KR102069199B1 - Photosensitive resin composition for transparent pixel - Google Patents

Abstract

The present invention (A) alkali soluble resin; (B) photopolymerizable compounds; (C) photoinitiator; And (D) a photosensitive resin composition for forming a transparent pixel comprising a solvent, wherein the alkali-soluble resin (A) is reactive to a photopolymerization initiator and UV irradiation (A '), and the (meth) acrylic equivalent is 1500 g / eq to 3800 g. / eq reactive alkali-soluble resin and (A ") photopolymerization initiator and non-reactive alkali-soluble resin which is non-reactive with respect to UV irradiation, (A ') reactive alkali-soluble resin is 14 weight% compared with the solid content of the whole photosensitive resin composition. It provides a photosensitive resin composition for forming transparent pixels, characterized in that it comprises from 30% by weight.

Description

Photosensitive resin composition for transparent pixel formation {PHOTOSENSITIVE RESIN COMPOSITION FOR TRANSPARENT PIXEL}

The present invention relates to a photosensitive resin composition for forming a transparent pixel, which is easy to form a fine pixel pixel and implements a contact hole for forming a transparent electrode.

Recently, the display industry has undergone a drastic change from CRT to flat panel displays represented by PDP, OLED, and LCD. Among them, 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 liquid crystal for light transmission control, a TFT array layer, which is an electric signal device for driving the liquid crystal, and a black matrix patterned substrate, and each pixel pattern In order to provide flatness between the layers, a color filter layer coated with an overcoat and a TFT spacer layer and a column spacer for maintaining a cell gap in the step of bonding the color filter layer together. 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 use.

However, as the use environment of the liquid crystal display (LCD) is used as an information transmission medium such as outdoor advertisements indoors, a problem of sharply deteriorating visibility due to a problem of deterioration of luminance caused by external sunlight is occurring. 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, but it has not been sufficiently solved due to the problem of power consumption and limitation of the coloring material. On the other hand, a method of forming an empty space without luminance loss of a backlight in a pixel pixel composed of red, green, and blue has been proposed.

However, the color filter having the transparent layer according to the above method was able to improve the visibility due to the external light in a large amount due to the brightness enhancement effect, but it became a cause of poor liquid crystal driving due to the increased step with the surrounding color layer. Transparent pixel pixels of the same thickness as color pixels are required.

Accordingly, in order to realize the transparent pixel, a transparent pixel layer was manufactured using an overcoat or a photosensitive column spacer among the existing transparent materials described in Korean Patent Application Publication No. 2007-0007895, but it is difficult to implement a transparent pixel pattern. In particular, there is a problem that can not produce a fine contact hole (40-μm) contact hole (Contact-hole).

Republic of Korea Publication No. 2007-0007895

The present invention, to solve the problems of the prior art as described above, not only a 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 film ratio It is an object to provide a resin composition.

The present invention (A) alkali soluble resin; (B) photopolymerizable compounds; (C) photoinitiator; And (D) a photosensitive resin composition for forming a transparent pixel comprising a solvent, wherein the alkali-soluble resin (A) is reactive to a photopolymerization initiator and UV irradiation (A '), and the (meth) acrylic equivalent is 1500 g / eq to 3800 g. / eq reactive alkali-soluble resin and (A ") photopolymerization initiator and non-reactive alkali-soluble resin which is non-reactive with respect to UV irradiation, (A ') reactive alkali-soluble resin is 14 weight% compared with the solid content of the whole photosensitive resin composition. It provides a photosensitive resin composition for forming transparent pixels, characterized in that it comprises from 30% by weight.

In addition, the present invention provides a color filter formed by 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, it is easy to form a fine pixel pixel, and it is possible to implement a contact hole for forming a transparent electrode, thereby providing a high quality color filter. can do.

When the photosensitive resin composition for forming transparent pixels of the present invention is used, the taper is less attracted and has a stable residual film ratio and a proper hole size (Hole-Size) compared to a mask hole under process conditions of 50 to 100 sec. You can get it.

In addition, by using the photosensitive resin composition for forming a transparent pixel of the present invention, it is possible to obtain a proper tap-size with less taper drag, thereby reducing the malfunction of the liquid crystal panel and improving the contrast and luminance of the liquid crystal panel.

Hereinafter, the present invention will be described in detail. The following detailed description is for the description of one embodiment of the present invention, even though there is a limiting expression, it does not limit the scope of rights defined by the claims.

The present invention (A) alkali soluble resin; (B) photopolymerizable compounds; (C) photoinitiator; And (D) a photosensitive resin composition for forming a transparent pixel comprising a solvent, wherein the alkali-soluble resin (A) is reactive to a photopolymerization initiator and UV irradiation (A '), and the (meth) acrylic equivalent is 1500 g / eq to 3800 g. / eq reactive alkali-soluble resin and (A ") photopolymerization initiator and non-reactive alkali-soluble resin which is non-reactive with respect to UV irradiation, (A ') reactive alkali-soluble resin is 14 weight% compared with the solid content of the whole photosensitive resin composition. It provides a photosensitive resin composition for forming transparent pixels, characterized in that it comprises from 30% by weight. Hereinafter, each component of the present invention will be described in detail.

(A) alkali-soluble resin

The alkali soluble resin (A) serves to remove the non-exposed portion of the transparent pixel photosensitive resin layer formed by using the photosensitive resin composition for forming transparent pixels, making it soluble in alkali, and to leave the exposure area. In particular, the present invention provides that (A) alkali-soluble resins are reactive with (A ') photopolymerization initiator and UV irradiation and (A ") non-reactive alkali-soluble resins which are unreactive with respect to photoinitiator and UV irradiation. The (A ') reactive alkali-soluble resin is a copolymer having a (meth) acrylic equivalent of 1500 g / eq to 3800 g / eq, and is 14 to 30% by weight relative to the solids of the entire photosensitive resin composition. When it is included, it is easy to form a fine pixel pixel when forming a transparent pixel of a color filter, and it is possible to implement a contact hole for forming a transparent electrode, and experimentally confirms that taper drag is significantly reduced even at various process margins to complete the present invention. It was.

The (meth) acryl equivalent is calculated as the number of moles of the (meth) acryl group relative to the weight of the total solid content of the reactive alkali-soluble resin. If the (meth) acrylic sugar is less than 1500 g / eq, the concentration of the (meth) acryl group in the alkali-soluble resin increases, so that photopolymerization proceeds easily due to the incident UV light, resulting in a high degree of curing, but a smaller contact hole size and taper. The attraction is severe. On the contrary, when the (meth) acrylic equivalent is higher than 3800 g / eq, the concentration of the (meth) acryl group is lowered, so that the degree of curing is lowered and the contact hole size is larger than necessary, and the residual film ratio is lowered by the process conditions. The control of the (meth) acrylic equivalent can be controlled by adjusting the content of the monomer containing a (meth) acryl group at the time of copolymerization.

When the (A ′) reactive alkali-soluble resin includes 14 wt% to 30 wt% of the solids of the entire photosensitive resin composition, it is easy to form fine pixel pixels when forming transparent pixels of the color filter, and the contact hole size is appropriate. In addition, taper drag is significantly reduced at various process margins.

The reactive alkali-soluble resin (A ') used in the present invention is an air obtained by further polymerizing a copolymer by polymerization of compounds including the following (A'1) and (A'2) and the following (A'3) compound. It may be coalescing.

The reactive alkali-soluble resin (A ') used in the present invention can also be polymerized by adding other monomers in addition to (A'1), (A'2) and (A'3). That is, the case where another monomer other than said (A'1)-(A'3) compound is further contained and superposed | polymerized is also included in the scope of the present invention.

(A'1) component contained in the said (A ') reactive alkali-soluble resin is a compound which has an unsaturated bond and a carboxylic acid group in 1 molecule, and if it is a carboxylic acid compound which has a unsaturated double bond which can superpose | polymerize, Each can be used individually or in combination of 2 or more types. 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 anhydrides of the dicarboxylic acids; and mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as? -carboxypolycaprolactone mono (meth) acrylate. Acrylic acid and methacrylic acid among the compounds are preferred because of their excellent copolymerization reactivity and solubility in a developing solution.

The component (A'2) included in the (A ') reactive alkali-soluble resin 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 that can be polymerized. Specific examples thereof 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, pentyl (meth) acrylate, cyclophene Tenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, pentadienyl (meth) acrylate, isobornyl (meth) acrylic Unsaturated carboxylic ester compounds including alicyclic substituents such as late, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, and pineneyl (meth) acrylate; 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) acryloyloxymethyl) -3-ethyloxetane, 3-((meth) acryloyloxymethyl) -2-methyl Unsaturated carboxylic ester compounds including 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 ester compounds containing a substituent having an aromatic ring such as benzyl (meth) acrylate and phenoxy (meth) acrylate; Aromatic vinyl compounds, such as styrene, (alpha) -methylstyrene, and vinyltoluene; Carboxylic acid vinyl esters, such as vinyl acetate and a vinyl propionate; And vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile. Among these, an aromatic vinyl compound is preferable for sensitivity improvement and outgas reduction. These can be used individually or in combination of 2 or more types, respectively.

As used herein, (meth) acrylate means acrylate and / or methacrylate.

In the copolymer obtained by polymerizing the compounds containing (A'1) and (A'2) used in the present invention, the ratio of the constituents derived from each of (A'1) and (A'2) is It is preferable to exist in the following ranges by mole fraction with respect to the total number of moles of the (A'1) and (A'2) component of the.

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

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

In particular, it is more preferable that the ratio of said structural component is the following ranges.

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

Structural unit derived from (A'2): 40 to 90 mole%,

If said composition ratio is in the said range, since alkali solubility and heat resistance balance are favorable, a preferable copolymer can be obtained.

The copolymer obtained by superposing | polymerizing the compound containing (A'1) and (A'2) used by this invention can be manufactured by the following method as an example.

Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot and a nitrogen introduction tube, 0.5 to 20 times the amount of solvent was introduced to the total weight of (A'1) and (A'2) and the atmosphere in the flask was Substitute with nitrogen. Then, after raising the solvent to 40-140 degreeC, 0-20 times of the predetermined amount of (A'1) and (A'2) and the total weight of (A'1) and (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 to the total number of moles of (A'1) and (A'2) (stirred and dissolved under room temperature or heating) Was added dropwise to the above flask from 0.1 dropping lot over 0.1 to 8 hours, and further stirred at 40 to 140 ° C for 1 to 10 hours.

In addition, a part or whole quantity of a polymerization initiator may be put in a flask at the said process, and a part or whole quantity of (A'1) and (A'2) may be put in a flask. Moreover, in order to control molecular weight and molecular weight distribution, (alpha) -methylstyrene dimer and a mercapto compound can also be used as a chain transfer agent. The amount of the α-methylstyrene dimer or mercapto compound is 0.005 to 5% by weight based on the total weight of (A'1) and (A'2). In addition, the said polymerization conditions can also adjust an input method and reaction temperature suitably in consideration of the heat generation amount by a manufacturing facility, superposition | polymerization, etc ..

(A ') reactive alkali-soluble resin contained in the photosensitive resin composition for transparent pixel formation of this invention is (A'3) to the copolymer obtained by superposing | polymerizing the compound of (A'1) and (A'2) as an example. It can obtain by making a compound react further. By adding (A'3) to the copolymer, it is possible to impart light / thermosetting to the alkali-soluble resin, thereby improving 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 the unsaturated bond may be provided by a (meth) acryl group. Specific examples include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, methylglycidyl (meth) acrylate Etc. can be mentioned. Among these, glycidyl (meth) acrylate is preferably used. These can be used individually or in combination of 2 or more types, respectively.

The (A'3) is preferably reacted at 5 to 80 mol% based on the number of moles of (A'1) contained in the copolymer, particularly preferably 10 to 80 mol%. When the composition ratio of (A'3) is within the above range, it is preferable because it is excellent in exposure sensitivity and developability.

In the present invention, the (A ') reactive alkali-soluble resin reacts the copolymer obtained by copolymerizing (A'1) and (A'2) with (A'3) by, for example, the following method. It can manufacture.

The atmosphere in the flask was replaced by nitrogen to air, and 5 to 80 mole% of (A'3), a carboxyl group and an epoxy group reaction catalyst in molar fraction with respect to the structural unit derived from (A'1) in the copolymer. For example, trisdimethylaminomethylphenol is 0.01 to 5% by weight based on the total weight of (A'1) to (A'3) and polymerization inhibitor, for example, hydroquinone is 0.001 to 5% by weight relative to the total weight. The said copolymer and (A'3) can be made to react by putting in a flask and reacting at 60-130 degreeC for 1 to 10 hours. In addition, similarly to the polymerization conditions, the charging method and the reaction temperature may be appropriately adjusted in consideration of the amount of heat generated by the production equipment, the polymerization and the like.

In the present invention, the (A ′) reactive alkali-soluble resin preferably has a weight average molecular weight in terms of polystyrene in the range of 3,000 to 100,000, more preferably in the range of 5,000 to 50,000. When the weight average molecular weight of the (A ′) reactive alkali-soluble resin is in the range of 3,000 to 100,000, film reduction of the exposed portion is unlikely to occur at the time of development, and is preferable since the solubility of the non-exposed portion tends to be good.

The acid value of the (A ′) reactive alkali-soluble resin is preferably in the range of 30 to 150 mgKOH / g based on solid content. If the acid value is less than 30 mgKOH / g, solubility in the alkaline developer is low and there is a risk of leaving a residue on the substrate, if the acid value exceeds 150 mgKOH / g is more likely to break the pattern.

It is preferable that it is 1.0-6.0, and, as for the molecular weight distribution of (A ') reactive alkali-soluble resin, it is more preferable that it is 1.5-4.0. 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 may be prepared in the same manner as the (A ′)-reactive alkali-soluble resin, except that (A ″) non-reactive alkali-soluble resin is irradiated with UV irradiation and photopolymerization in the molecular chain. Copolymerization of (A'3) included in the (A ') reactive alkali-soluble resin is omitted because the polymerization must be performed in the absence of unsaturated double bonds that may cause photopolymerization by the initiator, and (A "1) to ( Prepared by copolymerizing A ″ 2). The method example is the same as that of the general synthesis example of (A ') reactive alkali-soluble resin, (A "1) component and (A" 2) component are the said (A'1) component and (A'2) component, respectively. The materials illustrated as may be used.

In the present invention, the (A ″) non-reactive alkali-soluble resin preferably has a weight average molecular weight in terms of polystyrene in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 40,000. (A ″) If the weight average molecular weight of the non-reactive alkali-soluble resin is in the range of 3,000 to 100,000, the film reduction of the exposed portion is unlikely to occur at the time of development, and is preferable since the solubility of the non-exposed portion tends to be good.

The acid value of the (A ″) non-reactive alkali-soluble resin is preferably in the range of 30 to 150 mgKOH / g based on solids. If the acid value is less than 30 mgKOH / g, the solubility in alkaline developers is low and residues may remain on the substrate. If the acid value exceeds 150 mgKOH / g, the tearing of the pattern is more likely to occur.

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. A molecular weight distribution of 1.0 to 6.0 is preferable because of its excellent developability.

Content of the said (A) alkali-soluble resin is 20 to 85 weight% normally with respect to solid content in the photosensitive resin composition for transparent pixel formation, Preferably it is the range of 40 to 75 weight%. (A) When the content of the alkali-soluble resin is 20 to 85% by weight 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 reduction of the exposed portion hardly occurs during development. Since the solubility of a non-exposed part tends to be favorable, it is preferable.

(B) Photopolymerizable  compound

The photopolymerizable compound (B) contained in the photosensitive resin composition for forming a transparent pixel of the present invention is a compound which can be polymerized by the action of light and a photopolymerization initiator described later, and is a monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, or the like. Can be mentioned.

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

As a specific example of a bifunctional monomer, 1, 6- hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.

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

Of these, bifunctional or higher polyfunctional monomers are preferably used. Especially preferably, it is a polyfunctional monomer more than 5-functional.

The photopolymerizable compound (B) is usually used in the range of 10 to 60% by weight, preferably 20 to 50% by weight, based on the solid content in the photosensitive resin composition for forming transparent pixels. If the photopolymerizable compound (B) is in the range of 10 to 60% by weight based on the above criteria, the intensity of the pixel portion, the residual film ratio with the progress of the process, and the contact hole characteristics tend to be good.

(C) Photopolymerization Initiator

The (C) photopolymerization initiator contained in the photosensitive resin composition for forming transparent pixels 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 transparent pixel formation containing the above-mentioned (C) photoinitiator is high sensitivity, and the film | membrane formed using this composition becomes favorable in the intensity | strength and the contact hole characteristic of the pixel part.

Moreover, when (C-1) photoinitiator adjuvant is used together with (C) photoinitiator, the photosensitive resin composition for transparent pixel formation containing these becomes more sensitive, and the productivity at the time of forming a color filter using this composition improves. It is preferable as it is.

As a triazine type compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl) -6, for example. -(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- Yl) 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 and the like.

As an acetophenone type compound, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2- Hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 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 one-on oligomers. Moreover, the compound represented by following formula (1) is mentioned.

(Formula 1)

In the above formula,

R1 to R4 each independently represent a hydrogen, a halogen, 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 an alkyl group having 1 to 12 carbon atoms Substituted or unsubstituted naphthyl group.

Specific examples of the compound represented by Formula 1 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one and 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) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholi Nophenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propane-1- On, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. may be mentioned. have.

As a biimidazole compound, it is 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2,3-, for example). Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimi Dazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, a phenyl group at the 4,4', 5,5 'position is carbo The imidazole compound substituted with the alkoxy group etc. are mentioned. Among them, 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole is preferably used.

As an oxime compound, the following general formula (2), 3, 4, etc. are mentioned.

(Formula 2)

(Formula 3)

(Formula 4)

Moreover, as long as it does not impair the effect of this invention, the other photoinitiator etc. which are normally used in this field can also be used together. As another photoinitiator, a benzoin compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound etc. are mentioned, for example. These can be used individually or in combination of 2 or more types, respectively.

As a benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As a benzophenone type compound, for example, benzophenone, methyl 0- benzoyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3, 3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-di (N, N'-dimethylamino) -benzophenone, etc. are mentioned.

As a thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. Can be mentioned.

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

Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl, a titanocene compound, etc. are mentioned as another photoinitiator.

In the present invention, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and the like may be preferably used as the (C-1) photopolymerization initiation assistant 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-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4'- Aromatic amine compounds, such as bis (diethylamino) benzophenone, are mentioned. As an amine compound, an aromatic amine compound is used preferably.

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 (C) photopolymerization initiator in the transparent pixel-forming photosensitive resin composition of the present invention is 0.1 to 20% by weight, preferably 1 to 10% by weight based on the total solid component, and (C-1) of the photopolymerization initiation aid The amount used is usually 0.1 to 20% by weight, preferably 1 to 10% by weight based on the above criteria.

When the usage-amount of the said (C) photoinitiator exists in the said range, since the photosensitive resin composition for transparent pixel formation becomes highly sensitive, the intensity | strength of a pixel part and smoothness in the surface of this pixel part are preferable, and it is preferable. When the amount of the photopolymerization initiation aid (C-1) is in the above range, the sensitivity efficiency of the photosensitive resin composition for forming transparent pixels is further increased, and the productivity of the color filter formed by using this composition tends to be improved. desirable.

(D) solvent

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

Specific examples of the solvent (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, and diethylene. Diethylene glycol dialkyl ethers such as glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, and propylene glycol Alkylene glycol alkyl ether acetates such as propylene glycol alkyl ethers such as monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate and methoxypentyl acetate , Ben Aromatic hydrocarbons such as, toluene, xylene, mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol Alcohols such as glycerin, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone.

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

These (D) solvents can be used individually or in mixture of 2 or more types, respectively.

The content of the solvent (D) in the photosensitive resin composition for forming transparent pixels of the present invention is usually 60 to 90% by weight, preferably 70 to 85% by weight, based on the total amount of the photosensitive resin composition for forming a transparent pixel containing a solvent. %to be. (D) When the content of the solvent is in the range of 60 to 90% by weight based on the above criteria, it is applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, or the like. Since coating property tends to become favorable at the time, it is preferable.

(E) additive

The photosensitive resin composition for transparent pixel formation of this invention can also be combined with (E) additives, such as a filler, another high molecular compound, a hardening | curing agent, an adhesion promoter, antioxidant, a ultraviolet absorber, and an aggregation inhibitor, as needed.

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

Specific examples of the other high molecular compound include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. Can be.

The curing agent is used to increase the core hardening and mechanical strength, and the curing agent includes an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, and the like.

Examples of the epoxy compound in the curing agent include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, noblock type epoxy resins, other aromatic epoxy resins, and alicyclic compounds. Aliphatic, cycloaliphatic or aromatic epoxy compounds, butadiene (co) polymer epoxides other than group epoxy resins, glycidyl ester resins, glycidylamine resins, or brominated derivatives of such epoxy resins, epoxy resins and brominated derivatives thereof 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 bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, and cyclohexane dicarboxylic acid bis oxetane. 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 acid, polyhydric carboxylic anhydride, an acid generator, etc. are mentioned, for example. Commercially available carboxylic anhydrides or epoxy resin curing agents can be used. As an epoxy resin hardening | curing agent, a brand name (adekahadona EH-700) (made by Adeka industry), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), a brand name (MH-700) (new Nippon Ewha Co., Ltd.) etc. are mentioned. The said hardening | curing agent can be used individually or in mixture of 2 or more types.

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 Propyl trimethoxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, etc. are mentioned.

These adhesion promoters can be used individually or in combination of 2 or more types, respectively, Usually, 0.01-10 weight%, Preferably it is 0.05-2 weight% with respect to solid content in the photosensitive resin composition for transparent pixel formation.

Specific 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 transparent pixel formation of this invention can be manufactured, for example by the following method. (A) Alkali-soluble resin, (B) photopolymerizable compound, (C) photoinitiator, (D) solvent are mixed at an appropriate ratio, and the other components used are further added as needed, and the photosensitive for forming a desired transparent pixel is added. Obtain a resin composition.

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

The pattern forming method of the photosensitive resin composition for forming a transparent pixel according to the present invention comprises the steps of applying the above-mentioned 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, it can apply | coat on a base material as follows and form a pattern by photocuring and developing, and it can be used as a black matrix or a coloring and transparent pixel (color image).

First, the composition is applied to a substrate (not limited, usually glass or silicon wafer) or a layer containing the solids of the photosensitive resin composition for forming a transparent pixel, which is formed first, and preliminarily dried to remove volatile components such as a solvent and smooth it. Get a coating. The thickness of the coating film at this time is about 1-3 micrometers normally. In order to obtain the desired pattern to the coating film obtained in this way, an ultraviolet-ray is irradiated to a specific area | region through a mask. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that a parallel light beam may be irradiated uniformly to the whole exposure part, and a mask and a board | substrate exactly match. In addition, the desired pattern can be produced by contacting the aqueous solution of which the curing is completed with an aqueous alkali solution to dissolve and develop the non-exposed areas. After image development, it can dry after about 10 to 60 minutes at 150-230 degreeC as needed.

The developing solution used for image development after patterned exposure is the aqueous solution containing an alkaline compound and surfactant normally. The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compounds 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 bicarbonate And potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like.

In addition, specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, ethanolamine, etc. are mentioned. These inorganic and organic alkaline compounds can be used individually or in combination of 2 or more types, respectively.

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

Surfactant in alkaline developing solution can use all of 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 and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.

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

These surfactant can be used individually or in combination of 2 or more types, respectively.

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

Hereinafter, a 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 above-mentioned photosensitive resin composition for forming transparent pixels in a predetermined pattern.

The pattern formation method of the photosensitive resin composition for transparent pixel formation is based on the above-mentioned, and detailed description is abbreviate | 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, patterning exposure to the resulting dry coating film, and developing the photosensitive resin composition for forming a transparent pixel. In addition, a color filter can be obtained by repeating such an operation by the number of unit pixels required for the color filter. Since the configuration and manufacturing method of the color filter are well known in the art, detailed description thereof will be omitted.

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

Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by an Example. In addition, "%" and "part" which show content in a following example and a comparative example are a basis of weight unless there is particular notice.

<Production example>

Preparation Example 1 Synthesis of Reactive Alkali Soluble Resin (A ′)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, and 84.2 parts by weight of benzyl methacrylate, 39 parts by weight of methacrylic acid, 22 parts by weight of tricyclodecyl methacrylate, and t- 4 parts by weight of butylperoxy-2-ethylhexanoate and 40 parts by weight 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 n-dodecanethiol 6 Part by weight and 24 parts by weight of PGMEA were added and stirred to prepare a chain transfer dropping lot. Thereafter, 395 parts by weight of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, followed by stirring, thereby raising the temperature of the flask to 90 ° C. Next, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was carried out for 2 h each while maintaining 90 ° C., and after 1 h, the temperature was raised to 110 ° C. and maintained for 3 h. Then, a gas introduction tube was introduced to prevent bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas. Started. Subsequently, 14.2 parts by weight of glycidyl methacrylate, 0.4 part by weight of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 part by weight of triethylamine were added to the flask for 8 hours at 110 ° C. The reaction was continued and then cooled to room temperature to obtain a solid content of 29.1% by weight, a weight average molecular weight of 32500, an acid value of 105 mgKOH / g, and a (meth) acrylic equivalent of 1506 g / eq resin A-1.

Synthesis of the other resin was synthesized by the same method as described above in the mol% composition ratio as shown in Table 1.

   Mol% in reactive alkali-soluble resin Solid content (% by weight) Acid value (mgKOH / g) Mw (Meth) acrylic equivalent (g / eq) BzMA MAA GMA TCDMA A-1 45 35 10 10 29.1 105 32500 1506 A-2 45 38 7 10 29.5 125 29800 2151 A-3 45 40 5 10 29.8 139 26900 3012 A-4 45 41 4 10 28.5 146 29000 3765 A-5 45 42 3 10 30.1 153 28600 5020 A-6 45 34 11 10 29.4 98 31000 1369

BzMA = benzyl methacrylate (molecular weight = 187.19)

MAA = methacrylic acid (molecular weight = 86.06)

GMA = glycidyl methacrylate (molecular weight = 142.15)

TCDMA = tricyclodecyl methacrylate (molecular weight = 220.31)

Preparation Example 2 Synthesis of Non-Reactive Alkali Soluble Resin A ″

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, and 300 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was added and heated to 75 ° C while stirring. A solution of 165.2 parts by weight of 3,4-epoxy-8- (acryloyloxy) tricycloyl [5.2.1.02,6] decane (EDCPA), 18 parts by weight of acrylic acid (AA) and 170 parts by weight of PGMEA was dissolved in a flask. It was dripped for 5 hours using the dropping lot. On the other hand, the solution which melt | dissolved 30 weight part of polymerization initiator azobisisobutyronitrile in 200 weight part of PGMEA was dripped over 5 hours using another dropping lot. After the dropping of the polymerization initiator was completed, Resin B having a solid content of 29.4 wt%, a weight average molecular weight of 11200, and an acid value of 120 mgKOH / g was obtained while maintaining the temperature for about 4 hours and then cooling to room temperature.

Molecular weight evaluation

About the measurement of the weight average molecular weight (Mw) of said (A) alkali-soluble resin, it carried out on condition of the following using GPC method.

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

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

Column temperature: 40 ℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection volume: 50 μl

Detector: RI

Sample concentration measured: 0.6 wt% (solvent = tetrahydrofuran)

Calibration standard: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

<Solid content>

About 1 g of the polymer solution was weighed into an aluminum cup, and about 3 g of acetone was added to dissolve it, followed by air drying at normal temperature. And after drying at 160 degreeC under vacuum for 3 hours using the hot-air dryer (made by EPSP Co., Ltd. brand name: PHH-101), it left to cool in a desiccator and weighed. Solid content of the polymer solution was calculated from the weight loss amount.

<Acid value>

3 g of a resin solution was precisely weighed and dissolved in acetone 90 g / water 10 g mixed solvent, and a titration blue solution was used as an titration solution using a 0.1 N KOH aqueous solution as a titration liquid. -555), the acid value of the polymer solution was measured, 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.

<(Meth) acrylic equivalent calculation>

(Meth) acrylic equivalent (g / eq) = solid content weight of copolymer / mol number of GMA

<Contact contact hole size and taper drag>

The substrate prepared in the above example was placed, and a 40 μm × 40 μm square contact hole of the photomask was observed, the size of the contact hole was measured, and the take drag was observed and the picture was taken. The contact hole size is preferably between 30 μm and 40 μm.

OM equipment: ECLIPSE LV100POL Nikon Corporation

Evaluation criteria of taper attraction

O: Tapered state

(Triangle | delta): A taper drag of one side is 2 micrometers or less

X: The taper drag of one side is 3 micrometers or more

<Residual Rate Measurement>

Each of the transparent pixel-forming photosensitive resin compositions was coated on a glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. After irradiating an ultraviolet-ray, the film thickness of the pattern was measured using the film thickness measuring apparatus (DEKTAK 6M; Veeco company make). After the thickness measurement was completed, the substrate was immersed in a KOH aqueous solution developing solution of pH 10.5 for 80 seconds and developed, and then the thickness was measured.

Residual film ratio (%) = thickness after development (µm) / thickness before development (µm)

If the residual film ratio is less than 80%, it is judged to have a significant effect on the film hardness and process margin.

<Process margin evaluation result>

O: Remaining film ratio is 80% or more, contact hole size is between 30 µm and 40 µm, and taper drag is O

X: Remaining film ratio is 79% or less, contact hole size is out of 30 micrometers-40 micrometers, and taper drag is X

If any of the above three conditions deviates from the conditions ×

< Examples and Comparative example >

Example  1-8 and Comparative example  1-4: Transparent pixels  Preparation of Photosensitive Resin Composition for Formation

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 then sufficiently stirred to make the transparent pixels of Examples 1-8 and Comparative Examples 1-4. The photosensitive resin composition for formation was obtained.

Item (A ') reactive alkali-soluble resin (A ") alkali-soluble resin
Resin B (B) photopolymerization
compound
(weight%) (C) photoinitiator
(weight%) Kinds Acrylic equivalent g / eq content
(weight%) content
(weight%) Example 1 A-1 1506 19.6 43.6 33.9 2.9 Example 2 A-2 2151 19.6 43.6 33.9 2.9 Example 3 A-2 2151 29.3 33.9 33.9 2.9 Example 4 A-2 2151 14.7 48.5 33.9 2.9 Example 5 A-3 3012 19.6 43.6 33.9 2.9 Example 6 A-3 3012 29.3 33.9 33.9 2.9 Example 7 A-3 3012 14.7 48.5 33.9 2.9 Example 8 A-4 3765 19.6 43.6 33.9 2.9 Comparative Example 1 A-5 5020 19.6 43.6 33.9 2.9 Comparative Example 2 A-6 1369 19.6 43.6 33.9 2.9 Comparative Example 3 A-2 2151 13 50.2 33.9 2.9 Comparative Example 4 A-2 2151 32 31.2 33.9 2.9

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

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

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

Experimental Example

Experimental Example  1 to 8 and Comparative Experiment  1 to 4. Color Filter Glass Substrate) manufacturing

The color filter was manufactured using the photosensitive resin composition for transparent pixel formation manufactured by the said Examples 1-8 and Comparative Examples 1-4. That is, each of the transparent pixel-forming photosensitive resin compositions was applied on a glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. Subsequently, a test photomask having a square pattern ranging from 50 µm x 50 µm to 10 µm x 10 µm and a line / space pattern of 1 µm to 100 µm was placed on the thin film and 300 µm apart from the test photomask. Ultraviolet light was irradiated.

At this time, the ultraviolet light source was irradiated with an exposure amount (365 nm) of 50 mJ / cm 2 under an atmospheric 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 UV-irradiated thin film was immersed in a KOH aqueous solution developing solution of pH 10.5 for 80 seconds and developed. The thin plate coated with the thin glass plate 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 manufactured above was 3.0 μm.

In addition, in the case of the substrate for followability evaluation, the first production was carried out in the same manner as the color filter manufacturing example using the blue photosensitive resin composition, and then the front surface was coated with the photosensitive resin composition for forming transparent pixels and the front surface was exposed separately. Produced.

The contact hole size and followability of the color filter were measured and evaluated as follows, and the results are shown in Table 3 below.

Item Photosensitive resin composition 40 x 40㎛ Contact Hole (Photomask) Before and after
Residual rate (%) Contact hole size (㎛) Tapered Experimental Example 1 Example 1 32 O 88 Experimental Example 2 Example 2 33 O 84 Experimental Example 3 Example 3 31 O 87 Experimental Example 4 Example 4 34 O 83 Experimental Example 5 Example 5 35 O 82 Experimental Example 6 Example 6 33 O 85 Experimental Example 7 Example 7 39 O 80 Experimental Example 8 Example 8 37 O 81 Comparative Experimental Example 1 Comparative Example 1 43 O 75 Comparative Experiment 2 Comparative Example 2 29 × 90 Comparative Experiment 3 Comparative Example 3 36 O 79 Comparative Experiment 4 Comparative Example 4 26 × 92

Experimental Example  9-12 and Comparative Experiment  5-12.Color Filter Glass Substrate) manufacturing

The results obtained by changing the process conditions are shown in Table 4 below.

Except for the exposure amount (mJ / cm2) and the development time (sec), the remaining process conditions were the same as in Experimental Example 1.

Item Photosensitive resin composition Exposure Developing time 40 x 40㎛ Contact Hole (Photomask) Before and after Fair margin result mJ / cm2 (sec) Contact hole size (㎛) Tapered Residual rate (%) Experimental Example 9 Example 2 40 80 35 O 82 O Experimental Example 10 60 80 31 O 85 Experimental Example 11 50 50 30 O 86 Experimental Example 12 50 100 36 O 83 Comparative Example 5 Comparative Example 3 40 80 37 O 75 * × Comparative Experiment 6 60 80 34 O 81 Comparative Experiment 7 50 50 32 O 81 Comparative Experiment 8 50 100 39 × 76 * Comparative Experiment 9 Comparative Example 4 40 80 28 * × 90 × Comparative Experimental Example 10 60 80 24 * × 95 Comparative Experiment 11 50 50 21 * O 95 Comparative Experiment 12 50 100 29 * × 89

* Deviates from good results

Referring to the results of Experimental Examples to Comparative Experiments of Tables 3 and 4, the (meth) acrylic equivalent of the (A ') alkali-soluble resin is 1500 to 3800 g / eq, and 14% by weight of the solids of the total photosensitive resin composition. When included, the contact hole size, taper drag, and residual film ratio showed good results.

In the results of Experimental Examples to Comparative Experiments of Table 4, the (meth) acrylic equivalent of the (A ') alkali-soluble resin is 1500 to 3800 g / eq, and 14% to 30% by weight relative to the solids of the entire photosensitive resin composition. It can be clearly seen that the composition comprising a large process margin, such as the exposure dose and the development time, compared to the composition that does not.

Claims (8)

(A) alkali-soluble resins; (B) photopolymerizable compounds; (C) photoinitiator; And (D) a photosensitive resin composition for forming a transparent pixel comprising a solvent, wherein the alkali-soluble resin (A) is reactive to a photopolymerization initiator and UV irradiation (A '), and the (meth) acrylic equivalent is 1500 g / eq to 3800 g. / eq reactive alkali-soluble resin and (A ") photopolymerization initiator and non-reactive alkali-soluble resin which is non-reactive with respect to UV irradiation, (A ') reactive alkali-soluble resin is 14 weight% compared with the solid content of the whole photosensitive resin composition. To 30% by weight,
Non-reactive alkali-soluble resins which are unreactive to the photopolymerization initiator and UV irradiation (A ″) include 3, 4-epoxy-8- (acryloyloxy) tricycloyl [5.2.1.02,6] decane and acrylic acid A photosensitive resin composition for forming transparent pixels, which is a copolymer prepared by the method. The method according to claim 1,
Alkali-soluble resin reactive with the said (A ') photoinitiator and UV irradiation is polymerized with the compound which has an unsaturated bond and a carboxylic acid group in (A'1) 1 molecule, and (A'2) said (A'1). It is a copolymer obtained by superposing | polymerizing the compound containing the compound which has a unsaturated bond which is possible, and the compound obtained by further superposing | polymerizing the compound which has an unsaturated bond and an epoxy group in 1 molecule (A'3), The photosensitive resin composition for transparent pixel formation characterized by the above-mentioned. . The method according to claim 2,
The compound which has an unsaturated bond and an epoxy group in 1 molecule of said (A'3) is a compound which has a (meth) acryl group and an epoxy group, The photosensitive resin composition for transparent pixel formation characterized by the above-mentioned. delete The method according to claim 2,
Compounds having an unsaturated bond and a carboxylic acid group in one molecule of (A'1) include monocarboxylic acids, dicarboxylic acids, anhydrides of dicarboxylic acids, and mono (mono) having a carboxyl group and a hydroxyl group at both terminals. One or more selected from the group consisting of meta) acrylates,
The compound which has a unsaturated bond which can superpose | polymerize with (A'1) of said (A'2) is an unsubstituted or substituted alkyl ester compound of an unsaturated carboxylic acid, the unsaturated carboxylic ester compound containing an alicyclic substituent, and thermosetting Unsaturated carboxylic acid ester compounds containing possible substituents, monosaturated carboxylic acid ester compounds of glycols, unsaturated carboxylic acid ester compounds having a substituted or unsubstituted aromatic ring, aromatic vinyl compounds; At least one selected from the group consisting of a carboxylic acid vinyl ester and a vinyl cyanide compound, the photosensitive resin composition for forming a transparent pixel. The method according to claim 2,
Compounds having an unsaturated bond and a carboxylic acid group in one molecule of (A'1) include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, mesaconic acid, itaconic acid, fumaric anhydride, mesaconic anhydride, itaconic anhydride, and ω- At least one selected from the group consisting of carboxypolycaprolactone mono (meth) acrylates,
The compound which has an unsaturated bond which can superpose | polymerize with (A'1) of said (A'2) is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) Acrylate, aminoethyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylic Latex, pentyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, pentadienyl (meth) ) Acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, pineneyl (meth) acrylate, 3- ( (Meth) acryloyloxymethyl) jade Ethane, 3-((meth) acryloyloxymethyl) -3-ethyloxetane, 3-((meth) acryloyloxymethyl) -2-methyloxetane, 3-((meth) acryloyloxy Methyl) -2-trifluoromethyloxetane, oligoethylene glycol monoalkyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) acrylate, α-methylstyrene, vinyltoluene, vinyl acetate, propionic acid At least one selected from the group consisting of vinyl, (meth) acrylonitrile, and α-chloroacrylonitrile,
Compounds having an unsaturated bond and an epoxy group in one molecule of (A'3) include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 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 acrylate and methylglycidyl (meth) acrylate. The method according to claim 1,
About solid content in the photosensitive resin composition for transparent pixel formation,
(A) 20 to 85% by weight of alkali-soluble resin;
(B) 10 to 60% by weight of the photopolymerizable compound; And
(C) A photosensitive resin composition for forming transparent pixels, comprising 0.1 to 20 weight of photopolymerization initiator. The color filter formed using the photosensitive resin composition for transparent pixel formation of any one of Claims 1-3 and 5-7.