JP5699293B2 - Photosensitive coloring composition for color filter and color filter - Google Patents

Description

  The present invention relates to a photosensitive color composition for a color filter used for producing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter including a filter segment formed using the same. It is about.

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. The liquid crystal display device can perform color display by providing a color filter between two polarizing plates. Therefore, liquid crystal display devices are being developed for use in televisions and personal computer monitors.

  Other typical liquid crystal display devices include an in-plane switching (IPS) method in which a pair of electrodes is provided on one substrate and electrolysis is applied in a direction parallel to the substrate, negative dielectric anisotropy Vertical alignment (VA) method for vertically aligning nematic liquid crystal with optical properties, and Optical Convencence Bend (OCB) method in which the optical axes of uniaxial retardation films are orthogonal to each other to perform optical compensation Etc., and each has been put to practical use.

  A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged vertically and horizontally. It is made up of those arranged in In general, it is often formed from filter segments of three colors of red, green, and blue. Each of these segments is as fine as several microns to several hundreds of microns, and is neatly arranged in a predetermined arrangement for each hue. ing.

  The filter segments that make up the color filter are activated by proximity exposure (ultraviolet light source exposure) through a photomask for pixel formation after applying a photosensitive material on a glass substrate, drying and removing excess solvent. It is formed by irradiating energy rays, curing (negative type) or increasing alkali solubility (positive type), removing a portion that dissolves with an alkali solution, etc., and heating to 230 ° C. or more called post-baking. By repeating this for each color of red, green and blue, for example, a color filter is produced.

  The quality item required for the color filter is brightness. When a color filter with low brightness is used, the light transmittance is low, resulting in a dark screen. In order to obtain a bright screen, it is necessary to increase the number of backlights that are light sources. For this reason, from the viewpoint of suppressing an increase in power consumption, increasing the brightness of color filters has become a trend.

  Furthermore, as described above, since color liquid crystal devices have been used for televisions, personal computer monitors, etc., color filters are required to have high lightness and high reliability (heat resistance, light resistance). .

  Moreover, a voltage holding ratio is mentioned as an index showing the display performance of a liquid crystal display device. Liquid crystal is an extremely high insulating material, and when the polar compound remaining in the color filter coloring composition elutes into the liquid crystal cell, the voltage between the electrodes decreases, leading to a decrease in voltage holding ratio, and display unevenness. Generation | occurrence | production, alignment failure, etc. arise and it becomes the cause of reducing the performance as a liquid crystal display device. Therefore, the color filter coloring composition is required to be insoluble in liquid crystals.

  Conventionally, it is common to use a copper halide phthalocyanine pigment (for example, CI Pigment Green 36 or CI Pigment Green 7) as a colorant used for forming a green filter segment (pixel). However, as long as copper halide phthalocyanine can be used, it has been difficult to achieve both high contrast ratio and high brightness. Therefore, a green coloring composition for a color filter containing a zinc phthalocyanine pigment has been proposed. However, zinc phthalocyanine-based pigments have high acidity and are easily extracted into the liquid crystal phase laminated on the color filter layer, leading to a decrease in voltage holding ratio, resulting in display unevenness and poor alignment. There has been a problem that the performance as a liquid crystal display element is lowered. (Patent Document 1)

  In order to solve these problems, a green coloring composition for a color filter containing an aluminum phthalocyanine pigment and a yellow pigment (Patent Document 2), and a color filter containing a phthalocyanine dye having various structures and a quinophthalone dye. The proposal of a green coloring composition (patent documents 3-6) etc. is made. However, these green coloring compositions for color filters have a problem that lightness is insufficient.

  Moreover, when using as a green coloring composition, since the absorption of the coloring material in an ultraviolet region is large, the raw material used as a material for hardening is limited. Furthermore, in order to increase photocurability, if the components such as photopolymerization initiator and photopolymerizable monomer are increased, yellowing occurs in the post-baking process at 230 ° C or more, and the brightness of the green filter segment is reduced. There is a problem that it becomes a factor to cause.

JP 2010-168531 A JP 2004-333817 A JP-A-6-220339 Japanese Patent Laid-Open No. 8-171201 JP 2009-51896 A JP 2010-168531 A

  A problem to be solved by the present invention is a color filter coloring composition that has good heat resistance, light resistance, and voltage holding ratio, and can suppress a decrease in lightness even in a color filter forming process, and To provide a color filter using

  As a result of intensive studies, the present inventors have found that a coloring composition for a color filter containing a phthalocyanine dye having a specific structure and an antioxidant can solve the above-described problems, and has led to the present invention. It was.

[一般式（１）中、Ａ¹〜Ａ¹⁶は、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、置換基を有してもよいアルキル基、または置換基を有してもよいアリール基を表す。
Ｒ¹およびＲ²は、それぞれ独立して、水素原子、ヒドロキシ基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、または−ＯＲ³を表し、Ｒ¹とＲ²とが互いに結合して環を形成しても良い。
Ｒ³は、置換基を有してもよいアルキル基、または置換基を有してもよいアリール基である。］ That is, the present invention is a photosensitive coloring composition for a color filter containing a colorant, a binder resin, an antioxidant, a photopolymerization initiator, and a photopolymerizable monomer, and the colorant is represented by the following general formula: It is related with the photosensitive coloring composition for color filters characterized by containing the phthalocyanine pigment | dye represented by Formula (1).
General formula (1)

[In General Formula (1), A ^{1 to} A ¹⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, an alkyl group that may have a substituent, or an aryl that may have a substituent. Represents a group.
R ¹ and R ² are each independently hydrogen atom, hydroxy group, an optionally substituted alkyl group, an optionally substituted aryl group, or an -OR ^3, and R ¹ R ² may be bonded to each other to form a ring.
R ³ is an alkyl group which may have a substituent or an aryl group which may have a substituent. ]

  In the present invention, the antioxidant is at least one or more antioxidants selected from the group consisting of hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfur antioxidants. It is related with the said photosensitive coloring composition for color filters characterized by the above-mentioned.

  In the color filter, the total amount of the antioxidant is 0.5 to 5.0% by weight based on the solid content weight of the photosensitive coloring composition for color filter. The present invention relates to a photosensitive coloring composition.

  The present invention also relates to a color filter comprising a filter segment formed on the substrate from the photosensitive coloring composition for a color filter.

  By using the coloring composition for a color filter of the present invention, the heat resistance, light resistance, and voltage holding ratio are good, and the color composition for a color filter that can suppress a decrease in lightness even in the color filter forming step. And a color filter using the same can be provided.

Hereinafter, the present invention will be described in detail.
In the present application, when “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” is particularly described, Unless otherwise indicated, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. It shall represent.
Further, “CI” mentioned in the present specification means a color index (CI).

  The present invention is a photosensitive coloring composition for a color filter comprising a colorant, a binder resin, an antioxidant, a photopolymerization initiator, and a photopolymerizable monomer, wherein the colorant is represented by the general formula (1). The photosensitive coloring composition for color filters characterized by containing the phthalocyanine pigment | dye represented by this.

[一般式（１）中、Ａ¹〜Ａ¹⁶は、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、置換基を有してもよいアルキル基、または置換基を有してもよいアリール基を表す。
Ｒ¹およびＲ²は、それぞれ独立して、水素原子、ヒドロキシ基、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、または−ＯＲ³を表し、Ｒ¹とＲ²とが互いに結合して環を形成しても良い。
Ｒ³は、置換基を有してもよいアルキル基、または置換基を有してもよいアリール基である。］ <Colorant>
The photosensitive coloring composition for a color filter of the present invention contains a phthalocyanine dye represented by the general formula (1) (hereinafter sometimes referred to as “specific phthalocyanine dye”) as a colorant.
(Phthalocyanine dye represented by the general formula (1))
General formula (1)

[In General Formula (1), A ^{1 to} A ¹⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, an alkyl group that may have a substituent, or an aryl that may have a substituent. Represents a group.
R ¹ and R ² are each independently hydrogen atom, hydroxy group, an optionally substituted alkyl group, an optionally substituted aryl group, or an -OR ^3, and R ¹ R ² may be bonded to each other to form a ring.
R ³ is an alkyl group which may have a substituent or an aryl group which may have a substituent. ]

Examples of the halogen atom in A ^{1 to} A ¹⁶ include fluorine, chlorine, bromine, and iodine.

Examples of the alkyl group which may have a substituent in A ^{1 to} A ¹⁶ and R ^{1 to} R ³ include a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms. . Examples of the “substituent” include halogen atoms such as chlorine, fluorine and bromine, alkoxy groups such as methoxy group, nitro groups and the like. Specific examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2,2,3,3-tetrafluoropropyl group, 2-nitropropyl group, Isopropyl group, isobutyl group, isopentyl group, 2-ethylhexyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl Group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4 It can be a decyl cyclohexyl group, but not limited thereto.

Examples of the aryl group which may have a substituent in A ^{1 to} A ¹⁶ and R ^{1 to} R ³ include a monocyclic or condensed polycyclic aromatic group having 6 to 18 carbon atoms. Examples of the “substituent” include halogen atoms such as chlorine, fluorine and bromine, alkoxy groups such as alkyl groups and methoxy groups, amino groups and nitro groups. Specific examples include phenyl group, naphthyl group, anthranyl group, p-methylphenyl group, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-methoxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2 -Aminoanthraquinonyl group and the like.

As a specific phthalocyanine dye that can be used in the photosensitive coloring composition for a color filter of the present invention, A ^{1 to} A ¹⁶ are any one of a hydrogen atom, a halogen atom, and a methyl group from the viewpoint of dispersibility and color characteristics. preferable. More preferably, A ^{1 to} A ¹⁶ are all hydrogen atoms.

Furthermore, as a specific phthalocyanine dye that can be used in the photosensitive coloring composition for a color filter of the present invention, from the viewpoint of dispersibility and color characteristics, at least one of R ¹ and R ² may have a substituent. It is preferably a good aryl group or an aryloxy group which may have a substituent (in —OR ³ , R ³ is an aryl group which may have a substituent). More preferably, R ¹ and R ² may be an aryl group which may have a substituent, or an aryloxy group which may have a substituent (in —OR ³ , R ³ may have a substituent). It is preferable that R ¹ and R ² are a phenyl group or a phenoxy group because of excellent lightness.

  Specific examples of the specific phthalocyanine dye that can be used in the photosensitive coloring composition for a color filter of the present invention are shown below, but are not limited thereto.

(Other colorants)
The photosensitive coloring composition for a color filter of the present invention may further contain a yellow pigment within a range that does not impair the effects of the present invention in order to further adjust the chromaticity. The yellow pigment is not particularly limited, and generally includes a yellow dye or a yellow pigment.

  Yellow dyes include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes , Naphthoquinone dyes and oxazine dyes.

  Therefore, specific examples of yellow dyes include C.I. I. Acid Yellow 2,3, 4, 5, 6, 7, 8, 9, 9: 1, 10, 11, 11: 1, 12, 13, 14, 15, 16, 17, 17: 1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40: 1, 41, 42, 42: 1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199 Etc.

  In addition, C.I. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134 etc. are also mentioned.

  In addition, C.I. I. Basic Yellow 1, 2, 5, 11, 13, 14, 15, 19, 21, 24, 25, 28, 29, 37, 40, 45, 49, 51, 57, 79, 87, 90, 96, 103, 105, 106 and the like.

  In addition, C.I. I. Solvent Yellow 2, 3, 4, 7, 8, 10, 11, 12, 13, 14, 15, 16, 18, 19, 21, 22, 25, 27, 28, 29, 30, 32, 33, 34, 40, 42, 43, 44, 45, 47, 48, 56, 62, 64, 68, 69, 71, 72, 73, 77, 79, 81, 82, 83, 85, 88, 89, 90, 93, 94, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135, 138, 141, 143, 145, 146, 147, 157, 160, 162, 163, 167, 172, 174, 175, 176, 177, 179, 181, 182, 183, 184, 185, 186, 187, 188, 190, 191, 192, 194, 195 and the like are also included.

  In addition, C.I. I. Disperse Yellow 1, 2, 3, 5, 7, 8, 10, 11, 13, 13, 23, 27, 33, 34, 42, 45, 48, 51, 54, 56, 59, 60, 63, 64 67, 70, 77, 79, 82, 85, 88, 93, 99, 114, 118, 119, 122, 123, 124, 126, 163, 184, 184: 1, 202, 211, 229, 231, 232 233, 241, 245, 246, 247, 248, 249, 250, 251 and the like.

  As the yellow pigment, organic or inorganic pigments can be used alone or in admixture of two or more, and pigments having high color development properties and high heat resistance, particularly pigments having high heat decomposition resistance are preferred. Organic pigments are used. As the organic pigment, commercially available ones can be used, and natural pigments and inorganic pigments can be used in combination according to the desired hue of the filter segment.

Below, the specific example of the yellow organic pigment which can be used for the said coloring composition is shown. Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, Yellow pigments such as 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214 can be used. In particular, from the viewpoint of heat resistance, light resistance, and brightness of the filter segment, C.I. I. Pigment Yellow 138, 139, 150, and 185 are preferable.
These yellow pigments can be used alone or in combination of two or more depending on the desired color characteristics.

  Further, a green pigment can be added for the purpose of adjusting the hue. Examples of the green pigment include C.I. I. And green pigments such as CI Pigment Green 7, 10, 36, 37, and 58.

  In the present invention, when a green dye is used in combination with the phthalocyanine dye represented by the general formula (1), the weight ratio of the green dye / the phthalocyanine dye represented by the general formula (1) is 50/50 to 95 / The range of 5 is more preferable because the brightness and color reproducibility are good.

  When a yellow pigment is used in combination with the phthalocyanine pigment represented by the general formula (1), the weight ratio of the yellow pigment / the phthalocyanine pigment represented by the general formula (1) is in the range of 40/60 to 90/10. The brightness and the color reproducibility are preferable.

  The preferred colorant content in all the non-volatile components of the photosensitive coloring composition according to the present invention is 10 to 90% by weight, more preferably 15 to 85% by weight from the viewpoint of sufficient color reproducibility and stability. And most preferably 20 to 80% by weight.

(Miniaturization of pigment)
When the colorant used in the photosensitive coloring composition of the present invention is a pigment, it can be refined by a salt milling treatment or the like. It is preferable that the average primary particle diameter calculated | required by TEM (transmission electron microscope) of a pigment is the range of 5-90 nm. When the thickness is smaller than 5 nm, dispersion in an organic solvent becomes difficult. When the thickness is larger than 90 nm, a sufficient contrast ratio cannot be obtained. For these reasons, a more preferable average primary particle size is in the range of 10 to 70 nm.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

<Binder resin>
The binder resin contained in the photosensitive coloring composition of the present invention is one that disperses or dyes or penetrates a colorant, and includes conventionally known thermoplastic resins and thermosetting resins. The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

  Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like.

Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.
In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali development type colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. As a result, the colorant is fixed, heat resistance is improved, and fading (lightness reduction) due to heat of the colorant can be suppressed. In addition, there is also an effect of suppressing aggregation and precipitation of the colorant component in the development process.

  Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Energy ray curable resins having an ethylenically unsaturated active double bond include polymers having reactive substituents such as hydroxy groups, carboxyl groups, amino groups, and reactive groups such as isocyanate groups, aldehyde groups, and epoxy groups. A resin in which a photo-crosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a substituent or cinnamic acid is used. Further, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  A thermoplastic resin having both alkali-soluble performance and energy ray curing performance is also preferable as the photosensitive coloring composition for color filters.

The following are mentioned as a monomer which comprises the said thermoplastic resin. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypoly Ji glycol (meth) acrylate of (meth) acrylates,
Alternatively, (meth) acrylamide (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, etc. Acrylamides, styrenes, styrenes such as α-methylstyrene, ethyl vinyl ethers, n-propyl vinyl ethers, isopropyl vinyl ethers, n-butyl vinyl ethers, vinyl ethers such as isobutyl vinyl ethers, fatty acid vinyls such as vinyl acetate or vinyl propionate Kind.

  Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4′-bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-1,3-phenylenedimaleimide, N, N′-1,4- Phenylene dimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-sc N-imidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzimidazolyl) phenyl N-substituted maleimides such as maleimide and 9-maleimide acridine.

  Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins. Especially, an epoxy resin and a melamine resin are used more suitably from a viewpoint of heat resistance improvement.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 80,000, more preferably in the range of 7,000 to 50,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw / Mn is preferably 10 or less.

  Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are HLC-8220GPC (manufactured by Tosoh Corporation) as a device, and TSK-GEL SUPER HZM-N is connected in series as a column. Is a molecular weight in terms of polystyrene measured using THF.

  When the binder resin is used as a photosensitive coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that functions as an alkali-soluble group during development, an aliphatic group that functions as an affinity group for the colorant carrier and solvent, and The balance of the aromatic group is important for the dispersibility, penetrability, developability and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern does not remain by development.

  The binder resin is preferably used in an amount of 20 to 500 parts by weight with respect to 100 parts by weight of the colorant. If it is less than 20 parts by weight, the film formability and various resistances are insufficient, and if it is more than 500 parts by weight, the concentration of the colorant becomes low and color characteristics cannot be expressed.

<Antioxidant>
The photosensitive coloring composition for a color filter of the present invention can form a color filter having a high coating film transmittance by containing a phthalocyanine dye represented by the general formula (1) and an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the photosensitive coloring composition for color filters from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. The transmittance can be increased. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di- -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-tert-butyl-5-methylphenol), 2,2'-thio- Su- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2′thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) ) -Propionate, 1,1,3-tris- (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -butane, 2,2′-methylene-bis- (6- (1-methyl) -Cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydro Cinnamamide) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

  Specific examples of the hindered phenol antioxidant include Yoshinox BHT (= 2,6-di-t-butyl-4-methylphenol), Tominox TT (= tetrakis- [methylene-3- (3,5 ′). -Di-t-butyl-4'-hydroxyphenyl) propionate] methane), Yoshinox SR, Yoshinox BB, Yoshinox 2246G, Yoshinox 425, Yoshinox 250, Yoshinox 930, Tominox SS, Tominox 917, GSY-314 (or more, Manufactured by API Corporation), IRGANOX245, IRGANOX259, IRGANOX565, IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1098, IRGANOX1135, IRGANOX107 , IRGANOX 1425WL, IRGANOX 1222, IRGANOX 1330 (above, manufactured by BASF Japan Ltd.), ADK STAB AO-70, ADK STAB AO-50, ADK STAB AO-330, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-80 (Asahi Denka) (Manufactured by Kogyo Co., Ltd.), Sumizer BM, Sumizer GM, Sumizer GP, Sumizer GS, Sumizer GA-80, Sumizer BP-101, Sumizer BP-76, and Sumizer BP-101 (manufactured by Sumitomo Chemical Co., Ltd.).

  Examples of hindered amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4 -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi ) Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2, 2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomer type having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  Specific examples of the hindered amine-based antioxidant include Sanol LS-770, Sanol LS-765, Sanol LS-622LD, Kimasorp 944 (Sankyo Co., Ltd.), CYASORB UV-3346 (San Chemical Co., Ltd.), Knock rack 224, knock rack CD, Uvasil 299-299LM (above, Ouchi Shinsei Chemical Industry Co., Ltd.), MARK LA-63, MARKLA-68 (above, Asahi Denka Kogyo Co., Ltd.), TINUVIN 144, TINUVIN 312 (above, BASF・ Made by Japan).

  Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2 , 4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (3-methyl-) 6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxyphosphonoxy) -ben Zen, ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl), and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  Specific examples of phosphorus-based antioxidants include IRGAFOS168, IRGAFOS12, IRGAFOS38, IRGAFOSEPQ, (manufactured by BASF Japan Ltd.), Sumizer Z-16 (manufactured by Sumitomo Chemical Co., Ltd.), ADK STAB PEP-4C, ADK STAB PEP-8F, ADK STAB PEP-8, ADK STAB PEP-45, ADK STAB PEP-11C, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB P, ADK STAB C, ADK STAB QL, ADK STAB 135A, ADK STAB 1178, ADK STAB 1500, ADK STAB 1500 ADK STAB 3010, ADK STAB 522A, ADK STAB TPP (above, manufactured by Asahi Denka Kogyo Co., Ltd.), GSY-202 (above, AP Aiko Ltd. poration), SANKOHCA (Sanko Co., Ltd.), JPH1200, JP302, JPM313, JP304, JP308, JPP100, JP333E, JP318E, JP312 (manufactured by API Corporation) and the like.

  As sulfur-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

  Specific examples of sulfur-based antioxidants include IRGANOXPS800FD, IRGANOXPS802FD (above, manufactured by BASF Japan), Adekastab AO-503, Adekastab AO-412S (above, made by Asahi Denka Kogyo Co., Ltd.), Sumizer TPL-R, Sumizer TPM, TP Sumitizer TP-D, Sumitizer TL, Sumitizer MB (above, manufactured by Sumitomo Chemical Co., Ltd.), DLTP “Yoshitomi”, DSTP “Yoshitomi”, DMTP “Yoshitomi”, DTTP “Yoshitomi” (above, manufactured by API Corporation).

  As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.

  Specific examples of the benzotriazole antioxidant include Tomisorp 600 (manufactured by Yoshitomi Fine Chemical), TINUVIN 326, TINUVIN 327, TINUVIN P, TINUVIN 328 (above, manufactured by BASF Japan Ltd.), VIOSORB583, VIOSORB590 (manufactured by Kyodo Yakuhin). .

  As the benzophenone-based antioxidant, oligomer type and polymer type compounds having a benzophenone structure can be used.

  Examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4 -Octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4 -Methoxy-5 sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone, LA-51 (manufactured by Asahi Denka Kogyo Co., Ltd.) and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  Specific examples of the benzophenone antioxidant include Tomisorp 800 (manufactured by API Corporation) and LA-51 (manufactured by Asahi Denka Kogyo Co., Ltd.).

  Examples of the triazine antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

  Specific examples of the triazine antioxidant include CYASORB UV-1164 (manufactured by Sun Chemical Co., Ltd.).

  Specifically, a compound such as IRGASTABFS042 (above, manufactured by BASF Japan Ltd.) can be used as the hydroxylamine-based antioxidant.

  Examples of the salicylate ester antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  Further, the content of the antioxidant is more preferably 0.5 to 5.0% by weight based on the solid content weight of the photosensitive coloring composition for a color filter because the brightness and sensitivity are good.

<Organic solvent>
In the photosensitive coloring composition of the present invention, a colorant is sufficiently dispersed and permeated in a colorant carrier, and applied to a glass substrate or the like so as to have a dry film thickness of 0.2 to 5 μm. An organic solvent is included to facilitate the formation of the segments. The organic solvent is selected in consideration of good applicability of the photosensitive coloring composition, solubility of each component of the photosensitive coloring composition, and safety.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane. 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N- Dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether , Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol Monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  Among them, the dispersibility of the colorant, the penetrability, and the coating property of the photosensitive coloring composition are good, so ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol It is preferable to use glycol acetates such as monoethyl ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  Moreover, since the organic solvent can adjust the photosensitive coloring composition to an appropriate viscosity and can form a filter segment with a desired uniform film thickness, it is an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant. It is preferable to use it.

<Photopolymerizable monomer>
The photopolymerizable monomer added to the photosensitive coloring composition of the present invention includes a monomer or an oligomer that is cured by ultraviolet rays or heat to generate a transparent resin.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability. .

<Photopolymerization initiator>
In the photosensitive coloring composition of the present invention, the composition is cured by ultraviolet irradiation, and a photopolymerization initiator is added to form a filter segment by a photolithography method, and a solvent development type or alkali development type photosensitive coloring is added. It can be prepared in the form of a composition.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as dimethyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) Nyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] Or an oxime ester compound such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; An imidazole compound; or a titanocene compound or the like is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  Among these, it is preferable to contain an acetophenone compound or an oxime ester compound as a photopolymerization initiator in order to produce a color filter having a good pattern shape and linearity.

  The oxime ester-based compound absorbs ultraviolet rays to cleave the N—O bond of the oxime to generate an iminyl radical and a benzoyloxy radical. Since these radicals are further decomposed to generate radicals with high activity, a pattern can be formed with a small exposure amount. As oxime ester photoinitiators, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), 1,2- Octadione-1- [4- (phenylthio)-, 2- (O-benzoyloxime)] is preferred.

  An acetophenone compound is cleaved to generate a radical having an amino group that becomes an active hydrogen donor, so that it is possible to reduce the influence of oxygen inhibition, which is a problem in UV curing, and to cure the surface of the coating film. . Examples of the acetophenone compound include α-aminoalkylacetophenone compounds, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Butanone is preferred.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the photosensitive coloring composition of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the photosensitive coloring composition, and 5 to 50 from the viewpoint of photocurability and developability. More preferred are parts by weight.

<Amine compound>
Moreover, the photosensitive coloring composition of the present invention can contain an amine compound having a function of reducing dissolved oxygen.

  Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the photosensitive coloring composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the photosensitive coloring composition (100% by weight).

  Particularly preferred as a leveling agent is a type of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, and having a hydrophilic group but low solubility in water, and when added to a photosensitive coloring composition It has the characteristics that its surface tension lowering ability is low, and it is useful to have good wettability to the glass plate despite its low surface tension lowering ability, and it does not cause coating film defects due to foaming Those that can sufficiently suppress chargeability in terms of amount can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the photosensitive coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Til-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The photosensitive coloring composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.

<Method for producing photosensitive coloring composition>
In the photosensitive coloring composition of the present invention, the colorant is first mixed in a dye carrier such as a binder resin and / or a solvent, preferably together with a dispersion aid, a kneader, a two roll mill, a three roll mill, a ball mill, a horizontal type A finely dispersed pigment dispersion is produced using various dispersing means such as a sand mill, a vertical sand mill, an annular bead mill, or an attritor, and an antioxidant, a photopolymerization initiator, and photopolymerization are produced in the pigment dispersion. The photosensitive monomer and, if necessary, a solvent, other pigment dispersants, additives and the like can be mixed to prepare a solvent developing type or alkali developing type photosensitive coloring composition.

  Further, the photosensitive coloring composition containing two or more pigments may be prepared by dispersing a specific aluminum phthalocyanine dye and other colorants in a colorant carrier simultaneously when producing a pigment dispersion, or separately. What was dispersed in the colorant carrier may be mixed. In addition, when the colorant has high solubility, specifically, it is highly soluble in the solvent to be used, and if it is dissolved by stirring and no foreign matter is confirmed, it is necessary to manufacture by finely dispersing as described above. There is no.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a large effect of preventing reaggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness and viscosity stability. Become good.

  Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003 128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094773, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916 Gazettes, Japanese Patent No. 4585781 etc. can be used. These may be used alone or in combination of two or more. When a pigment derivative is used, one having a quinophthalone skeleton is preferable from the viewpoint of brightness.

  The content of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less.

  The resin-type dispersant has a colorant-affinity part having the property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160 manufactured by Nippon Lubrizol Corporation, such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. 0, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. -EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7 54,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When a resin-type dispersant and a surfactant are added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the content is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May affect.

<Removal of coarse particles>
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. Coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention comprises a red filter segment, a green filter segment, and a blue filter segment, and the green filter segment is formed from the photosensitive coloring composition of the present invention. The color filter may further comprise a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment, and the cyan color filter segment is formed from the photosensitive coloring composition of the present invention. It may be.

  The red filter segment can be formed using a normal red coloring composition comprising a red pigment and a colorant carrier. Examples of the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 242, 246, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, Mention may be made of red pigments such as 280, 281, 282, 283, 284, 285, 286 or 287. Also, red dyes such as xanthene, azo, disazo, and anthraquinone can be used. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

  In addition, red coloring compositions include C.I. I. Pigment orange 43, 71, or 73, and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,185,187,188,193,194,198,199,213,214,218,219,220, or may be used in combination of a yellow pigment 221, and the like. Also, orange dyes and / or yellow dyes such as quinoline, azo, disazo, and methine dyes can be used.

  The blue filter segment can be formed using a normal blue coloring composition containing a blue pigment and a colorant carrier. Examples of blue pigments include C.I. I. Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. are used. A purple pigment can be used in combination with the blue coloring composition. Examples of purple pigments that can be used in combination include C.I. I. And violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50. In addition, a basic dye or a salt-forming compound of an acid dye exhibiting blue or purple can be used. When the dye is used, a triarylmethane dye or a xanthene dye is preferable in terms of lightness.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.

  The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When forming a filter segment by a photolithography method, the photosensitive coloring composition prepared as the solvent developing type or alkali developing type coloring resist material is spray coated, spin coated, slit coated, roll coated, etc. on a transparent substrate. The coating method is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method or the like in addition to the above method, but the photosensitive coloring composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

  A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

  The average primary particle diameter of the pigment and the weight average molecular weight (Mw) of the resin are as follows.

(Average primary particle diameter of pigment)
The average primary particle diameter of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission (TEM) electron microscope. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the primary pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size.

(Weight average molecular weight of resin (Mw))
The weight average molecular weight (Mw) of the resin was measured using HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, TSK-GEL SUPER HZM-N connected in series as a column, and THF as a solvent. The molecular weight in terms of polystyrene.

  First, the binder resin solution, the colorant, the pigment dispersant solution, and the method for producing the pigment dispersion used in Examples and Comparative Examples will be described.

<Method for producing binder resin solution>
(Preparation of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 20.7 A mixture of 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Was added to prepare an acrylic resin solution 1. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution. After cooling to room temperature, sample 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20% by mass. Thus, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18000.

<Method for producing colorant>
(Production of hydroxyaluminum phthalocyanine 1)
In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-amyl alcohol and stirred. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Further, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in a reaction vessel. The mixture was stirred at 40 ° C. for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The blue precipitate was filtered, washed with water and dried to obtain 102 parts of hydroxyaluminum phthalocyanine 1 represented by the following formula (2).

(Production of blue colorant (B-1))
In a reaction vessel, 100 parts of methanol, 100 parts of hydroxyaluminum phthalocyanine 1 and 49.5 parts of diphenyl phosphate were added, heated to 40 ° C., and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of a specific phthalocyanine dye represented by formula (1-1).

  Subsequently, a salt milling process was performed. 100 parts of the specific phthalocyanine dye represented by the formula (1-1), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 98 parts of a colorant (B-1) were obtained. The average primary particle size was 31.2 nm.

(Production of green colorant (G-1))
C. I. 100 parts of Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product is poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a whole day and night. 97 parts of a colorant (G-1) were obtained. The average primary particle size was 28.2 nm.

(Production of yellow colorant (Y-1))
C. I. 100 parts of Pigment Yellow 138 (trade name Paliotor Yellow K0961HD, manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. 98 parts of colorant (Y-1) were obtained. The average primary particle size was 35.5 nm.

<Manufacture of pigment dispersion>
(Green pigment dispersion (DG-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. A green pigment dispersion (DG-1) was produced by filtration through a 0.0 μm filter. At this time, when the coated substrate is used, the blue colorant (B-1) and the yellow colorant (Y-1) are matched with the C light source so that the chromaticity is x = 0.290 and y = 0.600. The ratio was selected.

Blue colorant (B-1) 3.4 parts Yellow colorant (Y-1) 7.6 parts Resin-type dispersant ("BYK-LPN6919" manufactured by Big Chemie) 5.5 parts Acrylic resin solution 1 28.5 parts Propylene glycol monomethyl ether acetate 39.0 parts Cyclohexanone 16.0 parts

(Green pigment dispersion (DG-2))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. A green pigment dispersion (DG-2) was produced by filtration through a 0.0 μm filter. At this time, when the coated substrate is used, the blue colorant (B-1) and the yellow colorant (Y-1) are matched with the C light source so that the chromaticity is x = 0.290 and y = 0.600. The ratio was selected.

Green colorant (G-1) 7.2 parts Yellow colorant (Y-1) 3.8 parts Resin type dispersant ("BYK-LPN6919" manufactured by Big Chemie) 5.5 parts Acrylic resin solution 1 28.5 parts Propylene glycol monomethyl ether acetate 39.0 parts Cyclohexanone 16.0 parts

[Example 1]
(Green photosensitive coloring composition (RG-1))
A mixture having the following composition was stirred and mixed uniformly, and then filtered through a 1.0 μm filter to obtain a green photosensitive coloring composition (RG-1).

Green pigment dispersion (DG-1) 55.0 parts Acrylic resin solution 2 8.4 parts Photopolymerizable monomer (“Aronix M402” manufactured by Toagosei Co., Ltd.) 3.8 parts Photopolymerization initiator A (Ciba Japan) "Irgacure 379" manufactured by the company) 1.9 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.3 parts Antioxidant A 0.16 parts Pentaerythritol tetrakis [3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate propylene glycol monomethyl ether acetate 20.44 parts cyclohexanone 10.0 parts

[Examples 2-8 and Comparative Examples 1-2]
(Green photosensitive coloring composition (RG-2 to 10))
With the composition and blending amount (parts by weight) shown in Table 1, the pigment dispersion, the acrylic resin solution, the antioxidant, the photopolymerization initiator, the sensitizer, the photopolymerizable monomer, and the organic The mixture with the solvent was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain each photosensitive coloring composition.

Abbreviations in Table 1 are shown below.
Photopolymerizable monomer: Dipentaerythritol hexaacrylate / pentaacrylate mixture (“Aronix M402” manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator A: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (“Irga” manufactured by Ciba Japan) Cure 379 ")
Photopolymerization initiator B: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime)
("Irgacure OXE02" manufactured by Ciba Japan)
Sensitizer: 4,4′-diethylaminobenzophenone (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.)
)
Antioxidant A: hindered phenol antioxidant pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate Antioxidant B: sulfur antioxidant 3,3 '-Thiodipropanoic acid dioctadecyl, antioxidant C: phosphorus antioxidant tris [2,4-di- (tert) -butylphenyl] phosphine, antioxidant D: hindered amine antioxidant bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate / antioxidant E: salicylate-based antioxidant p-octylphenyl salicylate / organic solvent PGMAC; propylene glycol monomethyl ether acetate anone; cyclohexanone

  About the obtained green photosensitive coloring composition, the following method evaluated the brightness, sensitivity, heat resistance, light resistance, and voltage holding ratio. The results are shown in Table 2.

[Brightness evaluation]
The green photosensitive coloring composition (RG-1 to 10) is applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, and then dried at 70 ° C. for 20 minutes to obtain ultrahigh pressure mercury. Using a lamp, UV exposure was performed with an integrated light amount of 150 mJ / cm ² and development was performed with an alkaline developer at 23 ° C. to obtain a coated substrate. Then, after heating at 220 ° C. for 30 minutes and allowing to cool, the brightness Y (C) of the obtained coating film substrate was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). The prepared coated substrate was adjusted to a chromaticity of x = 0.290 and y = 0.600 with a C light source after heat treatment at 220 ° C. The alkali developer was 1.5% by weight of sodium carbonate, 0.5% by weight of sodium hydrogen carbonate, 8.0% by weight of an anionic surfactant (“Perex NBL” manufactured by Kao Corporation), and 90% by weight of water. The thing which consists of was used.

[Sensitivity evaluation]
After coating the obtained green photosensitive coloring composition (RG-1 to 10) on a 10 cm × 10 cm glass substrate by a spin coating method, the solvent was removed by heating at 70 ° C. for 15 minutes in a clean oven, A coating film of about 2 μm was obtained. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask having a stripe pattern of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) using an ultrahigh pressure mercury lamp. Thereafter, the substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated at 230 ° C. for 30 minutes in a clean oven. The pattern film thickness in the 100 μm photomask portion of the filter segment formed by the above method was measured, and the minimum exposure amount that was 90% or more with respect to the film thickness after coating was evaluated. The smaller the minimum exposure, the higher the sensitivity and the better the photosensitive coloring composition.
The rank of evaluation is as follows.
○: Less than 50 mJ / cm ² Δ: 50 mJ / cm ² or more and less than 100 mJ / cm ² ×: 100 mJ / cm ² or more

[Evaluation of heat resistance of coating film]
The green photosensitive coloring composition (RG-1 to 10) is applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, and then dried at 70 ° C. for 20 minutes to obtain ultrahigh pressure mercury. Using a lamp, UV exposure was performed with an integrated light amount of 150 mJ / cm ² and development was performed with an alkaline developer at 23 ° C. Subsequently, it was heated at 220 ° C. for 30 minutes and allowed to cool to obtain a coated substrate. The prepared coated substrate was adjusted to a chromaticity of x = 0.290 and y = 0.600 with a C light source after heat treatment at 220 ° C. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated in the following three stages.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
○: ΔEab * is less than 5.0 Δ: ΔEab * is 5.0 or more and less than 10.0 ×: ΔEab * is 10.0 or more

[Evaluation of light resistance of coating film]
A coated substrate is prepared in the same manner as in the heat resistance evaluation, and the chromaticity ([L * (1), a * (1), b * (1)]) with a C light source is measured with a microspectrophotometer ( Measurement was performed using “OSP-SP100” manufactured by Olympus Optical Co., Ltd. Subsequently, an ultraviolet cut filter (“COLORED OPTICAL GLASS L38” manufactured by Hoya Co., Ltd.) is attached on the substrate, and irradiated with ultraviolet rays using a 470 W / m ² xenon lamp for 100 hours, and then the chromaticity ([ L * (2), a * (2), b * (2)]) were measured, and the color difference ΔEab * was determined by the above formula and evaluated according to the same criteria as for heat resistance.

[Evaluation of voltage holding ratio]
The green photosensitive coloring composition (RG-1 to 10) was applied on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater so that the film thickness of the dry film was 2.0 μm. The film was exposed to ultraviolet light with an integrated light quantity of 50 mJ / cm ² and developed with an alkaline developer at 23 ° C. to obtain a coated substrate. Next, after heating and cooling at 220 ° C. for 30 minutes, 0.05 parts of the coating film was scraped off from the obtained coated substrate, and then immersed in 1.5 parts of liquid crystal (MLC-2041). After aging at 120 ° C. for 1 hour and centrifugation at 4000 rpm for 15 minutes, a supernatant liquid was collected to prepare a coating film extraction liquid crystal sample liquid.

On the other hand, two glass substrates having an ITO transparent electrode with an effective electrode size of 10 mm × 10 mm are placed facing each other so that the ITO transparent electrode surfaces face each other, and a small cell is produced using a sealing agent so that the cell gap is 9 μm. did. A resist extraction liquid crystal sample solution is injected into the small cell between the cell gaps, a voltage of 5 V is applied at 60 ° C. for 60 μsec, and the cell voltage [V1] after 16.67 msec after the voltage is released is expressed as Toyo. Measured with VHR-1S manufactured by Technica. The measurement was repeated 5 times, and the measured cell voltages were averaged. And using the obtained cell voltage, voltage retention (%) was calculated | required from the following formula, and it evaluated in the following three steps.
Voltage holding ratio (%) = ([V1] / 5) × 100
○: 95% or more △: 90% or more and less than 95% ×: less than 90%

  As shown in Table 2, the filter segment formed using the photosensitive coloring composition containing the phthalocyanine dye represented by the general formula (1) and the antioxidant, which is a feature of the present invention, has a lightness. It was excellent and showed good results in sensitivity, heat resistance, light resistance, and voltage holding ratio.

  On the other hand, when no antioxidant was used as in Comparative Example 1, the brightness was low and the heat resistance was poor. Further, Comparative Example 2 using CI Pigment Green 58 had a poor voltage holding ratio as compared with the Example.

<Production of color filter>
First, the red photosensitive coloring composition and the blue photosensitive coloring composition used for preparation of a color filter were produced.

(Preparation of red photosensitive coloring composition (RR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. A red pigment dispersion (DR-1) was prepared by filtration through a 0.0 μm filter.

Red pigment (CI Pigment Red 254) 9.6 parts Red Pigment (CI Pigment Red 177) 2.4 parts Resin-type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin Solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a red photosensitive coloring composition (RR-1).

Red pigment dispersion (DR-1) 42.0 parts Acrylic resin solution 2 13.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907") 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Ethylene glycol monomethyl ether acetate 39.6 parts

(Preparation of blue photosensitive coloring composition (RB-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. A blue pigment dispersion (DB-1) was produced by filtration through a 0.0 μm filter.

Blue pigment (CI Pigment Blue 15: 6) 7.2 parts Purple Pigment (CI Pigment Violet 23) 4.8 parts Resin Type Dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

Then, after stirring and mixing the mixture of the following composition so that it might become uniform, it filtered with a 1.0 micrometer filter, and produced the blue photosensitive coloring composition (RB-1).

Blue pigment dispersion (DB-1) 34.0 parts Acrylic resin solution 2 15.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907") 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 45.1 parts ethylene glycol monomethyl ether acetate

(Production of color filter)
A black matrix is patterned on a glass substrate, and the red photosensitive coloring composition (RR-1) is applied to the substrate with a spin coater in a C light source (hereinafter also used for green and blue) x = 0.640, y The film was applied to a film thickness such that = 0.330 to form a colored film. The film was irradiated with ultraviolet rays of 150 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. Formed. By using the same method, the blue photosensitive coloring composition (RB-1) was prepared so that x = 0.290 and y = 0.600 using the green photosensitive coloring composition (RG-6) of the present invention. A green filter segment and a blue filter segment were formed so that x = 0.150 and y = 0.060 were used to obtain a color filter.

  By using the green photosensitive coloring composition (RG-6) of the present invention, it is possible to increase the brightness of the color filter, and it is also suitable for the physical properties of sensitivity, heat resistance, light resistance, and voltage holding ratio. Could be used.

Claims (4)

A photosensitive coloring composition for a color filter comprising a colorant, a binder resin, an antioxidant, a photopolymerization initiator, and a photopolymerizable monomer, wherein the colorant is represented by the following general formula (1): The photosensitive coloring composition for color filters characterized by containing the phthalocyanine pigment | dye used.
General formula (1)

[In General Formula (1), A ^{1 to} A ¹⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, an alkyl group that may have a substituent, or an aryl that may have a substituent. Represents a group.
R ¹ and R ² are each independently hydrogen atom, hydroxy group, an optionally substituted alkyl group, an optionally substituted aryl group, or an -OR ^3, and R ¹ R ² may be bonded to each other to form a ring.
R ³ is an alkyl group which may have a substituent or an aryl group which may have a substituent. ]   The antioxidant is at least one antioxidant selected from the group of hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfur antioxidants. The photosensitive coloring composition for color filters according to claim 1.   3. The color filter according to claim 1, wherein the content of the antioxidant is 0.5 to 5.0% by weight based on the solid content weight of the photosensitive coloring composition for a color filter. Photosensitive coloring composition.   A color filter comprising a filter segment formed on the substrate from the photosensitive coloring composition for a color filter according to any one of claims 1 to 3.