TWI613516B - Photosensitive resin composition for transparent pixel - Google Patents

Abstract

The present invention provides a photosensitive resin composition for forming transparent pixels and a color filter formed using the photosensitive resin composition for forming transparent pixels. The photosensitive resin composition for forming transparent pixels comprises (A) (B) a photopolymerizable compound; (C) a photopolymerization initiator; and (D) a photosensitive resin composition for transparent pixel formation of a solvent, wherein the (A) alkali-soluble resin is (A ' ) alkali-soluble resins that are reactive to radical photoinitiators and UV irradiation and (A " ) alkali-soluble resins that are non-reactive to radical photoinitiators and UV irradiation at 8: 2 ~ 1: 7 The weight ratio of the alkali-soluble resin (A " ) which is non-reactive to radical photoinitiators and UV irradiation is 10,000 to 30,000.

Description

Photosensitive resin composition for forming transparent pixels and color filter formed using the same

The present invention relates to a photosensitive resin composition for transparent pixel formation that can easily form fine pixels and can realize a contact hole for a transparent electrode, and a color filter formed using the photosensitive resin composition for transparent pixel formation.

In recent years, the display industry has reached a drastic change from CRT to flat panel displays represented by PDP, OLED, LCD, etc. Among them, liquid crystal display devices (LCDs) are widely used as image display devices in almost all industries, and their application range is continuously expanding. Generally, a liquid crystal display device is composed of a liquid crystal, a TFT array layer, a color filter layer, and a columnar spacer for controlling light transmission. The TFT array layer is an electrical signal device for driving the liquid crystal, and the color filter layer refers to A red, green, and blue pixel pattern is formed on a black matrix-patterned substrate, and a protective film is applied to provide flatness between the respective pixel patterns; a columnar spacer is bonded to the TFT array layer and the color filter layer The stage is used to maintain the cell gap. The liquid crystal display device (LCD) thus constructed is widely used in all industries such as mobile devices, industrial machinery, military, and medical applications.

However, as the use environment of liquid crystal display devices (LCDs) is used for information transmission media such as indoor to outdoor advertising, there has been a problem that visibility is drastically reduced due to a decrease in brightness due to external sunlight. In order to solve such problems, a method of increasing the brightness of the backlight source or increasing the transmittance of the red, green, and blue pixels of the color filter layer is adopted. However, the above problems cannot be completely solved due to the power consumption problem and the limit physical properties of the coloring material. , Among other methods, a method consisting of red, green and blue A method of forming a space without loss of backlight brightness in the pixels.

However, in terms of the visibility of the color filter with a transparent layer formed by the method in external light, the brightness improvement effect has been greatly improved, but as the difference from the surrounding coloring material layer becomes larger, the liquid crystal drive becomes poor. For this reason, transparent pixels with the same thickness as the colored pixels are required.

For this reason, in order to realize the transparent pixels, a transparent pixel layer is manufactured using a protective film, a photosensitive columnar spacer, and the like in the existing transparent materials described in Korean Laid-Open Patent No. 2007-0007895, but it is difficult to achieve transparency. The pixel pattern has a problem that, in particular, a contact-hole having a size of 40 μm or less cannot be formed.

Prior art literature

Patent Document 1: Korean Published Patent No. 2007-0007895

An object of the present invention is to solve the above-mentioned problems in the prior art, and to provide a transparent pixel that can not only form fine contact holes, but also minimize tapered smear, and exhibit excellent residual film rate when forming a transparent pixel pattern. Forming photosensitive resin composition.

The present invention provides a photosensitive resin composition for forming transparent pixels, which is used for forming transparent pixels comprising (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a solvent. The photosensitive resin composition, wherein the (A) alkali-soluble resin is (A ' ) an alkali-soluble resin reactive with a radical photoinitiator and UV irradiation, and (A " ) is free of a radical photoinitiator and UV irradiation. The reactive alkali-soluble resin is an alkali-soluble resin mixed in a weight ratio of 8: 2 to 1: 7. The molecular weight of the alkali-soluble resin (A " ) which is non-reactive to radical photoinitiator and UV irradiation is 10,000 ~ 30,000.

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

When the transparent pixel of the color filter is formed using the photosensitive resin composition for transparent pixel formation of the present invention, the flatness of the pixel portion is excellent, and fine pixels are easily formed. Not only can the contact holes for forming transparent electrodes be realized, but also color filters with excellent heat resistance and chemical resistance can be provided.

FIG. 1 is a view showing photographs of a color filter (glass substrate) of a manufacturing example manufactured according to the present invention and a color filter (glass substrate) of a comparative manufacturing example; FIG. 2 is a view showing application of conventional R, G, B, etc. The flatness level (top image) formed by the colored photosensitive composition is compared with the flatness level (bottom image) formed by applying a conventional transparent photosensitive resin composition; FIG. 3 is a graph showing the evaluation of the transparency for the formation of transparent pixels. A diagram of a method for flatness of a flexible resin composition.

Hereinafter, the present invention will be described in detail. Since the following specific description relates to an embodiment of the present invention, even in a limited expression, there is no limitation on the scope of the patent claim to the scope of the right to be protected.

The present invention relates to a photosensitive resin composition for transparent pixel formation comprising (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a solvent, and formation using the transparent pixel The color filter formed from a photosensitive resin composition, wherein the (A) alkali-soluble resin is (A ' ) an alkali-soluble resin that is reactive to a radical photoinitiator and UV irradiation, and (A " ) An alkali-soluble resin that is non-reactive to radical photoinitiators and UV irradiation is mixed in a weight ratio of 8: 2 to 1: 7. In addition, the (A " ) is characterized by radical photoinitiation The molecular weight of the alkali-soluble resin that is non-reactive with the UV irradiation agent is 10,000 to 30,000.

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

(A) Alkali-soluble resin

The (A) alkali-soluble resin functions to remove the non-exposed portions of the transparent pixel photosensitive resin layer formed of the photosensitive resin composition for transparent pixel formation with alkali-soluble properties and to leave exposed areas. In particular, the (A) alkali-soluble resin of the present invention is characterized by mixing (A ' ) an alkali-soluble resin reactive with a radical photoinitiator and UV irradiation and (A " ) a radical photoinitiator and UV irradiation. When the non-reactive alkali-soluble resin is mixed in a weight ratio of 8: 2 to 1: 7, experiments have shown that when forming transparent pixels of a color filter, it is easy to form fine pixels, which can be used to form transparent The contact hole of the electrode completes the present invention.

The mixing ratio of the (A) alkali-soluble resin is preferably (A ' ) a reactive alkali-soluble resin and (A " ) a non-reactive alkali-soluble resin, respectively, 8: 2 to 1: 7, and more preferably 7: 3 to 1: 6. If the content of the reactive alkali-soluble resin is less than 2, the residual film development rate will decrease; on the contrary, if it exceeds 8, the curing degree will become higher, and conical tailing will occur not only in the contact hole, but also heat resistance and Chemical resistance is reduced.

In addition to (A '1), (A ' 2) and (A 'than 3), used in the present invention, (A') the reaction of the alkali-soluble resin may be added together with other monomers. That is, the case of further polymerizing other monomers other than the compounds (A ′ 1) to (A ′ 3) is also included in the scope of the present invention.

The (A ') the reaction of the alkali-soluble resin contained in the (A' 1) component is a compound having an unsaturated bond in the molecule and a carboxyl group, as long as the carboxylic acid compound having a polymerizable unsaturated double bond is not limited in , Can be used individually 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 anhydrides of the dicarboxylic acids; ω-carboxy polycaprolactone Mono (meth) acrylates, etc. of polymers having a carboxyl group and a hydroxyl group at both ends, such as ester mono (meth) acrylates. Among these compounds, acrylic acid and methacrylic acid are preferred because they have excellent copolymerization reactivity and developer solubility.

The (A ') the reaction of the alkali-soluble resin contained in the (A' 2) component is a compound (A '1) a polymerizable unsaturated bond, if it is a compound having a polymerizable unsaturated double bond Use without restrictions. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, aminoethyl (meth) acrylate, and the like Unsubstituted or substituted alkyl esters of unsaturated carboxylic acids; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methyl cyclohexyl (meth) acrylate, (meth) acrylic acid Cycloheptyl, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate , Cyclooctenyl (meth) acrylate, menthyl dimethacrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, (meth) Unsaturated carboxylic acid ester compounds containing alicyclic substituents, such as adamantyl acrylate, norbornyl (meth) acrylate, and fluorenyl (meth) acrylate; 3-((meth) acryloxymethyl) Oxetane, 3-((meth) acryloxymethyl) -3-ethyloxetane, 3-((meth) acryloxymethyl) -2-methyl Oxetane, 3-((meth) acryloxymethyl Group) Unsaturated carboxylic acid ester compounds containing a heat-curable substituent, such as 2-trifluoromethyloxetane; and ethylene glycol-based monomers such as oligoethylene glycol mono (meth) acrylate Saturated carboxylic acid ester compounds; Unsaturated carboxylic acid ester compounds containing a substituent having an aromatic ring, such as benzyl (meth) acrylate and phenoxy (meth) acrylate; styrene, α-methylstyrene, vinyl Aromatic vinyl compounds such as toluene; vinyl carboxylates such as vinyl acetate and vinyl propionate; and cyanated vinyl compounds such as (meth) acrylonitrile and α-chloroacrylonitrile. Among these, in order to increase sensitivity and reduce exhaust gas, an aromatic vinyl compound is preferable. These can be used individually or in combination of 2 or more types.

The (meth) acrylic acid in this specification means an acrylate and / or methyl methacrylate.

Polymerizable compound contained in the copolymer used in the present invention, (A '1) ~ (A ' 2) being obtained, respectively, by the ratio of (A '1) ~ (A ' 2) derived constituent component is preferably relatively The total number of moles of the constituents (A ′ 1) to (A ′ 2) described above is calculated in the following range by the molar fraction.

Composition unit derived from (A ' 1): 2 ~ 70 mole%

Composition unit derived from (A ' 2): 30 ~ 98 mole%

In particular, the ratio of the constituent components is more preferably in the following range.

Composition unit derived from (A ' 1): 10 ~ 60 mole%

Composition unit derived from (A ' 2): 40 ~ 90 mole%

If the composition ratio is within the above range, both the alkali solubility and the heat resistance are uniform. Since the balance is good, a preferable copolymer can be obtained.

In the present invention, the method for producing the (A ′ ) reactive alkali-soluble resin is taken as an example, and when (A ′ 1) to (A ′ 2) compounds are copolymerized, it can be produced by the following method.

Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, a solvent in an amount of 0.5 to 20 times the total weight of (A ' 1) to (A ' 2) was introduced, and the atmosphere in the flask was changed from Air was replaced with nitrogen. Then, after the solvent is heated to 40 to 140 ° C, a predetermined amount of (A ' 1) to (A ' 2) is 0 to 20 times the total weight of (A ' 1) to (A ' 2). Solvent, and polymerization initiators such as azobisisobutyronitrile and benzoyl peroxide, and a solution containing 0.1 to 10 mol% relative to the total mole number of (A ' 1) ~ (A ' 2) (room Stir and dissolve under warm or heating) Drop into the flask from the dropping funnel over 0.1 ~ 8 hours, and stir for another 1 ~ 10 hours at 40 ~ 140 ° C.

In addition, a part or all of the polymerization initiator may be added to the flask in the aforementioned step, or a part or all of (A ′ 1) to (A ′ 2) may be added to the flask. In addition, in order to control the molecular weight or molecular weight distribution, an α-methylstyrene dimer and a mercapto compound can be used as a chain transfer agent. The amount of the α-methylstyrene dimer and the mercapto compound is 0.005 to 5% by weight relative to the total weight of (A ′ 1) to (A ′ 2). In addition, the polymerization conditions take into consideration the production equipment, the amount of heat generated by polymerization, and the like, and the method of addition and the reaction temperature can be appropriately adjusted.

Copolymers of the present invention the transparent pixel forming the photosensitive resin composition contained in the (A ') a reactive exemplary alkali-soluble resin can be obtained by polymerizing (A' obtained in 1) ~ (A '2) a further compound It is reacted with a compound (A '3) obtained. By the additional copolymer (A '3), light / heat-curable may be provided to the alkali-soluble resin, thereby improving heat resistance and chemical resistance.

The (A ') contained in the reaction of the alkali-soluble resin (A' 3) component is a compound having an unsaturated bond in the molecule and an epoxy group, specific examples include (meth) acrylate, ( 3,4-epoxycyclohexyl methacrylate, -3,4-epoxy cyclohexyl methyl (meth) acrylate, methyl glycidyl (meth) acrylate, and the like. Among these, glycidyl (meth) acrylate is preferably used. These may be used alone or in combination of two or more.

Number of moles of unsaturated bond and a carboxyl group '(1 a molecule of the (A A) Compound 3) a molecule having an unsaturated bond and an epoxy group is preferably contained in the copolymer' as having In the standard, the reaction is performed at 5 to 80 mol%, especially 10 to 80 mol% is preferred. If (A '3) composition ratio is within the range, the exposure sensitivity and developability is excellent and preferable.

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

The atmosphere in the flask was replaced with nitrogen gas from air, added to the copolymer (A '. 1) to constituent units derived from the calculated molar fraction of 5 to 80 mole% of (A' with respect to the flask catalyst 3), with respect to the total weight of (a '1) ~ (a ' 3) is 0.01 to 5% by weight of a carboxyl group with an epoxy group such as tris (dimethylaminomethyl) phenol, and with respect to A polymerization inhibitor, such as hydroquinone, with a total weight of 0.001 to 5% by weight, reacts at 60 to 130 ° C. for 1 to 10 hours, so that the aforementioned copolymer can react with (A ' 3). In addition, under the same conditions as the polymerization, the addition method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

In the present invention, the (A ′ ) reactive alkali-soluble resin preferably has a polystyrene equivalent weight average molecular weight in the range of 3,000 to 100,000, and 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 3000 to 100,000, it is difficult to reduce the film in the exposed portion during development, and the non-exposed portion has good solubility, which is preferred.

(A ' ) The acid value of the reactive alkali-soluble resin is preferably 30 to 150 mg based on the solid content.

KOH / g range. When the acid value is less than 30 mgKOH / g, the solubility of the alkali developing solution is reduced, and residues may remain on the substrate. When the acid value exceeds 150 mgKOH / g, the possibility of causing pattern corrosion is high.

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

The (A " ) non-reactive alkali-soluble resin used in the present invention can be produced by the same method as the (A ' ) reactive alkali-soluble resin. However, since (A " ) is in the molecular chain of the non-reactive alkali-soluble resin in '(3 a reactive alkali-soluble resin contained) copolymerizable UV irradiation process and a free radical photoinitiator to cause light to be obtained by polymerizing polymerizable unsaturated double bond in a state does not exist, and thus are omitted (a)' , Produced by copolymerization (A " 1) ~ (A " 2), or produced by copolymerization (A " 3) ~ (A " 5). This method example is the same as a general synthesis example of a (A ' ) reactive alkali-soluble resin.

(A "1) and the component (A" 2) component may be used as the substance (A '1) and the component (A' 2) component are exemplified.

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

(A " 3) Compounds having unsaturated bonds and carboxyl groups in the molecule

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

(A " 5) A dicarbonylamidoimine derivative having a polymerizable unsaturated bond with (A " 3) to (A " 4)

In addition to (A " 3), (A " 4), and (A " 5), the (A " ) reactive alkali-soluble resin used in the present invention may be polymerized by adding other monomers. That is, the case of further polymerizing other monomers other than the compounds (A " 3) to (A " 5) is also included in the scope of the present invention.

The (A ") a non-reactive alkali-soluble resin contained in the (A" 3) with the component (A ') contained in the reaction of the alkali-soluble resin (A' 1) the same as the (A ") a non-reactive Examples of the aliphatic polycyclic compound (A " 4) having an epoxy group and an unsaturated bond contained in the alkali-soluble resin include dicyclopentane, tricyclodecane, norbornane, isonorbornane, and dicyclooctane. Alkane, cyclononane, bicycloundecane, tricycloundecane, bicyclododecane, tricyclododecane and the like. Further preferably, (A " 4) the aliphatic polycyclic compound having the epoxy group and the unsaturated bond preferably contains at least one selected from the group consisting of a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2 A compound.

(In the chemical formulas 1 and 2, R is each independently a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms substituted or unsubstituted by a hydroxyl group, and X is a single bond independently, or contains or does not include a hetero atom (C1-C6 alkylene)

In the chemical formulas 1 and 2, R may specifically be a hydrogen atom; an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, or t-butyl; hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxy-n-propyl, 2-hydroxy-n-propyl, 3-hydroxy-n-propyl, 1-hydroxyisopropyl, 2-hydroxyisopropyl, 1-hydroxy Hydroxy-containing alkyl groups such as n-butyl, 2-hydroxy-n-butyl, 3-hydroxy-n-butyl, and 4-hydroxy-n-butyl. Among them, R is preferably a hydrogen atom, a methyl group, a methylol group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and particularly preferably a hydrogen atom or a methyl group.

In the chemical formulas 1 and 2, X may specifically be a single bond; an alkylene group such as methylene, ethylene, or propylene; an oxomethylene, oxoethylene, oxopropylene, Heteroatom-containing alkylene groups such as thiomethylene, thioethylene, thiopropylene, aminomethylene, aminoethylene, and aminopropylene. Among them, X is preferably a single bond, methylene, ethylene, oxymethylene or oxoethylene, and particularly preferably a single bond or oxoethylene.

The compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 may be used alone or in combination of two or more kinds. In particular, the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 may be mixed and used in any ratio.

Examples of the (A " 5) dicarbonylfluorenimine derivative contained in the (A " ) non-reactive alkali-soluble resin include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide imine, N-succinimideimino-3-maleimide benzoate, N-succinimide-4-maleimide butyrate, N -Succinimidyl-6-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate, N- (9-acridyl) maleimide Amines, among these, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, etc. are due to copolymerization reactivity and solubility in alkaline aqueous solution. Preferred.

The (A " ) non-reactive alkali-soluble resin used in the present invention is a copolymer obtained by copolymerizing (A " 3), (A " 4), and (A " 5). The total molar number of the constituent components constituting the copolymer is in the following range as calculated by the molar fraction.

(A " 3) Derived constituent units: 2 ~ 40 mole%

(A " 4) Derived constituent units: 2 ~ 95 mole%

(A " 5) Derived constituent units: 1 ~ 65 mole%

The ratio of the constituent components is more preferably in the following range.

(A " 3) Derived constituent units: 5 ~ 35 mole%

(A " 4) Derived constituent units: 5 ~ 80 mole%

(A " 5) Derived constituent units: 1 ~ 60 mole%

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

In the present invention, the feature of the (A " ) non-reactive alkali-soluble resin is that the weight average molecular weight in terms of polystyrene is in the range of 10,000 to 30,000. When the molecular weight of the (A " ) non-reactive alkali-soluble resin is in the range of 10,000 to 10,000 At 30,000, experiments have confirmed that the development residual film rate, heat resistance, chemical resistance, and flatness are excellent, and transparent pixels capable of achieving fine patterns can be formed.

(A " ) The acid value of the non-reactive alkali-soluble resin is preferably 30 to 150 mg based on the solid content.

KOH / g range. When the acid value is less than 30 mgKOH / g, the solubility in the alkali developing solution is reduced, and residues may remain on the substrate. When the acid value exceeds 150 mgKOH / g, the possibility of pattern corrosion becomes high.

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

The content of the (A) alkali-soluble resin is usually from 20 to 85% by weight, and preferably from 40 to 75% by weight based on the solid content in the photosensitive resin composition for transparent pixel formation. If the content of the (A) alkali-soluble resin is 20 to 85% by weight based on the above-mentioned standard, the solubility in the developing solution is sufficient, it is difficult to generate development residues on the substrate in the non-pixel portion, and it is difficult to generate a film in the exposed portion during development. Decreased, and the solubility of the non-exposed part tends to be good, which is preferable.

(B) Photopolymerizable compound

The (B) photopolymerizable compound contained in the photosensitive resin composition for transparent pixel formation of the present invention is a polymerizable compound under the action of light and a photopolymerization initiator described later, and examples thereof include monofunctional monomers and difunctional monomers. Functional monomers, other polyfunctional monomers, etc.

Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, and acrylic acid-2- Hydroxyethyl, N-vinylpyrrolidone and the like.

Specific examples of the difunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethyl Glycol di (meth) acrylate, bisphenol A (propylene ethoxyethyl) ether, 3-methyl-pentanediol di (meth) acrylate, and the like.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxylated trimethylol Propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxy Dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate or dipentaerythritol hexa (meth) acrylate, and the like.

Among these, it is preferable to use a difunctional or more polyfunctional monomer. In particular, a polyfunctional monomer having a pentafunctional or higher function can be preferably used, and a hydroxyl value of the following Chemical Formula 3 is more preferably 70 to 130 mg.

KOH / g of dipentaerythritol (poly) acrylate.

(In the chemical formula 3, R is hydrogen or a propylene fluorenyl group having 2 to 6 carbon atoms)

The (B) photopolymerizable compound is usually used in a range of 10 to 60% by weight, preferably 20 to 50% by weight based on the solid content in the photosensitive resin composition for transparent pixel formation. If the (B) photopolymerizable compound is in the range of 10 to 60% by weight based on the aforementioned calculation, the strength of the pixel portion, the residual film rate due to the progress of the process, and the contact hole characteristics tend to be good, which is preferable.

(C) Photopolymerization initiator

The (C) photopolymerization initiator contained in the photosensitive resin composition for transparent pixel formation of the present invention is not limited, and is selected from the group consisting of a triazine compound, an acetophenone compound, a biimidazole compound, and an oxime compound. More than one compound. The photosensitive resin composition for transparent pixel formation containing the (C) photopolymerization initiator has high sensitivity, and the strength and the contact hole of the pixel portion of a film formed using the composition Good characteristics.

In addition, if (C-1) a photopolymerization initiation adjuvant is used in combination with the (C) photopolymerization initiator, the photosensitive resin composition for forming transparent pixels containing them has a higher sensitivity, and a filter is formed using the composition. The productivity at the time of a color device improves, and it is preferable.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) ) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperidyl-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) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethylene Group] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1, 3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-triazine and the like.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzophenone dimethyl ketal, and 2-hydroxy-1 -[4- (2-hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl ) -2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-hydroxy-2-methyl 1-1- [4- (1-methylvinyl) phenyl] propane-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-? Phenolinyl) butane-1-one and the like. In addition, a compound represented by the following Chemical Formula 4 may be mentioned.

In the formula, R1 to R4 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group substituted or unsubstituted with an alkyl group having 1 to 12 carbon atoms, or a benzyl group substituted or unsubstituted with an alkyl group having 1 to 12 carbon atoms. Or naphthyl substituted or unsubstituted by alkyl having 1 to 12 carbon atoms.

Specific examples of the compound represented by the chemical formula 4 include 2-methyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-propyl-2-amino (4 -Morpholinophenyl) ethane-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-methyl-2-amino (4-? Phenolinophenyl) propane-1-one, 2-methyl-2-amino- (4-morpholinophenyl) butane-1-one, 2-ethyl-2-amino (4-morpholino Phenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butane-1-one, 2-methyl-2-methylamino- (4-morpholino Phenyl) propane-1-one, 2-methyl-2-dimethylamino- (4-morpholinophenyl) propane-1-one, 2-methyl-2-diethylamino (4- Morpholinyl) propane-1-one and the like.

Examples of the biimidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3 -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (alkane) Oxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole, 4,4', 5 , The 5 'position of the phenyl group is replaced by an alkoxycarbonyl group, an imidazole compound, and the like. Among these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorobenzene) are preferably used. Group) -4,4 ', 5,5'-tetraphenylbiimidazole.

The oxime compound is, for example, the following chemical formulas 5, 6, 7, and the like.

[Chemical Formula 7]

Moreover, unless the effect of this invention is impaired, you may use together other photoinitiator etc. which are generally used in this field. Other photopolymerization initiators such as benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, anthracene-based compounds, and the like. These can be used individually or in combination of 2 or more types.

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, orthobenzoyl benzoate, 4-phenylbenzophenone, and 4-benzophenyl-4'-methyldiphenyl sulfide. , 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-bis (N, N' -Dimethylamino) benzophenone and the like.

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

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

In addition, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10- Phenanthrenequinone, camphorquinone, methyl phenylacetate, titanocene compound, etc. are used as other photopolymerization initiators.

In the present invention, the (C-1) photopolymerization initiation adjuvant which can be used in combination with the (C) photopolymerization initiator can be preferably selected from one or more compounds selected from the group consisting of an amine compound and a carboxylic acid compound.

Specific examples of the amine compound in the photopolymerization initiation aid include triethanol. Aliphatic amine compounds such as amine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate Ester, 2-dimethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethyl-p-toluidine, 4,4′-bis (dimethylamino) Aromatic amine compounds such as benzophenone (commonly known as lindone) and 4,4′-bis (diethylamino) benzophenone. As the amine compound, an aromatic amine compound can be preferably used.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, and methoxyphenylthio Acetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, etc. Aromatic heteroacetic acids.

In the photosensitive resin composition for transparent pixel formation of the present invention, the content of the (C) photopolymerization initiator is 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the total solid content. (C- 1) The amount of the photopolymerization initiation adjuvant is usually 0.1 to 20% by weight, preferably 1 to 10% by weight on the basis of the foregoing.

When the amount of the (C) photopolymerization initiator is within the above range, the photosensitive resin composition for forming transparent pixels is highly sensitive, and the strength of the pixel portion and the smoothness of the surface of the pixel portion tend to be high. It is preferable because it becomes good. In addition, if the amount of the photopolymerization initiation aid (C-1) is within the above range, the sensitivity efficiency of the photosensitive resin composition for forming transparent pixels becomes high, and the productivity of a color filter formed using the composition tends to be high. It is preferable because it is increased.

(D) Solvent

The solvent (D) contained in the photosensitive resin composition for transparent pixel formation of this invention is not specifically limited, Various organic solvents used in the field of the photosensitive resin composition 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; diethyl ether; Dimethyl glycol ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether And other diethylene glycol dialkyl ethers; methyl cellosolve acetate, ethyl cellosolve acetate and other ethylene glycol alkyl ether acetates; propylene glycol monomethyl ether and other propylene glycol dialkyl ethers Class; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, butyl methoxyacetate, and methoxypentyl acetate, and other alkylene glycol alkyl ether acetates Esters; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone; ethanol, propanol , Butanol, hexanol, cyclohexanol, ethylene glycol, glycerol and other alcohols; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; γ-butyrolactone Isocyclic esters and so on.

Among the solvents, in view of coating properties and drying properties, organic solvents having a boiling point of 100 ° C. to 200 ° C. in the solvent are preferable, and alkylene alcohol alkyl ether acetates and ketones are more preferable. Ester such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, more preferably, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexyl Ketones, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

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

The content of the (D) solvent in the transparent resin-forming photosensitive resin composition of the present invention is usually 60 to 90% by weight based on the total weight of the transparent resin-forming photosensitive resin composition containing the solvent. %, Preferably 70 to 85% by weight. If the content of the (D) solvent is within the range of 60 to 90% by weight based on the above-mentioned calculation, use a roll coater, a spin coater, a slit spin coater, a slit coater (also referred to as a slot film coating) When coating is performed by a coating device such as a printer or an inkjet system, the coating properties tend to be good, so it is preferred.

(E) Additives

When necessary, the photosensitive resin composition for transparent pixel formation of the present invention may be combined with fillers, other polymer compounds, curing agents, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, antiflocculants, and the like ( E) Additives.

Specific examples of the filler include glass, silicon dioxide, and alumina.

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

The curing agent is used to improve deep curing and mechanical strength. Examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

Examples of the epoxy compound include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, and novolac. Epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidylamine resins or brominated derivatives of such epoxy resins, epoxy resins and brominated epoxy resins thereof Aliphatic alicyclic or aromatic epoxy compounds other than derivatives, epoxy of butadiene (co) polymer, epoxy of isoprene (co) polymer, glycidyl (meth) acrylate Ester (co) polymer, triglycidyl isocyanurate, and the like.

Among the curing agents, examples of the oxetane compound include carbonate dioxetane, xylene dioxetane, adipic acid dioxetane, and terephthalate. Oxetane, di-oxetane and the like.

The curing agent may contain, together with the curing agent, a curing auxiliary compound that rings-opens and polymerizes an epoxy group of an epoxy compound and an oxetane skeleton of an oxetane compound. Examples of the curing auxiliary compound include polycarboxylic acids, polycarboxylic anhydrides, and acid generators.

As the carboxylic acid anhydride, a commercially available product can be used as an epoxy resin curing agent. Examples of the epoxy resin curing agent include a trade name (Edico Curing Agent EH-700) (manufactured by Asahi Denki Co., Ltd.), a trade name (RIKACIDHH) (manufactured by Shin Nippon Chemical Co., Ltd.), and a trade name (MH-700) ( (Manufactured by New Japan Chemical Co., Ltd.). The curing agents may be used alone or in combination of two or more.

As the pigment dispersant, a commercially available surfactant can be used, and examples thereof include silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. These substances can be used individually or in combination of two or more kinds use. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, For example, tertiary amine-modified polyurethanes, polyethyleneimines, and the like, in addition to the trade names: KP (made by Shin-Etsu Chemical Industry Co., Ltd.), POLYFLOW (made by Kyoeisha Chemical Co., Ltd.), EFTOP (Tochem Products) (Manufactured by the company), MEGAFAC (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), FLOURAD (manufactured by Sumitomo 3M Co., Ltd.), ASAHI GUARD, SURFLON (above, manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (manufactured by Jerica), EFKA (manufactured by EFKA Chemicals) , PB821 (manufactured by Ajinomoto), etc.

These pigment dispersants can be used singly or in combination of two or more kinds, and are usually 0.01 to 15% by weight based on the solid content in the photosensitive resin composition for forming a transparent pixel.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, and N- (2-aminoethyl) -3. -Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxy Propyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane , 3-isocyanatepropyltriethoxysilane and the like.

These adhesion promoters can be used singly or in combination of two or more, and they are usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on the solid content in the photosensitive resin composition for transparent pixel formation.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, and the like.

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

Specific examples of the agglutination preventive agent include sodium polyacrylate.

The photosensitive resin composition for transparent pixel formation of this invention can be manufactured by the following method, for example. Mixing (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a solvent in an appropriate ratio, and further adding other components to be used as necessary to obtain a target transparent pixel-forming photosensitive agent Sexual resin composition.

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

The method for forming a pattern of the photosensitive resin composition for transparent pixel formation according to the present invention includes a step of selectively coating the transparent pixel forming photosensitive resin composition on the substrate, A stage in which a part of the photosensitive resin composition is exposed and a stage in which an exposed region or a non-exposed region of the photosensitive resin composition for forming a transparent pixel is removed.

One example thereof is to be coated on a substrate as described below, and subjected to photocuring and development to form a pattern, and can be used as a black matrix, or as a colored and transparent pixel (colored image).

First, the composition is applied to a substrate (without limitation, usually glass or silicon wafer) or a layer containing a solid component of a photosensitive resin composition for transparent pixel formation formed previously, and the solvent is removed by pre-drying. Volatile components give a smooth coating film. At this time, the thickness of the coating film is approximately 1 to 3 μm. In order to obtain a target pattern, a specific area of the coating film thus obtained is irradiated with ultraviolet rays through a mask. At this time, it is preferable to irradiate the entire exposure portion with parallel light, and it is preferable to accurately align the mask and the substrate using a device such as a mask aligner or a stepper. In addition, after that, the cured coating film is brought into contact with an alkaline aqueous solution, and the non-exposed regions are dissolved and developed, so that a target pattern can be produced. After development, if necessary, it can be dried at 150 ~ 230 ° C for 10 ~ 60 minutes.

The developing solution used for development after the patterned exposure is usually an aqueous solution containing a basic compound and a surfactant. Basic compounds can also be inorganic and organic basic compounds. Specific examples of the inorganic basic 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 bicarbonate, potassium bicarbonate, boric acid Sodium, potassium borate, ammonium borate, etc.

Specific examples of the organic basic compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, and trimethylamine. Ethylamine, monoisopropylamine, diisopropylamine, ethanolamine, etc. These inorganic and organic basic compounds can be used individually or in combination of 2 or more types.

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

As the surfactant in the alkali developing solution, any of a nonionic surfactant, an anionic surfactant, or a cationic surfactant can be used.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene derivatives, and oxyethylene / oxypropylene blocks. Copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkane Amines, etc.

Specific examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl sulfate and sodium oleate sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and dodecane. Alkyl aryl sulfonates such as sodium benzene sulfonate and sodium dodecylnaphthalene sulfonate.

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

These surfactants can be used alone or in combination of two or more kinds.

The concentration of the surfactant in the alkali developing solution is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, and still 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 by including a pixel formed by forming the photosensitive resin composition for transparent pixel formation into a predetermined pattern and then exposing and developing the same.

The pattern forming method of the photosensitive resin composition for transparent pixel formation is as described above Detailed description is omitted. As described above, the photosensitive resin composition solution for transparent pixel formation is subjected to various operations such as coating, drying, patterning exposure of the obtained dry coating film, and further developing to obtain a photosensitive resin composition equivalent to transparent pixel formation. Object pixels or black matrices. In addition, this operation is repeated by the number of unit pixels required for a color filter to obtain a color filter. Since the structure and manufacturing method of the color filter are well known in the art, detailed description is omitted.

The film thickness difference between the in-plane pixels of the color filter manufactured using the photosensitive resin composition for transparent pixel formation of the present invention is small. For example, the film thickness difference between 1 to 4 μm may be 0.15 μm or less. Or 0.05 μm or less. Therefore, the color filter thus obtained is excellent in smoothness, and by assembling it to a color liquid crystal display device, a liquid crystal display device of excellent weight can be manufactured with a high yield. In addition, if the color filter is used, an imaging element having an excellent weight can be manufactured.

Hereinafter, the present invention will be specifically described through examples, but the present invention is not limited to the examples. In the following examples and comparative examples, "%" and "parts" indicating content are weight basis unless otherwise specified.

<Synthesis example>

Synthesis Example 1-1: Synthesis of reactive alkali-soluble resin A '

Prepare a flask with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen introduction tube. On the other hand, add 84.2 parts of N-benzylmaleimide, 38.7 parts of methacrylic acid, and 22 parts of methyl Tricyclodecyl acrylate, 4 parts of tert-butyl peroxy-2-ethylhexanoate, and 40 parts of propylene glycol monomethyl ether acetate (hereinafter, referred to as "PGMEA") were stirred and mixed to prepare monomer drops. In a liquid funnel, 6 parts of n-dodecyl mercaptan and 24 parts of PGMEA were added and stirred to prepare a chain transfer agent dropping funnel. Thereafter, 395 parts of PGMEA was introduced into the flask, and the atmosphere in the flask was changed from air to nitrogen, and then the temperature of the flask was raised to 90 ° C. while stirring. Next, the monomer and the chain transfer agent were dropped from the dropping funnel. The dropping was maintained at 90 ° C. for 2 hours, and after 1 hour, the temperature was raised to 110 ° C. and maintained for 3 hours. Then, a gas introduction tube was introduced to start foaming of a mixed gas of oxygen / nitrogen = 5/95 (v / v). Next, 14.2 parts of glycidyl methacrylate, 0.4 part of 2,2'-methylenebis (4-methyl-6-tert-butylphenol), and 0.8 part of triethylamine were added to the flask. The reaction was continued at 110 ° C. for 8 hours, and then cooled to room temperature to obtain a resin A ′ having a solid content of 29.1% by weight, a weight average molecular weight of 32,000, and an acid value of 114 mgKOH / g.

Synthesis Example 1-2: Synthesis of reactive alkali-soluble resin A ' (A1-a)

Prepare a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen introduction tube. On the other hand, add 45 parts of N-benzylmaleimide, 45 parts of methacrylic acid, and 10 parts of methyl. Tricyclodecyl acrylate, 4 parts of tert-butyl peroxy-2-ethylhexanoate, and 40 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") were stirred and mixed to prepare a monomer drip. In a funnel, 6 parts of n-dodecyl mercaptan and 24 parts of PGMEA were added and stirred to prepare a chain transfer agent dropping funnel. Thereafter, 395 parts of PGMEA was introduced into the flask, and the atmosphere in the flask was changed from air to nitrogen, and then the temperature of the flask was raised to 90 ° C. while stirring. Next, the monomer and the chain transfer agent were dropped from the dropping funnel. The dropping was maintained at 90 ° C. for 2 hours, and after 1 hour, the temperature was raised to 110 ° C. and maintained for 3 hours. Then, a gas introduction tube was introduced to start foaming of a mixed gas of oxygen / nitrogen = 5/95 (v / v). Next, 10 parts of glycidyl methacrylate, 0.4 part of 2,2'-methylenebis (4-methyl-6-tert-butylphenol), and 0.8 part of triethylamine were added to the flask. The reaction was continued at 110 ° C. for 8 hours, and then cooled to room temperature to obtain a resin A ′ having a solid content of 29.1% by weight, a weight average molecular weight of 32,000, and an acid value of 114 mgKOH / g.

Synthesis Example 2-1: non-reactive alkali-soluble resin A "Synthesis

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube was prepared, and 300 parts of propylene glycol monomethyl ether acetate (PGMEA) was added, followed by stirring and heating to 75 degrees. 13.7 parts by weight of 3,4-epoxy-8- (propenyloxy) tricyclo [5.2.1.02,6] decane (EDCPA), 10.9 parts by weight of acrylic acid (AA), and 26.5 parts by weight of ethylene A solution in which toluene was dissolved in 170 parts by weight of PGMEA was dropped into a flask through a dropping funnel over 5 hours. On the other hand, a solution of 30 parts by weight of the polymerization initiator azobisisobutyronitrile in 200 parts by weight of PGMEA was dropped with another dropping funnel over 5 hours. After the dripping of the polymerization initiator was completed, the temperature was maintained for about 4 hours, and then, it was cooled to room temperature to obtain a resin A " having a solid content of 37.6% by weight, a weight average molecular weight of 10740, and an acid value of 111 mgKOH / g.

Synthesis Example 2-2: Non-reactive alkali-soluble resin A " Synthesis (A2-a)

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube was prepared, and 300 parts of propylene glycol monomethyl ether acetate (PGMEA) was added, followed by stirring and heating to 75 degrees. 76.8 parts by weight of 3,4-epoxy-8- (propenyloxy) tricyclo [5.2.1.02,6] decane (EDCPA) (60 mol%), 10.0 parts by weight of methacrylic acid ( A solution of MAA) (20 mol%) and 19.2 parts by weight of N-cyclohexylmaleimide (20 mol%) in 170 parts by weight of PGMEA was dropped into the flask over a 5 hour period using a dropping funnel. On the other hand, a solution in which 20 parts by weight of the polymerization initiator azobisisobutyronitrile was dissolved in 200 parts by weight of PGMEA was dropped with a dropping funnel over 5 hours. After the dropping of the polymerization initiator was completed, the temperature was maintained for about 4 hours, and then it was cooled to room temperature to obtain a resin A " having a solid content of 37.6% by weight, a weight average molecular weight of 15740, and an acid value of 121 mgKOH / g.

Synthesis Example 2-3 and Comparative Synthesis Examples 1-4: Non-reactive alkali-soluble resin A " Synthesis

The synthesis method is the same as the method of Synthesis Example 2-1. In order to adjust the molecular weight, the content of azobisisobutyronitrile was adjusted, and Synthesis Example 2-3 was produced as described in Table 1 below. Synthesis Examples 1 and 2 and Comparative Synthesis Examples 3 and 4 without N-cyclohexylmaleimide. The mole ratio of the reaction monomer and the synthesis result are shown in Table 1 below.

Evaluation of molecular weight

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

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

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (connected in series)

Column temperature: 40 ° C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0ml / min

Injection volume: 50μl

Detector: RI

Measured sample concentration: 0.6% by weight (solvent = tetrahydrofuran)

Calibration reference materials: TSK STANDARD POLYSTYRENEF-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

Solid content

Approximately 1 g of the polymer solution was weighed and placed in an aluminum cup. After adding about 3 g of acetone to dissolve, it was naturally dried at normal temperature. Then, after drying in a hot air dryer (manufactured by Espek Corporation, trade name: PHH-101) at 160 ° C. for 3 hours under vacuum, it was cooled in a dryer and the weight was measured. The solid content of the polymer solution was calculated from the weight reduction.

Acid value

Accurately weigh 3g of the resin solution, dissolve it in a mixed solvent of 90g of acetone / 10g of water, use thymol blue as an indicator, and use a 0.1N KOH aqueous solution as a titration solution. : COM-555) The acid value of the polymer solution is measured, and the acid value per gram of solid content is obtained from the acid value of the solution and the solid content of the solution.

<Examples and Comparative Examples>

Examples 1 to 7 and Comparative Examples 1 to 5: Production of a photosensitive resin composition for forming transparent pixels

As shown in Table 2 below, after mixing the components, dilute with propylene glycol monomethyl ether acetate to make the overall solid content 18% by weight, and stir well to obtain transparent pictures of Examples 1 to 7 and Comparative Examples 1 to 5. A photosensitive resin composition for element formation.

(A) Alkali-soluble resin

(A ' ) Reactivity: Synthesis Example 1-1

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

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

(C) Photopolymerization initiator: 1,2-octanedione-1- [4- (phenylthio) phenyl] -2-O-benzidine oxime (IRGACURE OXE 01; manufactured by Ciba specialty chemical company)

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

Examples 8 to 11 and Comparative Examples 6 to 12: Production of photosensitive resin composition for forming transparent pixels

After mixing the components as described in Tables 3 and 4 below, propylene glycol monomethyl ether acetate was used. After diluting the entire solid content to 18% by weight, the mixture was sufficiently stirred to obtain a colorless photosensitive resin composition for pixel formation.

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

(C) Photopolymerization initiator: 1,2-octanedione-1- [4- (phenylthio) phenyl] -2-O-benzoxime (IRGACURE OXE 01; manufactured by Ciba specialty chemical company)

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

<Production example of color filter (glass substrate)>

Manufacturing Example 1-11 and Comparative Manufacturing Example 1-12: Manufacturing of color filters

Using the photosensitive resin composition for transparent pixel formation manufactured in Examples 1 to 11 and Comparative Examples 1 to 12, the color filters of Manufacturing Examples 1 to 11 and Comparative Manufacturing Examples 1 to 12 were manufactured, respectively.

That is, the photosensitive resin composition for forming transparent pixels produced in the above-mentioned Examples 1 to 11 and Comparative Examples 1 to 12 was applied on a substrate by a spin coating method, and then placed on a hot plate and maintained at a temperature of 100 ° C for 3 A thin film was formed in minutes. Next, an experimental photomask with a square pattern of 50 μm × 50 μm to 10 μm × 10 μm horizontal and vertical and a line width / space pattern of 1 μm to 100 μm was placed on the film, and the experimental photomask was irradiated with ultraviolet rays at 300 μm intervals.

電機公司製造的超高壓水銀燈(商品名USH-250D)，在大氣氣氛下、使用50mJ/cm²的曝光量(365nm)進行光照射，不使用特殊的濾光器。將所述紫外線照射的薄膜在pH為10.5的KOH水溶液顯影溶液中浸漬80秒後顯影。將覆蓋所述薄膜的玻璃板用蒸餾水洗淨後，噴射氮氣並乾燥，用230℃的加熱爐加熱25分鐘，來製造濾色器。所製造的濾色器的薄膜厚度為3.0μm。 At this time, the ultraviolet light source is used

The ultra-high pressure mercury lamp (trade name USH-250D) manufactured by Denki Co., Ltd. irradiates light with an exposure amount (365 nm) of 50 mJ / cm ² in an atmospheric atmosphere, without using a special filter. The ultraviolet-irradiated film was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 80 seconds and developed. After the glass plate covering the film was washed with distilled water, nitrogen was sprayed and dried, and then heated in a heating furnace at 230 ° C. for 25 minutes to produce a color filter. The film thickness of the manufactured color filter was 3.0 μm.

<Experimental example>

Measurement of residual film rate

Each of the transparent resin-forming photosensitive resin compositions was coated on a glass substrate by a spin coating method, and then placed on a hot plate and held at a temperature of 100 ° C for 3 minutes to form a thin film. The whole was exposed without a mask. After irradiating ultraviolet rays of 50 mJ / cm ² under the lower layer, the film thickness of the pattern was measured with a film thickness measuring device (DEKTAK6M; manufactured by Veeco). The substrate after the thickness measurement was completed was immersed again in a KOH aqueous solution developing solution having a pH of 10.5 for 80 seconds, and the thickness was measured after development.

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

When the residual film rate is 85% or less, it is judged that the deterioration of the film hardness and the remaining effects of the process are large.

Observation of contact hole size and tapered tail

Place the substrate manufactured in the previous example, observe the 40 μm x 40 μm square contact hole in the photomask, measure the size of the contact hole, observe the tapered tail, and take a photo.

OM equipment: ECLIPSE LV100POL made by Nikon

Evaluation criteria for conical tailing

O: No tapering

△: One side of the tapered tail is less than 2 μm

X: One side of the tapered tail is more than 3 μm

The contact hole size, conical smear, and exposure / development residual film ratio of the color filter were measured and evaluated as follows. The results are shown in FIG. 1 and Tables 5 to 7 below.

Referring to FIG. 1 and the aforementioned Table 5, when (A ' ) the reactive alkali-soluble resin and (A " ) the non-reactive alkali-soluble resin of the present invention are mixed and used at 8: 2 to 1: 7, as in Production Examples 1 to 7 , Minimal taper smearing or minimizing taper smearing, can obtain the appearance of beautiful contact holes, and also can obtain the result that the residual film rate should meet more than 85%. It can be known in other proportions, such as comparing manufacturing examples 1 to 5 , The contact hole is blocked, or even if the contact hole is beautiful, the residual film rate is too low or the tapered tail is large.

Measurement of heat resistance

The color filter forming the transparent pixel is further heated in a heating furnace at 230 ° C. for 120 minutes, and the thickness of the transparent pixel pattern is measured.

Heat resistance (%) = thickness after additional baking (μm) / thickness before additional baking (μm)

When the heat resistance is below 96%, the surface of the LCD panel is wrinkled when it is manufactured.

Measurement of chemical resistance

After the color filter forming the transparent pixel was immersed in a chemical resistance evaluation solvent N-methyl-2-pyrrolidone (NMP) for 30 minutes at 60 ° C, the thickness of the transparent pixel pattern was measured.

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

When the chemical resistance is 110% or more, the phenomenon of swelling of the coating film rises severely, and there are problems that cause process defects and surface wrinkles.

Measurement of fine patterns

In the color filter forming the transparent pixels, the pattern size obtained by a line width / space pattern mask of 100 μm was measured by an OM equipment (ECLIPSE LV100POL Nikon Corporation).

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

If the value of the fine pattern is larger than 10 μm, it is difficult to realize fine pixels. If the value is negative, there is a case that the process is defective.

Evaluation of flatness

The substrate manufactured in the foregoing example was placed, and the entire thickness curve of a portion with a line width dimension of 50 μm and a space dimension of 100 μm in the blue pattern applied once was evaluated (see FIGS. 2 and 3). The measurement was performed using a film thickness measuring device DEKTAK6M (manufactured by Veeco).

The flatness calculation of the curve data of the measured film thickness was performed by the following method. With the center of the interval as the reference point, as the x value of the thickness difference between the surface and the reference line, only the interval length of 5% or less of the reference thickness (from the reference point) was measured.

Flatness (%) = (interval length with X value below 5% of reference thickness) / overall interval length

When the flatness is less than 80%, the liquid crystal driving in the upper part of the pixel is affected, and the light characteristics are reduced.

Evaluation of surface anomalies

The substrate manufactured in the foregoing example was visually judged.

Whether the surface is abnormal: Good level-no surface foreign matter is observed, poor level-surface whitening is observed.

When the state of the surface exhibits a whitening phenomenon, it has no practical value as a transparent pixel formation application. The evaluation results of the residual film development rate, heat resistance, chemical resistance, fine pattern, flatness, and surface abnormality of the color filter are shown in Tables 6 and 7 below.

When 8: 2 ~ 1: 7 is used and the (A ' ) reactive alkali-soluble resin and (A " ) non-reactive alkali-soluble resin of the present invention are mixed and used, as shown in Examples 8-11, the residual film development rate is obtained. As a result of excellent heat resistance and chemical resistance, in other ratios, such as Comparative Examples 6 and 7, the fine pattern changes greatly, and there are problems in forming small patterns compared to the size of the mask pattern. In addition, non-reactive adhesion When there is no dicarbonylamidoimine derivative in the monomer of the agent (A ' ), as in Comparative Example 11, sufficient flatness cannot be ensured, and when the molecular weight is increased in order to ensure flatness, as in Comparative Example 12, it is not possible due to surface abnormalities. Make good patterns.

On the other hand, even if the dicarbonylfluorenimine derivative is included, Comparative Example 8 having a small molecular weight has insufficient flatness, and Comparative Example 9 has a problem that the molecular weight is too high and the change in the fine pattern is large.

According to the present invention, 8: 2 to 1: 7 mixture (A ') with a reactive alkali-soluble resin (A ") a non-reactive alkali-soluble resin, in this case (A") a non-reactive monomer alkali-soluble resin It is a copolymer polymerized with (A " 3), (A " 4), and (A " 5). When the molecular weight is 10,000 to 30,000, it has excellent developing residual film rate, heat resistance, chemical resistance, and flatness, and can be formed. Enables transparent pixels with fine patterns.

Claims (8)

A photosensitive resin composition for forming transparent pixels. The photosensitive resin composition for forming transparent pixels contains (A) 20 to 85 weights relative to the solid content in the photosensitive resin composition for forming transparent pixels. % Alkali-soluble resin; (B) 10 to 60% by weight of a photopolymerizable compound; and (C) 0.1 to 20% by weight of a photopolymerization initiator; the (A) alkali-soluble resin is (A ' ) to free Alkali-soluble resins that are reactive with a base photoinitiator and UV irradiation and (A " ) alkali-soluble resins that are non-reactive with radical photoinitiators and UV irradiation are alkali-soluble with a weight ratio of 8: 2 to 1: 7 Resin; the molecular weight of the alkali-soluble resin (A " ) which is non-reactive to radical photoinitiators and UV irradiation is 10,000 to 30,000. The transparent pixel according to a request item for forming a photosensitive resin composition, wherein the (A ') by including (A of a free radical photoinitiator, and UV irradiation of the alkali-soluble resin is to make the reaction' ) A copolymer produced by polymerizing a compound having an unsaturated bond and a carboxyl group in one molecule and (A ′ 2) a compound having a compound having a polymerizable unsaturated bond with (A ′ 1), and (A ′ 3) a A copolymer obtained by further polymerizing a compound having an unsaturated bond and an epoxy group in a molecule. Forming a photosensitive resin composition, wherein the unsaturated bond and a carboxyl group of the (A '1) in a molecule having the transparent pixel 2 according to a request item from the group consisting of acrylic acid, methacrylic acid and crotonic acid Monocarboxylic acids; dicarboxylic acids containing fumaric acid, mesaconic acid and itaconic acid, and anhydrides of said dicarboxylic acids; and ω-carboxy polycaprolactone mono (meth) acrylates having at both ends One or more members selected from the group consisting of mono (meth) acrylates of carboxyl and hydroxy polymers, and the compound (A ′ 2) having an unsaturated bond polymerizable with (A ′ 1) is unsaturated Substituted or unsubstituted carboxylic acid alkyl ester compounds, unsaturated carboxylic acid ester compounds containing alicyclic substituents, unsaturated carboxylic acid ester compounds containing heat-curable substituents, and ethylene glycol monosaturated carboxylic acids One or more selected from the group consisting of an ester compound, an unsaturated carboxylic acid ester compound containing a substituent having an aromatic ring, an aromatic vinyl compound, a vinyl carboxylic acid ester, and a vinyl cyanide compound; Substituted or unsubstituted alkyl esters The compound contains methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and aminoethyl (meth) acrylate; said containing The unsaturated carboxylic acid ester compound of an alicyclic substituent includes cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methyl cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, Cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, (methyl ) Cyclooctenyl acrylate, Menthenedi (meth) acrylate, Isobornyl (meth) acrylate, Pinane (meth) acrylate, Adamantane (meth) acrylate, (Meth) acrylate Bornyl ester and methacrylate (meth) acrylate; the unsaturated carboxylic acid ester compound containing a heat-curable substituent comprises 3-((meth) acryloxymethyl) oxetane, 3 -((Meth) acryloxymethyl) -3-ethyloxetane, 3-((meth) acryloxymethyl) -2-methyloxetane, and 3 -((Meth) acryloxymethyl) -2-tri Fluoromethyloxetane; the ethylene glycol-based monosaturated carboxylic acid ester compound includes an oligoethylene glycol mono (meth) acrylic acid alkyl ester; the unsaturated carboxylic acid including a substituent having an aromatic ring The ester compound includes benzyl (meth) acrylate and phenoxy (meth) acrylate; the aromatic vinyl compound includes styrene, α-methylstyrene, and vinyl toluene; and the vinyl carboxylate includes the vinyl cyanide compound comprises a compound of (meth) acrylonitrile and α- chloro acrylonitrile, the (a '3) a molecule having an unsaturated bond and an epoxy group; vinyl acetate and vinyl propionate It consists of glycidyl (meth) acrylate, -3,4-epoxycyclohexyl (meth) acrylate, -3,4-epoxycyclohexyl methyl (meth) acrylate, and (meth) ) One or more selected from the group consisting of methyl glycidyl acrylate. The photosensitive resin composition for transparent pixel formation according to claim 1, wherein the (A " ) alkali-soluble resin that is non-reactive to radical photoinitiators and UV irradiation is obtained by including (A " 1) The copolymer produced by the polymerization of a compound having an unsaturated bond and a carboxyl group in the molecule, and a compound having (A " 2) a compound having a polymerizable unsaturated bond with (A " 1), is a molecule of the resin after the polymerization is completed. No polymerizable unsaturated double bond copolymer is present in the chain. The photosensitive resin composition for transparent pixel formation according to claim 1, wherein the (A " ) alkali-soluble resin that is non-reactive to a radical photoinitiator and UV irradiation passes through the (A " 3) molecule Compounds having an unsaturated bond and a carboxyl group, (A " 4) an aliphatic polycyclic compound having an epoxy group and an unsaturated bond, and (A " 5) having the same properties as (A " 3) to (A " 4) The copolymer produced by the polymerization of a polymerizable unsaturated bond dicarbonylsulfonium imine derivative is a copolymer having no polymerizable unsaturated double bond in the molecular chain of the resin after the polymerization is completed. The photosensitive resin composition for transparent pixel formation according to claim 5, wherein the (A " 4) aliphatic polycyclic compound having an epoxy group and an unsaturated bond is selected from dicyclopentane and tricyclic One or more selected from the group consisting of decane, norbornane, isonorbornane, bicyclooctane, cyclononane, bicycloundecane, tricycloundecane, bicyclododecane, and tricyclododecane. The photosensitive resin composition for transparent pixel formation according to claim 1, wherein the (A " 4) aliphatic polycyclic compound having an epoxy group and an unsaturated bond contains a compound represented by the following Chemical Formula 1 And at least one compound selected from the group consisting of a compound represented by the following Chemical Formula 2,

In the chemical formulas 1 and 2, R is each independently a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms substituted or unsubstituted by a hydroxyl group, and X is each independently a single bond, or a group containing or not containing a hetero atom. An alkylene group having 1 to 6 carbon atoms. A color filter formed using the photosensitive resin composition for forming a transparent pixel according to any one of claims 1 to 7.