KR20150110139A - Photosensitive resin composition for colorless pixel - Google Patents

Abstract

The present invention relates to a colorless photosensitive resin composition for forming a pixel, capable of preforming a fine pixel and a contact hole with the size smaller than or equal to 40 um. In addition, a process margin can be easily secured with respect to exposure quantity during performing a contact hole with the size smaller than or equal to 40 um. Moreover, provided are a color filter and a liquid crystal display device, with excellent properties of driving liquid crystal, and without decline of visibility caused by outside light, by using the colorless photosensitive resin composition for forming the pixel of the present invention.

Description

TECHNICAL FIELD [0001] The present invention relates to a colorless photosensitive resin composition for forming a pixel,

The present invention relates to a colorless photosensitive resin composition for forming a pixel, a color filter provided with transparent pixels manufactured using the same, and a liquid crystal display device including the same.

Recently, the display industry has undergone drastic changes from CRTs to flat panel displays represented by PDPs, OLEDs, and LCDs. Among them, a liquid crystal display (LCD) is widely used as an image display device in almost all industries, and its application range is continuously expanding.

Generally, a liquid crystal display device includes a liquid crystal for light transmission control, a TFT array layer which is an electric signal device for driving the liquid crystal, a pixel pattern of red, green and blue on a substrate on which a black matrix is patterned, A color filter layer coated with an overcoat to give a flatness between the TFT array layer and the color filter layer, and a column spacer for holding the cell gap in the step of bonding the TFT array layer and the color filter layer. Such a liquid crystal display (LCD) is widely used in all industrial fields such as portable equipment, industrial machinery, military, and medical applications.

However, as the use environment of the liquid crystal display (LCD) is used as an information delivery medium such as an outdoor advertisement in a room, a problem that the visibility deteriorates due to the luminance lowering due to the external sunlight has been caused.

In order to solve this problem, a method of improving the brightness of the backlight or increasing the transmittance of the red, green and blue pixels of the color filter layer has been used. However, due to the problem of power consumption and the limit physical properties of the coloring material, On the other hand, a method of forming an empty space without loss of luminance of the backlight in pixel pixels composed of red, green, and blue has been proposed.

However, the color filter having the transparent layer according to the above method can be improved to a considerable extent by the brightness enhancement effect in terms of visibility by the external light, but the step difference from the surrounding coloring material layer becomes large, A transparent pixel pixel having the same thickness as a colored pixel is required.

In order to realize the above-mentioned transparent pixel pixel, Korean Unexamined Patent Publication No. 2007-0007895 has fabricated a transparent pixel layer using an overcoat or a photosensitive column spacer among existing transparent materials, but it is difficult to realize a transparent pixel pattern, In particular, it has a problem that it is not possible to produce a fine contact hole of 40 μm or less.

Korea Publication No. 2007-0007895

In order to solve the problems of the related art as described above, it is an object of the present invention to provide a colorless photosensitive resin composition for pixel formation capable of realizing a fine pixel pixel and a contact hole of 40um or less.

Another object of the present invention is to provide a color filter and a liquid crystal display device which are free from deterioration of visibility due to external light and have excellent liquid crystal driving characteristics by using the colorless photosensitive resin composition for pixel formation of the present invention.

The present invention relates to (A) a compound comprising at least one selected from a melamine compound and a urea aldehyde compound; (B) an alkali-soluble resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator, and (E) a solvent.

According to a preferred embodiment of the present invention, the at least one compound selected from the group consisting of (A) the melamine compound and the urea aldehyde compound includes at least one compound selected from the group consisting of the following formulas (1) to (5) can do.

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

According to a preferred embodiment of the present invention, the compound containing at least one selected from the group consisting of (A) the melamine compound and the urea aldehyde compound is mixed with the alkali-soluble resin (B) And 0.1 to 20 parts by weight based on 100 parts by weight of the compound sum.

According to a preferred embodiment of the present invention, the alkali-soluble resin (B) comprises a photopolymerization initiator (B '), a reactive alkali-soluble resin reactive with UV radiation and / or a photopolymerization initiator (B' (B ') a photopolymerization initiator, a reactive alkali-soluble resin reactive with UV radiation, and a photopolymerization initiator (B' ') reactive with UV radiation and a non-reactive alkali- The resin may be contained in a weight ratio of 8: 2 to 2: 8.

According to a preferred embodiment of the present invention, the colorless photosensitive resin composition for forming a pixel may further comprise a UV stabilizer.

Another aspect of the present invention provides a color filter formed using the colorless photosensitive resin composition for forming a pixel of the present invention, and further provides a liquid crystal display device including the color filter of the present invention.

The present invention provides a colorless photosensitive resin composition for forming a pixel, and a color filter using the colorless photosensitive resin composition can form a fine colorless pixel pixel.

In addition, the colorless photosensitive resin composition for a pixel formation of the present invention has an effect of improving the degree of curing to thereby provide not only superior film hardness and chemical resistance, but also excellent process margin of fine contact holes.

Accordingly, the colorless photosensitive resin composition for a pixel formation of the present invention has the effect of providing a high quality color filter and a liquid crystal display device including the color filter by facilitating the formation of a contact hole for forming a colorless electrode and securing a process margin according to an exposure amount.

1A is a measurement image of a contact hole of the color filter of Embodiment 1. FIG.
1B is a measurement image of the contact hole of the color filter of Comparative Example 4. Fig.

Hereinafter, the present invention will be described in detail. The following detailed description is merely an example of the present invention, and therefore, the present invention is not limited thereto.

There is a problem in that it is difficult to realize a transparent pixel pattern, and in particular, it is impossible to produce a fine contact hole of 40 m or less.

Accordingly, the present inventors have succeeded in securing a process margin according to the amount of exposure when a contact hole of 40 um or less is included by including a compound containing at least one selected from a melamine compound and a urea aldehyde compound in a colorless photosensitive resin composition for pixel formation A colorless photosensitive resin composition for forming a pixel was found and the present invention was completed.

That is, the present invention relates to (A) a compound comprising at least one selected from the group consisting of a melamine compound and a urea aldehyde compound; (B) an alkali-soluble resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; And (E) a solvent. The present invention provides a colorless photosensitive resin composition for forming a pixel.

The colorless photosensitive resin composition for forming a pixel of the present invention means a photosensitive resin composition for forming a transparent pixel.

First, a compound containing at least one selected from (A) a melamine-based compound and a ureaaldehyde-based compound will be described.

In order to form a contact hole having a desired size with the colorless photosensitive resin composition for forming a pixel of the present invention and to easily ensure a process margin with respect to the exposure amount, the curing degree according to the reactive unsaturated bond group and the exposure amount of the composition should be controlled.

Ideally, it is best that the taper angle of the contact hole is clearly displayed because the difference in the degree of curing at the interface between the exposed part and the unexposed part clearly becomes apparent. However, the taper angle of the display device is 45 degrees Or less.

Therefore, it is necessary to control the amount of the reactive unsaturated bond group or to control the degree of curing by the exposure amount in order to secure a margin in the development process. In this case, the change of the other properties such as thermal stability and chemical resistance .

Specifically, the compound containing at least one selected from the group consisting of (A) the melamine compound and the urea aldehyde compound contained in the colorless photosensitive resin composition for a pixel-forming of the present invention is preferably used in a post- B) can react with the COOH group of the alkali-soluble resin and cure, thereby improving the thermal stability and chemical resistance of the resin composition.

In the present invention, it is possible to realize a fine pixel pixel and a contact hole of 40um or less by including the compound containing at least one selected from (A) the melamine-based compound and the urea aldehyde-based compound, And a residual film or the like can be provided.

Referring to FIG. 1, a color filter manufactured using the colorless photosensitive resin composition for forming a pixel of the present invention has a process margin of at least 10um at a maximum of 15um when manufacturing a contact hole of 15um, It can be seen that excellent contact holes are produced.

On the other hand, FIG. 1B, which is a view of a color filter contact hole when a colorless photosensitive resin composition for pixel formation according to the present invention is not used, shows that a contact hole having a poor process margin is generated at a maximum of 18um to a minimum of 3um . ≪ / RTI >

According to a preferred embodiment of the present invention, the compound containing the (A) melamine-based and / or ureaaldehyde-based compound may include at least one compound selected from the group consisting of the following formulas (1) to (5)

In addition to the above, it is also possible to use two or more kinds of curing agents together.

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

According to a preferred embodiment of the present invention, the content of the compound comprising at least one selected from the group consisting of (A) the melamine-based compound and the urea aldehyde-based compound is in the range of from (C) an alkali- ) May be contained in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total amount of the photopolymerizable compound.

When the content of the compound containing at least one selected from the group consisting of (A) the melamine-based compound and the urea aldehyde-based compound is in the above range, the colorless photosensitive resin composition for forming a pixel And the binder hardness and chemical resistance of the binder resin and the coupling aid (compound containing an epoxy group) contained in the composition are improved by heat, thereby improving the hardness and chemical resistance.

The following (B) alkali-soluble resin will be described.

The alkali-soluble resin (B) serves to make the unexposed portion of the colorless photosensitive resin layer for pixel formation, which is formed using the colorless photosensitive resin composition for pixel formation, to be made soluble in alkali and to remain in the exposed region .

According to a preferred embodiment of the present invention, the alkali-soluble resin (B) comprises a photopolymerization initiator (B '), a reactive alkali-soluble resin reactive with UV radiation and / or a photopolymerization initiator (B' Reactive non-reactive alkali-soluble resin.

First, (B ') a photopolymerization initiator and a reactive alkali-soluble resin which is reactive with UV irradiation will be described. (B') The reactive alkali-soluble resin is obtained by polymerizing the compounds (B'1) and (B'2) ≪ / RTI >

The compound (B'1) contained in the reactive alkali-soluble resin (B ') is not limited as long as it is a compound having an unsaturated bond and a carboxylic acid group in one molecule and is a carboxylic acid compound having an unsaturated double bond capable of polymerization, They may be used alone or in combination of two or more. Specific examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And an anhydride of the dicarboxylic acid; (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate, and the like. Of these compounds, acrylic acid and methacrylic acid are preferred because of their excellent copolymerization reactivity and solubility in a developing solution.

The compound (B'2) contained in the reactive alkali-soluble resin (B ') can be used without limitation as long as it is a compound having an unsaturated bond polymerizable with (B'1) and having a polymerizable unsaturated double bond. Specific examples of the unsaturated carboxylic acid include unsaturated carboxylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) Unsubstituted or substituted alkyl ester compounds; (Meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (Meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, pentadienyl An unsaturated carboxylic acid ester compound containing an alicyclic substituent group such as a phenanthryl (meth) acrylate, adamanthyl (meth) acrylate, norbornyl (meth) acrylate or pinenyl (meth) acrylate; 3-ethyloxetane, 3 - ((meth) acryloyloxymethyl) oxetane, 3 - ((meth) acryloyloxymethyl) Unsaturated carboxylic acid ester compounds containing thermosetting substituents such as oxetane and 3 - ((meth) acryloyloxymethyl) -2-trifluoromethyloxetane; Mono-saturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate; Unsaturated carboxylic acid ester compounds containing a substituent having an aromatic ring such as benzyl (meth) acrylate, phenoxy (meth) acrylate and the like; Aromatic vinyl compounds such as styrene,? -Methylstyrene, vinyltoluene, and N-benzylmaleimide; carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; cyanuric compounds such as (meth) acrylonitrile and? -Chloroacrylonitrile Vinyl compounds and the like. Of these, aromatic vinyl compounds are preferable for the purpose of improving sensitivity and reducing outgas. These may be used alone or in combination of two or more. The (meth) acrylate recorded in this specification means acrylate and / or methacrylate.

In the copolymer obtained by polymerizing the compounds (B'1) and (B'2) used in the present invention, the proportion of the component derived from each of (B'1) and (B'2) Is preferably in a molar fraction with respect to the total number of moles of the components (B'1) and (B'2) in the following range.

(B'1): 2 to 70 mol%,

(B'2): 30 to 98 mol%,

Particularly, it is more preferable that the ratio of the above components is in the following range.

(B'1): 10 to 60 mol%,

(B'2): 40 to 90 mol%,

When the composition ratio is in the above range, a good balance of alkali solubility and heat resistance is obtained, and thus a preferable copolymer can be obtained.

In the present invention, as an example of the production method of the above-mentioned (B ') reactive alkali-soluble resin, when the compounds (B'1) and (B'2) are copolymerized, they can be produced by the following method.

A solvent in an amount of 0.5 to 20 times the total mass of (B'1) and (B'2) was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, Nitrogen is substituted. Thereafter, the temperature of the solvent is raised to 40 to 140 占 폚, and a predetermined amount of (B'1) and (B'2) is added to the total mass of (B'1) A solvent and a solution in which 0.1 to 10 mol% of a polymerization initiator such as azobisisobutyronitrile or benzoyl peroxide is added to the total molar amount of (B'1) and (B'2) (stirring or dissolving at room temperature or under heating) Is added dropwise to the flask over a period of 0.1 to 8 hours from the dropping funnel and stirred at 40 to 140 ° C for 1 to 10 hours.

In the above step, a part or all of the polymerization initiator may be put into a flask, or a part or all of (B'1) and (B'2) may be put into a flask.

Further, alpha -methylstyrene dimer or mercapto compound may be used as a chain transfer agent to control molecular weight or molecular weight distribution. The amount of the? -methylstyrene dimer or mercapto compound used is 0.005 to 5% by weight based on the total weight of (B'1) and (B'2). The above-mentioned polymerization conditions may be appropriately adjusted depending on the production equipment or the amount of heat generated by polymerization and the like.

Meanwhile, according to a preferred embodiment of the present invention, the reactive alkali-soluble resin (B ') contained in the colorless photosensitive resin composition for forming a pixel of the present invention comprises (B'1) and (B'2) May be a copolymer obtained by further polymerizing the following compound (B'3) in a copolymer obtained by polymerization of compounds.

This is because the addition of (B'3) to the copolymer by polymerization of the compounds containing (B'1) and (B'2) gives the alkali-soluble resin light / thermosetting property to improve heat resistance and chemical resistance have.

The above-mentioned (B'3) is a compound having an unsaturated bond and an epoxy group in one molecule, and is preferably a glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, (Meth) acrylate, hexylmethyl (meth) acrylate, methylglycidyl (meth) acrylate and the like, more preferably glycidyl (meth) acrylate. These may be used alone or in combination of two or more .

The compound having an unsaturated bond and an epoxy group in one molecule of (B'3) is preferably a compound represented by (B'1) 1 (B'1) contained in the copolymer by polymerization of the compounds containing (B'1) The reaction is preferably carried out in an amount of 5 to 80 mol%, more preferably 10 to 80 mol%, based on the number of moles of the compound having an unsaturated bond and a carboxylic acid group in the molecule. (B'3) within the above range is preferable because of excellent exposure sensitivity and developability.

In the present invention, the reactive alkali-soluble resin (B ') may be produced by subjecting the copolymer (B'1) and (B'2) to an addition reaction with the copolymer (B'3) And the like.

The atmosphere in the flask is replaced with nitrogen in air and the amount of the component (B'1) and the component (B'2) 80% by mole of (B'3) is used as a reaction catalyst of a carboxyl group and an epoxy group, for example, 0.01 to 5% by weight of trisdimethylaminomethylphenol based on the total weight of (B'1) to (B'3) As the polymerization inhibitor, for example, hydroquinone may be reacted with (B'3) by adding 0.001 to 5 wt% of hydroquinone to the flask in the flask at 60 to 130 ° C for 1 to 10 hours . In addition, as in the case of the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production facility or the amount of heat generated by polymerization.

In the present invention, the reactive alkali-soluble resin (B ') 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 reactive alkali-soluble resin (B ') is in the range of 3,000 to 100,000, film reduction of the exposed portion is unlikely to occur at the time of development and the solubility of the unexposed portion tends to be good.

 The acid value of the reactive alkali-soluble resin (B ') may preferably be in the range of 30 to 150 mgKOH / g on the solid basis. If the acid value is less than 30 mgKOH / g, the solubility in the alkaline developer may be lowered and the residue may be left on the substrate. If the acid value exceeds 150 mgKOH / g, the possibility of pattern peeling may increase.

The molecular weight distribution of the (B ') reactive alkali-soluble resin may preferably be 1.0 to 6.0, more preferably 1.5 to 4.0. When the molecular weight distribution is 1.0 to 6.0, it may be preferable since the developing property is excellent.

On the other hand, the (B ') reactive alkali-soluble resin used in the present invention can be polymerized by adding other monomers besides (B'1), (B'2) and (B'3).

That is, the case where other monomers other than the above-mentioned (B'1) to (B'3) are further included and polymerized are also included in the scope of the present invention.

The following (B ") photopolymerization initiator and non-reactive alkali-soluble resin that is non-reactive with UV irradiation will be described.

The non-reactive alkali-soluble resin (B ') used in the present invention may be prepared in the same manner as the reactive alkali-soluble resin (B') except that the UV- (B ') contained in the reactive alkali-soluble resin is omitted, since (B' 1) one molecule (B '1) is included in the reactive alkali-soluble resin because polymerization is to be carried out in the absence of an unsaturated double bond capable of photopolymerization by a photoinitiator (B "2) a compound having an unsaturated bond and a carboxylic acid group and (B" 2) a compound containing a compound having an unsaturated bond polymerizable with the compound (B "1) (B "1) and (B" 2) may be the same as those used for the components (B'1) and (B'2) .

In the present invention, the non-reactive alkali-soluble resin (B '') preferably has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, more preferably 5,000 to 40,000. When the weight average molecular weight of the non-reactive alkali-soluble resin (B ") is in the range of 3,000 to 100,000, film reduction of the exposed part is unlikely to occur during development and the solubility of the unexposed part tends to be good.

 If the acid value is less than 30 mgKOH / g, the solubility in an alkali developing solution is lowered, and the residue on the substrate is lower than the solubility in an alkali developing solution. When the acid value is less than 30 mgKOH / g, If the acid value exceeds 150 mgKOH / g, there is a possibility that pattern peeling may occur.

The molecular weight distribution of the non-reactive alkali-soluble resin (B ") is preferably 1.0 to 6.0, more preferably 1.5 to 4.0. When the molecular weight distribution is 1.0 to 6.0, have.

According to a preferred embodiment of the present invention, the alkali-soluble resin (B) may be a mixture of a reactive alkali-soluble resin (B ') and a non-reactive alkali-soluble resin (B " ) And (B ") may be contained in a weight ratio of 8: 2 to 2: 8, and preferably in a weight ratio of 7: 3 to 3: 7. If the alkali-soluble resin (B) is a mixture of the components (B ') and (B') and the weight ratio thereof is the same as above, the residual film ratio is good and the degree of curing is adequate, so that the taper attraction in the contact hole can be reduced.

The content of the alkali-soluble resin (B) may be in the range of usually 20 to 85% by weight, preferably 40 to 75% by weight based on the solid content in the colorless photosensitive resin composition for pixel formation. When the content of the alkali-soluble resin (B) is 20 to 85% by weight on the basis of the above-mentioned criteria, solubility in a developing solution is sufficient and development residue is hardly generated on the substrate of the non-pixel portion, , And the solubility of the unexposed portions tends to be good.

The following (C) photopolymerizable compound will be described.

(C) The photopolymerizable compound (C) contained in the colorless photosensitive resin composition for forming a pixel of the present invention is a compound capable of polymerizing under the action of light and a photopolymerization initiator which will be described later and includes monofunctional monomers, bifunctional monomers, And the like.

Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrrolidone And the like.

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

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol Hexa (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

Of these, polyfunctional monomers having two or more functionalities can be preferably used, and more preferably, polyfunctional monomers having five or more functionalities can be used.

The photopolymerizable compound (C) may be used in an amount of usually 10 to 60% by weight, preferably 20 to 50% by weight based on the solid content in the colorless photosensitive resin composition for pixel formation. When the photopolymerizable compound (C) is in the range of 10 to 60% by weight based on the above-mentioned criteria, the strength of the pixel portion, the residual film ratio according to the progress of the process, and the contact hole characteristics tend to be favorable.

The following (D) photopolymerization initiator will be described.

The photopolymerization initiator (D) contained in the colorless photosensitive resin composition for forming a pixel of the present invention is not limited, but may be at least one selected from the group consisting of triazine-based compounds, acetophenone-based compounds, / RTI > The colorless photosensitive resin composition for forming a pixel containing the photopolymerization initiator (D) described above has high sensitivity, and the film formed using this composition has good strength and contact hole characteristics of the pixel portion.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 - (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, (Trichloromethyl) -6- [2- (5-methylfuran-2- (4-methoxystyryl) -1,3,5-triazine, Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4- ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- (4-methylthioxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- Methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one and 2-hydroxy- 1-one oligomers and the like. Further, a compound represented by the following formula (6) may be mentioned.

[Chemical Formula 6]

R 1 to R 4 in Formula 6 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group substituted or unsubstituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group substituted or unsubstituted with an alkyl group having 1 to 12 carbon atoms, Or a naphthyl group substituted or unsubstituted with an alkyl group having 1 to 12 carbon atoms.

Specific examples of the compound represented by Formula 6 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl- 2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl-2 2-amino (4-morpholinophenyl) propan-1-one, 2-methyl- 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one 2-dimethylamino (4-morpholinophenyl) propan-1-one and 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one .

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4' Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole and phenyl groups in the 4,4', 5,5 ' An imidazole compound substituted by a haloalkoxy group, and the like. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3- 5,5'-tetraphenylbiimidazole is preferably used.

Examples of the oxime compounds include the following chemical formulas (7), (8) and (9).

(7)

[Chemical Formula 8]

[Chemical Formula 9]

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. Examples of other photopolymerization initiators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds. These may be used alone or in combination of two or more.

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 4,4'-di (N, N'-dimethylamino) -benzophenone.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1-chloro-4-propanecioxanthone .

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

Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclyoxylic acid Methyl and titanocene compounds and the like can be mentioned as other photopolymerization initiators.

On the other hand, according to one preferred embodiment of the present invention, when the photopolymerization initiator (D-1) is used in combination with the photopolymerization initiator (D-1), the colorless photosensitive resin composition for pixel- The productivity in forming a color filter can be improved.

As the (D-1) photopolymerization initiation assistant which can be used in combination with the photopolymerization initiator (D) in the present invention, at least one compound selected from the group consisting of an amine compound and a carboxylic acid compound is preferably used.

(D-1) Specific examples of the amine compound in the photopolymerization initiation auxiliary include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone) and 4-dimethylaminobenzoic acid , 4'-bis (diethylamino) benzophenone, and the like. As the amine compound, an aromatic amine compound is preferably used.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenyl And aromatic heteroacetic acids such as thioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

The content of the photopolymerization initiator (D) in the colorless photosensitive resin composition for a pixel formation of the present invention is 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the solid content in the colorless photosensitive resin composition for pixel formation And the amount of the photopolymerization initiator (D-1) used is usually from 0.1 to 20% by weight, preferably from 1 to 10% by weight based on the above-mentioned criteria.

When the amount of the photopolymerization initiator (D) is in the above range, it is preferable that the colorless photosensitive resin composition for pixel formation has a high sensitivity, and the strength of the pixel portion and the smoothness on the surface of the pixel portion tend to be good . When the amount of the photopolymerization initiator (D-1) used is also in the above range, the sensitivity of the colorless photosensitive resin composition for forming a pixel is further increased, and the productivity of the color filter formed using the composition tends to be improved It may be preferable.

The following (E) solvent will be described.

The solvent (E) contained in the colorless photosensitive resin composition for forming a pixel of the present invention is not particularly limited and various organic solvents used in the field of the photosensitive resin composition can be used.

Specific examples of the solvent (E) 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; and esters such as methyl cellosolve acetate and ethyl cellosolve acetate; Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypropyl ether acetate; and ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, Alkylene glycol alkyl ether acetates such as methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; ; Ethanol, propanol, butanol, hexanol, cyclo Sanol, ethylene glycol, alcohols such as glycerol; a, 3-ethoxypropionate, ethyl 3-methoxy propionate, cyclic esters such as esters, lactones with γ- butynyl, such as methyl; And the like.

Among the above-mentioned solvents, organic solvents having a boiling point of 100 to 200 DEG C in the solvent are preferably used from the viewpoint of coatability and dryness, more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxy Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxypropionate, and the like, and more preferably, an ester such as ethyl propionate or methyl 3-methoxypropionate. More preferred examples thereof include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Ethyl methoxypropionate, methyl 3-methoxypropionate, and the like.

These (E) solvents may be used alone or in combination of two or more.

The content of the solvent (E) in the colorless photosensitive resin composition for forming a pixel of the present invention is usually 60 to 90% by weight, preferably 70 to 90% by weight, based on the total amount of the colorless photosensitive resin composition for forming a pixel, 85% by weight. When the content of the solvent (E) is in the range of 60 to 90% by weight on the basis of the above criteria, it may be applied by a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) It may be preferable since the coating property tends to be good.

According to a preferred embodiment of the present invention, the colorless photosensitive resin composition for forming a pixel may further include a UV stabilizer.

In the present invention, the colorless photosensitive resin composition for forming a pixel further contains a UV stabilizer, whereby the light resistance can be secured.

Specific examples of the UV stabilizer include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives and dibenzoylmethane derivatives.

Examples of specific benzophenone derivatives include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, Hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone;

Examples of specific benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, p-tart-butylphenyl salicylate, 2,4-di-tart- 4-hydroxybenzoate and hexadecyl-3,5-di-tart-butyl-4-hydroxybenzoate;

Specific examples of the benzotriazole derivatives include 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- 5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di- Chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-3 ', 5'-di-tart-amylphenyl) benzotriazole;

Specific examples of the triazine derivatives include hydroxyphenyltriazine and bisethylhexyloxyphenol methoxyphenyltriazine.

The UV stabilizer may be a commercially available one such as TINUVIN PS, TINUVIN 99-2, INUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479, TINUVIN 1577 And CHIMASSORB81 (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name).

Looking at the wavelength region, a UV stabilizer having a maximum absorption region at 350 nm or less (including j line) may be preferable. A UV stabilizer having a maximum absorption region of 350 nm or more may weaken the irradiation intensity of i-line.

Structurally, benzophenone derivatives and triazine derivatives of the UV stabilizer have a good absorption range at 350 nm or less. Commercially available products may be TINUVIN 400, TINUVIN 1577, CHIMASSORB81.

The above-mentioned UV stabilizers can be used alone or in combination of two or more, and the light resistance and yellowing of the colorless photosensitive resin composition for pixel formation of the present invention can be prevented.

If necessary, additives such as fillers, other polymer compounds, curing agents, dispersants, adhesion promoters, antioxidants, and anti-aggregation agents may be added to the colorless photosensitive resin composition for a pixel formation of the present invention.

Specific examples of the filler include glass, silica and alumina.

Specific examples of the other polymer compound include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester and polyurethane. .

The curing agent is used for enhancing deep curing and mechanical strength. Examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, and an oxetane compound.

Examples of the epoxy compound in the curing agent include a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol F epoxy resin, a Novolak epoxy resin, an aromatic epoxy resin, Based epoxy resins, glycidyl ester-based resins, glycidylamine-based resins, aliphatic, alicyclic or aromatic epoxy compounds other than the brominated derivatives, epoxy resins and brominated derivatives of such epoxy resins, butadiene (co) polymeric epoxides , Isoprene (co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate. Examples of the oxetane compound in the curing agent include carbonates such as carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like. have.

The curing agent may include a curing auxiliary compound capable of ring-opening polymerization of an epoxy group of an epoxy compound and an oxetane skeleton of an oxetane compound together with a curing agent. Examples of the curing aid compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, acid generators, and the like. As the carboxylic acid anhydrides, those commercially available as epoxy resin curing agents can be used. As the epoxy resin curing agent, for example, there may be mentioned epoxy resin curing agents such as trade name (ADEKA HARDONE EH-700) (ADEKA INDUSTRY CO., LTD.), Trade name (RICACIDO HH) Manufactured by Shin-Etsu Chemical Co., Ltd.). These curing agents may be used alone or in combination of two or more.

As the dispersing agent, a commercially available surfactant can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. These may be used alone or in combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes (Manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), And polyethyleneimine, (Manufactured by Asahi Glass Co., Ltd.), Surfon (manufactured by Asahi Glass Co., Ltd.), Mitsubishi Kasei Kogyo Co., Ltd., MEGAFAC (manufactured by Dainippon Ink and Chemicals Inc.), Flourad (manufactured by Sumitomo 3M Limited), Asahi guard, Surflon SOLSPERSE (manufactured by Genene), EFKA (manufactured by EFKA Chemical), PB 821 (manufactured by Ajinomoto), and the like.

Each of these dispersants may be used alone or in combination of two or more, and may be contained in an amount of usually 0.01 to 15% by weight based on the solid content in the colorless photosensitive resin composition for pixel formation.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane , N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Propyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. These adhesion promoting agents may be used alone or in combination of two or more kinds, and usually contain 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the solid content in the colorless photosensitive resin composition for pixel formation .

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

Specific examples of the anti-flocculant include sodium polyacrylate and the like.

The colorless photosensitive resin composition for forming a pixel of the present invention can be produced, for example, by the following method. (A) a compound containing at least one selected from a melamine compound and a urea aldehyde compound, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator and And further, other components used as needed are further added to obtain a desired colorless photosensitive resin composition for pixel formation.

Hereinafter, a pattern forming method using the colorless photosensitive resin composition for forming a pixel according to the present invention will be described.

The method for forming a pattern of a colorless photosensitive resin composition for forming a pixel according to the present invention includes the steps of applying the above-described colorless photosensitive resin composition on a substrate, selectively exposing a part of the photosensitive resin composition, And removing the exposed region or the non-exposed region of the colored resin composition for forming a colorless photosensitive resin composition.

As an example thereof, it is applied on a substrate as follows to form a pattern by photo-curing and development, and it becomes possible to use it in the production of a black matrix or a colored and transparent pixel (colored image).

More specifically, the composition is applied on a substrate (not limited to a glass or silicon wafer in general) or a layer containing a solid content of a colorless photosensitive resin composition for pixel formation formed in advance and preliminarily dried to remove volatile components such as a solvent To obtain a smooth coating film. The thickness of the coating film at this time is usually about 1 to 3 mu m. Ultraviolet rays are applied to a specific region through a mask to obtain a desired pattern on the thus obtained coating film. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so that the entire exposed portion is uniformly irradiated with parallel rays, and the mask and the substrate are accurately positioned. Thereafter, the coated film after curing is brought into contact with the aqueous alkaline solution to dissolve and expose the non-exposed region, thereby making it possible to produce a desired pattern. After development, if necessary, post-drying may be performed at about 150 to 230 DEG C for about 10 to 60 minutes.

On the other hand, the developer used for development after patterned exposure may be an aqueous solution containing an alkaline compound and a surfactant.

 The alkaline compound may be either an inorganic or an organic alkaline compound.

Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, , Potassium hydrogencarbonate, sodium borate, potassium borate and ammonia.

Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, ethanolamine and the like. These inorganic and organic alkaline compounds may be used alone or in combination of two or more.

The preferred concentration of the alkaline compound in the alkaline developer may be in the range of 0.01 to 10% by weight, more preferably 0.03 to 5% by weight.

The surfactant in the alkaline developer may be any of a nonionic surfactant, an anionic surfactant or a cationic surfactant.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, poly Oxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate and sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium naphthalenesulfonate.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, quaternary ammonium salts and the like.

Each of these surfactants may be used alone or in combination of two or more.

The concentration of the surfactant in the alkali developer is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight.

Meanwhile, another aspect of the present invention provides a color filter formed using the colorless photosensitive resin composition for pixel formation of the present invention, and further provides a liquid crystal display device including the color filter of the present invention.

Hereinafter, a color filter according to the present invention will be described.

The color filter according to the present invention is characterized by including the pixel formed by forming the above-mentioned colorless photosensitive resin composition for pixel formation in a predetermined pattern, and then exposing and developing the same.

The method of forming a pattern of a colorless resin composition for forming a pixel is not described in detail with respect to the above description.

As described above, a pixel or a black matrix corresponding to the photosensitive resin composition is obtained through the application of a solution of a colorless resin composition for a pixel formation, drying, patterned exposure to a dry film obtained, and development, By repeating the number of unit pixels required for the color filter to obtain the color filter.

The construction and manufacturing method of the color filter are well known in the art, and a detailed description thereof will be omitted.

The color filter produced by using the colorless photosensitive resin composition for pixel formation of the present invention has a small difference in the inter-pixel film thickness in the plane, for example, a film thickness of 1 to 4 mu m and an in-plane film thickness difference of 0.15 mu m or less, Mu m or less. Therefore, the color filter thus obtained has excellent smoothness, and by incorporating it into a color liquid crystal display device, a liquid crystal display device of excellent quality can be manufactured with high yield. In addition, by using the color filter described above, it is possible to manufacture an image pickup device of good quality.

Hereinafter, the present invention will be described in more detail with reference to examples, but it is needless to say that the present invention is not limited to the examples. In the following Examples and Comparative Examples, "%" and "part" representing the content are based on weight unless otherwise specified.

Synthesis Example 1 : ( B ' ) Synthesis of Reactive Alkali-Soluble Resin

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was provided with 45 parts by weight of N-benzylmaleimide, 45 parts by weight of methacrylic acid, 10 parts by weight of tricyclodecyl methacrylate, 4 parts by weight of butyl peroxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") were charged and stirred to prepare a monomer dropping lot. 6 parts by weight of thiol and 24 parts by weight of PGMEA were added and stirred to prepare a chain transfer agent dropping lot.

Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was changed to nitrogen in air, and the temperature of the flask was raised to 90 DEG C while stirring. Then, the monomer and the chain transfer agent were added dropwise from the dropping funnel. The mixture was heated at 110 ° C. for 1 h and maintained at 90 ° C. for 1 h. The temperature was raised to 110 ° C. for 3 h. Then, a gas introduction tube was introduced to bubbling oxygen / nitrogen gas with 5/95 (v / v) . Then, 10 parts by weight of glycidyl methacrylate, 0.4 part by weight of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 part by weight of triethylamine were charged into a flask, The reaction was continued and then cooled to room temperature to obtain a resin B 'having a solid content of 29.1% by weight and a weight average molecular weight of 32,000 and an acid value of 114 mgKOH / g.

Synthesis Example 2 : (B ") Non-reactive  Synthesis of alkali-soluble resin

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen-introducing tube was prepared, and 300 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was added and heated to 75 DEG C with stirring. 62.5 parts by weight of 3, 4-epoxy-8- (acryloyloxy) tricyclo [5.2.1.02,6] decane (EDCPA), 15.1 parts by weight of acrylic acid (AA) and 22.4 parts by weight of vinyltoluene were added to 170 parts by weight of PGMEA Solution was added dropwise for 5 hours using a dropping funnel.

On the other hand, a solution prepared by dissolving 30 parts by weight of azobisisobutyronitrile as a polymerization initiator in 200 parts by weight of PGMEA was added dropwise over 5 hours using a separate dropping funnel. After the dropwise addition of the polymerization initiator was completed, the temperature was maintained for about 4 hours while cooling to room temperature to obtain a solid content of 37.6% by weight, a weight average molecular weight of 10740, and an acid value of 111 mgKOH / g of resin B ".

Example  1 to 9 and Comparative Example  1 to 4

: For pixel formation Carraris  Preparation of Photosensitive Resin Composition

The components were mixed as shown in the following Table 1, diluted with propylene glycol monomethyl ether acetate so that the total solid content was 18% by weight, and sufficiently stirred to prepare a colorless photosensitive resin composition for pixel formation.

Item Exposure dose (A)
(B) (C) (D) (F) mJ / cm2 a b c d (B ') (B ") a b Example 1 40 0.5 19.53 45.08 27.91 2.33 4.65 Example 2 50 One 19.53 44.58 27.91 2.33 4.65 Example 3 60 One 19.53 44.58 27.91 2.33 4.65 Example 4 50 One 19.53 44.58 27.91 2.33 4.65 Example 5 50 One 19.1 46.89 28.71 2.39 1.91 Example 6 50 2 19.18 42.75 27.4 2.28 6.39 Example 7 50 One 21.57 46.5 28.6 2.33 Example 8 50 0.5 64.61 27.91 2.33 4.65 Example 9 40 0.5 64.61 27.91 2.33 4.65 Comparative Example 1 40 20.49 47.8 29.27 2.44 Comparative Example 2 50 20.49 47.8 29.27 2.44 Comparative Example 3 60 20.49 47.8 29.27 2.44 Comparative Example 4 60 20.49 44.51 27.91 2.44 4.65

(A): a compound containing at least one selected from a melamine compound and a urea aldehyde compound

    (a) 2,4,6-tris [bis (methoxymethyl) amino] -1,3,5-triazine

    (b) tetramethoxymethylglucuril

(c) 1,3-bis (methoxymethyl) urea

(d) 4,5-Dimethoxy-1,3-bis (methoxymethyl) imidazolidin-2-one

(B): Synthesis Examples 1 and 2

(C): photopolymerizable compound

Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D): Photopolymerization initiator

1,2-octanediol, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)] (IRGACURE OXE01, manufactured by Ciba Specialty Chemical)

(E): solvent

Propylene glycol monomethyl ether acetate (PGMEA)

(F): UV stabilizer

(a) 2- [4- [2-Hydroxy-3-tridecyloxypropyl] oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -Triazine- (TINUVIN 400, manufactured by Ciba Specialty Chemical)

(b) 2-Hydroxy-4- (octyloxy) benzophenone (CHIMASSORB81, manufactured by Ciba Specialty Chemical)

Manufacturing example  : Color filter ( Glass Board)

Color filters were prepared using the colorless photosensitive resin compositions for pixel formation prepared in Examples 1 to 9 and Comparative Examples 1 to 4.

That is, each of the above-mentioned colorless photosensitive resin compositions for pixel formation was coated on a glass substrate by a spin coating method, and then placed on a heating plate and held at a temperature of 100 캜 for 3 minutes to form a thin film. Subsequently, a test photomask having a square pattern of width x 50um x 50um to 10um x 10um and a line / space pattern of 1 mu m to 100 mu m was placed on the thin film and the distance between the test photomask and the test photomask was set to 300 mu m, Respectively.

At this time, the ultraviolet light source was irradiated with light at an exposure dose (365 nm) of 40, 50 and 60 mJ / cm 2 using an ultrahigh pressure mercury lamp (trade name: USH-250D) manufactured by Ushio DENKI Co., . The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 80 seconds to develop. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230 ° C for 25 minutes to prepare a color filter. The film thickness of the color filter prepared above was 3.0 mu m.

Experimental Example

The contact hole size, taper drag, and exposure / development residual film ratios of the color filters manufactured in the above production examples were measured and evaluated as follows, and the results are shown in Table 2 below.

Item Exposure dose 40 x 40um contact hole Minimum contact hole Exposure / Phenomenon responsibility mJ / cm2 Contact hole size Taper Residual film ratio NMP My ITO Castle Etchability Example 1 40 38 O 15 85% O O O Example 2 50 39 O 15 87% O O O Example 3 60 39 O 15 89% O O O Example 4 50 38 O 15 88% O O O Example 5 50 39 O 15 94% O O O Example 6 50 38 O 15 92% O O O Example 7 50 39 O 15 92% O O O Example 8 50 38 O 15 95% O O O Example 9 40 39 O 15 87% O O O Comparative Example 1 40 34 X 30 88% X X X Comparative Example 2 50 36 O 30 89% X X X Comparative Example 3 60 38 X 30 91% O X X Comparative Example 4 60 37 X 30 90% △ X X

When the compound containing at least one selected from (A) the melamine-based compound and the urea aldehyde-based compound of the present invention is used from Table 2, even when the exposure amount is changed to 40 to 60 mJ / cm 2 as in Examples 1 to 9 A minimum contact hole of 15 mu m was obtained.

However, it can be seen that a contact hole having a minimum contact hole of 30 mu m or less can not be obtained as in Comparative Examples 1 to 4 unless a compound containing at least one selected from (A) a melamine-based compound and a urea aldehyde-based compound is added.

[Evaluation of molecular weight]

The weight average molecular weight (Mw) of the alkali-soluble resin (A) was measured by the GPC method under the following conditions.

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 mass% (solvent = tetrahydrofuran)

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

[Solid content]

The polymer solution was weighed in an amount of about 1 g into an aluminum cup, and about 3 g of acetone was added to dissolve it, followed by natural drying at room temperature. Using a hot-air drier (trade name: PHH-101, manufactured by Espec Co., Ltd.), it was dried in a vacuum at 160 ° C for 3 hours, and then cooled in a desiccator and its weight was measured. The solid content of the polymer solution was calculated from the weight reduction amount.

[Mountain]

3 g of the resin solution was dissolved and dissolved in a mixed solvent of 90 g of acetone and 10 g of water. Using an automatic titration apparatus (trade name: COM-1 manufactured by Hiranuma Industrial Co., Ltd.) using 0.1 N KOH aqueous solution as indicator, 555), and the acid value per 1 g of the solid content was determined from the acid value of the solution and the solid content of the solution.

[Measurement of residual film ratio]

Each of the colorless photosensitive resin compositions for pixel formation was coated on a glass substrate by a spin coating method and then placed on a heating plate and held at a temperature of 100 ° C for 3 minutes to form a thin film. Then, a thin film was formed with a front exposure of 50 mJ / cm 2 , And the film thickness of the pattern was measured using a film thickness measuring device (DEKTAK 6M; Veeco). After the thickness measurement was completed, the substrate was again dipped in a KOH aqueous solution of pH 10.5 for 80 seconds, and then the thickness was measured.

Remaining film ratio (%) = thickness after development (um) / pre-development thickness (um)

When the residual film ratio was 85% or less, it was judged that the film hardness was weak and the process margin was greatly influenced.

[Contact hole size, taper trace observation and minimum contact hole]

The substrate prepared in the above-mentioned production example was placed, and a 40 mm x 40 um square contact hole of the photomask was observed. The size of the contact hole was measured, and the take drag was observed, and then a picture was taken. The minimum contact hole was defined as the minimum contact hole in which the reproduced contact hole size for the mask was reproduced by not less than 70%. (For example, a mask has a 15-μm contact hole and a size of 10.5 μm or more)

OM equipment: manufactured by ECLIPSE LV100POL Nikon

Evaluation criteria of tapered drawing

O: Taper free state

△: Taper drag of one side is 2um or less

X: Taper pull of one side is more than 3um

[responsibility]

The substrate prepared in this Preparation Example was immersed in NMP (N-methyl-2-pyrrolidone), heated at 100 ° C. for 30 minutes, and the thickness change before and after the film was measured.

NMP Tolerance Standard

O: 98% or more

?: 95% to 98%

X: 95% or less

[My ITO Castle]

The substrate prepared in the above-mentioned production example was subjected to ITO sputtering with a thickness of 1000 A to measure changes in film wrinkles.

O: no wrinkles

X: state of film wrinkle

[Etching resistance]

 The substrate prepared in this Preparation Example was immersed in an ITO etchant at 60 DEG C for 10 minutes, and the change in film thickness before and after immersion was measured and expressed as a percentage.

Etchability Evaluation Criteria

O: 98% or more

?: 95% to 98%

X: 95% or less

Claims (14)

(A) a compound comprising at least one selected from a melamine compound and a urea aldehyde compound; (B) an alkali-soluble resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator, and (E) a solvent. The method according to claim 1,
The compound containing at least one selected from the melamine-based compound and the ureaaldehyde-based compound (A)
A colorless photosensitive resin composition for pixel formation comprising at least one compound selected from the group consisting of the following formulas (1) to (5)
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

The method according to claim 1,
The compound containing at least one selected from the group consisting of (A) the melamine compound and the urea aldehyde compound is used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the sum of the alkali soluble resin (B) and the photopolymerizable compound (C) By weight based on the total weight of the composition. The method according to claim 1,
The alkali-soluble resin (B)
(B ') a photopolymerization initiator and a reactive alkali-soluble resin reactive with UV radiation; And
(B ") photopolymerization initiator and a non-reactive alkali-soluble resin that is non-reactive with respect to UV irradiation. 5. The method of claim 4,
(B ') a photopolymerization initiator and a non-reactive alkali-soluble resin that is non-reactive with UV radiation in a ratio of 8: 2 to 2: 8 by weight, the reactive alkali- Wherein the colorless photosensitive resin composition for forming a pixel is a colorless resin. 5. The method of claim 4,
The above-mentioned (B ') photopolymerization initiator and the reactive alkali-soluble resin which is reactive with UV irradiation,
(B'1) a copolymer obtained by polymerizing a compound having an unsaturated bond and a carboxylic acid group in one molecule and (B'2) a compound containing a compound having an unsaturated bond polymerizable with the above (B'1) 3) A colorless photosensitive resin composition for pixel formation, which is obtained by further polymerizing a compound having an unsaturated bond and an epoxy group in one molecule. The method according to claim 6,
Wherein the compound having an unsaturated bond and an epoxy group in one molecule of the compound (B'3) is a compound having a (meth) acrylic group and an epoxy group. 5. The method of claim 4,
The above-mentioned (B ") photopolymerization initiator and the non-reactive alkali-soluble resin which is non-
(B "2) a compound having an unsaturated bond and a carboxylic acid group in one molecule and (B" 2) a compound having an unsaturated bond polymerizable with the above (B & Wherein the resin is a copolymer having no unsaturated double bond polymerizable in the resin molecular chain after completion. The method according to claim 6,
The compound having an unsaturated bond and a carboxylic acid group in one molecule of the (B'1) may be a monocarboxylic acid, a dicarboxylic acid, an anhydride of a dicarboxylic acid, or a mono (metha) of a polymer having a carboxyl group and a hydroxyl group ) Acrylates, and at least one selected from the group consisting of
The compound having an unsaturated bond polymerizable with (B'2) above (B'1) can be obtained by reacting an unsubstituted or substituted alkyl ester compound of an unsaturated carboxylic acid, an unsaturated carboxylic acid ester compound containing an alicyclic substituent, An unsaturated carboxylic acid ester compound containing a possible substituent, a mono-saturated carboxylic acid ester compound of a glycol, an unsaturated carboxylic acid ester compound having a substituted or unsubstituted aromatic ring, an aromatic vinyl compound; A carboxylic acid vinyl ester, and a vinyl cyanide compound. The colorless photosensitive resin composition for forming a pixel according to claim 1, The method according to claim 6,
The compound having an unsaturated bond and a carboxylic acid group in one molecule of the (B'1) may be any one of acrylic acid, methacrylic acid, crotonic acid, fumaric acid, mesaconic acid, itaconic acid, fumaric acid anhydride, (Meth) acrylate, carboxypolycaprolactone mono (meth) acrylate,
(Meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and the like can be used as the compound having an unsaturated bond polymerizable with (B'2) (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (Meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (Meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (Meth) acryloyloxymethyl) (Meth) acryloyloxymethyl) -3-ethyloxetane, 3 - ((meth) acryloyloxymethyl) -2-methyloxetane, 3- (Meth) acrylate, phenoxy (meth) acrylate,? -Methylstyrene, vinyltoluene, vinyl acetate, vinyltoluene, (Meth) acrylonitrile, and [alpha] -chloroacrylonitrile, and at least one selected from the group consisting of
Examples of the compound having an unsaturated bond and an epoxy group in one molecule of (B'3) include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) Acrylate, and methylglycidyl (meth) acrylate. The colorless photosensitive resin composition for forming a pixel according to claim 1, The method according to claim 1,
Wherein the colorless photosensitive resin composition for pixel formation further comprises a UV stabilizer. The method according to claim 1,
The colorless photosensitive resin composition for forming a pixel is characterized in that it has a weight fraction based on the solid content in the colorless photosensitive resin composition for pixel formation,
(B) 20 to 85% by weight of an alkali-soluble resin;
(C) 10 to 60% by weight of a photopolymerizable compound; And
(D) 0.1 to 20% by weight of a photopolymerization initiator;
Wherein the solvent (E) comprises 60 to 90% by weight based on the total amount of the colorless photosensitive resin composition for pixel formation. A color filter formed using the colorless photosensitive resin composition for pixel formation according to any one of claims 1 to 12. A liquid crystal display device comprising the color filter of claim 13.

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