KR102093759B1 - Photosensitive resin composition for transparent pixel - Google Patents

Abstract

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

Description

Photosensitive resin composition for forming transparent pixels {PHOTOSENSITIVE RESIN COMPOSITION FOR TRANSPARENT PIXEL}

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

Recently, the display industry has undergone a rapid change from CRT to flat panel displays represented by PDP, OLED, and LCD. 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. In general, a liquid crystal display device forms red, green, and blue pixel patterns on a substrate on which a liquid crystal for light transmission control, a TFT array layer as an electrical signal device for driving the liquid crystal, and a black matrix are patterned, and each pixel pattern. It is composed of a column spacer for maintaining a cell gap in the step of bonding the color filter layer, the TFT array layer and the color filter layer, which are coated with an overcoat, to impart flatness between them. The liquid crystal display (LCD) configured as described above is widely used in all industrial fields such as portable equipment, industrial machinery, military, and medical applications.

However, as the use environment of a liquid crystal display (LCD) is used as an information transmission medium such as indoor or outdoor advertising, there is a problem in that visibility is rapidly deteriorated due to a decrease in luminance caused by external sunlight. In order to solve this problem, a method of improving the brightness of the backlight or increasing the transmittance of red, green, and blue pixels of the color filter layer was used, but it was not sufficiently solved by the problem of power consumption and the limiting properties of the coloring material. On the other hand, a method has been proposed in which a pixel space composed of red, green, and blue pixels is formed with an empty space without loss of backlight luminance.

However, the color filter having a transparent layer according to the above method was able to be improved considerably in terms of the brightness enhancement effect in terms of visibility by external light, but as a step difference with the surrounding coloring material layer increases, it causes a liquid crystal drive defect, A transparent pixel pixel having the same thickness as a colored color pixel is required.

Accordingly, in order to realize the transparent pixel pixel, a transparent pixel layer was manufactured using an overcoat or a photosensitive column spacer among the existing transparent materials described in Korean Publication No. 2007-0007895, etc., but it is difficult to implement a transparent pixel pattern, In particular, it has a problem that it is not possible to create a fine contact hole (40t) or less.

Republic of Korea Publication No. 2007-0007895

The present invention is to solve the problems of the prior art as described above, as well as the fine contact hole (Contact-hole) is possible when forming a transparent pixel pattern, the taper drag is minimized and the photosensitive for forming a transparent pixel exhibiting excellent residual rate It is an object to provide a resin composition.

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

In addition, the present invention provides a color filter formed using the photosensitive resin composition for forming the transparent pixels.

When a transparent pixel pixel of a 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 a fine pixel pixel is easy, and a contact hole for forming a transparent electrode can be implemented. In addition, it is possible to provide a high quality color filter due to its excellent heat resistance and chemical resistance.

1 is a view showing a picture of a color filter (Glass substrate) of a production example and a color filter (Glass substrate) of a comparative example prepared according to the present invention.
Figure 2 is a view showing a comparison between the flatness level formed by applying a conventional photosensitive composition of R, G, B, etc. (pictured above) and the flatness level formed by applying a conventional transparent photosensitive resin composition (pictured below) to be.
3 is a view showing a method for evaluating the flatness of a photosensitive resin composition for forming a transparent pixel.

Hereinafter, the present invention will be described in detail. Since the following detailed description is for one embodiment of the present invention, it is not intended to limit the scope of rights determined from the claims even if there is a limited expression.

The present invention (A) alkali-soluble resin; (B) photopolymerizable compounds; (C) photopolymerization initiator; And (D) a photosensitive resin composition for forming a transparent pixel comprising a solvent, and a color filter formed using the same, wherein (A) the alkali-soluble resin is (A ') an alkali-soluble initiator that is reactive with respect to a radical photoinitiator and UV irradiation It characterized in that the resin and (A ") radical photoinitiator and alkali-soluble resin which is non-reactive to UV irradiation are mixed in a weight ratio of 8: 2 to 1: 7. In addition, (A") radical photoinitiator and UV irradiation The molecular weight of the non-reactive alkali-soluble resin is 10,000 to 30,000.

Hereinafter, each component of the present invention will be described in detail.

(A) Alkali-soluble resin

The (A) alkali-soluble resin serves to make the non-exposed portion of the transparent pixel photosensitive resin layer formed by using the photosensitive resin composition for forming transparent pixels to be removed by making it alkali-soluble, and to remain the exposed area. In particular, the present invention is that the (A) alkali-soluble resin is (A ') a radical photoinitiator and an alkali-soluble resin reactive to UV irradiation and (A ") a radical photoinitiator and an alkali-soluble resin non-reactive to UV irradiation mixed. It is characterized in that, when mixed in a weight ratio of 8: 2 to 1: 7, it has been experimentally confirmed that it is easy to form fine pixel pixels when forming a transparent pixel of a color filter, and it is possible to implement a contact hole for forming a transparent electrode. The present invention has been completed.

The mixing ratio of the (A) alkali-soluble resin is preferably 8: 2 to 1: 7, and more preferably 7: 3 to (A ') the reactive alkali-soluble resin and the (A ") non-reactive alkali-soluble resin, respectively. 1: 6. When the content of the reactive alkali-soluble resin is lower than 2, the developing residual film rate decreases. Conversely, when it exceeds 8, the degree of hardening increases, resulting in a significant taper drag in the contact hole, as well as a decrease in heat resistance and chemical resistance. Occurs.

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

The component (A'1) contained in the (A ') reactive alkali-soluble resin is a compound having an unsaturated bond and a carboxylic acid group in one molecule, and is not limited as long as it is a carboxylic acid compound having an unsaturated double bond capable of polymerization. Each may be used alone or in combination of two or more. Specific examples include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; And the anhydride of the dicarboxylic acid. and mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate. Among the above compounds, acrylic acid and methacrylic acid are preferred because they have excellent copolymerization reactivity and solubility in a developer.

The (A'2) component included in the (A ') reactive alkali-soluble resin is a compound having an unsaturated bond polymerizable with (A'1), and any compound having an unsaturated double bond polymerizable may be used without limitation. Specific examples include unsaturated carboxylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and aminoethyl (meth) acrylate. Unsubstituted or substituted alkyl ester compounds; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclophene Tenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylic Unsaturated carboxylic acid ester compounds containing alicyclic substituents such as rate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, and pinenyl (meth) acrylate; 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) acryloyloxymethyl) -3-ethyloxetane, 3-((meth) acryloyloxymethyl) -2-methyl Unsaturated carboxylic acid ester compounds containing thermosetting substituents such as oxetane and 3-((meth) acryloyloxymethyl) -2-trifluoromethyloxetane; Monosaturated 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 or phenoxy (meth) acrylate; Aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; And vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile. Among these, aromatic vinyl compounds are preferable for improving sensitivity and reducing outgas. These may be used alone or in combination of two or more.

The (meth) acrylate recorded in the present 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) is the above It is preferable that it is in the following range in a molar fraction with respect to the total number of moles of the components (A'1) to (A'2).

Constituent unit derived from (A'1): 2 to 70 mol%,

Constituent unit derived from (A'2): 30 to 98 mol%,

In particular, it is more preferable that the ratio of the above-described constituent components is in the following range.

Constituent unit derived from (A'1): 10 to 60 mol%,

Constituent unit derived from (A'2): 40 to 90 mol%,

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

In this invention, as an example of the manufacturing method of the said (A ') reactive alkali-soluble resin, when it is obtained by copolymerizing the compound of (A'1)-(A'2), it can manufacture by the following method.

Into a flask equipped with a stirrer, thermometer, reflux cooling tube, dripping lot, and nitrogen introduction tube, 0.5 to 20 times the amount of the solvent was introduced with respect to the total mass of (A'1) to (A'2), and the atmosphere in the flask was aired. Replace with nitrogen. Thereafter, the temperature of the solvent was increased to 40 to 140 ° C., and then a predetermined amount of (A'1) to (A'2) and 0 to 20 times the total mass of (A'1) to (A'2) A solution in which 0.1 to 10 mol% of a solvent and a polymerization initiator such as azobisisobutyronitrile or benzoyl peroxide are added with respect to the total number of moles of (A'1) to (A'2) (dissolved under stirring at room temperature or heating) Was added dropwise from the dropping lot to the above flask over 0.1 to 8 hours, and further stirred at 40 to 140 ° C for 1 to 10 hours.

Further, in the above step, part or all of the polymerization initiator may be placed in the flask, or part or all of (A'1) to (A'2) may be added to the flask. Further, in order to control the molecular weight or molecular weight distribution, an α-methylstyrene dimer or mercapto compound can also be used as a chain transfer agent. The amount of the α-methylstyrene dimer or mercapto compound used is 0.005 to 5% by mass relative to the total mass of (A'1) to (A'2). In addition, the above-mentioned polymerization conditions may be appropriately adjusted for the input method and the reaction temperature in consideration of the production facility or the amount of heat generated by polymerization.

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

The component (A'3) contained in the (A ') reactive alkali-soluble resin is a compound having an unsaturated bond and an epoxy group in one molecule, and specific examples thereof include glycidyl (meth) acrylate and 3,4-epoxy. And cyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and methylglycidyl (meth) acrylate. Among them, 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 the molecule (A'3) is 5 to 80 mol% based on the number of moles of a compound having an unsaturated bond and a carboxylic acid group in the molecule (A'1) contained in the copolymer. It is preferred to react with, particularly 10 to 80 mol% is good. When the composition ratio of (A'3) is within the above range, it is preferable because it has excellent exposure sensitivity and developability.

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

As a reaction catalyst of a carboxyl group and an epoxy group of 5 to 80 mol% (A'3) in a molar fraction with respect to the constitutional unit derived from (A'1) in the copolymer, the atmosphere in the flask is replaced by nitrogen to air, e.g. For example, trisdimethylaminomethylphenol is 0.01 to 5% by mass relative to the total mass of (A'1) to (A'3), and as a polymerization inhibitor, for example, hydroquinone is 0.001 to 5% by mass relative to the total mass. The above copolymer and (A'3) can be reacted by placing them in a flask and reacting at 60 to 130 ° C for 1 to 10 hours. In addition, it is also possible to appropriately adjust the input method and the reaction temperature in consideration of the production facility or the amount of heat generated by polymerization as in the polymerization conditions.

In the present invention, the (A ') reactive alkali-soluble resin preferably has a weight average molecular weight in the range of 3,000 to 100,000 in terms of polystyrene, and more preferably in the range of 5,000 to 50,000. (A ') When the weight-average molecular weight of the reactive alkali-soluble resin is in the range of 3,000 to 100,000, it is difficult to reduce the film of the exposed portion during development, and it is preferable because the solubility of the non-exposed portion tends to be good.

(A ') The acid value of the reactive alkali-soluble resin is preferably in the range of 30 to 150 mgKOH / g on a solid basis. When the acid value is less than 30 mgKOH / g, the solubility in the alkali developer is lowered and there is a risk of leaving a residue on the substrate, and when the acid value exceeds 150 mgKOH / g, the possibility of pattern tearing increases.

(A ') The molecular weight distribution of the reactive alkali-soluble resin is preferably 1.0 to 6.0, and more preferably 1.5 to 4.0. A molecular weight distribution of 1.0 to 6.0 is preferred because of its excellent developability.

The (A ") non-reactive alkali-soluble resin used in the present invention can be prepared in the same way as the (A ') reactive alkali-soluble resin. However, (A") non-reactive alkali-soluble resin is irradiated with UV rays and radicals in the molecular chain. Since the polymerization must be performed in the absence of unsaturated double bonds, which may cause photopolymerization by photoinitiators, the process of copolymerizing (A'3) contained in (A ') the reactive alkali-soluble resin is omitted, and (A "1) to ( It is prepared by copolymerizing A "2), or by copolymerizing (A" 3) to (A "5). The method example is the same as the general synthetic example of (A ') reactive alkali-soluble resin.

As the component (A "1) and the component (A" 2), substances exemplified as the components (A'1) and (A'2) may be used, respectively.

In addition, the components (A "3) to (A" 5) are as follows:

(A "3) Compounds with unsaturated bonds and carboxylic acid groups in the molecule

(A "4) Aliphatic polycyclic compound having an unsaturated bond with an epoxy group

(A "5) A dicarbonyl imide derivative having an unsaturated bond polymerizable with (A" 3) to (A "4).

The (A ") reactive alkali-soluble resin used in the present invention can also be polymerized together by adding other monomers in addition to (A" 3), (A "4) and (A" 5). That is, when other monomers other than the above-mentioned (A "3) to (A" 5) compounds are further included, polymerization is also included in the scope of the present invention.

The component (A "3) contained in the (A") non-reactive alkali-soluble resin is the same as (A'1) contained in the (A ') reactive alkali-soluble resin,

Examples of the aliphatic polycyclic compound having an (A "4) epoxy group and an unsaturated bond contained in the (A") non-reactive alkali-soluble resin include, for example, dicyclopentane, tricyclodecane, norbornane, and isonorbornane. , Bicyclooctane, cyclononane, bicycloundecane, tricycloundecane, bicyclododecane, tricyclododecane, and the like. More preferably, the aliphatic polycyclic compound (A "4) having an unsaturated bond with the epoxy group is an aliphatic polycyclic compound having an unsaturated bond with the epoxy group from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2) It is preferred to include at least one compound selected.

(In the formulas 1 and 2, R is an alkyl group having 1 to 4 carbon atoms, each independently substituted or unsubstituted with a hydrogen atom or a hydroxyl group, and X is 1 to 6 carbon atoms each independently containing or not containing a single bond or a hetero atom. Is an alkylene group)

In Chemical Formulas 1 and 2, R is specifically a hydrogen atom; Alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group; Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxy-n-propyl group, 2-hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1-hydroxy -Isopropyl group, 2-hydroxy-isopropyl group, 1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-n -It may be a hydroxyl group-containing alkyl group such as a butyl group. Among them, R is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

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

The compound represented by the formula (1) and the compound represented by the formula (2) can be used alone or in combination of two or more, and in particular, by mixing the compound represented by the formula (1) and the compound represented by the formula (2) in any ratio You can also use

As the (A "5) dicarbonyl imide derivative contained in the (A") non-reactive alkali-soluble resin, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinim already Di- 3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N -(9-acridinyl) maleimide, and the like. Among them, N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide are preferable in terms of copolymerization reactivity and solubility in an aqueous alkali solution. .

The (A ") non-reactive binder resin used in the present invention is a copolymer obtained by copolymerizing (A" 3), (A "4) and (A" 5), and the proportion of constituent components derived from each is It is preferable that it is in the following range with a molar fraction with respect to the total number of moles of the component which comprises the said copolymer.

Structural unit derived from (A "3): 2-40 mol%

Constituent unit derived from (A "4): 2 to 95 mol%

The structural unit derived from (A "5): 1-65 mol%

Moreover, it is more preferable that the ratio of the said component is the following range.

Constituent unit derived from (A "3): 5 to 35 mol%

Constituent unit derived from (A "4): 5 to 80 mol%

Constituent unit derived from (A "5): 1 to 60 mol%

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

In the present invention, the (A ") non-reactive alkali-soluble resin is characterized in that its weight average molecular weight in terms of polystyrene is in the range of 10,000 to 30,000. The present inventor has a molecular weight of (A") non-reactive alkali-soluble resin. In the case of 10,000 to 30,000, it was experimentally confirmed that the developed residual film rate, heat resistance, chemical resistance, and flatness are excellent, and that a transparent pixel capable of realizing a fine pattern can be formed.

(A ") The acid value of the non-reactive alkali-soluble resin is preferably in the range of 30 to 150 mgKOH / g on a solid basis. When the acid value is less than 30 mgKOH / g, the solubility in the alkali developer is lowered and there is a risk of leaving residue on the substrate. , When the acid value exceeds 150 mgKOH / g, the possibility of tearing of the pattern increases.

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

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, as a mass fraction relative to the solid content in the photosensitive resin composition for forming a transparent pixel. (A) When the content of the alkali-soluble resin is 20 to 85% by mass based on the above criteria, the solubility in the developer is sufficient, so that development residues are less likely to occur on the substrate of the non-pixel portion, and film development of the exposed portion is less likely to occur during development. , It is preferable because it tends to have good solubility in the non-exposed portion.

(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, such as a monofunctional monomer, a bifunctional monomer, and other multifunctional monomers. Can be mentioned.

Specific examples of the monofunctional monomer include nonylphenylcarbitolacrylate, 2-hydroxy-3-phenoxypropylacrylate, 2-ethylhexylcarbitolacrylate, 2-hydroxyethylacrylate, and N-vinylpyrroli And money.

As specific examples of the bifunctional monomer, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, And 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, and pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol And hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

Among them, a bifunctional or higher polyfunctional monomer is preferably used. Particularly preferably, a polyfunctional monomer having 5 or more functionalities may be used, and more preferably, dipentaerythritol (poly) acrylate having a hydroxyl value of 70 to 130 mgKOH / g of the following Chemical Formula 3 is used. Do.

(In the formula (3), R is hydrogen or an acryloyl group having 2 to 6 carbon atoms)

The photopolymerizable compound (B) is usually used in a range of 10 to 60 mass%, preferably 20 to 50 mass%, in mass fraction relative to the solid content in the photosensitive resin composition for forming transparent pixels. (B) When the photopolymerizable compound is in the range of 10 to 60% by mass based on the above criteria, it is preferable because the strength of the pixel portion, the residual film ratio according to the process progress, and the contact hole characteristics tend to be good.

(C) Light polymerization 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 triazine compounds, acetophenone compounds, biimidazole compounds and oxime compounds. . The photosensitive resin composition for forming a transparent pixel containing the photopolymerization initiator (C) described above has high sensitivity, and a film formed using this composition has good pixel portion strength and contact hole characteristics.

In addition, when the (C) photopolymerization initiator is used in combination with the (C) photopolymerization initiator, the photosensitive resin composition for forming a transparent pixel containing them becomes more highly sensitive, thereby improving productivity when forming a color filter using this composition. Is preferred.

As the triazine-based compound, for example, 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, 2,4-bis (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2- 1) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of acetophenone-based compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxy-1- [4- (2- Hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane- And 1-on oligomers. Moreover, the compound represented by following formula (4) is mentioned.

(Formula 4)

In the above formula,

R1 to R4 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, or 1 to 12 carbon atoms. It represents a naphthyl group unsubstituted or substituted with an alkyl group.

Specific examples of the compound represented by Chemical Formula 4 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethane- 1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl- 2-amino (4-morpholinophenyl) propan-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholino) Nophenyl) propan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propan-1- And 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, and the like. have.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3). -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) ratio Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, phenyl group at 4,4', 5,5 'position And imidazole compounds substituted with a alkoxy group. Of these, 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole is preferably used.

Examples of the oxime compound include the following Chemical Formulas 5, 6, and 7.

(Formula 5)

(Formula 6)

(Formula 7)

Further, other photopolymerization initiators and the like commonly used in this field may be used in combination as long as the effects of the present invention are not impaired. Examples of other photopolymerization initiators include benzoin compounds, benzophenone compounds, thioxanthone compounds, and anthracene compounds. These may be used alone or in combination of two or more.

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

Examples of the benzophenone-based compound include benzophenone, 0-benzoylbenzoate methyl, 4-phenyl benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-di (N, N'-dimethylamino) -benzophenone, and the like.

Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. Can be mentioned.

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

Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, campoquinone, phenylclyoxylic acid A methyl, titanocene compound, etc. are mentioned as another photoinitiator.

In addition, in the present invention, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and the like can be preferably used as the (C-1) photopolymerization initiator adjuvant that can be used in combination with the (C) photopolymerization initiator. .

Specific examples of the amine compound in the photopolymerization initiation aid include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Mihiler 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 and dichlorophenyl 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 component, and the (C-1) photopolymerization initiator adjuvant The amount used is usually 0.1 to 20% by mass, preferably 1 to 10% by mass, based on the above.

When the amount of the photopolymerization initiator (C) used is in the above range, the photosensitive resin composition for forming a transparent pixel is highly sensitive, which is preferable because the strength of the pixel portion and the smoothness on the surface of the pixel portion tend to be good. In addition, when the amount of the photopolymerization initiation aid (C-1) used is in the above range, the sensitivity efficiency 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 (D) solvent 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 (D) solvent 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, and diethylene Diethylene glycol dialkyl ethers such as glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol Propylene glycol dialkyl ethers such as monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and alkylene glycol alkyl ether acetates such as methoxypentyl acetate Ryu, Aromatic hydrocarbons such as zen, toluene, xylene, mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene And alcohols such as glycol and glycerin, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionic acid, and cyclic esters such as γ-butyrolactone.

Among the above-mentioned solvents, organic solvents having a boiling point of 100 ° C to 200 ° C can be exemplified in terms of coatability and dryness, and more preferably alkylene glycol alkyl ether acetates, ketones, 3-to And esters such as ethyl methoxypropionate and methyl 3-methoxypropionate. More preferably, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3- Ethyl ethoxypropionate, methyl 3-methoxypropionate, and the like.

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

The content of the (D) solvent in the photosensitive resin composition for forming a transparent pixel of the present invention is usually 60 to 90 mass%, preferably 70 to 85 mass%, in mass fraction relative to the total amount of the photosensitive resin composition for forming a transparent pixel containing a solvent. %to be. (D) If the content of the solvent was in the range of 60 to 90% by mass based on the above criteria, it was coated with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), inkjet It is preferable because the coating property tends to be good at the time.

(E) Additive

In the photosensitive resin composition for forming a transparent pixel of the present invention, a filler, another polymer compound, a curing agent, and a pigment dispersant, if necessary. It is also possible to use (E) additives, such as an adhesion promoter, antioxidant, ultraviolet absorber, and aggregation inhibitor.

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

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

The curing agent is used to increase the core hardening and mechanical strength, and examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

As the epoxy compound in the curing agent, for example, bisphenol A-based epoxy resin, hydrogenated bisphenol A-based epoxy resin, bisphenol F-based epoxy resin, hydrogenated bisphenol F-based epoxy resin, no-block type epoxy resin, other aromatic epoxy resin, alicyclic Group-based epoxy resins, glycidyl ester-based resins, glycidylamine-based resins, or brominated derivatives of these epoxy resins, aliphatic resins other than epoxy resins and brominated derivatives thereof, alicyclic or aromatic epoxy compounds, butadiene (co) polymer epoxides , Isoprene (co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like.

Examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane. have.

The curing agent may include a curing aid compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent. As a hardening auxiliary compound, polyhydric carboxylic acids, polyhydric carboxylic anhydrides, acid generator, etc. are mentioned, for example.

As the carboxylic anhydride, commercially available ones can be used as the epoxy resin curing agent. As the epoxy resin curing agent, for example, a trade name (Adeka Hadona EH-700) (manufactured by Adeka Industries Co., Ltd.), a trade name (Rikasitdo HH) (manufactured by Shin Nippon Ehwa Co., Ltd.), a trade name (MH-700) Shin Nippon Ewha Co., Ltd.). The 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 silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic and amphoteric surfactants. These may be used alone or in combination of two or more. As the above-mentioned surfactant, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty phase esters, fatty acid modified polyesters, tertiary amine modified polyurethanes , Polyethyleneimines, etc. In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (POLYFLOW) (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), Megapack (MEGAFAC) (manufactured by Dai Nippon Ink Chemical Co., Ltd.), Florad (manufactured by Sumitomo 3M), Asahi guard, Surflon (above, manufactured by Asahi Glass Co., Ltd.), And SOLSPERSE (manufactured by Genecca Co., Ltd.), EFKA (manufactured by EFKA Chemicals), and PB 821 (manufactured by Ajinomoto Co., Ltd.).

These pigment dispersants may be used alone or in combination of two or more, respectively, and may be generally included in a mass fraction of 0.01 to 15% by mass with respect to the solid content in the photosensitive resin composition for forming a transparent pixel.

Examples of the adhesion promoter include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane. , N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercapto And propyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane.

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, with respect to the solid content in the photosensitive resin composition for forming a transparent pixel.

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

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone, and the like.

Specific examples of the aggregation inhibitor 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) Alkali-soluble resin, (B) photopolymerizable compound, (C) photopolymerization initiator, (D) solvent are mixed in an appropriate ratio, and other components used as necessary are further added to form the desired photosensitive properties for forming transparent pixels. 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 of forming a pattern of a photosensitive resin composition for forming a transparent pixel according to the present invention comprises the steps of applying the photosensitive resin composition for forming a transparent pixel on a substrate, and selectively exposing a portion of the photosensitive resin composition for forming a transparent pixel And removing an exposed area or a non-exposed area of the photosensitive resin composition for forming a transparent pixel.

As an example, a pattern is formed by applying on the substrate as described below, photocuring and developing, and can be used as a black matrix or colored and transparent pixels (colored images).

First, the composition is applied onto a layer containing a solid content of a photosensitive resin composition for forming a transparent pixel to form a substrate (not limited, usually a glass or a silicon wafer) or preliminarily dried to remove a volatile component such as a solvent to smooth it. Get a coating. The thickness of the coating film at this time is usually about 1 to 3 µm. In order to obtain a desired pattern on the coating film thus obtained, ultraviolet rays are irradiated to a specific region through a mask. At this time, it is preferable to use a device such as a mask aligner or a stepper so that parallel light is uniformly irradiated to the entire exposed portion and the mask and the substrate are accurately positioned. In addition, afterwards, a desired pattern can be produced by dissolving and developing a non-exposed region by contacting the coating film after curing with an aqueous alkali solution. After development, after drying at about 150 to 230 ° C. for about 10 to 60 minutes, drying may be performed as necessary.

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

Further, specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, and mono And isopropylamine, diisopropylamine, and ethanolamine. 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 alkali developer is in the range of 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

The surfactant in the alkali developer can be used either as a nonionic surfactant, anionic surfactant, or cationic surfactant.

Specific examples of 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 ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, and the like.

Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate ester or sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate, and sodium dodecylbenzenesulfonate. And alkyl aryl sulfonates such as sodium dodecyl naphthalene sulfonate.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride or quaternary ammonium salts.

These surfactants can 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, more preferably 0.1 to 5% by mass.

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

The color filter according to the present invention is characterized in that it comprises a pixel formed by exposing and developing the photosensitive resin composition for forming a transparent pixel described above in a predetermined pattern.

The method of forming a pattern of a photosensitive resin composition for forming a transparent pixel is as described above, and detailed description is omitted. As described above, a pixel or a black matrix corresponding to the photosensitive resin composition for forming a transparent pixel is obtained through each operation of coating, drying, and patterning exposure to the obtained dry coating film and developing the photosensitive resin composition for forming a transparent pixel, Also, a color filter can be obtained by repeating this operation as many times as the number of unit pixels required for the color filter. The configuration and manufacturing method of the color filter are well known in the art, and detailed description thereof will be omitted.

The color filter manufactured using the photosensitive resin composition for forming a transparent pixel of the present invention has a small difference in film thickness between in-plane pixels, for example, an in-plane film thickness difference of 0.15 μm or less, furthermore 0.05 μm, with a film thickness of 1 to 4 μm. It can be done as follows. Therefore, the color filter obtained in this way is excellent in smoothness, and by assembling it in a color liquid crystal display device, a liquid crystal display device of excellent quality can be manufactured with high yield. In addition, when the color filter is used, it is possible to manufacture an image pickup device of excellent quality.

Hereinafter, the present invention will be described more specifically by examples, but the present invention is not limited to the examples. In addition, "%" and "part" showing content in the following Examples and Comparative Examples are based on mass 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 cooling tube, a dropping lot, and a nitrogen introduction tube was prepared, while 84.2 parts of N-benzylmaleimide, 38.7 parts of methacrylic acid, 22 parts of tricyclodecyl methacrylate, and t-butylper 4 parts of oxy-2-ethylhexanoate, 40 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") were added, followed by stirring and mixing to prepare a monomer dropping lot, and 6 parts of n-dodecanthiol, PGMEA 24 Part was added and stirred and mixed to prepare a chain transfer agent dropping lot. Thereafter, 395 parts of PGMEA was introduced into the flask, the atmosphere in the flask was changed to nitrogen from air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, the monomer and the chain transfer agent were dripped from the dropping lot. The dropping, while maintaining at 90 ° C, proceeds for 2h each, and after 1h, the temperature is raised to 110 ° C and maintained for 3h, and then a gas introduction tube is introduced to bubble oxygen / nitrogen = 5/95 (v / v) mixed gas. Started. Subsequently, 14.2 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 parts of triethylamine were introduced into the flask to continue the reaction at 110 ° C for 8 hours. Then, while cooling to room temperature, a resin A 'having a solid content of 29.1 wt% and a weight average molecular weight of 32,000 having an acid value of 114 mgKOH / g was obtained.

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

A flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping lot, and a nitrogen introduction tube was prepared, while N-benzylmaleimide 45 parts, methacrylic acid 45 parts, tricyclodecyl methacrylate 10 parts, t-butylper 4 parts of oxy-2-ethylhexanoate, 40 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") were added, followed by stirring and mixing to prepare a monomer dropping lot, and 6 parts of n-dodecanthiol, PGMEA 24 Part was added and stirred and mixed to prepare a chain transfer agent dropping lot. Thereafter, 395 parts of PGMEA was introduced into the flask, the atmosphere in the flask was changed to nitrogen from air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, the monomer and the chain transfer agent were dripped from the dropping lot. The dropping, while maintaining 90 ° C, proceeds for 2h each, and after 1h, the temperature is raised to 110 ° C and maintained for 3h. Started. Subsequently, 10 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 parts of triethylamine were added into the flask to continue the reaction at 110 ° C for 8 hours. Then, while cooling to room temperature, a resin A 'having a solid content of 29.1% by weight and a weight average molecular weight of 32,000 with an acid value of 114 mgKOH / g was obtained.

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

Prepare a flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping lot, and a nitrogen introduction tube, and add 300 parts of propylene glycol monomethyl ether acetate (PGMEA) and heat to 75 degrees while stirring. 3,4-epoxy-8- (acryloyloxy) tricycloyl [5.2.1.02,6] decane (EDCPA) 13.7 parts by weight, acrylic acid (AA) 10.9 parts by weight, vinyltoluene 26.5 parts by weight PGMEA 170 parts by weight in the flask The solution dissolved in the part was dripped using a dropping lot for 5 hours. Meanwhile, a solution in which 30 parts by weight of the polymerization initiator azobisisobutyronitrile was dissolved in 200 parts by weight of PGMEA was added dropwise over 5 hours using a separate dropping lot. After the dropping of the polymerization initiator was completed, the temperature was maintained for about 4 hours, and then cooled to room temperature to obtain a resin A "having a solid content of 37.6 wt%, 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 )

Prepare a flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping lot, and a nitrogen introduction tube, and add 300 parts of propylene glycol monomethyl ether acetate (PGMEA) and heat to 75 degrees while stirring. 3,4-epoxy-8- (acryloyloxy) tricycloyl [5.2.1.02,6] decane (EDCPA) 76.8 parts by weight (60 mol%), methacrylic acid (MAA) 10.0 parts by weight (20 mol%) in the flask , N-cyclohexylmaleimide 19.2 parts by weight (20 mol%) was dissolved in 170 parts by weight of PGMEA and added dropwise using a dropping lot for 5 hours. Meanwhile, a solution in which 20 parts by weight of the polymerization initiator azobisisobutyronitrile was dissolved in 200 parts by weight of PGMEA was added dropwise over 5 hours using a separate dropping lot. After dropping of the polymerization initiator was completed, the temperature was maintained for about 4 hours, and then cooled to room temperature to obtain a resin A "having a solid content of 37.6 wt%, a weight average molecular weight of 15,740, and an acid value of 121 mgKOH / g.

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

The synthesis method was the same as the method of Synthesis Example 2-1, and by adjusting the content of azobisisobutyronitrile to control the molecular weight, Synthesis Example 2-3 was prepared as shown in Table 1 below, and the molecular weight of the present invention Comparative Synthesis Examples 1 and 2 out of range and Comparative Synthesis Examples 3 and 4 not containing N-cyclohexylmaleimide were prepared. Table 1 shows the molar percentage of the reaction monomer and the synthesis results.

Polymerized 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) tricycloyl [5.2.1.02,6] 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 Mountain 120 122 122 123 121

Molecular weight evaluation

About the weight average molecular weight (Mw) measurement of the said (A) alkali-soluble resin, it performed under the following conditions using GPC method.

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

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

Column temperature: 40 ° C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection volume: 50 μl

Detector: RI

Measurement sample concentration: 0.6% by 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 about 1 g into an aluminum cup, and dissolved by adding about 3 g of acetone, and then naturally dried at room temperature. Then, using a hot air dryer (manufactured by SPEC Co., Ltd., product name: PHH-101), dried under vacuum at 160 ° C. for 3 hours, allowed to cool in a desiccator and weighed. The solid content of the polymer solution was calculated from the weight reduction amount.

Mountain

3 g of resin solution is weighed, dissolved in a mixed solvent of 90 g of acetone / 10 g of water, and an automatic titration device (Hiranum Industries Co., Ltd.) using 0.1 N KOH aqueous solution as a titrant using thymol blue as an indicator. The acid value of the polymer solution was measured by -555), and the acid value per 1 g of solid content was determined from the acid value of the solution and the solid content of the solution.

< Example Comparative example >

Example  1-7 and Comparative example  1-5: Transparent pixels  Preparation of photosensitive resin composition for formation

After mixing the components as described in Table 2 below, after diluting with propylene glycol monomethyl ether acetate so that the total solid content is 18% by weight, and sufficiently stirred, the transparent pixels of Examples 1 to 7 and Comparative Examples 1 to 5 A photosensitive resin composition for formation was obtained.

Item (A) Alkali-soluble resin (B) Photopolymerizable compound (C) 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) alkali-soluble resin

     (A ') Reactivity: Synthesis Example 1-1

     (A ") Non-reactive: 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 pixels  Preparation of photosensitive resin composition for formation

After mixing the components as described in Tables 3 and 4, respectively, the mixture was diluted with propylene glycol monomethyl ether acetate so that the total solid content was 18% by weight, and then stirred sufficiently 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) Photopolymerizable compound 30 30 30 30 (C) 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) Photopolymerizable compound 30 30 30 30 30 30 30 (C) 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  1-11 and Comparative manufacturing example  1 ~ 12: Preparation of color filter

The color filters of Preparation Examples 1 to 11 and Comparative Production Examples 1 to 12 were prepared using the photosensitive resin compositions for forming transparent pixels prepared in Examples 1 to 11 and Comparative Examples 1 to 12, respectively.

That is, the photosensitive resin composition for forming transparent pixels prepared in Examples 1 to 11 and Comparative Examples 1 to 12 was coated on a glass substrate by spin coating, then placed on a heating plate and held at a temperature of 100 ° C. for 3 minutes to obtain a thin film. Formed. Subsequently, on the thin film, a test photomask having a square pattern ranging from 50 um x 50 um to 10 um x 10 um and a line / space pattern of 1 µm to 100 µm was placed, and the distance between the test photomask was set to 300 µm and UV light was emitted. Was investigated.

At this time, the ultraviolet light source was irradiated with an exposure amount (365 nm) of 50 mJ / cm 2 in an atmosphere using an ultra-high pressure mercury lamp (trade name USH-250D) manufactured by Ushio Denki Co., Ltd., and no special optical filter was used. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 80 seconds. The glass plate coated with the thin film was washed with distilled water, then 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 μm.

< Experimental example >

Residual rate measurement

Each photosensitive resin composition for forming transparent pixels 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, and then exposed to a total exposure of 50 mJ / cm2 without a photomask. After irradiating with ultraviolet rays, the film thickness of the pattern was measured using a film thickness measuring device (DEKTAK 6M; manufactured by Veeco). After the thickness measurement was completed, the substrate was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 80 seconds, and then the thickness was measured.

Residual rate (%) = thickness after development (um) / thickness before development (um)

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

Contact hole size  And Taper pull  observe

After placing the substrate prepared as an example of the above, observing a 40 um x 40 um square contact hole of the photomask, measuring the size of the contact hole, observing take drag, and taking a picture.

OM equipment: ECLIPSE LV100POL manufactured by Nikon

Criteria for evaluation of taper attraction

O: Without tapered

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

X: Taper drag on one side is 3um or more

The contact hole size, taper drag, and exposure / development residual rate of the color filter were measured and evaluated as follows, and the results are shown in FIGS. 1 and 5 to 7 below.

Item 40 x 40um contact hole (photomask) Before and after phenomenon
Residual rate (%) Contact hole size (um) Taper pull Preparation Example 1 29.7 O 92% Preparation Example 2 29.5 O 90% Preparation Example 3 30.9 O 90% Preparation Example 4 32.5 O 89% Preparation Example 5 33.8 O 87% Preparation Example 6 35.5 O 87% Preparation Example 7 33.8 O 85% Comparative Production 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 Production Example 5 39 O 75%

Referring to FIG. 1 and Table 5, when the (A ') reactive alkali-soluble resin and (A ") non-reactive alkali-soluble resin of the present invention are used in a mixture of 8: 2 to 1: 7, Preparation Examples 1 to 7 As shown in Fig. 1, the contact holes are clogged as in Comparative Production Examples 1 to 5. Or, even if the contact hole is formed cleanly, it can be seen that the residual film rate is too low, or the taper drag is largely generated.

Heat resistance measurement

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

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

When the heat resistance is less than 96%, surface wrinkles may be affected during LCD panel manufacturing.

Chemical resistance measurement

The color filter on which the transparent pixel was formed was immersed in chemical resistance evaluation solvent N-Methyl-2-pyrrolidone (NMP) for 30 minutes at 60 ° C., and then the thickness of the transparent pixel pattern was measured.

Chemical resistance (%) = thickness after immersion (um) / thickness before immersion (um)

When the chemical resistance is 110% or more, the swelling phenomenon of the coating film is severe, which may cause process defects and surface wrinkle problems.

Fine pattern measurement

The size of the pattern obtained through a line / space pattern mask of 100 µm among the color filters in which the transparent pixels were formed was measured by using OM equipment (ECLIPSE LV100POL manufactured by Nikon).

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

If the value of the fine pattern is greater than 10 μm, it is difficult to implement the micro-pixel, and having a negative value may cause process failure.

Flatness  evaluation

An example of the above example is placed and the overall thickness profile of a portion having a line size of 50 um and a space size of 100 um is evaluated in the primary coated blue pattern. (See FIGS. 2 and 3) The film thickness measurement equipment was measured using DEKTAK 6M (manufactured by Beeco).

The flatness of the measured film thickness is calculated by the following method. Using the center of the space as a reference point, only the length of the space whose x value, which is the thickness difference between the surface and the reference line, is 5% or less of the reference thickness (at the reference point) is measured.

Flatness (%) = (space length where the X value is 5% or less of the reference thickness) / total space length

When the flatness is 80% or less, the optical characteristics may be deteriorated by affecting the liquid crystal driving at the top of the pixel.

Surface abnormality evaluation

The substrate manufactured by the above example was visually judged.

Surface abnormality: good level-no surface foreign matter observed, bad level-surface whitening observed.

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

Example 8 Example 9 Example 10 Example 11 Remaining film rate (%) 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 rate (%) 94.3% 83.7% 82.6% 87.2% 90.0% 88.9% Measurement impossible Heat resistance (%) 94.1% 98.4% 98.5% 95.2% 97.9% 96.2% Measurement impossible Chemical resistance (%) 113.3% 103.1% 102.8% 108.2% 105.3% 110.3% Measurement impossible Fine pattern change (um) 12㎛  -2 μm  -4㎛ 3㎛ 23㎛ 4㎛ Measurement impossible Flatness (%) 95.1% 80.2% 76.1% 77.9% 84.6% 76.1% Measurement impossible Surface abnormality (whitening) Good Good Good Good Good Good Bad

When the (A ') reactive alkali-soluble resin of the present invention and (A ") non-reactive alkali-soluble resin are mixed and used at 8: 2 to 1: 7, as in Examples 8 to 11, the residual film ratio, heat resistance, and resistance Excellent chemical results were obtained, and in other ratios, there was a problem in that micropattern changes were large or small patterns were formed compared to the mask pattern size as in Comparative Examples 6 and 7. In addition, monomers of the non-reactive binder (A ") When there is no dicarbonyl imide derivative, sufficient flatness cannot be secured as in Comparative Example 11, or when the molecular weight is increased to secure flatness, a good pattern cannot be produced due to surface abnormalities as in Comparative Example 12.

On the other hand, even if the dicarbonyl imide derivative was included, Comparative Example 8 having a small molecular weight lacked flatness, and Comparative Example 9 had a problem that the micropattern change was too high because the molecular weight was too high.

According to the present invention, the (A ') reactive alkali-soluble resin and (A ") non-reactive alkali-soluble resin are mixed at 8: 2 to 1: 7, and the monomer of (A") non-reactive alkali-soluble resin is ( A "3), (A" 4), (A "5) is a copolymerized polymer. When the molecular weight is 10,000 to 30,000, it is excellent in developing residual film rate, heat resistance, chemical resistance, flatness, and realizing fine pattern. Transparent pixels could be formed.

Claims (9)

(A) alkali-soluble resin; (B) photopolymerizable compounds; (C) photopolymerization initiator; And (D) a photosensitive resin composition for forming a transparent pixel comprising a solvent,
The photosensitive resin composition for forming a transparent pixel does not contain a colorant,
The (A) alkali-soluble resin, (A ') a radical photoinitiator and an alkali-soluble resin reactive to UV irradiation and (A ") an alkali-soluble resin non-reactive to the radical photoinitiator and UV irradiation 8: 2 to 1: It is mixed in a weight ratio of 7,
The molecular weight of the (A ") alkali-soluble resin which is non-reactive to the radical photoinitiator and UV irradiation is 10,000 to 30,000,
The (A ") radical photoinitiator and alkali-soluble resin that is non-reactive to UV irradiation include (A" 3) compounds having an unsaturated bond and a carboxylic acid group in the molecule; (A "4) An aliphatic polycyclic compound having an unsaturated bond with an epoxy group; and vinyl toluene or (A" 5) a dicarbonyl imide derivative having an unsaturated bond polymerizable with (A "3) to (A" 4) As a copolymer by polymerization, it is characterized in that it is a copolymer without an unsaturated double bond polymerizable in the resin molecular chain after completion of polymerization,
The (A "4) aliphatic polycyclic compound having an unsaturated bond with an epoxy group is characterized by comprising 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) Photosensitive resin composition for forming transparent pixels.

In Formulas 1 and 2, R is an alkyl group having 1 to 4 carbon atoms, each independently substituted or unsubstituted with a hydrogen atom or a hydroxyl group, and X are each independently 1 to 6 carbon atoms with or without a single bond or a hetero atom. It is an alkylene group.
The method according to claim 1,
The (A ') radical photoinitiator and alkali-soluble resin reactive to UV irradiation are polymerized with (A'1) a compound having an unsaturated bond and a carboxylic acid group in one molecule and (A'2) (A'1). A photosensitive resin composition for forming a transparent pixel, characterized in that it is a copolymer obtained by further polymerizing a copolymer containing a compound having a possible unsaturated bond and a compound having an unsaturated bond and an epoxy group in one molecule (A'3). .
The method according to claim 2,
Compounds having an unsaturated bond and a carboxylic acid group in the molecule (A'1) include monocarboxylic acids containing acrylic acid, methacrylic acid, and crotonic acid; Dicarboxylic acids including fumaric acid, mesaconic acid and itaconic acid and anhydrides of the dicarboxylic acids; And ω-carboxy polycaprolactone mono (meth) acrylate is at least one selected from the group consisting of mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both ends,
The compound having an unsaturated bond polymerizable with (A'1) of (A'2) is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) Unsubstituted or substituted alkyl ester compounds of unsaturated carboxylic acids including acrylates and aminoethyl (meth) acrylates; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclophene Tenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylic Unsaturated carboxylic acid ester compounds containing alicyclic substituents including acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate and pinenyl (meth) acrylate ; 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) acryloyloxymethyl) -3-ethyloxetane, 3-((meth) acryloyloxymethyl) -2-methyl Unsaturated carboxylic acid ester compounds containing a thermosetting substituent including oxetane and 3-((meth) acryloyloxymethyl) -2-trifluoromethyloxetane; Monosaturated carboxylic acid ester compounds of glycols containing oligoethylene glycol monoalkyl (meth) acrylate; An unsaturated carboxylic acid ester compound containing a substituent having an aromatic ring containing benzyl (meth) acrylate and phenoxy (meth) acrylate; Aromatic vinyl compounds including styrene, α-methylstyrene and vinyl toluene; Carboxylic acid vinyl esters including vinyl acetate and vinyl propionate; And (meth) acrylonitrile and α-chloroacrylonitrile.
Compounds having an unsaturated bond and an epoxy group in the molecule (A'3) are glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) A photosensitive resin composition for forming a transparent pixel, characterized in that at least one selected from the group consisting of a vinyl cyanide compound containing acrylate and methylglycidyl (meth) acrylate.
The method according to claim 1,
The (A ") radical photoinitiator and alkali-soluble resin which is non-reactive to UV irradiation are polymerizable with (A" 1) a compound having an unsaturated bond and a carboxylic acid group in the molecule and (A "2) (A" 1). A photosensitive resin composition for forming a transparent pixel, which is a copolymer by polymerization of compounds containing a compound having an unsaturated bond, and is a copolymer without an unsaturated double bond polymerizable in a resin molecular chain after completion of polymerization.
delete The method according to claim 1,
The (A "4) aliphatic polycyclic compound having an unsaturated bond with an epoxy group is dicyclopentane, tricyclodecane, norbornane, isonorbornane, bicyclooctane, cyclononane, bicycloundecane, tricycloundecane , A photosensitive resin composition for forming a transparent pixel, characterized in that at least one selected from the group consisting of bicyclododecane and tricyclododecane.
delete The method according to claim 1,
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% by mass of a photopolymerizable compound; And
(C) Photopolymerization initiator Photosensitive resin composition for forming a transparent pixel, characterized in that it contains 0.1 to 20% by mass.
A color filter formed using the photosensitive resin composition for forming a transparent pixel of any one of claims 1 to 4, 6, and 8.

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