JP2007269970A - Colored resin composition, color filter and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored resin composition excellent in high-definition/fine pattern-processing and production stability and provided by using a polyimide precursor comprising 4,4'-oxydiphthalic acid dianhydride, so as to produce high-performance/high-quality color filters and liquid crystal displays, required by recent development of high-performance liquid crystal displays. <P>SOLUTION: The colored resin composition comprises a polyimide precursor having both of an amic acid structure, provided by reacting 4,4'-oxydiphthalic acid dianhydride with a diamine, and an imide structure, provided by imide ring closure of the amic acid structure, a solvent and a pigment, wherein amic acid equivalent M<SB>1</SB>of the polyimide precursor represented by formula (1) is ≥530 but ≤640. In formula (1), X is imide ring closure rate (%); and M<SB>0</SB>is the molecular weight of recurring unit of the polyimide precursor amic acid structure when supposed that the imide is not ring-closed. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a colored resin composition comprising a polyimide precursor, a solvent, and a pigment, and further relates to a color filter and a liquid crystal display device used in a liquid crystal display device produced using the colored resin composition. is there.

  Polyimide resins are widely used as electronic materials because of their excellent heat resistance, electrical insulation, toughness, and chemical resistance. Generally, aromatic tetracarboxylic dianhydrides and aromatic diamines are combined with N. -A polyimide precursor obtained by addition polymerization in an aprotic polar solvent such as methyl-2-pyrrolidone is used after imide ring closure. In particular, in electronic material applications, a solution in which a polyimide precursor is uniformly dissolved in a polar solvent such as N-methyl-2-pyrrolidone or γ-butyrolactone, or a polyimide precursor and a pigment, filler, etc. are uniformly dissolved in a polar solvent or After the dispersed solution is applied to a silicon wafer or glass substrate, solvent drying is performed at 100 to 150 ° C., patterning is performed by photolithography, and imidization is completed at a high temperature of 250 to 300 ° C. or more to obtain polyimide. For each application.

  Regarding the pattern processability of the surface protective film of the semiconductor element and the interlayer insulating film, the polyimide resin precursor with the imide ring closure rate adjusted to 5 to 40%, focusing on the ratio of the amic acid structure to the imide structure in the polyimide precursor Is disclosed (Patent Document 1), but there is no description regarding a colored pigment composition in which a pigment is dispersed in a polyimide precursor or a color filter for a liquid crystal display device.

  In a color filter for a color liquid crystal display device, a plurality of different colored pixels (for example, a resin black matrix and three primary colors of red, green, and blue light) are regularly arranged on a transparent substrate. As a method for producing a color filter, a photosensitive coloring composition is applied to a transparent substrate and patterned by photolithography to form colored pixels, and a non-photosensitive coloring resin composition and a photosensitive positive resist are formed on the transparent substrate. In general, a method is used in which colored pixels are formed by applying a pattern and processing a pattern by a photolithography technique. In the case of a color filter having a polyimide precursor as a main component of a colored pixel, a method using a non-photosensitive coloring composition in which a pigment is dispersed in a polyimide precursor solution is generally used.

  A composition in which a pigment is dispersed in a polyimide precursor solution obtained by reacting an aromatic or aliphatic tetracarboxylic dianhydride with a diamine compound, and the use thereof relates to light resistance used in liquid crystal displays and image sensors. A composition composed of a polyimide precursor and pigment for a color filter having excellent properties, heat resistance, chemical resistance, and the like, and a color filter formed using the same are known (for example, Patent Documents 2 and 3, 4). Furthermore, it is disclosed that a colored resin composition using a polyimide precursor having a molecular weight in a repeating unit of a polyimide precursor of 500 or less exhibits good pattern forming properties (Patent Document 5). None of these Patent Documents 2 to 5 describes the imide cyclization rate, and only Patent Document 5 describes that the development characteristics are improved by the molecular weight of the repeating unit. However, this Patent Document 5 also relates to the imide cyclization rate of the imide precursor. There is no description about the amic acid concentration.

On the other hand, it is disclosed that a high-quality color filter can be obtained using an evaluation method of imide ring closure rate by ¹ H-NMR of a polyimide precursor and a polyimide precursor having an imide ring closure rate of 5% to 20%. (Patent Document 6), there is no description regarding the molecular weight of the repeating unit in the polyimide precursor and no description regarding the amic acid concentration.

  Moreover, about the coloring resin composition using the polyimide precursor which consists of 4,4'- oxydiphthalic dianhydride, the polyimide precursor which used the aromatic tetracarboxylic dianhydride which has a diphenyl ether group was used, for example. By using the blue resin composition, the transmittance of the blue coating film is improved (Patent Document 7), and the color filter for a color filter using a mixture of polyimide precursors composed of 4,4′-oxydiphthalic dianhydride is used. A molecular thin film (Patent Document 8), a black resin composition composed of a polyimide precursor composed of 4,4′-oxydiphthalic dianhydride and titanic nitride is disclosed (Patent Document 9). Even in the patent literature, there is no description of the imide ring closure rate of the polyimide precursor, and there is also a description of the molecular weight of the repeating unit of the polyimide precursor. Not all be listed on Mick acid concentration.

  Furthermore, in recent years, with the improvement in performance of liquid crystal display devices, the color filter is required to have a high aperture ratio and high definition in mobile applications typified by color mobile phones. In order to increase the aperture ratio of the color filter, the linear light-shielding portion between adjacent openings in the black matrix is thinned. For high definition, the pitch width of the openings is reduced.

  In particular, in a transflective liquid crystal display device, which is the mainstream of liquid crystal display devices for color mobile phones, a transmissive region and a reflective region are provided in an opening in one pixel of a color filter, and chromaticity of reflection and transmission is further provided. Therefore, it is known to perform fine hole processing with a small diameter of several to several μm on the colored pixels in the reflective region (Non-patent Document 1). With such high definition, it is necessary to perform fine hole processing with high precision between narrow pixel pitches, and there is manufacturing variation in the processing area of the hole, and there is a residue of the colored resin composition in the hole. In such a case, there is a problem that the color varies in the reflected color display of the liquid crystal display device or the design color cannot be displayed.

  Colored resin composition using a conventionally known polyimide precursor made of 4,4'-oxydiphthalic dianhydride in high-definition and fine pattern processing of color filters, which has been demanded by high performance liquid crystal display devices in recent years Objects have various problems in high-definition and fine pattern processing.

For example, in the case of a colored resin composition for a resin black matrix, the edge shape of the black matrix pattern is poor and the patterning accuracy of fine portions is poor. The problem of light leakage occurs.
In the case of a colored resin composition of the three primary colors of red, green, and blue light, particularly in a color filter that requires a semi-transmissive hole processing, the patterning accuracy of the hole processing is poor, and the processing area of the hole As a result, there arises a problem that the designed color cannot be displayed in the reflective display due to the residue of the colored resin composition in the hole.

  The processing stability of a colored resin composition using a conventionally known 4,4′-oxydiphthalic dianhydride polyimide precursor in high-definition and fine pattern processing is the pattern processability of the polyimide precursor as a resin component. Depends heavily on. The pattern processability of the polyimide precursor largely depends on the ratio of the amic acid structure in which diamine is added to 4,4′-oxydiphthalic dianhydride and the imide structure formed by imide ring closure of the amic acid structure, and at the same time, the polyimide The study by the present inventors shows that it depends greatly on the molecular weight of the repeating unit constituting the precursor, and that one of the elements alone cannot solve the problem in high-definition and fine pattern processing. It became clear.

  The reason is that the amic acid structure in the polyimide precursor composed of 4,4′-oxydiphthalic dianhydride is soluble in an organic solvent and an alkaline developer suitably used for pattern processing, while an imide structure Are generally insoluble in organic solvents and such alkaline developers due to their strong intramolecular interactions. Furthermore, even if there is an amic acid structure that is soluble in an organic solvent or an alkaline developer, the concentration of amic acid is low, that is, if the amount of the amic acid structure in the polyimide precursor is small, it is disclosed in Patent Document 5. Even if only the molecular weight of the repeating unit of the polyimide precursor is small, or only the imide ring closure rate, which is just a ratio of the amic acid structure and the imide structure, as disclosed in Patent Documents 1 and 6, is low. The organic solvent and alkali solubility of the polyimide precursor are deteriorated. On the other hand, even if the ratio of the imide structure is high and the imide structure is insoluble in the alkaline developer, the concentration of the amic acid is high if the molecular weight of the repeating unit is sufficiently small. The solubility in the liquid is good.

The polyimide precursor composed of 4,4′-oxydiphthalic dianhydride is used as a raw material for acid dianhydride and diamine, particularly when used as a pigment-dispersed colored resin composition for liquid crystal display devices and color filters. When the molecular weight in the repeating unit determined from the structure and composition at the time of synthesis is M _{0, and} the imide cyclization rate of _the synthesized polyimide precursor is X, the coloring depends on the amic acid concentration in the polyimide precursor determined by M ₀ and X It has been clarified by the present inventors that the solubility of the polyimide precursor in the resin composition, the pigment dispersibility in the colored resin composition, and the coating property of the colored resin composition change.

  As for solubility, polymer precipitates were deposited in the colored paste due to poor solubility of the polyimide precursor composed of 4,4′-oxydiphthalic dianhydride. If the grain size is larger than the cell gap when bonded to the substrate, the color filter and the counter substrate are energized and short-circuited, resulting in display defects. In the pattern processability, with respect to the developed portion of the coating film obtained from the colored paste, the lower the amic acid concentration, that is, the smaller the amount of the amic acid structure in the repeating unit, the worse the solubility in the developer, and the glass substrate On top, it becomes a residue of the colored resin composition, the light transmittance and color characteristics are greatly impaired, and the higher the amic acid concentration of the polyimide precursor, the better the solubility.

In addition, it is known that the imide ring closure reaction generally proceeds at 0 ° C. or higher, and at the time of producing a polyimide precursor comprising 4,4′-oxydiphthalic dianhydride, an addition polymerization usually performed at 40 to 100 ° C. In parallel with the reaction, an imide ring closure reaction of an amic acid structure also occurs. Therefore, in the obtained polyimide precursor, an amic acid structure and an imide structure always coexist in the molecule, and as described above, the amic acid concentration of the polyimide precursor is particularly important in color filter applications. Conventionally, as a polyimide precursor, an imide cyclization ratio X which is a simple ratio between an amic acid structure and an imide structure as disclosed in Patent Documents 1 and 6, or a polyimide precursor as disclosed in Patent Document 5 is used. either repeating unit determined by the constituents of molecular weight M ₀ whereas only has not been taken into consideration.

In recent years, with the high-definition and fine pattern processing required for color filters as the performance of liquid crystal display devices increases, a conventionally known polyimide precursor composed of 4,4′-oxydiphthalic dianhydride or its polyimide precursor mixture is used. The inventors have clarified that the concentration of amic acid in the polyimide precursor is not in an appropriate range. Furthermore, the present inventors paid attention to both the molecular weight M ₀ of the repeating unit of the polyimide precursor using 4,4′-oxydiphthalic dianhydride and the imide ring closure rate X, and the concentration of amic acid in the polyimide precursor and As a result of intensive studies on the relationship between the colored resin composition and high-definition and fine pattern formation, a polyimide precursor composed of 4,4′-oxydiphthalic dianhydride and a polyimide precursor mixture containing the polyimide precursor As an index of the amic acid concentration of the polyimide precursor, from the imide ring closure rate X (%) obtained by measurement of the amide residue by ¹ H-NMR method, and the acid dianhydride and diamine as the constituent components of the polyimide precursor Amic acid equivalent M ₁ defined by the following formula (1) from molecular weight M ₀ in a repeating unit calculated as a polyamic acid structure Was found to be an important indicator. Here, the polyimide precursor having a higher amic acid concentration has a smaller amic acid equivalent defined by the following formula (1), and the lower the amic acid concentration, the larger the amic acid equivalent.

Furthermore, in a specific region different from the conventionally known range in the polyimide precursor in which the amic acid equivalent M ₁ is reacted with 4,4′-oxydiphthalic dianhydride and diamine, stable production of high-definition and fine pattern formation is achieved. It was found that a colored resin composition capable of being obtained was obtained, and reached the present invention.
JP-A-3-157427 JP 60-184202 A JP 60-184203 A JP-A-61-180203 JP-A-10-163112 JP 2003-183392 A JP-A-10-170714 JP 2000-136253 A Japanese Patent Laid-Open No. 2004-4651 Kubota's "Color filter for high color reproducibility LCD" monthly display, published in June 2003, p74-79

  The object of the present invention is to produce high-performance and high-quality color filters that are required in accordance with the recent high performance of liquid crystal display devices, and to produce high-performance liquid crystal display devices using the same, so that high-definition and fine patterns are used. Another object of the present invention is to provide a colored resin composition using a polyimide precursor composed of 4,4′-oxydiphthalic dianhydride having excellent processability and production stability.

The object of the present invention is achieved by the following constitution.
Colored resin composition containing a polyimide precursor having both an amic acid structure obtained by reacting 4,4′-oxydiphthalic dianhydride and diamine and an imide structure formed by imide ring closure of the amic acid structure, a solvent, and a pigment A colored resin composition characterized in that an amic acid equivalent M ₁ of a polyimide precursor represented by the following formula (1) is 530 or more and 640 or less,

(Here, X represents the imide ring closure rate (%), and M ₀ represents the molecular weight in the repeating unit of the amic acid structure of the polyimide precursor when it is assumed that no imide ring closure occurs.)
Further, a first polyimide precursor having both an amic acid structure obtained by reacting 4,4′-oxydiphthalic dianhydride and a diamine and an imide structure formed by imide ring closure of the amic acid structure, -An amic acid structure in which at least one acid dianhydride selected from biphenyltetracarboxylic dianhydride, 4,4'-benzophenone tetracarboxylic dianhydride, or pyromellitic dianhydride and a diamine are reacted; and A colored resin composition containing a second polyimide precursor having a imide structure formed by imide ring closure of an amic acid structure, a solvent, and a pigment, the first and second formulas represented by the following formula (2): A colored resin composition characterized in that the weight average equivalent M of the amic acid equivalent of the second polyimide precursor is 530 or more and 640 or less,

(Where X1 is the imide ring closure rate (%) of the first polyimide precursor, X2 is the imide ring closure rate of the second polyimide precursor, and (M1) ₀ is the case where it is assumed that no imide ring closure occurs. The molecular weight in the repeating unit of the amic acid structure of the first polyimide precursor, (M2) ₀ is the molecular weight in the repeating unit of the amic acid structure of the second polyimide precursor, assuming that the imide is not ring-closed, α1 is (The weight fraction of the first polyimide precursor, α2, represents the weight fraction of the second polyimide precursor, respectively, and α1 + α2 = 1.)
Furthermore, the diamine component is at least paraphenylenediamine, metaphenylenediamine, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylsulfone, 4 , 4′-diaminodiphenylsulfone, 9,9′-bis (4-aminophenyl) fluorene, bis-3- (aminopropyl) tetramethylsiloxane, a colored resin composition, and further black It is a colored resin composition characterized in that it is at least one pigment selected from a pigment, a blue pigment, and a purple pigment, and the black pigment is at least one selected from carbon black and titanium oxynitride A colored resin composition characterized by being a black pigment, A colored resin composition comprising at least one pigment selected from a blue pigment and a violet pigment, and further having a pixel comprising a colored layer provided in a desired pattern for each of a plurality of colors A color filter characterized by using these colored resin compositions in a filter, and further a liquid crystal display device characterized by using this color filter.

  In a colored resin composition containing a polyimide precursor comprising 4,4′-oxydiphthalic dianhydride and / or a polyimide precursor mixture containing the polyimide precursor, a solvent, and a pigment, In order to provide a colored resin composition excellent in processability and processing stability in a high-definition / fine pattern for the production of high-performance and high-quality color filters required in accordance with performance enhancement, the polyimide precursor or the Colored resin composition using the polyimide precursor or the mixture as a result of diligent investigation on high-definition / fine pattern processing using an amic acid equivalent and a colored resin composition, using an amic acid equivalent as an index of the amic acid concentration of the mixture , An amic acid equivalent of a polyimide precursor composed of a conventionally known 4,4′-oxydiphthalic dianhydride Found that there is a specific area in high-definition and fine-pattern processing that cannot be achieved at the equivalent of amic acid, and the high-performance and high-quality color filters required as the performance of liquid crystal display devices in recent years increases. An object of the present invention is to provide a colored resin composition excellent in processability and process stability of high-definition and fine pattern processing that can be suitably used for production.

  Hereinafter, the present invention will be described in more detail. The polyimide precursor in the present invention is a linear polymer obtained by reacting acid dianhydride and diamine, and is a polymer having a weight average molecular weight of 2000 or more.

  The polyimide precursor in the present invention is generally obtained by addition polymerization at 40 to 100 ° C. and is usually represented by the following general formula (4) in an amic acid represented by a repeating unit of a structural unit represented by the following general formula (3). ) And a polyimide precursor having both structures of the following general formula (5) and imide structure represented by the following general formula (6).

In the above general formulas (3) to (6), R ₁ is a tetravalent organic group having 2 to 22 carbon atoms, R ₂ is a divalent organic group having 1 to 22 carbon atoms, and n is 1 or 2.

  In general, aromatic acid dianhydrides and / or diamines are preferably used since heat resistance and insulation are required.

  As the acid dianhydride in the present invention, 4,4′-oxydiphthalic dianhydride is an essential component, but 4,4′-oxydiphthalic dianhydride and 2 known aromatic tetracarboxylic dianhydrides are used. It can be used in combination of more than one species. Further, a polyimide precursor composed of 4,4'-oxydiphthalic dianhydride and a polyimide precursor composed of a known acid dianhydride that does not necessarily require 4,4'-oxydiphthalic acid may be mixed. As the aromatic tetracarboxylic acid in the present invention, in addition to 4,4′-oxydiphthalic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride Anhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-paraterphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-meta A terphenyl tetracarboxylic dianhydride is mentioned. More preferably, 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-benzophenone tetracarboxylic dianhydride, or pyromellitic dianhydride is used. Further, when a fluorine-based tetracarboxylic dianhydride is used, a polyimide precursor composition that can be converted into a polyimide having good transparency in a short wavelength region can be obtained. Specific examples thereof include 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride and the like. One or two or more of these aromatic tetracarboxylic dianhydrides can be used in combination.

  Examples of aromatic diamines include paraphenylene diamine, metaphenylene diamine, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 1,3-bis (4-aminophenoxy) benzene, 1 , 4-bis (4-aminophenoxy) benzene, 2,2-bis (trifluoromethyl) benzidine, 9,9′-bis (4-aminophenyl) fluorene Can be used. More preferably, at least part of the diamine component is paraphenylenediamine, metaphenylenediamine, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl. It is preferably one or a mixture of two or more selected from sulfone, 4,4′-diaminodiphenylsulfone, and 9,9′-bis (4-aminophenyl) fluorene.

  Furthermore, if necessary, an acid anhydride such as maleic anhydride or phthalic anhydride may be added as a terminal blocking agent. In addition to aromatic compounds, Si-based acid anhydrides and / or diamines are preferably used for the purpose of improving adhesion to inorganic materials such as glass plates and silicon wafers. In particular, when a siloxane diamine typified by bis-3- (aminopropyl) tetramethylsiloxane is used, the adhesion to an inorganic substrate can be improved. Siloxane diamine is usually used in an amount of 1 to 20 mol% in the total diamine. If the amount of siloxane diamine is too small, the effect of improving the adhesiveness is not exhibited, and if it is too large, the heat resistance is lowered.

  In addition, the use of an alicyclic compound as a part of acid dianhydride and / or diamine for improving optical properties such as low birefringence does not hinder the present invention. The alicyclic compound may be a known one. Specific examples include 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, Bicyclo [2.2.1] heptane-2-endo-3-endo-5-exo-6-exo-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane -2-exo-3-exo-5-exo-6-exo-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6- Tetracarboxylic dianhydride, decahydro-dimethananaphthalenetetracarboxylic dianhydride, bis [2- (3-aminopropoxy) ethyl] ether, 1,4-butanediol-bis (3-aminopropyl) ether Ter 3,9-bis (3-amino (Lopyl) -2,4,8,10-tetraspiro-5,5-undecane, 1,2-bis (2-aminoethoxy) ethane, 1,2-bis (3-aminopropoxy) ethane, triethylene glycol-bis (3-aminopropyl) ether, polyethylene glycol-bis (3-aminopropyl) ether, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro-5,5-undecane, 1, 4-Butanediol-bis (3-aminopropyl) ether or the like is used.

  The synthesis of the polyimide precursor is generally performed by reacting tetracarboxylic dianhydride and diamine in a polar organic solvent. At this time, the polymerization degree of the polyamic acid obtained can be adjusted by the mixing ratio of tetracarboxylic dianhydride and diamine. As the solvent, amide polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide are used, and lactone is used to enhance the dispersion effect of the pigment as the colorant. Also preferred is a solvent comprising a main component or a lactone alone. Here, the solvent containing lactones as a main component refers to a solvent that is a mixed solvent and has a maximum weight ratio of the total amount of lactone solvents in the mixed solvent to the total solvent. Lactones are aliphatic cyclic esters having 3 to 12 carbon atoms. Specific examples include, but are not limited to, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, and the like. In particular, γ-butyrolactone is preferable from the viewpoint of solubility of the polyimide precursor. Examples of solvents other than lactones include, in addition to the above amide polar solvents, for example, 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, propylene glycol mono-methyl ether. Propylene glycol mono-methyl ether acetate, dipropylene glycol mono-methyl ether, tripropylene glycol mono-methyl ether, propylene glycol mono-tertiary-butyl ether Ter, isobutyl alcohol, isoamyl alcohol, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, butyl cellosolve acetate, methyl carbitol, methyl carbitol acetate, ethyl carbitol, ethyl carbitol acetate, etc. But not limited to

In the polyimide precursor of the present invention, the imide cyclization rate means the imide cyclization rate X determined by measurement of an amide residue by ¹ H-NMR method. The imide ring closure rate is calculated by the following formula (7) from the quantitative ratios of the above general formulas (4) and (5).

(In the formula 7, x ₁ represents the general formula (4) in quantitative ratio of the amide residue, the quantitative ratio of the amide residues in x ₂ in the general formula (5).)
In the structure of the general formula (6), since no amide proton is present, the content rate cannot be measured in the ¹ H-NMR method, but it is stochastic depending on the ratio of the general formula (4) and the general formula (5). It may be considered that the structure of the above general formula (6) exists, and the imide ring closure rate X (%) defined by the formula (7) is used as the imide ring closure rate in the present invention.

In the present invention, as a quantitative method of the imide ring closure rate of such polyimide precursor, using ^{1 H-NMR} method. Specifically, using the quantitative value of the amide residue in the formula (7) as the peak area value of amide hydrogen in ¹ H-NMR, the structure represented by the general formula (4) and the general formula (5) is quantified. To do. When the separation of the amide hydrogen peak is not good, after performing peak splitting in the spectrum, the structure represented by the general formula (4) and the general formula (5) is quantified. ^By measuring the imide ring closure rate of the polyimide precursor in a liquid state using ¹ H-NMR method, the imide ring closure rate can be quantified simply and accurately. ^As measurement conditions for ¹ H-NMR measurement, known conditions can be applied. As a method for adjusting the object to be measured provided in a liquid state, a polyimide precursor solution usually provided at a polyimide precursor concentration of 5 to 50% is one or more deuterated solvents that do not impair the solubility of the polyimide precursor. A dilution method is used. Diluent solvents include dimethyl sulfoxide deuteride or dimethylformamide deuteride. The concentration of the polyimide precursor in the measurement object provided in the liquid state is preferably 10 g / L or more and 500 g / L or less as a weight concentration. Further, the deuteride used for diluting the polyimide precursor solution is preferably sufficiently dehydrated. When the dehydration treatment is insufficient, the resolution of the amide peak is lowered due to the presence of water molecules, and there is a risk of lack of quantitativeness in calculating the imide ring closure rate. The moisture content of the object to be measured provided in the liquid state is preferably 0.01% or more and 0.5% or less, and moisture mainly derived from the polyimide precursor is allowed. Furthermore, in the present invention, in the case of a polyimide precursor composed of a plurality of diamines, a method for quantifying the amide hydrogen of the diamine having the largest content as the monomer is preferable. The molecular weight M in the repeating unit of the polyamic acid structure in the present invention. ₀ is the molecular weight of the structural formula in parentheses in the general formula (3), that is, the molecular weight of the repeating unit of the amic acid structure of the polyimide precursor when it is assumed that the imide is not ring-closed. The polyimide precursor of the present invention may be a polyimide precursor composed of a plurality of different acid dianhydrides and a plurality of different diamines, but the molecular weight M ₀ in the repeating unit of polyamic acid in that case Is a weighted average of molecular weights of the structural formula represented by the general formula (3).

The polyimide precursor in the present invention is obtained by reacting 4,4′-oxydiphthalic dianhydride and diamine, and an amic acid structure in which diamine is added to acid dianhydride and the amic acid structure is imide ring-closed. A polyimide precursor having both structures of an imide structure, the imide ring closure rate X (%) calculated by the above formula (7) obtained by measurement of an amide residue by ¹ H-NMR method, and the polyimide The amic acid equivalent M ₁ represented by the following formula (1) is 530 or more and 640 or less from the molecular weight M ₀ in the repeating unit calculated as a polyamic acid structure composed of an acid dianhydride and a diamine as constituents of the precursor. Is preferred.

Further, a first polyimide precursor obtained by reacting 4,4′-oxydiphthalic dianhydride and diamine, and an acid dianhydride not necessarily containing 4,4′-oxydiphthalic dianhydride as essential components, for example, 4,4 A second polyimide precursor in which at least one acid dianhydride selected from '-biphenyltetracarboxylic dianhydride, 4,4'-benzophenone tetracarboxylic dianhydride, and pyromellitic dianhydride is reacted with a diamine. The amic acid equivalent M of the polyimide precursor mixture is represented by the following formula (2):

(Where X1 is the imide ring closure rate (%) of the first polyimide precursor, X2 is the imide ring closure rate of the second polyimide precursor, and (M1) ₀ is the case where it is assumed that no imide ring closure occurs. The molecular weight in the repeating unit of the amic acid structure of the first polyimide precursor, (M2) ₀ is the molecular weight in the repeating unit of the amic acid structure of the second polyimide precursor, assuming that the imide is not ring-closed, α1 is (The weight fraction of the first polyimide precursor, α2, represents the weight fraction of the second polyimide precursor, respectively, and α1 + α2 = 1.)
The amic acid equivalent M of the polyimide precursor mixture is preferably 530 or more and 640 or less.
A mixture of one or more polyimide precursors obtained by reacting 4,4′-oxydiphthalic dianhydride and diamine, and having an amic acid equivalent M of 530 or more and 640 or less, can also be preferably used. .
Amic acid equivalent amount of the (M ₁ and M) are a precursor colored film and solubility too early in an alkaline developing solution is less than 530 for a fast etch rate of the photoresist coating and the polyimide precursor colored film When the etching is performed at the same time to form the pixel pattern, the etching of the polyimide precursor colored film proceeds earlier than the etching of the photoresist film, so that the pixel pattern is easily over-etched and the pixel shape is deteriorated. That is, during development, excessive dissolution tends to proceed due to the contact of the developer with the side wall surface of the pixel portion. Therefore, the pixel side wall shape is likely to be an overhanged reverse tapered edge shape. In the reverse taper edge shape, partial melting or omission of the upper reverse taper portion is likely to occur. Therefore, compared to the shape of the forward taper or vertical side wall shape, for example, the line of the light shielding line portion of the resin black matrix The width accuracy decreases and the light-shielding linear portion meanders, and the shape defect of the pixel edge of the RGB colored pixel portion and the processing accuracy in hole processing decrease.
If the above-mentioned amic acid equivalent (M ₁ and M) is 530 or more, the pre-baking temperature at the time of forming the photoresist film is increased, and the processing conditions are adjusted in the direction of increasing the pre-bake time, thereby the photoresist film It becomes possible to adjust the etching rate of the polyimide precursor colored coating. If the amic acid equivalent (M ₁ and M) is less than 530, the adjustment is difficult, and the shape of the pattern edge becomes worse due to variations and variations in the pre-baking temperature and pre-baking time during the pattern processing step, resulting in a fine pattern shape. Becomes unstable, making it difficult to perform stable pattern processing, resulting in decreased productivity. If the amic acid equivalent (M ₁ and M) is 530 or more, the influence of fluctuations in the pre-bake temperature and pre-bake time during the formation of the photoresist film is small, and high-definition and fine pattern processing can be produced stably.

On the other hand, amic acid equivalent amount of the (M ₁ and M) are the solubility in an alkaline developing solution exceeds 640 significantly decreases, patterning becomes insufficient, originally removed from the substrate by development to expose It is not preferable because a colored film remains as a residual film or residue on the surface that must be provided. Considering fluctuations and variations in the pre-bake temperature and prebaking time in patterning process, amic acid equivalent amount of the (M ₁ and M) is preferably at 640 or less, in this case, some of the pre-bake temperature and prebaking time Even if there is a fluctuation, no residual film or residue, which is a development residue of the polyimide precursor colored film, is generated, and a high-quality color filter can be produced.

  The colored resin composition of the present invention contains a polyimide precursor, a solvent, and a pigment. There is no restriction | limiting in particular as a solvent used by this invention, Although a general organic solvent can be used, It is desirable that it is a solvent which melt | dissolves a polyimide precursor. Solvents for dissolving the polyimide precursor include amides such as N, N-dimethylacetamide and N, N-dimethylformamide, lactones such as γ-butyrolactone, pyrrolidones such as 2-pyrrolidone and N-methyl-2-pyrrolidone. Polar organic solvents such as In addition, polyimide precursors usually do not dissolve the polyimide precursor alone, but include alcohols such as ethanol, butanol and isopropanol, cellosolves such as methyl cellosolve and ethyl cellosolve, and propylene glycol derivatives such as propylene glycol monomethyl ether. It can be used by mixing with a solvent that dissolves the body. Usually, as a solvent which does not dissolve the polyimide precursor alone, 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, propylene glycol mono-methyl ether, propylene glycol- Ru-mono-methyl ether acetate, dipropylene glycol mono-methyl ether, tripropylene glycol mono-methyl ether, propylene glycol mono-tertiary-butyl ether, isobutyl alcohol -Ethyl, isoamyl alcohol, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, butyl cellosolve acetate, methyl carbitol, methyl carbitol acetate, ethyl carbitol, ethyl carbitol acetate, etc. It is not limited. The amount of the solvent used is not particularly limited, but is preferably an amount sufficient for dissolving the resin and having an appropriate viscosity.

  Although there is no restriction | limiting in particular in the pigment used by this invention, The thing excellent in light resistance, heat resistance, and chemical resistance is desirable. Specific examples of typical pigments are indicated by color index (CI) numbers. Examples of red pigments include Pigment Red (PR-), 2, 3, 22, 38, 149, 166, 168, 177, 206, 207, 209, 224, 242, 254, Pigment Orange (PO-) 5, 13, 17, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, Pigment Yellow (PY-) 12, 13, 14, 17, 20, 24, 83, 86, 93, 94, 109, 110, 117, 125, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, Pigment Green (PG-) 7, 10, 36, 47, Pigment Blue (PB-) 15 (15: 1, 15: 2, 15: 3, 15: 4, 15: 6), 21, 22, 60, 64, Pigment Biore (PV-) 19,23,29,32,33,36,37,38,40,50 and the like. In the present invention, various pigments can be used without being limited thereto. These pigments may be used alone or in combination of two or more. The above pigment may be subjected to surface treatment such as rosin treatment, acidic group treatment, basic treatment, pigment derivative treatment and the like, if necessary.

  In addition, PR (Pigment Red), PY (Pigment Yellow), PG (Pigment Green), PV (Pigment Violet), PO (Pigment Orange), etc. are published by Color Index (CI; The Society of Dyers and Colourists) ) Symbol, and formally C. I. (For example, CI PR254 etc.). This defines a standard for pigments and dyeings, and each symbol designates a specific standard pigment and its color. In the following description of the present invention, in principle, the C.I. I. Is omitted (for example, PR254 is CI PR254).

  Examples of the black pigment include carbon black, metal oxynitride powder / metal oxide powder such as titanium oxynitride / titanium oxide / iron tetroxide, metal sulfide powder, and metal powder.

  In particular, carbon black is particularly preferable because of its excellent light shielding properties. Carbon black is manufactured by contact method called channel black, roller black, disc black, manufactured by furnace method called gas furnace black, oil furnace black, thermal black Those produced by a thermal method called acetylene black can be used, and channel black, gas furnace black, oil furnace black, and the like are particularly preferable.

Further, as the metal oxide, titanium oxynitride, titanium oxide or the like is preferably used, and more preferably, titanium oxynitride having excellent light shielding properties is used. Titanium oxynitride generally has a composition of TiNxOy (where 0 <x <2.0, 0.1 <y <2.0), and is manufactured by the following method, but is not limited to these. Absent.
(1) A method in which titanium dioxide or titanium hydroxide is reduced at high temperature in the presence of ammonia (Japanese Patent Laid-Open Nos. 60-65069 and 61-201610).
(2) A method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610).
Further, these black pigments may be used in which the pigment surface is coated with a resin or the like, if necessary, in order to improve the adhesion of the resin black matrix.

In the colored resin composition in the present invention, the polyimide precursor and the pigment are usually in a weight ratio of 10:90 to 90:10, preferably 20:80 to 80:20, more preferably 30:70 to 70:30. Used in a mixed range. If the amount of the resin is too small, the adhesion between the coating of the colored resin composition and the substrate may be poor, and conversely, if the amount of the pigment is too small, the degree of coloring may be a problem. In the colored resin composition, a pigment is directly dispersed in a resin solution using a disperser, or a pigment dispersion is prepared by dispersing a pigment in water or an organic solvent using a disperser. Manufactured by a method of mixing. The method for dispersing the pigment is not particularly limited, and various methods such as a ball mill, a sand grinder, a three-roll mill, and a high speed impact mill can be used, but a bead mill is preferred from the viewpoint of dispersion efficiency and fine dispersion. As the bead mill, a coball mill, a basket mill, a pin mill, a dyno mill, or the like can be used. As the beads of the bead mill, titania beads, zirconia beads, zircon beads and the like are preferably used.

  In the colored resin composition of the present invention, an adhesion improver can be added for the purpose of improving the adhesion to inorganic materials such as glass plates and silicon wafers. As the adhesion improving agent, a silane coupling agent or a titanium coupling agent can be used. Further, a surfactant is added to the colored resin composition of the present invention for the purpose of improving the coating property of the colored resin composition and the uniformity of the surface of the colored film, or for the purpose of improving the dispersibility of the pigment. be able to.

  The colored resin fat composition in the present invention is applied on a substrate by a dipping method, a roll coater method, a spinner method, a die coating method, a method using a wire bar, and the like, and then heated and dried using an oven or a hot plate. And curing. The heating conditions vary depending on the resin, solvent, and coating amount to be used, but it is usually preferable to heat at 50 to 400 ° C. for 1 to 300 minutes. Furthermore, the heat drying and curing are preferably performed from normal pressure to reduced pressure, but it is more preferable to use a hot plate under reduced pressure in order to shorten the process time. The film thus obtained is usually patterned using a method such as photolithography. After forming a photoresist film, exposure and development are performed to obtain a desired pattern. Thereafter, if necessary, the photoresist is removed and then heated and cured. The heat curing conditions are generally heated at 200 to 350 ° C. for 1 to 60 minutes.

  In the present invention, a color filter for liquid crystal display can be produced using this colored resin composition. In the color filter of the present invention, it is preferable to form a protective film layer on the color material after forming the resin black matrix and the three primary color layers. Examples of the material for the protective film layer include an epoxy film, an acrylic epoxy film, an acrylic film, a siloxane polymer film, a polyimide film, a silicon-containing polyimide film, and a polyimidesiloxane film. Furthermore, if necessary, a transparent conductive film can be formed after forming a colored layer of three primary colors or forming a protective film on the colored layer of three primary colors. An oxide thin film such as ITO is employed as the transparent conductive film, and an ITO film of about 0.1 μm is usually formed by sputtering or vacuum deposition.

Next, an example of the color filter manufacturing method of the present invention will be described. A resin black matrix is formed using the black resin composition of the present invention containing a polyimide precursor and a titanium oxynitride on an alkali-free glass. As for the black matrix, other known methods such as a metal thin film (thickness of about 0.1 to 0.2 μm) such as Cr, Al, Ni, or a photosensitive resin composition are used. You may make by the method using the resin black matrix etc. which become. A red colored layer is formed so as to fill the opening of the black matrix. Similarly, the green coloring layer is formed in the opening of the black matrix, and then the blue coloring layer is formed in the opening of the black matrix. Next, after forming a protective film as necessary, a transparent conductive film is laminated to complete the color filter of the present invention.
In the color filter of the present invention, a spacer fixed on the color filter may be formed. The fixed spacer is fixed to a specific location of a substrate for a liquid crystal display device as disclosed in JP-A-4-318816, and is in contact with a counter substrate when the liquid crystal display device is manufactured. As a result, a constant gap is maintained between the counter substrate and liquid crystal is injected between the gaps. By arranging the fixed spacer, the process of spraying the spherical spacer in the manufacturing process of the liquid crystal display device and the process of kneading the rod-shaped spacer in the sealing agent can be omitted. The fixed spacer is formed by a method such as photolithography, printing, or electrodeposition. However, since the spacer can be easily formed at a designed position, it is preferably formed by photolithography. In addition, the spacer may be formed in a laminated structure when the R, G, and B pixels are manufactured, or may be formed after the R, G, and B pixels are manufactured, either before or after the formation of the protective film or before or after the formation of the transparent electrode. Also good.

  Next, an example of a liquid crystal display device created using this color filter will be described. In the case where the color filter and the electrode substrate are further subjected to a rubbing treatment for liquid crystal alignment provided on the substrate, and a fixed spacer is not formed on the color filter side, a cell gap maintaining For this purpose, a spherical spacer is dispersed, or a fixed spacer is formed in advance on the electrode substrate side, and they are bonded to face each other through the spacer. Note that a thin film transistor (TFT) element, a thin film diode (TFD) element, a scanning line, a signal line, or the like is provided over the electrode substrate, whereby a TFT liquid crystal display device or a TFD liquid crystal display device can be manufactured. Next, after injecting liquid crystal from the injection port provided in the seal portion, the injection port is sealed. Next, a liquid crystal display device is completed by mounting an IC driver or the like.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example and a comparative example, this invention is not limited to a following example. Various samples prepared and measured in Examples and Comparative Examples are based on the following methods.
[Measurement of imide ring closure rate of polyimide precursor by ¹ H-NMR]
(1) Preparation of ¹ H-NMR measurement solution: 1 part by weight of a polyimide precursor solution having a weight concentration of about 20% using N-methyl-2-pyrrolidone and γ-butyrolactone as a solvent was sufficiently dehydrated using molecular sieves. Diluted with 4 parts by weight of dimethylformamide deuteride (d7 form) or dimethyl sulfoxide deuteride (d6 form). An appropriate amount of the obtained diluted solution was filled into an NMR glass sample tube having a diameter of about 5 mm.
(2) ¹ H-NMR measurement: JH-GX-270 (observation frequency: 270 MHz) manufactured by JEOL Ltd. was used under the following conditions. Observation nucleus: ¹ H, observation range: 6000 Hz, measurement method: ¹ H single pulse, pulse width: 4.7 μsec, observation repetition time: PD = 12 sec, ACQTM = 2.730 sec, temperature: room temperature, internal standard: tetramethylsilane Sample rotation speed: 15 Hz.
[Synthesis of polyimide precursor solution]
(Synthesis Example 1)
In a mixed solvent of γ-butyrolactone (2082.6 g) and N-methyl-2pyrrolidone (2082.6 g), paraphenylenediamine (161.7 g), 4,4′-diaminodiphenyl ether (138.2 g), bis- After reacting 3- (aminopropyl) tetramethylsiloxane (28.6 g) and 4,4′-oxydiphthalic dianhydride (711.7 g) at 80 ° C. for 3 hours, maleic anhydride (1.1 g) was added. Then, the mixture was further reacted at 80 ° C. for 1.5 hours to obtain a polyimide precursor solution A1 (polymer concentration: 20% by weight) having a molecular weight M ₀ of a repeating unit having a polyamic acid structure of 453.
Imide ring closure rate by the ¹ H-NMR measurement is 15.5%, the amic acid equivalent amount _{M 1} was 536.
(Synthesis Example 2)
In Synthesis Example 1, a polyimide precursor solution A2 was obtained in the same manner as in Synthesis Example 1, except that the reaction time after addition of maleic anhydride was 2 hours. ^The imide cyclization rate by ¹ H-NMR measurement was 17.0%, and the amic acid equivalent M ₁ was 546.
(Synthesis Example 3)
In Synthesis Example 1, a polyimide precursor solution A3 was obtained in the same manner as in Synthesis Example 1 except that the reaction time after addition of maleic anhydride was 2.5 hours. ^The imide cyclization rate by ¹ H-NMR measurement was 23.3%, and the amic acid equivalent M ₁ was 591.
(Synthesis Example 4)
In Synthesis Example 1, a polyimide precursor solution A4 was obtained in the same manner as in Synthesis Example 1 except that the reaction time after addition of maleic anhydride was 1 hour. ^The imide cyclization rate by ¹ H-NMR measurement was 14.0%, and the amic acid equivalent M ₁ was 527.
(Synthesis Example 5)
In Synthesis Example 1, a polyimide precursor solution A5 was obtained in the same manner as in Synthesis Example 1 except that the reaction time after addition of maleic anhydride was 3 hours. ^The imidation ratio by ¹ H-NMR measurement was 29.6%, and the amic acid equivalent M ₁ was 643.
(Synthesis Example 6)
In a mixed solvent of γ-butyrolactone (2082.6 g) and N-methyl-2pyrrolidone (2082.6 g), paraphenylenediamine (167.9 g), 4,4′-diaminodiphenyl ether (143.5 g), bis- 3- (Aminopropyl) tetramethylsiloxane (29.7 g) and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (695.6 g) were reacted at 80 ° C. for 3 hours, and then anhydrous maleic acid. By adding an acid (4.7 g) and further reacting at 80 ° C. for 2.5 hours, a polyimide precursor solution B (polymer concentration 20% by weight) having a polyamic acid structure repeating unit molecular weight M ₀ of 436 was obtained. . ^The imide cyclization rate by ¹ H-NMR measurement was 25.3%, and the amic acid equivalent M ₁ was 584.
(Synthesis Example 7)
9,9′-bis (4-aminophenyl) fluorene (528.1 g), bis-3- (aminopropyl) tetramethylsiloxane (19.8 g), 4,4 ′ in γ-butyrolactone (4165.2 g) -Oxydiphthalic dianhydride (490.1) is reacted at 70 ° C for 3 hours, then maleic anhydride (3.1 g) is added, and further reacted at 70 ° C for 2 hours to repeat the polyamic acid structure. A polyimide precursor solution C having a molecular weight M ₀ of 654 (polymer concentration 20% by weight) was obtained. ^The imide cyclization rate by ¹ H-NMR measurement was 5.6%, and the amic acid equivalent M ₁ was 693.
(Synthesis Example 8)
In a mixed solvent of γ-butyrolactone (3331.7 g) and N-methyl-2-pyrrolidone (833.5 g), 4,4′-diaminodiphenyl ether (403.4 g), bis-3- (aminopropyl) ) Tetramethylsiloxane (26.3 g), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (611.4 g) was added and reacted at 70 ° C. for 2.5 hours to form a polyamic acid structure. A polyimide precursor solution D (polymer weight concentration 20% by weight) having a molecular weight M ₀ of 496 was obtained. Imidation rate by the ¹ H-NMR measurement is 16.0%, the amic acid equivalent amount _{M 1} was 590.
Table 1 shows the polyimide precursors obtained in Synthesis Examples 1-8.

(In Table 1, ODPA: 4,4′-oxydiphthalic dianhydride, BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, PDA: paraphenylenediamine, 4,4′-DAE : 4,4'-diaminodiphenyl ether, FDA: 9,9'-bis (4-aminophenyl) fluorene, SiDA: bis-3- (aminopropyl) tetramethylsiloxane, MA: maleic anhydride .)
(Synthesis Example 9)
Titanium dioxide powder (4.0 kg) having an average primary particle size of 40 nm was charged into the reactor, then ammonia gas was flowed at a linear velocity of 3 cm / sec in the furnace, and the reaction was performed at a furnace temperature of 750 ° C. for 6 hours. Nitride A (3.2 kg) was obtained.

Example 1
(Preparation of black resin composition BK-1)
To the titanium oxynitride A (680 g) synthesized in Synthesis Example 9, the polyimide precursor solution A1 (600 g) synthesized in Synthesis Example 1, γ-butyrolactone (824 g), N-methyl-2-pyrrolidone (736 g), 3 -Methyl-3-methoxybutyl acetate (360 g) was mixed to prepare a preliminary dispersion. A pre-dispersion liquid is put into a dyno mill (manufactured by Shinmaru Enterprises) filled with 85% of 0.4 mmφ-zirconia beads, and dispersed for 4 h / kg at a disk peripheral speed of 7 m / s, whereby the total solid concentration is 25% by weight. Titanium oxynitride / polyimide precursor (weight ratio) = 85/15 titanium black dispersion was obtained.

Further, to this titanium black dispersion (2752 g), polyimide precursor solution A1 (1060 g), γ-butyrolactone (1012 g), N-methyl-2-pyrrolidone (4122 g), 3-methyl-3-methoxybutyl acetate (1056 g) Was added to obtain a black resin composition BK-1 having a total solid content of 9% by weight and titanic acid nitride / polymer (weight ratio) = 65/35.
(Create resin black matrix)
The black resin composition BK-1 was applied to an alkali-free glass substrate (Corning “1737 material”) with a curtain flow coater and dried on a hot plate at 130 ° C. for 10 minutes to form a black resin coating film. Apply positive photoresist (“SRC-100” manufactured by Shipley Co., Ltd.) with a reverse roll coater, pre-bake at 120 ° C. for 5 minutes with a hot plate, and color using an exposure machine “XG-5000” manufactured by Dainippon Screen Co., Ltd. After exposure by irradiating with 100 mJ / cm ² ultraviolet rays through a photomask having a pixel aperture width of 80 μm and a linear light-shielding portion between the apertures of 12 μm, a 2.25% tetramethylammonium hydroxide aqueous solution The photoresist development and etching of the resin coating are performed simultaneously to form a pattern, the resist is peeled off with methyl cellosolve acetate, and imidized by heating at 290 ° C. for 10 minutes on a hot plate to form a resin black matrix. Formed. The edge shape of the linear light shielding part of the obtained resin black matrix was good, and the side wall shape was a forward taper. The line width processing accuracy of the linear light shielding part was as good as 12.0 ± 1.5 μm. Furthermore, the linear light-shielding portion did not meander, and no residue was observed at the boundary between the glass and the linear light-shielding portion, and a good quality pattern could be formed.

Example 2
In Example 1, in place of the titanium oxynitride A, except that the polyimide precursor solution A2 synthesized in Synthesis Example 2 was used with carbon black A “MA100 made by Mitsubishi Chemical” (680 g) as a polyimide precursor solution, In the same manner as in Example 1, a black resin composition BK-2 was obtained. Further, a black resin composition BK-2 was used to form a resin black matrix in exactly the same manner except that the pre-baking hot plate temperature after application of the positive photoresist in Example 1 was 110 ° C. The edge shape of the linear light shielding part of the obtained resin black matrix was good, and the side wall shape was a forward taper. The line width processing accuracy of the linear light-shielding part was as good as 11.8 ± 1.4 μm. Furthermore, no linear light-shielding portion meandered, no residue was observed at the boundary between the glass and the linear light-shielding portion, and a good quality pattern could be formed.

Example 3
In Example 1, instead of titanium oxynitride A, carbon black A “MA100 manufactured by Mitsubishi Chemical” (442 g), blue pigment PB15: 6 (197 g), purple pigment PV23 (41 g) was used as a polyimide precursor solution for synthesis example A black resin composition BK-3 was obtained in the same manner as in Example 1 except that the polyimide precursor solution A3 synthesized in 3 was used. Further, a black resin composition BK-3 was used to form a resin black matrix in exactly the same manner except that the pre-baking hot plate temperature after application of the positive photoresist in Example 1 was set to 100 ° C. The edge shape of the linear light shielding part of the obtained resin black matrix was good, and the side wall shape was a forward taper. The line width processing accuracy of the linear light-shielding part was as good as 12.2 ± 1.6 μm. Furthermore, no linear light-shielding portion meandered, no residue was observed at the boundary between the glass and the linear light-shielding portion, and a good quality pattern could be formed.

Comparative Example 1
In Example 1, the polyimide precursor solution A4 was used instead of the polyimide precursor solution A1, and black resin composition BK-4 was obtained. Further, a black resin composition BK-4 was used to form a resin black matrix in exactly the same manner except that the pre-baking hot plate temperature after applying the positive photoresist in Example 1 was set to 120 ° C. The obtained resin black matrix had a bad edge shape and an inversely tapered shape, and the line width processing accuracy of the linear light-shielding part was extremely poor at 11.8 ± 3.0 μm. The black light shielding portion of the black matrix is also meandering, and no residue was observed at the boundary between the glass and the linear light shielding portion, but the pattern was poor in quality.

Comparative Example 2
In Example 2, the black precursor composition BK-5 was obtained by using the polyimide precursor solution A5 instead of the polyimide precursor solution A1. Further, a black resin composition BK-5 was used to form a resin black matrix in exactly the same manner except that the prebake hot plate temperature after application of the positive photoresist in Example 3 was set to 100 ° C. The resulting resin black matrix had a forward taper edge, but the line width of the linear light-shielding portion was as thick as 13.8 μm with respect to the mask line width of 12 μm, and the processing accuracy was 13.8 ± 2.0 μm. Somewhat bad. Although there was no meandering of the linear light-shielding portion, a residue was confirmed at the boundary between the glass and the linear light-shielding portion. It was a bad pattern.

Comparative Example 3
In Example 3, the polyimide precursor solution B was used instead of the polyimide precursor solution A1, and black resin composition BK-6 was obtained. Further, a black resin composition BK-6 was used to form a resin black matrix in exactly the same manner as in Example 3. The resulting resin black matrix had a forward tapered shape, but the line width of the linear light-shielding portion was as thick as 14.5 μm with respect to the mask line width of 12 μm, and the processing accuracy was 14.5 ± 2.6 μm. Although it was defective and there was no meandering of the linear light-shielding part, a residue was confirmed at the boundary between the glass and the linear light-shielding part. The pattern was extremely poor.

Example 4
(Preparation of colored resin composition)
PR254 (308 g) and PY138 (76 g) were mixed with the polyimide precursor solution D (564 g) synthesized in Synthesis Example 8, γ-butyrolactone (3972 g), and 3-methyl-3-methoxybutanol (1480 g) to prepare a red predispersion. A liquid was prepared. Total solid content concentration by adding red pre-dispersion liquid to dyno mill (manufactured by Shinmaru Enterprises) filled with 85% 0.4mmφ-zirconia beads and dispersing 2.5h / kg at disk peripheral speed 10m / s A red dispersion liquid of 7.8% by weight, pigment / polymer (weight ratio) = 77/23 was obtained. Furthermore, polyimide precursor solution D (1450 g), polyimide precursor solution C (480 g), γ-butyrolactone (2410 g), and 3-methyl-3-methoxybutanol (327) were added to this red dispersion liquid (5333 g). A red resin composition R-1 having a total solid content concentration of 8% by weight and a pigment / polyimide precursor mixture (weight ratio) = 40/60 was obtained. In addition, the weight ratio of the polyimide precursor mixture was polyimide precursor C / polyimide precursor D (weight ratio) = 20/80, and the amic acid equivalent M of the polyimide precursor mixture was 611.
(Create colored pixels)
Red resin composition R-1 was applied on the resin black matrix substrate prepared in Example 1 with a curtain flow coater, and dried on a hot plate at 130 ° C. for 10 minutes to form the red resin coating film. Thereafter, in the same manner as the resin black matrix formation, a positive photoresist was applied with a reverse roll coater and prebaked at 100 ° C. for 5 minutes with a hot plate. Then, using the same exposure machine as that for forming the resin black matrix, a photomask in which a transparent area is formed in the reflective area (red pixel area: approximately 29 μmφ × 3 in the reflective area 120 × 80 μm in the 240 × 80 μm area) Exposure to 100 mJ / cm ² of ultraviolet light through a photomask having a circular transparent area), and then using 2.25% tetramethylammonium hydroxide aqueous solution to develop the photoresist and the resin coating film. Etching was performed simultaneously to form a pattern, the resist was peeled off with methyl cellosolve acetate, and imidized by heating at 280 ° C. for 10 minutes with a hot plate to form a red pixel having a hole pattern. The shape of the hole edge is good, the hole in the reflective area can be processed with good pattern accuracy of 29.0 ± 1.5 μm, and there is no red resin composition residue in the hole, and the pattern has good quality. It was.

Comparative Example 4
In Example 4, red color is the same as in Example 4 except that the weight mixing ratio of the polyimide precursor mixture in the red coloring composition R-1 is polyimide precursor C / polyimide precursor D = 50/50. Resin composition R-2 was obtained. The amic acid equivalent M of the polyimide precursor mixture in the red resin composition R-2 was 642. Further, the same procedure as in Example 4 was performed except that the red resin composition R-2 was used instead of the red resin composition R-1 in Example 4 and the hot plate temperature was 90 ° C. during the pre-baking of the positive resist. A red pixel having a hole pattern was formed on the resin black matrix substrate. Although there was no problem with the shape of the hole edge part, the reflection area hole was 27.0 μm and the processing accuracy was slightly poor at 27.0 ± 2.1 μm compared to the 29 μm design, and the red resin composition was in the hole. This resulted in a poor quality pattern.

Comparative Example 5
In Example 4, except that the polyimide precursor solution D was used in place of the polyimide precursor solution C, and the weight mixing ratio was changed to polyimide precursor C / polyimide precursor D = 0/100, the same as in Example 4. Thus, a red resin composition R-3 was obtained. The molecular weight M of the polyimide precursor in the red resin composition R-3 was 590. Furthermore, the same procedure as in Example 4 was performed except that the red resin composition R-3 was used instead of the red resin composition R-1 in Example 4 and the hot plate temperature during pre-baking of the positive resist was 90 ° C. A red pixel having a hole pattern was formed on the resin black matrix substrate. The edge shape of the hole pattern is extremely meandering and defective, and the holes in the reflection region are small, with an average of 27.3 μm and a processing accuracy of 27.3 ± 2.4 μm, as compared with the 29 μm design. Further, a red resin composition residue was generated in the hole. The pattern was extremely poor in quality.

Example 5
Green resin composition G-1 was prepared in the same manner as in Example 4, except that PG36 (250 g) and PY138 (134 g) were used instead of PR254 (308 g) and PY138 (76 g) in Example 4. The amic acid equivalent M of the polyimide precursor mixture in the green resin composition G-1 was 611. Next, the green resin composition G-1 was applied on the resin black matrix substrate having red pixels prepared in Example 4 with a curtain flow coater, and dried on a hot plate at 130 ° C. for 10 minutes. Formed. Thereafter, in the same manner as the resin black matrix formation, a positive photoresist was applied with a reverse roll coater and prebaked at 100 ° C. for 5 minutes with a hot plate. Then, using the same exposure machine as in the case of the black paste, a photomask in which a transparent region is formed in the reflective region (green pixel: approximately circular with a size of 29 μmφ × 5 in the reflective region 120 × 80 μm in 240 × 80 μm) The photomask is exposed to 100 mJ / cm ² of UV light through a photomask having a transparent region, and then developed with a 2.25% tetramethylammonium hydroxide aqueous solution and etched with a resin coating. At the same time, a pattern was formed, the resist was peeled off with methyl cellosolve acetate, and imidized by heating at 280 ° C. for 10 minutes on a hot plate to form a green pixel. The shape of the hole in the reflection region was good, and the hole accuracy was 28.8 ± 1.6 μm, and a good patterning was possible. Further, no residue was generated in the hole. A pattern with good quality could be formed.

Comparative Example 6
In Example 5, a green resin was obtained in the same manner as in Example 5 except that the weight mixing ratio of the polyimide precursor in the green coloring composition G-1 was changed to polyimide precursor C / polyimide precursor D = 50/50. Composition G-2 was obtained. The amic acid equivalent M of the polyimide precursor mixture in the green resin composition G-2 was 642. Further, the same procedure as in Example 5 was performed except that the green resin composition G-2 was used instead of the green resin composition G-1 in Example 5 and the hot plate temperature during pre-baking of the positive resist was 130 ° C. A green pixel having a hole pattern was formed. Although there was no problem in the shape of the hole in the reflection area, the hole processing accuracy was as small as 27.5μm on average for the 29μmφ mask, and the processing accuracy was slightly poor at 27.5 ± 2.2μm. A residue of the composition was generated. It was a bad pattern.

Comparative Example 7
In Example 5, except that the polyimide precursor solution D was used in place of the polyimide precursor solution C and the weight mixing ratio was changed to polyimide precursor C / polyimide precursor D = 0/100, the same as in Example 5. Thus, a green resin composition G-3 was obtained. The amic acid equivalent M ₁ of the polyimide precursor in the green resin composition G-3 was 590. Further, the same procedure as in Example 5 was performed except that the green resin composition G-3 was used instead of the green resin composition G-1 in Example 5 and the hot plate temperature at the time of pre-baking the positive resist was 100 ° C. A green pixel having a hole pattern was formed. The shape of the pixel edge of the hole is meandering and is bad. The hole processing accuracy was as small as 26.5 μm on average for the 29 μm design, and the processing accuracy was 26.5 ± 2.8 μ, which was poor. A residue of the green resin composition was generated in the hole, and the quality was extremely poor.

Example 6
PB15: 6 (680 g), polyimide precursor solution A1 (600 g) synthesized in Synthesis Example 1, γ-butyrolactone (824 g), N-methyl-2-pyrrolidone (736 g), 3-methyl-3-methoxybutyl acetate (360 g) was mixed to prepare a preliminary dispersion. A pre-dispersion liquid is put into a dyno mill (manufactured by Shinmaru Enterprises) filled with 85% of 0.4 mmφ-zirconia beads, and dispersed for 4 h / kg at a disk peripheral speed of 12 m / s, whereby the total solid concentration is 25% by weight. A blue dispersion of pigment / polymer (weight ratio) = 85/15 was obtained. Further, to this blue dispersion (1271 g), polyimide precursor solution A1 (2912 g), γ-butyrolactone (951 g), N-methyl-2-pyrrolidone (3874 g), 3-methyl-3-methoxybutyl acetate (992 g) were added. The blue resin composition BL-1 having a total solid content of 9% by weight and a pigment / polymer (weight ratio) of 30/70 was obtained. The amic acid equivalent M ₁ of the polyimide precursor in the blue resin composition BL-1 was 536. Next, the blue resin composition BL-1 was applied on a resin black matrix substrate having red and green colored pixels having a hole pattern created in Example 5 with a curtain flow coater, and 130 ° C., 10 ° C. with a hot plate. Minute drying, the blue resin coating film was formed. Thereafter, as in the case of the black paste, a positive type photoresist was applied with a reverse roll coater and prebaked on a hot plate at 100 ° C. for 5 minutes. Then, using the same exposure machine as in the case of the black paste, a photomask having a transparent area formed in the reflective area (blue pixel: approximately circular with a size of 29 μmφ × 2 in the reflective area 120 × 80 μm in 240 × 80 μm) The photomask is exposed to 100 mJ / cm ² of UV light through a photomask having a transparent region, and then developed with a 2.25% tetramethylammonium hydroxide aqueous solution and etched with a resin coating. At the same time, a pattern was formed, the resist was peeled off with methyl cellosolve acetate, and imidized by heating at 280 ° C. for 10 minutes on a hot plate to form a blue pixel. The shape of the pixel edge of the hole was also good, and the hole in the reflection area could be processed with good pattern accuracy of 29.0 ± 1.4 μm. There was no residue of the blue resin composition in the hole, and the color filter was of good quality.

Example 7
PB15: 6 (544 g), PV23 (136 g), polyimide precursor solution A3 (600 g) synthesized in Synthesis Example 3, γ-butyrolactone (824 g), N-methyl-2-pyrrolidone (736 g), 3-methyl- 3-Methoxybutyl acetate (360 g) was mixed to prepare a preliminary dispersion. A pre-dispersion liquid is put into a dyno mill (manufactured by Shinmaru Enterprises) filled with 85% of 0.4 mmφ-zirconia beads, and dispersed for 4 h / kg at a disk peripheral speed of 12 m / s, whereby the total solid concentration is 25% by weight. A blue dispersion of pigment / polymer (weight ratio) = 85/15 was obtained. Further, to this blue dispersion (1271 g), polyimide precursor solution A3 (2282 g), polyimide precursor solution C (630 g), γ-butyrolactone (951 g), N-methyl-2-pyrrolidone (3874 g), 3-methyl- 3-Methoxybutyl acetate (992 g) was added to obtain a blue resin composition BL-2 having a total solid content of 9% by weight and a pigment / polymer (weight ratio) = 30/70. The mixing ratio of the polyimide resin precursor in the blue resin composition BL-2 is polyimide precursor A3 / polyimide precursor C (weight ratio) = 80/20, and the amic acid equivalent M of the polyimide precursor mixture is 611. Met. Next, the blue resin composition BL-2 was applied by a curtain flow coater on the resin black matrix substrate having red and green colored pixels having the hole pattern prepared in Example 5, and the hot plate was used at 130 ° C., 10 ° C. Minute drying, a resin coating film of the blue resin composition BL-2 was formed. Thereafter, blue pixels were formed in the same manner as in Example 6. The shape of the pixel edge of the hole was also good, and the hole in the reflective region could be processed with a good pattern accuracy of 29.2 ± 1.3 μm. The color filter was of good quality with no residue of the blue resin composition in the hole.

Comparative Example 7
In Example 7, a blue resin was prepared in the same manner as in Example 7 except that the weight mixing ratio of the polyimide precursor in the blue resin composition BL-2 was changed to polyimide precursor A3 / polyimide precursor C = 50/50. Composition BL-3 was obtained. The amic acid equivalent M of the polyimide precursor mixture in the blue resin composition BL-3 was 642. Further, the same procedure as in Example 7 was performed except that the blue resin composition BL-3 was used instead of the blue resin composition BL-2 in Example 7 and the hot plate temperature during pre-baking of the positive resist was 130 ° C. Thus, a blue pixel having a hole pattern was formed. Although there was no problem with the pixel edge shape of the hole, the hole diameter of the reflection region was as small as 27.9 μm on average with respect to the mask of 29 μmφ, and the processing accuracy was 27.9 ± 2.1 μm, which was poor. A residue of a blue resin composition was generated, and the CF was poor in quality.

Comparative Example 8
A blue resin composition BL-4 was obtained in the same manner as in Example 6 except that the polyimide precursor solution B was used in place of the polyimide precursor solution A1 and the polyimide precursor solution C. The amic acid equivalent M ₁ of the polyimide precursor in the blue resin composition BL-4 was 584. Further, the same procedure as in Example 6 was performed except that the blue resin composition BL-4 was used instead of the blue resin composition BL-2 in Example 6 and the hot plate temperature during pre-baking of the positive resist was 130 ° C. Thus, a blue pixel having a hole pattern was formed. The shape of the pixel edge of the hole is meandering, and the hole diameter of the reflection region is 31.5 μm on average with respect to the 29 μmφ mask, and the variation in hole diameter is 31.5 ± 3.2 μm. Although no residue of blue resin color was observed in the hole, the pattern was extremely poor in quality.

Comparative Example 9
In Example 6, a blue resin composition BL-5 was obtained in exactly the same manner except that the polyimide precursor solution D was used instead of the polyimide precursor solution A1 and the polyimide precursor solution C. The amic acid equivalent M ₁ of the polyimide precursor in the blue resin composition BL-5 was 590. Further, the same procedure as in Example 6 was performed except that the blue resin composition BL-5 was used instead of the blue resin composition BL-1 in Example 6 and the hot plate temperature at the time of pre-baking the positive resist was 100 ° C. Thus, a blue pixel having a hole pattern was formed. Although there was no problem with the pixel edge shape of the hole, the hole diameter was as small as 26.7 μm on average with respect to the 29 μmφ mask, and the variation in hole diameter was as large as 26.7 ± 2.8 μm. Further, a blue resin composition residue was generated in the hole. The pattern was extremely poor in quality.
The results are shown in Table 2 and Table 3.

(In Tables 2 and 3, ODPA: 4,4′-oxydiphthalic dianhydride, BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-DAE: 4,4 '-Diaminodiphenyl ether, PDA: paraphenylenediamine, SiDA: bis-3- (aminopropyl) tetramethylsiloxane, FDA: 9,9'-bis (4-aminophenyl) fluorene, TiBK: titanic acid nitride , CB: carbon, B: PB15: 6, V: PV23, R: PR254, Y: PY138, G: PG23, respectively, and determination of CF quality is ○: good, ×: slightly bad, XX: It is bad.)
Example 8
(Creation of protective film and transparent conductive film)
It is obtained by reacting the color filter substrate obtained in Example 7 with a hydrolyzate of γ-aminopropylmethyldiethoxysilane and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride. A solution of the curable composition was spin-coated on a substrate and heat-treated at 260 ° C. for 10 minutes to form an overcoat layer having a film thickness of 1.0 μm in a region outside the pixel. Further, an ITO film having a thickness of 0.15 μm was formed on the overcoat layer by a sputtering method.
(Production of color liquid crystal display device)
After the color filter substrate was washed with a neutral detergent, an alignment film made of a polyimide resin was applied by a printing method and baked on a hot plate at 200 ° C. for 10 minutes. The film thickness was 70 nm. Thereafter, the color filter was rubbed, the sealing agent was applied onto the black matrix by a dispensing method, and baked on a hot plate at 90 ° C. for 10 minutes.
On the other hand, a substrate on which a TFT array is formed on a Corning glass substrate 1737 is similarly washed, and then an alignment film is applied and baked. Thereafter, spacers are sprayed, 50 are superimposed on the color filter substrate, fired at 160 ° C. for 90 minutes while being pressurized in an oven, the resin is cured, and the panels are cut into individual panels. This panel was vacuum annealed at 150 ° C. and 10 ⁻³ torr, and then returned to normal pressure in a nitrogen atmosphere, and liquid crystal was injected again in a vacuum atmosphere. Liquid crystal injection was performed by placing the panel in a chamber and reducing the pressure to 10 ⁻³ torr at room temperature, and then dipping the liquid crystal injection hole in a liquid crystal tank and returning to normal pressure using nitrogen. After the liquid crystal injection, the liquid crystal injection hole was sealed using a UV curable resin. This panel was heated to a temperature not lower than the NI transition point to realign the liquid crystal.
Next, the polarizing plate was attached to the two glass substrates of the panel and processed in an autoclave at a temperature of 50 ° C. and a pressure of 5 kgf / cm 2 to complete the panel. When this panel was observed with a microscope, no light leakage or the like due to poor alignment was observed. Further, transmission and reflection display were observed, and very good display was obtained in lighting evaluation with reflection display and transmission display.

Claims (8)

Colored resin composition containing a polyimide precursor having both an amic acid structure obtained by reacting 4,4′-oxydiphthalic dianhydride and diamine and an imide structure formed by imide ring closure of the amic acid structure, a solvent, and a pigment A colored resin composition, wherein the amic acid equivalent M ₁ of the polyimide precursor represented by the following formula (1) is 530 or more and 640 or less.

(Here, X represents the imide ring closure rate (%), and M ₀ represents the molecular weight in the repeating unit of the amic acid structure of the polyimide precursor when it is assumed that no imide ring closure occurs.) A first polyimide precursor having both an amic acid structure obtained by reacting 4,4′-oxydiphthalic dianhydride and a diamine and an imide structure formed by imide ring closure of the amic acid structure, 4,4′-biphenyltetra An amic acid structure in which at least one acid dianhydride selected from carboxylic dianhydride, 4,4′-benzophenone tetracarboxylic dianhydride, or pyromellitic dianhydride and diamine are reacted with the amic acid structure Is a colored resin composition containing a second polyimide precursor having a imide structure formed by imide ring closure, a solvent, and a pigment, and represented by the following formula (2): A colored resin composition, wherein a weight average equivalent M of an amic acid equivalent of the polyimide precursor is 530 or more and 640 or less.

(Where X1 is the imide ring closure rate (%) of the first polyimide precursor, X2 is the imide ring closure rate of the second polyimide precursor, and (M1) ₀ is the case where it is assumed that no imide ring closure occurs. The molecular weight in the repeating unit of the amic acid structure of the first polyimide precursor, (M2) ₀ is the molecular weight in the repeating unit of the amic acid structure of the second polyimide precursor, assuming that the imide is not ring-closed, α1 is (The weight fraction of the first polyimide precursor, α2, represents the weight fraction of the second polyimide precursor, respectively, and α1 + α2 = 1.) The diamine component is at least paraphenylenediamine, metaphenylenediamine, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfone, 4,4 ′. The at least one of -diaminodiphenyl sulfone, 9,9'-bis (4-aminophenyl) fluorene, and bis-3- (aminopropyl) tetramethylsiloxane. Colored resin composition. The colored resin composition according to claim 1, which is at least one pigment selected from a black pigment, a blue pigment, and a purple pigment. The colored resin composition according to claim 1, wherein the black pigment is at least one black pigment selected from carbon black and titanium oxynitride. The colored resin composition according to any one of claims 1 to 5, wherein the colored resin composition is at least one pigment selected from a blue pigment and a purple pigment. A color filter having a pixel composed of a colored layer provided in a desired pattern for each of a plurality of colors, wherein the colored resin composition according to any one of claims 1 to 6 is used for the colored layer. filter. A liquid crystal display device using the color filter according to claim 7.