TWI685719B - Photosensitive resin composition, spacer, protection film and liquid crystal display element - Google Patents

Abstract

The present invention provides a photosensitive resin composition including an alkali-soluble resin (A), a compound having an ethylenically unsaturated group (B), a photoinitiator (C) and a solvent (D), wherein the alkali-soluble resin (A) includes a first alkali-soluble resin (A-1) and the first alkali-soluble resin (A-1) is produced by a polymerization of a mixture including an ethylenically unsaturated monomer having a carboxylic acid group (a-1-1) and an ethylenically unsaturated monomer having a silyl group (a-1-2) represented by formula (I), the photoinitiator (C) includes a first photoinitiator (C-1) having a structure represented by formula (C1-1).

Description

Photosensitive resin composition, gap body, protective film and liquid crystal display element

The present invention relates to a photosensitive resin composition, a gap body, a protective film, and a liquid crystal display element, and particularly to a photosensitive resin composition, a gap body, a protective film, and a liquid crystal display element with excellent resolution.

Generally speaking, the color-printed pixels and black matrix on the surface of the color filter layer will have irregularities. Generally, a protective film is formed on the surface of the color filter layer to hide the unevenness and achieve flatness. Claim.

However, in the manufacture of optical elements such as liquid crystal display elements or solid-state imaging devices, processing procedures under severe conditions are encountered, such as the treatment of immersing the substrate surface with an acidic solvent or alkaline solution or forming wiring by sputtering The electrode layer may 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 manufacturing. In order for the protective film to have the characteristics of resisting the above-mentioned treatment, the protective film needs to have excellent adhesion to the substrate, and also needs to have high transparency, high surface hardness, and a smooth surface. The protective film with high heat resistance and light resistance will not change color, yellowing or whitening under long-term use. In addition, the protective film also needs to have good water resistance, chemical resistance, solvent resistance, acid resistance, alkali resistance and other characteristics.

On the other hand, in the conventional technology, in the color liquid crystal display device, in order to maintain a fixed layer spacing between the two substrates, such as polystyrene beads or silicon beads are randomly sprayed on the entire substrate, wherein the diameter of the beads is The distance between the two substrates. However, in this conventional method, the position and density distribution of the bead are not uniform, which causes the light of the backlight to be scattered by the influence of the bead and further reduces the contrast of the display element. Therefore, the photosensitive composition for the gap body developed by the photolithography method has become the mainstream in the industry. The forming method of the gap body is to apply the photosensitive composition for the gap body to the substrate first, and then put a mask of a specified shape between the substrate and the exposure source, which can be developed after exposure to form a Gap body. According to this method, a gap body can be formed at a designated position outside the R, G, and B pixels to solve the problems of the conventional technology; the layer spacing can also be controlled by the thickness of the coating film formed by the photosensitive component to make the layer spacing The distance becomes easy to control and has the advantage of high accuracy.

Since the protective film or the gap system 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 gap body is not good, when applied to a liquid crystal display element, the brightness of the liquid crystal display element will be insufficient, which will affect the display quality of the liquid crystal display element.

In order to improve the transparency of the protective film or the gap body, Japanese Patent Laid-Open No. 2010-054561 discloses a photosensitive composition for a protective film, which contains (A) an alkali-soluble binding resin; (B) a compound of an ethylenically unsaturated group; ( C) photoinitiator; and (D) solvent; wherein the (B) ethylenically unsaturated group compound has an unsaturated bond binding equivalent of between 90 and 450 g/eq, and (B) ethylenic Among the saturated group compounds, the unsaturated double bonds of a single compound are between 2 and 4, and the weight average molecular weight of the (A) alkali-soluble binding resin is between 10,000 and 20,000. On the other hand, Japanese Patent Laid-Open No. 2004-240241 discloses a photosensitive composition, which contains (A) a copolymer, which is composed of an ethylenically unsaturated carboxylic acid (anhydride) and an epoxy-containing ethylene Unsaturated compound and other ethylenically unsaturated group compounds; (B) obtained by copolymerization of ethylenically unsaturated group polymers; and (C) photoinitiator, which is 2-butane Diketone-(4-methylthiobenzene)-2-(O-oxime acetate), 1,2-butanedione-1-(4-morpholinylphenyl)-2-(O-benzophenone) Oxime), 1,2-octanedione-1-(4-phenylthiobenzene)-2-[O-(4-methylbenzoyl)oxime] or the like. However, the photosensitive resin composition has the disadvantage of poor resolution, which is actually a problem that is urgently to be solved at present.

The present invention provides a photosensitive resin composition with good resolution.

式(I)     於所述式(I)中，所述X¹ 代表氫原子或甲基；所述X² 及X³ 分別獨立地代表苯基、C₁ -C₁₂ 烷基、C₁ -C₆ 烷氧基或如下式(II)所示的基團；

式(II)     於所述式(II)中，所述X⁵ 、X⁶ 與X⁷ 分別獨立地代表苯基或C₁ -C₁₂ 烷基；所述d代表2至13的整數；當d大於1時，複數個X⁶ 為相同或不同，且複數個X⁷ 為相同或不同；所述X⁴ 代表C₁ -C₆ 烷基或如下式(III)所示的基團；

式(III)     於所述式(III)中，所述X⁸ 、X⁹ 及X¹⁰ 分別獨立地代表苯基或C₁ -C₁₂ 烷基；所述a代表1至6的整數；所述b代表1至150的整數；當b大於1時，複數個X² 為相同或不同，且複數個X³ 為相同或不同；所述光起始劑(C)包括具有式(C1-1)所示結構的第一光起始劑(C-1)；

式(C1-1)     於所述式(C1-1)中，所述E³⁰ 代表含有C₃ -C₂₀ 環烷基的有機基團；所述E³¹ 及E³² 各自獨立地代表烷基或芳基；以及所述E³³ 表示烷基。A photosensitive resin composition of the present invention includes an alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, a photoinitiator (C), and a solvent (D). Wherein, the alkali-soluble resin (A) includes a first alkali-soluble resin (A-1), and the first alkali-soluble resin (A-1) is composed of an ethylenically unsaturated monomer having a carboxylic acid group (a -1-1) and a mixture of ethylenically unsaturated monomers (a-1-2) having a silane group represented by formula (I) are prepared by polymerization;

Formula (I) In the formula (I), X ¹ represents a hydrogen atom or a methyl group; X ² and X ³ independently represent phenyl, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ alkoxy or a group represented by the following formula (II);

Formula (II) In the formula (II), the X ⁵ , X ⁶ and X ⁷ independently represent a phenyl group or a C ₁ -C ₁₂ alkyl group; the d represents an integer of 2 to 13; when d When it is greater than 1, a plurality of X ⁶ are the same or different, and a plurality of X ⁷ are the same or different; the X ⁴ represents a C ₁ -C ₆ alkyl group or a group represented by the following formula (III);

Formula (III) In the formula (III), the X ⁸ , X ⁹ and X ¹⁰ independently represent a phenyl group or a C ₁ -C ₁₂ alkyl group; the a represents an integer of 1 to 6; b represents an integer from 1 to 150; when b is greater than 1, plural X ² are the same or different, and plural X ³ are the same or different; the photoinitiator (C) includes formula (C1-1) The first photoinitiator (C-1) of the structure shown;

Formula (C1-1) In the formula (C1-1), the E ³⁰ represents an organic group containing a C ₃ -C ₂₀ cycloalkyl group; the E ³¹ and E ³² each independently represent an alkyl group or Aryl; and the E ³³ represents an alkyl group.

In an embodiment of the present invention, the mixture used for polymerization to produce the first alkali-soluble resin (A-1) further includes an ethylenically unsaturated monomer (a-1-3) having a polycyclic structure .

In an embodiment of the present invention, the mixture used for polymerization to produce the first alkali-soluble resin (A-1) further includes an ethylenically unsaturated monomer having an alicyclic epoxy group (a-1 -4).

In an embodiment of the present invention, based on the total amount of the alkali-soluble resin (A) is 100 parts by weight, the usage amount of the compound (B) having an ethylenically unsaturated group is 10 to 200 parts by weight. The use amount of the photoinitiator (C) is 10 to 100 parts by weight, and the use amount of the solvent (D) is 500 to 5000 parts by weight.

In an embodiment of the present invention, based on the total amount of the alkali-soluble resin (A) is 100 parts by weight, the usage amount of the first alkali-soluble resin (A-1) is 3 to 100 parts by weight.

In an embodiment of the present invention, based on the total amount of the alkali-soluble resin (A) is 100 parts by weight, the amount of the first photoinitiator (C-1) used is 1 to 50 parts by weight.

In an embodiment of the present invention, based on the total amount of the alkali-soluble resin (A) is 100 parts by weight, the usage amount of the ethylenically unsaturated monomer (a-1-1) having a carboxylic acid group is 5 to 50 parts by weight, and the use amount of the ethylenically unsaturated monomer (a-1-2) represented by the formula (I) is 1 to 30 parts by weight.

In an embodiment of the present invention, based on the total amount of the alkali-soluble resin (A) is 100 parts by weight, the usage amount of the ethylenically unsaturated monomer (a-1-3) having a polycyclic structure is 0~40 parts by weight.

In an embodiment of the present invention, based on the total amount of the alkali-soluble resin (A) is 100 parts by weight, the ethylenically unsaturated monomer (a-1-4) having an alicyclic epoxy group The amount used is 0~40 parts by weight.

The present invention also provides a gap body having a pattern, which is prepared by sequentially applying a pre-baking process, an exposure process, a developing process, and a post-baking process to the photosensitive resin composition as described above.

The present invention also provides a protective film with a pattern, which is prepared by sequentially applying a pre-baking process, an exposure process, a developing process, and a post-baking process to the photosensitive resin composition as described above.

The invention also provides a liquid crystal display element including the above-mentioned gap body.

The invention also provides a liquid crystal display element including the protective film as described above.

Based on the above, the photosensitive resin composition of the present invention includes a first alkali-soluble resin (A-1) having a special structure and a first photoinitiator (C-1), so that the photosensitive resin composition of the present invention has Good resolution.

In order to make the above-mentioned features and advantages of the present invention more obvious and understandable, the embodiments are specifically described below in conjunction with the accompanying drawings for detailed description as follows.

The present invention provides a photosensitive resin composition including an alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, a photoinitiator (C), and a solvent (D). Hereinafter, each component of the photosensitive resin composition used in the present invention will be described in detail. Alkali soluble resin (A)

The alkali-soluble resin (A) of the present invention includes the first alkali-soluble resin (A-1). The first alkali-soluble resin ( A-1 )

The first alkali-soluble resin (A-1) is composed of a mixture including an ethylenically unsaturated monomer having a carboxylic acid group (a-1-1) and an ethylenically unsaturated monomer having a silane group (a-1-2) Produced by polymerization. In an embodiment, the above mixture may further include an ethylenically unsaturated monomer having a polycyclic structure (a-1-3), and an ethylenically unsaturated monomer having an alicyclic epoxy group (a-1-4 ) Or a combination thereof. Ethylene unsaturated monomer with carboxylic acid group (a-1-1)

Specific examples of the above-mentioned ethylenically unsaturated monomer having a carboxylic acid group (a-1-1) include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethylacrylic acid, cinnamic acid, 2-acrylonitrile Unsaturated monocarboxylic acid compounds such as ethoxy succinate, 2-methacryl ethoxy succinate; maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, Unsaturated dicarboxylic acid (anhydride) compounds such as citraconic acid, citraconic anhydride; and unsaturated polyvalent carboxylic acid (anhydride) compounds of more than three valences. The above-mentioned ethylenically unsaturated monomer having a carboxylic acid group (a-1-1) may be used alone or in combination.

The ethylenically unsaturated monomer (a-1-1) having a carboxylic acid group may preferably be acrylic acid, methacrylic acid, 2-acryl ethoxy succinate, 2-methacryl ethoxy Succinate or any combination of the above compounds.

In one embodiment, based on the total amount of the alkali-soluble resin (A) is 100 parts by weight, the amount of the ethylenically unsaturated monomer (a-1-1) having a carboxylic acid group is 5 to 50 The part by weight is preferably 10 to 45 parts by weight, and more preferably 15 to 40 parts by weight. Ethylene unsaturated monomer with silane group (a-1-2)

式(I)The ethylenically unsaturated monomer (a-1-2) having a silane group of the present invention is an ethylenically unsaturated monomer having a structure represented by the following formula (I):

Formula (I)

式(II)In formula (I), X ¹ represents a hydrogen atom or a methyl group; X ² and X ³ independently represent a phenyl group, a C ₁ -C ₁₂ alkyl group, a C ₁ -C ₆ alkoxy group, or the following formula (II) Groups shown:

Formula (II)

In formula (II), X ⁵ , X ⁶ and X ⁷ independently represent a phenyl group or a C ₁ -C ₁₂ alkyl group; d represents an integer of 2 to 13; when d is greater than 1, plural X ⁶ are the same Or different, and a plurality of X ⁷ are the same or different.

式(III)In formula (I), X ⁴ represents a C ₁ -C ₆ alkyl group or a group represented by the following formula (III):

Formula (III)

In formula (III), X ⁸ , X ⁹ and X ¹⁰ each independently represent a phenyl group or a C ₁ -C ₁₂ alkyl group.

In formula (I), the a represents an integer of 1 to 6; the b represents an integer of 1 to 150; when b is greater than 1, a plurality of X ² are the same or different, and a plurality of X ³ are the same or different.

Specific examples of the aforementioned C ₁ -C ₆ alkoxy group may be methoxy, ethoxy, propoxy or butoxy.

Specific examples of the aforementioned C ₁ -C ₁₂ alkyl group may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl.

式(I-1)

式(I-2)

式(I-3)

式(I-4)

式(I-5)

式(I-6)The ethylenically unsaturated monomer having a silane group as shown in formula (I) may include but is not limited to (meth)acrylic silanes ((meth)acrylic silanes), and a specific example thereof may be 3-methacryloxy 3-methacryloyloxypropyltrimethoxysilane (MPTMS), 3-methacryloyloxypropyl triethoxysilane (MPTES), 3-methacryloyloxypropyltrimethoxysilane (MPTES) 3-methacryloyloxypropylmethyldimethoxy silane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-propenyloxypropyltrimethoxysilane (3- acryloyloxypropyltrimethoxy silane), compounds represented by the following formulas (I-1) to (I-6), or products manufactured by Chisso Corporation, the models of which are FM-0711, FM-0721 or FM-0725:

Formula (I-1)

Formula (I-2)

Formula (I-3)

Formula (I-4)

Formula (I-5)

Formula (I-6)

The ethylenically unsaturated monomer (a-1-2) having a silane group represented by the aforementioned formula (I) can be used alone or in combination.

Preferably, the ethylenically unsaturated monomer having a silane group as shown in formula (I) may be 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethyl Oxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-propenyloxypropyltrimethoxy Silane, a compound represented by formula (I-3), a product (model FM-0711) manufactured by Chisso Corporation, or any combination of the above compounds.

In one embodiment, based on the total amount of the alkali-soluble resin (A) is 100 parts by weight, the use of the ethylenically unsaturated monomer (a-1-2) having a silane group shown in the formula (I) The amount is 1 to 30 parts by weight, preferably 3 to 27 parts by weight, and more preferably 5 to 25 parts by weight. Ethylene unsaturated monomer with polycyclic structure (a-1-3)

The structure of the ethylenically unsaturated monomer having a polycyclic structure is not particularly limited. In the specific examples of the present invention, the ethylenically unsaturated monosystem having a polycyclic structure is an ethylenically unsaturated monomer having a dicyclopentyl group Monomers, ethylenically unsaturated monomers with dicyclopentenyl groups or mixtures thereof.

式(a-1-3) 其中R³ 係為氫原子或甲烷基；及n係為0至2的整數。In a specific example of the present invention, the ethylenically unsaturated monomer having a dicyclopentyl group has a structure represented by the following formula (a-1-3):

Formula (a-1-3) wherein R ³ is a hydrogen atom or a methyl group; and n is an integer of 0 to 2.

式(a-1-3-1) 其中R⁴ 係為氫原子或甲烷基；及m係為0至2的整數。On the other hand, in a specific example of the present invention, the ethylenically unsaturated monomer having a dicyclopentenyl group has a structure represented by the following formula (a-1-3-1):

Formula (a-1-3-1) wherein R ⁴ is a hydrogen atom or a methyl group; and m is an integer of 0 to 2.

In a preferred embodiment of the present invention, the ethylenically unsaturated single system having a polycyclic structure is dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, (meth)acrylic acid Dicyclopentyloxyethyl, dicyclopentyloxyethyl (meth)acrylate or mixtures thereof.

In one embodiment, based on the total amount of the alkali-soluble resin (A) is 100 parts by weight, the usage amount of the ethylenically unsaturated monomer (a-1-3) having a polycyclic structure is 0-40 The part by weight is preferably 3 to 35 parts by weight, and more preferably 5 to 30 parts by weight. When the first alkali-soluble resin (A-1) is prepared by polymerizing a mixture containing an ethylenically unsaturated monomer (a-1-3) having a polycyclic structure, the gap formed by the photosensitive resin composition The body or protective film has better resolution. Ethylene unsaturated monomer with alicyclic epoxy group (a-1-4)

式(a-1-4-1)

式(a-1-4-2)

式(a-1-4-3)

式(a-1-4-4)

式(a-1-4-5)

式(a-1-4-6)

式(a-1-4-7)

式(a-1-4-8)

式(a-1-4-9)

式(a-1-4-10)

式(a-1-4-11)

式(a-1-4-12)

式(a-1-4-13)

式(a-1-4-14)

式(a-1-4-15)The ethylenically unsaturated monomer (a-1-4) having an alicyclic epoxy group is any compound represented by the following formula (a-1-4-1) to formula (a-1-4-15) .

Formula (a-1-4-1)

Formula (a-1-4-2)

Formula (a-1-4-3)

Formula (a-1-4-4)

Formula (a-1-4-5)

Formula (a-1-4-6)

Formula (a-1-4-7)

Formula (a-1-4-8)

Formula (a-1-4-9)

Formula (a-1-4-10)

Formula (a-1-4-11)

Formula (a-1-4-12)

Formula (a-1-4-13)

Formula (a-1-4-14)

Formula (a-1-4-15)

In the compounds represented by formula (a-1-4-1) to formula (a-1-4-15), R ^1d represents a hydrogen atom or a methyl group; R ^2d , R ^4d , and R ^6d each independently represent a hydrogen atom , Unsubstituted or substituted alkyl; R ^3d represents unsubstituted or substituted alkyl, unsubstituted or substituted aryl, or unsubstituted or substituted acetyl; R ^5d represents unsubstituted Substituted or substituted alkyl, unsubstituted or substituted aryl; R ^7d represents a hydrogen atom or a methyl group; R ^8d represents a C ₁ -C ₆ divalent aliphatic hydrocarbon group; X ¹ to X ³ represent a single bond or Bivalent organic group.

Preferably, the ethylenically unsaturated monomer (a-1-4) having an alicyclic epoxy group is from the formula (a-1-4-1) to the formula (a-1- 4-3) Any one of the compounds represented. More preferably, the ethylenically unsaturated monomer (a-1-4) having an alicyclic epoxy group is a compound represented by the formula (a-1-4-1).

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In an embodiment, based on the total amount of the alkali-soluble resin (A) is 100 parts by weight, the usage amount of the ethylenically unsaturated monomer (a-1-4) having an alicyclic epoxy group is 0 to 40 parts by weight, preferably 3 to 35 parts by weight, more preferably 5 to 30 parts by weight. When the first alkali-soluble resin (A-1) is prepared by polymerizing a mixture containing an ethylenically unsaturated monomer having an alicyclic epoxy group (a-1-4), the photosensitive resin composition The formed gap body or protective film has better resolution. Other copolymerizable ethylenically unsaturated monomers (a-1-5)

In one embodiment, the mixture used for polymerization to produce the first alkali-soluble resin (A-1) may further include other copolymerizable ethylenically unsaturated monomers (a-1-5). Specific examples of other copolymerizable ethylenically unsaturated monomers (a-1-5) of the present invention may include but are not limited to styrene, α-methylstyrene, vinyl toluene, p-chlorostyrene, methoxy Aromatic vinyl compounds such as styrene; N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p -Hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide Amine, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide, N-ring Maleimide compounds such as hexylmaleimide; methyl acrylate, methyl methacrylate, benzyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, methyl N-propyl acrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, second butyl acrylate, methacrylic acid Second butyl ester, third butyl acrylate, third butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, methacrylic acid-2 -Hydroxypropyl ester, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, methyl 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate , Phenyl acrylate, phenyl methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate, dodecyl methacrylate Lauryl methacrylate, tertadecyl methacrylate, cetyl methacrylate, octadecylmethacrylate, eicosane methacrylate Unsaturated carboxylic acid ester compounds such as eicosyl methacrylate and docosyl methacrylate; acrylic acid-N,N-dimethylaminoethyl, methacrylic acid-N,N- Dimethylaminoethyl, acrylic acid-N,N-diethylaminopropyl ester, methacrylic acid-N,N-dimethylaminopropyl ester, acrylic acid-N,N-dibutylaminopropyl ester, methyl -N-isobutylaminoethyl acrylate; glycidyl acrylate, glycidyl methacrylate, etc. Unsaturated carboxylic acid epoxypropyl ester compound; vinyl acetate, vinyl propionate, vinyl butyrate and other vinyl carboxylate compounds; vinyl methyl ether, vinyl ether, allyl epoxypropyl ether 、Unsaturated ether-based compounds such as methallyl epoxypropyl ether; acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinyl cyanide and other cyanide vinyl compounds; acrylamido, methyl Unsaturated amide compounds such as acrylamide, α-chloropropylamide, N-hydroxyethylacrylamide, N-hydroxyethylmethacrylamide; 1,3-butadiene, isoprene , Chlorinated butadiene and other aliphatic conjugated diene compounds or a combination of the above compounds; vinyl trimethoxy silane (vinyltrimethoxysilane (VTMS), vinyl triethoxy silane (vinyltriethoxysilane; VTES), vinyl methyl Vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, Vinyldimethylmethoxysilane or Vinyldimethylethoxysilane, p-benzene Ethylene trimethoxysilane and other ethylenically unsaturated monomers with silane groups different from (a-1-2). The other copolymerizable ethylenically unsaturated monomers (a-1-5) can be used alone or in combination.

Preferably, other copolymerizable ethylenically unsaturated monomers (a-1-5) may include but are not limited to styrene, N-phenylmaleimide, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, or any combination of the above compounds.

In one embodiment, based on the total amount of the alkali-soluble resin (A) is 100 parts by weight, the usage amount of the other copolymerizable ethylenically unsaturated monomer (a-1-5) is 0 to 94 The part by weight is preferably 10 to 80 parts by weight, and more preferably 20 to 70 parts by weight.

When preparing the first alkali-soluble resin (A-1), a solvent may be used, and the solvent may be used alone or in combination, and the solvent includes but is not limited to ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol Ethylene glycol ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether, triethylene glycol ether, propylene glycol methyl ether, propylene glycol ether, dipropylene glycol methyl ether, dipropylene glycol (Poly)alkylene glycol monoalkyl ethers such as ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol ether, etc.; ethylene glycol methyl ether (Poly)alkylene glycol monoalkyl ether acetates such as acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether acetate, etc.; diethylene glycol Alcohol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; 2 -Methyl hydroxypropionate, ethyl 2-hydroxypropionate and other alkyl lactates; 2-hydroxy-2-methylpropionic acid methyl ester, 2-hydroxy-2-methylpropionic acid ethyl ester, 3-methyl Methyl oxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate (EEP), ethoxyacetic acid Ethyl acetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate Ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, butyric acid N-propyl ester, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-methoxybutyl Other esters such as ethyl acid esters; aromatic hydrocarbons such as toluene and xylene; nitrogen-methylpyrrolidone (NMP), nitrogen, nitrogen-dimethylformamide (DMF), or nitrogen, nitrogen- Acetamides such as dimethylacetamide (DMAC). Preferably, the solvent is selected from propylene glycol methyl ether acetate, ethyl 3-ethoxypropionate, or a combination thereof. (Poly)alkylene glycol monoalkyl ethers refer to alkylene glycol monoalkyl ethers or polyalkylene glycol monoalkyl ethers. (Poly)alkylene glycol monoalkyl ether acetates refer to alkylene glycol monoalkyl ether acetates or polyalkylene glycol monoalkyl ether acetates.

The initiator used in the preparation of the first alkali-soluble resin (A-1) is generally a radical polymerization initiator. Specific examples may include, but are not limited to: 2,2'-azobisisobutyronitrile, 2, 2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-a Azo compounds such as 2,2'-azobis-2-methyl butyronitrile (AMBN); cumene hydroperoxide, diisopropylbenzene hydroperoxide , 2-tert-butyl peroxide, lauryl peroxide, benzoyl peroxide, tert-butyl isopropyl carbonate peroxide, tert-butyl peroxy-2-hexanoate, etc. Oxygen compounds. The above radical polymerization initiators can be used alone or in combination. At the same time, the radical polymerization initiator can be used together with transition metal salts or amines.

In addition, the acid value of the first alkali-soluble resin (A-1) is preferably 50 mgKOH/g to 200 mgKOH/g, and more preferably 60 mgKOH/g to 150 mgKOH/g.

In addition, the weight average molecular weight of the first alkali-soluble resin (A-1) may be appropriately set according to the purpose and application, and is generally 2,000 to 50,000, preferably 3,000 to 40,000, and more preferably 4,000 to 30,000.

In an embodiment, based on the total amount of the alkali-soluble resin (A) is 100 parts by weight, the usage amount of the first alkali-soluble resin (A-1) is 3 to 100 parts by weight, preferably 10 to 100 parts by weight, more preferably 20 to 100 parts by weight. Other alkali soluble resin (A-2)

In one embodiment, the alkali-soluble resin (A) of the present invention may also include other alkali-soluble resins (A-2). In this embodiment, the other alkali-soluble resin (A-2) is obtained by copolymerizing an ethylenically unsaturated monomer containing one or more carboxylic acid groups with other copolymerizable ethylenically unsaturated monomers. In this embodiment, based on the total amount of monomers used for copolymerization is 100 parts by weight, preferably, the other alkali-soluble resin (A-2) is from 5 parts by weight to 50 parts by weight containing one or more carboxyl groups The acid-based ethylenically unsaturated monomer is obtained by copolymerizing 50 to 95 parts by weight of other copolymerizable ethylenically unsaturated monomer.

In this embodiment, the ethylenically unsaturated monomers containing one or more carboxylic acid groups can be used alone or in combination, and the ethylenically unsaturated monomers containing carboxylic acid groups include but are not limited to acrylic acid, methacrylic acid (methacrylic acid (MAA), butenoic acid, α-chloroacrylic acid, ethacrylic acid, cinnamic acid, 2-acryloyl ethoxy succinate, or 2-methacrylic ethoxy succinate (2 -methacryloyloxyethyl succinate monoester (HOMS) and other unsaturated monocarboxylic acids; unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid and citraconic anhydride Acids (anhydrides); unsaturated polycarboxylic acids (anhydrides) with more than three carboxylic acid groups. Preferably, the ethylenically unsaturated monomer containing a carboxylic acid group is selected from acrylic acid, methacrylic acid, 2-acryl ethoxy succinate, or 2-methacryl ethoxy succinate . More preferably, the ethylenically unsaturated monomer containing a carboxylic acid group is selected from 2-acryloyl ethoxy succinate, or 2-methacrylo ethoxy succinate, which can improve pigment dispersibility And improve the development speed and reduce the occurrence of residues.

In this embodiment, other copolymerizable ethylenically unsaturated monomers can be used alone or mixed, and other copolymerizable ethylenically unsaturated monomers include but are not limited to styrene (SM), α- Aromatic vinyl compounds such as methylstyrene, vinyltoluene, p-chlorostyrene, methoxystyrene, etc.; N-phenylmaleimide (PMI), nitrogen-o-hydroxyl Phenylmaleimide, nitrogen-m-hydroxyphenylmaleimide, nitrogen-p-hydroxyphenylmaleimide, nitrogen-o-methylphenylmaleimide, nitrogen- M-methylphenylmaleimide, nitrogen-p-methylphenylmaleimide, nitrogen-o-methoxyphenylmaleimide, nitrogen-m-methoxyphenyl Maleimide such as maleimide, nitrogen-p-methoxyphenylmaleimide, nitrogen-cyclohexylmaleimide, etc.; methyl acrylate (MA), Methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate Ester, isobutyl acrylate, isobutyl methacrylate, second butyl acrylate, second butyl methacrylate, third butyl acrylate, third butyl methacrylate, 2-hydroxyethyl acrylate, methyl alcohol 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, methacrylic acid 2-hydroxybutyl ester, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, Benzyl acrylate, benzyl methacrylate (BzMA), phenyl acrylate, methacrylate, triethylene glycol methacrylate, triethylene glycol methacrylate, methyl methacrylate Lauryl acrylate, myristyl methacrylate, cetyl methacrylate, octadecyl methacrylate, eicosyl methacrylate, docosamethacrylate Unsaturated carboxylic acid esters such as alkyl esters, dicyclopentenyloxyethyl acrylate (DCPOA); acrylic acid-nitrogen, nitrogen-dimethylaminoethyl, methacrylic acid-nitrogen, nitrogen- Dimethylaminoethyl, acrylic acid-nitrogen, nitrogen-diethylaminopropyl, methacrylic acid-nitrogen, nitrogen-dimethylaminopropyl, nitrogen acrylate, nitrogen-dibutylaminopropyl , Iso-butylaminoethyl methacrylate; epoxypropyl acrylate, epoxypropyl methacrylate and other unsaturated carboxylic acid epoxypropyl esters; vinyl acetate, vinyl propionate Vinyl carboxylates such as esters and vinyl butyrate; unsaturated ethers such as vinyl methyl ether, vinyl ether, allyl epoxypropyl ether, methallyl epoxypropyl ether; Acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinyl cyanide and other nitrile vinyl compounds; acryloamide, methacryloamide, α-chloroacryloamide, nitrogen-hydroxyethylacrylonitrile Unsaturated amides such as amines, nitrogen-hydroxyethylmethacrylamide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chlorinated butadiene, etc.

Preferably, the other copolymerizable ethylenically unsaturated monomer is selected from styrene, nitrogen-phenylmaleimide, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, methyl 2-hydroxyethyl acrylate, benzyl acrylate, benzyl methacrylate, dicyclopentenyl ethyl acrylate, or a combination of these.

When preparing other alkali-soluble resin (A-2), a solvent can be used, and the solvent can be used alone or in combination, and the solvent includes but is not limited to ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethyl ether Glycol ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether, triethylene glycol ether, propylene glycol methyl ether, propylene glycol ether, dipropylene glycol methyl ether, dipropylene glycol ether , Dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol ether, etc. (poly) alkylene glycol monoalkyl ethers; ethylene glycol methyl ether acetate (Poly)alkylene glycol monoalkyl ether acetates such as esters, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether acetate, etc.; diethylene glycol Dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; 2- Alkyl lactates such as methyl hydroxypropionate and ethyl 2-hydroxypropionate; methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate (EEP), ethyl ethoxyacetate Ester, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionic acid Ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-butyrate Propyl ester, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-methoxybutyric acid Other esters such as ethyl esters; aromatic hydrocarbons such as toluene and xylene; nitrogen-methylpyrrolidone (NMP), nitrogen, nitrogen-dimethylformamide (DMF), or nitrogen, nitrogen-di Acetamides such as methylacetamide (DMAC). Preferably, the solvent is selected from propylene glycol methyl ether acetate, ethyl 3-ethoxypropionate, or a combination thereof. (Poly)alkylene glycol monoalkyl ethers refer to alkylene glycol monoalkyl ethers or polyalkylene glycol monoalkyl ethers. (Poly)alkylene glycol monoalkyl ether acetates refer to alkylene glycol monoalkyl ether acetates or polyalkylene glycol monoalkyl ether acetates.

The initiator used in the preparation of other alkali-soluble resins (A-2) is generally a radical polymerization initiator. Specific examples may include, but are not limited to: 2,2'-azobisisobutyronitrile, 2,2 '-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azo Azo compounds such as 2,2'-azobis-2-methyl butyronitrile (AMBN); cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2-Peroxyl such as 3-tert-butyl peroxide, lauryl peroxide, benzoyl peroxide, tert-butyl isopropyl carbonate, tert-butyl peroxy-2-hexanoate, etc. Compound. The above radical polymerization initiators can be used alone or in combination. At the same time, the radical polymerization initiator can be used together with transition metal salts or amines.

The weight average molecular weight of the other alkali-soluble resin (A-2) of the present invention may be appropriately set according to the purpose and application, and is generally 2,000 to 50,000, preferably 3,000 to 40,000, and more preferably 4,000 to 30,000.

The use amount of the alkali-soluble resin (A) is 100 parts by weight, and the use amount of the other alkali-soluble resin (A-2) is 0 to 97 parts by weight, preferably 0 to 90 parts by weight, and more preferably 0 to 80 Parts by weight. Compound with ethylenic unsaturated group (B)

The compound (B) having an ethylenically unsaturated group of the present invention can be selected from compounds having one ethylenically unsaturated group or compounds having two or more (including two) ethylenically unsaturated groups.

The aforementioned compound having one ethylenically unsaturated group may include, but is not limited to, (meth)acrylamide, (meth)acrylmorpholine, and (meth)acrylic acid-7-amino group -3,7-dimethyloctyl ester, isobutoxymethyl (meth)acrylamide, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, (methyl) 2-ethylhexyl acrylate, ethyl diethylene glycol (meth)acrylate, third octyl (meth)acrylamide, diacetone (meth)acrylamide, (meth)acrylic acid Methylaminoethyl, dodecyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, nitrogen, nitrogen-dimethyl (Meth)acrylamide, tetrachlorophenyl (meth)acrylate, 2-tetrachlorophenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate , Tetrabromophenyl (meth)acrylate, 2-tetrabromophenoxyethyl (meth)acrylate, 2-trichlorophenoxyethyl (meth)acrylate, tribromo (meth)acrylate Phenyl ester, 2-tribromophenoxyethyl (meth)acrylate, ethyl 2-hydroxy-(meth)acrylate, propyl 2-hydroxy-(meth)acrylate, vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl (meth)acrylate, pentachlorophenyl (meth)acrylate, pentabromophenyl (meth)acrylate, poly(ethylene) (meth)acrylate, poly(mono) Propylene (meth)acrylate, norbornene (meth)acrylate, etc. The aforementioned compound having one ethylenically unsaturated group can generally be used alone or in combination.

式(B-2-1)

式(B-2-2)

式(B-2-3)

式(B-2-4)The aforementioned compounds having 2 or more (including 2) ethylenic unsaturated groups include but are not limited to ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol di (Meth)acrylate, tetraethylene glycol di(meth)acrylate, tri(2-hydroxyethyl)isocyanate di(meth)acrylate, tri(2-hydroxyethyl)isocyanate tri (Meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanate tri (meth) acrylate, tri (meth) acrylate trimethylol propyl, ethylene oxide ( Referred to as EO) modified trimethylol propyl tri (meth)acrylate, propylene oxide modified (referred to as PO) trimethylol propyl tri (meth) acrylate, tripropylene glycol di (meth) acrylic acid Ester, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(methyl) Acrylic ester, pentaerythritol tetra(meth)acrylate, polyester di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate ) Acrylate, dipentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol penta(meth)acrylate, tetra(meth)acrylate ) Di(trimethylolpropane) tetra(meth)acrylate, bisphenol A modified with ethylene oxide di(meth)acrylate, bisphenol A modified with propylene oxide Di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate modified with ethylene oxide, hydrogenated bisphenol A di(meth)acrylate modified with propylene oxide, epoxy Propane-modified glycerol tri(meth)acrylate, ethylene oxide-modified bisphenol F di(meth)acrylate, novolak polyglycidyl ether (meth)acrylate, formula (B-2 -1) Compounds represented by formula (B-2-4), etc.

Formula (B-2-1)

Formula (B-2-2)

(B-2-3)

Formula (B-2-4)

The aforementioned compounds having two or more (including two) ethylenically unsaturated groups can generally be used alone or in combination.

Specific examples of the above-mentioned compound (B) having an ethylenically unsaturated group are: trimethylol propyl triacrylate, trimethylol propyl triacrylate modified with ethylene oxide, and the one modified with propylene oxide Trimethylolpropyl triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexaacrylate, tetra Ditrimethylol acrylate, propylene oxide-modified glycerol triacrylate, compounds represented by formula (B-2-1) to formula (B-2-4), or any combination of the above.

In one embodiment, based on the total amount of the alkali-soluble resin (A) is 100 parts by weight, the amount of the compound (B) having an ethylenically unsaturated group is 10 to 200 parts by weight, preferably 20 ~180 parts by weight, more preferably 30~150 parts by weight. Photoinitiator (C)

Preferably, the photoinitiator (C) may further include a first photoinitiator (C-1).

In one embodiment, based on the total amount of the alkali-soluble resin (A) is 100 parts by weight, the amount of the photoinitiator (C) used is 10 to 100 parts by weight, preferably 15 to 90 parts by weight , More preferably 20 to 80 parts by weight. First photoinitiator (C-1)

式(C1-1)In one embodiment, the first photoinitiator (C-1) has the structure shown in formula (C1-1):

Formula (C1-1)

In formula (C1-1), E ³⁰ represents an organic group containing a C ₃ -C ₂₀ cycloalkyl group, E ³¹ and E ³² each independently represent an alkyl group or an aryl group, and E ³³ represents an alkyl group.

Considering that the sensitivity can be further improved, E ³⁰ represents an organic group containing a C ₃ -C ₁₀ cycloalkyl group, and E ³⁰ represents an organic group containing a C ₅ -C ₈ cycloalkyl group.

E ³⁰ represents an organic group containing a C ₃ -C ₂₀ cycloalkyl group, which may be an organic group containing a cycloalkyl group interspersed with a divalent hydrocarbon group, and examples of the divalent hydrocarbon group are preferably alkylene The radical is more preferably C ₂ -C ₅ alkylene, most preferably ethyl.

The E ³⁰ is an organic group containing a C ₃ -C ₂₀ cycloalkyl group, preferably a cycloalkyl alkylene group, and more preferably a cyclopentylethyl group.

In the formula (C1-1), taking the further improvement of sensitivity into consideration, the E ³¹ is an alkyl group or an aryl group, preferably an alkyl group, more preferably a C ₁ -C ₅ alkyl group, most preferably a methyl group .

In the formula (C1-1), taking the further improvement of sensitivity into consideration, the E ³² is an alkyl group or an aryl group, preferably an alkyl group, more preferably a C ₁ -C ₁₀ alkyl group, most preferably an ethyl group .

In the formula (C1-1), considering the further improvement of the sensitivity, the E ₃₃ is an alkyl group, preferably a C ₁ -C ₅ alkyl group, and more preferably a methyl group.

In the formula (C1-1), the substitution position of E ³³ may be ortho, meta or para. Taking the further improvement of the sensitivity into consideration, it is preferably the neighbor.

In the example of the compound represented by the formula (C1-1), E ³⁰ is a cycloalkyl ethyl group, E ³¹ is a methyl group, E ³² is an ethyl group, E ³³ is a methyl group, and the specific product is, for example, Changzhou Qiangli Co., Ltd. TR-PBG-304 etc.

式(C-1-1)

式(C-1-2)

式(C-1-3)

式(C-1-4)

式(C-1-5)

式(C-1-6)

式(C-1-7)

式(C-1-8)

式(C-1-9)

式(C-1-10)Specific examples of the first photoinitiator (C-1) are, for example but not limited to, photoinitiators of compounds having structures represented by the following formula (C-1-1) to formula (C-1-10).

Formula (C-1-1)

Formula (C-1-2)

Formula (C-1-3)

Formula (C-1-4)

Formula (C-1-5)

Formula (C-1-6)

Formula (C-1-7)

Formula (C-1-8)

Formula (C-1-9)

Formula (C-1-10)

In one embodiment, based on the total amount of the alkali-soluble resin (A) is 100 parts by weight, the amount of the first photoinitiator (C-1) used is 1 to 50 parts by weight, preferably 3 ~45 parts by weight, more preferably 5~40 parts by weight. When the first alkali-soluble resin (A-1) and the first photoinitiator (C-1) are not used at the same time, the gap body or protective film formed by the photosensitive resin composition has a problem of poor resolution. Other photoinitiator (C-2)

In one embodiment, the photoinitiator (C) of the present invention may further include other photoinitiators (C-2). Specific examples of other photoinitiators (C-2) include, but are not limited to: O-acyl oxime compounds, triazabenzene compounds, acetophenone compounds, diimidazole compounds, benzophenone compounds Compounds, α-diketone compounds, ketol compounds, ketol ether compounds, acetylphosphine oxide compounds, quinone compounds, halogen-containing compounds, peroxides and the like.

Specific examples of the above-mentioned O-acyl oxime compounds are: 1-[4-(phenylthio)phenyl]-propane-3-cyclopentane-1,2-dione 2-(O-benzoyl Oxime), 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-phenyl acetyl oxime), 1-[4-(phenylthio) Phenyl]-octane-1,2-dione 2-(O-phenyl phenyl oxime), ethane ketone, 1-[9-ethyl-6-(2-methylbenzoyl carbonyl)-9 Hydrogen-carbazole-3-substituent]-,1-(oxy-acetyl oxime), 1,2-butanedione-1-[4-(methylthio)phenyl] 2-(O-acetyl Oxime).

The aforementioned O-acyl oxime compounds are 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-phenyl acetyl oxime), 1-[4- (Phenylthio)phenyl]-octane-1,2-dione 2-(O-phenyl acetyl oxime) and the like are preferred. The above-mentioned O-acyl oxime compounds can be used alone or in combination, depending on the actual needs.

The above-mentioned triazabenzene compounds may include, but are not limited to, vinyl-halomethyl-s-triazabenzene compounds, 2-(naphtho-1-substituted)-4,6-bis-halomethyl -S-triazabenzene compound and 4-(p-aminophenyl)-2,6-di-halomethyl-s-triazabenzene compound etc.

Specific examples of the aforementioned vinyl-halomethyl-s-triazabenzene compounds are: 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triaza Benzene, 2,4-bis(trichloromethyl)-3-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazabenzene, 2-trichloro Methyl-3-amino-6-p-methoxystyryl-s-triazabenzene and the like.

The specific example of the aforementioned 2-(naphtho-1-substituent)-4,6-bis-halomethyl-s-triazabenzene compound is: 2-(naphtho-1-substituent)-4 ,6-bis-trichloromethyl-s-triazabenzene, 2-(4-methoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triaza Heterobenzene, 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-substituted]-4,6-bis-trichloromethyl -S-triazabenzene, 2-[4-(2-butoxyethyl)-naphtho-1-substituted]-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-substituted)-4,6- Bis-trichloromethyl-s-triazabenzene, etc.

The specific example of the aforementioned 4-(p-aminophenyl)-2,6-di-halomethyl-s-triazabenzene compound is: 4-[p-N,N-bis(ethoxy Carbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-bis(ethoxycarbonylmethyl Group)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(tri Chloromethyl)-s-triazabenzene, 4-(p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-( P-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[p-N,N-bis(phenyl)amine Phenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(p-N-chloroethylcarbonylaminoaminophenyl)-2,6-bis(trichloromethyl Group)-s-triazabenzene, 4-[p-N-(p-methoxyphenyl)carbonylaminophenyl]-2,6-bis(trichloromethyl)-s-triaza Benzene, 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-di (Ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-chloro-p-N,N-bis(ethoxy Carbonylcarbonylmethyl)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-di (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-triaza Benzene, 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(trichloro Methyl)-6-[3-bromo-4-[N,N-bis(ethoxycarbonylmethyl)amino]phenyl]-1,3,5-triazabenzene, etc.

The aforementioned triazabenzene compound is 4-[m-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s -Triazabenzene, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene, etc. are preferred. The above triazabenzene-based compounds can be used alone or in combination, depending on the actual needs.

Specific examples of the above-mentioned acetophenone compounds are: p-dimethylaminoacetophenone, α,α'-dimethoxy azophenone, 2,2'-dimethyl-2- Phenylacetophenone, p-methoxyacetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-acetone, 2-benzyl- 2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone, etc. The aforementioned acetophenone compounds are 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-acetone, 2-benzyl-2-N,N-dimethyl Amine-1-(4-morpholinophenyl)-1-butanone and the like are preferred. The above acetophenone compounds can be used alone or in combination, depending on the actual needs.

Specific examples of the above-mentioned diimidazole compounds are: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o- (Fluorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyldi Imidazole, 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 Wait. The aforementioned diimidazole compound is preferably 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole. The above-mentioned diimidazole compounds can be used alone or in combination, depending on the actual needs.

Specific examples of the above-mentioned benzophenone compounds are: thioxanthone, 2,4-diethyl thioxanthone, thioxanthone-4-chlorobenzene, benzophenone, 4,4'-bis(dimethyl Amine) benzophenone, 4,4'-bis(diethylamine) benzophenone, etc. The aforementioned benzophenone compounds are preferably 4,4'-bis(diethylamine)benzophenone. The above benzophenone compounds can be used alone or in combination, depending on the actual needs.

Specific examples of the above-mentioned α-diketone compounds are: benzoyl acetyl and acetyl. A specific example of the above-mentioned ketol compound is benzophenone. Specific examples of the above-mentioned ketol ether compounds are: benzphenone methyl ether, benzphenone ethyl ether, benzphenone isopropyl ether, and the like. Specific examples of the above-mentioned acetylphosphine oxide compounds are: 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis-(2,6-dimethoxy phenyl acetyl)-2,4, 4-trimethylphenylphosphine oxide, etc. Specific examples of the above quinone compounds are: anthraquinone, 1,4-naphthoquinone, and the like. Specific examples of the halogen-containing compounds mentioned above are: benzyl chloride, tribromomethyl benzene, tris(trichloromethyl)-s-triazabenzene and the like. Specific examples of the above-mentioned peroxides are: di-third butyl peroxide and the like. The above-mentioned α-diketone compounds, ketol alcohol compounds, ketol ether compounds, acetylphosphine oxide compounds, quinone compounds, halogen-containing compounds, peroxides, etc. can be used alone or in combination. Depends on actual needs.

In one embodiment, based on the total amount of the alkali-soluble resin (A) is 100 parts by weight, the amount of the other photoinitiator (C-2) used is 0 to 99 parts by weight, preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight. Solvent (D)

The solvent (D) of the present invention refers to a solvent that can dissolve the alkali-soluble resin (A), the compound (B) having an ethylenically unsaturated group, and the photoinitiator (C), but does not react with the above components . The solvent preferably has appropriate volatility.

The solvent (D) may include but is not limited to ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether, triethylene glycol Glycol ether, propylene glycol methyl ether, propylene glycol ether, dipropylene glycol methyl ether, dipropylene glycol ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol monomethyl ether) or tripropylene glycol monoethyl ether (poly)alkylene glycol monoalkyl ether solvents; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (Poly)alkylene glycol monoalkyl ether acetate solvents such as ether acetate or propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether or tetrahydrofuran, etc. Ether solvents; ketone solvents such as methyl ethyl ketone, cyclohexanone, 2-heptanone or 3-heptanone; alkyl lactate solvents such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate ; 2-hydroxy-2-methyl propionic acid methyl ester, 2-hydroxy-2-methyl propionic acid ethyl ester, 3-methoxy propionic acid methyl ester, 3-methoxy propionic acid ethyl ester, 3-ethyl Methyl oxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methyl Oxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-acetic acid Amyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-pyruvate Other ester solvents such as propyl ester, methyl acetoacetate, ethyl acetoacetate or ethyl 2-oxybutyrate; aromatic hydrocarbon solvents such as toluene or xylene; nitrogen-methylpyrrolidone, nitrogen , N-dimethylformamide or nitrogen, nitrogen-dimethylacetamide and other carboxylic acid amide solvents. The solvent (D) may be used alone or in combination.

Based on that the alkali-soluble resin (A) is 100 parts by weight, the amount of the solvent (D) used is 500 to 5000 parts by weight, preferably 600 to 4500 parts by weight, and more preferably 700 to 4000 parts by weight. Additive (E)

Before the effect of the present invention is affected, the photosensitive resin composition of the present invention may optionally contain an additive (E). The additive (E) may contain a filler, a polymer other than the aforementioned alkali-soluble resin (A), adhesion promoter, antioxidant, ultraviolet absorber or anti-agglomeration agent.

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

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

Specific examples of the aforementioned adhesion promoter may include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, nitrogen-(2-aminoethyl) Group)-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-mercaptopropyltrimethoxysilane, 3- Methacryloyloxypropyltriethoxysilane or any combination of the above compounds.

Specific examples of the foregoing 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 above compounds .

Specific examples of the aforementioned ultraviolet absorber may include, but are not limited to, 2-(3-third butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide, alkoxy phenone ) Or any combination of the above compounds.

Specific examples of the aforementioned anti-agglomeration agent may include, but are not limited to, sodium polyacrylate.

Based on the alkali-soluble resin (A) being 100 parts by weight, the additive (E) is used in an amount of 0 to 10 parts by weight, preferably 1 to 9 parts by weight, and more preferably 3 to 8 parts by weight. Method for preparing photosensitive resin composition

The method that can be used to prepare the photosensitive resin composition is, for example: placing an alkali-soluble resin (A), a compound having an ethylenically unsaturated group (B), a photoinitiator (C), and a solvent (D) in a stirrer and stirring In order to make it evenly mixed into a solution state, if necessary, additives (E) may be added, and after uniformly mixed, a photosensitive resin composition in a solution state can be obtained.

In addition, the method for preparing the photosensitive resin composition is not particularly limited. The preparation method of the photosensitive resin composition is, for example, first dispersing a part of the alkali-soluble resin (A) and the compound (B) having an ethylenically unsaturated group in a part of the solvent (D) to form a dispersion solution; and then mixing The remaining alkali-soluble resin (A), the compound having an ethylenically unsaturated group (B), the photoinitiator (C), the solvent (D), and the additive (E). Formation of protective film and gap body

The present invention provides a protective film and a gap body formed using the above-mentioned photosensitive resin composition. The preparation method is described in detail below.

The method for forming the protective film of the present invention is to first form a pixel layer composed of red, green, and blue colored layers on a transparent substrate, and then apply the transparent photosensitive resin composition to form red, green, and blue. After waiting for the pixel colored layer on the substrate, steps such as exposure, development and post-baking are performed to remove the solvent therein to form a color filter protective film.

The method of forming the gap body of the present invention is to first form a transparent conductive film on a transparent substrate on which a protective film and a pixel layer have been formed, and then apply the transparent photosensitive resin composition to the transparent conductive film, and then , Perform exposure, development and post-baking steps to remove the solvent therein to form a gap body.

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

The above coating method may be, for example, a spray method, a roller coating method, a spin coating method, a bar coating method, an ink jet printing method, etc. . The above coating method can be preferably applied by using a spin coater, a spin loess coating machine, a slit-die coating machine, and the like.

The above pre-bake conditions vary according to the types of ingredients and the mixing ratio. Usually, pre-baking is performed at a temperature of 70°C to 90°C for 1 minute to 15 minutes. After pre-baking, the thickness of the pre-baking coating film is 0.15 μm to 8.5 μm, but preferably 0.15 μm to 6.5 μm, and more preferably 0.15 μm to 4.5 μm. It can be understood that the thickness of the pre-baked coating film refers to the thickness after removing the solvent.

After the pre-baked coating film is formed, heat treatment is performed with a heating device such as a hot plate or an oven. The temperature of the heat treatment is usually 150 to 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.

When a photoinitiator is used for the above-mentioned curable resin composition, if necessary, the curable resin composition may be coated on the surface of the substrate, and the solvent may be removed by pre-baking to form a pre-baking coating film. The pre-baked coating film is exposed to light.

The light used in the above-mentioned exposure process may be, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-rays, etc., but it is preferable to use ultraviolet light containing a wavelength of 190 nm to 450 nm.

The exposure amount of the above exposure process is preferably 100 J/m ² to 20,000 J/m ² , but preferably 150 J/m ² to 10,000 J/m ² .

After the above-mentioned exposure treatment, a heating device such as a hot plate or an oven can be used for heat treatment. The temperature of the heat treatment is usually 150 to 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.

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

Specifically, the manufacturing method of the color filter of the present invention is, for example, after forming a pixel colored layer of red, green, and blue and a protective film, under a vacuum environment with a temperature between 220°C and 250°C, Sputtering is performed on the surface of the protective film layer to form an ITO protective film. If necessary, the ITO protective film is etched and wired, and then an alignment film is coated on the surface of the ITO protective film, which can be manufactured including the present invention. The color filter of the cured product obtained by curing the photosensitive resin composition. Manufacturing method of liquid crystal display device

First, the color filter formed by the above-mentioned color filter manufacturing method and the substrate provided with the thin film transistor are oppositely arranged, and a gap (cell gap) is provided between the two. Next, the color filter and the surrounding part of the substrate are bonded with an adhesive and the injection hole is left. Then, liquid crystal is injected through the injection hole in the gap between the substrate surface and the adhesive, and finally the injection hole is sealed to form a liquid crystal layer. Subsequently, a liquid crystal display device is manufactured by providing a polarizing plate on the other side of the color filter that contacts the liquid crystal layer and the other side of the substrate that contacts the liquid crystal layer. The liquid crystal used above, that is, a liquid crystal compound or a liquid crystal composition, is not particularly limited here. However, any liquid crystal compound and liquid crystal composition can be used.

In addition, the liquid crystal alignment film used in making the color filter is used to restrict the alignment of the liquid crystal molecules, and there is no particular limitation, and any inorganic or organic substance may be used, and the present invention is not limited thereto. Examples

The present invention will be described in detail with examples below, but the present invention is not limited to the contents disclosed in these examples. Synthesis of the first alkali-soluble resin (A-1)

The amount of each reaction reagent used in the synthesis of the first alkali-soluble resin synthesis examples A-1-1 to A-1-12 of the present invention is listed in Table 1 below, and the name or structure of each reaction reagent is listed in Table 2 below . Synthesis Example A-1-1

Set a stirrer, thermometer, condenser and nitrogen inlet on a four-necked conical flask, and introduce nitrogen. Then, 100 parts by weight of propylene glycol methyl ether acetate (abbreviated as PGMEA) was added, and the temperature was raised to 100°C. Next, 30 parts by weight of monomer (a-1-1-1), 10 parts by weight of monomer (a-1-2-1), and 15 parts by weight of monomer (a-1-2-4) , 25 parts by weight of monomer (a-1-5-1), 20 parts by weight of monomer (a-1-5-2) and 4 parts by weight of 2,2'-azobis-2-methyl Butyronitrile (abbreviated as AMBN) is dissolved in 100 parts by weight of propylene glycol methyl ether acetate (abbreviated as PGMEA), and this mixed solution is dropped into a four-necked conical flask dropwise within 2 hours and reacted at 100°C for 6.5 hours After that, the first alkali-soluble resin (A-1-1) of Synthesis Example A-1-1 can be prepared. Synthesis Examples A-1-2 to A-1-12

表2

其他鹼可溶性樹脂 (A-2) 的合成 The first alkali-soluble resins in Synthesis Example A-1-2 to Synthesis Example A-1-12 were prepared in the same steps as in Synthesis Example A-1-1, and the difference was that: the synthesis of the first alkali-soluble resin was changed The types of ingredients used and their usage (as shown in Table 1). Table 1

Table 2

Synthesis of other alkali soluble resins (A-2)

The amounts, reaction temperature, and polymerization time of each reaction reagent used in the synthesis of other alkali-soluble resin synthesis examples A-2-1 to A-2-6 of the present invention are listed in Tables 3 and 4 below; The name or structure is listed in Table 5 below. Synthesis Example A-2-1

Set a stirrer, thermometer, condenser and nitrogen inlet on a four-necked conical flask, and introduce nitrogen. Then, 120 parts by weight of propylene glycol methyl ether acetate (abbreviated as PGMEA) was added, and the temperature was raised to 80°C. Next, 50 parts by weight of methacrylic acid (abbreviated as MAA), 20 parts by weight of dicyclopentyl methacrylate (abbreviated as FA-513M), 10 parts by weight of styrene (abbreviated as SM), and 20 parts by weight of Epoxypropyl methacrylate (abbreviated as GMA) and 4 parts by weight of 2,2'-azobisisobutyronitrile (abbreviated as AIBN) dissolved in 120 parts by weight of propylene glycol methyl ether acetate (abbreviated as PGMEA) , And the mixed solution was dropped into a four-necked conical flask dropwise within 2 hours and reacted at 80°C for 4.5 hours. Next, the temperature was raised to 100° C., and 0.5 parts by weight of 2,2′-azobisisobutyronitrile (abbreviated as AMBN) was added. After performing the polymerization reaction for 1 hour, another alkali-soluble resin (A-2-1) of Synthesis Example A-2-1 can be prepared. Synthesis Example A-2-2 to Synthesis Example A-2-6

表4

表5

感光性樹脂組成物的實施例 1~16 The alkali-soluble resins of Synthesis Example A-2-2 to Synthesis Example A-2-6 are prepared in the same steps as Synthesis Example A-2-1, and the difference is that the types of ingredients and their use amount, reaction Time and reaction temperature (as shown in Tables 3 and 4). table 3

Table 4

table 5

Examples 1 to 16 of photosensitive resin composition

The following describes Examples 1 to 16 and Comparative Examples 1 to 7 of the photosensitive resin composition: Example 1

40 parts by weight of the alkali-soluble resin of Synthesis Example A-1-1 (hereinafter abbreviated as A-1-1) and 60 parts by weight of the alkali-soluble resin of Synthesis Example A-2-1 (hereinafter abbreviated as A-2-1) , 40 parts by weight of dipentaerythritol hexaacrylate (hereinafter referred to as B-1), 10 parts by weight of the compound represented by formula (C-1-1) (hereinafter referred to as C-1-1) was added 800 parts by weight The propylene glycol methyl ether acetate (hereinafter abbreviated as D-1) was mixed with a shaking type stirrer to produce the photosensitive resin composition of Example 1. The obtained photosensitive resin composition was evaluated by the evaluation method described later, and the results are shown in Table 6. Example 2 to Example 16

表7

感光性樹脂組成物的比較例 1~7 The photosensitive resin compositions of Examples 2 to 16 were prepared in the same steps as in Example 1, and the difference was that the types of photosensitive resin compositions and their usage amounts were changed (as shown in Table 6 ), where the compounds corresponding to the symbols in Table 6 are shown in Table 7. The obtained photosensitive resin composition was evaluated by the evaluation method described later, and the results are shown in Table 6. Table 6

Table 7

Comparative Examples 1 to 7 of photosensitive resin composition

The amounts and evaluation results of the respective reaction reagents used in the synthesis of the photosensitive resin compositions of Comparative Examples 1 to 7 of the present invention are shown in Table 8 below. Comparative Example 1 to Comparative Example 7

評價 方式 解析度 The photosensitive resin compositions of Comparative Examples 1 to 7 were prepared in the same procedure as in Example 1, and the difference was that the types of photosensitive resin compositions and their usage amounts were changed (as shown in Table 8 ). The obtained photosensitive resin composition was evaluated by the evaluation method described later, and the results are shown in Table 8. Table 8

Evaluation method resolution

The prepared photosensitive resin composition is applied on a glass substrate by spin coating, and prebaked at 100°C for 2 minutes to obtain a prebaked coating film of about 1 μm. The pre-baked coating film (made by Japan Filcon) between the line and space is irradiated with 50 mJ/cm ² of ultraviolet light (exposure machine model AG500-4N; made by M&R Nano Technology) Then, develop with 0.84% potassium hydroxide aqueous solution at 23℃ for 1 minute, remove the unexposed part of the coating film on the substrate, then wash with pure water, and then bake at 235℃ for 30 minutes. A gap body or a protective film is formed on the glass substrate, which has a cylinder formed by a designated mask pattern. The gap body or the protective film formed on the above glass substrate is observed with a microscope or a scanning electron microscope to the minimum moldable diameter of the cylinder of the gap body or the protective film. ◎: Resolution≦10μm ○: 12μm≦Resolution<10μm △: 14μm≦Resolution<12μm ╳: Resolution>14μm

See Examples 3 to 5, 9 to 10, and 13 to 15 in Table 6. The first alkali-soluble resin (A-1) used in Examples 3 to 5, 9 to 10, and 13 to 15 contains a polycyclic structure. The mixture of ethylenically unsaturated monomers (a-1-3) is prepared by polymerization. Therefore, the gap body formed by the photosensitive resin composition prepared in Examples 3 to 5, 9 to 10, and 13 to 15 or The protective film has better resolution.

See Examples 6 to 9, 11, and 13 to 15 in Table 6. The first alkali-soluble resin (A-1) used in Examples 6 to 9, 11, and 13 to 15 consists of those containing alicyclic epoxy groups. When a mixture of ethylenically unsaturated monomers (a-1-4) is prepared by polymerization, the gap body or protective film formed by the photosensitive resin composition has a better resolution.

See Comparative Examples 1-7 in Table 8. Comparative Examples 1-7 do not use the first alkali-soluble resin (A-1) and the first photoinitiator (C-1) at the same time. Therefore, the preparation of Comparative Examples 1-7 The resolution of the gap body or protective film formed by the obtained photosensitive resin composition is not good.

In summary, the photosensitive resin composition of the present invention includes a first alkali-soluble resin (A-1) having a special structure and a first photoinitiator (C-1), which makes the photosensitive resin composition of the present invention Has excellent resolution.

Although the present invention has been disclosed as above with examples, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some changes and modifications without departing from the spirit and scope of the present invention. The scope of protection of the present invention shall be subject to the scope defined in the appended patent application.

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Claims (13)

A photosensitive resin composition comprising: an alkali-soluble resin (A); a compound (B) having an ethylenically unsaturated group; a photoinitiator (C); and a solvent (D), wherein the alkali-soluble resin ( A) includes a first alkali-soluble resin (A-1), and the first alkali-soluble resin (A-1) is composed of an ethylenically unsaturated monomer (a-1-1) having a carboxylic acid group and a formula ( I) A mixture of ethylenically unsaturated monomers (a-1-2) with a silane group shown in FIG.

Formula (I) In the formula (I), X ¹ represents a hydrogen atom or a methyl group; X ² and X ³ independently represent phenyl, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ alkoxy or a group represented by the following formula (II);

Formula (II) In the formula (II), the X ⁵ , X ⁶ and X ⁷ each independently represent a phenyl group or a C ₁ -C ₁₂ alkyl group; the d represents an integer of 2 to 13; when When d is greater than 1, plural X ⁶ are the same or different, and plural X ⁷ are the same or different; X ⁴ represents a C ₁ -C ₆ alkyl group or a group represented by the following formula (III);

Formula (III) In the formula (III), the X ⁸ , X ⁹ and X ¹⁰ independently represent a phenyl group or a C ₁ -C ₁₂ alkyl group; the a represents an integer of 1 to 6; b represents an integer from 1 to 150; when b is greater than 1, plural X ² are the same or different, and plural X ³ are the same or different; the photoinitiator (C) includes the formula (C1- 1) The first photoinitiator (C-1) of the structure shown;

Formula (C1-1) In the formula (C1-1), the E ³⁰ represents an organic group containing a C ₃ -C ₂₀ cycloalkyl group; the E ³¹ and E ³² each independently represent an alkyl group or Aryl; and the E ³³ represents an alkyl group. The photosensitive resin composition as described in item 1 of the patent application scope, the first alkali-soluble resin (A-1) is composed of a mixture containing an ethylenically unsaturated monomer (a-1-3) having a polycyclic structure From polymerization. The photosensitive resin composition according to item 1 of the patent application scope, the first alkali-soluble resin (A-1) is composed of an ethylenically unsaturated monomer (a-1-4) containing an alicyclic epoxy group ) Is polymerized. The photosensitive resin composition as described in item 1 of the patent application range, wherein the total amount of the alkali-soluble resin (A) is 100 parts by weight, and the amount of the compound (B) having an ethylenically unsaturated group is used 10 to 200 parts by weight, the amount of the photoinitiator (C) used is 10 to 100 parts by weight, and the amount of the solvent (D) used is 500 to 5000 parts by weight. The photosensitive resin composition as described in Item 1 of the patent application range, wherein the total amount of the alkali-soluble resin (A) is 100 parts by weight, and the usage amount of the first alkali-soluble resin (A-1) is 3~100 parts by weight. The photosensitive resin composition as described in item 1 of the patent application range, wherein the total amount of the alkali-soluble resin (A) is 100 parts by weight, and the amount of the first photoinitiator (C-1) used It is 1~50 parts by weight. The photosensitive resin composition as described in item 1 of the patent application range, wherein the total amount of the first alkali-soluble resin (A-1) is 100 parts by weight, and the ethylenically unsaturated monomer having a carboxylic acid group The use amount of the body (a-1-1) is 5-50 parts by weight, and the use amount of the ethylenically unsaturated monomer (a-1-2) having a silane group represented by the formula (I) is 1~ 30 parts by weight. The photosensitive resin composition as described in item 2 of the patent application range, wherein the total amount of the first alkali-soluble resin (A-1) is 100 parts by weight, and the ethylenically unsaturated monomer having a polycyclic structure The use amount of the body (a-1-3) is 0-40 parts by weight. The photosensitive resin composition as described in item 3 of the patent application range, wherein the total amount based on the first alkali-soluble resin (A-1) is 100 parts by weight, and the ethylenic property having an alicyclic epoxy group The amount of unsaturated monomer (a-1-4) used is 0-40 parts by weight. A gap body having a pattern by sequentially applying pre-baking treatment, exposure treatment, development treatment and post-baking to the photosensitive resin composition as described in any one of claims 1 to 9 Processed and made. A protective film with a pattern by sequentially applying a pre-baking treatment, an exposure treatment, a developing treatment, and a post-baking to the photosensitive resin composition as described in any one of claims 1 to 9 Processed and made. A liquid crystal display element includes a gap body as described in item 10 of the patent application. A liquid crystal display element includes the protective film as described in item 11 of the patent application scope.