JP5641412B2 - RESIN COMPOSITION FOR COLORED LAYER AND METHOD FOR PRODUCING COLOR FILTER USING THE SAME - Google Patents

Description

  The present invention relates to a resin composition for a colored layer used for a color filter for a liquid crystal display device comprising a substrate, and a colored layer, a light shielding part, and a spacer on the substrate. The present invention also relates to a method for producing a color filter using the colored layer resin composition.

  Conventionally, a color liquid crystal display device has been used as a flat display. In such a liquid crystal display device, a color filter and a thin film transistor (TFT) substrate face each other with a predetermined gap, and a liquid crystal material is injected into the gap to form a liquid crystal layer. In order to maintain the distance between the TFT substrate and the color filter facing each other, a spacer is provided between them, thereby maintaining the thickness of the liquid crystal layer between them uniformly in the plane.

  In particular, in a color filter used in a lateral electric field drive (IPS) type liquid crystal display device, a color filter is manufactured by providing a light shielding portion on a base material of the color filter and further providing a spacer on the light shielding portion. (For example, see Patent Document 1). By this spacer, the distance between the thin film transistor (TFT) substrate and the color filter 100 is maintained.

  In particular, various methods have been studied for providing spacers. For example, a method of forming a spacer by printing droplets made of ink substantially free of solid particles on a substrate by an ink jet method has been proposed (see, for example, Patent Document 2). However, this method requires an additional step after forming a colored layer on the substrate by photolithography. Therefore, the cost increases due to an increase in manufacturing processes and installation of manufacturing equipment.

  In addition, a method of forming a spacer (laminated column) formed by laminating a colored layer at the same time as forming a colored layer on a substrate by a photolithography method has been proposed (for example, see Patent Document 1). It was difficult to obtain a laminated column with a high height.

  Therefore, it is still desired to develop a colored layer resin composition capable of obtaining a spacer having a sufficiently high number of stacked columns while forming the stacked columns at the same time as forming the colored layer. In addition, development of a method for producing a color filter using the colored layer resin composition is also eagerly desired.

JP-A-10-177109 JP 2008-112138 A

  As a result of examining the above-described background art, the present inventors have increased the thickness of each layer by increasing the coating amount of the colored layer resist that forms each layer of the stacked column, and are composed of a sufficiently high stacked column. It has been found that spacers can be formed. However, this method has also been found to increase the cost because the amount of colored layer resist used increases. Therefore, it is required to reduce the cost to increase the thickness of the colored layer without increasing the coating amount of the colored layer resist.

  The present invention has been made in view of the above-mentioned background art and newly discovered problems, and its object is to form a stacked column having a sufficient height while forming a stacked column at the same time as forming a colored layer. It is in providing the resin composition for colored layers which can obtain a spacer. Another object of the present invention is to provide a method for producing a color filter using the colored layer resin composition.

  In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, in the step of forming the laminated pillar, the contact angle of the colored layer resin composition with respect to the lower layer is adjusted within a specific range. The present inventors have found that the problem can be solved and have completed the present invention.

That is, according to one aspect of the present invention,
A resin composition for a colored layer used for a color filter for a liquid crystal display device comprising a substrate and a light shielding part, a colored layer, and a spacer on the substrate,
The spacer is a stacked column formed by stacking two or more colored layers on the light shielding portion,
The colored layer resin composition forming the laminated column has the following conditions:
(I) the first colored layer resin composition for forming the first layer on the light shielding part has a contact angle of 4.0 degrees or more with respect to the light shielding part;
(II) Coloring satisfying that the second colored layer resin composition forming the second layer on the first layer has a contact angle of 4.0 degrees or more with respect to the first layer A layered resin composition is provided.

According to another aspect of the present invention,
A method for producing a color filter for a liquid crystal display device, comprising: a base material; and a light shielding portion, a colored layer, and a spacer on the base material,
The spacer is a stacked column formed by stacking two or more colored layers on the light shielding portion,
(A) using the first colored layer resin composition having a contact angle of 4.0 degrees or more with respect to the light shielding part, forming a first layer on the light shielding part;
(B) forming a second layer on the first layer using a second colored layer resin composition having a contact angle of 4.0 degrees or more with respect to the first layer. A method for producing a color filter is provided.

  By using the colored layer resin composition of the present invention, it is possible to obtain a spacer having a sufficiently high number of stacked pillars while forming the stacked pillars simultaneously with forming the colored layer. Furthermore, the cost can be reduced by suppressing the amount of the colored layer resist used. In addition, according to the method for producing a color filter of the present invention, a color filter having a spacer composed of a sufficiently high stacked pillar can be obtained.

It is a schematic cross section which shows an example of the color filter for liquid crystal display devices formed using the resin composition for colored layers of this invention. It is a figure which shows the contact angle of the resin composition for colored layers with respect to a lower layer. It is a figure which shows the preparation methods of the base material for a lamination rate measurement. It is a schematic cross section of the base material for a lamination rate measurement. It is a figure which shows the relationship between a contact angle and a lamination rate. It is a figure which shows the relationship between a polymer ratio (ratio of the polymer with respect to the sum total of a polymer and a monomer) and a contact angle. It is a figure which shows the relationship between the weight average molecular weight of a polymer, and a contact angle. It is a figure which shows the relationship between the functional group number of a monomer, and a contact angle.

Color filter In this invention, a color filter has a light-shielding part, a colored layer, and a spacer on a base material and a base material. Specifically, FIG. 1 shows a schematic sectional view of an example of the color filter according to the present invention. The color filter 10 shown in FIG. 1 includes a light shielding part 30 having an opening on a base material 20, and colored layers 40 of each color in the opening (a red colored layer 41, a green colored layer 42, and a blue colored layer 43). And a spacer 50 on the light-shielding portion 30. The spacer 50 is composed of three layers of stacked pillars in which colored layers 40 (a red colored layer 41, a green colored layer 42, and a blue colored layer 43) of each color are stacked on the light shielding portion 30. Each configuration will be described below.

Substrate According to a preferred embodiment of the present invention, since the substrate is on the light emitting side, a transparent substrate having high light transmittance is used. For example, the transparent base material which consists of material with high light transmittances, such as glass, quartz, or various resin, is mentioned. Moreover, the thickness of a base material is 0.1-10.0 mm normally.

Light-shielding part According to a preferred embodiment of the present invention, the light-shielding part is formed on the substrate and has an opening. As the light-shielding portion, one in which openings having the same shape are formed in a pattern at equal intervals is used. The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. A method for forming the light shielding part is not particularly limited as long as it can pattern the light shielding part, and a known method can be used. For example, it may be formed by a photolithography method using a black dispersion liquid containing a black coloring material and a photosensitive resin composition.

Colored layer According to a preferred embodiment of the present invention, the colored layer is formed in the opening of the light-shielding part on the substrate, and includes, for example, three colored patterns of red, green, and blue. Is good. The coloring pattern may be four colors of red, green, blue, and yellow, and five colors of red, green, blue, yellow, and cyan. Moreover, the colored layer of each color can be formed using the resin composition for colored layers containing the coloring material of each color. The colored layer is usually formed with a thickness of 1 μm to 5 μm. The method for forming the colored layer is not particularly limited as long as it can pattern the colored layer, and a known method can be used. For example, a photolithography method using a photosensitive resin composition is preferable because a stacked column on which a colored layer is stacked can be accurately formed at a desired position.

Colored Layer Resin Composition According to a preferred embodiment of the present invention, the colored layer resin composition includes a coloring material, a polymer, and a monomer, and further includes a polymerization initiator and a dispersant as necessary. And a solvent.

The colored layer resin composition of the present invention is 4.0 degrees or more, preferably 4.5 degrees or more and 20 degrees or less, more preferably 5.degree. It has a contact angle of 0 degree or more and 18 degrees or less. As an example, FIG. 2 shows a measurement diagram of the contact angle 120 of the colored layer resin composition 110 with respect to the lower layer 130 in the step of forming the stacked pillars. In addition, when forming the lamination | stacking pillar of n layer (n is an integer greater than or equal to 3), a lower layer means a light shielding part in the process of forming a 1st layer, In the process of forming a 2nd layer-nth layer Denote the first to (n-1) th layers, respectively. More specifically, the colored layer resin composition has the following conditions:
(I) the first colored layer resin composition forming the first layer on the light shielding part has a contact angle of 4.0 degrees or more with respect to the light shielding part;
(II) The second colored layer resin composition for forming the second layer on the first layer satisfies the contact angle of 4.0 degrees or more with respect to the first layer. . According to a preferred aspect, when the laminated pillar is an n layer, the following condition is satisfied: (III) The nth colored layer resin composition for forming the nth layer on the (n-1) th layer is the nth- It further satisfies that it has a contact angle of 4.0 degrees or more with respect to one layer, provided that when n is 4 or more, all of the third to nth colored layer resin compositions satisfy the condition (III). It is preferable to satisfy. When the colored layer resin composition has a contact angle in the above range with respect to the lower layer, the lamination rate of each layer of the laminated pillar can be improved.

  In the present invention, the colored layer resin composition used to form the n-layer laminated pillar includes first to nth colored layer resin compositions. The compositions of the first to nth colored layer resin compositions may all be different or may include the same composition as long as they can form a laminated column of at least two colors. For example, when the colored layer formed in the opening of the light-shielding part on the substrate is composed of three colored patterns of red, green, and blue, the colored layer resin composition is the first colored layer. A resin composition for a red colored layer as a resin composition for a resin, a resin composition for a green colored layer as a resin composition for a second colored layer, and a resin composition for a blue colored layer as a resin composition for a third colored layer Should be used.

In the present invention, the lamination ratio is the ratio of the film thickness of the layer laminated on the lower layer to the colored film thickness of the colored layer resin composition. As an example, as shown in FIG. 4, the stacking ratio he is expressed by the following formula (1).
Formula 1
he = (h1-h2) / h3 × 100 (%)
(Where h1 is the film thickness 220 after lamination, h2 is the lower film thickness 210, and h3 is the colored film thickness 230)
It can ask for. According to a preferred embodiment of the present invention, the lamination ratio he is preferably 30% or more, and more preferably 35% or more and 95% or less. If the lamination rate is in the above range, the height of the spacer made of the lamination pillars can be sufficiently obtained. The colored film thickness refers to the film thickness after applying the colored resin composition and post-baking at 230 ° C. for 25 minutes.

  According to a preferred embodiment of the present invention, the ratio of polymer to monomer (P: M) contained in the colored layer resin is preferably P: M = 30: 70 to 80:20, more preferably 50:50. -80: 20, more preferably 55: 45-80: 20. If the ratio of the polymer to the monomer is in the above range, the contact angle of the colored layer resin composition to the lower layer can be increased.

Coloring material As the coloring material used in the present invention, a known coloring material can be used. Examples of the red coloring material include perylene pigments, lake pigments, azo pigments, quinacdrine pigments, anthraquinone pigments, anthracene pigments, and isoindoline pigments. Examples of the green coloring material include phthalocyanine pigments, triphenylmethane pigments, isoindoline pigments, and isoindolinone pigments. Examples of blue coloring materials include phthalocyanine pigments, anthraquinone pigments, indanthrene pigments, indophenol pigments, cyanine pigments, and dioxazine pigments. These coloring materials may be used alone or in combination of two or more.

  In the present invention, it is preferable to use in the state of a dispersion in which the coloring material is dispersed in a solvent. The method for dispersing the coloring material is not particularly limited, and the coloring material can be dispersed using a known disperser. Examples of the dispersing machine for performing the dispersion treatment include roll mills such as two rolls and three rolls, ball mills such as a vibration ball mill, bead mills such as a paint conditioner, a continuous disk type bead mill, and a continuous annular type bead mill. The diameter of the beads used in the dispersion treatment is preferably 0.03 to 2.00 mm, more preferably 0.10 to 1.00 mm.

  In the present invention, when dispersing the pigment, it is preferable to add zirconia beads or the like as appropriate and perform dispersion for several hours using a paint shaker (manufactured by Asada Steel Corporation) or the like. For example, after dispersion for 1 hour with a relatively large bead diameter of 2 mm zirconia beads, it may be further dispersed for 2 hours with a relatively small bead diameter of 0.1 mm zirconia beads. Moreover, it is preferable to filter with a 5.0 μm membrane filter after dispersion. Thereby, the dispersibility of a coloring material can be improved more and the transmittance | permeability can be improved more.

Polymer According to a preferred embodiment of the present invention, the weight average molecular weight of the polymer is preferably from 4,000 to 100,000, more preferably from 5,000 to 50,000. If the weight average molecular weight of a polymer is about the said range, the contact angle of the resin composition for colored layers with respect to a lower layer can be increased.

  Examples of the polymer include ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, ethylene vinyl copolymer, polystyrene, acrylonitrile-styrene copolymer, ABS resin, polymethacrylic acid resin, ethylene methacrylic acid. Resin, polyvinyl chloride resin, chlorinated vinyl chloride, polyvinyl alcohol, cellulose acetate propionate, cellulose acetate butyrate, nylon 6, nylon 66, nylon 12, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl acetal, polyether ether Ketone, polyethersulfone, polyphenylene sulfide, polyarylate, polyvinyl butyral, epoxy resin, phenoxy resin, polyimide resin, polyamide Resin, polyamic acid resin, polyetherimide resin, phenol resin, urea resin, etc., and polymerizable monomers such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl Acrylate, isopropyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, n-octyl One or more of methacrylate, n-decyl acrylate, n-decyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, styrene, α-methyl styrene, N-vinyl-2-pyrrolidone, glycidyl (meth) acrylate, acrylic acid, Examples thereof include polymers or copolymers composed of at least one of methacrylic acid, dimer of acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof. These polymers may be used alone or in combination of two or more. When two or more types are used in combination, the average value of the weight average molecular weights of the two or more types of polymers may be within the above range. In the present invention, commercially available polymers can also be used. For example, Epicoat 180S70 (manufactured by Yuka Shell Epoxy Co., Ltd.), Aronix M-5600 (manufactured by Toagosei Co., Ltd.), Aronix M-6200 (Toagosei Co., Ltd.) Alonix M-7100 (manufactured by Toagosei Co., Ltd.) and Aronix M-9050 (manufactured by Toagosei Co., Ltd.) are preferred.

Monomer According to a preferred embodiment of the present invention, the weight average molecular weight of the monomer is preferably 300 or more and 1000 or less, more preferably 400 or more and 900 or less. Further, the average number of functional groups of the monomer is preferably 4 or more, more preferably 5 or more. If the weight average molecular weight and / or the number of functional groups of the monomer are in the above range, the contact angle of the colored layer resin composition to the lower layer can be increased.

  Examples of the monomer include allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2 Hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1 , 4-Butanegio Diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate Acrylate, tripropylene glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethylated trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane Triacrylate, butylene glycol diacrylate, 1,2,4-butanetriol triac 2,2,4-trimethyl-1,3-pentanediol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and the above acrylate groups Substituted with a methacrylate group, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, 2-hydroxyethylacryloyl phosphate, tetrahydrofurfuryl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, 3-butanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, hydroxypivalate ester neopent Glycol diacrylate, phenol-ethylene oxide modified acrylate, phenol-propylene oxide modified acrylate, N-vinyl-2-pyrrolidone, bisphenol A-ethylene oxide modified diacrylate, pentaerythritol diacrylate monostearate, tetraethylene glycol diacrylate, polypropylene Acrylate monomers such as glycol diacrylate, trimethylolpropane propylene oxide modified triacrylate, isocyanuric acid ethylene oxide modified triacrylate, trimethylolpropane ethylene oxide modified triacrylate, pentaerythritol pentaacrylate, pentaerythritol hexaacrylate, pentaerythritol tetraacrylate , And those obtained by substituting these acrylate groups with methacrylate groups, urethane acrylate oligomers in which an acrylate group is bonded to an oligomer having a polyurethane structure, polyester acrylate oligomers in which an acrylate group is bonded to an oligomer having a polyester structure, and having an epoxy group Epoxy acrylate oligomers with acrylate groups bonded to oligomers, urethane methacrylate oligomers with methacrylate groups bonded to oligomers with polyurethane structures, polyester methacrylate oligomers with methacrylate groups bonded to oligomers with polyester structures, and oligomers with epoxy groups Epoxy methacrylate oligomer bonded with methacrylate group, Polyureta having acrylate group Acrylate, polyester acrylate having an acrylate group, epoxy acrylate resin having an acrylate group, polyurethane methacrylate having a methacrylate group, polyester methacrylate having a methacrylate group, and epoxy methacrylate resin having a methacrylate group. These monomers may be used alone or in combination of two or more. When two or more types are used as a mixture, the average value of the weight average molecular weight and the number of functional groups of the two or more types of monomers may be within the above range. In the present invention, commercially available monomers can also be used. For example, SR399 (manufactured by Sartomer Co., Ltd.), Aronix M-400 (manufactured by Toagosei Co., Ltd.), and Aronix M-450 (manufactured by Toagosei Co., Ltd.) ) Is preferred.

Polymerization initiator As the polymerization initiator, a thermal polymerization initiator and a photopolymerization initiator can be used. For example, benzyl (also referred to as bibenzoyl), benzoin isobutyl ether, benzoin isopropyl ether, benzophenone, benzoylbenzoic acid, Methyl benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl sulfide, benzylmethyl ketal, dimethylaminomethylbenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 3,3 ′ -Dimethyl-4-methoxybenzophenone, methylobenzoyl formate, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpho Nophenyl) -butan-1-one, 1- (4-dodecylphenyl) -2hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1 -One, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dimethylthioxanthone , Isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, and the like. In the present invention, commercially available polymerization initiators can also be used. For example, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 907 (all manufactured by Ciba Specialty Chemicals), Darocur (Merck Corporation) )), Adeka 1717 (Asahi Denka Kogyo Co., Ltd.) and the like, and 2,2′-bis (o-chlorophenyl) -4,5,4′-tetraphenyl-1,2′biimidazole Biimidazole compounds such as (Kurokinkasei Co., Ltd.) are preferred.

Dispersant As the above-mentioned dispersant, for example, cationic, anionic, nonionic, amphoteric, silicone-based, fluorine-based surfactants can be used. Among these, polymeric surfactants (polymer dispersants) ) Is preferably used. Examples of the polymer surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like. And polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate, sorbitan fatty acid esters, fatty acid-modified polyesters, and tertiary amine-modified polyurethanes. In the present invention, commercially available dispersants can also be used. For example, various Solsperse dispersants such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 20000, 24000, 26000, and 28000 (Geneca Corp. ), And Disperbyk111 (by Big Chemie Japan Co., Ltd.) are preferable.

Solvent Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as α- or β-terpineol; acetone, methyl ethyl ketone, cyclohexanone, and N-methyl. Ketones such as 2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl Ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether Ether, glycol ethers such as triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, Examples include propylene glycol monoethyl ether acetate and acetates such as 3-methoxybutyl acetate. In the present invention, a commercially available solvent can also be used, for example, propylene glycol monomethyl ether acetate (produced by Daicel Chemical Industries, Ltd.), propylene glycol monoethyl ether (produced by Daicel Chemical Industries, Ltd.), and 3-methoxy. Butyl acetate (manufactured by Daicel Chemical Industries, Ltd.) is preferred.

Spacer According to a preferred aspect of the present invention, the spacer is formed on a portion other than the opening of the light shielding portion on the substrate. The spacer is composed of a stacked column in which two or more colored layers are stacked. The spacer may be formed by further laminating a protective layer or the like on the laminated pillar. In the present invention, the “spacer height” is the distance (thickness) from the peripheral part of the spacer (the colored layer of each color and / or the surface of the light shielding part) to the top of the stacked pillar in the vertical direction. For example, as shown in FIG. 1, the distance 60 is a distance 60 from the light shielding portion 30 around the spacer in the vertical direction to the top of the spacer. In the present invention, the height of the spacer is preferably 2.5 to 4.2 μm, and more preferably 2.8 to 3.8 μm. This is because a sufficient cell gap can be obtained if the height of the spacer is in the above range.

In the laminated columns present invention, laminated pillars, two or more colors, preferably not colored layer 2 color 5 colors are laminated. When the coloring pattern formed on the substrate has three colors of red, green, and blue, the stacked pillar is preferably formed by stacking colored layers of three colors of red, green, and blue. If the colored pattern formed in the opening on the substrate and the colored layer (laminated column) laminated on the light-shielding part have the same color, this is for an additional colored layer to form a laminated column This is because it is not necessary to use a resin composition and costs can be reduced.

  According to a preferred embodiment of the present invention, the laminated pillar is composed of a colored layer of two or more layers, preferably n layers (n is an integer of 3 or more, preferably 3 to 5). In the case where n colored layers are formed, if two or more colored layers are laminated, two or more colored layers of the same color may be present in the laminated column. In the present invention, it is preferable to set the number of stacked columns in accordance with the number of colored patterns formed in the opening on the substrate. If the number of stacked layers is in the above range, a sufficient height can be obtained. Note that the number of stacked columns provided on the light shielding portion may be the same or different.

  In this invention, each colored layer can be laminated | stacked by said lamination | stacking rate by forming the lamination | stacking pillar which consists of a several colored layer using said resin composition for colored layers. As described above, each of the colored layers can be adjusted to a desired thickness by setting the lamination rate to be preferably 30% or more, more preferably 35% or more and 95% or less. By laminating each colored layer constituting the laminated column at the above-mentioned lamination rate, the colored layer can be thickened without increasing the coating amount of the colored layer resist.

  In the present invention, the planar shape of the colored layer constituting the laminated column is not particularly limited as long as it can stably form the laminated column, and examples thereof include a circle, an ellipse, and a polygon. Moreover, it is preferable to form so that the area of the plane of the colored layer which comprises a lamination | stacking pillar may become the narrowest in order by the uppermost layer with the widest colored layer of the lowest layer. This is because the stacked pillars can be formed stably.

Manufacturing method of color filter The manufacturing method of the color filter of the present invention is a process of forming a stacked column in which two or more colored layers are stacked on a light shielding portion.
(A) using the first colored layer resin composition having a contact angle of 4.0 degrees or more with respect to the light shielding part, forming a first layer on the light shielding part;
(B) forming a second layer on the first layer using the second colored layer resin composition having a contact angle of 4.0 degrees or more with respect to the first layer. It is a waste. According to a preferred embodiment, when forming an n-layer stacked column,
(C) The nth layer is formed on the n-1th layer using the nth colored layer resin composition having a contact angle of 4.0 degrees or more with respect to the n-1th layer. The method further includes a step. However, when n is 4 or more, it is preferable to repeat step (c) in all of the third to nth colored layer resin compositions. By passing through such a process, the lamination | stacking rate of each layer of a lamination | stacking pillar can be improved, and the height of the spacer which consists of a lamination | stacking pillar can fully be obtained.

  According to a preferred aspect of the present invention, the step of forming a colored pattern (colored layer) in the opening on the substrate by the photolithography method using the photosensitive resin composition is formed of the laminated pillar on the light shielding portion. A step of forming a spacer is preferably performed. This is because an additional process for forming the laminated pillar is not required, and the manufacturing cost can be suppressed by shortening the manufacturing process and simplifying the manufacturing equipment.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is limited to the content of the following Examples, and is not interpreted.

Preparation of photosensitive resin composition First, 63 parts by weight of methyl methacrylate (MMA), 12 parts by weight of acrylic acid (AA), 6 parts by weight of 2-hydroxyethyl methacrylate (HEMA), diethylene glycol in a polymerization tank After 88 parts by weight of dimethyl ether (DMDG) was added and stirred to dissolve, 7 parts by weight of 2,2′-azobis (2-methylbutyronitrile) was added and dissolved uniformly. Then, it stirred at 85 degreeC under nitrogen stream for 2 hours, and also was made to react at 100 degreeC for 1 hour. Further, 7 parts by weight of glycidyl methacrylate (GMA), 0.4 parts by weight of triethylamine, and 0.2 parts by weight of hydroquinone were added to the obtained solution, and the mixture was stirred at 100 ° C. for 5 hours to obtain a copolymer resin solution ( 45% solids) was obtained. Next, the following materials were stirred and mixed at room temperature to obtain a photosensitive resin composition.
Composition of photosensitive resin composition / copolymer resin solution (polymer, weight average molecular weight: 8000, solid content: 45%):
12 parts by weight-dipentaerythritol pentaacrylate (monomer, functional group number 5, SR399, manufactured by Sartomer Co.): 14 parts by weight-trimethylolpropane triacrylate (monomer, functional group number 3, manufactured by Sartomer Co.): 14 weights Parts / orthocresol novolac type epoxy resin (weight average molecular weight: 500 to 800, Epicoat 180S70, manufactured by Yuka Shell Epoxy Co., Ltd.): 4 parts by weight / 2-methyl-1- (4-methylthiophenyl) -2-morpho Linopropan-1-one (polymerization initiator, Irgacure 907, manufactured by Ciba Specialty Chemicals):
4 parts by weight-propylene glycol monomethyl ether acetate: 41 parts by weight-3-methoxybutyl acetate: 17 parts by weight

Preparation of colored layer resin composition Next, a colored layer resin composition having the following composition was prepared using the photosensitive resin composition described above.
B. Composition of resin composition for red colored layer I. Pigment Red 177 (Chromofine Red 6605, manufactured by Dainichi Seika Co., Ltd.): 10 parts by weight, polysulfonic acid type polymer dispersant: 3 parts by weight, photosensitive resin composition: 5 parts by weight, propylene glycol monomethyl ether acetate: 57 Part by weight 3-methoxybutyl acetate: 25 parts by weight
C. Composition of resin composition for green colored layer I. Pigment Green 36 (Heliogen Green D9360, manufactured by BASF Corporation): 10 parts by weight-Polysulfonic acid type polymer dispersant: 3 parts by weight-Photosensitive resin composition: 5 parts by weight-Propylene glycol monomethyl ether acetate: 57 parts by weight・ 3-methoxybutyl acetate: 25 parts by weight
B. Composition of resin composition for blue colored layer I. Pigment Blue 15: 6 (Fastogen Blue EP-7, manufactured by DIC Corporation): 10 parts by weight, polysulfonic acid type polymer dispersant: 3 parts by weight, photosensitive resin composition: 5 parts by weight, propylene glycol monomethyl ether acetate : 57 parts by weight 3-methoxybutyl acetate: 25 parts by weight

As described above, a reference colored layer resist (reference resist) used in the following measurement was obtained. Table 1 shows the parameters of the reference resist.

なお、表中の略称は以下を示すものである。
・ＴＭＰＴＡ：トリメチロールプロパントリアクリレート
・ＤＰＰＡ：ジペンタエリスリトールペンタアクリレート
・ＤＰＨＡ：ジペンタエリスリトールヘキサアクリレート
・ＣＨＭ：マルカリンカーＣＨＭ
・ＴＨＰＩ−Ａ：３，４，５，６−テトラヒドロフサロイミド-エチルアクリレート
・ＰＥＴＩＡ：ペンタエリスリトールトリアクリレート
・ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
・ＭＢＡ：３−メトキシブチルアセテート
・ＭＭＢＡ：３−メチル−３−メトキシブチルアセテート
・Ｉｒｇ：イルガキュア Next, the composition of the reference resist was changed as shown in Table 2, and sample No. 1-41 were obtained.

The abbreviations in the table indicate the following.
TMPTA: trimethylolpropane triacrylate DPPA: dipentaerythritol pentaacrylate DPHA: dipentaerythritol hexaacrylate CHM: marcalinker CHM
THPI-A: 3,4,5,6-tetrahydrofusalimide-ethyl acrylate PETIA: pentaerythritol triacrylate PGMEA: propylene glycol monomethyl ether acetate MBA: 3-methoxybutyl acetate MMBA: 3-methyl- 3-Methoxybutyl acetate / Irg: Irgacure

Further, the following components were mixed and sufficiently dispersed by a sand mill to prepare a black pigment dispersion.
Composition of Black Pigment Dispersion / Black Pigment: 23 parts by weight / Polymer Dispersant (Bicchemy Japan Co., Ltd. Disperbyk111):
2 parts by weight / solvent (diethylene glycol dimethyl ether): 75 parts by weight

Next, the following amount of components were sufficiently mixed to obtain a resin composition for a light shielding part.
Composition of light-shielding part resin composition- Black pigment dispersion: 60 parts by weight-Photosensitive resin composition: 20 parts by weight-Diethylene glycol dimethyl ether: 30 parts by weight

Measurement of lamination rate The lamination rate was measured according to the following procedure. A schematic diagram of the following procedure is shown in FIG.
1. Preparation of measurement substrate First, a measurement substrate was prepared according to the following procedure.
(1) About 1.5 ml of a lower layer resist was dropped on a 10 × 10 cm ² glass plate (note that the lower layer resist uses a light shielding part resin composition for red and green measurements, The resin composition for the colored layer was used for the measurement for the above.
(2) After coating using a spin coater, it was dried under reduced pressure at 2.2 × 10 ⁻¹ using a vacuum drying apparatus (hereinafter referred to as “VCD”).
(3) Prebaked for 3 minutes on an 80 ° C. hot plate (hereinafter referred to as “HP”).
(4) The film was exposed using a stripe mask at an exposure amount of 60 mJ and GAP of 200 μm.
(5) Development was performed using a developing device at a development time of 80 seconds.
(6) Post-baked at 230 ° C. for 25 minutes.
(7) The film thickness of the created measurement substrate was measured.
(8) The red and green lower layer thicknesses were 1.8 ± 0.1 μm, and the blue lower layer thickness was 4.7 ± 0.1 μm.
2. Application of colored layer resin composition Next, the colored layer resin composition (colored layer resist) was applied in the following procedure.
(1) About 1.5 ml of colored layer resist was dropped onto a 10 × 10 cm ² glass plate.
(2) After coating using a spin coater, it was dried under reduced pressure at 2.2 × 10 ⁻¹ using VCD.
(3) Pre-baked with HP at 80 ° C. for 3 minutes.
(4) The measurement substrate was solid-exposed with an exposure amount of 40 mJ (no pattern).
(5) Development was performed using a developing device with a development time of 40 seconds.
(6) Post-baked at 230 ° C. for 25 minutes.
3. Measurement of Stacking Ratio FIG. 4 shows a schematic cross-sectional view of the substrate after applying the colored layer resin composition prepared in 2 above (after post-baking). The lower layer film thickness 210, the film thickness 220 after lamination, and the colored film thickness 230 shown in FIG. 4 were measured, and the lamination ratio was calculated using the following formula (1).
Formula 1
he = (h1-h2) / h3 × 100
(Where h1 is the film thickness 220 after lamination, h2 is the lower film thickness 210, and h3 is the colored film thickness 230)

Measurement of contact angle The contact angle of the colored layer resin composition to the lower layer (film) was measured according to the following procedure.
1. Production of measurement substrate First, a measurement substrate having a lower layer (film) formed on the substrate was produced by the following procedure.
(1) About 1.5 ml of a corresponding lower layer resist was dropped on a 10 × 10 cm ² glass plate (in order to form a colored layer in the order of light shielding part → red → green → blue, the light shielding part layer resin composition or The resin composition for the colored layer in the color of the previous step becomes the resist for the lower layer).
(2) After coating using a spin coater, it was dried under reduced pressure at 2.2 × 10 ⁻¹ using VCD.
(3) Pre-baked with HP at 80 ° C. for 3 minutes.
(4) The measurement substrate was solid-exposed with an exposure amount of 40 mJ (no pattern).
(5) Development was performed using a developing device with a development time of 40 seconds.
(6) Post-baked at 230 ° C. for 25 minutes.
2. Contact angle measurement After irradiating cleaning UV to the prepared measurement substrate, a droplet of the resin composition for the colored layer was dropped from the microsyringe, and 30 seconds later, the contact angle measuring device (CA-Z type, Kyowa Kaiun Kagaku) Was used to measure the contact angle.

  Table 2 shows the measurement results of the contact angle and the lamination ratio. FIG. 5 shows a graph showing the relationship between the contact angle and the lamination rate. When various components and solid content ratios contained in the colored layer resin composition were changed, it was found that the lamination rate increased when the contact angle was 4.0 degrees or more.

A graph showing the relationship between the contact angle and the polymer ratio (ratio of polymer to the sum of polymer and monomer) is shown in Table 3 and FIG. When the polymer ratio was 30% or more, particularly 50% or more, the contact angle could be further increased.

A graph showing the relationship between the contact angle and the weight average molecular weight of the polymer is shown in Table 4 and FIG. The contact angle could be increased more as the weight average molecular weight of the polymer was increased.

A graph showing the relationship between the contact angle and the number of functional groups of the monomer is shown in Table 5 and FIG. Increasing the number of functional groups of the monomer could increase the contact angle.

DESCRIPTION OF SYMBOLS 10 Color filter 20 Base material 30 Light-shielding part 40 Colored layer 41 Red colored layer 42 Green colored layer 43 Blue colored layer 50 Spacer (lamination pillar)
60 Height of spacer 110 Resin composition for colored layer 120 Contact angle 130 Lower layer 210 Lower layer thickness 220 Film thickness after lamination 230 Colored film thickness

Claims (12)

A resin composition for a colored layer used for a color filter for a liquid crystal display device comprising a substrate and a light shielding part, a colored layer, and a spacer on the substrate,
The colored layer resin composition includes a coloring material, a polymer, and a monomer, and a ratio of the polymer to the monomer (P: M) is P: M = 60: 40 to 80:20,
The spacer is a stacked column formed by stacking two or more colored layers on the light shielding portion,
The colored layer resin composition forming the laminated column has the following conditions:
(I) the first colored layer resin composition for forming the first layer on the light shielding part has a contact angle of 4.0 degrees or more with respect to the light shielding part;
(II) Coloring satisfying that the second colored layer resin composition forming the second layer on the first layer has a contact angle of 4.0 degrees or more with respect to the first layer Layer resin composition. The spacer is composed of laminated columns of n layers (n is an integer of 3 or more), and the colored layer resin composition has the following conditions:
(III) The nth colored layer resin composition forming the nth layer on the n-1th layer has a contact angle of 4.0 degrees or more with respect to the n-1th layer. It satisfy | fills further, However, When n is four or more, all the 3rd-nth colored layer resin compositions satisfy | fill the conditions of (III), The colored layer resin composition of Claim 1. The resin composition for colored layers according to claim 1 or 2 , wherein the polymer has a weight average molecular weight of from 4,000 to 100,000. The resin composition for colored layers according to any one of claims 1 to 3 , wherein the average number of functional groups of the monomer is 4 or more. A color filter for a liquid crystal display device comprising a base material, a light shielding part, a colored layer, and a spacer on the base material,
The said spacer is a lamination | stacking pillar by which the colored layer of 2 colors or more is laminated | stacked on the said light-shielding part, Each colored layer which comprises the said lamination | stacking pillar is as described in any one of Claims 1-4 . The color filter formed using the resin composition for colored layers. Each of the colored layers constituting the laminated pillar is represented by the following formula (1)
Formula 1
he = (h1-h2) / h3 × 100 (%)
(Where h1 is the film thickness after lamination, h2 is the lower film thickness, and h3 is the colored film thickness)
The color filter according to claim 5 , wherein the color filter is laminated at a lamination ratio of 30% or more obtained by the above. A method for producing a color filter for a liquid crystal display device, comprising: a base material; and a light shielding portion, a colored layer, and a spacer on the base material,
The spacer is a laminated pillar formed by laminating two or more colored layers on the light-shielding portion, and the laminated pillar is formed using a colored layer resin composition, and the colored layer resin composition Includes a coloring material, a polymer, and a monomer, and the ratio of the polymer to the monomer (P: M) is P: M = 60: 40 to 80:20,
(A) using the first colored layer resin composition having a contact angle of 4.0 degrees or more with respect to the light shielding part, forming a first layer on the light shielding part;
(B) forming a second layer on the first layer using a second colored layer resin composition having a contact angle of 4.0 degrees or more with respect to the first layer. A method for producing a color filter. The spacer is composed of stacked pillars of n layers (n is an integer of 3 or more), and the method includes:
(C) The nth layer is formed on the n-1th layer using the nth colored layer resin composition having a contact angle of 4.0 degrees or more with respect to the n-1th layer. The manufacturing method according to claim 7 , further comprising a step, wherein when n is 4 or more, the step (c) is repeated for all of the third to nth colored layer resin compositions. The method for producing a color filter according to claim 7 or 8 , wherein the polymer has a weight average molecular weight of from 4,000 to 100,000. The method for producing a color filter according to any one of claims 7 to 9 , wherein the average number of functional groups of the monomer is 4 or more. Each of the colored layers constituting the laminated pillar is represented by the following formula (1)
Formula 1
he = (h1-h2) / h3 × 100 (%)
(Where h1 is the film thickness after lamination, h2 is the lower film thickness, and h3 is the colored film thickness)
It is laminated in lamination of 30% or more as determined by the method for producing a color filter according to any one of claims 7-10. Produced by the production method according to any one of claims 7 to 11, the color filter.

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