KR20170132657A - Photosensitive resin composition and photo-cured pattern prepared from the same - Google Patents

Abstract

A photosensitive resin composition of the present invention comprises: an alkali soluble resin including a repeating unit containing an alicyclic epoxy group; a photopolymerization initiator including a compound represented by chemical formula 1; a photopolymerizable compound; and a solvent. A photo-cured pattern having an excellent elasticity recovery rate during curing and having hard properties with little deformation by external pressure can be formed from the photosensitive resin composition. The photo-cured pattern has high resolution, excellent substrate adhesion and excellent T/B ratios.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a photosensitive resin composition and a photocurable pattern produced therefrom. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a photosensitive resin composition, a photo-curing pattern made of the composition, and an image display device having the photo-curing pattern.

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

A method of forming a spacer by photolithography is a method in which a photosensitive resin composition is coated on a substrate, ultraviolet rays are irradiated through the mask, and a spacer is formed at a desired position on the substrate in accordance with a pattern formed on the mask.

2. Description of the Related Art In recent years, as a demand for a touch panel has increased due to popularization of smart phones and tablet PCs, a spacer, which maintains a gap between a color filter substrate and an array substrate constituting a display device, It is required to have a hard property and adhesion with a substrate so that there is no pixel deformation due to pressure. Thus, research on photosensitive resin compositions has been actively conducted, but still fails to satisfy demands for the elastic recovery rate, adhesiveness to a substrate, and the like.

For example, Korean Patent Laid-Open Publication No. 2009-005686 discloses a photosensitive resin composition comprising a binder resin that is a copolymer of an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride and an aliphatic polycyclic epoxy compound. However, Is still not met.

Korea Patent Publication No. 2009-005686

It is an object of the present invention to provide a photosensitive resin composition capable of forming a photo-curable pattern having a hard elasticity recovery rate after hardening and a hard property with little external stress.

Another object of the present invention is to provide a photosensitive resin composition capable of realizing a high resolution pattern upon curing.

Another object of the present invention is to provide a photosensitive resin composition having a substrate adhesion strength which is excellent in pattern formed during curing.

It is another object of the present invention to provide a photosensitive resin composition having an excellent T / B ratio value upon curing.

It is another object of the present invention to provide an image display device provided with the photo-curable pattern and the photo-curable pattern produced from the above-described photosensitive resin composition.

1. An alkali-soluble resin comprising a repeating unit containing an alicyclic epoxy group; A photopolymerization initiator comprising a compound represented by the following formula (1); Photopolymerizable compounds; And a solvent.

[Chemical Formula 1]

(Wherein R ₃ is C 1 -C 20 alkyl, R ₄ and R ₅ are each independently C 1 -C 20 alkyl, C 6 -C 20 aryl or C 3 -C 20 cycloalkyl, and A is nitro or cyano).

2. The resin composition according to 1 above, wherein the alkali-

A first resin polymerized with at least one compound selected from the group consisting of compounds represented by the following formulas (2) and (3); And

And a second resin comprising the repeating unit containing an alicyclic epoxy group.

(2)

(Wherein R ₁ is hydrogen, C ₁ -C 12 alkyl, allyl, phenyl, benzyl, halogen or C 1 -C 8 alkoxy)

(3)

(Wherein R < ₂ > is hydrogen, C1-C12alkyl, allyl, phenyl, benzyl, halogen or C1-C8alkoxy and n is an integer of 1 to 10)

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

4. The positive resist composition according to item 1, wherein the alkali-

A second resin comprising the alicyclic epoxy group-containing repeating unit; And

A third resin comprising a norbornene repeating unit.

5. The photosensitive resin composition according to 4 above, wherein said third resin further comprises 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. The photosensitive resin composition according to item 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 formulas (4) and (5)

[Chemical Formula 4]

(Wherein R < ₆ > is hydrogen or C1-C4 alkyl which is unsubstituted or substituted with a hydroxy group;

X is a single bond or a C1-C6 alkylene containing or not containing a hetero atom)

[Chemical Formula 5]

(Wherein R < ₇ > is hydrogen or C1-C4 alkyl optionally substituted by hydroxy group;

X is a single bond or a C1-C6 alkylene containing or not containing a heteroatom.

7. A compound according to item 1, wherein R < ₃ > is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, - hexyl,

R ₄ to R ₅ are each independently selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t- butyl, n-pentyl, , Naphthyl, biphenyl, terphenyl, anthryl, indenyl or phenanthryl.

8. The photosensitive resin composition according to 1 above, wherein the photopolymerization initiator further comprises at least one of an acetophenone derivative compound or a nonimidazole derivative compound.

9. The photosensitive resin composition according to the above 8, wherein the photopolymerization initiator comprises 40 to 90% by weight of the compound of the general formula (1) based on the total weight of the photopolymerization initiator.

10. The photosensitive resin composition according to 1 above, wherein the content of the photopolymerization initiator is 0.1 to 40 parts by weight based on 100 parts by weight based on the solids of the alkali-soluble resin and the photopolymerizable compound.

11. The photosensitive resin composition according to 1 above, 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.

12. A photocurable pattern produced from the photosensitive resin composition according to any one of the items 1 to 11 above.

13. The photocurable pattern according to 12 above, wherein the photocurable 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.

14. An image display apparatus having the photocuring pattern of the twelfth aspect.

The photosensitive resin composition of the present invention can form a photo-curable pattern having a hardness characteristic with little deformation at external pressure while having excellent elastic recovery rate after curing.

Further, the photosensitive resin composition of the present invention can realize a high resolution pattern upon curing

In addition, the photosensitive resin composition of the present invention has a good adhesion to the substrate when the pattern formed during curing is excellent.

Further, the photosensitive resin composition of the present invention shows an excellent T / B ratio.

Therefore, the photosensitive resin composition of the present invention can be usefully used in the production of a photocurable pattern, preferably a spacer pattern and an image display device.

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

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

Hereinafter, the present invention will be described in detail.

<Photosensitive resin composition>

Photopolymerization initiator

The photosensitive resin composition according to the embodiments of the present invention includes a photopolymerization initiator, and the photopolymerization initiator includes a compound represented by the following general formula (1).

[Chemical Formula 1]

R ₃ is C ₁ -C 20 alkyl, R ₄ to R ₅ are each independently C 1 -C 20 alkyl, C 6 -C 20 aryl or C 3 -C 20 cycloalkyl, and A represents nitro or cyano.

The photosensitive resin composition of the present invention includes a photopolymerization initiator containing the compound represented by the above formula (3), thereby maximizing the expected effect of an alkali-soluble resin to be described later, forming a pattern having excellent sensitivity and excellent substrate adhesion And the pattern stability, heat resistance and chemical resistance of the formed pattern are excellent.

The substituents comprising the "alkyl", "alkoxy" and other "alkyl" moieties described in the present invention include both linear and branched forms, and "cycloalkyl" includes not only a single ring system but also a plurality of cyclic hydrocarbons . &Quot; Aryl &quot; in the present invention means an organic radical derived from an aromatic hydrocarbon by one hydrogen elimination and is a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, And includes a form in which a plurality of aryls are connected by a single bond. &Quot; Hydroxyalkyl &quot; means OH-alkyl in which a hydroxy group is bonded to an alkyl group defined above, and &quot; hydroxyalkoxyalkyl &quot; means hydroxyalkyl-O-alkyl in which an alkoxy group is bonded to the hydroxyalkyl group.

In addition, the 'C1-C20 alkyl' group described in the present invention is preferably C1-C10 alkyl, more preferably C1-C6 alkyl. The 'C6-C20 aryl' group is preferably C6-C18 aryl. The 'C1-C20 alkoxy' group is preferably C1-C10 alkoxy, more preferably C1-C4 alkoxy. The 'C6-C2 aryl C1-C20 alkyl' group is preferably C6-C18 aryl C1-C10 alkyl, more preferably C6-C18 aryl C1-C6 alkyl. The 'hydroxyC1-C20 alkyl' group is preferably hydroxyC1-C10 alkyl, more preferably hydroxyC1-C6 alkyl. The 'hydroxyC1-C20 alkoxyC1-C20 alkyl' group is preferably hydroxyC1-C10 alkoxyC1-C10 alkyl, more preferably hydroxyC1-C4 alkoxyC1-C6 alkyl. The 'C3-C20 cycloalkyl' group is preferably C3-C10 cycloalkyl.

Specifically, R ₃ to R ₅ are each independently selected from the group consisting of hydrogen, bromo, chloro, iodo, methyl, ethyl, n-propyl, i-propyl, n- propyloxy, i-propyloxy, n-pentyl, n-hexyl, i-hexyl, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenanthryl, methoxy, ethoxy, Butoxy, i-butoxy, t-butoxy, hydroxymethyl, hydroxyethyl, hydroxy n-propyl, hydroxy n-butyl, hydroxy i-butyl, hydroxy n-pentyl, , Hydroxy n-hexyl, hydroxy i-hexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, Hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl; &lt; RTI ID = 0.0 &gt; R &lt; / RTI &gt;

A is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i- butyl, t- butyl, phenyl, naphthyl, biphenyl, terphenyl anthryl, indenyl, And examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, isobutyl, sec-butyl, Hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, amino, nitro, cyano or hydroxy, but is not limited thereto.

More specifically, R &lt; ₃ &gt; is hydrogen or n-butyl; R &lt; ₄ &gt; is methyl; R &lt; ₅ &gt; may be methyl, n-butyl or phenyl.

The photopolymerization initiator according to the present invention may further include at least one of an acetophenone derivative compound or a nonimidazole derivative compound in addition to the compound represented by the above formula (1). When the acetophenone derivative compound or the imidazole derivative compound is additionally used, the T / B ratio of the pattern can be further improved with excellent substrate adhesion.

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

Examples of the acetophenone derivative compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- (2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane -1-one oligomers, diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide, and the like.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, the phenyl group at the 4,4', 5,5 ' An imidazole compound substituted by an alkoxy group, and the like. Of these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- Tetraphenylbiimidazole, 2,2'4-tris (2-chlorophenyl) -5- (3,4-dimethoxyphenyl) -4 ', 5'- -Imidazole 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 Formula 1, based on the total weight of the photopolymerization initiator. The T / B ratio value of a further improved pattern can be obtained.

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

Further, as long as the effect of the present invention is not impaired, other photopolymerization initiators generally used in this field may be further used in combination. For example, benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, anthracene-based compounds, and the like. These may be used alone or in combination of two or more.

The photopolymerization initiator may be used in combination with a photopolymerization initiator. When the photopolymerization initiator is used in combination with the photopolymerization initiator, the photosensitive resin composition containing the photopolymerization initiator is more preferable because productivity can be improved when the spacer is formed.

As the photopolymerization initiation auxiliary, an amine compound or a carboxylic acid compound is preferably used.

The amount of the photopolymerization initiator to be used is 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the total of the alkali-soluble resin and the photopolymerizable compound to be described later. It is preferable that the photosensitive resin composition is highly sensitized in the above content range so that the strength and smoothness of the spacer formed using the composition become good.

Alkali-soluble resin

The alkali-soluble resin may be provided as a binder resin capable of forming a coating film by imparting adhesion to a substrate. According to exemplary embodiments, the alkali-soluble resin may have solubility in an alkali developing solution used in a developing process while being reactive to light or heat.

According to exemplary embodiments, the alkali-soluble resin is a resin in which the alkali-soluble resin according to the present invention comprises at least one compound (a11) selected from compounds represented by the following general formula (2) or (3) . &Lt; / RTI &gt;

(2)

In formula (2), R ₁ may represent hydrogen, C ₁ -C 12 alkyl, allyl, phenyl, benzyl, halogen or C 1 -C 8 alkoxy.

(3)

In formula (3), R- ₂ is hydrogen, C 1 -C 12 alkyl, allyl, phenyl, benzyl, halogen or C 1 -C 8 alkoxy, and n may be an integer of 1 to 10.

The alkali-soluble resin according to the present invention contains a repeating unit derived from at least one compound selected from the group consisting of the bulky compounds (2) and (3), and is excellent in the increase of the film density at the time of curing It is possible to form a photo-curable pattern having a rigid property with little elastic deformation at an external pressure while having an elastic recovery rate, and a high-resolution pattern can be formed.

The first resin of the alkali-soluble resin according to the present invention may contain, in addition to at least one compound (a11) selected from the general formulas (2) and (3), a compound having an unsaturated bond and a carboxyl group ). &Lt; / RTI &gt;

The compound (a12) having an unsaturated bond and a carboxyl group can be used without limitation as long as it is a carboxylic acid compound having an unsaturated double bond capable of being polymerized. The compound (a12) having an unsaturated bond and a carboxyl group may include, for example, an unsaturated monocarboxylic acid, a dicarboxylic acid having two or more carboxyl groups in the molecule such as an unsaturated dicarboxylic acid or an unsaturated tricarboxylic acid, and the like have. Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid. Examples of the unsaturated polycarboxylic 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 polycarboxylic acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polycarboxylic acid may also be a mono (2-methacryloyloxyalkyl) ester thereof, for example, mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxy Ethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be mono (meth) acrylate of the dicarboxylic polymer of both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like. have. The unsaturated polycarboxylic acid may be an unsaturated acrylate containing a hydroxyl group and a carboxyl group in the same molecule, for example,? - (hydroxymethyl) acrylic acid. Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used because of high copolymerization reactivity.

The above exemplified (a12) may be used alone or in combination of two or more.

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

The compound (a13) copolymerized with (a11) and (a12) and having an unsaturated bond is not limited as long as it is a compound having an unsaturated double bond capable of polymerization. Specifically, the above-mentioned (a13) is at least one monomer selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy- (Meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclohexyl (Meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (Meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl Unsaturated carboxylic acid ester compounds containing an alicyclic substituent such as acrylate and acrylate (meth) acrylate, mono-saturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate, (Meth) acrylate and phenoxy (meth) acrylate, aromatic vinyl compounds such as styrene,? -Methylstyrene and vinyltoluene, vinyl acetate, vinyl propionate (Meth) acrylonitrile,? -Chloroacrylonitrile, and other cyanide vinyl compounds, N-alkylmaleimides, N-cyclohexylmaleimides, N-phenylmaleimides, N- And maleimide compounds such as maleimide. These may be used alone or in combination of two or more, and the (meth) acrylates described in this specification means acrylate and / or methacrylate.

For example, the first resin may comprise repeating units 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.

(A11), (a12), and (a13) constituting the first resin, at least one compound (a11) selected from the group consisting of Formulas (1) and (2) 2 to 30 mol% of a compound (a12) having an unsaturated bond and a carboxyl group, 2 to 70 mol% of a compound (a12) having an unsaturated bond and a carboxyl group, and 2 to 95 mol% , Preferably 5 to 30 mol% of at least one compound (a11) selected from the group consisting of the formulas (1) and (2), 5 to 65 mol% of the compound (a12) having an unsaturated bond and a carboxyl group, May be obtained by copolymerizing 5 to 80 mol% of a compound (a13) copolymerized with the above (a11) and (a12) and having an unsaturated bond. In 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 in the alkali-soluble resin (A) can be obtained by further copolymerizing the compound (a14) having an unsaturated bond and an epoxy group in the above (a11), (a12) and (a13) Compounds may be further included and copolymerized.

(A14) imparts light / heat curability to the alkali-soluble resin. Specifically, (a14) is preferably at least one member selected from the group consisting of glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 2,3-epoxycyclopentyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (Meth) acrylate, methylglycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate), methylglycidyl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 2 6] decan-9-yl (meth) acrylate. These may be used alone or in combination of two or more.

(A11), (a12), (a13) and (a14) constituting the first resin, at least one compound selected from the general formulas (2) and (3) And 2 to 70 mol% of a compound (a12) having an unsaturated bond and a carboxyl group, and 2 to 95 mol% of a compound (a13) copolymerized with the above (a11) and (a12) May be obtained by copolymerizing 5 to 80 mol% of a compound (a14) having an unsaturated bond and an epoxy group based on the number of moles of the compound (a12), preferably at least one compound (a11 ) And 5 to 65 mol% of a compound (a12) having an unsaturated bond and a carboxyl group, and 5 to 80 mol% of a compound (a13) copolymerized with the unsaturated bond (a11) (A14) having an unsaturated bond and an epoxy group based on the number of moles of (a12) It may be obtained by the copolymerization%. In 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 according to the present invention preferably has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, more preferably 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, it exhibits hard properties without pixel 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, more preferably 1.8 to 4.0. When the molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) is 1.5 to 6.0, development is preferable.

Further, the alkali-soluble resin (A) according to the present invention comprises a second resin polymerized with a compound (a21) having an alicyclic epoxy group. Accordingly, the second resin may contain a repeating unit containing an alicyclic epoxy group. 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 general formulas (4) and (5).

[Chemical Formula 4]

In the general formula (4), R ₆ is hydrogen or C 1 -C 4 alkyl which is unsubstituted or substituted with a hydroxy group; X may represent a single bond or a C1-C6 alkylene containing or not containing a heteroatom. The single bond may mean that oxygen and the ring are directly connected.

[Chemical Formula 5]

In formula (5), R ₇ is hydrogen or C 1 -C 4 alkyl optionally substituted by hydroxy group; X may represent a single bond or a C1-C6 alkylene containing or not containing a heteroatom. The single bond may mean that oxygen and the ring are directly connected.

The second resin according to the present invention may be polymerized by further containing a compound (a22) having an unsaturated bond and a carboxyl group in the alicyclic epoxy compound (a21) to exhibit alkali solubility.

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

R _{6 in} Formula 4 or R ₇ in Formula 5 are each independently hydrogen; Alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, Hydroxy-n-propyl, 3-hydroxy-n-propyl, 1-hydroxy-isopropyl , A hydroxy-containing alkyl group such as 2-hydroxy-isopropyl, 1-hydroxy-n-butyl, 2-hydroxy-n-butyl, 3-hydroxy- Lt; / RTI &gt; Among them, R ₆ or R ₇ is preferably independently hydrogen, methyl, hydroxymethyl, 1-hydroxyethyl or 2-hydroxyethyl, more preferably hydrogen or methyl.

In the formulas 4 and 5, X is specifically a single bond; Alkylenes such as methylene, ethylene and propylene; Containing alkylene such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, heptylene, heptylene, Among them, X is preferably a single bond, methylene, ethylene, oxymethylene or oxyethylene, more preferably a single bond or oxyethylene.

Examples of the compound represented by the formula (4) include compounds represented by the following formulas (4-1) to (4-14).

[Formula 4-1] [Formula 4-2]

[Formula 4-3] [Formula 4-4]

[Formula 4-5] [Formula 4-6]

[Chemical Formula 4-7] [Chemical Formula 4-8]

[Formula 4-9] [Formula 4-10]

[Chemical Formula 4-11] [Chemical Formula 4-12]

[Chemical Formula 4-13] [Chemical Formula 4-14]

Examples of the compound represented by the formula (5) include compounds represented by the following formulas (5-1) to (5-14).

[Formula 5-1] [Formula 5-2]

[Formula 5-3] [Formula 5-4]

[Formula 5-5] [Formula 5-6]

[Chemical Formula 5-7] [Chemical Formula 5-8]

[Formula 5-9] [Formula 5-10]

[Formula 5-11] [Formula 5-12]

[Chemical Formula 5-13] [Chemical Formula 5-14]

The compound represented by the formula (4) or the compound represented by the formula (5) may be used alone or in combination of two or more.

The second resin may be copolymerized with a compound having an unsaturated bond polymerizable with (a21) and (a22) in addition to (a21) and (a22) Aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl methacrylate, 2-aminopropyl methacrylate, Dimethylaminopropyl acrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3- Unsaturated carboxylic acid aminoalkyl esters; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide; Maleimide, benzyl maleimide, N-phenyl maleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, Such as macromonomers and the like.

(A21) and (a22) constituting the second resin, the amount of the compound (a21) which contains the alicyclic epoxy group-containing compound (a21) in an amount of 5 to 95 mol% and the compound having an unsaturated bond and a carboxyl group (a22), preferably 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, Mol% of the copolymer. In the above range, it is possible to produce a photosensitive resin composition having good developability, solvent resistance, heat resistance and mechanical strength.

The acid value of the second resin is preferably in the range of 20 to 200 (KOH mg / g). When the acid value is in the above range, it becomes possible to produce a spacer having excellent elastic recovery.

The weight average molecular weight of the second resin in terms of polystyrene is 3,000 to 100,000, preferably 5,000 to 50,000. When the weight average molecular weight of the second resin is in the above range, it is preferable to prevent the decrease in film thickness during development and improve the missability of the pattern portion.

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, more preferably 1.8 to 4.0. When the molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) is within the above range, the developability is preferable.

According to exemplary embodiments, the alkali-soluble resin may include the first resin and the second resin described above together. In this case, the alkali-soluble resin preferably comprises 10 to 95% by weight of the first resin and 5 to 90% by weight of the second resin in a weight fraction based on the solid content of the alkali-soluble resin. It is possible to realize a photo-curable pattern having a good elastic recovery rate in the content ratio range and a hard property with little deformation at external pressure.

The term "solids" as used in this application means the sum of the components from which the solvent has been removed.

The alkali-soluble resin according to embodiments of the present invention may comprise a third resin polymerized from a norbornene-based compound.

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

[Chemical Formula 6]

As chemically unstable cyclic hydrocarbon units such as norbornene are contained, the resolution of the alkali-soluble resin or the photosensitive resin composition containing the alkali-soluble resin can be further improved.

In some embodiments, the third resin may further comprise a benzene ring-containing repeating unit, and the benzene ring-containing repeating unit may be derived from, for example, a monomer represented by the following general formula (7).

(7)

In formula (7), R ₃₁ represents 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, A C 1 -C 6 alkyl group, a C 4 -C 8 cycloalkyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, an oxirane group, an oxirane group, a substituted or unsubstituted cycloalkyl group or a C 6 -C 18 tricycloalkyl group, Group, a C4-C12 bicycloalkyl group or a C6-18 tricycloalkyl group.

The heat resistance and mechanical strength of the third resin may be improved by the benzene ring-containing repeating unit. In this respect, R ₃₁ preferably may be hydrogen or a C 1 -C 6 alkyl group (for example, a methyl group).

In some embodiments, the third resin may further comprise a carboxylic acid containing repeating unit, in which case the resolution can be further improved by the addition of a hydrogen donor unit.

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

In some embodiments, the third resin may further comprise an acrylate repeat unit formed by polymerizing further comprising an acrylate monomer commonly used and commonly known in the art for imparting or enhancing optical or thermosetting properties have.

The arylate monomer may be, for example, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (metha) acrylate, (Meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t- Butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (Meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl Methoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) (Meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (Meth) acrylates such as glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate,? -Phenoxyethoxyethyl acrylate, nonylphenoxypolyethylene glycol , Dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl Acrylate, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, glycidyl (meth) acrylate and the like. These may be used alone or in combination of two or more.

In one embodiment, the third resin has the formula Containing group, a repeating unit, a benzene ring-containing repeating unit, a carboxylic acid-containing repeating unit and an acrylate repeating unit in a molar ratio of 5 to 70 mol%, 5 to 50 mol%, 5 to 65 mol% and 5 to 70 mol%, respectively .

The third resin preferably has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, more preferably 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, more preferably 1.8 to 4.0. Excellent developability and resolution in the molecular weight distribution range can be ensured.

According to exemplary embodiments, the alkali-soluble resin may include the second resin and the third resin described above together. 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 in a weight fraction based on the solid content of the alkali-soluble resin. A high-resolution photocuring pattern can be realized while having good adhesion and elasticity in the content ratio range.

According to the above-described embodiments of the present invention, the alkali-soluble resin includes the second resin, and may further include at least one of the first resin or the third resin. Accordingly, chemical properties such as photo-curability, photoreactivity, resolution and developability and mechanical properties such as hardness, elasticity and adhesion can be improved together.

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 comprise a combination of the first resin, the second resin and the third resin.

The content of the alkali-soluble resin is usually in the range of 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 on the basis of the above-mentioned criteria, the preparation of a spacer having sufficient solubility in a developing solution and being excellent in developability and having a hardness with little change in external pressure, .

Photopolymerizable compound

The photopolymerizable compound contained in the photosensitive resin composition of the present invention is a compound capable of polymerizing under the action of the photopolymerization initiator, and examples thereof include monofunctional monomers, bifunctional monomers, and other polyfunctional monomers.

The photopolymerizable compound used in the present invention may be prepared by mixing two or more photopolymerizable compounds having different functional groups or different functional groups in order to improve developability, sensitivity, adhesion, surface problems, etc. of the resin composition for forming a spacer , There is no restriction on the range.

Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Money and so on.

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) Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

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) acrylate, tripentaerythritol octa (meth) acrylate, and the like. Of these, multifunctional monomers having two or more functional groups are preferably used.

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

solvent

The solvent may be any solvent as long as it is commonly used in the art.

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; Propylene glycol alkyl ether propionates; Butyldiol monoalkyl ethers; Butanediol monoalkyl ether acetates; Butanediol monoalkyl ether propionates; Dipropylene glycol dialkyl ethers; Aromatic hydrocarbons; Ketones; Alcohols; Esters; Cyclic esters and the like. These may be used alone or in combination of two or more.

The solvent may be selected from alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers and esters, and 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 and the like.

The content of the solvent may be in the range of 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-mentioned range is satisfied, it is preferable that the coating property is improved when applied with a coating apparatus such as a spin coater, a slit & spin coater, a slit coater (or a die coater, a curtain flow coater) or an ink jet.

additive

The photosensitive resin composition according to the present invention may further contain additives such as fillers, other polymer compounds, curing agents, leveling agents, adhesion promoters, antioxidants, ultraviolet absorbers, antiflocculants and chain transfer agents.

<Photocuring pattern and image display device>

The present invention also provides an image display device comprising the photo-curable pattern produced by the photosensitive resin composition described above and the photo-curable pattern.

The photocurable pattern prepared from the photosensitive resin composition is excellent in elastic recovery rate, adhesion, and the like. As a result, it can be used for various patterns such as an adhesive layer, an array flattening film, a protective film, an insulating film pattern, and the like in an image display apparatus, and can be used as a photoresist, a black matrix, a column spacer pattern, a black column spacer pattern, But is not limited thereto, and is particularly suitable as a spacer pattern.

The image display device having the light curing pattern or using the pattern during the manufacturing process may include a liquid crystal display device, an OLED, a flexible display, and the like. However, the present invention is not limited thereto, Can be exemplified.

The photo-curing pattern can be produced by applying the above-described photosensitive resin composition of the present invention onto a substrate and forming a photo-curable pattern (after the development step if necessary).

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 by the following Production Examples, Examples, Comparative Examples and Experimental Examples, .

[Manufacturing Example]

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) was carried out by the GPC method under the following conditions, and the ratio of the weight average molecular weight to the number average molecular weight was measured by a molecular weight distribution (Mw / Mn):

Apparatus: HLC-8120GPC (manufactured by TOSOH CORPORATION)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial connection)

Column temperature: 40 DEG C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection amount: 50 μl

Detector: RI

Measurement sample concentration: 0.6 wt% (solvent = tetrahydrofuran)

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by TOSOH CORPORATION)

[Preparation Example 1] Preparation of A-1 (first resin)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 182 g of propylene glycol monomethyl ether acetate, and the atmosphere in the flask was changed to nitrogen in air. After raising the temperature to 100 캜, 35.4 g (0.2 mol) of 2-hydroxy-o-phenylphenol propyl acrylate, and 136 g of propylene glycol monomethyl ether acetate was added to a mixture of azobisisobutyronitrile (0.30 mol), acrylic acid (36.0 g, 0.50 mol) Was added dropwise to the flask over 2 hours from the dropping funnel, and stirring was further continued at 100 占 폚 for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 22.5 g [0.15 mol (50 mol% based on the acrylic acid used in the present reaction) of glycidyl methacrylate], 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone And the reaction was continued at 110 캜 for 6 hours to obtain an unsaturated group-containing first resin A-1 having a solid acid value of 121.1 mgKOH / g. The weight average molecular weight measured by GPC in terms of polystyrene was 31,000 and the molecular weight distribution (Mw / Mn) was 2.2.

[Preparation Example 2] Preparation of A-2 (second resin)

A 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with nitrogen at 0.02 L / min to make a nitrogen atmosphere, and 150 g of diethylene glycol ethyl methyl ether was added and heated to 70 캜 with stirring. Next, 198.2 g (0.90 mol) of a mixture of the above-mentioned formulas (4-1) and (5-1) (molar ratio 50:50) and 8.6 g (0.10 mol) of methacrylic acid were dissolved in 150 g of diethylene glycol ethyl methyl ether, Lt; / RTI &gt;

[Formula 4-1] [Formula 5-1]

The resulting solution was dropped into a flask using a dropping funnel, 27.9 g (0.11 mol) of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 200 g of diethylene glycol ethyl methyl ether Was added dropwise to the flask over 4 hours using a separate dropping funnel. After the dropwise addition of the polymerization initiator solution was completed, the solution was maintained at 70 DEG C for 4 hours, and then cooled to room temperature to obtain a copolymer (resin A-2) having a solids content of 41.6% by weight and an acid value of 59 mg-KOH / 2) was obtained. The resin A-2 thus obtained had a weight average molecular weight Mw of 7,790 and a molecular weight distribution of 1.9.

[Preparation Example 3] Preparation of A-3 (third resin)

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was introduced at 0.02 L / min to make a nitrogen atmosphere, and 200 g of propylene glycol monomethyl ether acetate was introduced. After raising the temperature to 100 캜, 33.9 g Azobis (2,4-dimethylvaleronitrile) 3.6 (5 g) was added to a mixture containing 4.7 g (0.05 mol) of norbornene, 56.7 g (0.48 mol) of vinyltoluene and 150 g of propylene glycol monomethyl ether acetate g was added dropwise to the flask over a period of 2 hours from the dropping funnel, and stirring was further continued at 100 ° C for 5 hours.

Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 42.6 g of glycidyl methacrylate (0.30 mol (64 mol% based on the acrylic acid used in the present reaction)) was charged into the flask, and the reaction was continued at 110 DEG C for 6 hours To obtain an unsaturated group-containing resin A-1 having a solid acid value of 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.

[Preparation Example 4] Synthesis of unsaturated group-containing resin A-4

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, and the atmosphere in the flask was changed to nitrogen in air. After raising the temperature to 100 캜, benzyl methacrylate 88.1 A solution prepared by adding 3.6 g of azobisisobutyronitrile to a mixture containing 50 g (0.50 mol) of acrylic acid, 36.0 g (0.50 mol) of acrylic acid and 136 g of propylene glycol monomethyl ether acetate was added dropwise to the flask over 2 hours from the dropping funnel Stirring was continued at 100 &lt; 0 &gt; C for additional 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 22.5 g [0.15 mol (50 mol% based on the acrylic acid used in the present reaction) of glycidyl methacrylate], 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone And the reaction was continued at 110 캜 for 6 hours to obtain a resin A-3 having a solid acid value of 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 the examples and comparative examples were prepared by the composition and the content (unit: parts by weight) of the following Tables 1 and 2.

division Example One 2 3 4 5 6 7 8 9 10 11 12 Alkali-soluble resin
(A) A-1 30.00 35.00 40.00 25.00 20.00 30.00 30.00 30.00 30.00 30.00 - - A-2 30.00 25.00 20.00 35.00 40.00 30.00 30.00 30.00 30.00 30.00 30.00 25.00 A-3 - - - - - - - - - - 30.00 35.00 A-4 - - - - - - - - - - - - Photopolymerization initiator
(B) B-1 3.00 3.00 3.00 3.00 3.00 3.50 4.00 4.50 5.00 3.00 3.00 3.00 B-2 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 - 1.00 1.00 B-3 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 - 2.00 2.00 The photopolymerizable compound (C) 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 Additive (D) 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 solvent
(E) E-1 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 E-2 70.00 70.00 70.00 70.00 70.00 70.00 70.00 70.00 70.00 70.00 70.00 70.00

division Example Comparative Example 13 14 15 16 17 18 19 20 One 2 3 Alkali-soluble resin
(A) A-1 - - - - - - - - - 30.00 30.00 A-2 20.00 35.00 40.00 30.00 30.00 30.00 30.00 30.00 - - 30.00 A-3 40.00 25.00 20.00 30.00 30.00 30.00 30.00 30.00 30.00 - - A-4 - - - - - - - - 30.00 30.00 - Photopolymerization initiator
(B) B-1 3.00 3.00 3.00 3.50 4.00 4.50 5.00 3.00 3.00 3.00 - B-2 1.00 1.00 1.00 1.00 1.00 1.00 1.00 - 1.00 1.00 1.00 B-3 2.00 2.00 2.00 2.00 2.00 2.00 2.00 - 2.00 2.00 2.00 The photopolymerizable compound (C) 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 Additive (D) 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 solvent
(E) E-1 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 E-2 70.00 70.00 70.00 70.00 70.00 70.00 70.00 70.00 70.00 70.00 70.00

The specific components of each composition are as follows.

A-1: Resin (first resin) prepared in Production Example 1

A-2: Resin (second resin) prepared in Preparation Example 2

A-3: Resin (third resin) prepared in Production Example 3

A-4: The resin prepared in Preparation Example 3

B-1: 1- (9,9-H-7-Nitroploren-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 INTERNATIONAL CORP.)

B-3: diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide (IRGACURE-819: BASF)

C: Tripapentaerythritol octaacrylate (Viscoat # 802: Osaka Organic Chemical Industry Co., Ltd.)

D: dipentaerythrityl 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 glass substrate (Eagle 2000; Corning) having an aspect ratio of 2 inches was sequentially washed with a neutral detergent, water and alcohol, and then dried. The photosensitive resin compositions prepared in the above Examples and Comparative Examples were each spin-coated on this glass substrate, and then prebaked in a clean oven at 90 캜 for 3 minutes. The prebaked substrate was cooled to room temperature and light was irradiated at an exposure dose of 60 mJ / cm 2 (based on 405 nm) using an exposure apparatus (TME-150RSK; Topcon Co., Ltd.) with an interval of 150 μm from the quartz glass photomask Respectively. The irradiation of the polymerizable resin composition at this time was carried out by passing the radiation from the ultra-high pressure mercury lamp through an optical filter (LU0400, manufactured by Asahi Spectroscopy) and cutting light having a wavelength of 400 nm or less. At this time, the photomask used was a photomask in which the following pattern was formed on the same plane (a circular light-transmitting portion (pattern) having a diameter of 20 mu m, the interval of the pattern being 100 mu m).

After the light irradiation, the coating film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 캜 for 100 seconds and developed, and after post-baking at 220 캜 for 20 minutes in an oven. The obtained film thickness was 3 占 퐉. The film thickness was measured using a film thickness measuring apparatus (DEKTAK 6M; Veeco). The pattern thus obtained was evaluated for physical properties as described below, and the results are shown in Tables 3 and 4 below.

<Test Method>

(1) Bottom CD measurement

Using the three-dimensional shape measuring apparatus (SIS-2000 Systems, manufactured by SNU Precision Co., Ltd.), the height of the pattern and the bottom CD were set to 20 mu m and 3.0 mu m The pattern of the smallest size that keeps the thickness of the coating film at 2.85 mu m is measured.

As shown in FIG. 1, the value was defined as the value of Bottom CD, which is a linewidth of 5% of the height. The smaller the Bottom CD, the better the sensitivity is.

(2) Measurement of pattern width ratio (T / B ratio)

A point at 5% of the total height from the bottom surface of the pattern is referred to as a bottom CD (a), a bottom (bottom) at the bottom of the pattern is measured using a three-dimensional shape measuring apparatus (SIS-2000 Systems manufactured by SNU Precision) (= B / a x 100) obtained by dividing the length of (b) by the length of (a) and then multiplying by 100 is defined as a ratio T / B Respectively.

(3) Developing adhesion

The developed adhesion was evaluated by a microscope in which a pattern formed with a film thickness of 3 mu m by a photomask having 1000 circular patterns with a diameter of 5 mu m to 20 mu m at intervals of 1 mu m was counted by counting the number of missing patterns The developing adhesion (%) was calculated as shown in Equation 1, and the results are shown in Table 2 below.

[Equation 1]

Peel adhesion (%) = [1000- (number of missing patterns)] / 1000 x 100

(4) Mechanical characteristics (recovery rate)

The total amount of displacement (占 퐉) and the amount of elastic displacement (占 퐉) were measured under the following measurement conditions using a dynamic ultra-microhardness tester (DUH-W201; manufactured by Shimadzu Corporation) The recovery rate (%) was calculated using the following equation (2). When the total displacement was small and the recovery rate was high, it was judged to be rigid.

&Quot; (2) &quot;

Recovery rate (%) = [elastic displacement amount (占 퐉)] / [total displacement amount (占 퐉)] 占 100

[Measuring conditions]

Test mode: Load - Unload test

Test force: 5 gf [SI converted value 49.0 mN]

Load speed: 0.45 gf / sec [SI converted value 4.41 mN / sec]

Holding time: 5sec

Indenter: conical indenter (diameter 50 탆)

division Example One 2 3 4 5 6 7 8 9 10 11 12 Pattern precision evaluation Bottom CD (탆) 11.0 10.6 10.3 11.1 11.3 11.2 11.3 11.6 11.7 10.8 10.5 10.3 T / B ratio 82.0 80.1 78.9 82.8 84.0 82.1 82.2 82.1 82.1 75.1 83.0 82.1 Developing adhesion
(%) 100 100 100 100 100 100 100 100 100 80.0 100 100 Mechanical properties
evaluation Shout
Recovery rate
(%) 56.8 57.2 58.0 56.1 55.8 56.0 56.4 56.7 56.8 54.3 56.5 56.6

division Example Comparative Example 13 14 15 16 17 18 19 20 One 2 3 Pattern precision
evaluation Bottom CD (탆) 10.1 10.7 10.9 10.7 10.7 11.0 11.0 10.3 13.4 13.1 - T / B ratio 80.0 83.2 85.1 83.2 83.0 83.1 83.1 78.0 68 65 - Developing adhesion (%) 100 100 100 100 100 100 100 80.
0 88.0 100 - Mechanical properties
evaluation Shout
Recovery rate
(%) 57.0 55.9 53.8 53.0 53.4 53.4 53.7 53.8 52.1 48.5 -

Referring to the above Tables 3 and 4, in the embodiments in which the above-mentioned photopolymerization initiator (B-1) and the first resin or the third resin are optionally contained together with the second resin as the alkali-soluble resin, T / B ratio, elastic recovery rate, and development adhesion strength. Also, relatively improved resolution results were obtained for Examples 11 to 20 where a third resin was used with the second resin.

On the other hand, in the case of Comparative Examples 1 and 2 in which the second resin was omitted, the results were overall deteriorated as compared with the Examples. Also, in the case of Comparative Example 3 in which the photopolymerization initiator according to the embodiments of the present invention was omitted, no pattern was formed and it was impossible to measure the bottom CD, the T / B ratio, the developing adhesion and the elastic recovery rate.

Claims (14)

An alkali-soluble resin containing an alicyclic epoxy-containing repeating unit;
A photopolymerization initiator comprising a compound represented by the following formula (1);
Photopolymerizable compounds; And
A photosensitive resin composition comprising a solvent:
[Chemical Formula 1]

(Wherein R ₃ is C 1 -C 20 alkyl, R ₄ and R ₅ are each independently C 1 -C 20 alkyl, C 6 -C 20 aryl or C 3 -C 20 cycloalkyl, and A is nitro or cyano).
[2] The method according to claim 1, wherein the alkali-
A first resin polymerized with at least one compound selected from the group consisting of compounds represented by the following formulas (2) and (3); And
And a second resin comprising the repeating unit containing an alicyclic epoxy group.
(2)

(Wherein R ₁ is hydrogen, C ₁ -C 12 alkyl, allyl, phenyl, benzyl, halogen or C 1 -C 8 alkoxy)
(3)

(Wherein R &lt; ₂ &gt; is hydrogen, C1-C12alkyl, allyl, phenyl, benzyl, halogen or C1-C8alkoxy and n is an integer of 1 to 10)
The photosensitive resin composition according to claim 2, wherein the first resin further comprises an alkyl-substituted maleimide or an aryl-substituted maleimide-containing repeating unit.
[2] The method according to claim 1, wherein the alkali-
A second resin comprising the alicyclic epoxy group-containing repeating unit; And
A third resin comprising a norbornene repeating unit.
5. The photosensitive resin composition according to claim 4, wherein the third resin further comprises 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 Chemical Formula 4 or Chemical Formula 5:
[Chemical Formula 4]

(Wherein R &lt; ₆ &gt; is hydrogen or C1-C4 alkyl which is unsubstituted or substituted with a hydroxy group;
X is a single bond or a C1-C6 alkylene containing or not containing a hetero atom)
[Chemical Formula 5]

(Wherein R &lt; ₇ &gt; is hydrogen or C1-C4 alkyl optionally substituted by hydroxy group;
X is a single bond or a C1-C6 alkylene containing or not containing a heteroatom.
3. The compound of claim 1, wherein R &lt; ₃ &gt; in the formula (1) is methyl, ethyl, n-propyl, i-propyl, n-butyl, Lt;
R ₄ to R ₅ are each independently selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t- butyl, n-pentyl, , Naphthyl, biphenyl, terphenyl, anthryl, indenyl or phenanthryl.
The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator further comprises at least one of an acetophenone derivative compound or a nonimidazole derivative compound.
9. The photosensitive resin composition according to claim 8, wherein the photopolymerization initiator comprises 40 to 90% by weight of the compound of the general formula (1) based on the total weight of the photopolymerization initiator.
The photosensitive resin composition according to claim 1, wherein the content of the photopolymerization initiator is 0.1 to 40 parts by weight based on 100 parts by weight in total based on the solid content of the alkali-soluble resin and the photopolymerizable compound.
The photosensitive resin composition according to claim 1, 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.
A photocurable pattern produced from the photosensitive resin composition according to any one of claims 1 to 11.
13. The photocurable pattern according to claim 12, wherein the photocurable 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.
An image display apparatus having the photocuring pattern of claim 12.

Images