KR20120078498A - Photosensitive resin composition, spacer thereof and liquid crystal display comprising the same - Google Patents

Abstract

PURPOSE: A photosensitive resin composition, a spacer manufactured based on the composition, and a liquid crystal display device including the composition are provided to improve resolution by reducing the size of pixels. CONSTITUTION: A photosensitive resin composition includes an alkali soluble resin, an unsaturated ethylenically monomer, a photo-polymerization initiator, and a solvent. The photo-polymerization initiator is one or more selected from a compound represented by chemical formula 1 and a compound represented by chemical formula 2. In chemical formula 1, R1 is a hydrogen element, a halogen element, a phenyl group, a phenoxy carbonyl group, a C1 to C20 alkyl group, a C2 to C20 alkyl group substituted with a halogen element or a phenyl group, a phenyl group substituted with a C1 to C6 alkyl group, a halogen element, -OR, -OCH_2CH_2(CO)OR, or -O(CO)-R, an alkanoyl group substituted with a C1 to C6 alkyl group, a phenyl group, -OR, -OCH_2CH_2(CO)OR, or -O(CO)-R, a benzoyl group substituted with a C1 to C6 alkyl group, a phenyl group, -OR, -OCH_2CH_2(CO)OR, or -O(CO)-R, a C2 to C12 alkoxy carbonyl group substituted with one or more of -O- or hydroxyl groups, a phenoxy carbonyl group substituted with a C1 to C6 alkyl group, a halogen element, a phenyl group, -OR, -OCH_2CH_2(CO)OR, -O(CO)-R, a S(O)_m-phenyl group substituted with a ciano group, NO_2, a C1 to C4 haloalkyl group, C1 to C12 alkyl group, or SO_2-R; and R1 is a hydrogen element, a halogen element, a C1 to C6 alkyl group, a phenyl group, a ciano group, a phenoxyl group, or a C3 to C8 cycloalkyl group substituted with a ciano group or a phenyl group.

Description

Photosensitive resin composition, a spacer manufactured therefrom, and a liquid crystal display device comprising the same {PHOTOSENSITIVE RESIN COMPOSITION, SPACER THEREOF AND LIQUID CRYSTAL DISPLAY COMPRISING THE SAME}

The present invention relates to a photosensitive resin composition, a spacer prepared therefrom, and a liquid crystal display device including the same.

Generally, when forming a spacer by photolithography on the transparent substrate used for the process of forming a spacer, for example, a color filter, a proximity exposure machine is often used. In the case of such proximity exposure, a constant gap is provided between the photomask used for exposure and the board | substrate which formed the film of the photosensitive resin composition, and it exposes, and it is ideal to expose in a pattern similar to a photomask. Maintaining a constant gap at this time is to prevent the mask and the substrate from being in close contact, thereby preventing contamination of both the mask and the substrate.

However, since the gap is filled with air or nitrogen, and the light passing through the opening of the photomask is diffused and spread in the gap portion, there is a problem that the gap is exposed wider than the design size of the mask pattern.

In order to improve image quality, the pixel size is getting smaller, and according to the smaller pixel size, a smaller size of the spacer is also required. In the case of proximity exposure, the formation of the micropattern exposed in the same pattern as a photomask is required, maintaining a constant gap between the photomask used for exposure and the board | substrate which formed the film of the photosensitive resin composition.

On the other hand, Korean Patent Publication Nos. 1999-88297, 2002-76924, 2001-0100808, and 2002-0053757 use binder polymers as acrylic copolymers, and a photosensitive resin composition composed of a polyvalent acrylate crosslinking agent and a photoinitiator. Is applied to a substrate, a predetermined mask is interposed, ultraviolet rays are irradiated to cure a desired portion, and a method of forming a spacer having a dot shape or a stripe shape by washing with an aqueous base solution is removed. However, this situation does not meet the requirements.

The present invention includes a compound represented by Formula 1 according to the present invention and any one or more photopolymerization initiators selected from the compounds represented by the following Formula 2 is capable of forming a pattern with high sensitivity and high resolution, good pattern shape, compressive strength To provide a photosensitive resin composition having excellent adhesion to a transparent substrate and the like, a spacer prepared therefrom, and a liquid crystal display device including the same.

One embodiment of the present invention is any one or more photopolymerization initiator selected from [A] alkali-soluble resin, [B] unsaturated unsaturated ethylene monomer, [C] a compound represented by the formula (1) and a compound represented by the formula (2) and It is a photosensitive resin composition containing a [D] solvent.

<Formula 1>

Wherein R ₁ is a hydrogen atom, a halogen atom, a phenyl group, a phenoxycarbonyl group, C ₁ to C ₂₀ C ₂ to C ₂₀ substituted by alkyl, halogen atom or phenyl group Alkyl group, C ₁ to C ₆ phosphorus An alkyl group or a halogen atom or -OR, wherein R is a hydrogen atom, a hydroxy group, a thiol group, a cyano group, an alkyl group having ₁ to ₂₀ carbon atoms, a phenyl group, an alkenoxyl group having ₃ to ₆ carbon atoms, -OCH ₂ CH ₂ CN, -OCO-phenyl group) or -OCH ₂ CH ₂ (CO) OR wherein R is C ₁ ~ C ₄ Alkyl group) or -O (CO) -R wherein R is C ₁ -C ₄ Is a phenyl group substituted with an alkyl group, and C ₁ to C ₆ An alkyl group or a phenyl group or -OR, wherein R is a hydrogen atom, a hydroxy group, a thiol group, a cyano group, an alkyl group having ₁ to ₂₀ carbon atoms, a phenyl group, an alkenoxyl group having ₃ to ₆ carbon atoms, -OCH ₂ CH ₂ CN,- OCO-phenyl group) or -OCH ₂ CH ₂ (CO) OR where R is C ₁ ~ C ₄ Alkyl group) or -O (CO) -R wherein R is C ₁ -C ₄ An alkanoyl group substituted with an alkyl group, C ₁ to C ₆ An alkyl group or a phenyl group or -OR, wherein R is a hydrogen atom, a hydroxy group, a thiol group, a cyano group, an alkyl group having ₁ to ₂₀ carbon atoms, a phenyl group, an alkenoxyl group having ₃ to ₆ carbon atoms, -OCH ₂ CH ₂ CN,- OCO-phenyl group) or -OCH ₂ CH ₂ (CO) OR where R is C ₁ ~ C ₄ Alkyl group) or -O (CO) -R wherein R is C ₁ -C ₄ An alkyl group.), A C ₂ to C ₁₂ alkoxycarbonyl group substituted by one or more -O- or hydroxyl groups, C ₁ to C ₆ An alkyl group or a halogen atom or a phenyl group or -OR, wherein R is a hydrogen atom, a hydroxy group, a thiol group, a cyano group, an alkyl group having ₁ to ₂₀ carbon atoms, a phenyl group, an alkenoxyl group having ₃ to ₆ carbon atoms, -OCH ₂ CH ₂ CN, -OCO-phenyl group) or -OCH ₂ CH ₂ (CO) OR, wherein R is C ₁ ~ C ₄ Alkyl group) or -O (CO) -R wherein R is C ₁ -C ₄ Phenoxycarbonyl, cyano group or NO ₂ or C ₁ to C ₄ Haloalkyl group or C ₁ to C ₁₂ phosphorus An alkyl group or SO ₂ -R wherein R is C ₁ to C ₆ S (O) m-phenyl group substituted with an alkyl group, wherein m is an integer of 2 to 6, and C ₁ to C ₁₂ SO ₂ -Ophenyl group substituted by an alkyl group,

R ₂ is a hydrogen atom, a halogen atom, C ₃ ~ C ₈ substituted with an alkyl group having ₁ to ₆ carbon atoms, a phenyl group, a cyano group, a phenoxy group, a cyano group or a phenyl group Cycloalkyl group, a cyano group or a phenyl group substituted with C ₁ ~ C ₁₂ is a C ₂ alkyl group substituted by a cyano group or a phenyl group is ₅ ~ C Alkenyl group, a cyano group or a halogen-substituted phenyl group, a cyano group or a halogen atom-substituted C ₁ ~ C ₈ alkoxy group, a cyano cost as group or halogen-substituted benzyl oxy group, a halogen-substituted phenoxy group, C ₁ ~ C Phenoxy group substituted with a ₆ -membered alkyl group.)

<Formula 2>

Wherein R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, a halogen atom, a phenyl group, a cyano group, and C ₁ to C ₁₂ C ₃ to C ₈ substituted with alkyl, phenyl or cyano groups Cycloalkyl group, a C ₂ substituted with a phenyl group or a cyano group, a C ₁ ~ C ₁₂ alkyl group, a phenyl group or a cyano group substituted with a ₅ ~ C Alkenyl, C ₁ to C ₆ phosphorus With an alkyl group or a halogen atom or a cyano group or OA ₁ or SA ₂ or NA ₃ A ₄ Substituted phenyl groups, C ₁ to C ₆ With an alkyl group or a halogen atom or a cyano group or OA ₁ or SA ₂ or NA ₃ A ₄ Substituted C ₁ ~ C ₈ phosphorus alkoxy group, C ₁ ~ C ₆ phosphorus With an alkyl group or a halogen atom or a cyano group or OA ₁ or SA ₂ or NA ₃ A ₄ Substituted Benzyloxy group, C ₁ to C ₆ phosphorus Phenoxy group substituted with an alkyl group or a halogen atom.

R ₆ is a phenyl group, a naphthyl group, a benzoyl group or a naphthoyl group. They are substituted by halogen or C ₂ -C ₁₂ alkyl group or C ₃ -C ₈ cycloalkyl group or benzyl group or phenyl group or phenoxycarbonyl group, respectively; Each substituted with a phenyl group substituted by OA ₁ or SA ₂ or NA ₃ A ₄ ; Substituted with a C ₂ to C ₁₂ alkoxycarbonyl group each substituted with —O— or a hydroxy group; Or may be substituted by OA ₁ or SA ₂ or SOA ₂ or SO ₂ A ₂ or NA ₃ A ₄ , respectively.

A_OneSilver hydrogen atom, hydroxy group, thiol group, cyano group, C_One~ C₂₀sign Alkyl group, C₃~ C₆sign C substituted with alkenoxyl group, phenyl group_One~ C₃sign Alkyl group, -OCH₂CH₂CN, -OCH₂CH₂(CO) OR where R is C_One~ C₈sign Alkyl group), -O (CO) R, wherein R is a phenyl group, C_One~ C₈Is an alkyl group),-(CO) OR, where R is a hydrogen atom,₂~ C₁₂sign Is an alkyl group), -OR (where R is a halogen atom, a hydroxy group, C₂~ C₁₂sign Alkyl group,-(CH₂CH₂O)_{n + 1}H (n is an integer from 1 to 5),-(CH₂CH₂O)_n(CO) R where n is an integer from 1 to 5 and R is C_One~ C₈sign Alkyl group), C_One~ C₈sign Alkanoyl group, C₂~ C₁₂sign Alkenyl, C₃~ C₆sign Alkenoyl, C₃~ C₈sign Cycloalkyl group, C_One~ C₁₂sign Alkoxy group, phenoxy group, C_One~ C₁₂sign Alkylsulfanyl group, phenylsulfanyl group, -NR (where R is C_One~ C₁₂sign An alkyl group.), A phenyl group or a naphthyl group substituted with a diphenylamino group.)

A₂Is a hydrogen atom, hydroxyl group, thiol group, cyano group, unsubstituted C_One~ C₂₀sign Alkyl group, unsubstituted C₂~ C₁₂sign Alkenyl, Unsubstituted C₃~ C₈sign Cycloalkyl group, unsubstituted C₃~ C₆sign C substituted with alkenoxyl, oxygen or sulfur atoms₂~ C₁₂sign C substituted by alkyl group, oxygen atom or sulfur atom_One~ C₈sign C substituted with an alkanoyl group, oxygen atom or sulfur atom₂~ C₁₂sign C substituted with alkenyl, oxygen or sulfur atoms₃~ C₆sign Alkenoyl, C_One~ C₆sign Benzoyl group substituted with alkyl group, benzoyl group substituted with halogen, benzoyl group substituted with hydroxy group, C_One~ C₄sign Benzoyl group substituted with an alkoxy group, C_One~ C₄sign A benzoyl group substituted with an alkylsulfanyl group,

A ₃ and A ₄ are each independently a hydrogen atom, a benzoyl group, C ₁ to C ₂₀ Alkyl group, C ₂ ~ C ₄ phosphorus Hydroxyalkyl group, C ₂ ~ C ₁₀ phosphorus Alkoxyalkyl group, C ₂ ~ C ₅ phosphorus Alkenyl, C ₃ ~ C ₈ phosphorus Cycloalkyl group, phenyl-R, wherein R is C ₁ to C ₃ Alkyl group), C ₁ ~ C ₈ Alkanoyl group, C ₃ ~ C ₁₂ phosphorus Alkenoyl group, C ₃ to C ₁₂ Benzoyl group, C ₁ to C ₁₂ phosphorus A phenyl group substituted with an alkyl group, a phenyl group substituted with a benzoyl group, C ₁ to C ₁₂ Phenyl group substituted by alkoxy group, C ₁ to C ₁₂ Naphthyl group substituted with alkyl group, naphthyl group substituted with benzoyl group, C ₁ to C ₁₂ phosphorus Naphthyl, hydroxy or C ₁ to C ₄ substituted with an alkoxy group Alkoxy or C ₂ to C ₄ C ₂ ~ C ₆ substituted with an alkanoyloxy group or a benzooxy group Alkylene group.)

Another embodiment of the present invention is a photopolymerization initiator is a compound represented by the formula (1) is a photosensitive resin composition is a compound represented by the formula (3).

<Formula 3>

Another embodiment of the present invention is a photopolymerization initiator of the compound represented by Formula 2 is a photosensitive resin composition is a compound represented by the formula (4).

&Lt; Formula 4 >

Another embodiment of the present invention is 10 to 300 parts by weight of the [B] unsaturated ethylene monomer based on 100 parts by weight of the [A] alkali-soluble resin, [C] the compound represented by Formula 1 and Formula 2 It is a photosensitive resin composition containing 1-30 weight part of any 1 or more photoinitiators selected from the compound to become, and 200-800 weight part of [D] solvents.

Another embodiment of the present invention is a weight ratio of the compound represented by Formula 1 to the compound represented by Formula 2 when the compound represented by Formula 1 and the compound represented by Formula 2 as the [C] photopolymerization initiator It is a photosensitive resin composition which is 1-30: 1-30.

Another embodiment of the present invention, the [A] alkali-soluble resin is selected from the group consisting of a single or a mixture of two or more selected from [a1] unsaturated carboxylic acid and unsaturated carboxylic anhydride; And a photosensitive resin composition which is a copolymer of the [a2] epoxy group containing unsaturated compound.

Another embodiment of the present invention, the [A] alkali-soluble resin is selected from the group consisting of a single or a mixture of two or more selected from [a1] unsaturated carboxylic acid and unsaturated carboxylic anhydride; [a2] epoxy group-containing unsaturated compounds; And [a3] copolymers of olefinically unsaturated carboxylic acid ester compounds other than the above [a1] and [a2]; Or [a1] single or a mixture of two or more selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides; [a2] epoxy group-containing unsaturated compounds; And [a4] a copolymer of at least one compound selected from olefinically unsaturated compounds other than [a1], [a2] and [a3]; Or [a1] single or a mixture of two or more selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides; [a2] epoxy group-containing unsaturated compounds; [a3] Olefinic unsaturated carboxylic ester compound other than said [a1] and [a2]; And [a4] A photosensitive resin composition which is a copolymer of at least one compound selected from olefinically unsaturated compounds other than [a1], [a2], and [a3].

According to another embodiment of the present invention, the [a1]: [a2] component is a photosensitive resin composition included in a weight ratio of 1: 1.3 to 3.5.

According to another embodiment of the present invention, the [A] alkali-soluble resin is a photosensitive resin composition containing the component [a4] at 10 to 70 parts by weight based on 100 parts by weight of the [A] alkali-soluble resin solid content.

Another embodiment of the present invention is a spacer prepared using the composition.

According to another embodiment of the present invention, the spacer defines a point where 20% is raised from the bottom of the pattern as Bottom CD (a), a point where 95% is raised as Top CD (b), and the length of (b) is A spacer with a top / bottom ratio of 50 or more divided by length and multiplied by 100 (= b / a × 100).

Another embodiment of the present invention is a liquid crystal display device including the spacer.

The photosensitive resin composition, the spacer manufactured therefrom, and the liquid crystal display device including the same according to the present invention have a very high exposure sensitivity and excellent pattern stability after the development process, thereby forming a fine pattern with a small exposure amount, and thus, a low exposure amount. In addition to improving process margins due to pattern formation, productivity improvement due to shortening of process time can be expected. In addition, since fine patterns can be formed, the resolution can be improved by reducing the pixel size. In addition, it is possible to provide a photosensitive resin composition that can be applied to a high sensitivity and high resolution spacer that exhibits sufficient photosensitivity even at a low exposure amount and is easy to form a fine pattern.

1 schematically illustrates a process of compressive displacement and recovery rate of a pattern.
2 is a pattern formed by using the photosensitive resin composition according to Example 1, and then measured by using an electron microscope.
Figure 3 is after forming a pattern with the photosensitive resin composition according to Example 3, the pattern is measured using an electron microscope.

According to one embodiment of the invention, any one or more photopolymerization selected from [A] alkali-soluble resin, [B] unsaturated unsaturated ethylene monomer, [C] a compound represented by the following formula (1) and a compound represented by the following formula (2) It is providing the photosensitive resin composition containing an initiator and a [D] solvent.

<Formula 1>

Wherein R ₁ is a hydrogen atom, a halogen atom, a phenyl group, a phenoxycarbonyl group, C ₁ to C ₂₀ C ₂ to C ₂₀ substituted by alkyl, halogen atom or phenyl group Alkyl group, C ₁ to C ₆ phosphorus An alkyl group or a halogen atom or -OR, wherein R is a hydrogen atom, a hydroxy group, a thiol group, a cyano group, an alkyl group having ₁ to ₂₀ carbon atoms, a phenyl group, an alkenoxyl group having ₃ to ₆ carbon atoms, -OCH ₂ CH ₂ CN, -OCO-phenyl group) or -OCH ₂ CH ₂ (CO) OR wherein R is C ₁ ~ C ₄ Alkyl group) or -O (CO) -R wherein R is C ₁ -C ₄ Is a phenyl group substituted with an alkyl group, and C ₁ to C ₆ An alkyl group or a phenyl group or -OR, wherein R is a hydrogen atom, a hydroxy group, a thiol group, a cyano group, an alkyl group having ₁ to ₂₀ carbon atoms, a phenyl group, an alkenoxyl group having ₃ to ₆ carbon atoms, -OCH ₂ CH ₂ CN,- OCO-phenyl group) or -OCH ₂ CH ₂ (CO) OR where R is C ₁ ~ C ₄ Alkyl group) or -O (CO) -R wherein R is C ₁ -C ₄ An alkanoyl group substituted with an alkyl group, C ₁ to C ₆ An alkyl group or a phenyl group or -OR, wherein R is a hydrogen atom, a hydroxy group, a thiol group, a cyano group, an alkyl group having ₁ to ₂₀ carbon atoms, a phenyl group, an alkenoxyl group having ₃ to ₆ carbon atoms, -OCH ₂ CH ₂ CN,- OCO-phenyl group) or -OCH ₂ CH ₂ (CO) OR where R is C ₁ ~ C ₄ Alkyl group) or -O (CO) -R wherein R is C ₁ -C ₄ An alkyl group.), A C ₂ to C ₁₂ alkoxycarbonyl group substituted by one or more -O- or hydroxyl groups, C ₁ to C ₆ An alkyl group or a halogen atom or a phenyl group or -OR, wherein R is a hydrogen atom, a hydroxy group, a thiol group, a cyano group, an alkyl group having ₁ to ₂₀ carbon atoms, a phenyl group, an alkenoxyl group having ₃ to ₆ carbon atoms, -OCH ₂ CH ₂ CN, -OCO-phenyl group) or -OCH ₂ CH ₂ (CO) OR, wherein R is C ₁ ~ C ₄ Alkyl group) or -O (CO) -R wherein R is C ₁ -C ₄ Phenoxycarbonyl, cyano group or NO ₂ or C ₁ to C ₄ Haloalkyl group or C ₁ to C ₁₂ phosphorus An alkyl group or SO ₂ -R wherein R is C ₁ to C ₆ S (O) m-phenyl group substituted with an alkyl group, wherein m is an integer of 2 to 6, and C ₁ to C ₁₂ SO ₂ -Ophenyl group substituted by an alkyl group,

R ₂ is a hydrogen atom, a halogen atom, C ₃ ~ C ₈ substituted with an alkyl group having ₁ to ₆ carbon atoms, a phenyl group, a cyano group, a phenoxy group, a cyano group or a phenyl group Cycloalkyl group, a cyano group or a phenyl group substituted with C ₁ ~ C ₁₂ is a C ₂ alkyl group substituted by a cyano group or a phenyl group is ₅ ~ C Alkenyl group, a cyano group or a halogen-substituted phenyl group, a cyano group or a halogen atom-substituted C ₁ ~ C ₈ alkoxy group, a cyano cost as group or halogen-substituted benzyl oxy group, a halogen-substituted phenoxy group, C ₁ ~ C Phenoxy group substituted with a ₆ -membered alkyl group.)

<Formula 2>

Wherein R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, a halogen atom, a phenyl group, a cyano group, and C ₁ to C ₁₂ C ₃ to C ₈ substituted with alkyl, phenyl or cyano groups Cycloalkyl group, a C ₂ substituted with a phenyl group or a cyano group, a C ₁ ~ C ₁₂ alkyl group, a phenyl group or a cyano group substituted with a ₅ ~ C Alkenyl, C ₁ to C ₆ phosphorus With an alkyl group or a halogen atom or a cyano group or OA ₁ or SA ₂ or NA ₃ A ₄ Substituted phenyl groups, C ₁ to C ₆ With an alkyl group or a halogen atom or a cyano group or OA ₁ or SA ₂ or NA ₃ A ₄ Substituted C ₁ ~ C ₈ phosphorus alkoxy group, C ₁ ~ C ₆ phosphorus With an alkyl group or a halogen atom or a cyano group or OA ₁ or SA ₂ or NA ₃ A ₄ Substituted Benzyloxy group, C ₁ to C ₆ phosphorus Phenoxy group substituted with an alkyl group or a halogen atom.

R ₆ is a phenyl group, a naphthyl group, a benzoyl group or a naphthoyl group. They are substituted by halogen or C ₂ -C ₁₂ alkyl group or C ₃ -C ₈ cycloalkyl group or benzyl group or phenyl group or phenoxycarbonyl group, respectively; Each substituted with a phenyl group substituted by OA ₁ or SA ₂ or NA ₃ A ₄ ; Substituted with a C ₂ to C ₁₂ alkoxycarbonyl group each substituted with —O— or a hydroxy group; Or may be substituted by OA ₁ or SA ₂ or SOA ₂ or SO ₂ A ₂ or NA ₃ A ₄ , respectively.

A ₁ is a hydrogen atom, a hydroxyl group, a thiol group, a cyano group, C ₁ to C ₂₀ Alkyl group, C ₃ to C ₆ phosphorus C ₁ ~ C ₃ substituted with alkenoxyl, phenyl groups Alkyl group, -OCH ₂ CH ₂ CN, -OCH ₂ CH ₂ (CO) OR, wherein R is C ₁ -C ₈ Alkyl group), -O (CO) R (where R is a phenyl group, an alkyl group having ₁ to ₈ carbon atoms),-(CO) OR (where R is a hydrogen atom, C ₂ to C ₁₂ Is an alkyl group), -OR (wherein R is a halogen atom, a hydroxy group, C ₂ ~ C ₁₂ Alkyl group,-(CH ₂ CH ₂ O) _{n + 1} H (n is an integer from 1 to 5),-(CH ₂ CH ₂ O) _n (CO) R, where n is an integer from 1 to 5 , R is C ₁ to C ₈ Alkyl group), C ₁ ~ C ₈ Alkanoyl group, C ₂ ~ C ₁₂ phosphorus Alkenyl, C ₃ ~ C ₆ phosphorus Alkenoyl, C ₃ ~ C ₈ phosphorus Cycloalkyl group, C ₁ to C ₁₂ phosphorus Alkoxy group, phenoxy group, C ₁ ~ C ₁₂ phosphorus Alkylsulfanyl group, phenylsulfanyl group, -NR where R is C ₁ -C ₁₂ An alkyl group.), A phenyl group or a naphthyl group substituted with a diphenylamino group.)

A ₂ is hydrogen atom, hydroxy group, thiol group, cyano group, unsubstituted C ₁ ~ C ₂₀ Alkyl group, unsubstituted C ₂ ~ C ₁₂ phosphorus Alkenyl, unsubstituted C ₃ ~ C ₈ phosphorus Cycloalkyl group, unsubstituted C ₃ ~ C ₆ phosphorus C ₂ ~ C ₁₂ substituted with alkenoxyl, oxygen or sulfur C ₁ to C ₈ substituted with alkyl, oxygen or sulfur atoms C ₂ ~ C ₁₂ phosphorus substituted with an alkanoyl group, oxygen atom or sulfur atom C ₃ ~ C ₆ substituted with alkenyl, oxygen or sulfur atoms Alkenoyl group, C ₁ to C ₆ A benzoyl group substituted with an alkyl group, a benzoyl group substituted with a halogen, a benzoyl group substituted with a hydroxy group, and C ₁ to C ₄ A benzoyl group substituted with an alkoxy group, C ₁ to C ₄ A benzoyl group substituted with an alkylsulfanyl group,

A ₃ and A ₄ are each independently a hydrogen atom, a benzoyl group, C ₁ to C ₂₀ Alkyl group, C ₂ ~ C ₄ phosphorus Hydroxyalkyl group, C ₂ ~ C ₁₀ phosphorus Alkoxyalkyl group, C ₂ ~ C ₅ phosphorus Alkenyl, C ₃ ~ C ₈ phosphorus Cycloalkyl group, phenyl-R, wherein R is C ₁ to C ₃ Alkyl group), C ₁ ~ C ₈ Alkanoyl group, C ₃ ~ C ₁₂ phosphorus Alkenoyl group, C ₃ to C ₁₂ Benzoyl group, C ₁ to C ₁₂ phosphorus A phenyl group substituted with an alkyl group, a phenyl group substituted with a benzoyl group, C ₁ to C ₁₂ Phenyl group substituted by alkoxy group, C ₁ to C ₁₂ Naphthyl group substituted with alkyl group, naphthyl group substituted with benzoyl group, C ₁ to C ₁₂ phosphorus Naphthyl, hydroxy or C ₁ to C ₄ substituted with an alkoxy group Alkoxy or C ₂ to C ₄ C ₂ ~ C ₆ substituted with an alkanoyloxy group or a benzooxy group Alkylene group.)

Hereinafter, each component of the photosensitive resin composition according to the present invention will be described in detail.

[A] alkali-soluble resin

[A] alkali-soluble resin used for this invention is a single or mixture of 2 or more types selected from [a1] unsaturated carboxylic acid and unsaturated carboxylic anhydride; And [a2] a copolymer of an epoxy group-containing unsaturated compound, or a single or a mixture of two or more selected from [a1] unsaturated carboxylic acids and unsaturated carboxylic anhydrides; [a2] epoxy group-containing unsaturated compounds; And [a3] copolymers of olefinically unsaturated carboxylic acid ester compounds other than the above [a1] and [a2]; Or [a1] single or a mixture of two or more selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides; [a2] epoxy group-containing unsaturated compounds; And [a4] a copolymer of at least one compound selected from olefinically unsaturated compounds other than [a1], [a2] and [a3]; Or [a1] single or a mixture of two or more selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides; [a2] epoxy group-containing unsaturated compounds; [a3] Olefinic unsaturated carboxylic ester compound other than said [a1] and [a2]; And [a4] may be a copolymer obtained by radical polymerization of at least one compound selected from olefinically unsaturated compounds other than [a1], [a2], and [a3].

First, the unsaturated carboxylic acid and / or unsaturated carboxylic anhydride of the form [a1] can be used alone or in combination of anhydrides of acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and these dicarboxylic acids. . Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in view of copolymerization reactivity, heat resistance and easy availability.

Examples of the [a2] epoxy group-containing unsaturated compound include acrylic acid glycidyl ester, methacrylic acid glycidyl ester, α-ethyl acrylic acid glycidyl ester, α-n-propyl acrylic acid glycidyl ester, and α-n-butyl acrylic acid. Glycidyl ester, acrylic acid-3,4-epoxy butyl ester, methacrylic acid-3,4-epoxy butyl ester, acrylic acid-6,7-epoxy heptyl ester, methacrylic acid-6,7-epoxy heptyl ester, α -Ethyl acrylic acid-6,7-epoxy heptyl ester, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like have copolymerization reactivity and heat resistance and hardness of the obtained thin film. It is used preferably at the point of raising. These compounds [a2] are used individually or in combination.

As said compound [a3], For example, Methacrylic acid alkyl ester, such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate; Acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; Methacrylic acid cycloalkyl esters such as cyclohexyl methacrylate, 2-methyl cyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate and isoboroyl methacrylate; Acrylic acid cycloalkyl esters such as cyclohexyl acrylate, 2-methyl cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate and isoboroyl acrylate; Methacrylic acid aryl esters such as pentyl methacrylate and benzyl methacrylate; Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid; Hydroxyalkyl esters such as 2-hydroxy ethyl methacrylate, 2-hydroxy propyl methacrylate, and the like can be used.

Examples of the compound [a4] include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, acrylonitrile, methacrylonitrile, vinyl chloride, and vinyl chloride. Leaden, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

The copolymer [A] used in the present invention includes the components [a1]: [a2] in a weight ratio of 1: 1.3 to 3.5, and includes the component selected from [a3] and [a4], [a3] and [a4]. a4] may be selected from 35 to 65 parts by weight based on 100 parts by weight of the solid content of the [A] alkali-soluble resin.

Such an alkali-soluble resin [A] may contain the component [a4] in an amount of 10 to 70 parts by weight, preferably 20 to 60 parts by weight. If the content of the component [a4] is less than 10 parts by weight, the polymerization stability during the preparation of a polymer including all of the preservation safety of the copolymer [A] and the components of [a1] to [a4] is not easily controlled and becomes solid. When it exceeds 70 weight part, there exists a tendency for developability, heat resistance, surface hardness, a recovery rate, etc. of copolymer [A] to fall.

As a solvent used for the synthesis | combination of the said copolymer [A], Alcohol, such as methanol and ethanol; Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates, such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate, etc. are preferable.

As a polymerization initiator used for the synthesis | combination of the said copolymer [A], what is generally known as a radical polymerization initiator can be used. For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- dimethylvaleronitrile), 2,2'- azobis- (4-methoxy-2, Azo compounds, such as 4-dimethylvaleronitrile), organic peroxides, such as benzoyl peroxide, t-butyl peroxy pibarate, and 1,1'-bis- (t-butyl peroxy) cyclohexane, and hydrogen peroxide are mentioned. When using a peroxide as a radical polymerization initiator, you may use as a redox initiator by using a peroxide together with a reducing agent.

[B] unsaturated ethylenic monomers

The unsaturated ethylenic monomers used in the present invention are monofunctional or polyfunctional acrylic monomers having at least one unsaturated ethylene bond, and monofunctional, bifunctional, or trifunctional or higher (meth) acrylates have good polymerizability. It is preferable from the viewpoint of improving the heat resistance and the surface hardness of the protective film obtained.

As said monofunctional (meth) acrylate, 2-hydroxy ethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxy butyl (meth) acryl And 2- (meth) acryloyl oxyethyl 2-hydroxy propyl phthalate, and the like.

As said bifunctional (meth) acrylate, for example, ethylene glycol (meth) acrylate, 1,6-hexanediol (meth) acrylate, 1,9-nonanediol (meth) acrylate, propylene glycol ( Meta) acrylate, tetraethylene glycol (meth) acrylate, bisphenoxy ethyl alcohol fluorene diacrylate, and the like.

As said trifunctional or more than (meth) acrylate, for example, trishydroxyethyl isocyanate tri (meth) acrylate, trimethyl propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

Such mono-, bi-, or tri- or more (meth) acrylates are used alone or in combination.

The unsaturated ethylenic monomer is contained in 10 to 300 parts by weight based on 100 parts by weight of alkali-soluble resin. When the content of the unsaturated ethylenic monomer is in the above range, there is an effect of improving the developability of the pattern, and improve the hardness and heat resistance.

[C] photopolymerization initiator

The photoinitiator in the present invention means a compound which causes decomposition or bonding upon exposure and generates an active species capable of initiating polymerization of the above-mentioned [B] unsaturated ethylenic monomers such as radicals, anions and cations.

The photopolymerization initiator according to the present invention is preferably used at least one selected from a compound represented by the following formula (1) and a compound represented by the following formula (2).

<Formula 1>

Wherein R ₁ is a hydrogen atom, a halogen atom, a phenyl group, a phenoxycarbonyl group, C ₁ to C ₂₀ C ₂ to C ₂₀ substituted by alkyl, halogen atom or phenyl group Alkyl group, C ₁ to C ₆ phosphorus An alkyl group or a halogen atom or -OR, wherein R is a hydrogen atom, a hydroxy group, a thiol group, a cyano group, an alkyl group having ₁ to ₂₀ carbon atoms, a phenyl group, an alkenoxyl group having ₃ to ₆ carbon atoms, -OCH ₂ CH ₂ CN, -OCO-phenyl group) or -OCH ₂ CH ₂ (CO) OR wherein R is C ₁ ~ C ₄ Alkyl group) or -O (CO) -R wherein R is C ₁ -C ₄ Is a phenyl group substituted with an alkyl group, and C ₁ to C ₆ An alkyl group or a phenyl group or -OR, wherein R is a hydrogen atom, a hydroxy group, a thiol group, a cyano group, an alkyl group having ₁ to ₂₀ carbon atoms, a phenyl group, an alkenoxyl group having ₃ to ₆ carbon atoms, -OCH ₂ CH ₂ CN,- OCO-phenyl group) or -OCH ₂ CH ₂ (CO) OR where R is C ₁ ~ C ₄ Alkyl group) or -O (CO) -R wherein R is C ₁ -C ₄ An alkanoyl group substituted with an alkyl group, C ₁ to C ₆ An alkyl group or a phenyl group or -OR, wherein R is a hydrogen atom, a hydroxy group, a thiol group, a cyano group, an alkyl group having ₁ to ₂₀ carbon atoms, a phenyl group, an alkenoxyl group having ₃ to ₆ carbon atoms, -OCH ₂ CH ₂ CN,- OCO-phenyl group) or -OCH ₂ CH ₂ (CO) OR where R is C ₁ ~ C ₄ Alkyl group) or -O (CO) -R wherein R is C ₁ -C ₄ An alkyl group.), A C ₂ to C ₁₂ alkoxycarbonyl group substituted by one or more -O- or hydroxyl groups, C ₁ to C ₆ An alkyl group or a halogen atom or a phenyl group or -OR, wherein R is a hydrogen atom, a hydroxy group, a thiol group, a cyano group, an alkyl group having ₁ to ₂₀ carbon atoms, a phenyl group, an alkenoxyl group having ₃ to ₆ carbon atoms, -OCH ₂ CH ₂ CN, -OCO-phenyl group) or -OCH ₂ CH ₂ (CO) OR, wherein R is C ₁ ~ C ₄ Alkyl group) or -O (CO) -R wherein R is C ₁ -C ₄ Phenoxycarbonyl, cyano group or NO ₂ or C ₁ to C ₄ Haloalkyl group or C ₁ to C ₁₂ phosphorus An alkyl group or SO ₂ -R wherein R is C ₁ to C ₆ S (O) m-phenyl group substituted with an alkyl group, wherein m is an integer of 2 to 6, and C ₁ to C ₁₂ SO ₂ -Ophenyl group substituted by an alkyl group,

R ₂ is a hydrogen atom, a halogen atom, C ₃ ~ C ₈ substituted with an alkyl group having ₁ to ₆ carbon atoms, a phenyl group, a cyano group, a phenoxy group, a cyano group or a phenyl group Cycloalkyl group, a cyano group or a phenyl group substituted with C ₁ ~ C ₁₂ is a C ₂ alkyl group substituted by a cyano group or a phenyl group is ₅ ~ C Alkenyl group, a cyano group or a halogen-substituted phenyl group, a cyano group or a halogen atom-substituted C ₁ ~ C ₈ alkoxy group, a cyano cost as group or halogen-substituted benzyl oxy group, a halogen-substituted phenoxy group, C ₁ ~ C Phenoxy group substituted with a ₆ -membered alkyl group.)

<Formula 2>

Where R is₃, R₄ And R₅Are each independently a hydrogen atom, a halogen atom, a phenyl group, a cyano group, or C_One~ C₁₂sign C substituted with alkyl, phenyl or cyano group₃~ C₈sign C substituted with a cycloalkyl group, a phenyl group or a cyano group_One~ C₁₂C substituted with phosphorus alkyl, phenyl or cyano groups₂~ C₅sign Alkenyl, C_One~ C₆sign Alkyl group or halogen atom or cyano group or OA_One Or SA₂ Or NA₃A₄in Substituted phenyl groups, C_One~ C₆sign Alkyl group or halogen atom or cyano group or OA_One Or SA₂  Or NA₃A₄in Substituted C_One~ C₈Phosphorous alkoxy group, C_One~ C₆sign Alkyl group or halogen atom or cyano group or OA_One Or SA₂ Or NA₃A₄in Substituted Benzyloxy group, C_One~ C₆sign Phenoxy group substituted with an alkyl group or a halogen atom.

R ₆ is a phenyl group, a naphthyl group, a benzoyl group or a naphthoyl group. They are substituted by halogen or C ₂ -C ₁₂ alkyl group or C ₃ -C ₈ cycloalkyl group or benzyl group or phenyl group or phenoxycarbonyl group, respectively; Each substituted with a phenyl group substituted by OA ₁ or SA ₂ or NA ₃ A ₄ ; Substituted with a C ₂ to C ₁₂ alkoxycarbonyl group each substituted with —O— or a hydroxy group; Or may be substituted by OA ₁ or SA ₂ or SOA ₂ or SO ₂ A ₂ or NA ₃ A ₄ , respectively.

A ₁ is a hydrogen atom, a hydroxyl group, a thiol group, a cyano group, C ₁ to C ₂₀ Alkyl group, C ₃ to C ₆ phosphorus C ₁ ~ C ₃ substituted with alkenoxyl, phenyl groups Alkyl group, -OCH ₂ CH ₂ CN, -OCH ₂ CH ₂ (CO) OR, wherein R is C ₁ -C ₈ Alkyl group), -O (CO) R (where R is a phenyl group, an alkyl group having ₁ to ₈ carbon atoms),-(CO) OR (where R is a hydrogen atom, C ₂ to C ₁₂ Is an alkyl group), -OR (wherein R is a halogen atom, a hydroxy group, C ₂ ~ C ₁₂ Alkyl group,-(CH ₂ CH ₂ O) _{n + 1} H (n is an integer from 1 to 5),-(CH ₂ CH ₂ O) _n (CO) R, where n is an integer from 1 to 5 , R is C ₁ to C ₈ Alkyl group), C ₁ ~ C ₈ Alkanoyl group, C ₂ ~ C ₁₂ phosphorus Alkenyl, C ₃ ~ C ₆ phosphorus Alkenoyl, C ₃ ~ C ₈ phosphorus Cycloalkyl group, C ₁ to C ₁₂ phosphorus Alkoxy group, phenoxy group, C ₁ ~ C ₁₂ phosphorus Alkylsulfanyl group, phenylsulfanyl group, -NR where R is C ₁ -C ₁₂ An alkyl group.), A phenyl group or a naphthyl group substituted with a diphenylamino group.)

A ₂ is hydrogen atom, hydroxy group, thiol group, cyano group, unsubstituted C ₁ ~ C ₂₀ Alkyl group, unsubstituted C ₂ ~ C ₁₂ phosphorus Alkenyl, unsubstituted C ₃ ~ C ₈ phosphorus Cycloalkyl group, unsubstituted C ₃ ~ C ₆ phosphorus C ₂ ~ C ₁₂ substituted with alkenoxyl, oxygen or sulfur C ₁ to C ₈ substituted with alkyl, oxygen or sulfur atoms C ₂ ~ C ₁₂ phosphorus substituted with an alkanoyl group, oxygen atom or sulfur atom C ₃ ~ C ₆ substituted with alkenyl, oxygen or sulfur atoms Alkenoyl group, C ₁ to C ₆ A benzoyl group substituted with an alkyl group, a benzoyl group substituted with a halogen, a benzoyl group substituted with a hydroxy group, and C ₁ to C ₄ A benzoyl group substituted with an alkoxy group, C ₁ to C ₄ A benzoyl group substituted with an alkylsulfanyl group,

A ₃ and A ₄ are each independently a hydrogen atom, a benzoyl group, C ₁ to C ₂₀ Alkyl group, C ₂ ~ C ₄ phosphorus Hydroxyalkyl group, C ₂ ~ C ₁₀ phosphorus Alkoxyalkyl group, C ₂ ~ C ₅ phosphorus Alkenyl, C ₃ ~ C ₈ phosphorus Cycloalkyl group, phenyl-R, wherein R is C ₁ to C ₃ Alkyl group), C ₁ ~ C ₈ Alkanoyl group, C ₃ ~ C ₁₂ phosphorus Alkenoyl group, C ₃ to C ₁₂ Benzoyl group, C ₁ to C ₁₂ phosphorus A phenyl group substituted with an alkyl group, a phenyl group substituted with a benzoyl group, C ₁ to C ₁₂ Phenyl group substituted by alkoxy group, C ₁ to C ₁₂ Naphthyl group substituted with alkyl group, naphthyl group substituted with benzoyl group, C ₁ to C ₁₂ phosphorus Naphthyl, hydroxy or C ₁ to C ₄ substituted with an alkoxy group Alkoxy or C ₂ to C ₄ C ₂ ~ C ₆ substituted with an alkanoyloxy group or a benzooxy group Alkylene group.)

Specific examples of the compound represented by the formula (1) include a compound represented by the following formula (3).

<Formula 3>

Specific examples of the compound represented by the formula (2) include a compound represented by the following formula (4).

&Lt; Formula 4 >

When the compound represented by the formula (1) and the compound represented by the formula (2) are mixed and used as a photopolymerization initiator, the weight ratio of the compound represented by the formula (1) to the compound represented by the formula (2) is 1 to 30: 1 to 30 desirable. When the weight ratio of the compound represented by Chemical Formula 1 to the compound represented by Chemical Formula 2 is within the above range, the sensitivity of the protective film may be improved and the residual film rate may be prevented from decreasing.

In the present invention, by using any one or more selected from the compound represented by the formula (1) and the compound represented by the formula (2) as a photoinitiator, the exposure sensitivity is very high and the pattern stability after the development process is excellent, fine pattern (15㎛) with a small exposure amount It is possible to form the following), which is easy to form radicals by light and the generated radicals also have good mobility and fast reaction so that such an effect can be obtained even at a low exposure amount.

In addition, in the present invention, other photopolymerization initiators may be used together with the compound represented by Formula 1 and at least one compound selected from the compounds represented by Formula 2.

Examples of the other photopolymerization initiators include acetophenone compounds, imidazole compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, phosphine compounds, and triazine compounds. Etc. can be mentioned.

Examples of these compounds are thioxanthone, 2,4-diethyl thioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (diethylamino) benzophenone, acetophenone, p-dimethyl Aminoacetophenone, α, α'-dimethoxyacetoxybenzophenone, 2,2'-dimethoxy-2-petylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl]- 2-morpholino-1-propaneone, 2-benzyl-2-diethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl-1-phenyl Ketones such as propane-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 1,4-naphtho Quinones such as quinones 1,3,5-tris (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2-chlorophenyl) -s-triazine, 1, Halo such as 3-bis (trichlorophenyl) -s-triazine, phenacyl chloride, tribromomethylphenylsulfone, tris (trichloromethyl) -s-triazine And the like compounds di -t- butyl peroxide, 2,4,6-trimethylbenzoyl peroxide, such as diphenylphosphine acylphosphine oxides, such as oxides.

These photoinitiators can be used individually or in combination.

The photopolymerization initiator is included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the content of the photopolymerization initiator is less than 1 part by weight, the sensitivity of the protective film is not sufficient, so that the protective film is easily lost in the developing step, and there is a problem that the residual film ratio is lowered. In addition, even if the protective film is maintained in the developing step, it is difficult to obtain a protective film having a sufficiently high crosslinking density. When it exceeds 30 parts by weight, the heat resistance, the flattening property, and the like of the protective film tend to be lowered.

[D] solvent

As the solvent used in the present invention, the following materials can be used in the preparation of the copolymer [A] or as a solvent capable of maintaining the solid content and the viscosity of the composition. Specifically, Alcohol, such as methanol and ethanol; Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol diethyl ether; And propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate. Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate methyl ethyl ketone, cyclohexanone, 4-hydride from the viewpoint of solubility, reactivity with each component, and convenience of coating film formation among these solvents Methyl esters, ethyl esters, propyl esters, butyl esters of ketones and acetic acid such as oxy-4-methyl-2-pentanane; Ethyl ester and methyl ester of 2-hydroxypropionic acid; Ethyl ester of 2-hydroxy-2-methylpropionic acid; Methyl esters, ethyl esters, butyl esters of hydroxyacetic acid; Ethyl lactate, propyl lactate, butyl lactate; Methyl esters, ethyl esters, propyl esters, butyl esters of methoxyacetic acid; Methyl esters, ethyl esters, propyl esters, butyl esters of propoxyacetic acid; Methyl esters, ethyl esters, propyl esters, butyl esters of butoxyacetic acid; Methyl ester, ethyl ester, propyl ester, butyl ester of 2-methoxypropionic acid; Methyl ester, ethyl ester, propyl ester, butyl ester of 2-ethoxypropionic acid; Methyl ester, ethyl ester, propyl ester, butyl ester of 2-butoxypropionic acid; Methyl ester, ethyl ester, propyl ester, butyl ester of 3-methoxypropane; Methyl ester, ethyl ester, propyl ester, butyl ester of 3-ethoxypropionic acid; Ester, such as the methyl ester of 3-butoxy propionic acid, ethyl ester, propyl ester, and butyl ester, is mentioned.

Moreover, it is also possible to use a high boiling point solvent together with the said solvent. As a high boiling point solvent which can be used together, it is N-methyl formamide, N, N-dimethyl formamide, N-methyl acetamide, N, N-dimethyl acetamide, N-methyl pyrrolidone, dimethyl sulfoxide, for example. And benzyl ethyl ether.

The solvent is included in an amount of 200 to 800 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the content of the solvent is within the above range can be obtained a smooth coating effect, it is possible to obtain an effect that the thickness of the thin film can be easily adjusted.

[E] additive

Optionally other additives such as surfactants, adhesion aids, storage stabilizers, heat resistance enhancers and the like can be added to the photosensitive resin composition of the present invention in a range that does not impair the effects of the present invention as necessary.

The said surfactant is a component mix | blended in order to improve applicability | paintability, A fluorochemical surfactant and silicone type surfactant are preferable.

For example, 3M's FC-129, FC-170C, FC-430, DIC's F-172, F-173, F-183, F-470, F-475, Shin-Etsu Silicone's KP322, KP323, KP340, KP341, etc. Can be mentioned. Such surfactant is used in an amount of 5 parts by weight or less, preferably 2 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the content of the surfactant exceeds 5 parts by weight, bubbles tend to occur during application, and the film tends to become rough.

It is also possible to use an adhesion aid in order to improve the adhesion with the base. As such an adhesion aid, a functional silane coupling agent is preferably used. For example, trimethoxysilyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ -Isocyanate propyl triethoxysilane, (gamma)-glycidoxy propyl trimethoxysilane, etc. are mentioned. These adhesion aids can be used individually or in mixture of 2 or more types. Such adhesion aid is used in an amount of 20 parts by weight or less, preferably 10 parts by weight or less based on 100 parts by weight of the copolymer [A]. When content of the said adhesion | attachment adjuvant exceeds 20 weight part, heat resistance will fall easily.

In the method for producing a thin film and a pattern using the photosensitive resin composition of the present invention, first, the photosensitive resin composition is homogenized, filtered using a 0.1 to 5 μm filter, coated on a transparent substrate, and the thin film is heated to a temperature of 70 to 150 ° C. Pre-Bake for 30 seconds to 5 minutes at and then expose the thin film using a photo mask. Then, after the thin film is developed with an alkaline developer, the thin film is post-baked at a temperature of 150 to 300 ° C. for 30 minutes to 2 hours.

This will be described in detail below.

A transparent conductive film is formed on one surface of a transparent substrate, and after apply | coating the composition solution of the photosensitive resin composition of this invention on this transparent conductive film, a film is formed by heating a coating surface. As a transparent substrate used for formation of a spacer, a glass substrate, a resin substrate, etc. are mentioned, More specifically, glass substrates, such as a soda-lime glass and an alkali free glass, etc. are mentioned. When a coating film is formed, radiation is irradiated to 60 mJ / cm <2> or less in the state which put the photomask of a predetermined form on the obtained coating film. As the radiation used, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X rays and the like can be used, but radiation having a wavelength in the range of 190 to 450 nm is preferable. Next, by developing the film after exposure, an unnecessary part is removed and a predetermined pattern is formed.

Then, the spacer which has a predetermined shape can be obtained by heating and hardening for 30 to 2 hours with a heating apparatus, such as a hotplate or oven of 150-300 degreeC.

The spacer manufactured using the photosensitive resin composition according to the present invention defines a point where the CD is raised at the bottom of the pattern by 20% to the bottom CD (a) and the point where the 95% is raised as the top CD (b), and the length of (b) is ( The top / bottom ratio calculated by dividing by the length of a) and multiplying by 100 (= b / a × 100) may have a value of 50 or more, preferably 80 or more.

In addition, when the pattern is formed by performing proximity exposure with the photosensitive composition including the compound represented by Chemical Formula 1 or Chemical Formula 2, an effect of forming a high-resolution fine pattern with high sensitivity may be obtained.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described. However, the following embodiments are merely preferred embodiments of the present invention, and the present invention is not limited to the following embodiments.

<Manufacture example 1> Alkali-soluble resin A manufacture

In a reaction vessel equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis isobutyronitrile was dissolved in 200 parts by weight of propylene glycol monomethyl ether acetate as a polymerization initiator based on 100 parts by weight of an alkali-soluble resin. . Subsequently, 10 parts by weight of styrene, 15 parts by weight of methacrylic acid, 50 parts by weight of glycidyl methacrylate, and 25 parts by weight of dicyclopentanyl methacrylate were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 70 ° C. and maintained at this temperature for 6 hours to obtain a polymer solution containing a copolymer (hereinafter referred to as alkali soluble resin A). Solid content concentration of the obtained polymer solution was 30 weight%.

&Lt; Example 1 >

100 parts by weight of the copolymer solution [A] obtained in Preparation Example 1 (solid content) and [B] as a polyfunctional acrylic monomer having two or more ethylenically unsaturated bonds, dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Kaya CU)) 100 parts by weight, 5 parts by weight of 1,2-octanedione-1 [(4-phenylthio) phenyl] -2-benzoyl oxime as the photopolymerization initiator [C], propylene glycol monomethyl ether acetate as the solvent [D] Was used so that the total solids in the photosensitive resin composition was 30% by weight.

<Examples 1 to 8 and Comparative Examples 1 to 2>

Each composition solution was produced like Example 1 except using each component shown in following Table 1 as a component [A], a component [B], and a component [C].

division [A] component weight part [B] component weight part [C] component weight part Example 1 100 100 D-1 (5) Example 2 100 100 D-1 (10) Example 3 100 100 D-1 (2) / D-3 (5) Example 4 100 100 D-1 (2) / D-4 (5) Example 5 100 100 D-2 (5) Example 6 100 100 D-2 (10) Example 7 100 100 D-2 (2) / D-3 (5) Example 8 100 100 D-2 (2) / D-4 (5) Comparative Example 1 100 100 D-3 (10) Comparative Example 2 100 100 D-4 (10)

Note) The components of [D] in Table 1 are as follows.

D-1: 1,2-octanedione-1 [(4-phenylthio) phenyl] -2-benzoyl oxime

D-2: 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] ethane-1-one oxime-O-acetate

D-3: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one

D-4: 2-benzyl-2- (dimethylamino) -1- (morpholinophenyl) butan-1-one

Characterization

After the pattern was formed by the method described above with the compositions prepared in Examples 1 to 8 and Comparative Examples 1 and 2, physical properties were evaluated by the following method, and the results are shown in Table 2 below.

(1) Top / Bottom ratio of the pattern (in T / B ratio)

After the pattern was formed on the glass substrate on which the ITO was sputtered, the pattern was formed by observation with an electron microscope, and the bottom CD (a) and the top CD (b) were defined as 20% and 95% respectively. The value obtained by dividing the length of (b) by the length of (a) and multiplying by 100 (= b / a × 100) is defined as the T / B ratio.

(2) flatness

After the pattern was formed on the glass substrate on which ITO was spattered, the difference between the maximum thickness and the minimum thickness was obtained by using surface irregularities 3D-profilers of 25 different coating films, respectively. Was calculated.

<Equation 1>

Flatness = (Max Thickness-Min Thickness) ÷ (Max Thickness + Min Thickness) × 100

(3) sensitivity

Using a proximity exposure machine, the exposure gap was maintained at 50 μm, and patterns were formed while changing the exposure amounts to 20, 40, 60, 80, and 100 mJ / cm 2, respectively. The thickness of the thus formed pattern was measured for each exposure amount, and the minimum exposure amount having a thickness change of 200 kPa or less was wound. When this exposure amount is 60 mJ / cm <2> or less, it can be said that a sensitivity is favorable.

(4) solvent resistance

After the glass substrate on which the film was formed was immersed in a solution of 5% HCl, NMP, IPA, and acetone at 30 ° C. for 30 minutes, the change in appearance and thickness of the protective film was observed to evaluate the solvent resistance of the film.

Good: Appearance, no thickness change, Poor: Appearance, thickness change

(5) Method of measuring compression displacement and recovery rate

In the present invention, a dot pattern having a thickness T formed from the photosensitive composition having a thickness of 3 μm and a pattern width W of 9 (± 2) μm is used as a basic condition for measuring mechanical properties of the pattern, that is, compression displacement and elastic recovery rate. The shape was determined. SHIMADZU's ultra-compact hardness tester (model name: DHU-W201S) was used for measuring the compression displacement and elastic recovery rate.

A flat indenter with a diameter of 50㎛ was used as the indenter for pressing the pattern. The measurement principle was carried out by a load-unload method. The test loading standard was 5gf / ㎠, the load speed was 0.45 gf / sec, and the maintenance time ( The holding time was constantly performed at 5 seconds.

Compression displacement refers to the length (D1) the pattern is entered when given a constant force as shown in FIG. In Figure 1, A is the pattern state before pressing with the indenter, B is the pattern state with the indenter pressed, C is the restored pattern state when the pressing force is removed, T is the pattern height (film thickness), 3 (± 3 ) Μm, D1 is the change in compression until a constant force is applied (µm), and D2 is the difference between the initial film thickness and the final restored state.

Recovery rates can be expressed in two ways.

The first means the ratio of the recovered distance (D1-D2) to the length (D1) entered when given a constant force as shown in Figure 1 (recovery rate A), the second is the final for the height (T) of the original pattern It may mean the pattern height (T-D2) after deformation.

This is summarized as follows.

Compression Displacement = D1 (㎛)

Recovery Rate A (%) = (D1-D2) ÷ D1 × 100

Recovery Rate B (%) = (T-D2) ÷ T × 100

T / B ratio
(%) flatness
(%) Sensitivity (mJ / cm ² ) Solvent resistance Recovery rate A
(%) Recovery rate B
(%) Example 1 88 <1 40 Good 60 83 Example 2 84 <1 30 Good 58 82 Example 3 71 <1 60 Good 55 77 Example 4 65 <1 60 Good 54 76 Example 5 83 <1 30 Good 58 81 Example 6 80 <1 20 Good 59 80 Example 7 73 <1 60 Good 53 75 Example 8 68 <1 60 Good 54 74 Comparative Example 1 47 2 > 100 Good 49 70 Comparative Example 2 42 2 > 100 Good 48 68

As shown in Table 2, the photosensitive resin composition prepared in Examples 1 to 8 can be seen that the T / B ratio is improved, the sensitivity is faster, and the flatness is improved using the general formula (1).

In particular, in order to increase the T / B ratio, the length of the patterned top CD (b) should be equal to the length of the bottom CD (a), which is selected from the compound represented by Formula 1 and the compound represented by Formula 2 When the pattern is formed of the photosensitive composition including one or more, the length of (a) and the length of (b) become substantially the same, thereby obtaining an effect of increasing the T / B ratio.

In addition, a dot pattern having a thickness T formed from the photosensitive composition of the present invention having a thickness of 3 µm and a pattern W of 9 (± 2) µm satisfies the above requirements, whereby a color liquid crystal of the TFT method is used. When forming the column spacer of the display device, it is possible to prevent excessive erosion of the pattern according to securing the properties of uniformity with respect to thickness (increasing the compression displacement and improving the recovery rate) and to easily control the thickness by compression. There is this.

2 and 3 after forming a pattern with the photosensitive resin composition according to Examples 1 and 3 of the present invention, the pattern is measured using an electron microscope.

As shown in FIGS. 2 and 3, it is understood that optical radicals are generated quickly even with a small exposure amount, so that the sensitivity is increased and the T / B ratio is improved.

All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (12)

[A] alkali-soluble resin, [B] unsaturated unsaturated ethylene monomer, [C] containing at least one photoinitiator selected from a compound represented by the following formula (1) and a compound represented by the following formula (2) and a solvent [D] Photosensitive resin composition.

<Formula 1>

Wherein R ₁ is a hydrogen atom, a halogen atom, a phenyl group, a phenoxycarbonyl group, C ₁ to C ₂₀ C ₂ to C ₂₀ substituted by alkyl, halogen atom or phenyl group Alkyl group, C ₁ to C ₆ phosphorus An alkyl group or a halogen atom or -OR, wherein R is a hydrogen atom, a hydroxy group, a thiol group, a cyano group, an alkyl group having ₁ to ₂₀ carbon atoms, a phenyl group, an alkenoxyl group having ₃ to ₆ carbon atoms, -OCH ₂ CH ₂ CN, -OCO-phenyl group) or -OCH ₂ CH ₂ (CO) OR wherein R is C ₁ ~ C ₄ Alkyl group) or -O (CO) -R wherein R is C ₁ -C ₄ Is a phenyl group substituted with an alkyl group, and C ₁ to C ₆ An alkyl group or a phenyl group or -OR, wherein R is a hydrogen atom, a hydroxy group, a thiol group, a cyano group, an alkyl group having ₁ to ₂₀ carbon atoms, a phenyl group, an alkenoxyl group having ₃ to ₆ carbon atoms, -OCH ₂ CH ₂ CN,- OCO-phenyl group) or -OCH ₂ CH ₂ (CO) OR where R is C ₁ ~ C ₄ Alkyl group) or -O (CO) -R wherein R is C ₁ -C ₄ An alkanoyl group substituted with an alkyl group, C ₁ to C ₆ An alkyl group or a phenyl group or -OR, wherein R is a hydrogen atom, a hydroxy group, a thiol group, a cyano group, an alkyl group having ₁ to ₂₀ carbon atoms, a phenyl group, an alkenoxyl group having ₃ to ₆ carbon atoms, -OCH ₂ CH ₂ CN,- OCO-phenyl group) or -OCH ₂ CH ₂ (CO) OR where R is C ₁ ~ C ₄ Alkyl group) or -O (CO) -R wherein R is C ₁ -C ₄ An alkyl group.), A C ₂ to C ₁₂ alkoxycarbonyl group substituted by one or more -O- or hydroxyl groups, C ₁ to C ₆ An alkyl group or a halogen atom or a phenyl group or -OR, wherein R is a hydrogen atom, a hydroxy group, a thiol group, a cyano group, an alkyl group having ₁ to ₂₀ carbon atoms, a phenyl group, an alkenoxyl group having ₃ to ₆ carbon atoms, -OCH ₂ CH ₂ CN, -OCO-phenyl group) or -OCH ₂ CH ₂ (CO) OR, wherein R is C ₁ ~ C ₄ Alkyl group) or -O (CO) -R wherein R is C ₁ -C ₄ Phenoxycarbonyl, cyano group or NO ₂ or C ₁ to C ₄ Haloalkyl group or C ₁ to C ₁₂ phosphorus An alkyl group or SO ₂ -R wherein R is C ₁ to C ₆ S (O) m-phenyl group substituted with an alkyl group, wherein m is an integer of 2 to 6, and C ₁ to C ₁₂ SO ₂ -Ophenyl group substituted by an alkyl group,
R ₂ is a hydrogen atom, a halogen atom, C ₃ ~ C ₈ substituted with an alkyl group having ₁ to ₆ carbon atoms, a phenyl group, a cyano group, a phenoxy group, a cyano group or a phenyl group Cycloalkyl group, a cyano group or a phenyl group substituted with C ₁ ~ C ₁₂ is a C ₂ alkyl group substituted by a cyano group or a phenyl group is ₅ ~ C Alkenyl group, a cyano group or a halogen-substituted phenyl group, a cyano group or a halogen atom-substituted C ₁ ~ C ₈ alkoxy group, a cyano cost as group or halogen-substituted benzyl oxy group, a halogen-substituted phenoxy group, C ₁ ~ C Phenoxy group substituted with a ₆ -membered alkyl group.)

<Formula 2>

Wherein R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, a halogen atom, a phenyl group, a cyano group, and C ₁ to C ₁₂ C ₃ to C ₈ substituted with alkyl, phenyl or cyano groups Cycloalkyl group, a C ₂ substituted with a phenyl group or a cyano group, a C ₁ ~ C ₁₂ alkyl group, a phenyl group or a cyano group substituted with a ₅ ~ C Alkenyl, C ₁ to C ₆ phosphorus With an alkyl group or a halogen atom or a cyano group or OA ₁ or SA ₂ or NA ₃ A ₄ Substituted phenyl groups, C ₁ to C ₆ With an alkyl group or a halogen atom or a cyano group or OA ₁ or SA ₂ or NA ₃ A ₄ Substituted C ₁ ~ C ₈ phosphorus alkoxy group, C ₁ ~ C ₆ phosphorus With an alkyl group or a halogen atom or a cyano group or OA ₁ or SA ₂ or NA ₃ A ₄ Substituted Benzyloxy group, C ₁ to C ₆ phosphorus Phenoxy group substituted with an alkyl group or a halogen atom.
R ₆ is a phenyl group, a naphthyl group, a benzoyl group or a naphthoyl group. They are substituted by halogen or C ₂ -C ₁₂ alkyl group or C ₃ -C ₈ cycloalkyl group or benzyl group or phenyl group or phenoxycarbonyl group, respectively; Each substituted with a phenyl group substituted by OA ₁ or SA ₂ or NA ₃ A ₄ ; Substituted with a C ₂ to C ₁₂ alkoxycarbonyl group each substituted with —O— or a hydroxy group; Or may be substituted by OA ₁ or SA ₂ or SOA ₂ or SO ₂ A ₂ or NA ₃ A ₄ , respectively.
A ₁ is a hydrogen atom, a hydroxyl group, a thiol group, a cyano group, C ₁ to C ₂₀ Alkyl group, C ₃ to C ₆ phosphorus C ₁ ~ C ₃ substituted with alkenoxyl, phenyl groups Alkyl group, -OCH ₂ CH ₂ CN, -OCH ₂ CH ₂ (CO) OR, wherein R is C ₁ -C ₈ Alkyl group), -O (CO) R (where R is a phenyl group, an alkyl group having ₁ to ₈ carbon atoms),-(CO) OR (where R is a hydrogen atom, C ₂ to C ₁₂ Is an alkyl group), -OR (wherein R is a halogen atom, a hydroxy group, C ₂ ~ C ₁₂ Alkyl group,-(CH ₂ CH ₂ O) _{n + 1} H (n is an integer from 1 to 5),-(CH ₂ CH ₂ O) _n (CO) R, where n is an integer from 1 to 5 , R is C ₁ to C ₈ Alkyl group), C ₁ ~ C ₈ Alkanoyl group, C ₂ ~ C ₁₂ phosphorus Alkenyl, C ₃ ~ C ₆ phosphorus Alkenoyl, C ₃ ~ C ₈ phosphorus Cycloalkyl group, C ₁ to C ₁₂ phosphorus Alkoxy group, phenoxy group, C ₁ ~ C ₁₂ phosphorus Alkylsulfanyl group, phenylsulfanyl group, -NR where R is C ₁ -C ₁₂ An alkyl group.), A phenyl group or a naphthyl group substituted with a diphenylamino group.)
A ₂ is hydrogen atom, hydroxy group, thiol group, cyano group, unsubstituted C ₁ ~ C ₂₀ Alkyl group, unsubstituted C ₂ ~ C ₁₂ phosphorus Alkenyl, unsubstituted C ₃ ~ C ₈ phosphorus Cycloalkyl group, unsubstituted C ₃ ~ C ₆ phosphorus C ₂ ~ C ₁₂ substituted with alkenoxyl, oxygen or sulfur C ₁ to C ₈ substituted with alkyl, oxygen or sulfur atoms C ₂ ~ C ₁₂ phosphorus substituted with an alkanoyl group, oxygen atom or sulfur atom C ₃ ~ C ₆ substituted with alkenyl, oxygen or sulfur atoms Alkenoyl group, C ₁ to C ₆ A benzoyl group substituted with an alkyl group, a benzoyl group substituted with a halogen, a benzoyl group substituted with a hydroxy group, and C ₁ to C ₄ A benzoyl group substituted with an alkoxy group, C ₁ to C ₄ A benzoyl group substituted with an alkylsulfanyl group,
A ₃ and A ₄ are each independently a hydrogen atom, a benzoyl group, C ₁ to C ₂₀ Alkyl group, C ₂ ~ C ₄ phosphorus Hydroxyalkyl group, C ₂ ~ C ₁₀ phosphorus Alkoxyalkyl group, C ₂ ~ C ₅ phosphorus Alkenyl, C ₃ ~ C ₈ phosphorus Cycloalkyl group, phenyl-R, wherein R is C ₁ to C ₃ Alkyl group), C ₁ ~ C ₈ Alkanoyl group, C ₃ ~ C ₁₂ phosphorus Alkenoyl group, C ₃ to C ₁₂ Benzoyl group, C ₁ to C ₁₂ phosphorus A phenyl group substituted with an alkyl group, a phenyl group substituted with a benzoyl group, C ₁ to C ₁₂ Phenyl group substituted by alkoxy group, C ₁ to C ₁₂ Naphthyl group substituted with alkyl group, naphthyl group substituted with benzoyl group, C ₁ to C ₁₂ phosphorus Naphthyl, hydroxy or C ₁ to C ₄ substituted with an alkoxy group Alkoxy or C ₂ to C ₄ C ₂ ~ C ₆ substituted with an alkanoyloxy group or a benzooxy group Alkylene group.) The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator which is a compound represented by Chemical Formula 1 is a compound represented by the following Chemical Formula 3.

<Formula 3>

The photosensitive resin composition of claim 1, wherein the photopolymerization initiator is a compound represented by Chemical Formula 2.

&Lt; Formula 4 >

According to claim 1, 10 to 300 parts by weight of the [B] unsaturated unsaturated ethylene monomer based on 100 parts by weight of the [A] alkali-soluble resin, [C] the compound represented by the formula (1) and the compound represented by the formula (2) The photosensitive resin composition containing 1-30 weight part of any 1 or more photoinitiators selected from 200-800 weight part of [D] solvents. The weight ratio of the compound represented by the formula (1) to the compound represented by the formula (2) when the compound represented by the formula (1) and the compound represented by the formula (2) is mixed as the [C] photopolymerization initiator 30: 1-30 photosensitive resin composition. The method of claim 1, wherein the [A] alkali-soluble resin is selected from the group consisting of a single or a mixture of two or more selected from [a1] unsaturated carboxylic acid and unsaturated carboxylic anhydride; And [a2] A photosensitive resin composition which is a copolymer of an epoxy group-containing unsaturated compound. The method of claim 6, wherein the [A] alkali-soluble resin is selected from the group consisting of a single or a mixture of two or more selected from [a1] unsaturated carboxylic acid and unsaturated carboxylic anhydride; [a2] epoxy group-containing unsaturated compounds; And [a3] copolymers of olefinically unsaturated carboxylic acid ester compounds other than the above [a1] and [a2]; Or [a1] single or a mixture of two or more selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides; [a2] epoxy group-containing unsaturated compounds; And [a4] a copolymer of at least one compound selected from olefinically unsaturated compounds other than [a1], [a2] and [a3]; Or [a1] single or a mixture of two or more selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides; [a2] epoxy group-containing unsaturated compounds; [a3] Olefinic unsaturated carboxylic ester compound other than said [a1] and [a2]; And [a4] A photosensitive resin composition which is a copolymer of at least one compound selected from olefinically unsaturated compounds other than [a1], [a2] and [a3]. The photosensitive resin composition of claim 6, wherein the component [a1]: [a2] is included in a weight ratio of 1: 1.3 to 3.5. The photosensitive resin composition of Claim 6 in which the said [A] alkali-soluble resin contains the said [a4] component at 10-70 weight part with respect to 100 weight part of [A] alkali-soluble resin solid content. A spacer produced using the composition according to claim 1. The method of claim 10, wherein the spacer is defined as the bottom CD (a) 20% point raised from the bottom of the pattern, the top 95 (95%) point raised to the top CD (b), the length of (b) to the length of (a) Spacers with a top / bottom ratio of 50 or more, calculated by dividing and multiplying by 100 (= b / a × 100). A liquid crystal display device comprising the spacer according to claim 10.

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