200.

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

The alkali-soluble resins (A-1) of Synthesis Examples A-1-2 to A-1-9 and Synthesis Examples A-2-1 to A-2-2 were obtained by the same procedure as that of Synthesis Example A-1-1 were prepared, and the difference was that the monomers used for synthesizing the alkali-soluble resin (A-1) and their usage amount, and the amount of chain transfer agent (as shown in Table 1) were changed.

Table 2

Examples 1 to 11 and Comparative Examples 1 to 4

Examples 1 to 11 and Comparative Examples 1 to 4 of the photosensitive resin compositions will be described below:

Example 1

100 parts by weight of the alkali-soluble resin of Synthesis Example A-1-1 (hereinafter abbreviated as A-1-1), 50 parts by weight of ethylene glycol dimethacrylate (hereinafter abbreviated as B-1), 10 parts by weight Part of the compound represented by the formula (II-1) (hereinafter referred to as C-1-1) was added to 500 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as D-1), and the After stirring uniformly (shaking type stirrer), the photosensitive resin composition of Example 1 can be produced. The obtained photosensitive resin composition was evaluated by the following evaluation method, and Table 3 shows the result.

Example 2 to Example 11, Comparative Example 1 to Comparative Example 4

The photosensitive resin compositions of Examples 2 to 11 and Comparative Examples 1 to 4 were prepared in the same steps as those of Example 1, and the difference was that the types of the components of the photosensitive resin compositions and their composition were changed. The usage amount (as shown in Table 3), wherein the components corresponding to the labels in Table 3 are shown in Table 4. The obtained photosensitive resin composition was evaluated by the following evaluation method, and Table 3 shows the result.

Table 4

<Evaluation method>

Sensitivity

The photosensitive resin compositions prepared in the foregoing examples and comparative examples were respectively coated on a plain glass substrate of 100 mm × 100 mm × 0.7 mm by spin coating, and pre-baked at 90°C for 150 seconds, that is, Pre-baked coating films with a thickness of about 4 μm can be prepared.

Next, the prepared pre-baked coating film is exposed to an exposure step. Specifically, a photomask with a specific pattern was placed between the pre-baked coating film and an exposure machine (model AG500-4N; manufactured by M&R Nano Technology), and the photomasks were exposed at different exposure levels. UV irradiation pre-bake coating film. Then, after measuring the film thickness (δ) at any measurement point on the coating film, the coating film was immersed in a 0.0438 wt% potassium hydroxide (KOH) aqueous solution for 70 seconds and developed, and another measurement point was measured at the same measurement point. Film thickness (δd). Finally, the residual film rate can be obtained by the following formula (V).

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

The exposure amount when the above-mentioned residual film ratio is 90% or more is called sensitivity, and is evaluated according to the following criteria:

◎: Exposure ≦70mJ/cm ² ;

○: 70mJ/cm ² <exposure amount≦90mJ/cm ² ;

△: 90mJ/cm ² <exposure amount≦110mJ/cm ² ;

╳: Exposure > 110mJ/cm ² .

level difference

The photosensitive resin compositions prepared in the foregoing examples and comparative examples were respectively coated on a plain glass substrate of 100 mm × 100 mm × 0.7 mm by spin coating, and pre-baked at 90°C for 150 seconds, that is, Pre-baked coatings of about 4 μm can be prepared.

Then, this pre-baked coating film is placed under the specified mask pattern (partially halftone, transmittance 30%), and the ultraviolet light with energy of 60mJ/ ^cm2 (exposure machine model is AG500-4N, And it was irradiated by Keyi Technology Co., Ltd. (manufactured by M&RNano Technology) to perform the exposure step.

Next, the exposed coating film was immersed in a potassium hydroxide (KOH) aqueous solution having a concentration of 0.0438 wt % and developed for 70 seconds to remove unexposed portions. The receiver was washed with pure water and post-baked at 235°C for 30 minutes to obtain a gap body.

Among them, the height of the main spacer is Hm, the height of the secondary spacer (halftone part) is Hs, and Hm-Hs is the step difference.

◎: 0.1μm≦level difference≦0.3μm;

○: 0.3μm<level difference≦0.4μm;

△: 0.4μm<level difference≦0.5μm;

╳: Level difference >0.5μm or level difference <0.1μm.

<Evaluation result>

From Table 3, compared with the photosensitive resin composition (Comparative Example 1 and Comparative Example 2) that does not contain the alkali-soluble resin (A-1), the photosensitive resin that does not contain the photoinitiator (C-1) The composition (Comparative Example 3) and the photosensitive resin composition (Comparative Example 4) not containing both the alkali-soluble resin (A-1) and the photoinitiator (C-1) simultaneously containing the alkali-soluble resin (A-1) ) and the photoinitiator (C-1) of the photosensitive resin composition (Examples 1 to 11) have excellent sensitivity and can form a spacer excellent in level difference. Furthermore, the sensitivity of the photosensitive resin composition (Comparative Example 1 and Comparative Example 2) not containing the alkali-soluble resin (A-1) was poor; the photosensitive resin not containing the photoinitiator (C-1) The level difference of the spacers formed by the composition (Comparative Example 3) is not good; and the photosensitive resin composition (Comparative Example 4) that does not contain both the alkali-soluble resin (A-1) and the photoinitiator (C-1) The sensitivity is not good, and the level difference of the formed gap body is also not good.

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 level difference.

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

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

To sum up, the photosensitive resin composition of the present invention includes an alkali-soluble resin (A-1) having a specific structure and a photoinitiator (C-1) having a specific structure, which can effectively improve the sensitivity and the level difference of the spacer Bad question. Accordingly, the present invention provides a photosensitive resin composition which has excellent sensitivity and can form a spacer having an excellent level difference, which can be suitably used for a spacer and a protective film.

Although the present invention has been disclosed above with examples, it is not intended to limit the present invention. Any person skilled in the art can make some changes and modifications without departing from the spirit and scope of the present invention. Therefore, the present invention The scope of protection shall be subject to what is defined in the claims.

Claims (13)

1. A photosensitive resin composition comprising:

an alkali-soluble resin A;

a compound B containing an ethylenically unsaturated group;

a photoinitiator C; and

a solvent D;

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

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

R¹、R²and R³Each independently represents hydrogen or methyl;

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

AO represents C₂-C₂₀Oxyalkylene of (a);

x represents an integer of 0 to 2;

y represents 0 or 1;

n represents 2 or more;

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

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

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

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

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

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

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

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

R⁶and R⁷Can form a ring structure between;

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Substituted C₁-C₄Alkyl groups of (a); or

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

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

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

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

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

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

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

Substituted C₁-C₄Alkyl groups of (a); or

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

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

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

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

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

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

Substituted C₁-C₄Alkyl groups of (a); or

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

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

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

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

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

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

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

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

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

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

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

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

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