KR20150010555A - Photosensitive resin composition for transparent pixel - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for transparent pixels. The photosensitive resin composition for transparent pixels comprises (A) an alkaline soluble resin; (B) a photo-polymerizable compound; (C) a photopolymerization initiator; and (D) a solvent, wherein (A) the alkaline soluble resin is a mixture of (A′) an alkaline soluble resin reactive to the radical photo initiator and the UV irradiation, and (A″) an alkaline soluble resin non-reactive to the radical photo initiator and the UV irradiation at a weight ratio of 8:2 to 1:7, and the molecular weight of (A″) the alkaline soluble resin non-reactive to the radical photo initiator and the UV irradiation is 10,000-30,000.

Description

PHOTOSENSITIVE RESIN COMPOSITION FOR TRANSPARENT PIXEL FOR FORMING TRANSPARENT PIXELS

The present invention relates to a photosensitive resin composition for forming a transparent pixel, which can easily form a fine pixel pixel and can realize a contact hole for forming a transparent electrode.

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 transparent pixel pixel, a transparent pixel layer is fabricated using an overcoat, a photosensitive column spacer, or the like among conventional transparent materials described in Korean Patent Publication No. 2007-0007895. However, it is difficult to realize a transparent pixel pattern, In particular, it has a problem that it is impossible to create a contact-hole of less than 40um.

Korea Publication No. 2007-0007895

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and it is an object of the present invention to provide a method for forming a transparent pixel pattern, which not only enables fine contact holes, It is an object of the present invention to provide a resin composition.

The present invention relates to (A) an alkali-soluble resin; (B) a photopolymerizable compound; (C) a photopolymerization initiator; And (D) a solvent, wherein the alkali-soluble resin (A) comprises a radical photoinitiator (A '), an alkali-soluble resin (A ") reactive with UV radiation and a radical photoinitiator (A ") radical photoinitiator and an alkali-soluble resin which is non-reactive with respect to UV irradiation are mixed in a weight ratio of from 8: 2 to 1: 7, and a molecular weight of from 10,000 to 30,000 And a photosensitive resin composition for forming a transparent pixel.

The present invention also provides a color filter formed using the photosensitive resin composition for forming a transparent pixel.

When the transparent pixel pixel of the color filter is formed using the photosensitive resin composition for forming a transparent pixel of the present invention, the flatness of the pixel portion is excellent, the formation of the fine pixel pixel is easy, and the contact hole for forming the transparent electrode can be realized It is possible to provide a high-quality color filter having excellent heat resistance and chemical resistance.

Fig. 1 is a photograph showing a color filter (glass substrate) of a production example produced according to the present invention and a color filter (glass substrate) of a comparative production example.
FIG. 2 is a graph comparing the level of flatness (shown in the above figure) formed by applying conventional colored photosensitive compositions such as R, G, B and the level of flatness formed by applying a conventional transparent photosensitive resin composition to be.
3 is a diagram showing a method for evaluating the flatness of the photosensitive resin composition for forming a transparent pixel.

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.

The present invention relates to (A) an alkali-soluble resin; (B) a photopolymerizable compound; (C) a photopolymerization initiator; And (D) a solvent, and a color filter formed using the same, wherein the alkali-soluble resin (A) comprises (A ') a radical photoinitiator and an alkali soluble (A ") radical photoinitiator and an alkali-soluble resin which is non-reactive with respect to UV irradiation are mixed in a weight ratio of 8: 2 to 1: 7. Further, Soluble alkali-soluble resin has a molecular weight of 10,000 to 30,000.

Hereinafter, the constituent elements of the present invention will be described in detail.

(A) an alkali-soluble resin

The alkali-soluble resin (A) serves to make the unexposed portion of the transparent pixel photosensitive resin layer formed using the photosensitive resin composition for forming a transparent pixel alkali soluble and to remove the exposed region. In particular, the present invention relates to a resin composition comprising (A) an alkali-soluble resin, wherein (A ') a radical photoinitiator and an alkali-soluble resin which is reactive with UV radiation and (A ") a radical photoinitiator and an alkali- It is experimentally confirmed that formation of a fine pixel pixel is easy in formation of a transparent pixel of a color filter and mixing of a contact hole for forming a transparent electrode is possible in the case of mixing at a weight ratio of 8: 2 to 1: 7 Thus completing the present invention.

The mixing ratio of the alkali-soluble resin (A) is preferably 8: 2 to 1: 7, more preferably 7: 3 to 10: 1, 1: 6. When the content of the reactive alkali-soluble resin is less than 2, the developed residual film ratio is lowered. On the other hand, when the content exceeds 8, the degree of curing is increased to cause a remarkable taper drag at the contact hole, Occurs.

The reactive alkali-soluble resin (A ') used in the present invention can be polymerized by addition of monomers other than (A'1), (A'2) and (A'3). That is, the case where other monomers other than the above-mentioned (A'1) to (A'3) are further polymerized are also included in the scope of the present invention.

The component (A'1) contained in the reactive alkali-soluble resin (A ') 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, These 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 component (A'2) contained in the reactive alkali-soluble resin (A ') is a compound having an unsaturated bond polymerizable with (A'1), and can be used without limitation as long as it is a compound having an unsaturated double bond capable of polymerization. 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) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (Meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl 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, and vinyltoluene; Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; And vinyl cyanide compounds such as (meth) acrylonitrile and? -Chloroacrylonitrile. 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 containing (A'1) to (A'2) used in the present invention, the proportion of the component derived from each of (A'1) to (A'2) (A'1) to (A'2) in terms of the mole fraction with respect to the total number of moles of the components (A'1) to (A'2).

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

(A'2): 30 to 98% by mole,

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

(A'1): 10 to 60% by mole,

(A'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 method for producing the reactive alkali-soluble resin (A '), when the compound (A'1) to (A'2) is copolymerized, it can be produced by the following method.

A solvent of 0.5 to 20 times the total mass of (A'1) to (A'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 then a predetermined amount of (A'1) to (A'2) is added to the total mass of (A'1) to (A'2) A solvent and a polymerization initiator such as azobisisobutyronitrile or benzoyl peroxide in an amount of 0.1 to 10 mol% relative to the total molar amount of (A'1) to (A'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 (A'1) to (A'2) may be put into a flask. Further, an alpha -methylstyrene dimer or a mercapto compound may be used as a chain transfer agent to control the molecular weight or the molecular weight distribution. The amount of the? -methylstyrene dimer or mercapto compound to be used is 0.005 to 5 mass% with respect to the total mass of (A'1) to (A'2). In addition, the above-mentioned polymerization conditions may be appropriately adjusted depending on the production equipment or the amount of heat generated by polymerization, and the method of addition and the reaction temperature.

Examples of the reactive alkali-soluble resin (A ') contained in the photosensitive resin composition for forming a transparent pixel of the present invention include (A'3) a copolymer obtained by polymerizing the compounds (A'1) to (A'2) Can be obtained by further reacting the compound. By adding (A'3) to the above copolymer, light / heat curability can be imparted to the alkali-soluble resin to improve heat resistance and chemical resistance.

The component (A'3) contained in the reactive alkali-soluble resin (A ') is a compound having an unsaturated bond and an epoxy group in one molecule, and specific examples thereof include glycidyl (meth) acrylate, 3,4- (Meth) acrylate, cyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and methylglycidyl (meth) acrylate. Of these, glycidyl (meth) acrylate is preferably used. 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 the (A'3) is preferably used in an amount of 5 to 80 mol% based on the number of moles of the compound having an unsaturated bond and a carboxylic acid group in one molecule of the (A'1) , More preferably from 10 to 80 mol%. (A'3) within the above range is preferable because of excellent exposure sensitivity and developability.

In the present invention, the reactive alkali-soluble resin (A ') is obtained by reacting the copolymer (A'3) obtained by copolymerizing (A'1) to (A'2) with, for example, Can be manufactured.

(A'3) as a mole ratio of the constituent unit derived from (A'1) in the copolymer to (A'3) as a reaction catalyst for a carboxyl group and an epoxy group, For example, 0.01 to 5% by mass of trisdimethylaminomethylphenol relative to the total mass of (A'1) to (A'3), and 0.001 to 5% by mass of hydroquinone as a polymerization inhibitor, for example, (A'3) can be reacted with the above-mentioned copolymer by reacting at 60 to 130 DEG 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 (A ') 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 (A ') is in the range of 3,000 to 100,000, film reduction of the exposed area is unlikely to occur during development and the solubility of the unexposed area tends to be good.

The acid value of the reactive alkali-soluble resin (A ') is preferably in the range of 30 to 150 mgKOH / g based on the solid content. If the acid value is less than 30 mgKOH / g, the solubility in the alkaline developer is lowered and the residue may remain on the substrate. If the acid value exceeds 150 mgKOH / g, there is a high possibility that pattern peeling occurs.

The molecular weight distribution of the reactive alkali-soluble resin (A ') 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, it is preferable since the developing property is excellent.

The (A ") non-reactive alkali-soluble resin used in the present invention can be produced in the same manner as the reactive alkali-soluble resin (A ') except that (A") the UV- (A ') contained in the reactive alkali-soluble resin (A' 3) is omitted, since the polymerization should be carried out in the absence of an unsaturated double bond capable of causing photopolymerization by the photoinitiator, A "2), or by copolymerizing (A" 3) to (A "5). The method example is the same as the general synthesis example of the reactive alkali-soluble resin (A ').

The components (A'1) and (A'2) may be the same as the components (A'1) and (A'2), respectively.

The components (A "3) to (A" 5) are as follows:

(A "3) A compound having an unsaturated bond and a carboxylic acid group in a molecule

(A "4) An aliphatic polycyclic compound having an epoxy group and an unsaturated bond

(A "5) A dicarbonylimide derivative having an unsaturated bond polymerizable with the above (A" 3) to (A "4).

The reactive alkali-soluble resin (A ") used in the present invention may be polymerized by addition of monomers other than the above (A" 3), (A " That is, the case where other monomers other than the above-mentioned (A "3) to (A" 5) compounds are further polymerized and included in the scope of the present invention.

The component (A ") contained in the non-reactive alkali-soluble resin (A") is the same as the component (A'1) contained in the reactive alkali-

Examples of the aliphatic polycyclic compound having an epoxy group and an unsaturated bond (A "4) contained in the (A") non-reactive alkali-soluble resin include dicyclopentane, tricyclodecane, norbornane, isobornane , Bicyclooctane, cyclononane, bicycloundecane, tricyclooctane, bicyclododecane, tricyclododecane, and the like. More preferably, the aliphatic polycyclic compound (A "4) having an epoxy group and an unsaturated bond and the aliphatic polycyclic compound having an epoxy group and an unsaturated bond can be prepared from the group consisting of a compound represented by the following formula It is preferable to include at least one kind of compound selected.

(Wherein R in each of formulas (1) and (2) is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which is unsubstituted or substituted with a hydroxyl group, and each X independently represents a single bond or a hetero atom- Lt; / RTI >

In the formulas (1) and (2), R is specifically a hydrogen atom; An alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group; Hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1-hydroxy-1-hydroxypropyl group, N-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-n-butyl group, 2-hydroxy- -Butyl group and the like. Among them, R is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

In Formulas 1 and 2, X is specifically a single bond; Alkylene groups such as a methylene group, an ethylene group and a propylene group; Containing alkylene groups such as a methylene group, an oxyethylene group, an oxyethylene group, an oxyethylene group, an oxypropylene group, a thiomethylene group, a thioethylene group, a thiopropylene group, an aminomethylene group, an aminoethylene group and an aminopropylene group. Among them, X is preferably a single bond, a methylene group, an ethylene group, an oxymethylene group or an oxyethylene group, more preferably a single bond or an oxyethylene group.

The compound represented by the formula (1) and the compound represented by the formula (2) may be used alone or in combination of two or more thereof. In particular, the compound represented by the formula (1) and the compound represented by the formula (2) It can also be used.

Examples of the (A "5) dicarbonylimide derivative contained in the (A") non-reactive alkali-soluble resin include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, Maleimidobutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl- - (9-acridinyl) maleimide. Of these, N-phenylmaleimide, N-cyclohexylmaleimide and N-benzylmaleimide are preferred from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution .

The non-reactive binder resin (A ") used in the present invention is a copolymer obtained by copolymerizing (A" 3), (A "4) and (A" 5) It is preferable that the molar ratio with respect to the total number of moles of constituent components constituting the copolymer is in the following range.

(A "3); 2 to 40 mol%

(A "4); 2 to 95 mol%

(A "5); 1 to 65 mol%

It is more preferable that the ratio of the constituent components is in the following range.

(A "3); 5 to 35 mol%

(A "4); 5 to 80 mol%

(A "5); 1 to 60 mol%

When the composition ratio is in the above range, the storage stability of the photosensitive resin composition, the developability of the pattern obtained from the composition, the solvent resistance, the heat resistance, and the mechanical strength tend to be improved.

In the present invention, the (A ") non-reactive alkali-soluble resin has a weight average molecular weight in terms of polystyrene of 10,000 to 30,000. The present inventors have found that the molecular weight of the non-reactive alkali- Is 10,000 to 30,000, it has been experimentally confirmed that a transparent pixel capable of realizing a fine pattern can be formed with excellent developing residual film ratio, heat resistance, chemical resistance and flatness.

The acid value of the non-reactive alkali-soluble resin (A ") is preferably in the range of 30 to 150 mgKOH / g based on the solid content. When the acid value is less than 30 mgKOH / g, the solubility in the alkali developer is lowered, If the acid value exceeds 150 mgKOH / g, the possibility of pattern peeling increases.

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

The content of the alkali-soluble resin (A) is usually in the range of 20 to 85% by mass, preferably 40 to 75% by mass with respect to the solid content in the photosensitive resin composition for forming a transparent pixel. When the content of the alkali-soluble resin (A) is 20 to 85 mass% 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.

(B) Photopolymerization  compound

The photopolymerizable compound (B) contained in the photosensitive resin composition for forming a transparent pixel of the present invention is a compound capable of polymerizing under the action of light and a photopolymerization initiator described later, and includes monofunctional monomers, bifunctional monomers, .

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

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

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

Of these, multifunctional monomers having two or more functional groups are preferably used. Particularly preferably, a polyfunctional monomer having 5 or more functional groups can be used. More preferably, dipentaerythritol (poly) acrylate having a hydroxyl value of 70 to 130 mg KOH / g represented by the following formula 3 is preferably used Do.

(Wherein R is hydrogen or an acryloyl group having 2 to 6 carbon atoms)

The photopolymerizable compound (B) is used in a mass fraction of usually 10 to 60 mass%, preferably 20 to 50 mass%, based on the solid content in the photosensitive resin composition for forming a transparent pixel. When the photopolymerizable compound (B) is in the range of 10 to 60 mass% based on the above-mentioned standard, 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.

(C) Light curing Initiator

The photopolymerization initiator (C) contained in the photosensitive resin composition for forming a transparent pixel of the present invention is not limited, but is at least one compound selected from the group consisting of a triazine-based compound, an acetophenone-based compound, a nonimidazole-based compound and an oxime compound . The photosensitive resin composition for forming a transparent pixel containing the photopolymerization initiator (C) described above has high sensitivity, and the film formed using this composition has good strength and contact hole characteristics of the pixel portion.

When the photopolymerization initiator (C) is used in combination with the photopolymerization initiator (C-1), the photosensitive resin composition for forming a transparent pixel containing the photopolymerization initiator and the photopolymerization initiator improves the productivity .

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, 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- 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one, 1-one oligomers and the like. Further, a compound represented by the following formula (4) can be mentioned.

(Formula 4)

In the formula,

R 1 to R 4 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group substituted 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.

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

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, phenyl group at 4,4' An imidazole compound substituted by a haloalkoxy group, and the like. Of these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- 5,5'-tetraphenylbiimidazole is preferably used.

Examples of the oxime compounds include the following formulas (5), (6) and (7).

(Formula 5)

(Formula 6)

(Formula 7)

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, benzoin isobutyl ether and the like.

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, 1-chloro-4- .

Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 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, titanocene compounds and the like can be mentioned as other photopolymerization initiators.

Further, as the (C-1) photopolymerization initiator auxiliary which can be used in combination with the photopolymerization initiator (C) 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 .

Specific examples of the amine compound in the photopolymerization initiation auxiliary include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; aliphatic amine compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, N, N-dimethyl para-toluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'- And aromatic amine compounds such as bis (diethylamino) benzophenone. 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 (C) in the photosensitive resin composition for forming a transparent pixel of the present invention is 0.1 to 20 mass%, preferably 1 to 10 mass%, based on the total solid components, and the content of the (C-1) The amount to be used is usually 0.1 to 20% by mass, preferably 1 to 10% by mass, based on the above criteria.

When the amount of the photopolymerization initiator (C) to be used is within the above range, the photosensitive resin composition for forming a transparent pixel has 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 (C-1) used is within the above range, the sensitivity of the photosensitive resin composition for forming a transparent pixel is further increased, and the productivity of the color filter formed using the composition tends to be improved desirable.

(D) Solvent

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

Specific examples of the solvent (D) 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 dimethyl ether, diethylene Diethylene glycol dialkyl ethers such as 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, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, and other alkylene glycol alkyl ether acetates However, Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene Alcohols such as glycol and glycerin, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as? -Butyrolactone.

Among the above solvents, organic solvents having a boiling point of 100 ° C to 200 ° C in the solvent are preferably used from the viewpoint of coatability and dryness, more preferably alkylene glycol alkyl ether acetates, ketones, 3- Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3- (3-methoxypropionate) and the like, and more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Ethyl ethoxypropionate, methyl 3-methoxypropionate, and the like.

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

The content of the solvent (D) in the photosensitive resin composition for forming a transparent pixel of the present invention is usually 60 to 90% by mass, preferably 70 to 85% by mass with respect to the total amount of the photosensitive resin composition for forming a transparent pixel including a solvent %to be. (D) When the content of the solvent is in the range of 60 to 90% by mass based on the above-mentioned criteria, it may be applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater It is preferable since the coating property tends to be good.

(E) Additive

In the photosensitive resin composition for forming a transparent pixel of the present invention, a filler, other polymer compound, a curing agent, a pigment dispersant, (E) additives such as an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent may be used in parallel.

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, a melamine 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 pigment dispersant, commercially available surfactants 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 pigment 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 mass based on the solid content in the photosensitive resin composition for forming a transparent pixel.

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 promoters may be used alone or in combination of two or more, and usually contain 0.01 to 10% by mass, preferably 0.05 to 2% by mass, based on the solid content in the photosensitive resin composition for forming a transparent pixel.

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 ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone.

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

The photosensitive resin composition for forming a transparent pixel of the present invention can be produced, for example, by the following method. (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a solvent in an appropriate ratio and further adding other components as needed, To obtain a resin composition.

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

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

As an example, it is coated on a substrate as follows to form a pattern by photo-curing and development, and can be used as a black matrix or a colored and transparent pixel (colored image).

First, the composition is coated on a substrate (including but not limited to a glass or a silicon wafer) or a layer containing a solid content of a photosensitive resin composition for forming a transparent pixel formed in advance and preliminarily dried to remove volatile components such as a solvent, To obtain a coated 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.

The developing solution used for development after patterned exposure is usually 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 preferable concentration of the alkaline compound in the alkali developing solution is in the range of 0.01 to 10 mass%, more preferably 0.03 to 5 mass%.

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, Polyoxyethylene 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 alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

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

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 mass, preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass.

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-described photosensitive resin composition for forming a transparent pixel in a predetermined pattern, and then exposing and developing the same.

The method for forming a pattern of a photosensitive resin composition for forming a transparent pixel is described above, and a detailed description thereof will be omitted. As described above, a pixel or a black matrix corresponding to the photosensitive resin composition for forming a transparent pixel is obtained through application of a solution of the photosensitive resin composition for forming a transparent pixel, drying, patterning exposure to a dried film obtained, and development , And by repeating this operation for the number of unit pixels required for the color filter, a color filter can be obtained. 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 photosensitive resin composition for forming a transparent pixel of the present invention has a small difference in the inter-pixel film thickness in the plane, and has a thickness of, for example, 1 to 4 m and a thickness difference of 0.15 m or less, 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 on a mass basis unless otherwise specified.

< Synthetic example >

Synthetic example  1-1: Synthesis of Reactive Alkali-Soluble Resin A '

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen-introducing tube was prepared, and 84.2 parts of N-benzylmaleimide, 38.7 parts of methacrylic acid, 22 parts of tricyclodecyl methacrylate, 4 parts of oxy-2-ethylhexanoate and 40 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") were charged and stirred to prepare a monomer dropping tank. 6 parts of n-dodecanethiol, And the mixture was stirred and mixed to prepare a chain transfer agent dropping lot. Then, 395 parts of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen in air, and the temperature of the flask was raised to 90 DEG C with 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, 14.2 parts of glycidyl methacrylate, 0.4 part of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 part of triethylamine were put into a flask, and the reaction was continued at 110 ° C for 8 hours And then cooled to room temperature to obtain a resin A '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.

Synthetic example  1-2: Reactive alkali-soluble resin A ' Synthesis of A1-a )

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel, and a nitrogen inlet tube was prepared, and 45 parts of N-benzylmaleimide, 45 parts of methacrylic acid, 10 parts of tricyclodecyl methacrylate, 4 parts of oxy-2-ethylhexanoate and 40 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") were charged and stirred to prepare a monomer dropping tank. 6 parts of n-dodecanethiol, And the mixture was stirred and mixed to prepare a chain transfer agent dropping lot. Then, 395 parts of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen in air, and the temperature of the flask was raised to 90 DEG C with 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) . Subsequently, 10 parts of glycidyl methacrylate, 0.4 part of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 part of triethylamine were added into the flask, and the reaction was continued at 110 DEG C for 8 hours And then cooled to room temperature to obtain a resin A '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.

Synthetic example  2-1: Non-reactive  Synthesis of alkali-soluble resin A "

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared, and 300 parts of propylene glycol monomethyl ether acetate (PGMEA) was added and heated to 75 DEG C with stirring. 13.7 parts by weight of 3, 4-epoxy-8- (acryloyloxy) tricyclo [5.2.1.02,6] decane (EDCPA), 10.9 parts by weight of acrylic acid (AA) and 26.5 parts by weight of vinyltoluene were added to a flask, 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 resin A "having a solid content of 37.6% by weight, a weight average molecular weight of 10,740 and an acid value of 111 mgKOH / g.

Synthetic example  2-2: Non-reactive  Synthesis of alkali-soluble resin A " A2-a )

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared, and 300 parts of propylene glycol monomethyl ether acetate (PGMEA) was added and heated to 75 DEG C with stirring. 76.8 parts by weight (60 mol%) of 3,4-epoxy-8- (acryloyloxy) tricyclo [5.2.1.02,6] decane (EDCPA) and 10.0 parts by weight (20 mol%) of methacrylic acid (MAA) And 19.2 parts by weight (20 mol%) of N-cyclohexylmaleimide were dissolved in 170 parts by weight of PGMEA, and the solution was added dropwise for 5 hours using a dropping funnel. On the other hand, a solution prepared by dissolving 20 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, while maintaining the temperature for about 4 hours, the solution was cooled to room temperature and a resin A "having a solid content of 37.6% by weight, a weight average molecular weight of 15,740 and an acid value of 121 mgKOH / g was obtained.

Synthetic example  2-3 and Comparative Synthetic Example  1 to 4: Non-reactive  Synthesis of alkali-soluble resin A "

Synthesis Example 2-1 was carried out in the same manner as in Synthesis Example 2-1 except that the content of azobisisobutyronitrile was controlled to control the molecular weight. Synthesis Example 2-3 was prepared as shown in Table 1 below. Comparative Synthesis Examples 1 and 2 which did not contain N-cyclohexylmaleimide and Comparative Synthesis Examples 3 and 4 which did not contain N-cyclohexylmaleimide were prepared. The molar percent of the reactive monomer and the result of the synthesis are shown in Table 1 below.

Polymerizable monomer (mol%) Synthesis Example 2-3 Comparative Synthesis Example 1 Comparative Synthesis Example 2 Comparative Synthesis Example 3 Comparative Synthesis Example 4 A2-c A2-b A2-d A2-e A2-f E-DCPA
(3, 4-epoxy-8- (acryloyloxy) tricyclo [5.2.1.0 2,6] decane) 60 60 60 80 80 MAA
(Methacrylic acid) 20 20 20 20 20 CHMI
(N-cyclohexylmaleimide) 20 20 20 0 0 Solid content (%) 40.7% 39.6% 39.2% 41.3% 41.0% Weight average molecular weight 23,700 9.030 32,300 8,600 14,600 Acid value 120 122 122 123 121

Molecular weight evaluation

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)

Solids

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.

Acid value

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 a 0.1 N KOH aqueous solution as an indicator, thymol blue was used as an indicator, and an automatic titration apparatus (manufactured by Hiranuma Industrial Co., -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.

< Examples Comparative Example >

Example  1 to 7 and Comparative Example  1 to 5: Transparent pixel  Preparation of photosensitive resin composition for forming

After mixing the components as shown in Table 2 below, the mixture was diluted with propylene glycol monomethyl ether acetate so that the total solid content was 18% by weight, and sufficiently stirred to obtain transparent pixels of Examples 1 to 7 and Comparative Examples 1 to 5 A photosensitive resin composition for forming a photosensitive layer was obtained.

Item (A) an alkali-soluble resin (B) a photopolymerizable compound (C) a photopolymerization initiator (A ') Reactivity (A ") Non-reactive Weight ratio
(A ': A ") Example 1 55.17 13.79 8: 2 29.56 1.48 Example 2 48.3 20.7 7: 3 28.98 2.02 Example 3 41.35 27.57 6: 4 28.86 2.22 Example 4 34.2 34.2 5: 5 29.03 2.57 Example 5 27.23 40.84 4: 6 29.13 2.8 Example 6 20.39 47.57 3: 7 29.13 2.91 Example 7 13.53 54.11 2: 8 28.98 3.38 Comparative Example 1 0 67.63 0:10 28.99 3.38 Comparative Example 2 68.97 0 10: 0 29.55 1.48 Comparative Example 3 62.07 6.9 9: 1 29.55 1.48 Comparative Example 4 58.54 10.33 8.5: 1.5 29.35 1.78 Comparative Example 5 6.76 60.87 1: 9 28.99 3.38

- (A) an alkali-soluble resin

     (A ') Reactivity: Synthesis Example 1-1

     (A ") Non-reactivity: Synthesis Example 2-1

- (B) Photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

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

- (D) Solvent: Propylene glycol monomethyl ether acetate (PGMEA)

Example  8-11 and Comparative Example  6-12: Transparent pixel  Preparation of photosensitive resin composition for forming

After mixing the components as shown in Tables 3 and 4, the mixture was diluted with propylene glycol monomethyl ether acetate so that the total solid content became 18% by weight and sufficiently stirred to obtain a colorless photosensitive resin composition for pixel formation.

Example Example 8 Example 9 Example 10 Example 11 (A ') Reactivity Synthesis Example 1-2
A1-a 32 10.5 8 10.5 (A ") non-reactive Synthesis Example 2-2
A2-a 32 53.5 56 - Synthesis Example 2-3
A2-c - - - 53.5 (B) a photopolymerizable compound 30 30 30 30 (C) a photopolymerization initiator 4 4 4 4

Comparative Example Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 (A ') Reactivity Synthesis Example 1-2
A1-a 42.5 6.5 0 10.5 10.5 10.5 10.5 (A ") non-reactive Synthesis Example 2-2
A2-a 21.5 57.5 64 - - - - Comparative Synthesis Example 1
A2-b - - - 53.5 - - - Comparative Synthesis Example 2
A2-d - - - - 53.5 - - Comparative Synthesis Example 3
A2-e - - - - - 53.5 - Comparative Synthesis Example 4
A2-f - - - - - - 53.5 (B) a photopolymerizable compound 30 30 30 30 30 30 30 (C) a photopolymerization initiator 4 4 4 4 4 4 4

- (B) Photopolymerizable compound: dipentaerythritol polyacrylate having a hydroxyl value of 90 mgKOH / g (KAYARAD; manufactured by Nippon Kayaku Co., Ltd.)

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

- (D) Solvent: Propylene glycol monomethyl ether acetate (PGMEA)

<Color filter ( Glass Board) Manufacturing example >

Manufacturing example  1 to 11 and Comparative Manufacturing Example  1 to 12: Manufacture of color filters

Using the photosensitive resin compositions for forming a transparent pixel prepared in Examples 1 to 11 and Comparative Examples 1 to 12, the color filters of Production Examples 1 to 11 and Comparative Production Examples 1 to 12 were prepared, respectively.

That is, the photosensitive resin composition for forming a transparent pixel prepared in Examples 1 to 11 and Comparative Examples 1 to 12 was applied on a glass substrate by spin coating, then placed on a heating plate and maintained at a temperature of 100 ° C for 3 minutes to form a thin film / RTI &gt; 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 50 mJ / cm 2 using an ultrahigh pressure mercury lamp (trade name: USH-250D) manufactured by Ushio DENKI Co., Ltd. No special optical filter was used. 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 >

Measurement of residual film ratio

Each of the photosensitive resin compositions for forming a transparent pixel 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 front exposure of 50 mJ / cm 2 After irradiating ultraviolet rays, 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  And Taper  observe

A 40 um x 40 um square contact hole of the photomask was observed on the substrate prepared in the above example, the size of the contact hole was measured, the take-off was observed, and a picture was taken.

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

The contact hole size, taper drag, and exposure / development residual film ratios of the color filter were measured and evaluated as described below, and the results are shown in FIG. 1 and Tables 5 to 7.

Item 40 x 40um contact hole (photomask) Before and after development
Remaining film ratio (%) Contact Hole Size (um) Taper Production Example 1 29.7 O 92% Production Example 2 29.5 O 90% Production Example 3 30.9 O 90% Production Example 4 32.5 O 89% Production Example 5 33.8 O 87% Production Example 6 35.5 O 87% Production Example 7 33.8 O 85% Comparative Preparation Example 1 42 O 68% Comparative Production Example 2 Plugging holes - 94% Comparative Production Example 3 22 X 92% Comparative Production Example 4 25 X 90% Comparative Preparation Example 5 39 O 75%

1 and Table 5, when the reactive alkali-soluble resin (A ') of the present invention was mixed with the non-reactive alkali-soluble resin (A ") in an amount of 8: 2 to 1: 7, The contact hole can be obtained with a satisfactory contact hole of 85% or more, and satisfactory results can be obtained. In other ratios, the contact holes are clogged as in Comparative Manufacturing Examples 1 to 5 Or the contact hole is formed neatly, the residual film ratio is excessively low or the taper drag is large.

Heat resistance measurement

The color filter on which the transparent pixel was formed was again heated in a 230 DEG C heating oven for 120 minutes to measure the thickness of the transparent pixel pattern.

Heat resistance (%) = thickness after additional bake (um) / additional bake thickness (um)

When the heat resistance is 96% or less, the surface wrinkles may be affected when the LCD panel is manufactured.

Chemical resistance measurement

The thickness of the transparent pixel pattern was measured after immersing the color filter in which the transparent pixel was formed in N-methyl-2-pyrrolidone (NMP) for chemical resistance evaluation at 60 DEG C for 30 minutes.

Chemical Resistance (%) = Thickness after immersion (um) / Thickness before immersion (um)

If the chemical resistance is 110% or more, the coating film may have a large yellowing phenomenon, which may lead to process defects and surface wrinkles.

Fine pattern measurement

The pattern size obtained through a line / space pattern mask of 100 mu m among the color filters in which the transparent pixels were formed was measured through OM equipment (ECLIPSE LV100POL Nikon Co., Ltd.).

Fine pattern (Δum) = (line / space pattern mask size, 100 μm) - (measured pixel pattern size)

If the value of the fine pattern is larger than 10 mu m, the implementation of the fine pixel becomes difficult, and if it has the minus value, the process failure can be caused.

Flatness  evaluation

In the above example, the entire thickness profile of a portion having a line size of 50 [mu] m and a space size of 100 [mu] m is evaluated in a blue pattern primarily coated on the substrate. (See FIGS. 2 and 3) The film thickness measurement equipment was measured using DEKTAK 6M (Veeco).

The flatness of the measured film thickness data is calculated in the following manner. Only the length of the space having the reference thickness (at the reference point) of 5% or less is measured as the thickness difference between the surface and the reference line with the center of the space as a reference point.

Flatness (%) = (space length where X value is not more than 5% of reference thickness) / total space length

When the flatness is 80% or less, the liquid crystal driving of the upper portion of the pixel may be affected and the optical characteristics may be deteriorated.

Surface anomaly evaluation

The substrate prepared in the above example was visually inspected.

Surface abnormality: Good level - No surface water observed, Bad level - Observation of surface whitening.

If the surface state exhibits whitening, the utility value is lost as a transparent pixel forming purpose. Table 6 and Table 7 show evaluation results of the residual film ratio, heat resistance, chemical resistance, fine pattern, flatness and surface abnormality of the color filter.

Example 8 Example 9 Example 10 Example 11 Remaining film ratio (%) 92.7% 89.3% 86.4% 90.1% Heat resistance (%) 96.2% 97.4% 98.3% 97.6% Chemical Resistance (%) 108.0% 106.5% 103.3% 105.9% Fine pattern change (um) 9um 5 2 7 Flatness (%) 93.0% 87.1% 83.3% 90.7% Surface abnormality Good Good Good Good

Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Remaining film ratio (%) 94.3% 83.7% 82.6% 87.2% 90.0% 88.9% Not measurable Heat resistance (%) 94.1% 98.4% 98.5% 95.2% 97.9% 96.2% Not measurable Chemical Resistance (%) 113.3% 103.1% 102.8% 108.2% 105.3% 110.3% Not measurable Fine pattern change (um) 12 탆  -2 탆  - 4 탆 3 탆 23 탆 4 탆 Not measurable Flatness (%) 95.1% 80.2% 76.1% 77.9% 84.6% 76.1% Not measurable Surface abnormalities (white) Good Good Good Good Good Good Bad

When the reactive alkali-soluble resin (A ') of the present invention is mixed with the non-reactive alkali-soluble resin (A ") in the ratio of 8: 2 to 1: 7, The result was excellent in chemical properties. In other ratios, there was a problem that a fine pattern change was large or a pattern was small as compared with the mask pattern size as in Comparative Examples 6 and 7. In addition, a monomer of the non-reactive binder (A " In the absence of the dicarbonylimide derivative, sufficient flatness could not be secured as in Comparative Example 11, or when the molecular weight was increased for securing the flatness, a good pattern could not be formed due to surface abnormality as in Comparative Example 12. [

On the other hand, even if the dicarbonylimide derivative was included, Comparative Example 8 having a small molecular weight had insufficient flatness, and Comparative Example 9 had a problem that the molecular weight was too high to cause a fine pattern change.

According to the present invention, the reactive alkali-soluble resin (A ') and the non-reactive alkali-soluble resin (A ") are mixed at a ratio of 8: 2 to 1: A "3), (A" 4), and (A "5). When the molecular weight is 10,000 to 30,000, the copolymer has excellent residual film ratios, heat resistance, chemical resistance and flatness, Transparent pixels could be formed.

Claims (9)

(A) an alkali-soluble resin; (B) a photopolymerizable compound; (C) a photopolymerization initiator; And (D) a solvent, wherein the photosensitive resin composition for forming a transparent pixel,
The alkali-soluble resin (A) is obtained by mixing (A ') a radical photoinitiator and an alkali-soluble resin which is reactive with UV radiation and (A ") a radical photoinitiator and an alkali-soluble resin which is non- 7,
Wherein the molecular weight of the (A ") radical photoinitiator and the alkali-soluble resin that is non-reactive to UV irradiation is 10,000 to 30,000.
The method according to claim 1,
The alkali-soluble resin which is reactive with the radical photoinitiator (A ') and the UV radiation is a compound having (A'1) a compound having an unsaturated bond and a carboxylic acid group in one molecule and (A'2) (A'3) a copolymer obtained by further polymerizing a compound having an unsaturated bond and an epoxy group in one molecule, and a photosensitive resin composition for forming a transparent pixel, wherein the copolymer is a copolymer obtained by polymerizing compounds containing an unsaturated bond .
The method of claim 2,
The compound having an unsaturated bond and a carboxylic acid group in one molecule of (A'1) may be a monocarboxylic acid including acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids including fumaric acid, mesaconic acid and itaconic acid, and anhydrides of the dicarboxylic acids; And mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals, including? -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 (A'1) Unsubstituted or substituted alkyl ester compounds of unsaturated carboxylic acids comprising acrylate and aminoethyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (Meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl Unsaturated carboxylic acid ester compounds containing an alicyclic substituent group including (meth) acrylate, naphthalene (meth) acrylate, naphthyl (meth) acrylate, ; 3-ethyloxetane, 3 - ((meth) acryloyloxymethyl) oxetane, 3 - ((meth) acryloyloxymethyl) Unsaturated carboxylic acid ester compounds comprising a thermosetting substituent comprising oxetane and 3 - ((meth) acryloyloxymethyl) -2-trifluoromethyloxetane; Mono-saturated carboxylic acid ester compounds of glycols including oligoethylene glycol monoalkyl (meth) acrylate; An unsaturated carboxylic acid ester compound containing a substituent having an aromatic ring including benzyl (meth) acrylate and phenoxy (meth) acrylate; Aromatic vinyl compounds including styrene,? -Methylstyrene, and vinyltoluene; Carboxylic acid vinyl esters including vinyl acetate and vinyl propionate; And a vinyl cyanide compound containing (meth) acrylonitrile and? -Chloroacrylonitrile,
Examples of the compound having an unsaturated bond and an epoxy group in one molecule of the (A'3) compound include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl Acrylate, and a vinyl cyanide compound including methylglycidyl (meth) acrylate. The photosensitive resin composition for forming a transparent pixel according to claim 1,
The method according to claim 1,
The alkali-soluble resin which is non-reactive with the (A ") radical photoinitiator and the UV radiation is a compound which has an unsaturated bond and a carboxylic acid group in the molecule (A" A photosensitive resin composition for forming a transparent pixel, characterized in that it is a copolymer obtained by polymerization of a compound containing a compound having an unsaturated bond and having no polymerizable unsaturated double bond in the resin molecular chain after polymerization.
The method according to claim 1,
The alkali-soluble resin which is non-reactive with the (A ") radical photoinitiator and the UV radiation is a compound having an unsaturated bond and a carboxylic acid group in the molecule (A" 3), a compound having an unsaturated bond with the epoxy group (A "5) A copolymer obtained by polymerization of a dicarbonylimide derivative having an unsaturated bond polymerizable with the above (A" 3) to (A "4), wherein the polymerizable unsaturated Wherein the photosensitive resin composition is a copolymer having no double bond.
The method of claim 5,
The aliphatic polycyclic compound having an unsaturated bond with the epoxy group (A "4) is preferably selected from dicyclopentane, tricyclodecane, norbornane, isonorbornane, bicyclooctane, cyclononane, bicyclo- , Bicyclododecane, and tricyclododecane. The photosensitive resin composition for forming a transparent pixel according to claim 1,
The aliphatic polycyclic compound having an epoxy group and an unsaturated bond (A "4) comprises at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2) A photosensitive resin composition for forming a transparent pixel,

In the general formulas (1) and (2), R is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which is unsubstituted or substituted with a hydroxyl group, and each X independently represents a single bond or a Alkylene group.
The method according to claim 1,
As to the solid content in the photosensitive resin composition for forming a transparent pixel,
(A) 20 to 85% by mass of an alkali-soluble resin;
(B) 10 to 60 mass% of a photopolymerizable compound; And
(C) a photopolymerization initiator in an amount of 0.1 to 20 mass% based on the total amount of the photosensitive resin composition.
A color filter formed by using the photosensitive resin composition for forming a transparent pixel according to any one of claims 1 to 8.

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