JP2017211650A - Photosensitive resin composition and photocuring pattern produced therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that can form a photocuring pattern having hard properties and resisting deformation due to external pressure while showing an excellent elastic recovery rate after curing, and can form a photocuring pattern having high resolution, excellent substrate adhesion, and a high T/B ratio.SOLUTION: A photosensitive resin composition contains an alkali-soluble resin having an alicyclic epoxy group-containing repeating unit, a photopolymerization initiator containing a compound represented by chemical formula 1, a photopolymerizable compound, and a solvent.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a photosensitive resin composition, a photocuring pattern produced from the composition, and an image display device provided with the photocuring pattern.

  In general display devices, silica beads or plastic beads having a certain diameter have been used to maintain a certain distance between the upper and lower substrates. However, when these beads are randomly dispersed on the substrate and located inside the pixel, there is a problem that the aperture ratio is lowered and a light leakage phenomenon occurs. In order to solve this problem, a spacer formed by photolithography is used inside the display device. Currently, the spacer used in most display devices is formed by photolithography.

  A method for forming a spacer by photolithography is to apply a photosensitive resin composition on a substrate, irradiate ultraviolet rays through the mask, and then at a desired position on the substrate according to a pattern formed on the mask through a development process. It is to form a spacer.

  Recently, the demand for touch panels is increasing due to the spread of smartphones and tablet PCs. As a result, the spacer that maintains the distance between the color filter substrate and the array substrate constituting the display device is not only elastic recovery rate, which is a basic characteristic, but also a hard pixel that is not deformed by external pressure ( hard) characteristics and adhesion to the substrate are required. Thus, research on photosensitive resin compositions has been actively conducted, but it still does not satisfy the requirements such as the elastic recovery rate and the adhesion to the substrate.

  As an example, in Korean Patent Publication No. 2009-0056862, a photosensitive resin composition comprising a binder resin that is a copolymer of an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride and an aliphatic polycyclic epoxy compound. However, there is a limit to sufficiently realizing the adhesion force and the elastic recovery rate with the base material.

Korean Published Patent No. 2009-0056862

  An object of the present invention is to provide a photosensitive resin composition capable of forming a photocuring pattern having a hard property with little elasticity due to external pressure while having an excellent elastic recovery rate after curing. And

  Moreover, an object of this invention is to provide the photosensitive resin composition which can implement | achieve a high resolution pattern at the time of hardening.

  Furthermore, an object of this invention is to provide the photosensitive resin composition in which the formed pattern has the board | substrate adhesive force which was excellent at the time of hardening.

  Moreover, an object of this invention is to provide the photosensitive resin composition which has the value of the outstanding T / B ratio at the time of hardening.

  Another object of the present invention is to provide a photocuring pattern produced from the above-described photosensitive resin composition, and an image display device provided with the photocuring pattern.

  1. A photosensitive resin composition comprising an alkali-soluble resin having an alicyclic epoxy group-containing repeating unit, a photopolymerization initiator containing a compound represented by the following chemical formula 1, a photopolymerizable compound, and a solvent.

（化学式１中、Ｒ_３は、Ｃ１−Ｃ２０アルキル基であり、Ｒ_４及びＲ_５は、それぞれ独立して、Ｃ１−Ｃ２０アルキル基、Ｃ６−Ｃ２０アリール基、またはＣ３−Ｃ２０シクロアルキル基であり、Ａは、ニトロ基またはシアノ基である。）

(In Chemical Formula 1, R ₃ is a C1-C20 alkyl group, and R ₄ and R ₅ are each independently a C1-C20 alkyl group, a C6-C20 aryl group, or a C3-C20 cycloalkyl group. , A is a nitro group or a cyano group.)

2. In the item 1, the alkali-soluble resin is
A first resin polymerized containing at least one compound selected from the group consisting of compounds represented by the following chemical formulas 2 and 3;
The photosensitive resin composition containing the 2nd resin which has the said alicyclic epoxy group containing repeating unit.

（化学式２中、Ｒ_１は、水素原子、Ｃ１−Ｃ１２アルキル基、アリル基、フェニル基、ベンジル基、ハロゲン基、またはＣ１−Ｃ８アルコキシ基である。）

(In Chemical Formula 2, R ₁ is a hydrogen atom, a C1-C12 alkyl group, an allyl group, a phenyl group, a benzyl group, a halogen group, or a C1-C8 alkoxy group.)

（化学式３中、Ｒ_２は、水素原子、Ｃ１−Ｃ１２アルキル基、アリル基、フェニル基、ベンジル基、ハロゲン基、またはＣ１−Ｃ８アルコキシ基であり、ｎは、１〜１０の整数である。）

(In Chemical Formula 3, R ₂ is a hydrogen atom, a C1-C12 alkyl group, an allyl group, a phenyl group, a benzyl group, a halogen group, or a C1-C8 alkoxy group, and n is an integer of 1-10. )

  3. 2. The photosensitive resin composition according to item 2, wherein the first resin further has a repeating unit containing an alkyl-substituted maleimide or an aryl-substituted maleimide.

4). In the item 1, the alkali-soluble resin is
A second resin having the alicyclic epoxy group-containing repeating unit;
A photosensitive resin composition comprising a third resin having a norbornene repeating unit.

  5. The photosensitive resin composition according to item 4, wherein the third resin further includes at least one repeating unit selected from the group consisting of a benzene ring-containing repeating unit, a carboxylic acid-containing repeating unit, and an acrylate repeating unit.

  6). In the item 1, the alicyclic epoxy group-containing repeating unit is a photosensitive resin composition derived from at least one selected from the group consisting of compounds represented by the following chemical formula 4 or chemical formula 5.

（化学式４中、Ｒ_６は、水素原子またはヒドロキシ基で置換されているか又は置換されていないＣ１−Ｃ４アルキル基であり、
Ｘは、単結合またはヘテロ原子を含有しているか又は含有していないＣ１−Ｃ６アルキレン基である。）

(In Chemical Formula 4, R ₆ is a C1-C4 alkyl group substituted or unsubstituted with a hydrogen atom or a hydroxy group,
X is a C1-C6 alkylene group containing or not containing a single bond or heteroatom. )

（化学式５中、Ｒ_７は、水素原子またはヒドロキシ基で置換されているか又は置換されていないＣ１−Ｃ４アルキル基であり、
Ｘは、単結合またはヘテロ原子を含有しているか又は含有していないＣ１−Ｃ６アルキレン基である。）

(In Chemical Formula 5, R ₇ is a C1-C4 alkyl group substituted or unsubstituted with a hydrogen atom or a hydroxy group,
X is a C1-C6 alkylene group containing or not containing a single bond or heteroatom. )

7). In the item 1, in the chemical formula 1, R ₃ is methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, an i-pentyl group, an n-hexyl group, or an i-hexyl group,
R ₄ and R ₅ are each independently a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, i- A photosensitive resin composition, which is a pentyl group, n-hexyl group, i-hexyl group, phenyl group, naphthyl group, biphenyl group, terphenyl group, anthryl group, indenyl group, or penanthryl group.

  8). In the item 1, the photopolymerization initiator further includes at least one of an acetophenone derivative compound or a biimidazole derivative compound.

  9. 8. The photosensitive resin composition according to item 8, wherein the photopolymerization initiator contains 40 to 90% by weight of the compound of the chemical formula 1 with respect to the total weight of the photopolymerization initiator.

  10. In item 1, the content of the photopolymerization initiator is 0.1 to 40 parts by weight with respect to a total of 100 parts by weight based on the solid content of the alkali-soluble resin and the photopolymerizable compound. Photosensitive resin composition.

  11. In the item 1, the alkali-soluble resin is a photosensitive resin composition containing 5 to 90% by weight based on the solid content of the photosensitive resin composition.

  12 The photocuring pattern manufactured with the said photosensitive resin composition as described in any one of the said items 1-11.

  13. In the item 12, the photocuring pattern is a photocuring pattern selected from the group consisting of an array flattening film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, and a spacer pattern.

  14 The image display apparatus provided with the said photocuring pattern of the said item 12.

  The photosensitive resin composition of the present invention can form a photocuring pattern having a hard property with little deformation due to external pressure, while having an excellent elastic recovery rate after curing.

  Moreover, the photosensitive resin composition of the present invention can realize a high-resolution pattern when cured.

  Furthermore, the photosensitive resin composition of this invention has the board | substrate adhesive force in which the formed pattern was excellent at the time of hardening.

  Moreover, the photosensitive resin composition of this invention shows the value of the outstanding T / B ratio.

  Therefore, the photosensitive resin composition of the present invention can be usefully used for forming a photocuring pattern, preferably a spacer pattern, and manufacturing an image display device.

FIG. 1 is a diagram schematically showing the definition of the T / B ratio.

  The present invention includes a photosensitive resin composition containing an alkali-soluble resin, a photopolymerization initiator, a photopolymerizable compound, and a solvent, a photocuring pattern produced from the composition, and the photocuring pattern. The present invention relates to an image display device.

  Hereinafter, the present invention will be described in detail.

<Photosensitive resin composition>
Photopolymerizable Initiator The photosensitive resin composition according to the example of the present invention includes a photopolymerizable initiator, and the photopolymerizable initiator includes a compound represented by the following chemical formula 1.

化学式１中、Ｒ_３は、Ｃ１−Ｃ２０アルキル基であり、Ｒ_４及びＲ_５は、それぞれ独立して、Ｃ１−Ｃ２０アルキル基、Ｃ６−Ｃ２０アリール基、またはＣ３−Ｃ２０シクロアルキル基であり、Ａは、ニトロ基またはシアノ基である。

In Chemical Formula 1, R ₃ is a C1-C20 alkyl group, R ₄ and R ₅ are each independently a C1-C20 alkyl group, a C6-C20 aryl group, or a C3-C20 cycloalkyl group, A is a nitro group or a cyano group.

  The photosensitive resin composition of the present invention can maximize the expected effect of the alkali-soluble resin described later by including a photopolymerization initiator containing the compound represented by the chemical formula 1, and has excellent sensitivity. A pattern having excellent substrate adhesion can be formed, and the formed pattern has excellent pattern stability, heat resistance, chemical resistance, and the like.

  Substituents containing “alkyl group”, “alkoxy group” and other “alkyl group” moieties described herein include all linear or branched, and “cycloalkyl group” is simply It includes not only ring systems but also polycyclic hydrocarbons. An “aryl group” as described herein is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, suitably 4-7, preferably 5 or 6, on each ring. Including a single or fused ring system containing a plurality of ring atoms up to a form in which multiple aryl groups are linked by a single bond. “Hydroxyalkyl group” means an OH-alkyl group in which a hydroxy group is bonded to the alkyl group defined above. The “hydroxyalkoxyalkyl group” means a hydroxyalkyl-O-alkyl group in which an alkoxy group is bonded to the hydroxyalkyl group.

  In addition, the “C1-C20 alkyl” group described herein is preferably a C1-C10 alkyl group, more preferably a C1-C6 alkyl group. A “C6-C20 aryl” group is preferably a C6-C18 aryl group. A “C1-C20 alkoxy” group is preferably a C1-C10 alkoxy group, more preferably a C1-C4 alkoxy group. The “C6-C20 aryl C1-C20 alkyl” group is preferably a C6-C18 aryl C1-C10 alkyl group, more preferably a C6-C18 aryl C1-C6 alkyl group. A “hydroxy C1-C20 alkyl” group is preferably a hydroxy C1-C10 alkyl group, more preferably a hydroxy C1-C6 alkyl group. A “hydroxy C1-C20 alkoxy C1-C20 alkyl” group is preferably a hydroxy C1-C10 alkoxy C1-C10 alkyl group, more preferably a hydroxy C1-C4 alkoxy C1-C6 alkyl group. A “C3-C20 cycloalkyl” group is preferably a C3-C10 cycloalkyl group.

Specifically, R _{3 to} R ₅ are each independently a hydrogen atom, bromo group, chloro group, iodo group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group. I-butyl group, t-butyl group, n-pentyl group, i-pentyl group, n-hexyl group, i-hexyl group, phenyl group, naphthyl group, biphenyl group, terphenyl group, anthryl group, indenyl group, Penanthryl group, methoxy group, ethoxy group, n-propyloxy group, i-propyloxy group, n-butoxy group, i-butoxy group, t-butoxy group, hydroxymethyl group, hydroxyethyl group, hydroxy n-propyl group, Hydroxy n-butyl group, hydroxy i-butyl group, hydroxy n-pentyl group, hydroxy i-pentyl group, hydroxy n-hexyl group, hydroxy i Hexyl group, hydroxymethoxymethyl group, hydroxymethoxyethyl group, hydroxymethoxypropyl group, hydroxymethoxybutyl group, hydroxyethoxymethyl group, hydroxyethoxyethyl group, hydroxyethoxypropyl group, hydroxyethoxybutyl group, hydroxyethoxypentyl group, or hydroxy An ethoxyhexyl group.

  A is a hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, phenyl group, naphthyl group, biphenyl group, terphenyl. Group, anthryl group, indenyl group, penanthryl group, methoxy group, ethoxy group, propyloxy group, butoxy group, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxymethoxymethyl group, hydroxymethoxyethyl group, It may be a hydroxymethoxypropyl group, hydroxymethoxybutyl group, hydroxyethoxymethyl group, hydroxyethoxyethyl group, hydroxyethoxypropyl group, hydroxyethoxybutyl group, amino group, nitro group, cyano group, or hydroxy group. It is not limited.

More specifically, R ₃ may be a hydrogen atom or an n-butyl group, R ₄ may be a methyl group, and R ₅ may be a methyl group, an n-butyl group, or a phenyl group.

  The photopolymerization initiator according to the present invention may further include at least one of an acetophenone derivative compound or a biimidazole derivative compound in addition to the compound represented by Formula 1. When an acetophenone derivative compound or a biimidazole derivative compound is further used in combination, the T / B ratio of the pattern can be further improved together with excellent substrate adhesion.

  As shown in FIG. 1, the T / B ratio is a value obtained by dividing the upper diameter of the spacer pattern by the lower diameter, and the larger the T / B ratio, the better. In the present invention, the upper part of the pattern is defined as a horizontal plane at 95% of the overall height from the bottom with respect to the overall height of the pattern. Further, the lower part of the pattern is defined as a horizontal plane at a location 5% of the total height from the bottom with respect to the total height of the pattern.

  Examples of the acetophenone derivative compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl. ] -2-Methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one oligomer, diphenyl (2,4,6- And trimethylbenzoyl) -phosphine oxide.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl)- 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′- Bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxyphenyl) biimidazole, an imidazole compound in which the phenyl group at the 4,4 ′, 5,5 ′ position is substituted with a carboalkoxy group Etc. Among these, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′, 4-tris (2-chlorophenyl) -5- (3,4-dimethoxyphenyl) -4 ′, 5′-diphenyl-1,1′-biimidazole Is preferably used.

  The photopolymerization initiator preferably contains 40 to 90% by weight, more preferably 40 to 70% by weight, of the compound represented by Chemical Formula 1 with respect to the total weight of the photopolymerization initiator. Within the above range, a further improved T / B ratio value of the pattern can be obtained.

  The content ratio of the acetophenone derivative and the biimidazole derivative is not particularly limited, and may be, for example, 1: 9 to 9: 1.

  Moreover, as long as the effect of the present invention is not impaired, other photopolymerization initiators usually used in this field may be further used in combination. For example, it may further contain a benzoin compound, a benzophenone compound, a thioxanthone compound, an anthracene compound, and the like. These can be used alone or in combination of two or more.

  The photopolymerization initiator may be used in combination with a photopolymerization initiation assistant. When a photopolymerization initiation assistant is used in combination with the photopolymerization initiator, the photosensitive resin composition containing them becomes more sensitive, and it is desirable because it can improve the productivity during spacer formation.

  As the photopolymerization initiation assistant, amine compounds and carboxylic acid compounds are preferably used.

  The usage-amount of a photoinitiator is 0.1-40 weight part with respect to a total of 100 weight part of the alkali-soluble resin and photopolymerizable compound mentioned later, Preferably it is 1-30 weight part. When the content is in the above range, the photosensitive resin composition is highly sensitive, and the strength and smoothness of the spacer formed using this composition are preferable.

Alkali-soluble resin Alkali-soluble resin can be provided as a binder resin that provides adhesion to a substrate and enables the formation of a coating film. According to an exemplary embodiment, the alkali-soluble resin may be reactive to light and heat, and may be soluble in an alkali developer used in a development process.

  According to an exemplary embodiment, the alkali-soluble resin according to the present invention is a first resin that is polymerized by including at least one compound (a11) selected from compounds represented by the following Chemical Formula 2 or Chemical Formula 3. Can be included.

化学式２中、Ｒ_１は、水素原子、Ｃ１−１２アルキル基、アリル基、フェニル基、ベンジル基、ハロゲン基、またはＣ１−Ｃ８アルコキシ基を示す。

In Chemical Formula 2, R ₁ represents a hydrogen atom, a C1-12 alkyl group, an allyl group, a phenyl group, a benzyl group, a halogen group, or a C1-C8 alkoxy group.

化学式３中、Ｒ_２は、水素原子、Ｃ１−Ｃ１２アルキル基、アリル基、フェニル基、ベンジル基、ハロゲン基、またはＣ１−Ｃ８アルコキシ基であり、ｎは、１〜１０の整数であってもよい。

In Chemical Formula 3, R ₂ is a hydrogen atom, a C1-C12 alkyl group, an allyl group, a phenyl group, a benzyl group, a halogen group, or a C1-C8 alkoxy group, and n may be an integer of 1-10. Good.

  The alkali-soluble resin according to the present invention has a repeating unit derived from at least one compound selected from the chemical formula 2 or the chemical formula 3 that is bulky, thereby increasing the film density during curing. Therefore, it is possible to form a photocuring pattern having a hard property with little deformation due to external pressure while having an excellent elastic recovery rate, and a high-resolution pattern can be formed.

  In addition to at least one compound (a11) selected from Chemical Formula 2 or Chemical Formula 3, the first resin of the alkali-soluble resin according to the present invention includes an unsaturated bond known in the art in order to exhibit alkali solubility. The polymerization may further include the compound (a12) having a carboxyl group.

  As the compound (a12) having an unsaturated bond and a carboxyl group, any carboxylic acid compound having an unsaturated double bond capable of polymerization can be used without limitation. Examples of the compound (a12) having an unsaturated bond and a carboxyl group include many compounds having two or more carboxyl groups in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid. And carboxylic acid. Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid. Examples of the unsaturated polyvalent carboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the like. The polyvalent carboxylic acid may be an acid anhydride, and examples of the unsaturated polyvalent carboxylic acid anhydride include maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, and the like. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester such as succinic acid mono (2-acryloyloxyethyl) or succinic acid mono (2-methacryloyloxyethyl). , Mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, and the like. The unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. Moreover, the unsaturated polyvalent carboxylic acid may be an unsaturated acrylate containing a hydroxy group and a carboxyl group in the same molecule, and examples thereof include α- (hydroxymethyl) acrylic acid. Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used because of their high copolymerization reactivity.

  (A12) exemplified above can be used alone or in combination of two or more.

  In addition, the first resin according to the present invention may be polymerized by further including a compound (a13) copolymerized with the above (a11) and (a12) and having an unsaturated bond.

  The compound (a13) copolymerized with the above (a11) and (a12) and having an unsaturated bond is not particularly limited as long as it is a compound having a polymerizable unsaturated double bond. Specifically, (a13) is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-o-phenylphenol propyl acrylate, amino Unsaturated or substituted alkyl ester compounds of unsaturated carboxylic acids such as ethyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl ( (Meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meta) Unsaturated carboxylic acids containing alicyclic substituents such as acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, and pinenyl (meth) acrylate Ester compounds, monosaturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate, unsaturated carboxylic acid esters containing substituents having an aromatic ring such as benzyl (meth) acrylate and phenoxy (meth) acrylate Compounds, aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, (meth) acrylonitrile, α-chloro Vinyl cyanide compounds such as acrylonitrile, N- alkyl maleimide, N- cyclohexyl maleimide, N- phenylmaleimide, maleimide compounds such as N- benzyl maleimide. These can be used alone or in combination of two or more. In the present specification, (meth) acrylate means acrylate and / or methacrylate.

  For example, the first resin may have a repeating unit containing an alkyl-substituted maleimide or an aryl-substituted maleimide derived from the maleimide compound. The thermosetting property of the first resin can be further improved by the maleimide-containing repeating unit.

  The first resin is at least one compound (a11) selected from the group consisting of Chemical Formula 1 and Chemical Formula 2 on the basis of the total number of moles of (a11), (a12) and (a13) constituting the first resin. 2) to 30 mol%, 2 to 70 mol% of the compound (a12) having an unsaturated bond and a carboxyl group, and the compound (a13) 2 having an unsaturated bond copolymerized with the above (a11) and (a12) It may be obtained by copolymerization with ˜95 mol%. Preferably, 5 to 30 mol% of at least one compound (a11) selected from the group consisting of Chemical Formula 1 and Chemical Formula 2, and 5 to 65 mol% of the compound (a12) having an unsaturated bond and a carboxyl group, It may be obtained by copolymerizing (a11) and (a12) with 5-80 mol% of the compound (a13) having an unsaturated bond. Within the above range, it is possible to produce a photosensitive resin composition having good developability, solvent resistance, heat resistance and mechanical strength.

  The first resin of the alkali-soluble resin (A) is obtained by further copolymerizing the compound (a14) having an unsaturated bond and an epoxy group with the (a11), (a12), and (a13). It may also be a copolymer obtained by further containing another monomer compound.

  The (a14) imparts photo / thermosetting properties to the alkali-soluble resin. Specifically, (a14) is glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 2,3-epoxycyclopentyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate. , Methyl glycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3.4-epoxytricyclo [5.2.1.0 2,6] decan-9-yl Examples include (meth) acrylate. These can be used alone or in combination of two or more.

  The first resin is at least one compound selected from Chemical Formula 2 or Chemical Formula 3 based on the total number of moles of (a11), (a12), (a13) and (a14) constituting the first resin ( a11) Compound (a13) copolymerized with 2 to 30 mol%, compound (a12) 2 to 70 mol% with unsaturated bond and carboxyl group, and the above (a11) and (a12) It may be obtained by copolymerizing 2 to 95 mol% and 5 to 80 mol% of the compound (a14) having an unsaturated bond and an epoxy group based on the number of moles of the above (a12). Preferably, 5 to 30 mol% of at least one compound (a11) selected from Chemical Formula 2 or Chemical Formula 3, 5 to 65 mol% of the compound (a12) having an unsaturated bond and a carboxyl group, and the (a11) And (a12) 5-80 mol% of the compound (a13) having an unsaturated bond and the compound (a14) 10-80 having an unsaturated bond and an epoxy group based on the number of moles of the above (a12) It may be obtained by copolymerizing with mol%. Within the above range, a photosensitive resin composition having good developability, solvent resistance, heat resistance and mechanical strength can be produced.

  The first resin according to the present invention preferably has a polystyrene-equivalent weight average molecular weight in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 50,000. When the weight average molecular weight of the first resin is in the range of 3,000 to 100,000, the hard resin has no hard deformation.

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the first resin is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. . A molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of 1.5 to 6.0 is preferable because of excellent developability.

  Moreover, the alkali-soluble resin (A) according to the present invention includes a second resin polymerized by including the compound (a21) having an alicyclic epoxy group. Thereby, the second resin can include an alicyclic epoxy group-containing repeating unit. By including the second resin, the present invention can exhibit excellent developability, solvent resistance, heat resistance, and mechanical strength.

  Preferably, the compound (a21) having an alicyclic epoxy group may include at least one of the following Chemical Formula 4 and Chemical Formula 5.

化学式４中、Ｒ_６は、水素原子またはヒドロキシ基で置換されているか又は置換されていないＣ１−Ｃ４アルキル基であり、Ｘは、単結合またはヘテロ原子を含有しているか又は含有していないＣ１−Ｃ６アルキレン基である。前記単結合とは、酸素と環とが直接連結されていることを意味し得る。

In Formula 4, R ₆ is a C1-C4 alkyl group that is substituted or unsubstituted with a hydrogen atom or a hydroxy group, and X contains a single bond or a heteroatom that does or does not contain C1 -C6 alkylene group. The single bond may mean that oxygen and a ring are directly connected.

化学式５中、Ｒ_７は、水素原子またはヒドロキシ基で置換されているか又は置換されていないＣ１−Ｃ４アルキル基であり、Ｘは、単結合またはヘテロ原子を含有しているか又は含有していないＣ１−Ｃ６アルキレン基である。前記単結合とは、酸素と環とが直接連結されていることを意味し得る。

In Formula 5, R ₇ is a C1-C4 alkyl group that is substituted or unsubstituted with a hydrogen atom or a hydroxy group, and X contains a single bond or a heteroatom that does or does not contain C1 -C6 alkylene group. The single bond may mean that oxygen and a ring are directly connected.

  In order to show alkali solubility, the second resin according to the present invention is obtained by polymerizing the alicyclic epoxy compound (a21) further including a compound (a22) having an unsaturated bond and a carboxyl group. Also good.

  As the compound (a22) having an unsaturated bond and a carboxyl group, those described in the above (a12) of the unsaturated group-containing first resin can be selected and used. Accordingly, detailed description thereof will be omitted.

R _{6 in} Chemical Formula 4 and R _{7 in} Chemical Formula 5 are each independently a hydrogen atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group. Alkyl groups such as: hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxy-n-propyl group, 2-hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1- Hydroxy such as hydroxy-isopropyl group, 2-hydroxy-isopropyl group, 1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-n-butyl group It may be a containing alkyl group. Among these, R ₆ and R ₇ are each independently preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and particularly preferably a hydrogen atom or a methyl group. More preferably it is.

  X in the chemical formulas 4 and 5 is specifically a single bond; an alkylene group such as a methylene group, an ethylene group or a propylene group; an oxymethylene group, an oxyethylene group, an oxypropylene group, a thiomethylene group, a thioethylene group or a thiopropylene It may be a hetero atom-containing alkylene group such as a group, an aminomethylene group, an aminoethylene group, or an aminopropylene group. Among these, X is preferably a single bond, a methylene group, an ethylene group, an oxymethylene group or an oxyethylene group, and more preferably a single bond or an oxyethylene group.

  Specific examples of the compound represented by Chemical Formula 4 include compounds represented by the following Chemical Formulas 4-1 to 4-14.

  Specific examples of the compound represented by Chemical Formula 5 include compounds represented by the following Chemical Formulas 5-1 to 5-14.

  The compounds exemplified as the compound represented by the chemical formula 4 or the compound represented by the chemical formula 5 can be used alone or in combination of two or more.

  In addition to the (a21) and (a22), the second resin can be copolymerized with a compound having an unsaturated bond polymerizable with (a21) and (a22). For example, the second resin includes (a21) and (a22) together with 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl acrylate, Unsaturated carboxylic acid amino such as aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate Alkyl esters; carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate; vinyl methyl ether, vinyl ethyl ether Unsaturated ethers such as allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide; acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, Unsaturated amides such as N-2-hydroxyethylmethacrylamide; Unsaturated imides such as maleimide, benzylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide; Aliphatic conjugates such as 1,3-butadiene, isoprene and chloroprene Dienes; and polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane monoa It may also be copolymerized with such macro monomers having acryloyl group or a mono methacryloyl group.

  The second resin is based on the total number of moles of (a21) and (a22) constituting the second resin, and the compound (a21) having the alicyclic epoxy group is 5 to 95 mol%, an unsaturated bond, and It may be obtained by copolymerizing 5 to 75 mol% of a compound having a carboxyl group (a22). Preferably, it is obtained by copolymerizing 30 to 90 mol% of the compound (a21) having an alicyclic epoxy group and 10 to 70 mol% of a compound (a22) having an unsaturated bond and a carboxyl group. May be. Within the above range, a photosensitive resin composition having good developability, solvent resistance, heat resistance and mechanical strength can be produced.

  The second resin preferably has an acid value in the range of 20 to 200 (KOHmg / g). When the acid value is in the above range, a spacer having an excellent elastic recovery rate can be produced.

  The polystyrene equivalent weight average molecular weight of the second resin is 3,000 to 100,000, preferably 5,000 to 50,000. When the weight average molecular weight of the second resin is within the above range, it is preferable because a reduction in the film during development is prevented and the omission of the pattern portion is improved.

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the second resin is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. . It is preferable that the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is within the above range because the developability is excellent.

  According to an exemplary embodiment, the alkali-soluble resin may include both the first resin and the second resin described above. In this case, it is preferable that the alkali-soluble resin contains 10 to 95% by weight of the first resin and 5 to 90% by weight of the second resin based on the solid content of the alkali-soluble resin. When the content ratio is in the above range, it is possible to realize a photocuring pattern having a hard property with little deformation due to external pressure while having an excellent elastic recovery rate.

  The term “solid content” used in the present application means the sum of the components from which the solvent has been removed.

  The alkali-soluble resin according to the embodiment of the present invention may include a third resin polymerized from a norbornene compound.

  For example, the third resin may include a repeating unit represented by the following chemical formula 6.

  By including a chemically unstable cyclic hydrocarbon unit such as norbornene, the resolution of the alkali-soluble resin or the photosensitive resin composition containing the same can be further improved.

  In some embodiments, the third resin may further include a benzene ring-containing repeating unit. The benzene ring-containing repeating unit may be derived, for example, from a monomer represented by the following chemical formula 7.

化学式７中、Ｒ_３１は、水素原子、またはＣ１−Ｃ６アルコキシ基、Ｃ１−Ｃ６アルキル基、Ｃ４−Ｃ８シクロアルキル基、テトラヒドロフラニル基、テトラヒドロピラニル基、オキシラン基、オキセタン基、Ｃ４−Ｃ１２のビシクロアルキル基またはＣ６−Ｃ１８のトリシクロアルキル基で置換または非置換のＣ１−Ｃ６アルコキシ基、Ｃ１−Ｃ６アルキル基、Ｃ４−Ｃ８シクロアルキル基、テトラヒドロフラニル基、テトラヒドロピラニル基、オキシラン基、オキセタン基、Ｃ４−Ｃ１２ビシクロアルキル基またはＣ６〜１８トリシクロアルキル基である。

In Chemical Formula 7, R ₃₁ is a hydrogen atom, or a C1-C6 alkoxy group, a C1-C6 alkyl group, a C4-C8 cycloalkyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, an oxirane group, an oxetane group, or a C4-C12. A C1-C6 alkoxy group, a C1-C6 alkyl group, a C4-C8 cycloalkyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, an oxirane group, an oxetane substituted or unsubstituted with a bicycloalkyl group or a C6-C18 tricycloalkyl group Group, a C4-C12 bicycloalkyl group or a C6-18 tricycloalkyl group.

The benzene ring-containing repeating unit can improve the heat resistance and mechanical strength of the third resin. In this respect, R ₃₁ may preferably be a hydrogen atom or a C1-C6 alkyl group (for example, a methyl group).

  In some embodiments, the third resin may further include a carboxylic acid-containing repeating unit. In this case, the resolution can be further improved by adding a hydrogen donor unit.

  For example, the carboxylic acid-containing repeating unit may be derived from the compound (a12) having an unsaturated bond and a carboxyl group described above for the first resin.

  In some embodiments, the third resin may be polymerized to further include an acrylate monomer that is known in the art and commonly used to impart or improve light or thermosetting properties. It may further have an acrylate repeating unit formed.

  Examples of the acrylate monomer include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and trimethylolpropane. Tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, methyl (meth) acrylate, ethyl (meth) Acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) ) Acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl ( (Meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxy) Ethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate Diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl acrylate, nonylphenoxy polyethylene glycol (Meth) acrylate, cyclofentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (Meth) acrylate, tribromophenyl (meth) acrylate, tribromophe Ruokishiechiru (meth) acrylate, and the like glycidyl (meth) acrylate. These can be used alone or in combination of two or more.

  In one embodiment, the third resin comprises a repeating unit of Formula 6, a benzene ring-containing repeating unit, a carboxylic acid-containing repeating unit, and an acrylate repeating unit in an amount of 5 to 70 mol%, 5 to 50 mol%, and 5 to 65, respectively. It can be included in molar ratios of 5% to 70% by mole.

  The third resin preferably has a polystyrene-equivalent weight average molecular weight in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 50,000.

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the third resin is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. . When the molecular weight distribution is within the above range, excellent developability and resolution can be ensured.

  According to an exemplary embodiment, the alkali-soluble resin may include both the second resin and the third resin described above. In this case, it is preferable that the alkali-soluble resin contains 5 to 90% by weight of the second resin and 10 to 95% by weight of the third resin by weight based on the solid content of the alkali-soluble resin. When the content ratio is within the above range, a photocuring pattern having excellent adhesion and elasticity and having a high resolution can be realized.

  According to the embodiment of the present invention described above, the alkali-soluble resin includes the second resin, and may further include at least one of the first resin or the third resin. Thereby, both chemical characteristics such as photocurability, photoreactivity, resolution, and developability and mechanical characteristics such as hardness, elasticity, and adhesion can be improved.

  For example, the alkali-soluble resin may include the first resin and the second resin, or a combination of the second resin and the third resin. Alternatively, the alkali-soluble resin may include a combination of the first resin, the second resin, and the third resin.

  The content of the alkali-soluble resin is usually 5 to 90% by weight, preferably 10 to 70% by weight, based on the total solid content in the photosensitive resin composition. When the content of the alkali-soluble resin is 5 to 90% by weight based on the above criteria, the developer has sufficient solubility in the developing solution and excellent developability, has an excellent elastic recovery rate, and external It is possible to manufacture a spacer having a hard characteristic with little deformation due to pressure.

Photopolymerizable compound The photopolymerizable compound contained in the photosensitive resin composition of the present invention is a compound that can be polymerized by the action of the photopolymerization initiator, and is a monofunctional monomer, a bifunctional monomer, other A polyfunctional monomer etc. are mentioned.

  In order to improve the developability, sensitivity, adhesion, surface problems, etc. of the spacer-forming resin composition, the photopolymerizable compound used in the present invention has two different functional group structures and the number of functional groups. More photopolymerizable compounds can be mixed and used, and the range is not limited.

  Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone and the like.

  Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and bisphenol. Examples thereof include bis (acryloyloxyethyl) ether of A and 3-methylpentanediol di (meth) acrylate.

  Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) Examples thereof include acrylate and tripentaerythritol octa (meth) acrylate. Among these, polyfunctional monomers having two or more functions are preferably used.

  The photopolymerizable compound is used in an amount of 1 to 90 parts by weight, preferably 10 to 80 parts by weight, based on the solid content of the photosensitive composition, based on a total of 100 parts by weight of the alkali-soluble resin and the photopolymerizable compound. Can be used in a range. It is preferable that the photopolymerizable compound is in the above-mentioned range because the strength and smoothness of the formed spacer pattern are improved.

Any solvent solvent can be used without limitation as long as it is normally used in the field.

  Specific examples of the solvent include ethylene glycol monoalkyl ethers; diethylene glycol dialkyl ethers; ethylene glycol alkyl ether acetates; alkylene glycol alkyl ether acetates; propylene glycol monoalkyl ethers; propylene glycol dialkyl ethers; Ether propionates; butyldiol monoalkyl ethers; butanediol monoalkyl ether acetates; butanediol monoalkyl ether propionates; dipropylene glycol dialkyl ethers; aromatic hydrocarbons; ketones; Esters; cyclic esters and the like. These can be used alone or in admixture of two or more.

  As the solvent, alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers and esters can be preferably used in consideration of coating properties and drying properties. More preferably, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, or the like can be used. .

  The content of the solvent may be 40 to 95 parts by weight, preferably 45 to 85 parts by weight, based on 100 parts by weight of the total amount of the photosensitive resin composition. When the above range is satisfied, it is preferable because coating properties are improved when coating is performed by a coating apparatus such as a spin coater, a slit-and-spin coater, a slit coater (or “die coater” or “curtain flow coater”), and an ink jet.

Additives The photosensitive resin composition according to the present invention includes, as necessary, fillers, other polymer compounds, curing agents, leveling agents, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and chains. An additive such as a transfer agent may be further included.

<Photocuring pattern and image display device>
The present invention also provides a photocuring pattern produced from the above-described photosensitive resin composition and an image display device including the photocuring pattern.

  The photocuring pattern manufactured with the said photosensitive resin composition is excellent in an elastic recovery rate, adhesiveness, etc. As a result, it can be used for various patterns in an image display device, for example, an adhesive layer, an array planarizing film, a protective film, an insulating film pattern, etc., for a photoresist, a black matrix, a column spacer pattern, a black column spacer pattern, etc. It can also be used. However, it is not limited to these, and is particularly suitable as a spacer pattern.

  Examples of the image display device provided with such a photocuring pattern or using the pattern during the manufacturing process include a liquid crystal display device, an OLED, a flexible display, and the like. However, the present invention is not limited to these, and all image display devices that are applicable in the art can be used.

  A photocuring pattern can be manufactured by apply | coating the photosensitive resin composition of this invention mentioned above on a base material, and passing through the image development process as needed, and forming a photocuring pattern.

  Hereinafter, the present invention will be described in more detail with reference to production examples, examples, comparative examples, and experimental examples. However, the following production examples, examples, comparative examples and experimental examples are for illustrating the present invention, and the present invention is not limited to the following production examples, examples, comparative examples and experimental examples. Various modifications and changes can be made.

[Production example]
In Production Examples 1 to 4, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured using the GPC method under the following conditions. The ratio between the weight average molecular weight and the number average molecular weight was defined as molecular weight distribution (Mw / Mn).

Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG4000HXL + TSK-GELG2000HXL (series connection)
Column temperature: 40 ° C
Mobile phase solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Injection volume: 50 μl
Detector: RI
Measurement sample concentration: 0.6% by weight (solvent = tetrahydrofuran)
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

[Production Example 1] Production of A-1 (first resin) 182 g of propylene glycol monomethyl ether acetate was charged into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and the atmosphere in the flask Was changed from air to nitrogen and then heated to 100 ° C. Thereafter, 35.4 g (0.30 mol) of benzylmaleimide, 36.0 g (0.50 mol) of acrylic acid, 59.6 g (0.2 mol) of 2-hydroxy-o-phenylphenol propyl acrylate and propylene glycol monomethyl ether A solution in which 3.6 g of azobisisobutyronitrile was added to a mixture containing 136 g of acetate was dropped into the flask over 2 hours from the dropping funnel, and stirring was further continued at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, 22.5 g of glycidyl methacrylate [0.15 mol, (50 mol% based on acrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol and hydroquinone. 0.145 g was put into the flask, and the reaction was continued at 110 ° C. for 6 hours. This obtained unsaturated resin containing 1st resin A-1 whose solid content acid value is 121.1 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 31,000, and the molecular weight distribution (Mw / Mn) was 2.2.

[Production Example 2] Production of A-2 (second resin) Nitrogen was introduced into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer at a rate of 0.02 L / min to form a nitrogen atmosphere, and diethylene glycol ethyl methyl was produced. 150 g of ether was added and heated to 70 ° C. with stirring. Next, 198.2 g (0.90 mol) of the mixture of the chemical formula 4-1 and the chemical formula 5-1 (molar ratio is 50:50) and 8.6 g (0.10 mol) of methacrylic acid were dissolved in 150 g of diethylene glycol ethyl methyl ether. To prepare a solution.

  The prepared solution was dropped into the flask using a dropping funnel, and then 27.9 g (0.11 mol) of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was added to 200 g of diethylene glycol ethyl methyl ether. The solution dissolved in was dropped into the flask over 4 hours using another dropping funnel. After completion of the dropwise addition of the polymerization initiator solution, the temperature was maintained at 70 ° C. for 4 hours, and then cooled to room temperature. This obtained the solution of the copolymer (resin A-2) of solid content 41.6 mass% and acid value 59mg-KOH / g (solid content conversion). The obtained resin A-2 had a weight average molecular weight Mw of 7,790 and a molecular weight distribution of 1.9.

[Production Example 3] Production of A-3 (third resin) Into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was introduced at a rate of 0.02 L / min to form a nitrogen atmosphere, and propylene glycol monomethyl 200 g of ether acetate was added and the temperature was raised to 100 ° C. Thereafter, a mixture containing 33.9 g (0.47 mol) of acrylic acid, 4.7 g (0.05 mol) of norbornene, 56.7 g (0.48 mol) of vinyl toluene, and 150 g of propylene glycol monomethyl ether acetate was added to 2 , 2'-azobis (2,4-dimethylvaleronitrile) 3.6g was added dropwise to the flask over 2 hours from the dropping funnel, and stirring was further continued at 100 ° C for 5 hours.

  Next, the atmosphere in the flask was changed from nitrogen to air, and 42.6 g [0.30 mol (64 mol% with respect to acrylic acid used in this reaction)] of glycidyl methacrylate was charged into the flask and heated at 110 ° C. for 6 hours. The reaction continued. This obtained unsaturated group containing resin A-3 whose solid content acid value is 79 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 6,600, and the molecular weight distribution (Mw / Mn) was 1.9.

[Production Example 4] Synthesis of unsaturated group-containing resin A-4
182 g of propylene glycol monomethyl ether acetate was put into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube, and the atmosphere in the flask was changed from air to nitrogen, and then heated to 100 ° C. Thereafter, 3.6 g of azobisisobutyronitrile was added to a mixture containing 88.1 g (0.50 mol) of benzyl methacrylate, 36.0 g (0.50 mol) of acrylic acid and 136 g of propylene glycol monomethyl ether acetate. Was dropped into the flask from the dropping funnel over 2 hours, and stirring was further continued at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, 22.5 g of glycidyl methacrylate [0.15 mol, (50 mol% based on acrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol and hydroquinone. 0.145 g was put into the flask, and the reaction was continued at 110 ° C. for 6 hours. This obtained resin A-4 whose solid content acid value is 94 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 30,000, and the molecular weight distribution (Mw / Mn) was 2.1.

[Examples and Comparative Examples]
The photosensitive resin compositions of Examples and Comparative Examples were prepared with the compositions and contents (unit: parts by weight) shown in Tables 1 and 2 below.

Specific components of each composition are as follows.
A-1: Resin produced in Production Example 1 (first resin)
A-2: Resin manufactured in Production Example 2 (second resin)
A-3: Resin produced in Production Example 3 (third resin)
A-4: Resin produced in Production Example 4 B-1: 1- (9,9-H-7-Nitrofulleren-2-yl) -ethanone oxime-O-acetate B-2: 2,2 ′ , 4-Tris (2-chlorophenyl) -5- (3,4-dimethoxyphenyl) -4 ′, 5′-diphenyl-1,1′-biimidazole (CHEMCURE-TCDM: CHEMBRIDGE INTERNIONAL CORP.)
B-3: Diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide (IRGACURE-819: BASF)
C: Tripentaerythritol octaacrylate (Viscoat # 802: Osaka Organic Chemical Industry Co., Ltd.)
D: Dipentaerythritol hexakis (3-mercaptopropionate) (DPMP: SC ORGANIC CHEMICAL CO., LTD.)
E-1: Propylene glycol monomethyl ether acetate E-2: Diethylene glycol ethyl methyl ether

[Experimental example]
A 2-inch square glass substrate (Eagle 2000, Corning) was sequentially washed with a neutral detergent, water, and alcohol, and then dried. The glass substrate was spin-coated with the photosensitive resin compositions produced in the above examples and comparative examples, and then pre-baked at 90 ° C. for 3 minutes in a clean oven. After cooling the pre-baked substrate to room temperature, the distance from the photomask made of quartz glass is set to 150 μm, and the exposure dose (405 nm) is 60 mJ / cm ² using an exposure machine (TME-150RSK, manufactured by Topcon Corporation). (Reference). For irradiation to the polymerizable resin composition at this time, the light emitted from the ultra-high pressure mercury lamp was passed through an optical filter (LU0400, manufactured by Asahi Spectrometer Co., Ltd.), and light of 400 nm or less was cut off. At this time, a photomask in which the next pattern was formed on the same plane was used as the photomask (having a circular translucent portion (pattern) having a diameter of 20 μm, and the interval between the patterns was 100 μm).

  After the light irradiation, the coating film was developed by immersing it in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 25 ° C. for 100 seconds, and washed with water. Thereafter, post-baking was performed in an oven at 220 ° C. for 20 minutes. The thickness of the obtained film was 3 μm. The film thickness was measured using a film thickness measuring device (DEKTAK6M, manufactured by Veeco). The following physical property evaluation was performed on the pattern thus obtained. The results are shown in Tables 3 and 4 below.

<Test method>
(1) Measurement of Bottom CD Using the three-dimensional shape measuring device (SIS-2000 Systems, manufactured by SNU PRECISION), the height of the pattern and the bottom CD are applied to the photomask size and coating at this time. When the standard of the film thickness is 20 μm and 3.0 μm, respectively, the minimum size pattern in which the thickness of the coating film maintains 2.85 μm is measured.
As shown in FIG. 1, the line width at 5% of the height was defined as the value of Bottom CD. The bottom CD is better because the sensitivity is better as it is smaller.

(2) Measurement of pattern width ratio (T / B ratio)
Using the three-dimensional shape measuring device (SIS-2000 Systems, manufactured by SNU PRECISION Co., Ltd.), the dot pattern in (1) above is measured from Bottom CD (a) and floor surface at 5% of the total height from the bottom of the pattern. The point of 95% of the total height is defined as Top CD (b), and the value obtained by dividing the length of (b) by the length of (a) and multiplying by 100 (= b / a × 100) The T / B ratio was defined.

(3) Development adhesion The development adhesion is evaluated by using a photomask having 1000 circular patterns with a diameter of 5 μm to 20 μm, each spaced by 1 μm, and evaluating the pattern formed with a film thickness of 3 μm using a microscope. The number of the developed patterns was counted, and the development adhesion (%) was calculated as in the following mathematical formula 1. The results are shown in Table 2 below.

[Mathematical Formula 1]
Development adhesion (%) = [1000− (number of missing patterns)] / 1000 × 100

(4) Mechanical properties (recovery rate)
The cured film obtained above was measured using the dynamic ultra-micro hardness meter (DUH-W201, manufactured by Shimadzu Corporation), and the total displacement (μm) and elastic displacement (μm) were measured under the following measurement conditions. It was measured by. Using the measured numerical values, the recovery rate (%) was calculated as in the following mathematical formula 2. When the total displacement amount was small and the recovery rate was large, it was judged that it was hard.

[Mathematical formula 2]
Recovery rate (%) = [elastic displacement (μm)] / [total displacement (μm)] × 100

[Measurement condition]
Test mode: Load-unload test Test force: 5 gf [SI unit conversion value 49.0 mN]
Load speed: 0.45 gf / sec [SI unit converted value 4.41 mN / sec]
Holding time: 5 sec
Indenter: Conical indenter (diameter 50 μm)

  Referring to Table 3 and Table 4 above, in the case of an embodiment that alternatively includes the first resin or the third resin together with the second resin as the photopolymerization initiator (B-1) and the alkali-soluble resin described above, , Improved Bottom CD, T / B ratio, elastic recovery and development adhesion. In Examples 11 to 20 using the third resin together with the second resin, a relatively improved resolution was obtained.

  On the other hand, in the case of Comparative Examples 1 and 2 in which the second resin is omitted, the result of overall deterioration as compared with the Example was shown. Moreover, in the case of the comparative example 3 which abbreviate | omitted the photoinitiator which concerns on the Example of this invention, a pattern is not formed but Bottom CD, T / B ratio, image development adhesive force, and an elastic recovery factor are measured. I could not.

Claims (14)

An alkali-soluble resin having an alicyclic epoxy group-containing repeating unit;
A photopolymerization initiator containing a compound represented by the following chemical formula 1;
A photopolymerizable compound;
A photosensitive resin composition comprising a solvent.

(In Chemical Formula 1, R ₃ is a C1-C20 alkyl group, and R ₄ and R ₅ are each independently a C1-C20 alkyl group, a C6-C20 aryl group, or a C3-C20 cycloalkyl group. , A is a nitro group or a cyano group.) The alkali-soluble resin is
A first resin polymerized containing at least one compound selected from the group consisting of compounds represented by the following chemical formulas 2 and 3;
The photosensitive resin composition of Claim 1 containing the 2nd resin which has the said alicyclic epoxy group containing repeating unit.

(In Chemical Formula 2, R ₁ is a hydrogen atom, a C1-C12 alkyl group, an allyl group, a phenyl group, a benzyl group, a halogen group, or a C1-C8 alkoxy group.)

(In Chemical Formula 3, R ₂ is a hydrogen atom, a C1-C12 alkyl group, an allyl group, a phenyl group, a benzyl group, a halogen group, or a C1-C8 alkoxy group, and n is an integer of 1-10. )   The photosensitive resin composition according to claim 2, wherein the first resin further has a repeating unit containing an alkyl-substituted maleimide or an aryl-substituted maleimide. The alkali-soluble resin is
A second resin having the alicyclic epoxy group-containing repeating unit;
The photosensitive resin composition of Claim 1 containing 3rd resin which has a norbornene (norbornene) repeating unit.   The photosensitive resin composition according to claim 4, wherein the third resin further has at least one repeating unit selected from the group consisting of a benzene ring-containing repeating unit, a carboxylic acid-containing repeating unit, and an acrylate repeating unit. The photosensitive resin composition according to claim 1, wherein the alicyclic epoxy group-containing repeating unit is derived from at least one selected from the group consisting of compounds represented by the following chemical formula 4 or chemical formula 5.

(In Chemical Formula 4, R ₆ is a C1-C4 alkyl group substituted or unsubstituted with a hydrogen atom or a hydroxy group,
X is a C1-C6 alkylene group containing or not containing a single bond or heteroatom. )

(In Chemical Formula 5, R ₇ is a C1-C4 alkyl group substituted or unsubstituted with a hydrogen atom or a hydroxy group,
X is a C1-C6 alkylene group containing or not containing a single bond or heteroatom. ) In the chemical formula 1, R ₃ is a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, an i-pentyl group, an n-hexyl group or an i-hexyl group,
R ₄ and R ₅ are each independently a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, i- The pentyl group, the n-hexyl group, the i-hexyl group, the phenyl group, the naphthyl group, the biphenyl group, the terphenyl group, the anthryl group, the indenyl group, or the penanthryl group according to any one of claims 1 to 6. Photosensitive resin composition.   The said photoinitiator is a photosensitive resin composition as described in any one of Claim 1 thru | or 7 which further contains at least 1 sort (s) of an acetophenone derivative compound or a biimidazole derivative compound.   The photosensitive resin composition according to any one of claims 1 to 8, wherein the photopolymerization initiator contains 40 to 90% by weight of the compound represented by Formula 1 with respect to the total weight of the photopolymerization initiator. .   The content of the photopolymerization initiator is 0.1 to 40 parts by weight with respect to a total of 100 parts by weight based on the solid content of the alkali-soluble resin and the photopolymerizable compound. The photosensitive resin composition as described in any one of these.   The photosensitive resin composition according to any one of claims 1 to 10, wherein the alkali-soluble resin is contained in an amount of 5 to 90% by weight based on the solid content of the photosensitive resin composition.   The photocuring pattern manufactured with the said photosensitive resin composition as described in any one of Claims 1-11.   The photocuring pattern according to claim 12, wherein the photocuring pattern is selected from the group consisting of an array planarizing film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, and a spacer pattern.   The image display apparatus provided with the said photocuring pattern of Claim 12.

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