KR20160079319A - Negative-type Photoresist Composition - Google Patents

Abstract

The present invention relates to a negative-type photoresist composition, and more specifically, to a negative-type photoresist composition comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a photoacid generator, and a monofunctional compound having at least one epoxy group, oxetane group, or vinyl ether group within a molecular structure. The composition does not control physical properties of a non-exposure part, but controls physical properties of an exposure part. The composition is capable of improving sensitivity by lowering developing properties of the exposure part. The composition solves a brittle problem that the exposure part is caked due to conventional crosslinking, and is capable of being desirably applied to a filed requiring flexibility since there is not an excessive increase in the curing extent after performing the post-bake process.

Description

Negative-type Photoresist Composition < RTI ID = 0.0 >

The present invention relates to a negative type photoresist composition capable of suppressing an excessive increase in the degree of curing of an exposed portion and at the same time capable of selectively lowering developability.

Materials used for semiconductor devices are not changed in their properties even when they are exposed to light. In order to transfer a circuit design of a mask master plate to a wafer through an exposure process, a medium is required, which is called a photoresist.

A photoresist is a material that receives light of a specific wavelength and selectively removes a portion that receives light and a portion that does not receive light during a subsequent development process by using a property that the solubility of the developer is changed. The photoresist removes a portion selectively changed by light using a developing solution. A positive photoresist when the light-receiving portion is well dissolved by the developing solution, and a negative photoresist when the exposed portion remains on the contrary .

The photoresist having such characteristics is the first technical material for determining the line width of an ultra fine circuit when a semiconductor device such as an IC or an LSI is manufactured, and it can be said to be a key material that determines the achievement of high integration of a semiconductor.

Research and development are proceeding from various viewpoints such as photoresist materials, exposure techniques, and light sources to achieve ultrafine-line widths. From the material standpoint, there has been an attempt to improve the sensitivity of the photoresist in the development process to obtain a fine pattern.

The ideal photoresist, the negative type photoresist, is required to completely develop the unexposed portion when it exceeds the limit exposure amount, and not to develop it at all. In practice, the phenomenon occurs slightly in the exposure portion and the solubility of the exposed portion and the non- The difference is not so large and sufficient resolution can not be secured.

For example, U.S. Patent No. 4,139,391 discloses a photosensitive composition using an acrylic binder resin. In the case of this composition, the difference in solubility between the exposed portion and the non-exposed portion is not sufficiently large and the developing property is poor. There is a problem that it is difficult to obtain a fine pattern because the binder resin is partially dissolved in the developing solution.

In the case of the negative type photoresist, the development characteristics of the non-exposed portion pattern must be relatively higher than that of the exposed portion, so that the development of the non-exposed portion has been proceeded.

The photoresist currently used is based on an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a photoacid generator, and a solvent, and is used for controlling the sensitivity and developability by changing the composition of these compositions or adding a new composition There were various attempts.

WO 2007/010919 discloses that by using a copolymer copolymerized with a fluorine-containing and non-fluorine-based segment, excellent alkali developing property, sensitivity, resolution, transparency, adhesion, and alkali resistance can be obtained and a fine pattern can be formed with high precision Lt; / RTI >

Korean Patent Laid-Open Publication No. 2009-0121685 discloses that by using alkali-soluble polyimide resin and alkali-soluble novolak resin at a certain ratio, difference in developability between an exposed portion and an unexposed portion is increased to improve sensitivity and easy adjustment of side angle of pattern .

Korean Patent Laid-Open Publication No. 2008-0058558 discloses that the chemically modified carbon nanotubes are used to improve the developability of the exposed portion and the non-exposed portion during pattern formation and improve the sensitivity, resolution, and heat resistance .

In these patents, only the phenomenon difference between the exposed part and the non-exposed part is described, but it is not suggested how the difference of the developedness can be controlled in detail.

On the other hand, after development, the layer is washed with ordinary water and dried to obtain a predetermined pattern, and then a post-exposure bake or hard bake process is performed.

The post-baking process is performed at a temperature higher than the glass transition temperature (Tg) of this material, usually 180 ° C or more and 250 ° C or less, so as to prevent deformation of the photoresist. It is possible to obtain an effect that the post-baking step hardens the exposed pattern and improves the mechanical strength. It is a general process to add a curing agent such as an epoxy compound or an oxetane compound to the photoresist composition to improve the mechanical strength.

High post-bake mechanical properties may be required depending on the application area of the photoresist, but this may be an undesirable change in physical properties in areas where flexibility is required.

In the case of the spacer used for holding the cell gap of the liquid crystal display device, inorganic particles have been used in the past, but recently, a photoresist has been applied. For application to spacers, the photoresist must have a high degree of compressive displacement and a high elastic recovery rate with a certain degree of flexibility, but this property can not be sufficiently secured due to excessive curing due to the hardening agent or the post-baking process.

Korean Patent Registration No. 10-0793946 discloses a photosensitive resin composition comprising an alkali-soluble resin, a reactive unsaturated compound, a photoinitiator and a solvent having a specific structure for use as a column spacer, wherein the composition has excellent compressive displacement, And a residual film ratio.

In addition, International Publication (WO) 2013/018705 discloses a photosensitive resin composition having a hydrophilic resin, a polyfunctional (meth) acrylate, a radical trapping agent, a photopolymerization initiator and a metal element- And the like.

However, according to the contents of the respective examples of the Korean Patent Registration No. 10-0793946 and International Publication (WO) 2013/018705, the post-baking is performed in an oven at 220 ° C for 30 minutes or at 230 ° C for 30 minutes in an oven after exposure and cleaning , And it can be seen that the above-mentioned curing degree is still excessively increased.

International Publication (WO) 2007/010919 Korean Patent Publication No. 2009-0121685 Korean Patent Publication No. 2008-0058558 Korean Patent Registration No. 10-0793946 International Publication (WO) 2013/018705

The present applicant has conducted various studies to control the development characteristics of the exposed portion, not the non-exposed portion, to improve the sensitivity by controlling the development characteristics of the exposed portion and the unexposed portion in the negative type photoresist composition. As a result, A composition containing a monofunctional compound was prepared so that the functional group of the resin was protected with a functional group having high hydrophobicity to relatively lower the developability of the exposed part. The composition not only reduced the developability of the exposed part, It is confirmed that the degree of curing is not excessively increased, and the present invention has been completed.

Accordingly, an object of the present invention is to provide a negative-working photoresist composition which selectively lowers developability of an exposed portion in a developing process and does not excessively increase the degree of curing even after the post-baking process.

In order to achieve the above object, a negative type photoresist composition according to the present invention comprises an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a photoacid generator, and a polymer having at least one epoxy group, oxetane group or vinyl ether group And a functional compound.

The monofunctional compound may be a monofunctional epoxy compound, monofunctional oxetane compound, or monofunctional vinyl ether compound represented by the following formula.

Preferably, the monofunctional epoxy compound is a compound represented by:

Preferably, the monofunctional oxetane compound is a compound represented by:

Preferably, the monofunctional vinyl ether compound is a compound represented by the following formula:

The monofunctional compound is used in an amount of 0.5 to 30% by weight in 100% by weight of the total negative type photoresist composition.

Wherein the alkali-soluble resin has a carboxyl group or a hydroxy group in the molecular structure.

The negative photoresist composition according to the present invention has the effect of selectively lowering the developability of the exposed portion and suppressing an excessive increase in the degree of curing after the post-baking process.

Therefore, the composition can obtain a pattern consisting of only the exposed part selectively without residue after the development process, and the obtained pattern also has a problem of brittle the pattern due to the additional curing due to no excessive curing during the post-baking step And can be suitably applied to fields requiring flexibility of the pattern.

Such a negative type photoresist composition can be used as a photoresist material for processing a highly integrated semiconductor and a printed circuit board, a photosensitive material for a printing plate, and a photoresist material for processing various display devices, or as an insulating film, a protective film, a passivation film, Matrix, column spacer, and the like.

The present invention provides a negative type photoresist composition for controlling developability of an exposed portion, not a method for controlling developability of an unexposed portion for sensitivity control.

The negative type photoresist composition is a composition capable of selectively removing only the unexposed portion due to the developing property of the exposed portion / unexposed portion due to the protective reaction of the developing functional group only in the exposed portion. In general, the control of developability in a photoresist composition is considered only in the non-visible portion. However, in the present invention, a new concept is approached to sufficiently reduce the developability of the exposed portion and further increase the difference in developability of the exposed portion / non- do.

In addition to the above developments, the degree of curing can be considered in the exposure part. In general, the light exposure proceeds by UV exposure, and then a post bake process is performed, and further curing is carried out by such heat treatment. At this time, there is a problem that physical properties of a pattern to be finally obtained are changed due to excessive curing. In the present invention, not only the resolution and sensitivity can be increased due to deterioration of developability of the exposed part by exposure, There is provided a method capable of suppressing an excessive increase in the degree of curing of an exposed portion (i.e., a pattern) after a process.

Accordingly, the composition of a negative photoresist composition of a novel composition is designed so that an excessive increase in the degree of curing of the exposed portion is suppressed and at the same time, developability is selectively reduced.

The negative-type photoresist composition includes an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a photoacid generator, and a monofunctional compound having a specific functional group is used together for controlling the above-mentioned degree of curing and developability.

Preferably, the monofunctional compound may be a monofunctional epoxy compound, a monofunctional oxetane compound, and a monofunctional vinyl ether compound, and they are represented by the following formula:

≪ Monofunctional epoxy compound &

<Monofunctional oxetane compound>

&Lt; Monofunctional vinyl ether compound >

As for the monofunctional compounds having the above-described chemical structure, there is one epoxy group, oxetane group and vinyl group in the molecular structure. These functional groups react with a carboxyl group or a hydroxyl group present in the alkali-soluble resin to form an alkali-soluble functional group Lt; / RTI &gt; This alkali-soluble functional group protection does not cause excessive thermal curing in the exposed portion in the subsequent post-baking process.

As an example, in the case of the monofunctional epoxy compound, the monofunctional oxetane compound and the monofunctional vinyl ether compound in the following Reaction Schemes 1 to 3, the carboxyl group of the alkali-soluble resin may react with the double bond to protect the alkali-soluble functional group. For convenience, the alkali-soluble resin is represented by R in the remaining part other than the carboxylic acid.

[Reaction Scheme 1]

Referring to Reaction Scheme 1, the OH functional group of the carboxylic acid attacks an epoxy ring, and an ester bond is formed by a ring-opening reaction of the epoxy ring.

[Reaction Scheme 2]

Referring to Reaction Scheme 2, the OH functional group of the carboxylic acid attacks the oxetane ring and the ester bond is formed by ring-opening reaction of the oxetane ring.

[Reaction Scheme 3]

Referring to Reaction Scheme 3, the OH functional group of the carboxylic acid attacks the double bond of the vinyl ether compound to form an ester bond.

The monofunctional compound protects the alkali-soluble functional groups of the alkali-soluble resin by the reaction similar to the reaction schemes 1 to 3 above.

The alkali-soluble functional group of the alkali-soluble resin is protected by a hydrophobic functional group as shown in Reaction Scheme 1 to increase the insolubility (that is, the development degree) of the alkali developing solution in the patterning process to further improve the sensitivity of the exposed portion / . Such developability can be further preferably lowered due to high hydrophobicity when the monofunctional monofunctional epoxy compound is used.

Further, the content of the thermosetting functional group in the molecular structure is reduced, and the degree of curing of the post-baking pattern can be suppressed from increasing too much.

Conversely, when a bifunctional or multifunctional compound having two or more functional groups other than the monofunctional compound is used, the alkali solubility may be reduced. However, due to an excessive increase in the degree of curing, .

As described above, the technique for suppressing an increase in the degree of over-curing of the exposed portion can be applied to various fields requiring a soft texture, for example, as a column spacer CS of a liquid crystal display device.

These monofunctional compounds are limited in their contents in consideration of the effects of controlling the degree of curing and lowering of developability as described above, and the number of carboxyl groups and hydroxyl groups (i.e., acid value) present in the alkali- To limit its content. Preferably, 0.5 to 30% by weight, preferably 1.0 to 20% by weight, based on 100% by weight of the total negative photoresist composition, based on the solids content, can be used. If the content is less than the above range, the effect of lowering the developability can not be ensured as described above, and the functional groups of the alkali-soluble resin can not be sufficiently protected, so that the post-baking process proceeds further and the curing degree is excessively increased Lt; / RTI &gt; On the other hand, when the amount is above the above range, the content of the other composition is reduced, and there is no further increase in the effect, so that it is economically uneconomical.

The negative type photoresist composition proposed in the present invention together with the above monofunctional compound includes an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent and other additives.

The alkali-soluble resin has reactivity and alkali solubility due to the action of light or heat, and any binder resin that is soluble in the alkaline developer used in the development step can be used.

Preferably, the alkali-soluble resin having an acid value of 20 to 200 (KOH mg / g) is selected and used. The acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic polymer, and is related to the solubility. When the acid value of the resin falls within the above range, the solubility in the developer is improved, the non-exposed portion easily dissolves and the sensitivity is increased, and consequently the pattern of the exposed portion remains during development, thereby improving the film remaining ratio.

The alkali-soluble resin may vary depending on the field of application of the present negative-type photoresist composition. However, the weight-average molecular weight of the alkali-soluble resin may be in the range of 3,000 to 200,000 , Preferably 5,000 to 100,000, and the molecular weight distribution is 1.5 to 6.0, preferably 1.8 to 4.0.

Such an alkali-soluble resin includes one selected from the group consisting of a copolymer of a carboxyl group-containing unsaturated monomer, a copolymer of a monomer having a copolymerizable unsaturated bond and a combination thereof.

The carboxyl group-containing unsaturated monomer may be an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid. Specific examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof 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, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl ), Phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be mono (meth) acrylate of the both terminal dicarboxylic polymer, and examples thereof include omega -carboxypolycaprolactone monoacrylate, omega -carboxylic polycaprolactone monomethacrylate and the like . These carboxyl group-containing monomers may be used alone or in combination of two or more.

The monomer copolymerizable with the carboxyl group-containing unsaturated monomer may be an aromatic vinyl compound, an unsaturated carboxylic acid ester compound, an unsaturated carboxylic acid aminoalkyl ester compound, an unsaturated carboxylic acid glycidyl ester compound, a carboxylic acid vinyl ester compound, An aliphatic conjugated diene compound, a macromonomer having a monoacryloyl group or monomethacryloyl group at the end of the molecular chain, a vulcanizable monomer, and a combination thereof in the group consisting of an ether compound, a vinyl cyanide compound, an unsaturated imide compound, an aliphatic conjugated diene compound, One selected paper is available.

More specifically, the copolymerizable monomer is selected from the group consisting of styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m- Vinylbenzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl Aromatic vinyl compounds such as ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, Hydroxyethyl acrylate, ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, But are not limited to, acrylic esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, , 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, Methoxypropyleneglycol methacrylate, methoxypropyleneglycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate Dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, Acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacryl (meth) acrylate, norbornyl Unsaturated carboxylic acid esters such as glycerol monomethacrylate; Aminoethyl methacrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturated carboxylates such as methyl acrylate, ethyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, Acid amino alkyl ester compounds; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ether compounds 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 imide compounds 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, Macromonomers; A bulky monomer such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, or a monomer having a rosin skeleton which can lower the relative dielectric constant can be used.

Such an alkali-soluble resin may be used in an amount of 5 to 85% by weight, preferably 7 to 50% by weight, based on 100% by weight of the total negative type photoresist composition based on the solid content. Such an amount is a range selected considering various factors such as solubility in a developing solution, pattern formation, etc. When the composition is used within the above range, solubility in a developing solution is sufficient and pattern formation is easy, and pattern loss in the exposed portion is reduced do.

The photopolymerizable compound is a compound capable of polymerizing under the action of a photopolymerization initiator, and monofunctional monomers, bifunctional monomers, and other polyfunctional monomers can be used.

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, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) And pentaerythritol hexa (meth) acrylate. Of these, multifunctional monomers having two or more functional groups are preferably used.

Such a photopolymerizable compound may be used in an amount of 1 to 50% by weight, preferably 4 to 20% by weight, based on 100% by weight of the total negative type photoresist composition based on the solid content. Such a range is selected considering various tendencies such as the strength and smoothness of the pattern. If the content is less than the above range, the strength and smoothness of the pattern made of the composition are insufficient. On the other hand, The patterning is not easy due to high strength. Therefore, it is appropriately used within the above range.

The negative photoresist resin composition of the present invention together with the alkali-soluble resin and the photopolymerizable compound can be used without any particular limitation in the photopolymerization initiator used in the art.

These photopolymerization initiators can act as catalysts for the bonding reaction between the monofunctional compound and the alkali binder resin together with the initiation reaction of the photopolymerizable compound.

For example, there can be mentioned oxime compounds, acetophenone compounds, nonimidazole compounds, triazine compounds, acylphosphine oxide compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, anthracene compounds, They may be used alone or in admixture of two or more, preferably oxime compounds or other initiator compounds.

The oxime-based compound is preferably 1- (4-phenylthiophenyl) -1,2-octanedione -2- (O-benzoyloxime) Acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid ethyl ester - (4-methylsulfanyl-phenyl) -butan- O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid ethyl ester-O-benzoate, ethanone-1- [ Benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime).

The acetophenone compound is, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan- -Butanone, 2- (3-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -Morpholinophenyl) -butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- Amino-1- (4-morpholinophenyl) -butanone, 2- (2-butylbenzyl) -2-dimethylamino- -Dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,4-dimethyl 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-chlorobenzyl) 2- (3-chlorobenzyl) -2-dimethylamino-1- (4-morpholino) 2-dimethylamino-l- (4-morpholinophenyl) -butanone, 2- (3-bromobenzyl) Butanone, 2- (2-methoxyphenyl) -butanone, 2- (4-bromophenyl) Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methoxybenzyl) , 2- (2-methyl-4-methoxybenzyl) -2-dimethylamino-1-methyl- - (4-morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) - Bromo Methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy- -1-one oligomers and the like.

Examples of the non-imidazole-based 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) Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis Imidazole compounds in which 4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole or phenyl group at 4,4', 5,5 'position is substituted by a carboalkoxy group. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole or 2,2'-bis (2,3- , 5,5'-tetraphenylbiimidazole are preferably used.

The triazine-based compound as the photopolymerization initiator is, for example, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4- (Trichloromethyl) -6-piperonyl-1,3,5-triazine, 2, 3-bis (Trichloromethyl) -6- [2- (5-methylfuran) -1,3,5-triazine, 2,4-bis Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- -Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- Trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acylphosphine oxide compound as the photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'- Tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

The thioxanthone compound as a photopolymerization initiator is, for example, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Santon et al.

Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, .

In addition, photopolymerization initiators such as 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate and titanocene compounds can be used .

The photopolymerization initiator according to the present invention controls the content of the negative type photoresist composition so that the negative type photoresist composition is highly sensitized to shorten the exposure time, thereby improving the productivity and maintaining the high resolution. Preferably, the photopolymerization initiator is used in an amount of 0.1 to 40% by weight, preferably 0.5 to 30% by weight, based on the solid content, in the entire negative type photoresist composition. If the content is less than the above range, the polymerization rate is too slow. On the other hand, if the content exceeds the above range, the crosslinking reaction is excessively caused by excessive reaction and the physical properties of the coating film may be lowered.

The acetophenone-based photopolymerization initiator may be used in combination with another photopolymerization initiator or a photopolymerization initiator.

The combinable photopolymerization initiator includes benzoin-based compounds including benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal and the like; Benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'- Benzophenone compounds including phenol and the like; (Trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4 (Trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, 2- (p -tryl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho 1-yl) -4,6-bis (trichloromethyl) ) -s-triazine, 2- (4-methoxynaphtho-1-yl) -4,6-bis (trichloromethyl) 6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine, and the like; Sulfur compounds such as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone and 2-isopropylthioxane; Anthraquinone compounds such as 2-ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; Organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, cumene peroxide and the like; Thiol compounds such as 2-mercaptobenzoxazole and 2-mercaptobenzothiazole can be used.

The combinable photopolymerization initiator can be used in an amount of 0.1 to 0.5 parts by weight based on 1 part by weight of the acetophenone photopolymerization initiator.

The photopolymerization initiation auxiliary can be used for increasing the polymerization efficiency, and it is possible to use an amine compound, an alkoxyanthracene compound, a thioxanthone compound, or the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, (Diethylamino) benzophenone, 4,4'-bis (dimethylamino) benzophenone 4,4'-bis (ethylmethylamino) benzophenone, among which 4,4'-bis (diethylamino) benzophenone is preferable. Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10- Ethoxyacetylene and methoxyanthracene. Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Propanedioxanthone, and the like. The photopolymerization initiator may be prepared directly or a commercially available one may be used. For example, a trade name "EAB-F" [manufactured by Hodogaya Chemical Industry Co., Ltd.] may be used.

Such a photopolymerization initiator is preferably used in an amount of usually not more than 10 mol, preferably 0.01 to 5 mol, per mol of the photopolymerization initiator. When the photopolymerization initiator is used within the above range, the polymerization efficiency can be increased and the productivity improvement effect can be expected.

In addition, a photoacid generator (PAG) is used in connection with deterioration of developability in an exposed portion to be obtained in the present invention.

The photoacid generator is a material capable of generating an acid upon photodegradation by irradiation with an actinic ray or radiation. The acid generated at this time acts as a catalyst to lower the alkali solubility by introducing a protecting group into the alkali-soluble functional groups of the alkali- .

And serves as a catalyst in the bonding reaction between the alkali-soluble resin and the monofunctional compound in the exposed region. As a result, the use of the photoacid generator results in further lowering the developability of the exposed portion, thereby further increasing the difference in solubility between the exposed portion and the unexposed portion.

The type of photoacid generator which can be used is not particularly limited in the present invention, and any photoacid generators known in this field can be used.

And examples thereof include a diazonium salt base, a phosphonium salt base, a sulfonium salt base, an iodonium base base, an imidosulfonate base, an oxime sulfonate base, a diazodisulfone base, a disulfone base, an ortho-nitrobenzylsulfonate base, Based compounds, and combinations thereof.

More specifically, it may include a sulfonium salt-based compound represented by the following formula 1:

[Chemical Formula 1]

(In the formula 1,

R ₁ , R ₂ and R ₃ are each independently hydrogen; halogen; A substituted or unsubstituted, straight, branched or cyclic alkyl group having 1 to 18 carbon atoms; A substituted or unsubstituted, straight, branched or cyclic alkoxy group having 1 to 18 carbon atoms; A carboxyl group; An alkoxycarbonyl group having 1 to 18 carbon atoms; A mercapto group; Cyano; A hydroxyl group; A nitro group; A substituted or unsubstituted phenyl group; And a substituted or unsubstituted benzyl group,

X ^- represents a halogen ion, OH _- , ClO ₄ ^- , a sulfonic acid ion, a sulfate ion, a carbonate ion, a phosphate ion, a fluorophosphate ion, a borate ion, AlCl ₄ ^- , BiF ₆ ^- , fluoroantimonic acid ion, It is a dissolution ion.)

The compound represented by the formula (1) is not particularly limited as long as it satisfies the above formula (1), and examples thereof include triphenylsulfonium, tris (4-tolylsulfonyl), tris Tris (4-chlorophenyl) sulfonium, diphenyl (4-hydroxyphenyl) sulfonium, dibenzylphenylsulfonium, di Benzyl (4-hydroxyphenyl) sulfonium, benzyl (4-hydroxyphenyl) sulfonium, methylphenyl (4-hydroxyphenyl) (Methoxy) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxy) sulfonium, dimethyl (butoxy) (Octadecanoxy) sulfonium, dimethyl (isopropoxy) sulfonium, dimethyl (tert-butoxy) (2-chloroethoxy) sulfonium, dimethyl (3-bromoproxy) sulfonium, dimethyl (4-cyanobutoxy) sulfonium , Dimethyl (8-nitrooctyloxy) sulphonium, dimethyl (18-trifluoromethyloctadecanoxy) sulphonium, dimethyl (2-hydroxyisopropoxy) Sulfonium and the like. Among them, triphenylsulfonium, tris (4-tolyl) sulfonium, benzylmethyl (4-hydroxyphenyl) 2-methylphenyl) sulfonium is preferable, and tris (4-tolyl) sulfonium, benzylmethyl (4-acetoxyphenyl) sulfonium and benzylmethyl (4-hydroxyphenyl) -Hydroxyphenyl) sulfonium is more preferable.

These photoacid generators can be sufficiently chemically catalyzed by an acid and limit their contents in consideration of the effect that uniform application can be achieved when applying the composition. Preferably, it is used in an amount of 0.1 to 25% by weight, preferably 0.5 to 15% by weight, based on 100% by weight of the total negative type photoresist composition based on the solid content. If the content is less than the above range, the effect of lowering the developing performance can not be ensured as described above. On the other hand, if the content exceeds the above range, the content of the other composition is decreased, , And is appropriately used within the above range.

Any solvent may be used as long as it can dissolve or disperse the above-mentioned composition, and the solvent is not particularly limited in the present invention. Preferably, an organic solvent having a boiling point of 100 to 200 DEG C in terms of coatability and dryness can be used.

The solvent is used for dissolving or dispersing an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a photo acid generator in addition to the above-described monofunctional compound, and the same solvent as that used in a conventional negative photoresist composition can be used .

Representative examples include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; cyclic esters such as? And esters such as lactone. These solvents may be used alone or in combination of two or more.

The content of the solvent may be used as the remainder to satisfy 100% by weight of the total composition, or the total content of the above-mentioned components may be designed to be 100% by weight, and then the content thereof may be set to have a concentration of 5 to 90% have.

The content of the solvent may be in the range selected from the viewpoint of the dispersion stability of the composition and the ease of processing in the manufacturing process (for example, applicability), and may be selected from the group consisting of a roll coater, a spin coater, a slit and spin coater, ), A coating device such as an inkjet, and the like.

In the negative photosensitive resin composition of the present invention, various kinds of additives may be used in the composition as required.

For example, the additives include pigments, dyes, fillers, polymer compounds other than alkali-soluble binder polymers, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, organic acids, organic amino compounds, curing agents and the like.

The pigment may further comprise an organic pigment, an inorganic pigment or a mixture thereof.

The organic pigments may be various pigments used in printing ink, ink jet ink, etc. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, Anthanthrone pigments, indanthrone pigments, pyranthrone pigments, pyranthrone pigments, pyranthrone pigments, pyranthrone pigments, pyranthrone pigments, pyranthrone pigments, pyranthrone pigments, ) Pigments, diketopyrrolopyrrole pigments, and the like.

Examples of the inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specific examples of the inorganic pigments include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, Or composite metal oxides.

The dyes include, for example, cyan, azant, azo, anthraquinone, metal complex, quinoline, and pyrazolone dyes. These may be used alone or in combination of two or more.

The filler includes glass, alumina and the like.

The polymer compound includes polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, and the like.

The surfactant includes a nonionic surfactant, a cationic surfactant, an anionic surfactant, and the like.

The adhesion promoter may be selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane And the like.

The antioxidant includes 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and the like.

The ultraviolet absorber includes 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.

The anti-aggregation agent includes sodium polyacrylate and the like.

The organic acid may be an aliphatic monocarboxylic acid including formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, capronic acid, diethylacetic acid, enanthic acid, caprylic acid and the like; There may be mentioned oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, , Aliphatic dicarboxylic acids including cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mezaconic acid and the like; Aliphatic tricarboxylic acids including tricarboxylic acid, aconitic acid, camphoronic acid and the like; Aromatic monocarboxylic acids including benzoic acid, toluic acid, cumenic acid, hemellitic acid, mesitylenic acid and the like; Aromatic dicarboxylic acids including phthalic acid, isophthalic acid, terephthalic acid and the like; Aromatic polycarboxylic acids including trimellitic acid, trimesic acid, melomatic acid, pyromellitic acid, and the like.

The organic amino compound may be at least one selected from the group consisting of n-propylamine, i-propylamine, n-butylamine, i-butylamine, s-butylamine, t-butylamine, n-pentylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, Mono (cyclo) alkylamines including amines and the like; Diethylamine, diethylamine, diethylamine, methylnopropylamine, ethyl-propylamine, di-n-propylamine, di-i-propylamine, di- Di (cyclo) alkylamines including butylamine, di-t-butylamine, di-n-pentylamine, di-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine and dicyclohexylamine; Propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-propylamine, tri-ethylamine, triethylamine, Butylamine, tri-t-butylamine, tri-n-pentylamine, tri-n-hexylamine, dimethylcyclohexylamine, Tri (cyclo) alkylamines including diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine and the like; Amino-1-pentanol, 6-amino-1-hexanol, 4-amino-1-butanol, Mono (cyclo) alkanolamine including 1-cyclohexanol and the like; Di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine, di- Di (cyclo) alkanolamine including 4-cyclohexanol) amine and the like; Tri-n-propanolamine, tri-n-propanolamine, tri-n-butanolamine, tri-i-butanolamine, tri-n-pentanolamine, tri- -Cyclohexanol) amine and the like; tri (cyclo) alkanolamine; Amino-1, 2-butanediol, 4-amino-1, 3-butanediol, 4-amino- 1,3-cyclohexanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino- Amino (cyclo) alkanediols including propanediol, 2-diethylamino-1,3-propanediol and the like; Aminocyclopentanone methanol, 4-aminocyclopentanone methanol, 4-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentane methanol, 4-diethylaminocyclopentane methanol, 4 Amino group-containing cycloalkane methanol including dimethylaminocyclohexane methanol, 4-diethylaminocyclohexane methanol and the like; aminobutyric acid, 1-aminocaproic acid, 1-aminocaproic acid, 1-aminocaproic acid, 2-aminobutyric acid, Aminocarboxylic acids including 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid and the like; Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, Aromatic amines including naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, N-dimethylaniline and the like; aminobenzyl alcohols including o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol and the like; aminophenols including o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol and the like; aminobenzoic acid including m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid, and the like.

The production of the negative type photoresist composition including the above-described monofunctional compound, alkali-soluble resin, photopolymerizable compound, photopolymerization initiator, photoacid generator, solvent and various additives is not particularly limited in the present invention, .

For example, they can be prepared by simply mixing a monofunctional compound, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a photoacid generator, a solvent, and various additives, or separately dividing them into a solvent, have.

At this time, a conventional mixing apparatus may be used for mixing, and stirring may be performed if necessary.

The negative type photoresist composition proposed in the present invention can form a pattern by a method known in the art, and the method can be appropriately selected by a person having ordinary skill in the art.

For example, a negative photoresist composition may be coated on a substrate, followed by exposure and development to form a pattern, wherein a prebake process or a postbake process may be performed between the respective steps.

First, a negative type photoresist composition is coated on a substrate and dried to form a coating film.

The substrate may be a glass substrate, a silicon wafer, a silicon wafer, a plastic, or the like. The coating may be a conventional wet coating method such as spin coating, roller coating, or spray coating. The coating thickness may vary depending on the use of the negative type photoresist composition, and may be, for example, 0.5 to 10 mu m.

The drying is a process for removing a solvent or a volatile component in the composition, and the drying temperature and time may vary depending on the solvent used. The coating film obtained here is composed of the solid components of the negative photoresist composition and contains little volatile components.

After drying, if necessary, a prebake step can be performed. Prebaking is performed by heating with an oven, a hot plate or the like. At this time, the heating temperature and the heating time in the pre-baking are appropriately selected depending on the solvent to be used, for example, at a temperature of 80 to 150 ° C for 1 to 30 minutes.

Next, an exposure process for irradiating the coating film with light through a photomask is performed.

The light source used for the irradiation may be an UV ray, an electron beam and an X ray in a range of 190 to 450 nm, and for example, a g line (wavelength: 436 nm) and an i line (wavelength: 365 nm) are usually used. The photomask is for shielding light rays, and the area of the exposed portion / non-exposed portion is defined according to the shape of the photomask.

Next, the coating film is treated with an alkali developing solution to dissolve the non-visible portion and form a pattern of the exposed portion.

Examples of the alkali developing solution include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine By weight of an aqueous solution of an organic alkali is used at a concentration of 0.01 to 5% by weight, preferably 0.05 to 2.5% by weight. The alkali developing solution may be a surfactant such as a nonionic surfactant having a function of promoting the removal of development residue, or a water-soluble organic solvent such as methanol or ethanol in an appropriate amount.

The developing process can be generally dipping, showering, or spraying. The developing process is performed for about 30 to 60 seconds to remove the unexposed area and selectively leave only the exposed area to form a pattern.

After development, the substrate is cleaned with water, dried and, if necessary, a post-baking process, which is a heat treatment, is performed at a temperature of 180 to 250 캜.

The pattern obtained through the above steps maintains the developability of the non-exposed portion having high developability, but further lowers the developability of the exposed portion having low developability, and the sensitivity is improved due to the difference in developability of the exposed portion / non- It is possible to produce a pattern of excellent quality with a wide process margin.

In addition, even when the post-baking process is performed, the degree of hardening of the exposed portion is not excessively increased, and the problem of brittle pattern due to excessive curing of the conventional post-baking process can be solved, .

The negative type photoresist composition of the present invention can be applied to various fields. For example, the negative type photoresist composition of the present invention can be applied to various display devices such as an insulating film, a protective film, a passivation film, a black matrix, and a column spacer.

The column spacer is used for maintaining a space between the color filter substrate and the array substrate constituting the display device, and physical properties such as flexibility, high shrinkage ratio and high elastic recovery rate are required so as to prevent pixel deformation due to external pressure . Particularly, when external pressure is applied to the display device, if the column spacer becomes too brittle, the shrinkage rate and elastic recovery rate can not be secured to a satisfactory level.

In particular, considering the further curing in the post-baking process, a new approach to composition is needed for application as a column spacer. Thus, the negative type photoresist composition proposed in the present invention can fundamentally block the excessive increase in the degree of curing in the post-baking step by protecting the functional groups of the alkali-soluble resin by the monofunctional compound. Accordingly, it is possible to satisfy the not too hard, i.e., soft properties required in the column spacer without significantly increasing the hardness before and after the postbake process. According to a preferred experimental example of the present invention, it can be seen that the hardness slightly increases with the pencil hardness measured in the 1H range. This means that the conventional composition does not cause excessive thermosetting in the post-baking process as compared with the case where the pencil hardness before and after the post-baking process is hardened by a change of about 3H or more at least 2H.

The height of the column spacer varies depending on the mode of the display device, but is usually 3 to 5 占 퐉 in consideration of the response speed. The shape of the column spacer is not particularly limited as long as it is a shape of a column spacer commonly used in this field, but it is preferably square, rectangular, circular, elliptical, It is preferable that the direction of the long axis is horizontal or orthogonal to the rubbing direction and it is preferably square, rectangular or trapezoidal when viewed from the side, more preferably a trapezoid. In addition, the upper portion of the trapezoid may be rounded, or the lower portion of the trapezoid may have a trailing edge.

As described above, the composition according to the present invention can be applied to an insulating film, a protective film, a passivation film, a black matrix, and the like of various display devices in addition to the column spacer. With the popularization of smart phones and tablet PCs, The likelihood of such compositions is also expected to increase.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims. In the following, "%" and "part" representing the content are on a mass basis unless otherwise specified.

[Example]

Manufacturing example  1: Preparation of alkali-soluble resin

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 replaced with nitrogen in air.

Next, vinyl toluene, 47.2g (0.40 mol) and then the temperature was raised to 100 ℃, methacrylic acid, 43.0g (0.50 mol), 2- (octahydro-4,7-methano -1 H - inden-5-yl) methyl -2-propenoate and 136 g of propylene glycol monomethyl ether acetate was added dropwise to the flask over a period of 2 hours from a dropping funnel to obtain a solution containing 100 g of 100 &lt; RTI ID = 0.0 &gt;Lt; RTI ID = 0.0 &gt; C &lt; / RTI &gt; for 5 hours.

Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 30 g of glycidyl methacrylate (0.20 mol (40 mol% based on methacrylic acid used in the present reaction)), 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone And the reaction was continued at 110 DEG C for 6 hours to obtain an unsaturated group-containing first resin A having a solid acid value of 99 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 28,000 and the molecular weight distribution (Mw / Mn) was 2.2.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dispersion resin were measured by using HLC-8120GPC (manufactured by TOSOH CORPORATION), and the columns were TSK-GELG4000HXL and TSK-GELG2000HXL connected in series , The column temperature was 40 占 폚, the mobile phase solvent was tetrahydrofuran, the flow rate was 1.0 ml / min, the injection amount was 50 占 퐇 and the detector RI was used. The sample concentration was 0.6% by mass (solvent = tetrahydrofuran) TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500 and A-500 (manufactured by TOSOH CORPORATION) were used.

The ratio of the weight average molecular weight to the number average molecular weight obtained above was defined as a molecular weight distribution (Mw / Mn).

Example  1-5 Comparative Example  1-2

After adding a solvent to the mixer, a monofunctional or bifunctional compound, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator were added thereto and uniformly mixed by stirring to prepare a liquid composition. Wherein the compositions are according to the composition of Table 1 below.

Composition (% by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Monofunctional compound Epoxy-1 ¹⁾ 4.6 0 0 0 0 0 0 0 Epoxy-2 ²⁾ 0 4.6 0 0 0 0 0 0 Oxetane-1 ³⁾ 0 0 4.6 0 0 0 0 0 Oxetane-2 ⁴⁾ 0 0 0 4.6 0 0 0 0 Vinyl ether-1 ⁵⁾ 0 0 0 0 4.6 0 0 0 Vinyl ether-2 ⁶⁾ 0 0 0 0 0 4.6 0 0 Bifunctional compound Bisoxetane ^{7 )} 0 0 0 0 0 0 0 4.6 Alkali-soluble resin The resin of Production Example 1 23 23 23 23 23 23 23 23 Photopolymerizable compound Kayarad DPHA ^{8 )} 23 23 23 23 23 23 23 23 Photopolymerization initiator Irgacure 369 ⁹⁾ 2.3 2.3 2.3 2.3 2.3 2.3 2.3 2.3 Photoacid generator IRGACURE PAG103 ^{10 )} 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 menstruum PGMEA ^{11 )} 28.87 28.87 28.87 28.87 28.87 28.87 33.47 28.87 MEDG ^{12 )} 18 18 18 18 18 18 18 18 total 100 100 100 100 100 100 100 100

The materials used in Tables 1 and 2 are as follows:

1) Epoxy-1:

2) Epoxy-2:

3) Oxetane-1:

4) Oxetane-2:

5) Vinyl ether-1:

6) Vinyl ether-2:

7) Bisoxetane: Carbonate Bisoxetane

8) Kayarad DPHA: dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.

9) Irgacure 369: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, product of Ciba Specialty Chemical

10) 2- (propylsulfonyloxyimino) -2,3-dihydrothiophen-3-ylidene] (o-tolyl) acetonitrile, a product of Ciba Specialty Chemical

11) Propylene glycol monomethyl ether acetate

12) Methyl ethyl diglymeglycol

Experimental Example  One: Photoresist  Testing the composition

A glass substrate (Eagle 2000; Corning) having a width of 2 inches was washed with a neutral detergent, water and alcohol, and then dried.

The photosensitive resin compositions prepared in the above Examples and Comparative Examples were respectively spin-coated on the glass substrate and then pre-baked at 90 DEG C for 125 seconds using a hot plate.

After the prebaked substrate was cooled to room temperature, light was emitted at an exposure dose of 60 mJ / cm 2 (based on 365 nm) using an exposure apparatus (UX-1100SM; Ushio Co., Ltd.) with a distance of 150 μm from the quartz glass photomask Respectively. At this time, the photomask used was a photomask in which the following pattern was formed on the same plane.

The coating film was immersed in an aqueous developer containing a 0.12% nonionic surfactant and 0.04% potassium hydroxide at a temperature of 25 캜 for 60 seconds after irradiation with light and having a quadrangular pattern with a diameter of 30 탆, And post-baking was performed in an oven at 230 캜 for 30 minutes. The obtained pattern height was 3 占 퐉.

The developability, residual film ratio and hardness of each pattern were evaluated by the following method. The results are shown in Table 2 below.

(One) Developability

The pattern shape was evaluated by observing a pattern shape formed in a contact hole having a line width of 30 mu m of the thermosetting film with a scanning microscope by the following criteria.

◎: Rectangle is good and residue is not visible in unexposed area.

○: The rectangle is good, but the residue is seen on the surface of the unexposed portion or the residual film is formed.

X: Rectangle is defective or not resolved.

(2) Residual film ratio  evaluation

The residual film ratio was evaluated by evaluating the thickness of the resist film before and after development and by the following equation (1). At this time, it was judged that the case where the residual film ratio was 80% or more was excellent (⊚), the case where it was 70% or more and less than 80% was evaluated as good (∘), and the case of less than 70%

[Equation 1]

[Remaining film ratio = (film thickness after development / film thickness before development) X 100]

(3) Evaluation of surface hardness

The surface hardness of the pattern was measured before and after the post bake process.

The surface hardness was measured by contacting a Mitsubishi Pencil with a pencil hardness tester (Pencil Hardness Tester) and placing a weight of 500 g on the substrate. The surface hardness was measured at a rate of 50 mm / And the surface hardness was measured by observing the surface.

The measurement standard was evaluated based on the case where the surface abrasion, peeling, tearing and scratching were not observed at the level corresponding to the pencil hardness.

Pattern developability Residual film ratio Surface hardness Post-baking After post-baking Example 1 ◎ ◎ 2H 3H Example 2 ◎ ◎ 2H 3H Example 3 ◎ ◎ 2H 3H Example 4 ◎ ◎ 2H 3H Example 5 ◎ ◎ 2H 3H Comparative Example 1 × × 2H 4H Comparative Example 2 × × 2H 5H

Referring to Table 2, the compositions of Examples 1 to 5 prepared from the monofunctional compounds of the present invention showed excellent pattern development and excellent residual film ratios.

In addition, when comparing the surface hardnesses before and after the post-baking, it can be seen that the change is a 1H difference, and a severe level of additional hardening does not occur in the post-baking step.

In comparison, the composition of Comparative Example 1 which does not contain a monofunctional compound has a low developing property and a low residual film ratio.

Further, in the case of the composition of Comparative Example 2 using the bifunctional compound, the difference in the surface hardness between the 2H and 3H levels before and after the post-baking process becomes large, and the additional curing reaction occurs very seriously.

The negative-type photoresist composition proposed in the present invention can be applied to a photoresist material for processing a highly integrated semiconductor and a printed circuit board, a photoresist material for printing plate, a photoresist material for processing various display devices, or an insulating film, a protective film, a passivation film, Matrix, column spacer, and the like.

Claims (8)

An alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a photoacid generator, and a monofunctional compound having at least one epoxy group, oxetane group or vinyl ether group in the molecular structure. The negative type photoresist composition according to claim 1, wherein the monofunctional epoxy compound having an epoxy group is represented by the following formula:

The negative type photoresist composition according to claim 1, wherein the monofunctional compound having an oxetane group is represented by the following formula:

The negative type photoresist composition according to claim 1, wherein the monofunctional compound having a vinyl ether group is represented by the following formula:

The negative type photoresist composition according to claim 1, wherein the monofunctional compound is contained in an amount of 0.5 to 30% by weight in 100% by weight of the total negative type photoresist composition. The negative type photoresist composition according to claim 1, wherein the negative type photoresist composition comprises 5 to 85% by weight of an alkali-soluble resin, 1 to 50% by weight of a photopolymerizable compound, 0.1 to 40% by weight of a photopolymerization initiator, 0.1 to 25% %, And a solvent as the balance. The negative type photoresist composition according to claim 1, wherein the alkali-soluble resin has a carboxyl group or a hydroxyl group in a molecular structure. The photoacid generator according to claim 1, wherein the photoacid generator is at least one selected from the group consisting of a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imidosulfonate, an oxime sulfonate, a diazodisulfone, A benzyl sulfonate-based compound, and a thraazine compound-based compound.